Thermosetting resin composition and use thereof for an electronic part

A thermosetting resin composition is provide, which contains a compound of ##STR1## wherein substituents R.sub.1 -R.sub.6 each represents a hydrogen atom or a saturated alkyl group having 1-6 carbon atoms, substituents R.sup.7 -R.sup.12 each represents a hydrogen atom, a saturated alkyl group having 1-4 carbon atoms or an alkoxy group having 1-4 carbon atoms, X.sub.a -X.sub.e each represents a hydrogen atom, a chlorine atom or a bromine atome, and the average repeating unit number n denotes a numeral from 0 to 5, and a polyamide compound having two or more maleimide groups and, if desired, a compound of ##STR2## wherein R.sub.1 and R.sub.2 each represents a methyl group or a phenyl group, and R.sub.3 represents a hydrogen atom or a functional group containing an amino group, a glycidyl group or an alicylic epoxy group, l denotes a numeral in the range of 0-500, and m denotes a numeral in the range of 1-500, or ##STR3## wherein R.sub.1 and R.sub.2 each represents a methyl group or a phenyl group, and R.sub.3 represents a hydrogen atom or a functional group containing an amino group, a glycidyl group or an alicyclic epoxy group, and p denotes a numeral in the range of 0-500. The composition is useful for electronic parts.

The present invention relates to a thermosetting resin composition. More 
particularly, it relates to a thermosetting resin composition excellent in 
processability and heat resistance and an electronic part with use of it. 
Thermosetting resins are used for a variety of electric insulating 
materials, structural materials, adhesives and the like as materials for 
casting, impregnation, lamination or molding. Recently, these materials 
tend to be used for these applications under more restricted conditions, 
and the materials are required to have heat resistance as an essential 
property. 
Hitherto, thermosetting polyimde resins have been used for such purposes, 
but heating at high temperature for a long time was required for their 
processing. 
Also, epoxy resins which have been improved in heat resistance are 
excellent in processability, but they have insufficient heat resistance at 
high levels such as mechanical properties and electric properties at high 
temperature and long term heat deterioration characteristics. 
As one of alternatives of these materials, there have been proposed, for 
example, a thermosetting mixture comprising a polyimide, an alkenylphenyl 
and/or an alkenylphenol ether (Japanese Patent Application Kokai 
(Laid-Open) No. 994/1977), a heat resistant resin composition comprising a 
maleimide type compound, a poly-allylated phenol compound and an epoxy 
resin (Japanese Patent Application Kokai (Laid-Open) No. 134099/1978) and 
the like. 
The polyallylated phenol compound used in the aforementioned composition is 
prepared from a bicyclic compound or a phenol novolak and thus contains 
the allyl ether of the bicyclic compound or a Claisen rearrangement 
product as a volatile component, so that it tends to remain unaltered on 
the heat curing or even after curing and has problems on its moldability 
or the curing physical properties or heat deterioration characteristics at 
high temperature. 
From these backgrounds, present inventors conducted researches on resin 
compositions having an excellent heat resistance and an excellent 
processability. As a result, they found that a resin composition 
comprising a certain resin and a maleimide compound served the purpose and 
thus reached the accomplishment of the present invention. 
That is, the present invention is to provide a thermosetting resin 
composition comprising (A) an allyl etherified compound obtained by allyl 
etherification of the hydroxyl groups of a polyvalent phenol represented 
by the following formula (I) 
##STR4## 
wherein substituent R.sup.1 -R.sup.6 each represents a hydrogen atom or a 
saturated alkyl group having 1-6 carbon atoms, substituent 
R.sup.7-R.sup.12 each represents a hydrogen atom, a saturated alkyl group 
having 1-4 carbon atoms or an alkoxy group having 1-4 carbon atoms, 
X.sub.a -X.sub.e each represents a hydrogen atom, a chlorine atom or a 
bromine atom, and the average repeating unit number n denotes a numeral 
from 0 to 5, and (B) a polymaleimide compound containing two or more 
maleimide groups in the molecule The present invention also provides a 
thermosetting resin composition comprising silicone resins having the 
specific structures in addition to the composition containing (A) and (B) 
above mentioned. 
The respective components of present invention are further explained in 
detail below. 
In the formula (I), specific examples of R.sup.1, R.sup.2, R.sup.3, 
R.sup.4, R.sup.5 and R.sup.6 include preferably a hydrogen atom, a methyl 
group, an ethyl group, a propyl group, a butyl group, an amyl group, a 
hexyl group and the like, preferably a hydrogen atom, a methyl group, an 
ethyl group, a propyl group and a butyl group. 
Furthermore, specific examples of R.sup.7, R.sup.8, R.sup.9, R.sup.10, 
R.sup.11 and R.sup.12 include a hydrogen atom, a methyl group, an ethyl 
group, a propyl group, a butyl group and a methoxy group, preferably a 
hydrogen atom, a methoxy group and a methyl group, particularly a hydrogen 
atom. 
The more n is, the higher heat resistance is. However, if it is too large, 
the melting viscosity of the allyl compound (I) is increased and the 
processability and moldability thereof are lowered. Thus, n is preferably 
in the range of 5 or less. 
The polyvalent phenol moiety of the formula (I) of the present invention is 
obtained by condensing an aromatic carbonyl compound represented by the 
formula (IV) below mentioned and a phenol. 
##STR5## 
wherein R corresponds to R.sup.11 or R.sup.12 in the formula (I), R' and 
R" correspond to R.sup.7, R.sup.8, R.sup.9 or R.sup.10 in the formula (I) 
and Y corresponds to X.sub.b or X.sub.d in the formula formula (I). 
