FR2459256A1 - COMPOSITIONS BASED ON EPOXIDE RESIN - Google Patents

Abstract

EPOXIDE RESIN COMPOSITIONS CONTAIN EPOXIDE RESINS AND A CATALYTIC AMOUNT OF CURING CATALYSTS CONSISTING OF ORGANOSILICIAL COMPOUNDS CONTAINING HYDROXY RADICALS AND OR HYDROLYSABLE RADICALS AND ORGANIC RADINUM COMPOUNDS; THESE RESINS HARDEN QUICKLY AT ELEVATED TEMPERATURES TO FORM PRODUCTS WITH VARIOUS EXCELLENT CHARACTERISTICS.

Description

The present invention relates to epoxy resin compositions

  and more particularly an epoxy resin composition which hardens rapidly at elevated temperatures

  a form having various excellent characteristics.

  Epoxy resins, when cured, can exhibit various useful physical characteristics such as good adhesion, as well as good mechanical, electrical characteristics.

  and thermal. Generally, agents for curing epoxy resins

  , may contain a hardener selected from polyamines, acid anhydrides, phenols or the like and a catalyst of

  curing selected from boron trifluoride complexes (BF3).

  tertiary amines or the like.

  Polyamines can react strongly with resin

  epoxide so that it can not be stored for long periods of time.

  along the resins containing them. Acid anhydrides and phenols

  may require high temperatures and

  lined so that the epoxy resin hardens. Although the complexes of

  BF3 make it possible to harden the epoxy resin at temperatures

  the hardened resin obtained has characteristics of

  electrical and mechanical ticks inappropriate at high temperatures

  Vees. Tertiary amines require high temperatures to

harden the resin.

  It has recently been proposed to use a metal chelate as a latent curing agent for epoxy resins. However, the chelates must be used in a relatively large amount and they require temperatures up to 2000C or more to cure the epoxy resins and it is difficult to dissolve the amount

  catalytic necessary in epoxy resins.

  There is also known a hardening process according to which an epoxy resin is subjected to a hardening reaction.

  with an organosilicone having a silanol radical and an organic compound

  boron or an organic titanium compound, but the hard

  The resulting product exhibits altered electrical characteristics

  that it is not generally suitable for use.

The object of the invention is;

  an epoxy resin composition that is easy to

  cir in relatively moderate temperature conditions; and

  an epoxy resin composition which, when dur-

  cit, has good electrical, thermal and mechanical properties

  picnics. The invention relates to an epoxy resin composition which consists of an epoxy resin; and

  a catalytic amount of a hardening catalyst

  composed of: (A) one or more organosilicon compounds comprising at least one radical chosen from hydroxyl radicals and hydrolyzable radicals attached directly to the silicon atom, these compounds

  organosilicates being selected from organosilanes and organosilanes.

siloxannes, and

  (B) one or more aluminum compounds having radicals

organic caux.

  As previously indicated, the epoxy resin composition of the invention contains a catalytic amount of a curing catalyst consisting of (A) an organosilicon compound

  and (B) an aluminum compound. When using an organic compound

  with hydrolysable radicals, the catalyst for

  This corresponding element has a latent curing power. The term "curing catalyst" is understood here to mean an agent which accelerates and completes the curing reaction of an epoxy resin but which

  practice does not participate directly in the curing reaction.

  A "latent" catalyst does not exhibit this function at normal ambient temperatures, but possesses it at elevated temperatures, for example from 100 to 130 ° C or more. Consequently, the composition of the invention containing such a catalyst has a latent power of

  hardening and has good storage stability.

  The organosilicon compound (A) is selected from

  nosilanes and organosiloxanes having a hydroxy radical and / or a hydrolyzable radical attached directly to the silicon atom. The preferred organosilanes have the following formula (R) Si (R * (I) n (H) mo each of the symbols R independently represents an alkyl, phenyl, aralkyl, vinyl or allyl radical, R represents a hydroxyl radical or a hydrolysable radical , 2 is equal to 1, 2 or 3, m is 0, 1 or 2 and n is 1, 2 or 3, provided that the sum of 2 + m + n is equal to 4. When R represents an alkyl or aralkyl radical, the alkyl moiety may comprise up to about 20 carbon atoms and preferably up to 5 carbon atoms, and the alkyl radicals include methyl, ethyl, propyl, butyl,

  pentyl or the like. Among the aralkyl radicals are the radical

  benzyl cal or the like. The radical R may be substituted with a non-hydrocarbon radical, with the exception of radicals containing a

  amino nitrogen atom, for example a halogeno radical or the like.

