DE2746789C3 - Thermosetting resin composition and its use - Google Patents

Description

The invention relates to a thermosetting resin composition excellent in heat resistance and resistance to fracture or cracking.

In recent years the need for both miniaturization and weight saving has increased in electronic components as well as electrical or electronic devices. To this it is on the other hand necessary to have resins with even more favorable thermal properties, with which allow such products to be completely or partially potted.

To solve this problem, heat-curable ones are already available (cf. JP-AS 31 000/77 by the same applicant) Resin compositions have been indicated to be polyfunctional Contain epoxy compounds, polyfunctional isocyanate compounds and curing catalysts. Cured molded articles obtained from these compositions have a higher than class H lying heat resistance; when used as pouring media for electrical devices or the like, which contain complicated details in the cast material, however, detachment occurs in numerous cases or peeling from the cast-in components as well as cracking if the corresponding products cooling and heating cycles during practical operation under less favorable application conditions are subjected, which worsens the function and operational safety of such devices. To the Avoidance of such disadvantageous interferences, a method was specified in which by increasing the Compounding ratio of an inorganic filler to the actual potting medium is the expansion capacity a hardened potting medium to the expansion capacity of the potted product is to be adapted, the expansion capacity of the potting medium is reduced; further a method was specified for this, in which the hardened potting medium by compounding the thermosetting resin composition can be made more flexible with an agent that imparts flexibility target. With the first method, however, there are numerous disadvantages in that there is an increase in the proportion the inorganic filler not only tends to damage the surface of cast objects increases due to the inorganic filler, but also the proportion of resin in the potting compound is correspondingly reduced, whereby, since the. Resin in contact with the surface of the poured Object is located, the adhesion or bond between the molded object and the Reduced potting compound and thereby also caused detachment in numerous cases. At the second method reduces the thermal degradation of the flexibility-increasing agent by heating cycles in in many cases the heat resistance of the hardened potting compound itself, as the heat resistance of the used Means of flexibility is generally insufficient.

In addition to miniaturization and weight savings in numerous electronic and electrical components Devices are generally also strictly prescribed fire resistance. For this reason Resins used to encapsulate components or entire devices must also be excellent Have heat resistance and fire resistance.

Accordingly, it is an object of the invention to provide a thermosetting resin composition excellent in heat resistance, crack resistance and fracture resistance as well as fire resistance, which contains a fire-resistant flexibilizing agent without reducing the heat resistance.
The object is achieved according to the claim.
The invention provides a thermosetting resin composition

a polyfunctional epoxy compound (a),
a polyfunctional isocyanate (b) and
a hardener (c), which is characterized in that it contains at least one flexibilizing agent (d) selected from:
- Butadiene polymers with terminal hydroxyl groups or terminal amino groups of the formula

(CH ₂ -CH = CH-

Y-RCH ₂ -CH = CH-CH ₂ I -CH, 1 ^

CH ₂ -CH ^J

--Y

where mean:

Y is a hydroxyl or amino group,

R is a hydrogen atom, an alkyl group with preferably 1 to 10 carbon atoms, a Alkenyl group with preferably 1 to 10 carbon atoms, a nitrile or phenyl group and

a> 0.7, 6 <0.3 with a + b = 1,

whereby

η is an integer and defines the molecular weight of the butadiene polymer in the range from 500 to 5000,

Polybutadienes with terminal hydroxyl groups of the formula

60

65 HO

CH, -CH

CH

OH

whereby

η is an integer and the molecular weight of the

Polybutadiene in the range from 500 to 5000

Are defined,
and

Reaction products obtained by reacting a polyfunctional epoxy compound or an epoxy compound having one or more halogen atoms with a butadiene polymer the formula

CH, —CH = CH- CH ₂ ^ —f CH ₂ -CH-

-X

X-RCH ₁ -CH = CH-CH ₂ ^ ₅ - ^ CH-CH ₂

are preserved

whereby

X is a hydroxyl or carboxyl group and
R, a, b and η have the above meanings.

As polyfunctional epoxy compounds for component (a) in the invention Compositions, for example, the following bifunctional epoxy compounds are used:

Diglycidyl ether of bisphenol A, butadiene diepoxide,

3.4-epoxycyclohexylmethyl- (3.4-epoxy) -cyclo-

hexane carboxylate,
Vinylcyclohexene dioxide,
4.4'-Di- (1.2-epoxyethyl) -diphenylether, 4.4'-(1.2-epoxyethyl) -diphenyl,
2.2-bis (3.4-epoxycyclohexyl) propane, diglycidyl ether of resorcinol,
Diglycidyl ether of phloroglucine, diglycidyl ether of methylphlorogluxcine, bis (2.3-epoxycyclopentyl) ether, 2- (3.4-epoxy) -cyclohexane-5.5-spiro (3.4-epoxy) -

cyclohexane-m-dioxane,
Bis (3.4-epoxy-6-methylcyc] ohexyl) adipate, N.N'-m-phenylene-bis ^ .S-epoxy-l ^ -cyclohexanedicarboximide) and the like;

30th

35

45

trivalent or higher polyfunctional epoxy compounds such as

Triglycidyl ether of p-aminophenol, polyallyl glycidyl ether,

1.3.5-tri (1.2-epoxyethyl) benzene, 2.2 ', 4.4'-tetraglycidoxybenzophenone, Tetraglycidoxytetraphenylmethane, tetraglycidoxytetraphenylethane, polyglycidyl ethers of phenol-formaldehyde novolaks,

Triglycidyl ether of glycerine, ^ o

Triglycidyl ether of trimethylolpropane, triglycidyl isocyanurate,
Polyglycidyl ethers of cresol-formaldehyde novolak and the like.

The following compounds, for example, can be used as polyfunctional isocyanates for component (b):

b5 Bifunctional isocyanates such as methane diisocyanate, butane-1.2-diisocyanate, butane-1.1-diisocyanate

Ethane-1,2-diisocyanate, trans-vinyl diisocyanate, Propane-1.3-diisocyanate. Butane-1,4-diisocyanate, 2-butene-1.4-diisocyanate, 2-methylbutane-1.4-diisocyanate, Pentane-1.S-diisocyanate, 2.2-dimethylpentane-1.5-diisocyanate, Hexane-1,6-diisocyanate, heptane-U-diisocyanate, Octane-1.8-diisocyanate, nonane-1.9-diisocyanate, Decane-1.10-diisocyanal, dimethylsilane-diisocyanate, Diphenylsilane diisocyanate, w ^ '- 1,3-dimethylbenzene diisocyanate, ω, ω'-1,4-dimethylbenzene diisocyanate, ω, ω'-1 J-dimethylcyclohexane diisocyanate, ω, ω'-1 ^ -dimethylcyclohexane diisocyanate, ω, ω'-1 .4-dimethylbenzene diisocyanate, ω, ω'-1,4-dimethylnaphthalene diisocyanate, ω, ω'-l.T-dimethylnaphthalene diisocyanate, ω, ω'-1,5-dimethylnaphtha-diisocyanate, Cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate,