Specific examples of the aforementioned aromatic carbonyl compound include 
hydroxybenzaldehyde, methylhydroxybenzaldehyde, 
dimethylhydroxybenzaldehyde, methoxyhydroxybenzaldehyde, 
chlorohydroxybenzaldehyde, bromobenzaldehyde, hydroxyacetophenone, 
hydroxyphenyl ethyl ketone, hydroxyphenyl butyl ketone and the like, 
preferably hydroxybenzaldehyde, particularly p-hydroxy-benzaldehyde. 
Another carbonyl compound may also be employed in a small amount in 
combination with said aromatic carbonyl compound. Such a carbonyl compound 
includes, for example, formaldehyde, acetaldehyde, crotonaldehyde, 
acrolein, glyoxal and benzaldehyde. 
Examples of the phenol include phenol, cresol, ethylphenol, propylphenol, 
butylphenol, amylphenol, hexylphenol, methylpropylphenol, 
methylbutylphenol, methylhexylphenol, methylphenylphenol, chlorophenol, 
bromophenol, chlorocresol, bromocresol and the like, preferably o-cresol. 
The condensation of the aromatic carbonyl compound and the phenol is 
carried out by allowing about 0.5-10 moles of the latter to react with 1 
mole of the former at a temperature in the range of 30.degree.-180 
.degree. C. in the presence of a well-known acidic catalyst for the 
synthesis of novolaks, for example, a mineral acid such as hydrochloric 
acid, sulfuric acid or phosphoric acid, an organic acid such as oxalic 
acid or toluenesulfonic acid, or a salt such as zinc acetate. 
In this connection, an aromatic solvent such as toluene or chlorobenzene 
may also be used in the condensation. 
Moreover, in order to increase the repeating units in the oligomer, it is 
sufficient that the condensation is carried out with a decreased ratio of 
the phenol at a higher temperature in the presence of an increased amount 
of the catalyst. 
The polyvalent phenol thus obtained may also be halogenated by a well-known 
method with chlorine or bromine. 
The allyl etherification is conducted by a well-known method for allyl 
etherification of the phenol. That is, the allyl etherification product is 
obtained by allowing the condensation product to react with an allyl 
halide such as allyl chloride, allyl bromide or allyl iodide in the 
presence of an alkali such as sodium hydroxide. The alkali is used in an 
equivalent amount to the portion of the phenolic hydroxyl groups which are 
desired to be allyl etherified. The amount of the allyl halide used is an 
amount which is equivalent to or more than the amount of the alkali. The 
allyl etherification rate of the phenolic hydroxyl group is preferably in 
the range of 20-100 %, more preferably in the range of 30-70 %. 
An allyl phenol may be obtained by a method for rearranging the 
aforementioned allyl etherified phenol by the action of heat (Claisen 
rearrangement). 
As the N,N'-bismaleimide compound used in the present invention, there are 
mentioned N,N'-diphenyl-methane bismaleimide, N,N'-phenylene bismaleimide, 
N,N'-diphenyl ether bismaleimide, N.N'-diphenylsulfone bismaleimide, 
N.N'-dicyclohexylmethane bismaleimide, N,N'-xylene bismaleimide, 
N,N'-tolylene bismaleimide, N,N'-xylylene bismaleimide, 
N.N'-diphenylcyclohexane bismaleimide (including isomers, respectively), 
N,N'-ethylene bismaleimide, N,N'-hexamethylene bis-maleimide and 
prepolymers having an N,N'-bismaleimide skeleton terminal which are 
obtained by addition reaction of the N,N'-bismaleimide compounds with a 
diamine. 
In the resin composition of the present invention, particularly the allyl 
etherified polyvalent phenol has a low melting viscosity, so that it is 
easily mixed with the bismaleimide resin and thus has an excellent 
processability. Moreover, the partly allyl etherified polyvalent phenol 
has phenolic hydroxyl groups and allyl groups, so that it has a high 
reactivity with the bismaleimide resin and is suited for an encapsulant or 
the like. 
In the resin composition of the present invention, particularly the 
aromatic nucleus substituted allyl polyvalent phenol which has been 
obtained by the Claisen rearrangement, in spite of its high melting 
viscosity, produce a cured product excellent in toughness. Further, the 
partly aromatic nucleus substituted allyl polyvalent phenol is rapidly 
curable and thus suited for a molding compound. 
In the resin composition of the present invention, the amount ratio of the 
partly allyl ether substituted phenol novolak resin and the 
N,N'-bis-maleimide compound is preferably determined so that the ratio of 
the double bonds in the latter to those in the former is in the range of 2 
or less. If the ratio exceeds 2, the content of the unaltered allyl group 
undesirably increases in the cured product. 
In this connection, the N,N'-bismaleimide compound may be preliminarily 
allowed to react with an allyl group to such an extent that gelation will 
not be caused. 
As silicone resins used in the present invention, there are mentioned those 
represented by the following formulae (II) or (III): 
##STR6## 
wherein R.sub.1 and R.sub.2 each represents a methyl group or a phenyl 
group, and R.sub.3 represents a hydrogen atom or a functional group 
containing an amino group, a glycidyl group or an alicyclic epoxy group, l 
denotes a numeral in the range of 0-500, preferably 0-150, and m denotes a 
numeral in the range of 1-500, preferably 0-150, or wherein R.sub.1 and 
R.sub.2 each represents a methyl group or a phenyl group, and R.sub.3 
represents a hydrogen atom or a functional group containing an amino 
group, a glycidyl group or an alicyclic epoxy group, and p denotes a 
numeral in the range of 0-500, preferably 0-150. 
The silicone resin represented by the formula (II) tends to gel, and thus 
the one represented by the formula (III) is preferred. 
These silicone resins may be used in combination of the two or more. 
