U.S. patent application number 15/071192 was filed with the patent office on 2016-10-06 for thermosetting resin composition, metal-clad laminated plate, insulating sheet, printed wiring board, method of manufacturing printed wiring board, and package substrate.
The applicant listed for this patent is Panasonic Intellectual Property Management Co., Ltd.. Invention is credited to SHINYA ARAKAWA, SHIGETOSHI FUJITA, YASUNORI HOSHINO, KOJI KISHINO, SHIMPEI OBATA, HIROYUKI SHIRAKI, RYUJI TAKAHASHI, HIROKI TAMIYA, TAKAHIRO YAMADA.
Application Number | 20160293538 15/071192 |
Document ID | / |
Family ID | 57016674 |
Filed Date | 2016-10-06 |
United States Patent
Application |
20160293538 |
Kind Code |
A1 |
TAMIYA; HIROKI ; et
al. |
October 6, 2016 |
THERMOSETTING RESIN COMPOSITION, METAL-CLAD LAMINATED PLATE,
INSULATING SHEET, PRINTED WIRING BOARD, METHOD OF MANUFACTURING
PRINTED WIRING BOARD, AND PACKAGE SUBSTRATE
Abstract
A thermosetting resin composition according to the invention
contains: a thermosetting resin component; and silica having an
average particle diameter equal to or greater than 0.2 .mu.m and
treated with isocyanate. It is preferable that the content of the
silica is in a range of 50% by mass to 300% by mass with respect to
the thermosetting resin component. It is also preferable that the
thermosetting resin composition contains core shell rubber having
content in a range of 20% by mass to 80% by mass with respect to
the thermosetting resin component.
Inventors: |
TAMIYA; HIROKI; (Fukushima,
JP) ; KISHINO; KOJI; (Fukushima, JP) ;
TAKAHASHI; RYUJI; (Fukushima, JP) ; HOSHINO;
YASUNORI; (Fukushima, JP) ; YAMADA; TAKAHIRO;
(Fukushima, JP) ; OBATA; SHIMPEI; (Fukushima,
JP) ; SHIRAKI; HIROYUKI; (Osaka, JP) ;
ARAKAWA; SHINYA; (Fukushima, JP) ; FUJITA;
SHIGETOSHI; (Fukushima, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Panasonic Intellectual Property Management Co., Ltd. |
Osaka |
|
JP |
|
|
Family ID: |
57016674 |
Appl. No.: |
15/071192 |
Filed: |
March 15, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K 9/04 20130101; C08L
2203/20 20130101; C08L 2207/53 20130101; H01L 23/49827 20130101;
H01L 23/145 20130101; H01L 2224/16225 20130101; C08K 9/04 20130101;
C08L 63/00 20130101 |
International
Class: |
H01L 23/498 20060101
H01L023/498; C08L 63/00 20060101 C08L063/00; H01L 21/48 20060101
H01L021/48; C08K 9/04 20060101 C08K009/04 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 31, 2015 |
JP |
2015-071297 |
Claims
1. A thermosetting resin composition comprising: a thermosetting
resin component; and silica having an average particle diameter
equal to or greater than 0.2 .mu.m and treated with isocyanate.
2. The thermosetting resin composition according to claim 1,
wherein a content of the silica is in a range of 50% by mass to
300% by mass with respect to the thermosetting resin component.
3. The thermosetting resin composition according to claim 1,
further comprising: core shell rubber having a content in a range
of 20% by mass to 80% by mass with respect to the thermosetting
resin component.
4. A metal-clad laminated plate comprising: an insulating layer
containing a hardened material of the thermosetting resin
composition according to claim 1; and a metal foil.
5. An insulating sheet formed of an insulating layer containing a
hardened material of the thermosetting resin composition according
to claim 1.
6. A printed wiring board comprising: an insulating layer
containing a hardened material of the thermosetting resin
composition according to claim 1; and conductive wirings.