  When R represents a hydrolyzable radical, it is generally chosen from the following radicals: an alcohol or alkoxy radical represented by the formula -OR '(where R' represents an alkyl radical, generally a C 1 -C 4 alkyl radical, and preferably a methyl radical); a carboxylic acid ester radical represented by the formula:

-O-C-R '

  (where R 'represents an alkyl radical generally comprising up to

carbon atoms); -

  a halogeno radical represented by the formula -X (o X represents a halogen atom, for example a chlorine, bromine, iodine or fluorine atom); and an oxime radical represented by the formula: -O-N = C (H) aR'2-a (o R 'represents a hydrogen atom or an alkyl radical and a is

equal to 0 or 1).

  The preferred organosiloxanes can be represented by the formula: (R 1) (R) 2 (R) t (R) st 2 1 SiO- (SiO) a- (SiO) b Si (II) (OH) 3.s ( OH) 2-t (OH) 3. R1, R2, R and R independently represent a hydrogen atom, an alkyl, phenyl, vinyl, aralkyl or allyl radical, or a hydrolyzable radical, at least one of the hydrocarbon radicals being present; s and u are each equal to 0, lou 2; t is 0, 1 or 2; and a and b are each 0 or 1 or an integer greater than 1; or by the formula: c6! (R) (R 3) sio (SiO) x (R) 3 (III) wherein R 5, R 6 and R 7 independently represent a hydrogen atom, an alkyl, phenyl, vinyl, aralkyl or allyl radical or a hydrolysable radical, at at least one of the hydrocarbon radicals and at least one hydrolyzable radical being present, and x is 0 or 1 or

an integer greater than 1.

  In formulas (II) and (III), the hydrocarbon radicals

  (ie, alkyl, phenyl, vinyl, aralkyl or allyl) and the hydrolyzable radical are the same as in formula (I). In these formulas the sum of a + b, or x, are generally equal to a number

  greater than 50. In addition, it is possible to use as organo-

  silicone resins having SiOH radicals or radi-

  hydrolyzable clays united directly to the silicon atom.

  The organosilicon compounds (A) above can be used

  in the form of a mixture of two or more. generally

  The organosilicon compound (A) may be used in an amount of from 0.0001 to 10% by weight and preferably from about 0.01 to

  at 5% by weight relative to the weight of the epoxy resin used.

  The other ingredient (B) of the curing catalyst according to the invention is an aluminum compound having organic radicals. The organic moiety joined to the aluminum moiety may be an alkoxy, phenoxy, substituted phenoxy, acyl or acyloxy radical or a polycarbonyl compound or the like. Examples of such aluminum compounds include alcoholates such as methylate, ethylate, isopropylate or the like; phenolates

  such as phenolate, p-methylphenolate or the like; com

  acyloxy-type poses such as acetate, stearate, butyrate, propionate, isopropionate or the like; chelates with a

  ligand such as acetylacetone, trifluoroacetylacetone, penta

  fluoroacetylacetone, ethylacetoacetate, salicylaldehyde, di-

  ethylmalonate or the like; these aforementioned compounds being of course

  each of the compounds of aluminum.

  The above-mentioned aluminum compounds (B) can be used as a mixture of two or more. We generally use

  the aluminum compound (B) is from 0.0001 to 10% and preferably

  from 0.001 to 5% by weight based on the weight of the epoxy resin.

  The epoxy resin which is the main component of the composition of the invention is known in the art and many of these resins are commercially available. The epoxy resin that is used in the composition of the invention has no particular limitation and may for example consist of: a bisphenol A type epoxy resin; an epoxy resin of Bisphenol F type; a phenolic novolac epoxy resin; an alicyclic epoxy resin; a resin

  heterocyclic epoxide such as a triglycidisocyanate resin

  dyle or hydantoin; an aliphatic epoxy resin such as

  the diglycidyl ether of propylene glycol or a polyglycidyl ether

  pentaerythritol; an epoxy resin of bisphenol A type hy-

  drogénée; an epoxy resin obtained by reaction of a carboxylic acid

  aliphatic or alicyclic aromatic boxylic box with epichlorohydrin; an epoxide resin of the glycidyl ether type such as the reaction product of an o-allylphenol novolak and epichlorohydrin; a spirocyclic epoxy resin; a glycidyl ether epoxy resin which is the product of the reaction of a diallylbisphenol compound whose allyl radicals are ortho to the hydroxy radicals of bisphenol A and epichlorohydrin, or the like. However, it is preferred to avoid epoxy resins

  derived from N, N-diglycidylphenylamine.

