Curable composition containing a difunctional epoxy resin,a polyfunctional epoxy resin,a difunctional phenol and a polyfunctional phenol

CURABLE COMPOSITION CONTAINING A DIFUNCTIONAL EPOXY RESIN, A POLYFUNCTIONAL EPOXY RESIN, A DIFUNCTIONAL PHENOL AND A POLYFUNCTIONAL PHENOL C׳

The present invention concerns curable compositions containing difunctional epoxy resins, polyfunetional epoxy resins difunctional phenols and c polyfunctional phenols as well as cured products thereof.

Electrical laminates are usually prepared from bisphenol A based epoxy resins advanced with tetrabromobisphenol A and cured with a biguanide such as dicyandiamide. These electrical laminates are adequate for applications wherein the glass transition temperature (Tg) requirements of the resin from which the laminates are prepared are below 135°C and the moisture absorbance of the laminate is greater than 1 percent by weight. However, in some applications, it would be desirable to have electrical laminates prepared from resin systems which when cured have glass 20 transition temperatures above 135°C, particularly above 150°C and which laminates have moisture absorbance below 1 percent by weight.

36,138-F

-ו-2One aspect of the present invention pertains to a composition which comprises (A) an epoxy-containing component consisting essentially of (1) from 5 to 95 percent by weight of at least one epoxy resin having an average of more than 1 but not more than 2 vicinal epoxide groups per molecule; and (2) from 95 to 5 percent by weight of at least one epoxy resin having an average of more than 2 vicinal epoxide groups per molecule; and (B) a phenolic hydroxyl-containing component consisting essentially of (1) from 10 to 70 equivalent percent of at least one phenolic hydroxyl-containing compound having an average of more than 1 but not more than 2 phenolic hydroxyl groups per molecule; and (2) from 90 to 30 equivalent percent of at least one phenolic hydroxyl-containing compound having an average of more than 2 phenolic hydroxyl groups per molecule; and wherein components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from 0.75:1 to 1.2:1.

Another aspect of the present invention pertains to a composition which comprises (A) an epoxy-containing component consisting essentially of

36,138-F

־3- (1) from 5 to 95 percent by weight of at least one epoxy resin having an average of more than 1 but not more than 2 vicinal epoxide groups per molecule; and (2) from 95 to 5 percent by weight of at least one epoxy resin .having an average of more than 2 vicinal epoxide groups per molecule;

(B) a phenolic hydroxyl-containing component consisting essentially of (1) from 10 to 70 equivalent percent of at least one phenolic hydroxyl-containing compound having an average of more than 1 but not more than 2 phenolic hydroxyl groups per molecule; and (2) from 90 to 30 equivalent percent of at least one phenolic hydroxyl-containing compound having an average of more than 2 phenolic hydroxyl groups per molecule; and (C) a catalytic quantity of at least one catalyst for effecting the reaction between components (A) and (B); and wherein components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from 0.75:1 to 1.2:1.

A further aspect of the present invention pertains to a laminating varnish component comprising (A) an epoxy-containing component consisting essentially of (1) from 5 to 95 percent by weight of at least one epoxy resin having an average of more

36,138-F

-4than 1 but not more than 2 vicinal epoxide groups per molecule; and (2) from 95 to 5 percent by weight of at least one epoxy resin having an average of more than 2 vicinal epoxide groups per molecule;

(B) a phenolic hydroxyl-containing component consisting essentially of (1) from 10 to 70 equivalent percent of at least one phenolic hydroxyl-containing compound having an average of more than 1 but not more than 2 phenolic hydroxyl groups per molecule; and (2) from 90 to 30 equivalent percent of at least one phenolic hydroxyl-containing compound having an average of more than 2 phenolic hydroxyl groups per molecule; and (C) a catalytic quantity of at least one catalyst for effecting the reaction between components (A) and (B); and optionally (D) one or more solvents in an amount of from 1 to 75 percent by weight of the total composition; and wherein components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from 0.75:1 to 1.2:1.

