U.S. patent application number 12/810387 was filed with the patent office on 2010-11-04 for thermosetting resin composition and prepreg and laminate both made with the same..
Invention is credited to Masanori Akiyama, Tomohiko Kotake, Shinji Tsuchikawa.
Application Number | 20100279129 12/810387 |
Document ID | / |
Family ID | 40800918 |
Filed Date | 2010-11-04 |
United States Patent
Application |
20100279129 |
Kind Code |
A1 |
Tsuchikawa; Shinji ; et
al. |
November 4, 2010 |
THERMOSETTING RESIN COMPOSITION AND PREPREG AND LAMINATE BOTH MADE
WITH THE SAME.
Abstract
The present invention provides a thermosetting resin composition
comprising (A) a metal salt of disubstituted phosphinic acid, (B) a
maleimide compound having a N-substituted maleimide group in a
molecule, (C) a 6-substituted guanamine compound or dicyandiamide
and (D) an epoxy resin having at least two epoxy groups in a
molecule and a prepreg and a laminated plate which are prepared by
using the same. The prepregs obtained by impregnating or coating a
base material with the thermosetting resin compositions of the
present invention and the laminated plates produced by laminating
and molding the above prepregs are balanced in all of a copper foil
adhesive property, a glass transition temperature, a solder heat
resistance, a moisture absorption, a flame resistance, a relative
dielectric constant and a dielectric loss tangent, and they are
useful as a printed wiring board for electronic instruments.
Inventors: |
Tsuchikawa; Shinji;
(Ibaraki, JP) ; Akiyama; Masanori; (Ibaraki,
JP) ; Kotake; Tomohiko; (Ibaraki, JP) |
Correspondence
Address: |
ANTONELLI, TERRY, STOUT & KRAUS, LLP
1300 NORTH SEVENTEENTH STREET, SUITE 1800
ARLINGTON
VA
22209-3873
US
|
Family ID: |
40800918 |
Appl. No.: |
12/810387 |
Filed: |
June 19, 2008 |
PCT Filed: |
June 19, 2008 |
PCT NO: |
PCT/JP2008/061256 |
371 Date: |
June 24, 2010 |
Current U.S.
Class: |
428/457 ;
524/100 |
Current CPC
Class: |
C08G 59/56 20130101;
B32B 15/20 20130101; C08L 63/04 20130101; B32B 5/02 20130101; C08J
5/24 20130101; C08K 5/5333 20130101; C09J 2301/408 20200801; Y10T
428/31678 20150401; C09J 163/00 20130101; H05K 1/0353 20130101;
C08J 2363/00 20130101; C08K 3/22 20130101; B32B 2457/08 20130101;
C08L 63/00 20130101; C08K 3/32 20130101; C08K 2003/2227 20130101;
C08J 2363/04 20130101; B32B 15/092 20130101; C09J 163/04 20130101;
C08L 2201/02 20130101; C08K 3/36 20130101 |
Class at
Publication: |
428/457 ;
524/100 |
International
Class: |
B32B 15/08 20060101
B32B015/08; C08K 5/3492 20060101 C08K005/3492 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 25, 2007 |
JP |
2007-332857 |
Claims
1. A thermosetting resin composition comprising: (A) a metal salt
of disubstituted phosphinic acid, (B) a maleimide compound having a
N-substituted maleimide group in a molecule, (C) a 6-substituted
guanamine compound represented by the following Formula (1) or
dicyandiamide and (D) an epoxy resin having at least two epoxy
groups in a molecule: ##STR00013## (wherein R.sub.1 represents
phenyl, methyl, allyl, vinyl, butyl, methoxy or benzyloxy).
2. The thermosetting resin composition according to claim 1,
wherein the maleimide compound having a N-substituted maleimide
group in a molecule contains a compound having an acidic
substituent and an unsaturated maleimide group represented by the
following Formula (3) or Formula (4), which is a product produced
by reacting (b-1) a maleimide compound having at least two
N-substituted maleimide groups in a molecule with (b-2) an amine
compound having an acidic substituent represented by the following
Formula (2) in an organic solvent: ##STR00014## (wherein R.sub.2
each represents independently an acidic substituent selected from a
hydroxyl group, a carboxy group and a sulfonic acid group; R.sub.3
each represents independently a hydrogen atom, an aliphatic
hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; x
is an integer of 1 to 5, and y is an integer of 0 to 4; and a sum
of x and y is 5); ##STR00015## (wherein R.sub.2, R.sub.3, x and y
represent the same ones as in Formula (2); R.sub.4 each represents
independently a hydrogen atom, an aliphatic hydrocarbon group
having 1 to 5 carbon atoms or a halogen atom); ##STR00016##
(wherein R.sub.2, R.sub.3, x and y represent the same ones as in
Formula (2); R.sub.5 and R.sub.6 each represent independently a
hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon
atoms or a halogen atom; and A is an alkylene group, an alkylidene
group, an ether group, a sulfonyl group or a group represented by
the following Formula (5); ##STR00017##
3. A prepreg obtained by impregnating or coating a base material
with the thermosetting resin composition according to claim 1 and
then subjecting it to a B stage.
4. A laminated plate obtained by laminating and molding the prepreg
according to claim 3.
5. The laminated plate according to claim 4, wherein it is a metal
clad laminated plate obtained by superposing a metal foil on at
least one side of the prepreg and then heating, pressing and
molding it.
6. A prepreg obtained by impregnating or coating a base material
with the thermosetting resin composition according to claim 2 and
then subjecting it to a B stage.
7. A laminated plate obtained by laminating and molding the prepreg
according to claim 6.
8. The laminated plate according to claim 7, wherein it is a metal
clad laminated plate obtained by superposing a metal foil on at
least one side of the prepreg and then heating, pressing and
molding it.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a thermosetting resin
composition which is balanced in all of a metal foil adhesive
property, a heat resistance, a moisture resistance, a flame
resistance, a metal-stuck heat resistance and dielectric
characteristics (a relative dielectric constant and a dielectric
loss tangent), low in a toxicity and excellent in a safety and a
working environment and which is suitably used for electronic parts
and the like and a prepreg and a laminated plate which are prepared
by using the same.
RELATED ART
[0002] Thermosetting resins are widely used in the fields of
electronic parts and the like to which a high reliability is
required since a specific cross-linking structure thereof displays
a high heat resistance and a high dimensional stability.
Particularly in copper clad laminated plates and interlayer
insulating materials, a high copper foil adhesive property for
forming fine wirings and a workability in carrying out works such
as boring and the like by drilling and punching are required as
well in order to meet requirements for density growth in recent
years.
[0003] Mounting of electronic parts produced by using lead-free
solders and flame retardation free of halogens are required due to
environmental problems in recent years, and this requires the
higher heat resistance and the higher flame resistance than those
of conventional ones. Further, in order to enhance a safety of the
products and the working environment, desired is a thermosetting
resin composition which is constituted only from components having
a low toxicity and which does not generate toxic gases and the
like.