Dicyclohexylmethane-i ^ '- diisocyanate, 1.3-phenylene diisocyanate, 1.4-phenylene diisocyanate, 1 -Methylbenzene ^ diisocyanate, 1 -Methylbenzene ^ .S-diisocyanate, 1 -Methylbenzene ^ .ö-diisocyanate, 1 -Methylbenzene-S.S-diisocyanate, Diphenyl ether 4,4'-diisocyanate, diphenyl ether 2,4'-diisocyanate, naphthalene 1,4-diisocyanate, Naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, S.S'-dimethyldiphenyM ^ '- diisocyanate, 2.3'-dimethoxydiphenyl-4.4'-diisocyanate, diphenylmethane-4.4'-diisocyanate, S-S'-dimethoxydiphenylmethane ^^ '-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate and the like;

trivalent or higher polyfunctional isocyanates such as

Polymethylene polyphenyl isocyanate, triphenyl methane triisocyanate, tris (4-phenyl isocyanate thiophosphate), 3.3 ', 4.4'-diphenylmethane tetraisocyanate and the like.

It is also possible to use diners and trimers of these isocyanates in the same way.

Halogenated polyfunctional isocyanates can also be used as polyfunctional isocyanates for components (b) find use.

Examples of such halogenated isocyanates are approximately:

i-bromomethylbenzene ^ .ö-diisocyanate, 1 -chlorobenzene ^ -diisocyanate, l.S-dichlorobenzene ^ -diisocyanate, 1 -Bromobenzene - ^ - diisocyanate,

l-bromomethylbenzene ^^ - diisocyanate, l.S-Dibrotnbenzol ^^ - diisocyanate and the like.

It is preferred to use 0.1 to 25.0 equivalents in the compositions according to the invention, even more preferred 1.5 to 15.0 equivalents of the polyfunctional isocyanate per 1.0 equivalent of the polyfunctional epoxy compound to use.

The butadiene polymers used according to the invention with terminal hydroxyl groups or terminal groups Amino groups are polybutadiene-based polymers of the formula

Y-RCH, - CH = CH-CH ₂ V- -f CH -CH ₂ 1- + - Y

R L

or

Υ — HCH ₂ -CH = CH-CH ₂ ) - / - CH ₂ -CH

with Y, R, a, b and η as above.

In the above formulas, η can represent an integer from 10 to 110, for example, and b = Osein.

The butadiene polymers with terminal hydroxyl groups or terminal amino groups can Units of the formulas

<-CH- CH ₂

and

, —CH

with C + rf = b included at the same time.

The butadiene polymers with terminal hydroxyl groups can be activated by activating the two chain ends a butadiene polymer obtained by polymerizing butadiene and ethylene, styrene, Acrylonitrile, propylene, 1-butene, 2-butene, 13-butadiene, 1,4-pentadiene and the like using a butyllithium complex. Na-naphthalene complex, Li-naphthalene complex, Li-methylnaphthalene or the like as a catalyst in the presence of a solvent such as Tetrahydrofuran, pentane, benzene, diethyl ether, toluene. Cyclohexane, heptane and the like is accessible, with a conventional polymerization process is applied and activation by reaction under Use of an alkylene oxide, aldehyde, ketone and the like can be carried out.

Such butadiene polymers with terminal hydroxyl groups are available commercially (cf. Examples 91-94). These products can also be e.g. B. contain 25% styrene or 15% acrylonitrile (see. The Examples 25-31).

The molecular weight of the butadiene copolymers with terminal hydroxyl groups is in the range of 500 to 5000. When the molecular weight is over 5000, the viscosity increases and the processability is unfavorably deteriorated, while with products having a molecular weight below 500 no cured molded articles with high Toughness are accessible and the crack resistance also tends to be unfavorable reduction. To achieve excellent crack resistance, the values for a and b in the formulas given above should satisfy the following conditions: a> 0.7 and b <0.3.

To achieve excellent physical properties of the cured products, especially with regard to the heat resistance and crack resistance become preferably 3 to 100 parts by weight, more preferably 10 to 60 parts Parts by weight, of the butadiene copolymer with terminal Hydroxyl groups with 100 parts by weight of the total amount of polyfunctional epoxy compound (component (a)), poryfunctional isocyanate (component (b)) and the hardener (component (c)) mixed.

The butadiene polymers with terminal amino groups can, for example, by reacting the above-mentioned butadiene polymers with terminal hydroxyl groups prepared with excess ammonia will. Amino-terminated copolymers of butadiene are also commercially available (cf.

see Examples 9-16).

The molecular weight of the amino-terminated butadiene polymers is in the range of 500 to 5000. When the molecular weight is over 5000, the viscosity increases and the processability is unfavorably deteriorated, while when the molecular weight is less than 500, on the other hand, no cured products with high Toughness are accessible and the crack resistance shows an unfavorable tendency to decrease. To achieve hardened products of high toughness, ie with excellent crack resistance, the values for a and b in the above formulas should correspond to the following conditions: a> 0.7 and b <03.

To achieve excellent physical properties of the cured products, particularly high heat resistance and breaking strength, are preferred 100 parts by weight of the butadiene copolymer with terminal amino groups with 100 parts by weight of the

Total weight of polyfunctional epoxy compound (component (a)), polyfunctional isocyanate (Component (b)) and the hardener (component (c)) mixed.

The polybutadienes with terminal hydroxyl groups correspond to the formula

10

HO-Z ¹ CH ₂ -CH ^ -OH
CH
CH ₂ ;

in which π is an integer defining the molecular weight of the polybutadienes in the range from 500 to 5000; for example: 17 <η <92 (η integer).

The hydroxyl terminated polybutadienes can be obtained by making 'living' polymers using n-butyllithium complex, Na-naphthalene complex, Li-naphthalene complex, Li-methylnaphthalene and the like as an initiator in the presence of a Solvents such as tetrahydrofuran, pentane, benzene, diethyl ether, toluene, cyclohexane, heptane and the like a conventional polymerization process, wherein the living polymer with a Alkylene oxide, an aldehyde, a ketone and the like. The terminal polybutadienes Hydroxyl groups usually have at least 90% 1.2 content.

Hydroxyl terminated polybutadienes are commercially available (see Examples 1-6). Such commercial products can also be, for. B. a 1.2 content of 90% and a molecular weight of 2000 exhibit.

The molecular weight of the hydroxyl-terminated polybutadienes is in the range from 500 to 5000. When the molecular weight is over 5000, the viscosity increases and the processability becomes while, on the other hand, when the molecular weight is below 500, none hardened products with high toughness are accessible and the crack resistance leads to an unfavorable reduction tends.

To obtain excellent physical properties of the cured products, especially good ones Heat resistance and crack resistance are preferably 3 to 100 parts by weight of the terminal polybutadiene Hydroxyl groups with 100 parts by weight of the total amount mixed from components (a), (b) and (c).