Another aspect of the present invention pertains to a laminate resulting from curing one or more plies of a substrate material which has been impregnated with the aforementioned laminating varnish.

36,138-F

The curable compositions described above when cured have glass transition, Tg, temperatures above

135°C, usually above 150°C. The laminates described above prepared from these curable compositions absorb moisture to an extent of less than 1 percent by weight.

The epoxy resin compositions can be prepared by blending the components together in any suitable manner such as, for example, mixing the two epoxy resins together in a solvent at elevated temperatures to form a uniform mixture, then cooling to room temperature and blending in the two phenolic compounds to form a uniform mixture.

The epoxy resin mixture can suitably contain from 5 to 95, more suitably from 5 )to 60, most suitably from 5 to 40 percent by weight of £he epoxy resin having an average of more than 1 but not more than 2 vicinal epoxide groups per molecule 'based on the combined weight of this resin and the epoxy resin having an average of more than 2 vicinal epoxide groups per molecule. Correspondingly, the epoxy resin having an average of more than 2 vicinal epoxide groups per molecule is suitable employed in an amount of from 95 to 5, more suitably from 95 to 40, most suitably from 95 to 60 percent by weight based on the combined weight of this epoxy resin and the epoxy resin having an average of'more than 1 but not more than 2 vicinal epoxide groups per molecule.

Any epoxy resin having an average of more than one but not greater than two vicinal epoxy groups per molecule can be employed herein. Suitable such epoxy resins include, for example, those diglycidyl ethers of dihydric phenols represented by the formulas I and II

36,138-F ־5-7wherein each A is independently a divalent hydrocarbyl group having from 1 to 10, more suitably from 1 to 5, most suitably from 1 to 3» carbon atoms, -S-, -S-S-, SO-, -S02־» -CO-, or -0-; each R is independently hydrogen or an alkyl group having from 1 to 3 carbon atoms; each X is independently hydrogen, an alkyl group having from 1 to 10, more suitably from 1 to 5, most suitably from 1 to 3» carbon atoms or a halogen, preferably chlorine or bromine; each n independently has a value of zero or 1; and n' has a value from zero to 10, more suitably from zero to 2, most suitably from zero to 0.5.

Particularly suitable epoxy resins having an average of more than 1 but not more than 2 vicinal epoxy groups per molecule include, for example, the diglycidyl ethers of bisphenol A, tetrabromobisphenol A where the bromine atoms are in the ortho or meta positions relative to the ether oxygen atoms, bisphenol K, bisphenol F, bisphenol S, and mixtures thereof.

Suitable epoxy resins having an average of more than 2 vicinal epoxy groups per molecule include, for example, those represented by the formulas III and IV

<img file="IL86138A_D0001.tif" />

36,138-F

FORMULAI

<img file="IL86138A_D0002.tif" />

H₂C — C-CH2 I R

<img file="IL86138A_D0003.tif" />

A¹’* ?' .0־O־CH2-C-CH2

R

<img file="IL86138A_D0004.tif" />

FORMULAII

004 \

<img file="IL86138A_D0005.tif" />

(1)4

FORMULA III

<img file="IL86138A_D0006.tif" />

FORMULA IV

<img file="IL86138A_D0007.tif" />

-סוwherein each R and X are as described above; each A' !פ independently a divalent hydrocarbyl group having from to 10, more suitably from 1 to 4, most suitably from to 2, carbon atoms or a divalent polycyclopentadiene group; each R' is independently hydrogen or a hydrocarbyl group having from 1 to 10, more suitably from 1 to 5, most suitably from 1 to 2, carbon atoms; m has a value from 0.1 to 7, more suitably from 1 to 5, most suitably from 1 to 4; and m* has a value from zero ¹⁰ to 3, more suitably from zero to 2, most suitably from zero to 1.