  It is particularly preferred to add the curing catalysts to a bisphenol A type epoxy resin, a phenolic novolac epoxy resin or an alicyclic epoxy resin because the metal corrosive nature of the epoxy resin is considerably reduced and the electrical characteristics are greatly improved. Of the epoxy resin compositions of the invention, those containing a hydrolyzable silicon compound have the advantage of having good

  storage and be easy to handle as they harden easily

  For example, at temperatures of 100 to 130 ° C or higher. The proper choice of the nature of the epoxy resin and the formula of the composition provides solvent-free compositions suitable for casting, dipping or molding. They also dissolve easily in a weakly polar low boiling solvent such as dioxane, tetrahydrofuran or the like

  so that they can easily be used to form

  posites by impregnating or coating a glass fabric, paper or the like. In addition, the cured resins are excellent with respect to heat resistance, mechanical properties and

electrical insulation.

  The epoxy resin compositions of the invention may contain inorganic fillers such as graphite particles.

  The invention is illustrated by the nonlimiting examples

  the following comparative examples in which the parties and

  percentages are by weight.

  Examples 1 to 3 and Comparative Examples 1 and 2

  Three different compositions are prepared by hot melting epoxy resins and curing catalysts whose

  The nature and quantity are shown in Table I below.

  The composition of Example 1 gelled at 1000C in 60 minutes and at 1500C in 10 minutes. The composition of Example 2

  gels at 1000 ° C. in 10 minutes and at 120 ° C. in 4 minutes. The composition

  Example 3 is gelled at 1000C in 30 minutes and at 1500C.

in 12 minutes.

  Each of the above compositions is heated to 1200 ° C.

  for 2 hours then at 1500C for 5 hours to obtain a

  duit hardened hard and transparent orange pfle. Various characteristics of the products are given in Table I. For comparison, two compositions are prepared by hot melting an epoxy resin and a conventional curing agent the nature and amounts of which are shown in Table I. Table I also shows the various characteristics of these comparative compositions when they were cured at 100 ° C. for 2 hours and at 150 ° C. for 5 hours for Comparative Example 1 and at 10 ° C. for 2 hours and at 150 ° C. for 4 hours for the example

comparative 2.

Example 4

  It is dissolved in methyl ethyl ketone at 100 ° C., in order to obtain

  a 55% solids solution, a mixture of 400 parts of Shodain 540 (a brand of a diglycidyl hexahydrophthalate type epoxy resin manufactured by Showa Denko KK), 800 parts of Epikote 1001 (an epoxy resin brand) Bisphenol A / epichlorohydrin manufactured by Shell Chemical Corp. having the formula specified in note 1)

  of Table I where n is about 2 and a molecular weight of about

  900), 1500 parts of Epikote 152 (a brand of a novolak type epoxy resin manufactured by Shell Chemical Corp., having the formula

  indicated in note 3 (3) of Table I where n is approximately equal to 1) and 100

  parts of SH-6018. 2.6 parts of triethylamine are added to this solution.

  aluminum acetoacetate and 2.6 parts of TSR-160 (a mark of a poly-

  Methylphenylsiloxane manufactured by Toshiba Silicon K.K. comprising

  4 to 5% of hydroxy radicals) and the combination is mixed to obtain

find a solution.

  The resulting solution was used to impregnate an epoxysilane-pretreated canvas woven glass cloth and dried in air, and the impregnated fabric was dried at 100 ° C. for 10 to 30 minutes to obtain a prepreg. The prepreg contains about 45% of

solids.

  8 leaves measuring 200 x 200 mm are cut from the

  impregnated and superimposed to obtain a composite plate by pressing at 180 ° C. for 30 minutes and then postcure at 180 ° C. for 5 hours. Several samples are cut and the weight loss and electrical characteristics are measured. Weight loss

  heating at 200 ° C. for 1 000 hours is 11% and the characteristics

  Electrical ticks are shown in Table II below.