7. The printed wiring board according to claim 6, further
comprising through holes.
8. A method of manufacturing a printed wiring board, comprising:
forming holes penetrating through the insulating layer in the
metal-clad laminated plate according to claim 4; and performing a
desmear treatment with respect to an inner wall of each of the
holes.
9. A method of manufacturing a printed wiring board, comprising:
forming holes penetrating through the insulating layer in the
insulating sheet according to claim 5; and performing a desmear
treatment with respect to an inner wall of each of the holes.
10. A package substrate comprising: the printed wiring board
according to claim 6; and a semiconductor chip mounted on the
printed wiring board.
11. A package substrate comprising: the printed wiring board
manufactured by the method according to claim 8 and a semiconductor
chip mounted on the printed wiring board.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a thermosetting resin
composition, a metal-clad laminated plate, an insulating sheet, a
printed wiring board, a method of manufacturing a printed wiring
board, and a package substrate. The invention specifically relates
to a thermosetting resin composition containing silica, a
metal-clad laminated plate including an insulating layer formed of
the thermosetting resin composition, an insulating sheet including
an insulating layer formed of the thermosetting resin composition,
a printed wiring board including an insulating layer formed of the
thermosetting resin composition, a method of manufacturing the
printed wiring board, and a package substrate including the printed
wiring board.
[0003] 2. Description of the Related Art
[0004] A package substrate including a printed wiring board and a
semiconductor chip mounted on the printed wiring board is easily
warped. This is because a coefficient of thermal expansion (CTE) of
the semiconductor chip is smaller than that of a typical printed
wiring board. Therefore, an insulating layer of a printed wiring
board has been manufactured using a thermosetting resin composition
containing silica, in order to prevent the warpage of the package
substrate (see Japanese Patent unexamined Publication No.
2008-150578). Thus, a modulus of elasticity of the insulating layer
is increased and the warpage is prevented.
SUMMARY OF THE INVENTION
[0005] However, when holes for through holes are formed in a
printed wiring board including an insulating layer containing
silica, an inner wall of the hole may be excessively affected, in a
case of performing a desmear treatment with respect to the holes.
When the inner wall of the hole is excessively affected, failures
in formation of through holes may easily occur, diameters of
through holes may vary, and it is difficult to realize fine
conductive wirings.
[0006] The invention is made in consideration of these
circumstances and an object thereof is to provide a thermosetting
resin composition which contains silica but forms a hardened
material having high resistance to the desmear treatment, a
metal-clad laminated plate which includes an insulating layer
containing the hardened material of the thermosetting resin
composition, an insulating sheet which is formed of the insulating
layer containing the hardened material of the thermosetting resin
composition, a printed wiring board which includes the insulating
layer containing the hardened material of the thermosetting resin
composition, and a method of manufacturing a printed wiring board
using the metal-clad laminated plate.
[0007] According to an aspect of the invention, there is provided a
thermosetting resin composition which contains a thermosetting
resin component and silica treated with isocyanate having an
average particle diameter equal to or greater than 0.2 .mu.m.
[0008] According to another aspect of the invention, there is
provided a metal-clad laminated plate including an insulating layer
containing a hardened material of a thermosetting resin
composition, and a metal foil.
[0009] According to still another aspect of the invention, there is
provided an insulating sheet formed of an insulating layer
containing a hardened material of a thermosetting resin
composition.
[0010] According to still another aspect of the invention, there is
provided a printed wiring board including an insulating layer
containing a hardened material of a thermosetting resin
composition, and conductive wirings.
[0011] According to still another aspect of the invention, there is
provided a method of manufacturing a printed wiring board including
forming holes penetrating through an insulating layer of a
metal-clad laminated plate, and performing a desmear treatment on
an inner wall of each of the holes.
[0012] According to still another aspect of the invention, there is
provided a method of manufacturing a printed wiring board including
forming holes penetrating through an insulating layer of an
insulating sheet, and performing a desmear treatment on an inner
wall of each of the holes.