As the silicone resin wherein R.sub.3 represents a hydrogen atom, there are 
mentioned X-21-7628 manufactured by SINETSU KAGAKU KOGYO K.K and the like; 
as the one wherein R.sub.3 represents a functional group containing an 
amino group (referred to hereinafter as amino group containing silicone 
resin), X-22-161A manufactured by SINETSU KAGAKU KOGYO K.K., SF-8417 
manufactured by TORAY-DOW CORNING SILICONE K.K. and the like; and as the 
one wherein R.sub.3 represents a functional group containing an alicyclic 
epoxy group (referred to hereinafter as epoxy group containing silicone 
resin), BX16-855B, BX-16-854B manufactured by TORAY-DOW CORNING SILICONE 
K.K. and the like. 
While the molecular weight is not critical, a silicone resin having a 
molecular weight in the range of about 500 to 30,000, preferably 500 to 
10,000, is used. 
While these silicone resins are used by only mixing them with (A) the 
allylated product of the polyvalent phenol and (B) the polymaleimide 
compound, they are preferably allowed to react preliminarily with (A) the 
allylated product of the polyvalent phenol or (B) the polymaleimide 
compound. 
The reaction between the hydrogen group-containing silicone resin and the 
allyl group in the allylated product of the polyvalent phenol as the 
component (A) is a hydrosilylation reaction, which is easily conducted as 
usual with use of a platinum catalyst and the like. 
The glycidyl group- or alicyclic epoxy group-containing silicone resin may 
also be allowed to react easily with the hydroxy group in the allylated 
product of the polyvalent phenol as the component (A) in the presence of a 
basic catalyst (for example, triethyl-amine or the like). 
Furthermore, the amino group-containing silicone resin is allowed to react 
easily with the maleimide group of the bismaleimide as the component (B) 
in the composition of the present invention. 
These reactions successfully avoid the bleeding of silicone from a cured 
product and produce a low stress thermosetting resin composition wherein 
silicone is homogeneously dispersed in the cured product from the 
standpoint of morphology. 
The silicone resin is desirably incorporated in an amount ratio of 3-30 % 
by weight of the total amount of the resin components (allylated product 
of the polyvalent phenol (A) the polymaleimide compound (B) + the silicone 
resin). If the amount of the silicone resin is lower than the 
above-mentioned ratio, the silicone resin exhibits a poor effect of low 
stress property; if the silicone resin is incorporated in an amount not 
lesser than the above-mentioned ratio, curing characteristics and heat 
resistance are undesirably lowered. 
Moreover, two members selected from the allylated product of the polyvalent 
phenol, allyl etherified poly-phenols modified by silicone, polymaleimides 
modified by silicone, and the polymaleimide resin in the composition 
according to the present invention may be preliminarily allowed to react 
to form prepolymers, respectively. Thus, the molding characteristics is 
further improved and a morphologically homogeneous cured product is 
obtained, so that the characteristics of the present invention is further 
improved. 
With reference to the process for heat curing the resin composition of the 
present invention, while curing is permittable even in the absence of a 
catalyst, it is conducted more easily by the use of a curing accelerator. 
Such a catalyst include organic phosphine compounds such as 
triphenylphosphine, tri-4-methylphenyl-phosphine, 
tri-4-methoxyphenylphosphine, tributyl-phosphine, trioctylphosphine and 
tri-2-cyanoethyl-phosphine, radical polymerization initiators such as 
benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, lauroyl peroxide, 
acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 
t-butyl hydroperoxide and azobisisobutyronitrile, as well as tertiary 
amines such as tributylamine, triethylamine and triamylamine, quaternary 
ammonium salts such as benzyl triethylammonium chloride and benzyl 
trimethylammonium hydroxide, imidazoles, boron trifluoride complexes, 
transition metal acetylacetonates and the like without limitation thereto. 
Among these catalysts, the organic phosphine compounds and imidazoles are 
particularly preferred. 
It is also possible to combine a well-known inhibitor in order to control 
the curing rate. The inhibitor includes phenols such as 
2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 
4,4'-methylenebis(2,6-di-t-butylphenol), 
4.4'-thiobis-(3-methyl-6-t-butylphenol) and hydroquinone monomethy ether, 
polyvalent phenols such as hydroquinone, catechol, p-t-butylcatechol, 
2,5-di-t-butylhydroquinone, methylhydroquinone, t-butylhydroquinone and 
pyrogallol, phenothiazine compounds such as phenothiazine, 
benzo-phenothiazine and acetamidephenothiazine, and N-nitroso-amine 
compounds such as N-nitrosodiphenylamine and N-nitrosodimethylamine. 
Well-known epoxy resins and epoxy-curing agents may be used in combination 
in the resin composition of the present invention. Examples of the epoxy 
resins include a novolak epoxy resin derived from a novolak resin which is 
a reaction product of a phenol such as phenol or o-cresol and 
formaldehyde, a glycidyl ether compound derived from a phenol having a 
valency of 3 or more such as phloroglycine, tris(4-hydroxy-phenyl)methane 
or 1,1,2,2-tetrakis(4-hydroxyphenyl)-ethane, a diglycidyl ether compound 
derived from a divalent phenol such as bisphenol A, bisphenol F, 
hydroquinone or resorcin or from a halogenated bisphenol such as 
tetrabromobisphenol A, an amine epoxy resin derived from p-aminophenol, 
m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, 
4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 
4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 
1,4-bis(4-aminophenoxy)-benzene, 1,4-bis(3-aminophenoxy)benzene, 
1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 
2,2-bis(4-aminophenoxyphenyl)propane, p-phenylenediamine, 
m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenedi-amine, 
p-xylylenediamine, m-xylylenediamine, 1,4-cyclo-hexanebis(methylamine) or 
1,3-cyclohexanebix(methyl-amine), a glycidyl ester compound derived from 
an aromatic carboxylic acid such as p-oxybenzoic acid, m-oxybenzoic acid, 
terephthalic acid or isophthalic acid, a hydantoin epoxy resin derived 
from 5,5-dimethyl-hydantoin or the like, an alicyclic epoxy resin such as 
2,2-bis(3,4-epoxycyclohexyl)propane, 
2,2-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide or 
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 
N,N-diglycidylaniline or the like. One or more of these epoxy resins are 
used. 