[0004] A bismaleimide compound is a curing agent for thermosetting
resins which are excellent in dielectric characteristics, a flame
resistance and a heat resistance. Publicly known bismaleimide
compounds do not have a curing reactivity with epoxy resins, and
therefore when they are used as they are for thermosetting resins
of an epoxy curing base, the problem that the heat resistance is
short has been involved therein. That is, disclosed are cases
(refer to, for example, a patent document 1 and a patent document
2) regarding thermosetting resins in which adducts of bismaleimide
compounds and aminophenol are produced by heating and kneading
without using solvents and used. However, a yield of the adducts of
the bismaleimide compounds and aminophenol is low, and when they
are used for copper clad laminated plates and interlayer insulating
materials, the heat resistance, the workability and the like are
short.
[0005] Melamine resins which are thermosetting resins and guanamine
compounds are excellent in an adhesive property, a flame resistance
and a heat resistance, but they are short of a solubility in
organic solvents, and there have been involved therein the problems
that it is difficult to produce thermosetting resin compositions
without using a large amount of nitrogen atom-containing organic
solvents such as N,N-dimethylformamide and the like which are
highly toxic and that the storage stability is short. Further,
copper clad laminated plates and interlayer insulating materials
which are prepared by using the above thermosetting resins have
involved the problem that they contaminate various chemical liquids
such as a plating liquid and the like when producing electronic
parts and the like.
[0006] A lot of cases regarding thermosetting resins prepared by
using melamine resins and guanamine compounds are known as resins
for solving the above problems (refer to, for example, patent
documents 3 to 7).
[0007] They are thermosetting resins prepared by condensing
melamine resins and guanamine compounds using aldehydes such as
formaldehyde and the like and improved in a solubility in organic
solvents, but they have a low thermal decomposition temperature and
generate toxic cracked gases, so that they deteriorate the working
environment and are short of a heat resistance against lead-free
solders and a copper-stuck heat resistance which are required in
recent years. Further, in fine working treatment and formation of
wirings, they are short of a copper foil adhesive property, a
flexibility and a toughness, and brought about are the failures
that the circuit patterns are broken or peeled and that cracks are
produced in carrying out works such as boring and the like by
drilling and punching.
[0008] Also, a case (refer to, for example, a patent document 8)
regarding methyloled guanamine resins is disclosed, but problems on
the heat resistance, the adhesive property, the workability and the
like are involved therein as is the case with those described
above.
[0009] Further, disclosed is a case (refer to, for example, a
patent document 9) regarding thermosetting resins prepared by using
adducts of bismaleimide compounds and aminobenzoic acid which are
produced without using an organic solvent, benzoguanamine
formaldehyde condensation products and the like, but they have a
low thermal decomposition temperature and are short of a heat
resistance against lead-free solders and a copper-stuck heat
resistance which are required in recent years.
[0010] Also, phosphorus-containing compounds used as publicly known
non-halogen base flame retardants include red phosphorus, soluble
phosphoric ester compounds such as triphenyl phosphate and the
like, reactive phosphorus-containing compounds such as
phosphorus-containing epoxy resins and the like and ammonium
polyphosphate and the like. It has been found that thermosetting
resins prepared by using the above compounds are notably reduced in
dielectric characteristics (a relative dielectric constant and a
dielectric loss tangent), a heat resistance, a moisture resistance,
an electric corrosion resistance and the like.
Patent document 1: Japanese Patent Publication No. 34899/1988
Patent document 2: Japanese Patent Application Laid-Open No.
32969/1994 Patent document 3: Japanese Patent Publication No.
46584/1987 Patent document 4: Japanese Patent Application Laid-Open
No. 67942/1998 Patent document 5: Japanese Patent Application
Laid-Open No. 11672/2001 Patent document 6: Japanese Patent
Application Laid-Open No. 258820/1990 Patent document 7: Japanese
Patent Application Laid-Open No. 145476/1991 Patent document 8:
Japanese Patent Publication No. 61051/1987 Patent document 9:
Japanese Patent Publication 8342/1994
DISCLOSURE OF THE INVENTION
[0011] In light of the above existing situations, an object of the
present invention is to provide a thermosetting resin composition
which is balanced in all of a metal foil adhesive property, a heat
resistance, a moisture resistance, a flame resistance, a
metal-stuck heat resistance, a relative dielectric constant and a
dielectric loss tangent and a prepreg and a laminated plate which
are prepared by using the same.
[0012] Intensive researches repeated by the present inventors in
order to achieve the object described above have resulted in
finding that a thermosetting resin composition comprising a metal
salt of disubstituted phosphinic acid, a maleimide compound, a
6-substituted guanamine compound or dicyandiamide and an epoxy
resin meets the object described above and that it is
advantageously used as a thermosetting resin composition for a
laminated plate. The present invention has been completed based on
the above knowledge.
[0013] That is, the present invention provides a thermosetting
resin composition, a prepreg and a laminated plate each shown
below.
1. A thermosetting resin composition comprising: (A) a metal salt
of disubstituted phosphinic acid, (B) a maleimide compound having a
N-substituted maleimide group in a molecule, (C) a 6-substituted
guanamine compound represented by the following Formula (1) or
dicyandiamide and (D) an epoxy resin having at least two epoxy
groups in a molecule:
##STR00001##
(wherein R.sub.1 represents phenyl, methyl, allyl, vinyl, butyl,
methoxy or benzyloxy). 2. The thermosetting resin composition
according to the above item 1, wherein the maleimide compound (B)
having a N-substituted maleimide group in a molecule contains a
compound having an acidic substituent and an unsaturated maleimide
group represented by the following Formula (3) or Formula (4),
which is a product produced by reacting (b-1) a maleimide compound
having at least two N-substituted maleimide groups in a molecule
with (b-2) an amine compound having an acidic substituent
represented by the following Formula (2) in an organic solvent:
##STR00002##
(wherein R.sub.2 each represents independently an acidic
substituent selected from a hydroxyl group, a carboxy group and a
sulfonic acid group; R.sub.3 each represents independently a
hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon
atoms or a halogen atom; x is an integer of 1 to 5, and y is an
integer of 0 to 4; and a sum of x and y is 5):
##STR00003##
(wherein R.sub.2, R.sub.3, x and y represent the same ones as in
Formula (2); R.sub.4 each represents independently a hydrogen atom,
an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a
halogen atom);
##STR00004##
(wherein R.sub.2, R.sub.3, x and y represent the same ones as in
Formula (2); R.sub.5 and R.sub.6 each represent independently a
hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon
atoms or a halogen atom; and A is an alkylene group, an alkylidene
group, an ether group, a sulfonyl group or a group represented by
the following Formula (5):
##STR00005##
3. A prepreg obtained by impregnating or coating a base material
with the thermosetting resin composition according to the above
item 1 or 2 and then subjecting it to a B stage. 4. A laminated
plate obtained by laminating and molding the prepreg according to
the above item 3. 5. The laminated plate according to the above
item 4, wherein it is a metal clad laminated plate obtained by
superposing a metal foil on at least one side of the prepreg and
then heating, pressing and molding it.
[0014] The thermosetting resin composition of the present invention
is balanced in all of a metal foil adhesive property, a heat
resistance, a moisture resistance, a flame resistance, a
metal-stuck heat resistance, a relative dielectric constant and a
dielectric loss tangent, and it has a low toxicity and is excellent
as well in a safety and a working environment.