The butadiene polymers terminated with hydroxyl groups or terminal carboxyl groups are Polybutadiene-based polymers of the formula

X-

(CH ₂ -CH = CH-CH ₂ ^ - f CH ₂ -Ql ·

(CH ₂ -CH = CH-CH ₂ ^ -f-CH-CH ₂

R ι ».

with X, R, a, b and η as defined above.

The buiadiene polymers with terminal hydroxyl groups or terminal carboxyl groups can at the same time also be units of the formulas

- / ¹ CH ₂ -CH

CH-CH,

with c + d = b included.

The butadiene polymers with terminal hydroxyl groups are accessible as indicated above.

The butadiene polymers with terminal carboxyl groups can, for example, by preparing a Polymers of butadiene and ethylene and the like obtained by a conventional polymerization method , the polymer being reacted with an excess amount of carbon dioxide - butadiene polymers with Terminal carboxyl groups are commercially available (see Examples 17-22). Such commercial products, NISSO-PB C-2000, Hycar CTB 2000 χ 16Ζ Hycar CTBN 1300 χ 15 are also z. B. polybutadienes with terminal carboxyl groups, the molecular weights between 1300 and 4000 and a 1,2-content of 90% and can optionally contain acrylonitrile.

The molecular weight of the hydroxyl-terminated or carboxyl-terminated butadiene polymers is in the range of 500 to 5000. When the molecular weight is over 5000, the viscosity increases and the processability is unfavorably deteriorated, while, on the other hand, when the molecular weight is below 500, no cured products are accessibility with high toughness and crack resistance to unfavorable reduction tends to obtain cured products high toughness, that is excellent in crack resistance, the values for a and b should satisfy the conditions in the above formulas: a> 0.7 and b <0.3 .

The products obtained by reacting a polyfunctional epoxy compound or an epoxy compound having one or more halogen atoms with the above-mentioned butadiene polymer having terminal hydroxyl groups or terminal carboxyl groups are prepared, for example, as follows:
A mixture of 100 parts by weight of the above-mentioned butadiene copolymer and 5 to 200 parts by weight of a polyfunctional epoxy compound as above as component (a) or an epoxy compound having one or more halogen atoms is used in

The presence or absence of a catalyst is heated ^{to 100 to 170 ° C.}

Examples of epoxy compounds with one or more halogen atoms in the molecule are: Glycidyl ethers of halogenated phenols such as brominated epoxy compounds made using Tetrabromobisphenol A or dibromobisphenol A are available as starting material, chlorinated epoxy compounds, those using tetrachlorobisphenol A or dichlorobisphenol A as the starting material are available, brominated epoxy compounds obtained by using dibromophenol or tribromophenol available as starting material are brominated epoxy compounds obtained by the synthesis of glycidyl ethers p-bromophenol novolaks are available, and the like. To the extent that these products are polyfunctional, they can can also be used as component (a).

To achieve excellent physical properties of the cured products, especially higher ones Heat resistance and crack resistance, are preferably 3 to 100 parts by weight of the reaction product passed through Reaction of a polyfunctional epoxy compound or an epoxy compound with one or more Halogen atoms with the butadiene copolymer with terminal hydroxyl groups or terminal Carboxyl groups is obtained with 100 parts by weight of the total amount of components (a), (b) and (c) mixed.

As a hardener (component (c)), which leads to the formation of isocyanurate and oxazolidone rings in the molecular Structure when heating the composition of the invention is able to use amines, quaternary Ammonium salts, imidazoles, organic compounds with at least one atom from group Vb des Periodic table and the like can be used.

Examples of amines which can be used in the compositions according to the invention are:

Alkylamines such as

Trimethylamine, triethylamine, tetramethylbutanediamine,

Tetramethylpentanediamine,

Tetramethylhexanediamine;
Hydroxyalkylamines such as

Dimethylaminoethanol, dimethylaminopentanol and the like;

Dimethylaniline.tris-dimethylaminomethylphenol

N-methylmorpholine, N-ethylmorpholine,

Triethylenediamine, N, N-dimethylaniline,

N.N-dimethylbenzylamine, tributylamine, Tripropylamine, N-methylpiperazine,

N-ethylpiperazine. N-methylpiperidine and the like

Examples of quaternary ammonium salts which can be used in the compositions according to the invention are about:

Cetyltrimethylammonium bromide,

Cetyl trimethylammonium chloride,

Dodecyltrimethylammonium iodide, 60 and

Trimethyldodecylammonium chloride,

Benzyldimethyltetradecylammonium chloride,

Benzyldimethylpalmitylammonium chloride,

Allyl dodecyltrimethylammonium bromide,

AUyldodecyltrimethylammonium bromide, Benzyldimethylstearylammonium bromide,

Stearyltrimethylarnmonioum-cMorid,

Benzyldimethyltetradecylammonium acetate and the like.

Examples of imidazoles which can be used according to the invention are for example:

2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-methyl-4-ethylimidazole, 1-butylimidazole, l-propyl-2-methylimidazole, l-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, l-cyanoethyl-2-undecylimidazole, l-cyanoethyl-2-phenylimidazole, l- (4.6-diamino-s-triazinyl-2-ethyl) -2-methyl-

imidazole,
l- (4.6-diamino-s-triazinyl-2-ethyl) -2-phenyl-

imidazole,
l- (4.6-Diamip, os-triazinyl-2-ethy!) - isopropy! -

imidazole,
1- (4.6-diamino-s-triazinyl-2-ethyl) -2-ethyl-

imidazole,
1- (4,6-diamino-s-triazinyl-2-ethyl) -2-undecylimidazole and the like.

Examples of organic compounds containing at least one atom from group Vb of the periodic table contain compounds of P, As, Sb, Bi and N in combination with tetrasubstituted borates of the Formulas:

^{+ +} - R ₅ R ₅ -BR ₅
Rs > = <
R, -N NR ₆
■ γ
R ₃ R ₅ ^R - R ₅ -BR ₅ R ₂ -NR ₄ I " Ri R ₅ -BR ₅
I. I.
I. R ₅ -BR ₅ R ₂ -As-R ₄
I. I.
R ₅ R ₅ -BB ₅ R ₂ -Sb-R ₄ I. I.
R ₃

R ₂ -Bi-R ₄

R ₅ -B-R ₅

wherein R ₁ , R ₂ , R3, Rt and Re are independently hydrogen,

Alkyl groups with preferably 1 to 11 carbon atoms, alkenyl groups with preferably 1 to 11 carbon atoms, Denotes phenyl or aralkyl groups and Rs represents phenyl or an aralkyl group.

These include the compounds containing N and P due to their ready availability and good processability preferred.

The hardener is preferably used in an amount of 0.1 to 10.0% by weight based on the weight of the thermosetting resin composition is used.