The phenolic hydroxyl-containing component suitably contains from 10 to 70, more suitably from TO 15 to 50, most suitably from 10 to 35, equivalent percent phenolic hydroxyl-containing compound having an average of more than 1 but not more than 2 phenolic hydroxyl groups per molecule based upon the combined weight of 2θ phenolic hydroxyl-containing compound having an average of not more than 2 phenolic hydroxyl groups per molecule and phenolic hydroxyl-containing compound having ,an average of more than 2 phenolic hydroxyl groups per molecule. Correspondingly, the phenolic hydroxyl-containing component suitably contains from 90 to 30» more suitably from 90 to 50, most suitably from 90 to 65, equivalent percent phenolic hydroxylcontaining compound having an average of more than 2 phenolic hydroxyl groups per molecule based upon the combined weight of phenolic hydroxyl-containing compound having an average of not more than 2 phenolic hydroxyl groups per molecule and phenolic hydroxylcontaining compound having an average of more than 2 phenolic hydroxyl groups per molecule.

36,138-F

-11Among the compounds which are suitable as the phenolic hydroxyl-containing compound having an average of more than 1 but not more than 2 phenolic hydroxyl groups per molecule include, for example, those represented by the following formulas V and VI

FORMULA V

OH

<img file="IL86138A_D0008.tif" />

(X)4

FORMULA VI

<img file="IL86138A_D0009.tif" />

wherein A, X and n are as previously defined. Particularly suitable phenolic hydroxyl-containing compounds having an average of more than 1 but not more than 2 phenolic hydroxyl groups per molecule include, for example, bisphenol A, bisphenol K, bisphenol F, bisphenol S, the halogenated, particularly the brominated, derivatives of the aforementioned bisphenols wherein the halogen atoms are either ortho or meta with respect to the ether oxygen atoms, resorcinol, catechol, hydroquinone,

36,138-F

-12tetramethylbisphenol A, 4,4'-dihydroxybiphenyl,

3♦5»3'5'-tetramethyl-4,4'dihydroxybiphenyl, 3,5,3¹5'tetrabromodihydroxybiphenyl, 3>5,3'5'-tetramethyl2,6,2*,6'-tetrabromo-4,4'-dihydroxybiphenyl, and any combination thereof.

Among the compounds which are suitable as the phenolic hydroxyl-containing component having an average of more than 2 phenolic hydroxyl groups per molecule include, for example, those represented by the following formulas VII and VIII

<img file="IL86138A_D0010.tif" />

<img file="IL86138A_D0011.tif" />

<img file="IL86138A_D0012.tif" />

<img file="IL86138A_D0013.tif" />

36,138-F

-13FORMULA VIII

<img file="IL86138A_D0014.tif" />

wherein A',R׳, X and m are as previously defined. Particularly suitable phenolic hydroxyl-containing compounds having an average of more than 2 phenolic hydroxyl groups per molecule include, for example, the phenol-formaldehyde novolac resins, cresol-formaldehyde novolac resins, brominated phenol-formaldehyde novolac resins, brominated cresol-formaldehyde novolac resins, 3,3',5,5'-tetramethyl-(1,1'-biphenyl)-2,4,4'-triol, pyrogallol, and any combination thereof.

The term hydrocarbyl as employed herein means any aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic or cycloaliphatic, or aliphatic or cycloaliphatic substituted aromatic groups.

The epoxy-containing component and the phenolic hydroxyl-containing component are employed in quantities which provide a phenolic hydroxyl group to epoxy group ratio of from 0.75:1 to 1.2:1, more

36,Ί 38—F

-14suitably from 0.85:1 to 1.1:1, most suitably from 0.95:1 to 1:1.

Suitable catalysts for effecting the reaction 2 between the epoxy resin and the phenolic hydroxyl-containing compound include, for example, those disclosed in U.S. Pat. Nos. 3,306,872; 3,341,580; 3,379,684; 3,477,990; 3,547,881; 3,637,590; 3,843,605;

3,948,855; 3,956,237; 4,048,141; 4,093,650; 4,131,633;

4,132,706; 4,171,420; 4,177,216; 4,302,574; 4,320,222;

4,358,578; 4,366,295; and 4,389,520.