[0015] Accordingly, a prepreg and a laminated plate which have
excellent performances can be provided by the present invention
using the above thermosetting resin composition.
BRIEF EXPLANATION OF THE DRAWING
[0016] FIG. 1 is a gas chromatographic chart drawing showing a
result obtained by analyzing a solution of the maleimide compound
(B-2) obtained in Production Example 2 by GPC.
BEST MODE FOR CARRYING OUT THE INVENTION
[0017] The present invention shall be explained below in
details.
[0018] The thermosetting resin composition of the present invention
is characterized by comprising (A) a metal salt of disubstituted
phosphinic acid, (B) a maleimide compound having a N-substituted
maleimide group in a molecule, (C) a 6-substituted guanamine
compound represented by the following Formula (1) or dicyandiamide
and (D) an epoxy resin having at least two epoxy groups in a
molecule.
[0019] First, the metal salt of disubstituted phosphinic acid which
is the component (A) can be represented by the following Formula
(6):
##STR00006##
(wherein R.sub.7 and R.sub.8 each represent independently an
aliphatic hydrocarbon group having 1 to 5 carbon atoms or an
aromatic hydrocarbon group; M represents metal selected from Li,
Na, K, Mg, Ca, Sr, Ba, Al, Ge, Sn, Sb, Bi, Zn, Ti, Zr, Mn, Fe and
Ce; and r is an integer of 1 to 9).
[0020] The above metal salt of disubstituted phosphinic acid can be
produced by a method described in Japanese Patent Application
Laid-Open No. 2686/2001. Also, it can be obtained commercially from
Clariant AG. Addition of the above metal salt of disubstituted
phosphinic acid as an essential component makes it possible to
provide the excellent flame resistance, low dielectric
characteristics and heat and moisture resistance.
[0021] The metal M in Formula (6) is preferably Al or Na from the
viewpoints of making it possible to increase a content of
phosphorus in the compound and the moisture resistance, and it is
particularly preferably Al from the viewpoint of the dielectric
characteristics.
[0022] Further, R.sub.9 and R.sub.10 in Formula (6) are preferably
an aliphatic hydrocarbon group having 1 to 5 carbon atoms from the
viewpoint of making it possible to increase a content of phosphorus
in the compound, and they are particularly preferably methyl, ethyl
or propyl.
[0023] The maleimide compound having a N-substituted maleimide
group in a molecule which is the component (B) includes
N-phenylmaleimide and N-hydroxyphenylmaleimide as the maleimide
compound having one N-substituted maleimide group in a molecule,
and the maleimide compound having two N-substituted maleimide
groups in a molecule is preferred.
[0024] The maleimide compound having at least two N-substituted
maleimide groups in a molecule which is the component (B) includes,
for example, bis(4-maleimidephenyl)methane,
poly(maleimidephenyl)methane, bis(4-maleimidephenyl)ether,
bis(4-maleimidephenyl)sulfone,
3,3-dimethyl-5,5-ethyl-4,4-diphenylmethanebismaleimide,
4-methyl-1,3-phenylnebismaleimide, m-phenylenebismaleimide,
2,2-bis[4-(4-maleimidephenoxy)phenyl]propane and the like. Among
them, bis(4-maleimidephenyl)methane, m-phenylenebismaleimide and
bis(4-maleimidephenyl)sulfone which have a high reactivity and can
provide the thermosetting resin composition with a higher heat
resistance are preferred, and m-phenylenebismaleimide and
bis(4-maleimidephenyl)methane are more preferred from the viewpoint
that they are inexpensive. Bis(4-maleimidephenyl)methane is
particularly preferred in terms of a solubility in solvents.
[0025] Further, the compound having an acidic substituent and an
unsaturated maleimide group which is produced by reacting (b-1) the
maleimide compound having at least two N-substituted maleimide
groups in a molecule as described above with (b-2) the amine
compound having an acidic substituent represented by the following
Formula (2) in an organic solvent is suitably used as the component
(B):
##STR00007##
[0026] (wherein R.sub.2 each represents independently an acidic
substituent selected from a hydroxyl group, a carboxy group and a
sulfonic acid group; R.sub.3 each represents independently a
hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon
atoms or a halogen atom; x is an integer of 1 to 5, and y is an
integer of 0 to 4; and a sum of x and y is 5).
[0027] The amine compound (b-2) represented by Formula (2)
includes, for example, m-aminophenol, p-aminophenol, o-aminophenol,
p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid,
o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid,
p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline,
3,5-dicarboxyaniline and the like, and among them, m-aminophenol,
p-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and
3,5-dihydroxyaniline are preferred from the viewpoints of a
solubility and a yield in the synthesis. o-Aminophenol,
m-aminophenol and p-aminophenol are more preferred from the
viewpoint of a heat resistance, and p-aminophenol is particularly
preferred from the viewpoint of dielectric characteristics.
[0028] In respect to a use ratio of the maleimide compound (b-1) to
the amine compound (b-2), an equivalent ratio of an equivalent of a
maleimide group in the maleimide compound (b-1) to an equivalent of
the amine compound (b-2) in terms of a --NH.sub.2 group falls
preferably in a range represented by the following equation: [0029]
1.0.ltoreq.(equivalent of maleimide group)/(equivalent in terms of
a --NH.sub.2 group).ltoreq.10.0 and the above equivalent ratio
falls more preferably in a range of 2.0 to 10.0. The above
equivalent ratio falling in the range described above prevents the
thermosetting resin from being short of a solubility in a solvent
and the gelation from being brought about and prevents the
thermosetting resin from being reduced in a heat resistance.
[0030] The organic solvent used in the above reaction shall not
specifically be restricted and includes, for example, alcohol base
solvents such as ethanol, propanol, butanol, methyl cellosolve,
butyl cellosolve, propylene glycol monomethyl ether and the like,
ketone base solvents such as acetone, methyl ethyl ketone, methyl
isobutyl ketone, cyclohexanone and the like, ether base solvents
such as tetrahydrofuran and the like, aromatic solvents such as
toluene, xylene, mesitylene and the like, nitrogen-containing
solvents such as dimethylformamide, dimethylacetamide,
N-methylpyrrolidone and the like, sulfur-containing solvents such
as dimethyl sulfoxide and the like. They can be used alone or in a
mixture of two or more kinds thereof.
[0031] Among the above organic solvents, cyclohexanone, propylene
glycol monomethyl ether and methyl cellosolve are preferred in
terms of a solubility, and cyclohexanone and propylene glycol
monomethyl ether are more preferred in terms of a low toxicity.
Propylene glycol monomethyl ether which has a high volatility and
is less liable to remain as a residual solvent in producing the
prepreg is particularly preferred.
[0032] A use amount of the organic solvent is preferably 10 to 1000
parts by mass, more preferably 100 to 500 parts by mass and
particularly preferably 200 to 500 parts by mass per 100 parts by
mass of the sum of the maleimide compound (b-1) and the amine
compound (b-2).
[0033] Controlling a use amount of the organic solvent to 10 parts
by mass or more makes the solubility sufficiently high, and
controlling it to 1000 parts by mass or less prevents the reaction
time from being extended too much.