Also, as for the epoxy resin-curing agent, a well-known agent is used. 
Examples of the agent include a novolak resin such as phenol novolak or 
cresol novolak, an aromatic polyamine such as diaminodiphenyl-methane or 
diaminodiphenylsulfone, an acid anhydride such as pyromellitic dianhydride 
or benzophenonetetra-carboxylic anhydride, without limitation thereto. 
It is also possible to add an inorganic filler in the present invention. As 
the filler used, there are mentioned silica powder, alumina, talc, calcium 
carbonate, titanium white, clay, asbestos, mica, blood red, glass fiber 
and the like, and particularly silica powder and alumina are preferred. 
The inorganic filler on its use for an encapsulant is preferably 
incorporated in an amount of 25-90% by weight in proportion of the total 
amount of the resin composition, more preferably in an amount of 60-80% by 
weight. 
In the present invention, there may be added a mold-release agent such as a 
natural wax, a synthetic wax, a higher fatty acid or a metal salt thereof 
or a paraffin, a coloring agent such as carbon black, a coupling agent or 
the like, if necessary. There may be also added a flame-retardant such as 
antimony trioxide, a phosphorus compound or a brominated epoxy resin. 
The resin composition thus obtained is compounded by melt kneading with an 
ordinary kneading machine such as a roll or a kneader. 
The electronic part of the present invention is easily prepared by 
subjecting the compound to transfer molding or compression molding at a 
temperature of 160.degree.-200 .degree. C. 
Also, a copper-clad laminate as one of the electronic parts of the present 
invention is prepared according to a well-known method. For example, a 
resin varnish obtained by dissolving the aforementioned resin composition 
into an organic solvent is impregnated into a base and heat treated to 
give a prepreg sheet, which is then superposed on a copper foil and heat 
laminate molded to give a copper-clad laminate. As the solvent, there are 
mentioned methyl ethyl ketone, ethylene glycol monomethyl ether, 
N,N-dimethylformamide, N-methyl-2-pyrrolidone and the like. As the 
examples of the base, there are mentioned a woven fabric, unwoven fabric, 
mat or paper comprising an inorganic or organic fiber such as a glass 
fiber, a polyester fiber or a polyamide fiber, or a combination thereof. 
The heat treatment condition is appropriately determined depending on the 
kind or amount of a solvent, a catalyst or an additive to be used. 
As the heat treatment condition, there is mentioned the press molding at a 
temperature of 150.degree.-250 .degree. C. under a pressure of 10-100 
kg/cm.sup.2 for 20-300 minutes. 
As described above, the thermosetting resin composition of the present 
invention is excellent in processability and thus produce a cured product 
having an excellent heat resistance. Furthermore, the electronic part 
obtained with use of the thermosetting resin composition is very excellent 
in heat resistance, dimensional stability, low stress characteristics and 
adhesive properties as compared with conventional known electronic parts 
and thus has a great industrial value. 
The present invention is specifically explained with reference to examples. 
The functional group containing silicone resins used in examples are shown 
in the following: 
##STR7##

Referential Example 1 
Synthesis of a polyvalent phenol as a raw material 
Into a reactor equipped with a thermometer, a stirring device and a reflux 
condenser were charged 431.6 g (4 equivalents) of o-cresol, 122.1 g (1 
equivalent) of p-hydroxybenzaldehyde, 3.0 g of p-toluene-sulfonic acid as 
a catalyst and 872 g of n-heptane as a reaction solvent. After the resin 
had been completely dissolved, the mixture was heated to a temperature of 
105 .degree. C. to carry out azeotropic dehydration. The mixture was 
maintained at a temperature of 105 .degree. C. for 7 hours and then cooled 
to room temperature. The reaction product deposited by cooling was 
filtered, dissolved in 2895 g of methanol at room temperature, washed with 
water and dried after washing at reduced pressure at 80 .degree. C. for 24 
hours to give 260.5 g of a reddish brown powder (OH equivalent: 110.9 
g/eq). (which is referred to as TPM-1). 
Referential Example 2 
Synthesis of an allyl ether compound 
Into a reactor equipped with a thermometer, a stirring device, a dropping 
funnel and a reflux condenser were charged 120 g (1.08 equivalents) of the 
polyvalent phenol TPM-1 obtained in Referential Example 1, and 420 g of 
dimethylsulfoxide as a reaction solvent. After the resin had been 
completely dissolved, 21.9 g (0.54 equivalent) of 99% sodium hydroxide was 
added and the mixture was sufficiently stirred. After 43.6 g (0.56 
equivalent) of allyl chloride had been added dropwise over a period of 1 
hour while maintaining the temperature of the reaction system at 40 
.degree. C., the temperature was raised up to 50 .degree. C. and 
maintained for 5 hours. After the dimethylsulfoxide had been removed by 
distillation, 600 g of methyl isobutyl ketone was charged to dissolve the 
resin. The solution was washed with water and filtered to remove inorganic 
salts, and the filtrate was concentrated to give 132.6 g of a reddish 
brown semisolid resin which was free of a nucleus-substituted allyl group 
and had an allyl etherification Yield of 50% and an OH equivalent of 262 
g/eq, (which is referred to as ALN-1). 