[0013] According to still another aspect of the invention, there is
provided a package substrate including a printed wiring board, and
a semiconductor chip mounted on the printed wiring board.
[0014] According to the aspect of the invention, it is possible to
obtain a thermosetting resin composition which can form a hardened
material having high resistance to the desmear treatment, even when
containing silica.
[0015] According to the aspect of the invention, it is also
possible to obtain a metal-clad laminated plate, an insulating
sheet, a printed wiring board, and a package substrate which
include an insulating layer having high resistance to the desmear
treatment, even when containing silica.
BRIEF DESCRIPTION OF DRAWING
[0016] The Figure is a sectional view showing a package substrate
of one exemplary embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0017] A thermosetting resin composition according to the exemplary
embodiment contains a thermosetting resin component and silica. An
average particle diameter of silica is equal to or greater than 0.2
.mu.m and silica is treated with isocyanate.
[0018] In the exemplary embodiment, since the thermosetting resin
composition contains silica, a hardened material of the
thermosetting resin composition can have a high modulus of
elasticity and an insulating layer containing the hardened material
can also have a high modulus of elasticity. In a case where the
thermosetting resin composition contains a solvent, the hardened
material of the thermosetting resin composition is a hardened
material having a component excluding the solvent in the
thermosetting resin composition. Accordingly, a package substrate
obtained by mounting a semiconductor chip on a printed wiring board
including such an insulating layer is hardly warped due to a
difference in coefficients of thermal expansion (hereinafter, also
referred to as a CTE) between the semiconductor chip and the
printed wiring board.
[0019] Since silica is treated with isocyanate, even when holes are
formed in the insulating layer containing the hardened material and
a desmear treatment is performed with respect to an inner wall of
the hole, it is less likely that the inner wall of the hole will be
excessively affected. That is, resistance to the desmear treatment
of the insulating layer is increased. This may be because particles
of silica are hardly separated from the inner wall of the hole by
performing a treatment with isocyanate. Therefore, it is possible
to prevent failures of formation of through holes in the printed
wiring board including the insulating layer.
[0020] As described above, it is necessary that the average
particle diameter of silica is 0.2 .mu.m or greater. When the
average particle diameter thereof is less than 0.2 .mu.m, the
particles of silica are easily separated from the inner wall of the
hole at the time of the desmear treatment, the inner wall of the
hole is easily excessively affected, and voids may be generated in
the insulating layer due to deterioration in fluidity of the
thermosetting resin composition.
[0021] The composition of the thermosetting resin composition
according to the exemplary embodiment will be described in
detail.
[0022] The thermosetting component in the thermosetting resin
composition is a component which is cured by heat. The
thermosetting component, for example, contains a thermosetting
resin and a hardener.
[0023] The thermosetting resin can contain at least one kind of
component selected from a group consisting of an epoxy resin, a
phenolic resin, an imide resin, a cyanate ester resin, an
isocyanate resin, a modified polyphenylene ether resin, a
benzoxazine resin, and an oxetane resin, for example. In a case
where the thermosetting resin contains an epoxy resin, the epoxy
resin can contain at least one kind of component selected from a
group consisting of a bisphenol type epoxy resin such as a
bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a
bisphenol S type epoxy resin; a novolac type epoxy resin such as a
phenol novolac type epoxy resin and a cresol novolac type epoxy
resin; an arylalkylene type epoxy resin such as a biphenyl type
epoxy resin, a xylylene type epoxy resin, a phenol aralkyl type
epoxy resin, a biphenyl aralkyl type epoxy resin, a biphenyl
climethylene type epoxy resin, a trisphenolmethane novolac type
epoxy resin, a glycidyl ether, trifunctional or tetrafunctional
glycidyl amines, and a tetramethyl biphenyl type epoxy resin; a
naphthalene skeleton-modified epoxy resin such as a naphthalene
skeleton-modified cresol novolac type epoxy resin, a
methoxynaphthalene-modified cresol novolac type epoxy resin, and a
methoxynaphthalene climethylene type epoxy resin; an anthracene
type epoxy resin; a clicyclopentadiene type epoxy resin; a
norbornene type epoxy resin; a fluorene type epoxy resin; and a
flame-retarded epoxy resin obtained by performing halogenation of
these resins, for example.