Example 5

  It is dissolved homogeneously in methylethyl

  ketone between 50 and 60 ° C to obtain a 50% solution of solids, a mixture of 100 parts of Chissonox 221, 200 parts

  Araldite ECN 1299 (a brand of an epoxy resin type polyether

  O-cresol novolac glycidyl represented by the formula: I2-O 1 2-O, C 2- O-O

CH CH CH

I I0

CH CH CH

O OO

CHC CH 2

3 -H ....

  and having an epoxy radical equivalency of 235, manufactured by Ciba Geigy) and 3 parts of SH-6018. 120 parts of this solution

  0.3 parts of aluminum triethylacetoacetate are gradually added

  and 40 parts of particulate natural graphite powder having an average size of 55 μm, and the combination is shaken to obtain a molding composition. The solution is filtered under reduced pressure to remove the solvent and then placed in a mold at 180C and exerted a pressure of 176.5 bar to obtain a plate. We submit

  then the plate at a postcure at 200C and measure its coeffi-

  friction friction with a friction-abrasion machine type EFMII-B (Toyo Baldwin K.K.) and found that it is 0.23 under a load of 100 kg. At this moment the exothermic temperature

  is 1650C and the polymerization index is 4,100.

Example 6

  To a mixture of 40 parts Epikote 828 and 60 parts

  Epikote 807 (a brand of bisphenol IF epichlorohydrin epoxy resin represented by the formula

0 OH

CH - CH-CH O / CH O-CH - -CH

2-CH - CH-CH-CH2

-o / "CH2- -o-CH2-

  (where n is approximately equal to 0) 3, manufactured by Shell Chemicals)

  3 parts of diphenylmethylsilanol and 2 parts of triacetyl-

  aluminum acetonate. The mixture was cured by heating at 160 ° C. for 15 hours to obtain a resin plate. The tangent of inductance (tg 6) is 0.56% at 130 ° C., 1.71 at 150 ° C. and

3.10% at 180 C.

  By way of comparison, the following procedure is repeated:

  except that 3 parts of boron trifluoride complex and ethanolamine are used instead of silanol and aluminum triacetylacetonate to obtain a resin plate. We measure its loss factor (tg 6) which is 20.5% at 130 C and which is too high for

be measurable at 150 C and above.

Example 7

  To a mixture of 80 parts of Epikote 828 and 20 parts

  100 parts of Epikote 1001, 3 parts of phenyldiethylsilanol and

  1 part of aluminum isopropoxide (hereinafter abbreviated

  Al-OiPr); the mixture was cured at 160 ° C. for 15 hours to obtain a resin plate. This plate has a loss factor

  from 0.63% at 130 C, 2.03% at 150 C and 2.91% at 180 C.

  Examples 8 to 14 and Comparative Examples 3 and 4

  Nine compositions, two of which are comparative compositions, are prepared from epoxy resins and curing catalysts, the nature and amounts of which are shown in FIG.

  Table III below. The gelling times of these compounds are measured

  positions at different temperatures; the results appear in

Table III.

  As shown in Table III, the addition of a mixture

  aluminum triacetylacetonate and a silane containing

  Methoxy or siloxane cels greatly accelerates the curing reaction. The compositions prepared in the examples are introduced

  and 13 in casting molds and cured at 100 C

  3 hours, at 150 ° C. for 3 hours and then at 180 ° C. for 10 hours to obtain hardened resin plates 2 mm thick. 20 x 20 mm samples are cut from each of the plates and their weight loss is determined by heating and the electrical characteristics of the rest of the plates are measured. The results

  are shown in Table IV below.

Example 15 and Comparative Example 5

  It is cured at 90 ° C. for 8 hours and then at 180 ° C. for

  12 hours a resin composition containing 100 parts Chisso

  nox 221, 0.5 part of Ql-3037 and 0.5 parts of aluminum triacetylacetonate. The temperature of hot distortion under load and the electrical characteristics (loss factor) are measured; the

  The results are shown in Table V below.

  For comparison, as in the above, a resin composition consisting of 100 parts of Chissonox 221 and 0.5 part of aluminum triacetylacetonate is cured and the product is subjected to

  hardened to the same measures as above. The results are also shown

in Table V.