Particularly suitable catalysts are those quaternary phosphonium and ammonium compounds such as, 15 for example, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltripheny!phosphonium iodide, ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium diacetate 20 (ethyltriphenylphosphonium acetate-acetic acid complex), ethyltriphenylphosphonium tetrahaloborate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, ₂₅ tetrabutylphosphonium acetate, tetrabutylphosphonium diacetate (tetrabutylphosphonium acetate-acetic acid complex), tetrabutylphosphonium tetrahaloborate, butyltriphenylphosphonium tetrabromobisphenate, butyltriphenylphosphonium bisphenate, butyltriphenylphosphonium bicarbonate, benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, benzyltrimethylammonium tetrahaloborate, tetramethylammonium hydroxide, tetrabutylammonium

36,138־F

-15hydroxide, tetrabutylammonium tetrahaloborate, and mixtures thereof.

Other suitable catalysts include tertiary _c amines such as, for example, triethylamine,

כ tripropylamine, tributylamine, an imidazole such as 2methylimidazole, benzyldimethylamine, and mixtures thereof.

Other suitable catalysts include ammonium compounds such as, for example, triethylamine-HCl complex, triethylamine.HBr complex, triethylamine.HI complex, triethylamine.tetrahaloboric acid complex, tributylamine.HC1 complex, tributylamine.HBr complex, 15 tributylamine.HI complex, tributylamine.tetrahaloboric acid complex, N,N'-dimethyl-1,2diaminoethane.tetrahaloboric acid complex, and mixtures thereof.

Other suitable catalysts include quaternary and tertiary ammonium, phosphonium, and arsonium adducts or complexes with suitable non-nucleophilic acids such as, for example, fluoboric, fluoarsenic, fluoantimonic, fluophosphorie, perchloric, perbromic, periodic, and OR mixtures thereof.

The catalysts are employed in any quantity which will promote the reaction between the phenolic hydroxyl-containing compound and the epoxy-containing 3° compound. Usually, a suitable quantity of catalyst is from zero to 0.1, more suitably from 0.00005 to 0.05, most suitably from 0.0001 to 0.03 moles of catalyst per part by weight of the epoxy-containing component.

in some instances, in order to prevent premature reaction between the epoxy-containing

36,138-F

-16compounds and the aromatic hydroxyl-containing compounds, it may be desirable to include in the composition one or more stabilizers to prevent this premature reaction from taking place. This is especially true when the compositions are to be subjected to prolonged storage at elevated temperatures.

Suitable stabilizers include, for example, organic and inorganic acids, salts and esters of organic and inorganic acids such as, for example, sulfonic acid,fluoboric acid, perchloric acid, boric acid, chloric acid, bromic acid, iodic acid, and nitric acid.

Particularly suitable stabilizers include, for example, p-toluene sulfonic acid, benzene sulfonic acid, methyl p-toluene sulfonate, ammonium perchlorate, fluoboric acid, perchloric acid, nitric acid, and mixtures thereof.

These stabilizers when employed, are employed in amounts from 0.05 to 1, more suitably from 0.1 to 0.8 percent by weight based upon the combined weight of the epoxy-containing component.

In the preparation of laminates from the curable compositions of the present invention, the curable compositions are dissolved into one or more solvents and applied to the substrate material from which the prepreg is to be prepared. Suitable such solvents ihclude, for example, aromatic hydrocarbons, ketones, glycol ethers, alcohols, aliphatic hydrocarbon, cyclic ethers, halogenated hydrocarbons, amides, and the like. Particularly suitable solvents

36,138-F

-17include, for example acetone, methyl ethyl ketone, methanol, ethanol, propylene glycol methyl ether, dimethylformamide, and any combination thereof. The amount of solvent which is employed is that quantity which provides the laminating varnish or other curable composition with the desired application viscosity.

Usually, an amount of solvent is suitably from 1 to 75, more suitably from 1 to 50, most suitably from 1 to 25 parts of solvent by weight based upon the total weight of the laminating varnish.