[0024] The hardened material can contain at least one kind of
component selected from a group consisting of dicyandiamide and a
multi-functional phenolic compound, for example. In this case,
excellent electrical characteristics, toughness, flexibility, and
adhesiveness can be applied to the insulating layer formed of the
thermosetting resin composition and stress in the insulating layer
is easily alleviated, in a case where this insulating layer is
heated. When the hardener contains phenol novolac, it is possible
to obtain excellent resistance to the desmear treatment while
preventing a decrease of a glass transition point of the insulating
layer. When a decrease of a glass transition point of the
insulating layer can be prevented, a decrease in a modulus of
elasticity of the insulating layer at the time of heating is
prevented, and accordingly, warpage of the metal-clad laminated
plate, the printed wiring board, and the package substrate is
particularly prevented. It is preferable that the content of the
hardener in the thermosetting resin composition is in a range of 4
parts by mass to 70 parts by mass with respect to 100 parts by mass
of the thermosetting resin.
[0025] The thermosetting resin composition may contain a hardening
accelerator. The hardening accelerator can contain at least one
kind of component selected from a group consisting of an organic
acid metal salt such as an imidazole compound, an amine compound, a
thiol compound, and metal soap.
[0026] Silica in the thermosetting resin composition will be
described. As described above, the average particle diameter of
silica is equal to or greater than 0.2 .mu.m. The average particle
diameter is a particle diameter (so-called median diameter) which
is 50% of an integrated value calculated from a particle size
distribution acquired by a laser diffraction and scattering method.
An upper limit of the average particle diameter of silica is not
particularly limited, and when the average particle diameter is
equal to or smaller than 10 .mu.m, an inner surface of the through
hole can be smoothed.
[0027] As described above, silica is treated with isocyanate.
Isocyanate can contain 3-isocyanate propyl triethoxysilane, for
example. As a method of performing a treatment with respect to
silica with isocyanate, a method of dipping silica in a solution
containing isocyanate is used, for example.
[0028] It is preferable that the content of silica is in a range of
50% by mass to 300% by mass with respect to the thermosetting resin
component. In this case, a modulus of elasticity of the insulating
layer and a modulus of elasticity of an insulating sheet formed of
the insulating layer are appropriately adjusted while ensuring
excellent formability of the thermosetting resin composition, and
accordingly, it is possible to effectively prevent warpage of the
package substrate.
[0029] The thermosetting resin composition may further contain an
inorganic filler other than silica. Examples of the inorganic
filler other than silica include aluminum hydroxide, magnesium
hydroxide, aluminum silicate, magnesium silicate, talc, clay, and
mica.
[0030] It is preferable that the thermosetting resin composition
contains core shell rubber. In this case, it is possible to
decrease the CTE of the hardened material and also decrease the CTE
of the insulating layer containing the hardened material.
Accordingly, the package substrate is further hardly warped due to
a difference in the CTEs between the semiconductor chip and the
printed wiring board. In addition, when the thermosetting resin
composition contains the core shell rubber, adhesiveness between
the insulating layer and metal foil or conductive wirings hardly
decreases in a case where the insulating layer is heated, and even
when the insulating layer is heated to 150.degree. C., for example,
excellent adhesiveness between the insulating layer and metal foil
or conductive wirings is maintained.
[0031] The core shell rubber is made of rubber particles, each of
which includes a core part and a shell part coating the core part.