  Examples 16 to 18 and Comparative Examples 6 and 7.

  Compositions containing Chissonox 221 are prepared,

  of ETS and aluminum triacetylacetonate in the quantities

  Table VI below and harden at the indicated temperatures.

  in this same table. The tangents of inductance 6 of the cured materials obtained at various temperatures are measured. The results

  also appear in Table VI.

  By way of comparison, two compounds are prepared and hardened.

  containing different amounts of ingredients indicated in Table VI. The characteristics are measured under the same conditions

  the results are shown in Table VI.

  As shown in Table VI, the resin compositions of Examples 16, 17 and 18 produce cured materials having

  better characteristics than the compositions of the exam-

  Comparative plots 6 and 7 in which triacetylacetoacetone

  aluminum nate to the epoxy resin. After curing at 140C, this temperature being lower than that at which the compositions of Comparative Examples 6 and 7 are cured, the resin composition

  of Example 18 has better characteristics.

  Example 19 and Comparative Examples 8 and 9

  Compositions of which the nature and amounts of the ingredients are included in the test tube are introduced into test tubes.

  Table VII below, one masks to avoid contact with the outside world.

and stored at 300C.

  We measure the number of days necessary for the

  viscosity of the compositions exceeds 1000 cP at 30 ° C., the result

  a measure of storage stability. The results are

Table VII.

  11. As shown in Table VII, the resin composition according to the invention has a higher storage stability than an epoxide resin containing a conventional acid anhydride.

Example 20.

  The procedure of Example 5 is repeated except that Epikote 152 and Ql-3037 are used instead of Araldite ECN 1299 and SH-6018, respectively, to obtain a resin solution that it is treated to form a molded plate. We measure the coefficient of friction? of the plate as in Example 5. The coefficient of friction is 0.18 under a load of 100 kg, the exotherm temperature is in this case 1620C and the polymerization index

of 4,000.

Example 21.

  A portion of the resin solution prepared in Example 20 was used to coat an aramid resin ribbon (Nomex, du Pont mark) and dried at 1000C for 10 minutes for the resin coating to reach the resitol stage. . The amount of resin on the ribbon is 15 g / m. The tape is wrapped with a half-cover around a steel tube having an outside diameter of 10 mm and a length of 150 mm and heated at 180-2000C for minutes. The ribbon is unwound but the adjacent layers of ribbon

  strongly adhere to each other and are torn off.

  The above-mentioned resin solution is also used to impregnate a 0.13 mm thick glass fabric ribbon

  19 mm and 10 mm long (distribution of glass wicks: longitudinal

  nally 40 wicks / 25 mm; transversely 38 wicks / 25 mm). This impregnated tape is passed at a speed of 1.5 m / min through a vertical oven 1 m high maintained at an internal temperature of 1050C in its upper part, 1400C in its middle part and 1000C in its lower part . The ribbon is thus dried and converted into resitol. It contains 32% of resitol. The tape is easy to handle and forms an excellent insulation material on which there is no foam after winding and heating at 180C for

10 hours.

  The electrical characteristics of the material are determined

  insulation obtained; the results are shown in Table VIII below.

  Examples 22 to 25 and Comparative Example 10

  Five different compositions are prepared, one of which is

  comparative position with the ingredients whose nature and quantities

  listed in Table IX below.

  These compositions are cured at 1600 ° C. for 15 hours in order to obtain resin plates whose measurement factors are measured.

  losses (tg 6) as shown in Table IX.

  Examples 26 to 28 and Comparative Examples 11 and 12.

  Compositions are prepared by mixing the ingredients

  whose nature and quantities are shown in Table X below.

  after. The viscosity of the compositions is measured at 500C. The compositions were cured at 1600C for 15 hours to obtain cured resin plates. The loss factors of the plates are then measured at various temperatures. The results are shown in Table X.

  As the examples and comparative examples show

  above, the resin-based compositions of the invention

  come as insulating materials for electrical appliances or

  to form composite plates, molding materials, pre-

  impregnated, adhesive tapes, shims, bearings or the like as they can be used for impregnation and casting and are soluble in organic solvents weakly

  polar low boiling point.

  Of course various modifications can be made.

  by those skilled in the art to the devices or methods that come

  to be described solely as non-limiting examples without

shot from the scope of the invention.