Further, the thermosetting resin composition of the present invention may also contain one, if desired or contain several inorganic fillers, for example silicon dioxide or quartz, clays, gypsum, Quartz glass powder. Calcium carbonate, kaolin, mica, hydrated aluminum oxide, talc, dolomite, zircon, Titanium oxide, magnesite, molybdenum disulfide, antimony trioxide, antimony sulfide, bismuth sulfide, triphenylantimony, antimony chloride and the like

When a coupling agent is added to the thermosetting resin composition of the present invention, to make the inorganic filler more compatible with the resin, the viscosity of the Casting resin is reduced and its processability is improved, as is the moisture resistance after hardening. Coupling agents are those from the series of the epoxysilanes and the aminosilanes preferred.

As cured products obtained from the thermosetting resin composition of the present invention according to conventional Process like pouring. Drop, immersion. Impregnate. Injection molding and the like have excellent heat resistance, crack resistance and fire resistance, the thermosetting Resin composition for the production of potting or casting compounds for electronic parts, electrical devices and the like are advantageously used.

Furthermore, since the heart composition of the present invention can be liquid at room temperature, it can find use as a solvent-free paint with excellent workability.

The invention is explained in more detail below on the basis of exemplary embodiments; unless otherwise indicated, all parts and percentages are by weight.

Examples 1 to 3

A mixture (A) was prepared by mixing 100 parts of diglycidyl ether of bisphenol A (epoxy equivalent 174), 200 parts of diphenylmethane diisocyanate (isocyanate equivalent of 140) and 0.5 part of N, N-dimethylbenzylamine. A polybutadiene (I) with terminal hydroxyl groups (molecular weight 1000, 1,2 content 90%) in the amounts indicated in Table 1 was added to the mixture (A). The resulting composition was determined by 1 h heating at 8O ⁰ C and 15 h cured at 18O ⁰ C To determine the heat resistance, the heat distortion temperature was measured.

The crack resistance was determined as follows: A bundle of 30 insulated wires coated with polyamide-imide resin (diameter in each case ZO mm, length 10 cm) was inserted into a test tube of 18 mm in diameter, followed by the above-mentioned one The composition was poured and cured under the same conditions as above to form a shaped body. A temperature cycle test was carried out on the resulting molded article, in which the sample was left at an upper temperature for 1 hour and immediately thereafter left at a lower temperature for 1 hour, these steps (1 cycle) being repeated until cracks occurred. The upper temperature was fixed at room temperature; the lower temperature varied from 0 ° C to -1O ⁰ C, -20 "C, -30 ⁰ C, -40 ⁰ C, -50 ° C, -6O ⁰ C after the end of a cycle. The crack resistance was on hand of the temperature at which cracks occurred.

The results obtained are shown in Table 1.

Examples 4 to 6

To the mixture (A) obtained in Example 1, a polybutadiene '(II ·) having terminal hydroxyl groups was added (Molecular weight 3,000, 1,2 content 90%) added in the amounts specified in ο Table 1. With the The resulting compositions were found to have heat resistance and crack resistance in the same manner as in FIG Example 1 determined.

The results obtained are also shown in Tables 1, ₅ .

Comparative example 1

The mixture (A) obtained in Example 1 was cured in the same manner as in Example alone, whereupon Heat resistance and crack resistance were determined in the same manner as in Example 1. The received Results are shown in Table 1

Examples 7 and 8

A mixture (B) was obtained by mixing 100 parts of diglycidyl ether of bisphenol A (epoxy equivalent 174), 200 parts of diphenylmethane diisocyanate (isocyanate equivalent 140) and 0.5 part of 1-cyanoethyl-2-ethyl-4-methylimidazoi (Molecular weight 163). The polybutadiene (II) was added to the mixture (C) as used in Examples 4 to 6 and a polybutadiene (III) with terminal hydroxyl groups (Molecular weight 5000, 1,2-content 90%) in the in The amounts indicated in Table 1 were also added in the amounts indicated in Table 1 Quartz glass powder from fused quartz glass is gradually added with stirring in such a way that the Material has been sufficiently dispersed. The mixture was then stirred under a pressure of 1 torr for 5 minutes degassed after which the final composition was obtained using the resulting compositions In the same manner as in Example 1, heat resistance and crack resistance were determined

The results obtained are shown in Table 1.

Comparative example 2

To the mixture (B) obtained in Example 7, 300 parts of powdered fused quartz glass was added Quartz glass (grain size 0.147 to 0.041 mm (100 to 350 mesh, Tyler sieve series) gradually with stirring in the Manner that the material was sufficiently dispersed. With the resulting mixture In the same manner as in Example 1, heat resistance and crack resistance were determined

The results obtained are shown in Table 1

Table 1

example
] 2

Comparative example

1 2

Composition (parts)
Polybutadiene (I)
Polybutadiene (II)
Polybutadiene (III)

Quartz glass powder (0.147-0.041 mm grain size,
100-350 mesh)
Diglycidyl ether of
Bisphenol A.
Diphenylmethane diisocyanate

N, N-dimethylbenzylamine
l-cyanoethyl-2-ethyl-4-methylimidazoi

Heat release temperature
(C)

Cracking temperature ( ⁰ C)
*) Crack formation during hardening.

20th

0.5

50

100 20

50

100

40 90 10 10 350 400

0.5 0.5 0.5 0.5 0.5

300

100 100 100 100 100 100 100 100 100 100 200 200 200 200 200 200 200 200 200 200

0.5 0.5

> 220> 220 200> 220> 220> 200> 220 > 220> 220> 200 -30 -50 <-60 -30 -50 <-60 <-60 <-60 *) -10

As can be seen from the results in Table 1, the addition of the polybutadienes can be terminated with Hydroxyl groups to the mixture of a polyfunctional epoxy compound, a polyfunctional one Isocyanate and a hardener increase the crack resistance of the cured products without reducing the heat resistance to enhance.

Examples 9 to 6

Mixtures of diglycidyl ether of bisphenol A (epoxy equivalent 174), diphenylmethane diisocyanate (isocyanate equivalent 140) and a hardener (N ₁ N-dimethylbenzylamine or 1-cyanoethyl ^ -äthyl ^ -methylimidazo!) Were prepared in the proportions given in Table 2. A copolymer of butadiene and acrylonitrile with terminal amino groups (acrylonitrile content 18%, molecular weight 3400, a = 0.8, b = 0.2) was added to the mixtures in the respective amounts given in Table 2; In Examples 15 and 16, quartz glass powder (grain size 0.041 to 0.147 mm, 100 to 350 mesh, 35

45

50

Tyler sieve series) mixed in with sufficient stirring in the amounts given in Table 2, whereupon thermosetting resin compositions were obtained. With the resulting compositions In the same manner as in Example 1, heat resistance and crack resistance were determined.

The results obtained are shown in Table 2.

Comparative Examples 3 and 4

Mixture without content of copolymer of butadiene and acrylonitrile with terminal amino groups as in Table 2 was cured, followed by heat resistance and crack resistance in the same manner as in Example 1 were determined.

The results obtained are shown in Table 2 .

As can be seen from the results in Table 2. is made by adding polybutadiene-based copolymers with terminal amino groups a remarkable improvement in crack resistance without reduction the heat resistance achieved.