Referential Example 3 
Synthesis of an allyl ether compound 
Reaction was conducted in the same manner as in Referential Example 2 
except that the amount of the polyvalent phenol TPM-1 was changed from 120 
g (1.08 equivalents) to 60 g (0.54 equivalent), the amount of the 
dimethylsulfoxide was changed from 420 g to 210 g and the amount of the 
methyl isobutyl ketone was changed from 600 g to 300 g to obtain 76.3 g of 
a reddish brown semisolid resin which was free of a nucleus-substituted 
allyl group and had an allyl etherification yield of 100% and an OH 
content of 0.2%, (which is referred to as ALN-2). 
Referential Example 4 
Synthesis of a polyvalent phenol as a raw material 
Into a reactor, were charged 215.8 g (2 equivalents) of o-cresol, 122 g (1 
equivalent) of p-hydroxy-benzaldehyde, 3.0 g of p-toluenesulfonic acid and 
528 g of n-heptane. 
A reaction was conducted by azeotropic dehydration at 105 .degree. C. for 7 
hours in the same manner as in Referential Example 1. After the reaction 
product was filtered, it was dissolved in 1148 g of methyl isobutyl ketone 
and washed with water. After separating was made into layers, the oil 
layer was concentrated to give 249.0 g of a reddish brown semisolid resin 
which had an OH equivalent of 125.9 g/eq, (which is referred to as TPM-2). 
Referential Example 5 
Synthesis of an allyl ether compound 
Into a reactor, were charged 140 g (1.112 equivalents) of the polyvalent 
phenol TPM-2 obtained in Referential Example 4, 322 g of dimethylsulfoxide 
as a reaction solvent, 22.2 g (0.556 equivalent) of 99% sodium hydroxide 
and 44.8 g (0.586 equivalent) of allyl chloride, and a reaction was 
conducted in the same manner as in Referential Example 2 to give 140.6 g 
of a reddish brown semisolid resin which was free of a nucleus-substituted 
allyl group and had an allyl etherification yield of 50% (calculated from 
the aromatic protons and allyl group protons in .sup.1 H-NMR), (which is 
referred to as ALN-3). 
Referential Example 6 
Synthesis of a polyvalent phenol as a raw material 
Into a reactor, were charged 656.8 g (4 equivalents) of 
2-t-butyl-5-methylphenol, 122.1 g (1 equivalent) of p-hydroxybenzaldehyde, 
3.0 g of p-toluene-sulfonic acid as a catalyst and 1300 g of n-heptane as 
a reaction solvent, and a reaction was conducted in the same manner as in 
Referential Example 1. The reaction product deposited by cooling was 
separated by filtration, dissolved in 4400 g of methanol and treated in 
the same manner as in Referential Example 1 to give 367.5 g of a reddish 
brown semisolid resin which had an OH equivalent of 144.1 g/eq, (which is 
referred to as TPM-3). 
Example 7 
Synthesis of an allyl ether compound 
Into a reactor, were charged 70 g (0.487 equivalent) of the polyvalent 
phenol TPM-2 obtained in Referential Example 6, 162 g of dimethylsulfoxide 
as a reaction solvent, 9.84 g (0.246 equivalent) of 99% sodium hydroxide 
and 19.8 g (0.259 equivalent) of allyl chloride, and a reaction was 
conducted in the same manner as in Referential Example 2 to give 71.9 g of 
a reddish brown semisolid resin which was free of a nucleus-substituted 
allyl group and had an allyl etherification yield of 60% (calculated from 
the aromatic protons and allyl group protons in .sup.1 H-NMR), (which is 
referred to as ALN-4). 
Referential Example 8 
Synthesis of a polyvalent phenol as a raw material 
Reaction was conducted in the same manner as in Referential Example 6 
except that the charged amount of 2-t-butyl-5-methylphenol was changed 
from 656.8 g (4 equivalents) to 328.4 g (2 equivalents) to give 293.2 g of 
a reddish brown semisolid resin which had an OH equivalent of 140.0 g/eq, 
(which is referred to as TPM-4). 
Referential Example 9 
Synthesis of an allyl ether compound 
Into a reactor, were charged 100.0 g (0.714 equivalent) of the polyvalent 
phenol TPM-4 obtained in Referential Example 8, 230 g of dimethylsulfoxide 
as a reaction solvent, 14.4 g (0.361 equivalent) of 99% sodium hydroxide 
and 29.1 g (0.380 equivalent) of allyl chloride, and a reaction was 
conducted in the same manner as in Referential Example 2 to give 105.0 g 
of a reddish brown semisolid resin which was free of a nucleus-substituted 
allyl group and had an allyl etherification yield of 48% (calculated from 
the aromatic protons and allyl group protons in .sup.1 H-NMR), (which is 
referred to as ALN-5). 
Referential Example 10 
Synthesis of a polyvalent phenol as a raw material 
Into a reactor, were charged 492.6 g (3 equivalents) of 
2-t-butyl-5-methylphenol, 108 g (1 equivalent) of m-cresol, 122.1 g (1 
equivalent) of p-hydroxybenzaldehyde, 3.0 g of p-toluenesulfonic acid and 
528 g of n-heptane and a reaction was conducted in the same manner as in 
Referential Example 1. The reaction product was treated in the same manner 
as in Referential Example 4 to give 394.7 g of a reddish brown semisolid 
resin which had an OH equivalent of 131.6 g/eq, (which is referred to as 
TMP-5). 
Referential Example 11 
Synthesis of an allyl ether compound 
Into a reactor, were charged 100 g (0.760 equivalent) of the polyvalent 
phenol TPM-5 obtained in Referential Example 10, 230 g of 
dimethylsulfoxide as a reaction solvent, 15.4 g (0.384 equivalent) of 99% 
sodium hydroxide and 30.9 g (0.404 equivalent) of allyl chloride, and a 
reaction was conducted in the same manner as in Referential Example 2 to 
give 107 g of a reddish brown semisolid resin which was free of a 
nucleus-substituted allyl group and had an allyl etherification yield of 
37% (calculated from the aromatic protons and allyl group protons in 
.sup.1 H-NMR), (which is referred to as ALN-6). 