[0034] The reaction temperature is preferably 50 to 200.degree. C.,
more preferably 100 to 160.degree. C. The reaction time is
preferably 0.1 to 10 hours, more preferably 1 to 8 hours.
[0035] A reaction catalyst can optionally be used, if necessary, in
the above reaction. The reaction catalyst shall not specifically be
restricted and includes, for example, amines such as triethylamine,
pyridine, tributylamine and the like, imidazoles such as
methylimidazole, phenylimidazole and the like and phosphorus base
catalysts such as triphenylphosphine and the like. They can be used
alone or in a mixture of two or more kinds thereof.
[0036] The compound having an acidic substituent and an unsaturated
maleimide group represented by the following Formula (3) or Formula
(4) is synthesized by reacting a bis(4-maleimidephenyl) compound
used as the maleimide compound (b-1) with the amine compound (b-2)
according to the above reaction:
##STR00008##
(wherein R.sub.2, R.sub.3, x and y represent the same ones as in
Formula (2); R.sub.4 each represents independently a hydrogen atom,
an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a
halogen atom);
##STR00009##
(wherein R.sub.2, R.sub.3, x and y represent the same ones as in
Formula (2); R.sub.5 and R.sub.6 each represent independently a
hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon
atoms or a halogen atom; and A is an alkylene group, an alkylidene
group, an ether group, a sulfonyl group or a group represented by
the following Formula (5):
##STR00010##
[0037] The component (C) is a 6-substituted guanamine compound
represented by the following Formula (1) or dicyandiamide. The
6-substituted guanamine compound represented by Formula (1)
includes, for example, 2,4-diamino-6-phenyl-s-triazine called
benzoguanamine, 2,4-diamino-6-methyl-s-triazine called
acetoguanamine, 2,4-diamino-6-vinyl-s-triazine and the like. Among
them, benzoguanamine and 2,4-diamino-6-vinyl-s-triazine which have
a high reactivity and which can provide the higher heat resistance
and the lower dielectric constant are more preferred, and
benzoguanamine is particularly preferred from the viewpoint of a
low cost and a solubility in a solvent. Dicyandiamide is
particularly preferred as well from the viewpoints that it is
excellent in a storage stability in the vanish and can provide the
higher heat resistance and the lower dielectric constant and that
it is inexpensive. The 6-substituted guanamine compound represented
by Formula (1) and dicyandiamide may be used in combination.
##STR00011##
(wherein R.sub.1 represents phenyl, methyl, allyl, vinyl, butyl,
methoxy or benzyloxy).
[0038] The component (D) shall not specifically be restricted as
long as it is an epoxy resin having two or more epoxy groups in a
molecule, and it includes, for example, glycidyl ethers of a
bisphenol A base, a bisphenol F base, a biphenyl base, a novolac
base, a multifunctional phenol base, a naphthalene base, an
alicyclic base and an alcohol base, glycidyl amines, glycidyl
esters and the like. They can be used alone or in a mixture of two
or more kinds thereof.
[0039] Among them, bisphenol F type epoxy resins, dicyclopentadiene
type epoxy resins, naphthalene ring-containing epoxy resins,
biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins,
phenol novolac type epoxy resins and cresol novolac type epoxy
resins are preferred from the viewpoints of dielectric
characteristics, a heat resistance, a moisture resistance and a
metal foil adhesive property, and the dicyclopentadiene type epoxy
resins, the biphenyl aralkyl type epoxy resins, the biphenyl type
epoxy resins and the phenol novolac type epoxy resins are more
preferred from the viewpoints of dielectric characteristics and a
high glass transition temperature. The phenol novolac type epoxy
resins and the dicyclopentadiene type epoxy resins are particularly
preferred from the viewpoint of a moisture and heat resistance.
[0040] A content of the component (A) contained in the
thermosetting resin composition of the present invention is set to
preferably 1 to 99 parts by mass, more preferably 5 to 70 parts by
mass and particularly preferably 5 to 50 parts by mass based on 100
parts by mass of a sum of the masses of the components (B) to (D)
in terms of a solid matter. Setting a content of the component (A)
to 1 part by mass or more enhances the flame resistance, and
setting it to 98 parts by mass or less prevents the heat resistance
and the adhesive property from being reduced.
[0041] The contents of the components (B) to (D) contained in the
thermosetting resin composition of the present invention are set
preferably as follows in terms of a mass based on 100 parts by mass
of a sum of the masses of the components (B) to (D) in terms of a
solid matter.
[0042] A content of the component (B) is set to preferably 1 to
98.9 parts by mass, more preferably 20 to 98.9 parts by mass and
particularly preferably 20 to 90 parts by mass. Setting a content
of the component (B) to 1 part by mass or more enhances the flame
resistance, the adhesive property and the dielectric
characteristics, and setting it to 98.9 parts by mass or less
prevents the heat resistance from being reduced.
[0043] A content of the component (C) is set to preferably 0.1 to
50 parts by mass, more preferably 0.5 to 50 parts by mass and
particularly preferably 0.5 to 30 parts by mass. Setting a content
of the component (C) to 0.1 part by mass or more enhances the
solubility and the dielectric characteristics, and setting it to 50
parts by mass or less prevents the flame resistance from being
reduced.
[0044] A content of the component (D) is set to preferably 1 to 80
parts by mass, more preferably 10 to 70 parts by mass and
particularly preferably 20 to 60 parts by mass. Setting a content
of the component (D) to 1 part by mass or more enhances the heat
resistance, the flame resistance and the moldability in using the
thermosetting resin composition for a prepreg, and setting it to 80
parts by mass or less prevents the dielectric characteristics from
being reduced.
[0045] A curing agent and a curing accelerating agent for an epoxy
resin may be used as a component (E) in combination for the
thermosetting resin composition of the present invention. The
examples of the curing agent for an epoxy resin include acid
anhydrides such as maleic anhydride, maleic anhydride copolymers
and the like, amine compounds such as diaminodiphenylmethane and
the like and phenol compounds such as phenol novolac, cresol
novolac and the like. Also, the examples of the curing accelerating
agent for an epoxy resin include imidazoles and derivatives
thereof, tertiary amines, quaternary ammonium salts and the like.
Among them, the maleic anhydride copolymers which improve the heat
resistance are preferred, and copolymer resins of polymerizable
monomers constituted from carbon atoms and hydrogen atoms such as
styrene, ethylene, propylene, isobutylene and the like with maleic
anhydride are more preferred since the dielectric constant can be
reduced. Copolymer resins of styrene with maleic anhydride or
copolymer resins of isobutylene with maleic anhydride are
particularly preferred in terms of a solubility in a solvent and a
compatibility with resins blended.
[0046] A content of the component (E) is set to preferably 0 to 50
parts by mass, more preferably 5 to 40 parts by mass and
particularly preferably 5 to 30 parts by mass based on 100 parts by
mass of a sum of the masses of the components (B) to (D) in terms
of a solid matter. Setting a content of the component (E) to 50
parts by mass or less prevents the moldability, the adhesive
property and the flame resistance from being reduced.