The core part is, for example, formed of one or more kinds of
materials selected from a group consisting of a silicon resin, an
acrylic resin, butadiene rubber, and isoprene rubber. The shell
part is, for example, formed of at least one material of a
polymethacrylate resin such as polymethylmethacrylate (PMMA) and
polystyrene.
[0032] It is preferable that the content of the core shell rubber
is in a range of 20% by mass to 80% by mass with respect to the
thermosetting resin component. When the content of the core shell
rubber is equal to or greater than 20% by mass with respect to the
thermosetting resin component, the CTE of the insulating layer is
particularly decreased. In addition, when the content of the core
shell rubber is equal to or smaller than 80% by mass with respect
to the thermosetting resin component, it is possible to ensure
excellent formability of the thermosetting resin composition.
[0033] The thermosetting resin composition may contain a
thermoplastic resin, a flame retardant, a colorant, a coupling
agent, and the like, if necessary.
[0034] The thermosetting resin composition may contain a solvent.
The solvent can contain at least one component selected from a
group consisting of ethers such as ethylene glycol monomethyl
ether, acetone, methyl ethyl ketone (MEK), dimethylformamide,
benzene, and toluene.
[0035] Components configuring the thermosetting resin composition
are combined with each other, stirred, and mixed with each other,
and accordingly, the thermosetting resin composition can be
obtained.
[0036] A prepreg including a base material and a resin layer can be
obtained by using the thermosetting resin composition. The resin
layer is a semi-hardened material of the thermosetting resin
composition which impregnates the base material. The thermosetting
resin composition impregnates the base material and the
thermosetting resin composition is heated at a temperature in a
range of 110.degree. C. to 140.degree. C., for example, to vaporize
the solvent for semi-hardening, and accordingly, a prepreg can be
obtained. The base material is, for example, a woven fabric formed
of a glass fiber or an organic fiber, or a non-woven fabric. A
resin content of the prepreg, that is, a rate of the semi-hardened
material (resin layer) of the thermosetting resin composition in
the prepreg is in a range of 30% by mass to 80% by mass with
respect to the entire prepreg, for example.
[0037] It is possible to obtain a metal-clad laminated plate, an
insulating sheet, and a printed wiring board including the
insulating layer containing the hardened material of the
thermosetting resin composition using this prepreg.
[0038] The metal-clad laminated plate, for example, includes an
insulating layer, and a metal foil on one surface (hereinafter,
referred to as a first surface) of the insulating layer in a
thickness direction. The metal-clad laminated plate may further
include a metal foil on a surface (hereinafter, referred to as a
second surface) which is on a side opposite to the first surface of
the insulating layer. The insulating layer contains the hardened
material of the prepreg. Each metal foil is a copper foil, a silver
foil, an aluminum foil, or a stainless steel foil, for example. A
thickness of each metal foil is, for example, in a range of 3 .mu.m
to 105 .mu.m and preferably in a range of 12 .mu.m to 35 .mu.m.
[0039] The metal foil is overlapped with one prepreg or a laminate
of the plurality of prepregs and a resultant material is heated and
pressed to manufacture the metal-clad laminated plate. In this
case, one prepreg is hardened or a laminate is hardened to form an
insulating layer. In conditions of heating and pressing, a heating
temperature is in a range of 140.degree. C. to 200.degree. C., a
pressing pressure is in a range of 0.5 MPa to 5.0 MPa, and a
treatment time is in a range of 40 minutes to 240 minutes, for
example.
[0040] The insulating sheet is a member formed of only the
insulating layer. For example, one prepreg or a laminate of the
plurality of prepregs is heated and pressed to manufacture the
insulating sheet. In this case, one prepreg is hardened or a
laminate is hardened to form an insulating layer. In conditions of
heating and pressing, a heating temperature is in a range of
140.degree. C. to 200.degree. C., a pressing pressure is in a range
of 0.5 MPa to 5.0 MPa, and a treatment time is in a range of 40
minutes to 240 minutes, for example.