Referential Example 12 
Modification by silicone 
Into a reactor, were charged 100 g of ALN-1 obtained in Referential Example 
2, 2 g of a platinum catalyst (platinum black containing 1% Pt) and 331 g 
of xylene. After water had been completely removed from the reaction 
system by azeotropic dehydration, 28.1 g of the silicone resin (a) was 
added dropwise under refluxing xylene over a period of about 1 hour and 
the mixture was maintained at the temperature for about 5 hours under the 
reflux of xylene. After the solution was then filtered to remove 
completely the platinum catalyst, a product modified by silicone was 
obtained by concentrating the filtrate (referred to as the modified 
product (a)). 
Referential Example 13 
Modification by silicone 
Into a reactor, were charged 100 g of N,N'-diphenylmethane bismaleimide 
(referred to hereinafter as BMI) and 369 g of 1,4-dioxane as a reaction 
solvent, and the mixture was heated to a temperature of 100 .degree. C. to 
dissolve completely BMI. Then, 58 g of the silicone resin (b) was added 
dropwise over a period of about 1 hour, and the mixture was maintained at 
the temperature for about 1 hour. The dioxane was removed by distillation 
to give a product modified by silicone (referred to as the modified 
product (b)). 
Referential Example 14 
Modification by silicone 
Into a reactor, were charged 100 g of ALN-1 obtained in Referential Example 
2, 5 g of triethylamine and 331 g of xylene as a reaction solvent. After 
the mixture was heated to a temperature of 140 .degree. C. to dissolve 
completely the resin, 28.1 g of the silicone resin (c) was added dropwise 
over a period of about 1 hour and the mixture was maintained at the 
temperature for about 15 hours. The xylene and the triethylamine were then 
removed by distillation to give a product modified by silicone (referred 
to as the modified product (c)). 
Referential Example 15 
Modification by silicone 
Into a reactor, were charged 100 g of ALN-3 obtained in Referential Example 
5, 5 g of triethylamine and 331 g of xylene as a reaction solvent. After 
the mixture was heated to a temperature of 140 .degree. C. to dissolve 
completely the resin, 25.9 g of the silicone resin (d) was added dropwise 
over a period of about 1 hour and the mixture was maintained at the 
temperature for about 20 hours. The xylene and the triethylamine were then 
removed by distillation to give a product modified by silicone (referred 
to as the modified product (d)). 
Examples 1-11 
The allylated products of the polyvalent phenols, the modified products 
(a)-(d) obtained in Referential Examples and BMI were blended at ratios 
specified in Table 1, melt mixed by heating at about 130 .degree. C., 
maintained at this temperature for 30 minutes and then immediately cooled 
to give prepolymers, respectively. The prepolymers thus obtained, curing 
accelerators, fillers, coupling agents and mold release agents were melt 
kneaded with a heat roll according to the ratios specified in Table 1 
under the conditions at 50.degree.-120 .degree. C. for 5 minutes and 
ground after cooling to give compounds, respectively. Next, these 
compounds were transfer molded under the conditions at 175 .degree. C. at 
70 kg/cm.sup.2 for 3 minutes and postcured at 200 .degree. C. for 5 hours, 
and the physical properties of the molded products were evaluated. The 
results are shown in Table 2. 
Comparative Example 1 
An o-cresol novolak epoxy resin (epoxy equivalent: 195 g/eq), a phenol 
novolak resin (OH equivalent: 110 g/eq), a curing accelerator, a filler, a 
mold release agent and a coupling agent were kneaded according to the 
ratio specified in Table 1 in the same manner as in Examples to give 
compounds. The compounds were then transfer molded under the conditions at 
175 .degree. C. at 70 kg/cm.sup.2 for 5 minutes, postcured at 180 .degree. 
C. for 5 hours, and the physical properties of the molded products were 
evaluated. The results are shown in Table 2. 
Examples 12-19 
The allylated products of the polyvalent phenols obtained in Referential 
Examples and BMI were blended at ratios specified in Table 3, melt mixed 
by heating at 150.degree. C.-160 .degree. C., maintained with stirring at 
this temperature for 10 to 20 minutes to give prepolymers of which 
viscosities were in the range of 6-7 poise. A 60 parts each of the 
prepolymers was dissolved in 40 parts of N,N-dimethylformamide to give a 
resin varnish in which N,N'-diphenylmethane bismaleimide was not 
deposited. The varnish was impregnated in a glass cloth (manufactured by 
KANEBO K.K., KS-1600, treated with aminosilane), heat treated in an oven 
at 160 .degree. C. for 10-20 minutes to give a prepreg. Six prepregs were 
superposed on a copper foil (manufactured by FURUKAWA CIRCUIT FOIL K.K., 
TTAI treated, thickness: 35 .mu.m) and press molded at a pressure of 50 
kg/cm.sup.2 at 200 .degree. C. for 2 hours to give a copper-clad laminate 
having a thickness of 1 mm. The physical properties of the laminates were 
measured according to JIS-C-6431 to give results shown in Table 3. For the 
measurement of bending strength at 240 .degree. C., laminates molded with 
8 aforementioned prepregs under the same condition and having thickness of 
1.6 mm were used. 
Comparative Example 2 
A varnish obtained by dissolving 60 parts of Kerimid.RTM. 601 (manufactured 
by Rhone Poulenc) in 40 parts of N,N-dimethylformamide was impregnated in 
a glass cloth and heat treated in the same manner as Examples to form a 
prepreg, which was press molded at 200 .degree. C. at 50 kg/cm.sup.2 for 2 
hours to give a copper-clad laminate. The physical properties of the 
laminate are shown in Table 3. 