[0047] An inorganic filler can optionally be added as a component
(F) to the thermosetting resin of the present invention. The
examples of the inorganic filler include silica, mica, talc, short
fibers or fine powders of glass and hollow glass, antimony
trioxide, calcium carbonate, quartz powder, aluminum hydroxide,
magnesium hydroxide and the like. Among them, silica, aluminum
hydroxide and magnesium hydroxide are preferred from the viewpoints
of the dielectric characteristics, the heat resistance and the
flame resistance, and silica and aluminum hydroxide are more
preferred since they are inexpensive.
[0048] A content of the component (F) is preferably 0 to 300 parts
by mass, more preferably 20 to 200 parts by mass and particularly
preferably 20 to 150 parts by mass based on 100 parts by mass of a
sum of the masses of the components (B) to (D) in terms of a solid
matter. Setting a content of the component (F) to 300 parts by mass
or less prevents the moldability and the adhesive property from
being reduced.
[0049] Publicly known thermoplastic resins, elastomers, flame
retardants, organic fillers and the like can optionally be added as
resin compositions to the thermosetting resin composition of the
present invention to such an extent that the properties of the
thermosetting resin are not damaged.
[0050] The examples of the thermoplastic resin include
polytetrafluoroethylene, polyethylene, polypropylene, polystyrene,
polyphenylene ether resins, phenoxy resins, polycarbonate resins,
polyester resins, polyamide resins, polyimide resins, xylene
resins, petroleum resins, silicone resins and the like.
[0051] The examples of the elastomer include polybutadiene,
polyacrylonitrile, epoxy-modified polybutadiene, maleic
anhydride-modified polybutadiene, phenol-modified polybutadiene,
carboxy-modified polyacrylonitrile and the like.
[0052] The examples of the flame retardant include halogen base
flame retardants containing bromine and chlorine, phosphorus base
flame retardants such as triphenyl phosphate, tricresyl phosphate,
trisdichloropropyl phosphate, phosphazene, red phosphorus and the
like and flame retardants of inorganic matters such as antimony
trioxide, aluminum hydroxide, magnesium hydroxide and the like.
Among the above flame retardants, the phosphorus base flame
retardants and the flame retardants of inorganic matters are
preferred in terms of the environment. Also, the phosphorus base
flame retardants used in combination with the flame retardants of
inorganic matters such as aluminum hydroxide and the like are
particularly preferred from the viewpoints that they are
inexpensive and that the flame resistance and the heat resistance
are consistent with other characteristics.
[0053] The examples of the organic filler include silicone powders
and organic powders of polytetrafluoroethylene, polyethylene,
polypropylene, polystyrene, polyphenylene ether and the like.
[0054] In the thermosetting resin composition of the present
invention, an organic solvent can optionally be used as a diluent
solvent. The above organic solvent shall not specifically be
restricted and includes, for example, ketone base solvents such as
acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone
and the like, alcohol base solvents such as methyl cellosolve and
the like, ether base solvents such as tetrahydrofuran and the like
and aromatic solvents such as toluene, xylene, mesitylene and the
like. They can be used alone or in a mixture of two or more kinds
thereof.
[0055] Further, a UV absorber, an antioxidant, a
photopolymerization initiator, a fluorescent whitening agent, an
adhesion improving agent and the like can optionally be added as
well to the above thermosetting resin composition. They shall not
specifically be restricted and include, for example, a UV absorber
such as benzotriazoles and the like, an antioxidant such as
hindered phenols, styrenated phenols and the like, a
photopolymerization initiator such as benzophenones, benzyl ketals,
thioxanthones and the like, a fluorescent whitening agent such as
stilbene derivatives and the like, a urea compound such as urea
silane and the like and an adhesion improving agent such as silane
coupling agents and the like.
[0056] The prepreg of the present invention is obtained by
impregnating or coating a base material with the thermosetting
resin composition of the present invention and then subjecting it
to a B stage. That is, the base material is impregnated or coated
with the thermosetting resin composition of the present invention
and then semi-cured (subjected to a B stage) by heating or the like
to produce the prepreg of the present invention. The prepreg of the
present invention shall be explained below in details.
[0057] Known base materials used for laminated plates for various
electric insulating materials can be used for the base material
used for the prepreg of the present invention. The examples of the
material thereof include fibers of inorganic matters such as E
glass, D glass, S glass, Q glass and the like, fibers of organic
matters such as polyimides, polyesters, polytetrafluoroethylene and
the like and mixtures thereof. The above base materials have shapes
such as a woven fabric, an unwoven fabric, a roving, a chopped
strand mat, a surfacing mat and the like. The material and the
shape are selected according to the uses and the performances of
the targeted molding, and the materials and the shapes can be used,
if necessary, alone or in combination of two more kinds
thereof.
[0058] A thickness of the base material shall not specifically be
restricted, and the base material having a thickness of, for
example, about 0.03 to 0.5 mm can be used. The base materials
subjected to surface treatment with a silane coupling agent and the
like or mechanically subjected to fiber opening treatment are
suited from the viewpoints of a heat resistance, a moisture
resistance and a workability. The base material is impregnated or
coated with the resin composition so that an amount of the resin
composition adhered on the base material is 20 to 90% by mass in
terms of a resin content in the prepreg after dried, and then it is
semi-cured (subjected to a B stage) by heating and drying usually
at a temperature of 100 to 200.degree. C. for 1 to 30 minutes,
whereby the prepreg of the present invention can be obtained.
[0059] The laminated plate of the present invention can be obtained
by laminating and molding the prepreg of the present invention.
That is, it is laminated and molded in a constitution in which, for
example, 1 to 20 sheets of the prepreg of the present invention are
superposed and in which a metal foil of copper, aluminum or the
like is disposed on one surface or both surfaces thereof.
Conditions in methods of, for example, laminated plates and
multilayer plates for electric insulating materials can be applied
to the molding conditions thereof, and the laminated plate can be
molded in the ranges of a temperature of 100 to 250.degree. C., a
pressure of 0.2 to 10 MPa and a heating time of 0.1 to 5 hours by
means of, for example, a multistage press, a multistage vacuum
press, continuous molding, an autoclave molding machine and the
like. Further, the prepreg of the present invention combined with a
wiring board for an inner layer is laminated and molded, whereby a
multilayer plate can be produced as well.
EXAMPLES
[0060] Next, the present invention shall be explained with
reference to examples shown below, but the present invention shall
not be restricted by these examples.
[0061] The performances of copper clad laminated plates obtained in
the following examples were measured and evaluated by the following
methods.
(1) Evaluation of a Copper Foil Adhesive Property (Copper Foil
Peeling Strength)
[0062] A base plate for evaluation was prepared by dipping a copper
clad laminated plate in a copper etching liquid to thereby remove
the copper foil allowing a band part having a width of 1 cm to
remain, and a peeling strength of the band part was measured by
means of an autograph (AG-100C manufactured by Shimadzu
Corporation).
(2) Measurement of Glass Transition Temperature (Tg)
[0063] A base plate of 5 mm square for evaluation was prepared by
dipping a copper clad laminated plate in a copper etching liquid to
thereby remove the copper foil, and a glass transition temperature
thereof was evaluated by observing a thermal expansion
characteristic of the base plate for evaluation by means of a TMA
test equipment (TMA2940 manufactured by Du Pont Co., Ltd.).