[0041] The insulating sheet may be obtained by forming the
thermosetting resin composition in a sheet shape, drying, if
necessary, and heating the sheet-like material to be hardened.
[0042] The printed wiring board, for example, includes the
insulating layer and conductive wirings on the first surface of the
insulating layer. In the exemplary embodiment, the printed wiring
board also includes conductive wirings on the second surface of the
insulating layer. In the exemplary embodiment, the printed wiring
board further includes through holes.
[0043] The printed wiring board is manufactured using the
metal-clad laminated plate as a material, for example. In this
case, at the time of manufacturing the printed wiring board, first,
holes penetrating through the insulating layer and the metal foil
are formed in the metal-clad laminated plate by an appropriate
method such as drilling or laser beam machining, for example. In
the exemplary embodiment, since adhesiveness between the insulating
layer and the metal foil is hardly decreased, even when the
insulating layer is heated, the metal foil is hardly peeled from
the metal-clad laminated plate, even when holes are formed by laser
beam machining.
[0044] The inner wall of the hole is subjected to a desmear
treatment. The desmear treatment can be performed using a desmear
solution containing permanganate or the like. Then, conductive
wirings are formed by performing a treatment with respect to the
metal foil by a subtractive process. The through holes are formed
by forming a hole plating on the inner wall of the hole.
Accordingly, a printed wiring board including the insulating layer,
the conductive wirings, and the through holes are obtained.
[0045] The printed wiring board may be manufactured using the
insulating sheet as a material. In this case, at the time of
manufacturing the printed wiring board, first, holes penetrating
through the insulating sheet (that is, the insulating layer) are
formed by an appropriate method such as drilling or laser beam
machining, for example. The inner wall of the hole is subjected to
a desmear treatment. The desmear treatment can be performed by a
well-known method using a well-known desmear solution containing
permanganate or the like. Then, conductive wirings are formed by
performing a treatment with respect to the insulating sheet by an
additive process. The through holes are formed by forming a hole
plating on the inner wall of the hole. Accordingly, a printed
wiring board including the insulating layer, the conductive
wirings, and the through holes are obtained.
[0046] When the printed wiring board is manufactured as described
above, since the insulating layer contains the hardened material of
the thermosetting resin composition in the exemplary embodiment,
the inner wall of the hole is not excessively affected, even when
the desmear treatment is performed with respect to the inner wall
of the hole. Thus, in the exemplary embodiment, failures in
formation of through holes rarely occur.
[0047] The printed wiring board may be a multilayer printed wiring
board including a plurality of insulting layers. In this case, at
least one of the plurality of insulating layers may contain the
hardened material of the thermosetting resin composition according
to the exemplary embodiment. It is particularly preferable that all
of the plurality of insulating layers contain the hardened material
of the thermosetting resin composition according to the exemplary
embodiment. The multilayer printed wiring board is obtained by
forming multi-layers of a core material including an insulating
layer and conductive wirings by a build-up process, for
example.
[0048] It is possible to obtain a package substrate using the
printed wiring board. An example of the package substrate is shown
in the Figure. This package substrate includes printed wiring board
1 and semiconductor chip 2 mounted on printed wiring board 1.
Printed wiring board 1 includes insulating layer 3, conductive
wirings 51 (hereinafter, referred to as first conductive wirings
51) on first surface 41 of insulating layer 3, and conductive
wirings 52 (hereinafter, referred to as second conductive wirings
52) on second surface 42 of insulating layer 3. Printed wiring
board 1 further includes through holes 6 which electrically connect
first conductive wirings 51 and second conductive wirings 52 to
each other. Semiconductor chip 2 includes bumps 7. Semiconductor
chip 2 is mounted on printed wiring board 1 in a face-down manner
so that the semiconductor chip opposes first surface 41 and bumps 7
of semiconductor chip 2 are electrically connected to first
conductive wirings 51. In the exemplary embodiment, since
insulating layer 3 of printed wiring board 1 contains the hardened
material of the thermosetting resin composition and the
thermosetting resin composition contains silica, a modulus of
elasticity of insulating layer 3 is high. Accordingly, the package
substrate is hardly warped due to a difference in the CTEs between
semiconductor chip 2 and printed wiring board 1. In addition, when
the thermosetting resin composition contains the core shell rubber,
it is possible to decrease the CTE of insulating layer 3.