TABLE I

Composition (parts)

Example ComExExample

  Ingredients Example Example Example J paratificative

1 2 3 12

Epikote 8281) 100 - - 100 100

  Epoxy resins Chissonox 221) - - -

Epichlon 830 3) - 100

Diphenylsilediol-0.05 ---

  Hard Catalyst - :: zls Annealing of the Invention - SH 6084) tion c) 3 g 6) Conventional Agent for Complex BF 3-Et - - - 3 Hardening 2.HZ-CN 7) - 10 Temperature (C) of hot distortion

8) 175 163 161 135 140

  under load M o tA NO TABLE I (continued 1) Composition (parts)

  Example Example Example Com Example Comp Example

* parative parative

1 2 3 1 12

  118 0 18 107 i15 1 l at 25 C 1.8 x 1018 2.3 x 10 3.2 x 107 7.8 x 105 8.2 x 1015 C 26 x 10 63.2 x101 10 7 x 10 I 3 2 x 10 53 x 10

Specific resistivity

  9) at 25 ° C after 25 ° C after 1 hour of boiling 1.7 x 10 2.1 x 10 2.9 x 10 1.2 x 10 1.9 x 10 (n.cm ) Facteude ratio pr 9) at 25 C 0.30 0.43 0.42 0.64 0.78 Loss factor

  (%) M at 150 C 0.83 1.28 1.58 24.3 15.8

at 220 C 4.40 4.05 8.10 40.40

  Resistance to 25 C 13.1 15.6 10.3 8.7 9.9) flexion (kg / mm) at 1500C 7, 2 9.5 6.3 2.4 4.1 Weight loss (%) ) after 500 hours of 42 127 1.6 35.6 21.5 heating at 2500 ° C _

_L 6 _5, _21 __, 5__

  Note: 1) A brand of epoxy resin of the type: Bisphenol A / Epichlorohydrin Shell Chem. Corp. represented ft- Uq% 0 M% A us 4TABLE I (continued 2) / o \

CH 2 -CH-CII 2-

  (n = about 0) and having an average molecular weight of about 380.

  2) Brand of alicyclic epoxy resin (Chisso KK product) represented by the formula o 3) Brand of a novolak type epoxy resin (product of Dainippon Ink & Chemicals, Inc.) of the formula: CHS C, 2 o fH2% 0 CH / CH,

(n = about 0)

  4) Brand of a polymethylphenylsiloxane (Toray Silicon K.K.) having a molecular weight of about

  1,600 and a hydroxyl equivalent of about 400. TABLE 1 (continued 3)) Aluminum triacetylacetonate.

  6) Boron trifluoride-monoethylamine complex.

  7) Brand of imidazole (product of Shikoku Kasei K.K.).

  8) According to American Standard ASTM 684 (a).

  9) According to the Japanese JIS K-6911 standard.

  ) According to Japanese JIS K-7203.

Cru ru us N

TABLE II

  Characteristics Measuring conditions Measured value RsistivitspcCommon temperature 71015

Resistivity speci-_.

  (.cm) 12 C 63 x 102 Ordinary temperature 0.7 Loss factor _

(%) 1800C 7.9

t-, -J you wb

TABLE III

  vCompositions (Parts) Ingredients E xamples _______ Comparative Examples i _ _ _ _ _ __ _ _ _ _ _ _ _ _ 8 9 10 1i 1 12 13 14 3 4

  Chissonox resins 221 100 100 100O 100 - _ - 100 -

  epoxies Shodain.540 - - - - 100 100 100 -

Q1-30371) 1 - -

ETS2) 0.5 - 2 0.5 catalysts

  hardening PTS3). 0.5 - - _ 0.5 -

  | Al (acac) 3 1 0,5 0,5 0,05 1 | 0.5 0.5

50 - - - _ ..

  Time of Tempera- 120 - 18> 180 32 - - -.

  gelation of 140 180 13 50 20 -> 180 -> 180 - -

  hardening 160 35 8 8 9 - 65 43 - -

  (s) 180 13 1 6 5 - 87 32 20 - -

(C) 200 10 1 - - 54 12 9 53 90

  Brand of a polymethylphenylsiloxane containing

  (3,4-Cyclohexenoxy) -2-ethyltrimethoxysilane.

  3-Glycidyloxypropyltrimethoxysilane.