Suitable substrate materials include natural and synthetic fibrous materials in filament, mat, woven or the like form. Suitable fibrous materials include, fiberglass, nylon, orlon, cotton, aramid, graphite, boron, cellulose, polyethylene, polypropylene, and the like.

Also, if desired, the curable compositions of the present invention can alio contain pigments, dyes, fillers, surfactants, flow modifiers, and any combination thereof. Particularly suitable fillers or pigments or flow modifiers include, for example, titanium dioxide, iron oxide, calcium carbonate, quartz, fused silica, silicates, silanes, metal powders such as, for example, aluminum, iron, magnesium, and any combination thereof.

The curable compositions of the present invention are particularly useful in the preparation of laminating varnishes for preparing prepreg materials from which electrical laminates can be prepared. One or more plies of the prepreg material are pressed together while being heated in order to prepare a laminate therefrom. One or more layers of an

36,138-F

-18electrically conductive material is employed as an outer layer of the laminate which can be one of the outer layers of the multiply prepreg materials which is pressed together under heat or the electrically conductive outer layer can be applied later by means of an adhesive. Also, if the electrical conductive layer is employed as one of the plies which is pressed together under heat, there can be, if desired, an adhesive layer placed between it and the prepreg material.

Suitable electrically conductive materials which can be employed herein include, for example the electrically conductive metals such as, aluminum, copper, gold, silver, platinum and the like and the electrically conductive organic polymers such as polyacrylonitrile, which have been carbonized and any combination thereof.

The following examples are illustrative of the invention, but are not to be construed as to limiting the scope thereof in any manner.

EXAMPLE 1

A solution was prepared by mixing in a suitable vessel 1200 g (6.64 equiv.) of a diglycidyl ether of bisphenol A having an epoxide equivalent weight (EEW) of 180.8, 2400 g (13.03 equiv.) of a 5 functional phenol-formaldehyde novolac epoxy resin having an EEW of 184.16, 1605 g (5.9 equiv.) of tetrabromobisphenol A wherein the bromine atoms are ortho in relationship to the ether oxygen atoms, 1432.1 g (13.71 equiv.)of a 5.6 functional phenol-formaldehyde novolac resin having a phenolic hydroxyl equivalent weight of 104, 37.08 ml of

36,138-F

-1935 percent tetrabutylphosphonium acetate״acetic acid complex in methanol containing a stoichiometric amount of fluoboric acid as a catalyst and 2212.3 g of methyl ethyl ketone (MEK). To this solution was added a sufficient amount of propylene glycol methyl ether to provide a solvent mixture of 66 weight percent MEK and 33 weight percent propylene glycol methyl ether at a solids (non-volatiles) level of 62 weight percent. To this solution was added 0.05 weight percent, based on the solids content, of 2-methyl imidazole. This solution has a stroke cure plate gel time of 146 seconds at 345°F (174°C).

This laminating varnish was then applied to 7628/1617 woven glass cloth by pulling the cloth through a resin bath containing the laminating varnish and then up through a doctor bar set at 0.015 in. (0.381 mm) and then through three heating zones of 300°F, 35O°F and 350°F (149°C, 177°C and 177°C). The total length of the heating zones was 24 feet (7.31 ni). The length of each of the three heated zones was 8 feet (2.43 m). This prepreg was passed through the resin bath and the heating zones at a rate of 9 feet/min. (2.74 m/min.), with a residence time in the heated zones of 2.5 minutes. The resultant prepreg contains 42 percent resin by weight and has a gel time of 68 seconds at 345°F (174°C).

Eight plies of this prepreg was then pressed into a laminate having a thickness of 0.060 inches (1.5 mm) by using the following press schedule.

10°F/min. (5.6°C/min), room temp, to 275°F (135°C), 30 psig (206.8 kPa).

15°F/min. (8.3’C/min), 275°F to 350°F (135°C to 176.7°C), 30 psig (206.8

36,138־F

-20kPa) to 500 psig (3447.4 kPa) in 2 minutes;

and

Cooled at 500 psig (3447.4 kPa) to 150°F (65.6°C) in 6 min.