Table 2

example
9 10

12 13 14 15

16

Comparative example

Composition (parts)
Butadiene-acrylonitrile-copoly- 50 70
trier with terminal amino groups

Diglycidyl ether of 100 100

Bisphenol A.

50 70 90 80 80

100 100 100 100 100 100 100

130 218/266

continuation

Composition (parts)

Diphenylmethane diisocyanate

Quartz glass powder 0.041 -
0.147mm (100-350 mesh)
Ν, Ν-dimethylbenzylamine

1-cyanoethyl-2-ethyl-4-methylimidazole

115 115 230 230 230 115 115 115 115

380 430

0.3 0.3 0.3 0.6 0.6 0.6

0.8

0.5 0.5

Heat deformation temperature ( ⁰ C)>220>220>220>220>220>220>220>200> 220 cracking temperature CC) -50 <-60 <-60 -50 <-60 <-60 <-6Q <-60 *) -10

*) Crack formation during hardening.

25th

Examples 17-19

A reaction product (I) was obtained by heating 100 parts of a copolymer of butadiene and acrylonitrile with terminal carboxyl groups (acrylonitrile content 18%, molecular weight 3400) and 50 parts of diglycidyl ether of bisphenol A (epoxy equivalent 174) by reaction at 120 to 17O ⁰ C for 5 hours Obtain nitrogen flow.

On the other hand, a mixture (C) was prepared by mixing 100 parts of diglycidyl ether and bisphenol A (epoxy equivalent 174), 200 parts of diphenylmethane diisocyanate (isocyanate equivalent 140) and 1.0 part of 2-phenyliniidazole. The reaction product (1) was mixed with the mixture (C) in the proportions given in Table 3 to give the desired compositions. The resulting compositions were 5 h at 7O ⁰ C and 5 h cured at 160 ° C and thereafter for 10 h at 180 ° C.

To determine the heat resistance, the heat deformation temperature was measured.

The crack resistance was determined in the same manner as in Example 1 except that the above specified curing conditions were applied.

The results obtained are shown in Table 3.

B cis ρ ic I e 20 to 22

35

40

45

A reaction product (11) was obtained by heating 100 parts of a copolymer of butadiene and acrylonitrile with terminal (.lrboxyl groups (acrylonitrile content 27%. Molecular weight 3400), 20 parts of diglycidyl ether of bisphenol Λ (epoxy equivalent 500) and 0.15 part of triphenylphosphine during 5 h under a stream of nitrogen at 120 to 150 ⁰ C obtained.

To the mixture (C) obtained in Example 17, became the reaction product (H) added in the amounts shown in Table 3, whereupon the desired Compositions were obtained. With the resulting compositions, heat resistance became and crack resistance determined in the same manner as in Example 17.

The results obtained are shown in Table 3.

Examples 23-25

There was a reaction product (III) by heating 100 parts of a copolymer of butadiene and acrylonitrile with terminal carboxyl groups (as in Examples 17 to 19), 100 parts of diglycidyl ether of bisphenol A (epoxy equivalent 174) and 0.2 part of triphenylphosphine for 5 hours Reaction obtained under a stream of nitrogen at 100 to 130 ^° C.

To the mixture (C) obtained in Example 17, became the reaction product (III) was added in the proportions given in Table 3, whereupon the desired compositions were obtained. With these compositions, heat resistance and crack resistance in the same manner as in Example 17 were determined.

The results obtained are shown in Table 3.

B e i s ρ i e 1 e 26 to 28

A reaction product (IV) was obtained by heating 100 parts of a copolymer of butadiene and acrylonitrile with terminal hydroxyl groups (acrylonitrile content 15%, molecular weight 4500, a = 0.85 and b = 0.15), 50 parts of diglycidyl ether of bisphenol A, epoxy equivalent to 170 ⁰ C. were obtained 174) and 1.5 parts of sodium ethylate in 5 h reaction time at 120 under a nitrogen stream.

To the mixture (C) obtained in Example 17, the reaction product (IV) was added in the form shown in Table 3 specified amounts were added, whereupon the desired compositions were obtained. With these Compositions were determined in the same manner as in Example 17 for heat resistance and crack resistance.

The results obtained are shown in Table 3.

Examples 29-31

A reaction product (V) was obtained by heating 100 parts of a copolymer of butadiene and styrene with terminal hydroxyl groups (styrene content 25%, molecular weight 3000, a = 0.75 and b = 0.25), 100 parts of diglycidyl ether of bisphenol A (epoxy equivalent 174) and 1.5 parts of sodium ethylate in 5 h

Response time obtained at 120 to 170 ⁰ C under a stream of nitrogen.

To the mixture (C) obtained in Example 17, the reaction product (V) was shown in Table 3 specified amounts were added, whereupon the desired compositions were obtained. With the The resulting compositions were found to have heat resistance and crack resistance in the same manner as in FIG Example conveyed.

The results obtained are shown in Table 3

Comparative example 5

The mixture (C) obtained in Example 17 became alone hardened; Heat resistance and crack resistance were determined in the same manner as in Example 17.

The results obtained are shown in Table 3.

Table 3 example

17 18

19th

21

23

24

Composition (parts)
Reaction product (I)
Reaction product (II)
Reaction product (III)
Reaction product (IV)
Reaction product (V)
Diglycidyl ether of
Bisphenol A.

Diphenylmethane diisocyanal
2-phenylimidazole

Heat distortion ^{temperature (0} C)
Cracking temperature ( ⁰ C)

31

100

40

100

23

100

32

100

100

41

100

57

100

200 200 200 200 200 200 200 200 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 > 200 > 200 > 200 > 200 > 200 > 200 > 200 > 200 -40 -50 <-60 -40 -50 <-60 -40 -50

Table 3 (continued)

example 26th 27 28 29 30th 31 *) 25th 5

Composition (parts)
Reaction product (I)
Reaction product (II)
Reaction product (III)
Reaction product (IV)
Reaction product (V)
Diglycidyl ether of
Bisphenol A.

Diphenylmethane diisocyanate
2-phenylimidazole

Heat distortion temperature ("C)
Cracking temperature ('C)

*) Comparative example.
**) Crack formation during hardening.

75

- 31 40 53 - - - - - - - - 23 32 43 - 100 100 100 100 100 100 100 100 200 200 200 200 200 200 200 200 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 > 200 > 200 > 200 > 200 > 200 > 200 > 200 > 200 <-60 -40 -50 <-60 -40 -50 <-60 **)

As can be seen from the results in Table 3, the addition of the reaction products becomes more polyfunctional Hydroxyl-terminated epoxy compounds and butadiene-type copolymers or terminal carboxyl groups a remarkable improvement in the crack resistance without reducing the Heat resistance achieved.

Examples 32 to 41

Fs became a reaction product (VI) by heating 100 parts of brominated diglycidyl ether of Bisphenol A (epoxy equivalent 350, bromine content 48%), 100 parts of a copolymer of butadiene and

Acrylonitrile with terminal hydroxyl groups (as in Examples 26 to 28) and 1.5 parts of sodium ethylate in 4 h reaction time at 120 to 15O ⁰ C obtained under a nitrogen flow. The reaction product (VI) was brown and had a viscosity of about 500 poise at room temperature.