(3) Evaluation of a Solder Heat Resistance
[0064] A base plate of 5 mm square for evaluation was prepared by
dipping a copper clad laminated plate in a copper etching liquid to
thereby remove the copper foil, and it was left standing on the
conditions of 121.degree. C. and 0.2 MPa for 4 hours by means of a
pressure cooker test equipment (manufactured by Hirayama
Manufacturing Corporation). Next, it was dipped in a solder bath
having a temperature of 288.degree. C. for 20 seconds, and then an
appearance of the base plate for evaluation was observed to thereby
evaluate a solder heat resistance.
(4) Evaluation of a Copper-Stuck Heat Resistance (T-288)
[0065] A base plate of 5 mm square for evaluation was prepared from
a copper clad laminated plate, and time passing until blister was
generated on the base plate for evaluation at 288.degree. C. was
measured to thereby evaluate the copper-stuck heat resistance by
means of a TMA test equipment (TMA2940 manufactured by Du Pont Co.,
Ltd.).
(5) Evaluation of a Moisture Absorption (Water Absorption
Coefficient)
[0066] A base plate for evaluation was prepared by dipping a copper
clad laminated plate in a copper etching liquid to thereby remove
the copper foil, and it was left standing on the conditions of
121.degree. C. and 0.2 MPa for 4 hours by means of a pressure
cooker test equipment (manufactured by Hirayama Manufacturing
Corporation). Then, a water absorption coefficient of the base
plate for evaluation was measured.
(6) Evaluation of a Flame Resistance
[0067] A base plate for evaluation was prepared by dipping a copper
clad laminated plate in a copper etching liquid to thereby remove
the copper foil, and a base plate for evaluation was prepared by
cutting out from the above base plate for evaluation in a length of
127 mm and a width of 12.7 mm and evaluated according to a test
method (V method) of UL94.
(7) Measurement of a Relative Dielectric Constant and a Dielectric
Loss Tangent
[0068] A base plate for evaluation was prepared by dipping a copper
clad laminated plate in a copper etching liquid to thereby remove
the copper foil, and a relative dielectric constant and a
dielectric loss tangent thereof were measured at a frequency of 1
GHz by means of a relative dielectric constant measuring device
(HP4291B, manufactured by Hewlett-Packard Company).
Production Example 1
Production of a Maleimide Compound (B-1)
[0069] A reactor having a volume of 2 liter which was equipped with
a thermometer, a stirring device and a moisture determining device
equipped with a reflux condenser and which could be heated and
cooled was charged with 358.0 g of bis(4-maleimidephenyl)methane,
54.5 g of m-aminophenol and 412.5 g of propylene glycol monomethyl
ether ((maleimide group equivalent)/(equivalent in terms of a
--NH.sub.2 group)=4.0), and they were reacted for 5 hours while
refluxing to obtain a solution of a maleimide compound (B-1).
Production Example 2
Production of a Maleimide Compound (B-2)
[0070] A reactor having a volume of 2 liter which was equipped with
a thermometer, a stirring device and a moisture determining device
equipped with a reflux condenser and which could be heated and
cooled was charged with 358.0 g of bis(4-maleimidephenyl)methane,
54.5 g of p-aminophenol and 412.5 g of propylene glycol monomethyl
ether ((maleimide group equivalent)/(equivalent in terms of a
--NH.sub.2 group)=4.0), and they were reacted for 5 hours while
refluxing to obtain a solution of a maleimide compound (B-2).
[0071] The above solution was analyzed by GPC (gel permeation
chromatography, eluent: tetrahydrofuran), and a result thereof is
shown in FIG. 1.
[0072] According to FIG. 1, a peak of p-aminophenol appearing in
the vicinity of an elution time of about 19 minutes was not
observed, and peaks (B) and (C) originating in the addition
products were confirmed. In this case, the peak (A) shows
bis(4-maleimidephenyl)methane which is the synthetic raw material;
the peak (B) shows a reaction product represented by the following
chemical formula (7); and the peak (C) shows a side-reaction
product represented by the following chemical formula (8):
##STR00012##
Production Example 3
Production of a Maleimide Compound (B-3)
[0073] A reactor having a volume of 2 liter which was equipped with
a thermometer, a stirring device and a moisture determining device
equipped with a reflux condenser and which could be heated and
cooled was charged with 358.0 g of bis(4-maleimidephenyl)methane,
27.4 g of p-aminobenzoic acid and 385.4 g of N,N-dimethylacetamide
((maleimide group equivalent)/(equivalent in terms of a --NH.sub.2
group)=10.0), and they were reacted at 140.degree. C. for 5 hours
to obtain a solution of a maleimide compound (B-3).
Production Example 4
Production of a Maleimide Compound (B-4)
[0074] A reactor having a volume of 1 liter which was equipped with
a thermometer, a stirring device and a moisture determining device
equipped with a reflux condenser and which could be heated and
cooled was charged with 268.0 g of m-phenylenebismaleimide, 109.0 g
of m-aminophenol and 377.0 g of N,N-dimethylacetamide ((maleimide
group equivalent)/(equivalent in terms of a --NH.sub.2 group)=2.0),
and they were reacted at 140.degree. C. for 5 hours to obtain a
solution of a maleimide compound (B-4).
Production Example 5
Production of a Maleimide Compound (B-5)
[0075] A reactor having a volume of 2 liter which was equipped with
a thermometer, a stirring device and a moisture determining device
equipped with a reflux condenser and which could be heated and
cooled was charged with 442.0 g of
3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 54.5 g of
p-aminophenol and 496.5 g of propylene glycol monomethyl ether
((maleimide group equivalent)/(equivalent in terms of a --NH.sub.2
group)=4.0), and they were reacted for 5 hours while refluxing to
obtain a solution of a maleimide compound (B-5).
Production Example 6
Production of a Maleimide Compound (B-6)
[0076] A reactor having a volume of 2 liter which was equipped with
a thermometer, a stirring device and a moisture determining device
equipped with a reflux condenser and which could be heated and
cooled was charged with 442.0 g of
3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 54.5 g of
o-aminophenol and 496.5 g of propylene glycol monomethyl ether
((maleimide group equivalent)/(equivalent in terms of a --NH.sub.2
group)=4.0), and they were reacted for 5 hours while refluxing to
obtain a solution of a maleimide compound (B-6).
Production Example 7
Production of a Maleimide Compound (B-7)
[0077] A reactor having a volume of 2 liter which was equipped with
a thermometer, a stirring device and a moisture determining device
equipped with a reflux condenser and which could be heated and
cooled was charged with 408.0 g of bis(4-maleimidephenyl)sulfone,
54.5 g of p-aminophenol and 462.5 g of N,N-dimethylacetamide
((maleimide group equivalent)/(equivalent in terms of a --NH.sub.2
group)=4.0), and they were reacted at 100.degree. C. for 2 hours to
obtain a solution of a maleimide compound (B-7).
Production Example 8
Production of a Maleimide Compound (B-8)
[0078] A reactor having a volume of 2 liter which was equipped with
a thermometer, a stirring device and a moisture determining device
equipped with a reflux condenser and which could be heated and
cooled was charged with 360.0 g of bis(4-maleimidephenyl)methane,
54.5 g of p-aminophenol and 414.5 g of N,N-dimethylacetamide
((maleimide group equivalent)/(equivalent in terms of a --NH.sub.2
group)=4.0), and they were reacted at 100.degree. C. for 2 hours to
obtain a solution of a maleimide compound (B-8).