  18% radicals -OCH3 (manufactured by Toray Silicon K.K.).

Note: 1) 2) 3) Co Ln ut o ut

TABLE IV

TABLE V

  Samples Example 10 Example 13 Weight loss (%) after 8.5 6.9 1000 h heating at 190 C Specific resistivity 18 1 8 c C (n cm) J 8.3 x 1018 2.1x1018 Loss factor at 180 C

(7) 1.5 4.5

Characteristic samples

  Characteristics Example 15 Comparative Example

  ratif 5 Distortion temperature 16 hot under load (C) 3 156

at 130 C 0.84 1.08

  Factor at 1800C 1.32 1.88 losses (%) i at 2200C 2.86 8.33

at 260 C 1 5.20 9.70

TABLE VI

Composition (parts)

IgeExempnles Comparative Examples

Ratifying ingredients

16 17 18 6 7

Chissonox 221 100 100 100 100 100

ETS 0.2 0.5 0.5 - -

  Al (acac) 3 0.2 0.5 0.5 0.2 0.5 Curing temperature 180 180 140 180 10

(OC) 180 180 140 180 180

  (c) Temperature Factor 180 0 98 0.95 0.31 no 1.85 cured of hardness 220 1.57 1.80 2.91 not 3.33 losses hardened () | (C) 260 6, 76 5,42 6,56 non 9,70 (0c) j _______ hardened

TABLE VII

  Compositions (Parts) Ingredients Example Comparative Examples 19 d 8 9 Chissonox 221 100 100 100

Q1-3037 0.5 - -

A1l (acac) 3 0.5 0.5 -

HN 2200 * - - 50

  Time (j) required for the viscosity> 30 j> 30 to exceed 1000 cP *: Brand of an anhydride hardening agent

  methyltetrahydrophthalic acid manufactured by Hitachi Kasei K.K.

TABLE VIII

  Specific Resistivity 5, L x 1018 (180 C), (.n..cm) Induction Ratio (180 C) 84 Loss Factor (180C), (M) 2.5

TABLE IX

  Composition (parts) Ingredients Examples Example

22 23 24 25 compared

  tif 10 Epikote 828 40 50 60 50 40 Epikote 1001 60 50 40 -

Epikote 807 - - - 50 -

TSR-165 *) 2 - 1 2 -

Ph2Si (OCH3) 2 - 2 - - -

Al (acac) 3 2 1 - 2 -

A1-OiPr - - 1 - -

  Complex BF3-EtNH2 - - 3 Temperature Factor 100 0.51 0.47 0.56 0.45 4.5 ture 130 0.70 0.59 0.65 0.61 21.2 Losses Measurement 150 2, 51 2.60 2.40 1, 90 Impossible to measure (%.) (C) b 3.31 3.10 3.39 3.01 Impossible to measure *) Brand of methylphenylsilicone resin (product Toshiba Silicone KK) having a molecular weight of 650 and containing

% by weight of -OCH3 radicals.

*) Diphenyldimethoxysilane.

PAINTINGS

Composition (parts)

  Ingredients - Examples Examples

rations

__ 26 27 28 11 12

  Epikote 828 50 50 40 50 50 Epikote 807 50. 50 60 50 50

Ph2Si (OCOCH3) 2 2 - 2 - -

Ph2Si (OE t ** - 2 - -

Al (acac) 3 2 2 1 - 2

Imidazole - - - 3 -

  Storage Stability (j) *** Factor Plqemnon Temper-130 Factor 0.81 0.85 0.71 pll of a loss of 150 2.79 3.10 2.90 hard non-soft plate ( %) measurement plate non (OC) m180 3.51 4.02 3.98 soft hardened *) Diphenyldiacetoxysilane **) Diphenyldiethoxysilane ** i) Number of days required for the viscosity to reach

1,000 cP.