The compositions obtained using the reaction product (VI) were prepared as shown in Table 4. The resulting compositions were cured for 1 h at 80 ⁰ C, 5 h at 160 ° C and 14 h at 180 ° C. The heat distortion temperature was determined to determine the heat resistance.

To determine the fire protection effect, the fire resistance according to the norm (UL standard, Subjects 94 and 492)

The crack resistance was determined in the same manner as in Example 1 except that the above specified curing conditions were applied.

The results obtained are shown in Table 4

For the purpose of comparison, a composition was also examined which the reaction product (VI) does not (Comparative Example 6).

Table 4

example 33 38 '34 39 40 35 36 32 Composition (parts) 30th 60 30th 90 90 30th 60 Reaction product (VI) 30th 90 80 80 100 90 70 100 Diglycidyl ether of bisphenol A
(Epoxy equivalent 174) 100 200 200 200 200 200 400 200 Diphenylmethane diisocyanate
(Isocyanate equivalent 140) 200 1.0 1.0 1.0 1.0 1.0 1.0 1.0 N-methylmorpholine 1.0 10 20th 20th - 10 30th Polyglycidyl ether of a phenolic
Formaldehyde novolaks (epoxy
equivalent 175) > 200 > 200 > 200 > 200 > 200 > 200 > 200 Heat distortion temperature ("C) > 200 -20 -30 -20 -50 -50 -10 -30 Formation temperature (C) -20 MAY BE SE-O MAY BE SE-O SE-O SE-O SE-O Fire resistance (UL standard) MAY BE Table 4 (continued) *) example 41 6th 37 Composition (parts) 90 - Reaction product (VI) 60 80 90 Diglycidyl ether of bisphenol A
(Epoxy equivalent 174) 90 200 200 Diphenylmethane diisocyanate
(Isocyanate equivalent 140) 200 1.0 1.0 N-methylmorpholine 1.0 20th 10 Polyglycidyl ether of a phenolic
Formaldehyde novolaks (epoxy equiv. 175) 10 > 200 > 200 Heat distortion temperature C C) > 200 -50 **) Cracking temperature (C) -30 SE-O - Fire resistance (UL standard) SE-O

*) Comparative example.
**) Crack formation during hardening.

B e i s ι

42 to 51

It was a reaction product (VII) by heating 100 parts of brominated diglycidyl ether of bisphenol A (epoxy equivalent 480, bromine content 20%), 100 parts of a copolymer of butadiene and acrylonitrile with terminal hydroxyl groups (as in Examples 32 to 41) and 1.5 to 170 ⁰ C receive parts of sodium ethylate in 5 h reaction time at 120 under a nitrogen stream.

Using the reaction product (VII), the desired compositions were obtained as in Table 5 indicated produced. With these resulting compositions, heat resistance, crack resistance

strength and fire resistance were determined in the same manner as in Example 32.

The results obtained are shown in Table 5.

For the purpose of comparison, a composition which did not contain the reaction product (VII) was examined (Comparative Example 7).

Examples 52 to

It was a reaction product (VIII) by heating 100 parts of brominated diglycidyl ether of bisphenol A (epoxy equivalent 350, bromine content 48%), 100 parts of a copolymer of butadiene and acrylonitrile with terminal carboxyl groups (as in Examples 17 to 19) and 0.2 Parts of triphenylamine are obtained in a reaction time of 5 h at 1-20 to 17O ⁰ C under a stream of nitrogen. With this reaction product (VIII), the aimed compositions became

Table 5

prepared as indicated in Table 6. With these resulting compositions, heat resistance, The crack resistance and fire resistance were determined in the same manner as in Example 32.

For comparison purposes, a composition which did not contain the reaction product (VIII) was also used, investigated (Comparative Example 8).

The results obtained are shown in Table 6.

example 43 44 45 46 I. 42 H
1 Composition (parts) 200 200 300 300 Reaction product (VII) 200 90 80 100 90 I. Diglycidyl ether of bisphenol A 100 I. (Epoxy equivalent 174) 200 200 200 200 ί Diphenylmethane diisocyanate 200 I. (Isocyanate equivalent 140) 1.0 1.0 1.0 1.0 k N-methylmorpholine 1.0 10 20th - 10 I.
i Polyglycidyl ether of a phenolic - I. Formaldehyde novolaks (epoxy I. equivalent 175) > 200 > 200 > 200 > 200 i Heat distortion ^{temperature (0} C) > 200 <-60 <-60 <-60 <-60 I. Cracking temperature (° C) <-60 SE-O SE-O SE-O SE-O fr Fire resistance (UL standard) SE-O

Table 5 (continued)

example 48 49 50 51 7th 47

Composition (parts)
Reaction product (VIl)

Diglycidyl ether of bisphenol A
(Epoxy equivalent 174)

Diphenylmethane diisocyanate
(Isocyanate equivalent 140)

N-methylmorpholine
Polyglyeidyl ether of a phenol-formaldehyde novolak (epoxy equivalent 175)

Heat distortion ^{temperature (0} C)
Cracking temperature ( ⁰ C)
Fire resistance (UL standard)

*) COMPARISON EXAMPLE
**) Crack formation during hardening.

300 250 250 250 250 - 80 100 100 100 100 100 200 200 200 200 200 200 1.0 0.5 1.0 1.5 2.0 1.0 20th - - - - - > 200 > 200 > 200 > 200 > 200 > 200 <-60 <-60 <-60 <-60 <-60 **) SE-O SE-O SE-O SE-O SE-O _

Table 6

Composition (parts)
Reaction product (VIII)
Diglycidyl ether of bisphenol A
(Epoxy equivalent 174)

Diphenylmethane diisocyanate
(Isocyanate equivalent 140)

N-methylmorpholine
Polyglycidyl ether of a phenol-formaldehyde novolak (epoxy equivalent 175)

Heat distortion temperature ("C)
Cracking temperature ("C)
Fire resistance (UL standard)

Table 6 (continued)

26th

Example 52

54

55

56

30 100

200 0.8

> 200

-30

MAY BE

200

> 200

-30

MAY BE

30th
80

800

0.8
20th

> 200

-30

MAY BE

60
100

200
0.8

> 200

-60

SE-O

60 90

200

0.8 10

> 200

-60

SE-O

Example 57

59

60

61

Composition (parts)

Reaction product (VIII) 60 90

Diglycidyl ether of bisphenol A 80 100

(Epoxy equivalent 174)

Diphenyl.tiethane diisocyanate 200 200

(Isocyanate equivalent 140)

N-methylmorpholine 0.8 0.8

Polyglycidyl ether of a phenol 20

Formaldehyde novolaks (epoxy equivalent 175)

Heat forming temperature (° C) > 200> 200

Cracking temperature (C) -60 <-60

Fire resistance (UL standard) SE-O SE-O

*) Comparative example.
**) Crack formation during hardening.