Production Example 9
Production of a Maleimide Compound (B-9)
[0079] A reactor having a volume of 2 liter which was equipped with
a thermometer, a stirring device and a moisture determining device
equipped with a reflux condenser and which could be heated and
cooled was charged with 570.0 g of
2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 54.5 g of
P-aminophenol and 624.5 g of propylene glycol monomethyl ether
((maleimide group equivalent)/(equivalent in terms of a --NH.sub.2
group)=4.0), and they were reacted at 120.degree. C. for 2 hours to
obtain a solution of a maleimide compound (B-9).
Production Example 10
Production of a Maleimide Compound (B-10)
[0080] A reactor having a volume of 2 liter which was equipped with
a thermometer, a stirring device and a moisture determining device
equipped with a reflux condenser and which could be heated and
cooled was charged with 282.0 g of
4-methyl-1,3-phenylenebismaleimide, 54.5 g of p-aminophenol and
336.5 g of N,N-dimethylacetamide ((maleimide group
equivalent)/(equivalent in terms of a --NH.sub.2 group)=4.0), and
they were reacted at 120.degree. C. for 2 hours to obtain a
solution of a maleimide compound (B-10).
Examples 1 to 20 and Comparative Examples 1 to 8
[0081] Used were an aluminum salt of methyl ethyl phosphinate
(manufactured by Clariant AG.) or an aluminum salt of diethyl
phosphinate (manufactured by Clariant AG.) as a metal salt of
disubstituted phosphinic acid which was the component (A),
bis(4-maleimidephenyl)methane (manufactured by Daiwakasei Industry
Co, Ltd.), 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane
(manufactured by Daiwakasei Industry Co, Ltd.) or the maleimide
compounds (B-1 to 10) obtained in Production Examples 1 to 10 as
the maleimide compound of the component (B), benzoguanamine
(manufactured by Nippon Shokubai Co., Ltd.), acetoguanamine,
2,4-diamino-6-vinyl-s-triazine or dicyandiamide (manufactured by
Kanto Chemical Co., Inc.) as the 6-substituted guanamine compound
of the component (C), a phenol novolac type epoxy resin (D-1, trade
name: Epicron N-770, manufacture by Dainippon Ink & Chemicals
Inc.) or a dicyclopentadiene type epoxy resin (D-2, trade name:
HP-7200H, manufacture by Dainippon Ink & Chemicals Inc.) as the
epoxy resin of the component (D), a copolymer resin of styrene and
maleic anhydride (E-1, trade name: SMA-EF-40, manufacture by
Sartomer Co., Ltd.) or a copolymer resin of isobutylene and maleic
anhydride (E-2, trade name: Isobam #600, manufacture by Kuraray
Co., Ltd.) as the epoxy resin curing agent of the component (E),
crushed silica (F-1, trade name: F05-30, manufacture by Fukushima
Yogyo Co., Ltd., average particle diameter: 10 .mu.m) or aluminum
hydroxide (F-2, trade name: HD-360, manufacture by Showa Denko
K.K., average particle diameter: 3 g m) as the inorganic filler of
the component (F) and methyl ethyl ketone as the diluent solvent,
and they were mixed in blend proportions (parts by mass) shown in
Table 1 to Table 4 to obtain homogeneous vanishes having a resin
content of 65% by mass.
[0082] In Comparative Examples 4 to 6, red phosphorus (trade name:
Hishiguard TP-10F, manufacture by Nippon Chemical Industrial Co.,
Ltd.), triphenyl phosphate (manufacture by Kanto Chemical Co.,
Inc.) or phosphoric ester (trade name: PX-200, manufacture by
Daihachi Chemical Industry Co., Ltd.) was used in place of a metal
salt of disubstituted phosphinic acid which was the component
(A).
[0083] Next, an E glass cloth having a thickness of 0.2 mm was
impregnated and coated with the vanish described above and heated
and dried at 160.degree. C. for 10 minutes to obtain a prepreg
having a resin content of 55% by mass.
[0084] Four sheets of the above prepregs were superposed, and
electrolytic copper foils of 18 .mu.m were disposed at the upper
and lower sides and pressed at a pressure of 2.45 MPa and a
temperature of 185.degree. C. for 90 minutes to obtain a copper
clad laminated plate. The copper clad laminated plate thus obtained
was used to measure and evaluate a copper foil adhesive property
(copper foil peeling strength), a glass transition temperature, a
solder heat resistance, a moisture absorption (water absorption
coefficient), a flame resistance, a relative dielectric constant (1
GHz) and a dielectric loss tangent (1 GHz) by the methods described
above. The evaluation results thereof are shown in Table 1 to Table
4.
TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 Thermosetting resin
composition (parts by mass) Component (A) Aluminum salt (A-1) of
methyl ethyl phosphinate 10 10 20 20 20 Aluminum salt (A-2) of
diethyl phosphinate 10 Component (B) 40
Bis(4-maleimidephenyl)methane 30 30
2,2'-Bis[4-(4-maleimidephenoxy)phenyl]propane 30 Maleimide compound
(B-1) 40 Maleimide compound (B-2) 40 Maleimide compound (B-3) 40
Component (C) Benzoguanamine 10 10 10 10 10 Acetoguanamine 10
2,4-Diamino-6-vinyl-s-triazine Dicyandiamide Component (D) Phenol
novolac type epoxy resin (D-1) 60 60 60 50 50 50 Dicyclopentadiene
type epoxy resin (D-2) Component (E): curing agent for epoxy resin
Copolymer resin (E-1) of styrene and maleic anhydride Copolymer
resin (E-2) of isobutylene and maleic anhydride Component (F):
inorganic filler Crushed silica (F-1) 40 30 40 40 40 40 Aluminum
hydroxide (F-2) 10 20 10 Measurement and evaluation results (1)
Copper foil adhesive property (copper foil 1.60 1.65 1.69 1.62 1.61
1.60 peeling strength: kN/m) (2) Glass transition temperature (Tg,
.degree. C.) 200 205 198 230 230 235 (3) Solder heat resistance
Good Good Good Good Good Good (4) Copper-stuck heat resistance
(T-288, minute) >60 >60 >60 >60 >60 >60 (5)
Moisture absorption (water absorption 0.5 0.5 0.5 0.5 0.6 0.5
coefficient: %) (6) Flame resistance V-0 V-0 V-0 V-0 V-0 V-0 (7)
Relative dielectric constant (1 GHz) 4.2 4.3 4.3 4.0 4.1 4.0 (8)
Dielectric loss tangent (1 GHz) 0.006 0.006 0.006 0.005 0.005
0.005
TABLE-US-00002 TABLE 2 Example 7 8 9 10 11 12 Thermosetting resin
composition (parts by mass) Component (A) Aluminum salt (A-1) of