TABLE 1 
__________________________________________________________________________ 
Example Comparative 
1 2 3 4 5 6 7 8 9 10 11 Example 1 
__________________________________________________________________________ 
ALN-1 26.8 
-- -- -- -- -- -- 24.9 
-- -- -- 
ALN-2 -- 29.7 
-- -- -- -- -- -- -- -- -- -- 
ALN-3 -- -- 29.0 
-- -- -- -- -- -- -- -- -- 
ALN-4 -- -- -- 33.2 
-- -- -- -- -- -- -- -- 
ALN-5 -- -- -- -- 30.6 
-- -- -- -- -- -- -- 
ALN-6 -- -- -- -- -- 32.0 
-- -- -- -- -- -- 
Modified product (a) 
-- -- -- -- -- -- 31.9 
-- -- -- 31.9 
-- 
Modified product (b) 
-- -- -- -- -- -- -- 19.1 
-- -- 13.6 
-- 
Modified product (c) 
-- -- -- -- -- -- -- -- 31.9 
-- -- -- 
Modified product (d) 
-- -- -- -- -- -- -- -- -- 34.0 
-- -- 
BMI 73.2 
70.3 
71.0 
66.8 
69.4 
68.0 
68.1 
56.0 
68.1 
66.0 
54.5 
-- 
ESCN-195XL -- -- -- -- -- -- -- -- -- -- -- 100 
Phenol novolak 
-- -- -- -- -- -- -- -- -- -- -- 56 
Triphenylphosphine 
0.8 
0.8 
0.8 
0.8 
0.8 
0.8 
0.8 
0.8 0.8 
0.8 
0.8 
0 
4-Methylimidazole 
0.7 0.7 
0.7 
0.7 
0.7 
0.7 
0.7 
0.7 0.7 
0.7 
0.7 
-- 
1,8-Diazabicyclo- 
-- -- -- -- -- -- -- -- -- -- -- 2 
(5,4,0)undecene-7 
HOECHST WAX OP 
0.7 0.7 
0.7 
0.7 
0.7 
0.7 
0.7 
0.7 0.7 
0.7 
0.7 
1 
Silane coupling 
2 2 2 2 2 2 2 2 2 2 2 -- 
agent A 
Silane coupling 
-- -- -- -- -- -- -- -- -- -- -- 2 
agent B 
Molten silica 
233 233 
233 
233 
233 
233 
-- -- -- -- -- 364 
Spherical molten 
-- -- -- -- -- -- 317 
317 317 
317 
317 
-- 
silica 
__________________________________________________________________________ 
(Numerals in the table represent parts by weight) 
BMI: manufactured by SUMITOMO CHEMICAL CO., LTD., Bestlex .RTM. BH180. 
ESCN195XL: manufactured by SUMITOMO CHEMICAL CO., LTD., ocresol novolak 
type epoxy resin (epoxy equivalent: 195 g/eq). 
Phenol novolak resin: OH equivalent: 110 g/eq, softening point: 90.degree 
C. 
Silane coupling agent A: manufactured by SHINETSU SILICONE K.K., KBM573. 
Silane coupling agent B: manufactured by TORAYDOW CORNING SILICONE K.K., 
SH6040. 
Molten silica: manufactured by DENKI KAGAKU KOGYO, K.K., FS891. 
Spherical molten silica: manufactured by DENKI KAGAKU KOGYO K.K., FB90. 
TABLE 2 
__________________________________________________________________________ 
Example 
1 2 3 4 5 6 
__________________________________________________________________________ 
Spiral flow* 
38 40 35 37 38 37 
(inch) 175.degree. C. .times. 
70 kg/cm.sup.2 
Barcol Hardness** 
(Barcol 935) 
175.degree. C. .times. 90 sec 
81 65 80 80 81 83 
175.degree. C. .times. 180 sec 
86 72 84 83 84 84 
Glass transition 
255 283 256 253 250 255 
temperature, 
TG***(.degree.C.) 
Thermal expan- 
1.8 1.7 1.9 1.7 1.8 1.9 
sion coefficient 
(TEC)*** .times. 10.sup.-5 
.degree.C..sup.-1 
Flexural 
strength (kg/mm.sup.2) 
20.degree. C. 
14.8 14.5 14.4 14.2 14.4 14.3 
240.degree. C. 
6.5 8.1 6.1 6.6 6.8 6.3 
Flexural modulus 
(kg/mm.sup.2) 
20.degree. C. 
1610 1620 1580 1600 1630 1610 
240.degree. C. 
720 750 700 710 700 720 
Volume resistivity 
(.OMEGA.cm), Pressure 
cooker, 121.degree. C. .times. 
100% RH 
Ordinary state 
6.8 .times. 10.sup.16 
6.1 .times. 10.sup.16 
5.8 .times. 10.sup.16 
5.5 .times. 10.sup.16 
6.0 .times. 10.sup. 16 
5.1 .times. 10.sup.16 
100 hours 1.4 .times. 10.sup.15 
1.8 .times. 10.sup.15 
1.3 .times. 10.sup.15 
1.2 .times. 10.sup.15 
1.2 .times. 10.sup.15 
1.3 .times. 10.sup.15 
300 hours 6.1 .times. 10.sup.14 
7.2 .times. 10.sup.14 
5.8 .times. 10.sup.14 
6.0 .times. 10.sup.14 
5.5 .times. 10.sup.14 
4.3 .times. 10.sup.14 
500 hours 4.5 .times. 10.sup.14 
5.1 .times. 10.sup.14 
3.9 .times. 10.sup.14 
4.2 .times. 10.sup.14 
5.0 .times. 10.sup.14 
3.9 .times. 10.sup.14 
Water absorp- 
tion (%), 
Pressure cooker, 
121.degree. C. .times. 