Examples 62-71

It was a reaction product (IX) by heating 50 of 100 parts of brominated diglycidyl ether of bisphenol Λ (epoxy equivalent 350, bromine content 48%), parts of a copolymer of butadiene and acrylonitrile with terminal carboxyl groups (as in Examples 20 to 22) and 0.2 Parts of triphenylamine are obtained in a reaction time of 55 h at 120 to 170 ^° C. under a stream of nitrogen.

Table 7

90
80

200

0.8
20th

100
100

200
0.8

150
100

200
0.8

100 200 0.8

> 200> 200

<-60 <-60
SE-O SE-O

> 200> 200

<-60 **) SE-O

Using the reaction products (IX), the aimed compositions were obtained as in Table 7 indicated produced. With these resulting compositions, heat strength wedge, crack resistance and fire resistance in the same manner -as in Example 32 crsiiiicit

For comparison purposes, a composition which did not contain the reaction product (IX) was also used, investigated (Comparative Example 9).

The results obtained are shown in the table.

Composition (parts)
Reaction product (BQ

Diglycidyl ether of bisphenol A
(Epoxy equivalent 174)

example 63 64 65 66 62 60 60 60 60 60 90 80 100 100 100

continuation

Example 62

64

66

Composition (parts)

Diphenylmethari diisocyanate
(Isocyanate equivalent 140)

Benzyldimethylamine

Dibromophenyl glycidyl ether
(Epoxy equivalent 308)

KitzeverforrnungsternperatuT ( ⁰ C)
Cracking temperature (° C)
Fire resistance (UL standard)

800 600 400 180 220 1.0 1.0 1.0 1.0 1.0 - 10 20th - - > 200 > 200 > 200 > 200 > 200 -30 -30 -30 -30 -30 SE-O SE-O SE-O SE-O SE-O

Table 7 (continued)

' Example 68 69 70 71 *) 67 9

Composition (parts)
Reaction product (IX)

Diglycidyl ether of bisphenol A
(Epoxy equivalent 174)

Diphenylmethane diisocyanate
(Isocyanate equivalent 140)
Benzyldimethylamine

Dibromophenyl glycidyl ether
(Epoxy equivalent 308)

Heat distortion temperature (° C)
Cracking temperature ("C)
Fire resistance (UL standard)

*> Comparative example.
**) Crack formation during hardening.

90 90 90 100 100 - 100 90 80 100 100 100 200 200 200 400 600 200 1.0 1.0 1.0 1.5 1.5 1.0 - 10 20th - 10 - > 200 > 200 > 200 > 200 > 200 > 200 -50 -50 -50 <-60 <-60 **) SE-O SE-O SE-O SE-O SE-O

B is ρ i c ie 72 bis

There was obtained a reaction product (X) by heating 100 parts of brominated diglycidyl ether of Bisphenol A (epoxy equivalent 350, bromine content 48%), 100 parts of a copolymer of butadiene and styrene with terminal hydroxyl groups (styrene content 25%. Molecular weight 3000) and 0.3 parts of triphenylamine in 5 h reaction time at 120 to 170 ° C under one Obtain nitrogen flow.

Using the reaction product (X), the aimed compositions were obtained as in Table 8 indicated. With the resulting compositions, heat resistance and crack resistance were obtained and fire resistance determined in the same manner as in Example 32

For comparison purposes, a composition was also used which did not contain the reaction product (X) were investigated in the same way (comparative example 10).

The results obtained are shown in Table S.

As stated above, according to the invention, thermosetting resin compositions can be obtained, which have excellent heat resistance, crack resistance and fire resistance.

Further, since the resin compositions obtained are liquid at room temperature, they can be used as solvent-free paints with excellent workability are used; for their application there are considerably broader possibilities than for conventional compositions in which halogen compounds Find use.

Table 8 example 27 46 789 75 76 30th 78 *) 29 72 10 60 90 120 Composition (parts) 60 90 90 77 100 - Reaction product (X) 100 73 74 100 Diglycidyl ether from Bis 120 phenol A (epoxy equiva- 90 120 200 200 90 200 lent 174) 200 100 100 200 Diphenylmethane diisocyanate 1.5 1.5 1.0 (Isocyanate equivalent 140) 1.5 > 200 > 200 200 > 200 1.5 N-methylmorpholine > 200 200 200 -30 ■ -40 -50 > 200 Heat distortion temperature (C) -30 SE-O SE-O 1.5 SE-O **) Cracking temperature (C) SE-O 1.5 1.5 > 200 - Fire resistance (UL standard) > 200 > 200 -50 -40 -50 SE-O SE-O SE-O

♦) Comparative example.

*) Crack formation during hardening.

Examples 79 to 82

A mixture (D) was obtained by mixing 100 parts of diglycidyl ether of bisphenol A (epoxy equivalent 174), 200 to 800 parts of diphenylmethane diisocyanate (Isocyanate equivalent 140) and 0.5 part of N, N-dimethylbenzylamine. To the mixture (D) became a copolymer of butadiene and acrylonitrile terminated with hydroxyl groups (as in the examples 26 to 28) added in the amounts given in Table 9, whereupon the desired compositions were obtained. The resulting compositions became heat resistance and crack resistance in the same way as in example! 1 determined.

The results obtained are shown in Table 9

Examples 83 to 86

To the mixture (D) obtained in Example 79, but with the proportions of the constituents as in Table 9 were used, a copolymer of butadiene and acrylonitrile was terminated Hydroxyl groups (as in Examples 26 to 28) in the amounts indicated in Table 9 were added.

after which the intended compositions were obtained. With the resulting compositions In the same manner as in Example 1, heat resistance and crack resistance were determined.

The results obtained are shown in Table 9.

Examples 87 to 90

To the mixture (D) obtained in Example 79. however, the proportions of the constituents are as in Table 9 were used, a copolymer of butadiene and acrylonitrile was terminated Hydroxyl groups (as in Examples 26 to 28) in the proportions given in Table 9 added, whereupon the intended compositions were obtained. With the resulting compositions In the same manner as in Example 1, heat resistance and crack resistance were determined

The results obtained are shown in Table 9

δ e i!> ρ ι e 1 c SI oiS 94

To the mixture (D) obtained in Example 79, a polybutadiene having a terminal hydroxyl group was added (Molecular weight 2700 added in the proportions given in Table 9, whereupon the desired Compositions were obtained. With the resulting compositions, heat resistance became and crack resistance determined in the same manner as in Example 1

The results obtained are shown in Table S.