This laminate has a glass transition temperature, Tg, of 175.9°C by Differential Scanning Calorimetry (DSC) using a calibrated DuPont instrument model no. 912 with a 1090 controller. Samples were run under a nitrogen atmosphere with a heat up rate of 20°C/minute. After being immersed in boiling water for 160 hours, the sample has a water absorption (pickup) of 0.5 percent by weight.

EXAMPLE 2

The components of the following formulation, except the catalyst, were mixed at 150°C until homogeneous. The catalyst was then blended into the blend of resins and phenolic components. After the catalyst was blended into the formulation, the resultant catalyzed blend was cured at 177°C for 1.5 hours. The Tg of the resultant cured product is 158°C.

3.8 g (0.021 equiv.) of a diglycidyl ether of bisphenol A having an EEW of 180.8;

0.2 g (0.0011 equiv.) of a 5 functional phenol-formaldehyde based epoxy novolac resin having an EEW of 181.8;

0.6 g (0.1 equiv.) of tetrabromobisphenol A;

2.07 g (0.9 equiv.) of a 5 functional phenolformaldehyde novolac resin; and

36,138-F

-210.1 ml of the reaction product of tetrabutyl phosphonium acetate«acetic acid complex and fluoboric acid catalyst.

EXAMPLE 3

The components of the following formulation, except the catalyst, were mixed at 150°C until homogeneous. The catalyst was then blended into the blend of resins and phenolic components. After the catalyst was blended into the formulation, the resultant catalyzed blend was cured at 177°C for 1.5 hours. The Tg of the resultant cured product is 138°C.

3.8 g (0.021 equiv.) of a diglycidyl ether of bisphenol A having an EEW of 181;

0.2 g (0.0011 equiv.) of a 5 functional phenol-formaldehyde based epoxy novolac resin having an EEW of 181.8;

4.21 g (0.7 equiv.) of tetrabromobisphenol A;

0.69 g (0.3 equiv.) of a 5 functional phenolformaldehyde novolac resin; and

0.1 ml of the reaction product of tetrabutyl phosphonium aaetateeacetic acid complex and fluoboric acid catalyst.

EXAMPLE 4

The components of the following formulation, except the catalyst, were mixed at 150°C until homogeneous. The catalyst was then blended into the blend of resins and phenolic components. After the catalyst was blended into the formulation, the

36,138-F

-22resultant catalyzed blend was cured at 177°C for 1.5 hours. The Tg of the resultant cured product is 206°C.

0.2 g (0.0011 equiv.) of a diglycidyl ether of bisphenol A having an EEW of 181;

3.8 g (0.0208 equiv.) of a 5 functional phenol-formaldehyde based epoxy novolac resin having an EEW of 181.8;

0.6 g (0.1 equiv.) of tetrabromobisphenol A;

. 2.05 g (0.9 equiv.) of a 5 functional phenolformaldehyde novolac resin; and

0.1 ml of the reaction product of tetrabutyl phosphonium acetate»acetic acid complex and fluoboric acid catalyst.

EXAMPLE 5

The components of the following formulation, except the catalyst, were mixed at 150°C until homogeneous. The catalyst was then blended into the blend of resins and phenolic components. After the catalyst was blended into the formulation, the resultant catalyzed blend was cured at 177°C for 1.5 hours. The Tg of the resultant cured product is 177°C.

0.2 g (0.0011 equiv.) of a diglycidyl ether of bisphenol A having an EEW of 181;

3.8 g (0.0208 equiv.) of a 5 functional phenol-formaldehyde based epoxy novolac resin having an EEW of 181.8;

4.17g (0.7 equiv.) of tetrabromobisphenol A;

36,138-F

-230.68 g (0.93 equiv.) of a 5 functional phenolformaldehyde novolac resin; and

0.1 ml of the reaction product of tetrabutyl phosphonium acetate-acetic acid complex and fluoboric acid catalyst.