100% RH 
100 hours 1.05 0.99 1.00 1.06 1.03 0.98 
300 hours 1.17 1.10 1.07 1.17 1.15 1.08 
500 hours 1.22 1.17 1.18 1.23 1.21 1.20 
Heat resistance 
0/10 0/10 0/10 0/10 0/10 0/10 
of solder**** 
(number of 
crack) 
__________________________________________________________________________ 
Example Comparative 
7 8 9 10 11 Example 1 
__________________________________________________________________________ 
Spiral flow* 
28 26 30 28 27 43 
(inch) 175.degree. C. .times. 
70 kg/cm.sup.2 
Barcol Hardness** 
(Barcol 935) 
175.degree. C. .times. 90 sec 
65 65 67 64 65 80 
175.degree. C. .times. 180 sec 
71 72 77 72 72 84 
Glass transition 
251 260 255 264 254 158 
temperature, 
TG***(.degree.C.) 
Thermal expan- 
1.3 1.1 1.2 1.1 1.0 2.4 
sion coefficient 
(TEC)*** .times. 10.sup.-5 
.degree.C..sup.-1 
Flexural 
strength (kg/mm.sup.2) 
20.degree. C. 
14.5 12.5 13.1 13.8 14.5 15.6 
240.degree. C. 
5.3 5.2 4.8 5.0 5.3 1.8 
Flexural modulus 
(kg/mm.sup.2) 
20.degree. C. 
1250 1280 1190 1210 1110 1400 
240.degree. C. 
630 680 590 610 550 110 
Volume resistivity 
(.OMEGA.cm), Pressure 
cooker, 121.degree. C. .times. 
100% RH 
Ordinary state 
5.2 .times. 10.sup.16 
6.1 .times. 10.sup.16 
5.8 .times. 10.sup.16 
7.1 .times. 10.sup.16 
6.5 .times. 10.sup.16 
8.4 .times. 10.sup.16 
100 hours 1.0 .times. 10.sup.15 
1.3 .times. 10.sup.15 
1.1 .times. 10.sup.15 
1.5 .times. 10.sup.15 
1.8 .times. 10.sup. 15 
1.6 .times. 10.sup.15 
300 hours 3.5 .times. 10.sup.14 
6.2 .times. 10.sup.14 
4.2 .times. 10.sup.14 
7.1 .times. 10.sup.14 
7.2 .times. 10.sup.14 
4.3 .times. 10.sup.14 
500 hours 2.1 .times. 10.sup.14 
4.1 .times. 10.sup.14 
2.2 .times. 10.sup.14 
5.2 .times. 10.sup.14 
5.3 .times. 10.sup.14 
4.2 .times. 10.sup.14 
Water absorp- 
tion (%), 
Pressure cooker, 
121.degree. C. .times. 
100% RH 
100 hours 1.02 0.95 1.01 0.98 0.90 0.86 
300 hours 1.10 1.07 1.08 1.09 1.01 1.00 
500 hours 1.21 1.15 1.19 1.20 1.12 1.08 
Heat resistance 
0/10 0/10 0/10 0/10 0/10 10/10 
of solder**** 
(number of 
crack) 
__________________________________________________________________________ 
*Spiral flow: EMMI 1-66 REVISION A 
**Barcol Hardness: ASTM D 258367 
***TMA method with use of a thermal analyzer model DT40, manufactured by 
SHIMADZU SEISAKUSHO, LTD. 
**** QFP 84 pin, 34 mmt, IC chip 10 .times. 10 mm; packages in which 
cracking has been generated after the treatment in a pressure cooker at 
121.degree. C. at 100% RH for 24 hours and the dipping into a solder bat 
at 260.degree. C. for 10 seconds. 
TABLE 3 
__________________________________________________________________________ 
Physical properties of laminates 
Example Comparative 
12 13 14 15 16 17 18 19 Example 
__________________________________________________________________________ 
2 
ALN-1 (parts by weight) 
26.8 -- -- -- -- -- 25.5 -- 
ALN-2 (parts by weight) 
-- 29.7 -- -- -- -- -- 28.2 
ALN-3 (parts by weight) 
-- -- 29.0 -- -- -- -- -- 
ALN-4 (parts by weight) 
-- -- -- 33.2 -- -- -- -- 
ALN-5 (parts by weight) 
-- -- -- -- 30.6 -- -- -- 
ALN-6 (parts by weight) 
-- -- -- -- -- 32.0 -- -- 
BMI (parts by weight) 
73.2 70.3 71.0 66.8 69.4 68.0 69.5 66.8 
ESCN-195XL (parts by weight) 
-- -- -- -- -- -- 5 5 
Glass transition temperature 
240 255 240 238 232 235 225 230 204 
Tg*, (.degree.C.) 
Thermal expansion ratio 
1.42 1.40 1.45 1.66 1.58 1.56 1.61 1.83 2.29 
(20.degree. C.-260.degree. C.)*, (%) 
Peeling strength of copper 
1.4 1.2 1.5 1.3 1.4 1.3 1.6 1.6 1.2 
foil (kg/cm) 
Flexural strength at 240.degree. C., 
32.1 38.2 32.5 32.0 29.8 28.5 26.3 27.7 23.3 
(kg/mm.sup.2) 
Heat resistance of 
solder, at 300.degree. C. 
Ordinary state &gt;3 min 
&gt;3 min 
&gt;3 min 
&gt;3 min 
&gt;3 min 
&gt;3 min 
&gt;3 min 
&gt;3 min 
2 min 
2 hours after &gt;3 min 
&gt;3 min 
&gt;3 min 
&gt;3 min 
&gt;3 min 
&gt;3 min 
&gt;3 min 
&gt;3 min 
1 min plus 
boiling 40 
__________________________________________________________________________ 
sec. 
*According to the TMA method with use of a thermal analyzer model DT40, 
manufactured by SHIMADZU SEISAKUSHO, LTD.