methyl ethyl phosphinate 20 20 20 20 20 20 Aluminum salt (A-2) of
diethyl phosphinate Component (B) Maleimide compound (B-1)
Maleimide compound (B-2) Maleimide compound (B-3) Maleimide
compound (B-4) 40 Maleimide compound (B-5) 40 Maleimide compound
(B-6) 40 Maleimide compound (B-7) 40 Maleimide compound (B-8) 40
Maleimide compound (B-9) 40 Maleimide compound (B-10) Component (C)
Benzoguanamine 10 10 10 10 10 10 Acetoguanamine
2,4-Diamino-6-vinyl-s-triazine Dicyandiamide Component (D) Phenol
novolac type epoxy resin (D-1) 50 50 50 50 50 50 Dicyclopentadiene
type epoxy resin (D-2) Component (E): curing agent for epoxy resin
Copolymer resin (E-1) of styrene and maleic anhydride Copolymer
resin (E-2) of isobutylene and maleic anhydride Component (F):
inorganic filler Crushed silica (F-1) 40 40 40 40 40 40 Aluminum
hydroxide (F-2) Measurement and evaluation results (1) Copper foil
adhesive property (copper foil 1.60 1.65 1.65 1.65 1.65 1.65
peeling strength: kN/m) (2) Glass transition temperature (Tg,
.degree. C.) 240 235 225 245 245 245 (3) Solder heat resistance
Good Good Good Good Good Good (4) Copper-stuck heat resistance
(T-288, minute) >60 >60 >60 >60 >60 >60 (5)
Moisture absorption (water absorption 0.6 0.5 0.5 0.5 0.6 0.5
coefficient: %) (6) Flame resistance V-0 V-0 V-0 V-0 V-0 V-0 (7)
Relative dielectric constant (1 GHz) 4.1 3.8 3.7 4.1 4.1 4.1 (8)
Dielectric loss tangent (1 GHz) 0.004 0.003 0.002 0.003 0.003
0.003
TABLE-US-00003 TABLE 3 Example 13 14 15 16 17 18 19 20
Thermosetting resin composition (parts by mass) Component (A)
Aluminum salt (A-1) of methyl ethyl 20 50 10 10 10 10 phosphinate
Aluminum salt (A-2) of diethyl phosphinate 20 20 Component (B)
Maleimide compound (B-1) 40 40 30 40 40 60 Maleimide compound (B-2)
Maleimide compound (B-3) Maleimide compound (B-4) 40 Maleimide
compound (B-5) Maleimide compound (B-6) Maleimide compound (B-7)
Maleimide compound (B-8) Maleimide compound (B-9) Maleimide
compound (B-10) 40 Component (C) Benzoguanamine 10 10
Acetoguanamine 2,4-Diamino-6-vinyl-s-triazine 10 10 Dicyandiamide 1
2 2 5 Component (D) Phenol novolac type epoxy resin (D-1) 50 50 50
40 50 25 Dicyclopentadiene type epoxy resin (D-2) 50 50 Component
(E): curing agent for epoxy resin Copolymer resin (E-1) of styrene
and maleic 29 8 10 anhydride Copolymer resin (E-2) of isobutylene
and 8 maleic anhydride Component (F): inorganic filler Crushed
silica (F-1) 40 40 20 40 40 40 40 Aluminum hydroxide (F-2) 20 10 10
10 10 Measurement and evaluation results (1) Copper foil adhesive
property (copper 1.60 1.65 1.65 1.65 1.60 1.60 1.60 1.60 foil
peeling strength: kN/m) (2) Glass transition temperature (Tg,
.degree. C.) 240 235 225 245 200 200 200 250 (3) Solder heat
resistance Good Good Good Good Good Good Good Good (4) Copper-stuck
heat resistance (T-288, >60 >60 >60 >60 >60 >60
>60 >60 minute) (5) Moisture absorption (water absorption 0.5
0.5 0.6 0.5 0.2 0.5 0.5 0.3 coefficient: %) (6) Flame resistance
V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 (7) Relative dielectric constant
4.1 3.8 3.7 4.1 3.9 4.0 3.9 3.9 (1 GHz) (8) Dielectric loss tangent
(1 GHz) 0.004 0.003 0.002 0.003 0.002 0.005 0.003 0.002
TABLE-US-00004 TABLE 4 Comparative Example 1 2 3 4 5 6 7 8
Thermosetting resin composition (parts by mass) Component (A)
Aluminum salt (A-1) of 20 methyl ethyl phosphinate Aluminum salt
(A-2) of diethyl phosphinate Component (B) Bis(4-maleimidephenyl)-
30 40 30 30 methane 2,2'-Bis[4-(4- 30 30 30 maleimidephenoxy)-
phenyl]propane Component (C) Benzoguanamine 10 10 Acetoguanamine 10
2,4-Diamino-6-vinyl-s- 10 10 triazine Dicyandiamide 10 5 Component
(D) Phenol novolac type epoxy 90 60 60 60 resin (D-1)
Dicyclopentadiene type 60 60 60 60 epoxy resin (D-2) Component (F):
inorganic filler Crushed silica (F-1) 20 Aluminum hydroxide (F-2)
20 (Phosphorus base flame retardant) Red phosphorus (F-1) 20
Triphenyl phosphate (F-2) 20 Phosphoric ester (F-3) 20 20 20
Measurement and evaluation results (1) Copper foil adhesive 0.90
0.90 0.70 0.45 0.45 0.45 0.40 0.45 property (copper foil peeling
strength: kN/m) (2) Glass transition 140 150 130 120 120 120 120
120 temperature (Tg, .degree. C.) (3) Solder heat resistance
Swollen Swollen Swollen Swollen Swollen Swollen Swollen Swollen (4)
Copper-stuck heat 1 1 1 0 0 0 0 0 resistance (T-288, minute) (5)
Moisture absorption 1.1 1.1 0.8 1.1 1.1 1.1 1.3 1.5 (water
absorption coefficient: %) (6) Flame resistance V-1 Burned Burned
V-1 Burned Burned Burned Burned (7) Relative dielectric 4.9 4.9 5.1
5.1 5.1 5.1 5.2 5.3 constant (1 GHz) (8) Dielectric loss 0.014
0.014 0.017 0.023 0.023 0.023 0.025 0.026 tangent (1 GHz)
[0085] As apparent from the results shown in Table 1 to Table 3, a
balance is kept in all of the copper foil adhesive property (copper
foil peeling strength), the glass transition temperature (Tg), the
solder heat resistance (T-288), the moisture absorption (water
absorption coefficient), the flame resistance, the relative
dielectric constant (1 GHz) and the dielectric loss tangent (1 GHz)
in the examples of the present invention.
[0086] On the other hand, as apparent from the results shown in
Table 4, the laminated plates which are balanced in all of a copper
foil adhesive property, a glass transition temperature, a solder
heat resistance, a moisture absorption, a flame resistance, a
relative dielectric constant and a dielectric loss tangent are not
found in the comparative examples, and they are inferior in any of
characteristics.
INDUSTRIAL APPLICABILITY
[0087] The prepregs obtained by impregnating or coating the base
material with the thermosetting resin compositions of the present
invention and the laminated plates produced by laminating and
molding the above prepregs are balanced in all of a copper foil
adhesive property, a glass transition temperature, a solder heat
resistance, a moisture absorption, a flame resistance, a relative
dielectric constant and a dielectric loss tangent, and they are
useful as a printed wiring board for electronic instruments.
* * * * *