Claims (18)

R E V E N D I C A T I 0 NS   1. Composition based on epoxy resin, characterized in that it consists of: an epoxy resin; and a catalytic amount of a curing catalyst consisting of:   (A) one or more organosilicon compounds comprising   both at least one hydroxy radical and / or one hydrolysable radical,   at the silicon atom, these organosilicon compounds being chosen from organosilanes and organosiloxanes; and (B) one or more aluminum compounds having organic radicals.   2. Composition according to claim 1, characterized   in that the organosilicon compound (A) is selected from   silanes of formula: (R) y (R) = / if (R *) o each R independently represents an alkyl, phenyl, aralkyl, vinyl or allyl radical, R represents a hydroxyl radical or a hydrolyzable radical, Y is equal to 1, 2 or 3, m is 0, 1 or 2 and n is 1, 2 or 3 provided that the   sum of t + m + n is equal to 4.   3. Composition according to claim 2, characterized   in that the radical R 1 is a hydroxyl radical.   4. Composition according to claim 3, characterized   in that the organosilane is diphenylsilanediol, diphenylmethyl-   silanol, phenyldiethylsilanol or a mixture thereof.   5. Composition according to claim 2, characterized   in that the symbol R * represents a hydrolysable radical.   6. Composition according to Claim 5, characterized in that the hydrolyzable radical is an alkoxide radical, a radical   carboxylic acid ester, a halogeno radical or an oxime radical.   7. Composition according to claim 5, characterized in   the organosilane is (3,4-cyclohexene-2-oxy) ethyltrimethoxy-   silane, 3-glycidyloxypropyltrimethoxysilane, diphenyldimethoxy   silane, diphenyldiacetoxysilane, diphenyldiethoxysilane or a of their mixtures.   8. Composition according to claim 1, characterized in that the organosilicon compound (A) is an organosilane represented by the formula: R1) 234   (Rs) (RZ) (R 3) (R) s i -t sio- (siO) a (sio) b si (OH) / (OH) 2 -t (OH) 3 -uo R 1 2 3 4 o R 1, R 2 , R and R independently represent a hydrogen atom, an alkyl, phenyl, vinyl, aralkyl or allyl radical or a hydrolyzable radical, at least one of the hydrocarbon radicals being present; s and u are each equal to 0, 1 or 2; test equal to 0, 1 or 2 and a and b are each equal to zero, to 1 or to a higher integer to 1.   9. Composition according to Claim 8, characterized   in that the sum of a and b is equal to 50 or less.   10. Composition according to claim 1, characterized   in that the organosilicon compound (A) is selected from   siloxanes represented by the formula: (, 6) (R) 3 -SiO (SiO) x (R7) 3o R5 R6 and R7 independently represent a hydrogen atom,   an alkyl, phenyl, vinyl, aralkyl or allyl radical or a radical   hydrolysable cal, at least one hydrocarbon radical and at least one hydrolyzable radical being present; and x is 0, 1 or an integer greater than 1.   11. Composition according to claim 10, characterized   in that x is 50 or less.   12. Composition according to claim 1, characterized in that the aluminum compound (B) is an alkoxide, phenolate,   derivative of the acyloxy or aluminum chelate type or a mixture thereof.   13. Composition according to claim 2, characterized in that the aluminum compound is aluminum triethylacetonate, aluminum triethylacetoacetate, aluminum isopropoxide or a mixture of mixtures.   14. A composition according to claim 1, characterized in that the epoxy resin is chosen from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenolic novolak type epoxy resin, an alicyclic epoxy resin. , a heterocyclic epoxy resin, a hydrogenated bisphenol A type epoxy resin, an aliphatic epoxy resin, an epoxy resin obtained by reaction of an aromatic carboxylic acid, aliphatic or alicyclic with epichlorohydrin, a spirocyclic epoxy resin, a resin   glycidyl ether type epoxide obtained by reaction of a novolak   o-allylphenol lacquer with epichlorohydrin or a glycidyl ether type epoxy resin obtained by reaction of a diallylbisphenol compound, the allyl radicals of which are ortho to the hydroxy radicals, with bisphenol A.   15. Composition according to any one of the claims   preceding, characterized in that the curing catalyst consists of the organosilicon compound (A) in a proportion of 0.0001 to 10% by weight   and the aluminum compound (B) at 0.001-15% by weight, these two   centers being expressed in relation to the weight of the epoxy resin.   16. Composition according to Claim 15, characterized   in that it is diluted with a relatively weak organic solvent   polar and low boiling point.   17. Composition according to Claim 15, characterized   in that it contains an organic filler.   18. Composition according to claim 1, characterized in that the organosilicon compound (A) is a silicone resin comprising SiOH radicals and / or united hydrolyzable radicals. directly to the silicon atom.