Examples 95 to 98

A copolymer of butadiene and styrene with terminal hydroxyl groups (styrene content 25%, a = 0.75, b = 0.25. Π = 54) in the proportions given in Table 9 was added to the mixture (D) obtained in Example 79, whereupon the intended compositions were obtained. The resulting compositions were evaluated for heat resistance and crack resistance in the same manner as in Example 1

The results obtained are shown in Table 9

31

Table 9

32

example

79

S3

84

Composition (parts) of butadiene-acrylonitrile copolymer (see Examples 26-28) polybutadiene with terminal hydroxyl groups, M = 2700 (see Examples 91-94) Butadiene-styrene copolymer (cf. Examples 29-31) Diglycidyl ether of bisphenol A (Epoxy equivalent 174) diphenylmethane diisocyanate (isocyanate equivalent 140) '- N, N-dimethylbenzylamine

'Heat distortion temperature ("C). Cracking temperature (' C)

10 20 50 100 10 20 50

100 100 100 100 100 100 100 200 200 200- 200 400 400 400 0.5 0.5 0.5 0.5 0.5 0.5 0.5 > 220 > 220 > 220 > 220 > 220 > 220 > 220 -40 -50 <-80 <-60 -30 -40 -50

Table 9 (continued)

example

86

90

91

Composition (parts) ^: Butadiene-acrylonitrile copolymer. (see examples 26-28)

Polybutadiene with endst. Hydroxyl: groups, M = 2700 -. <(cf. Examples 91-94) H butadiene-styrene copolymer >. (see Examples 29-31) diglycidyl ether of bisphenol A (epoxy equivalent 174)

1: Diphenylmethane diisocyanate (isocyanate equivalent 140)

^N N, N-Dimethylbenzylamine iii Heat deformation temperature ( ⁰ C) · '' Cracking temperature ("C)

100 10 20 50

• 100

10 20

100 100 100 100 100 100 100 400 1800 800 "800 ■> '800 '200 200 0.5 -0.5 ^ 0.5 0.5 0.5 0.5 0.5 > 220 > 220 > 220 > 220 > 220 > 220 > 220 -60 -20 -30 -40 -40 -10 -20

Table 9 (continuation)

example 94 95 96 97 98 *) 93 11th

■ Composition (parts) of butadiene-acrylonitrile copolymer (see Examples 26-28) Polybutadiene with endst. Hydroxyl groups, M = 2700 (see examples 91-94)

Butadiene-styrene copolymer - - *

(see examples 29-31)

Diglycidyl ether of bisphenol A 100

(Epoxy equivalents 174)

10 20th 50 100 - 100 100 100 100 1Θ0 130 218/266

33 34

continuation

example 94 95 96 97 98 *) 93 Il

0.5 0.5 0.5 0.5 0.5 0.5 0.5 > 220 210 > 220 > 220 > 220 210 > 220 -50 -60 -10 -20 -50 -50 **)

Composition (parts)

Diphenylmethane diisocyanate 200 200 200 200 200 200 200

(Isocyanate equivalent 140)

N, N-dimethylbenzylamine heat distortion temperature (° Q cracking temperature ( ⁰ C) *) comparative example. ♦ *) Crack formation during hardening.

Table 10 given proportions under

Comparative Example 11 Stirring added so that the materials

20 have been sufficiently dispersed. The resulting

For comparison purposes, the compositions in Example 79 were then used under one obtained mixture (D) hardened alone, whereupon the c pressure of 1 torr degassed for 5 min. With these Heat resistance and crack resistance in the same manner as compositions became heat resistance and crack resistance Example 1 were determined. in the same manner as in Example 1.

The results obtained are also in Table 9. 25 The results obtained are in Table 10

listed. listed.

B e i s ρ i e 1 e 99 to 104 'comparative example 12

A mixture was made by mixing 100 parts. For comparison purposes, a composition was

Diglycidyl ether of bisphenol A (epoxy equivalent 174), which is not a copolymer of butadiene and acrylonitrile

200 parts of diphenylmethane diisocyanate (isocyanate equivalent with terminal hydroxyl groups contained, in the same

valent 140) and 0.5 parts of 1-cyanoäthyW-äthyM-me-way investigated.

ihylimidazole (molecular weight 163). The results obtained are also shown in Table 10

this mixture was listed as a copolymer of butadiene.

and hydroxyl-terminated acrylonitrile (such as 35 As from the results in Tables 9 and 10

in Examples 26 to 28) in Table 10 ■ can be seen by adding a polymer or

specified amounts added, after which the desired copolymers based on polybutadiene with terminal

th compositions were obtained. The composite hydroxyl groups are a remarkable improvement

Powdered quartz glass was also used, which increases the crack resistance without reducing the heat resistance

fine silica powder and calcium carbonate in the in 40 achieved.

Table 10

Composition (parts)

Poly bd® CN-15 50 100 50 100 50 100

Quartz glass powder (0.041-0.147mm, 350 400 - - - - 300

100-350 mesh, Tyler sieve series)

Silica powder (0.041-0.147 mm, - - 350 400 200 200

100-350 mesh, Tyier sieve series)

Calcium carbonate powder - If) O 150

(0.041-0.147mm, 100-350 mesh,
Tyler sieve row) |

Diglycidyl ether of bisphenol A 100 100 100 100 100 100 100

(Epoxy equivalent 174)

Diphenylmethane diisocyanate 200 200 200 200 200 200 200

(Isocyanate equivalent 140)

1-cyanoethyl-2-ethyl-4-methylimidazole heat distortion temperature ("C) crack formation temperature ( ⁰ C) *) comparative example 12.

0.5 0.5 0.5 0.5 0.5 0.5 0.5 > 220 > 220 > 220 > 220 > 220 > 220 > 220 <-60 <-60 <-60 <-60 <-60 <-60 -10

Claims (3)

Patent claims: 1. A thermosetting resin composition comprising a polyfunctional epoxy compound (a), a polyfunctional isocyanate (b) and a hardener (c),
characterized in that it contains at least one flexibilizing agent (d) selected from: - Butadiene polymers with terminal hydroxyl groups or terminal amino groups of the formula ₂ toilets u Y — PfCH ₂ -CH = CH-CH ₂ ^ - ^ CH ₂ - CH- where mean: Y is a hydroxyl or amino group, R is a hydrogen atom, an alkyl group, a Alkenyl group, a nitrile or phenyl group peund
a> 0.7, b <0.3 with a + b = 1, where η is an integer and defines the molecular weight of the butadiene polymer in the range from 500 to 5000, - Polybutadiene with terminal hydroxyl groups of the formula HO CH, -CH CH II Ch ₂ ; -OH whereby η is an integer and the molecular weight of the Polybutadiene in the range from 500 to 5000 Are defined,
and - Reaction products obtained by reacting a polyfunctional epoxy compound or a Epoxy compound having one or more halogen atoms with a butadiene polymer of formula X- X- (CH ₂ - CH = CH-CH ₂ ^ --f CH ₂ -CH- \ R (CH ₂ -CH = CH-CH ₂ ) S-f CH-CH ₂ - are preserved whereby X denotes a hydroxyl or carboxyl group and R, a, b and η have the above meanings. 2. Composition according to claim 1, characterized in that the flexibilizing agent (d) in an amount of 3 to 100 parts by weight per 100 -X Parts by weight of the total amount of components (a), (b) and (c) is included. 3. Use of the compositions according to claim 1 or 2 for the production of moldings, Lacquers, surface coatings as well as for potting and pouring in electronic components, electrical circuits and devices.