Therefore, it is possible to decrease a difference in the CTEs
between insulating layer 3 and semiconductor chip 2 and further
reduce warpage occurring due to a difference in the CTEs between
semiconductor chip 2 and printed wiring board 1.
[0049] It is preferable that a modulus of elasticity of the
insulating layer of the metal-clad laminated plate and a modulus of
elasticity of the insulating sheet formed of the insulating layer
are in a range of 20 GPa to 50 GPa. In this case, warpage of the
package substrate is effectively prevented. Such a modulus of
elasticity of the insulating layer can be achieved by adjusting the
content of silica in the thermosetting resin composition to be in a
range of the exemplary embodiment, for example.
[0050] It is preferable that coefficients of thermal expansion of
the insulating layer of the metal-clad laminated plate and the
insulating sheet formed of the insulating layer in a direction
orthogonal to the thickness direction is equal to or smaller than
10 ppm/.degree. C. In this case, warpage of the package substrate
is further prevented. Such coefficients of thermal expansion of the
insulating layer can be achieved by adjusting the content of core
shell rubber in the thermosetting resin composition to be in a
range of the exemplary embodiment, for example.
EXAMPLES
[0051] Hereinafter, the invention according to this disclosure will
be described in detail with reference to the examples.
[0052] Thermosetting Resin Composition
[0053] In respective examples and comparative examples, components
shown in the following table are combined with each other, diluted
using a solvent (methyl ethyl ketone), stirred, and mixed with each
other for homogenization, and accordingly a thermosetting resin
composition is prepared. Details of the components shown in the
table are as follows.
[0054] Epoxy resin 1: tetrafunctional naphthalene type epoxy resin
(EPICLON HP-4710 manufactured by DIC Corporation)
[0055] Hardener: phenol novolac (TD-2090 manufactured by DIC
Corporation)
[0056] Hardening accelerator: 2-ethyl-4-methylimidazole (2E4MZ)
[0057] Core shell rubber: silicone-acryl composite rubber (SRK200A
manufactured by Mitsubishi Rayon Co., Ltd.)
[0058] Acryl: SG-80H manufactured by Nagase ChemteX Corporation
[0059] Silica 1: product obtained by performing a surface treatment
with isocyanate, average particle diameter of 0.1 .mu.m,
manufactured by Admatechs Co., Ltd.
[0060] Silica 2: product obtained by performing a surface treatment
with isocyanate, average particle diameter of 0.2 .mu.m,
manufactured by Admatechs Co., Ltd.
[0061] Silica 3: product obtained by performing a surface treatment
with isocyanate, average particle diameter of 2 .mu.m, SC-610G-GND
manufactured by Admatechs Co., Ltd.
[0062] Silica 4: product obtained by performing a surface treatment
with isocyanate, average particle diameter of 12 .mu.m,
manufactured by Admatechs Co., Ltd.
[0063] Silica 5: product obtained by performing a surface treatment
with an epoxy compound, average particle diameter of 2 .mu.m,
manufactured by Admatechs Co., Ltd.
[0064] Silica 6: product obtained by performing a surface treatment
with an amino compound, average particle diameter of 2 .mu.m,
manufactured by Admatechs Co., Ltd.
[0065] Silica 7: product obtained by performing a surface treatment
with a vinyl compound, average particle diameter of 2 .mu.m,
manufactured by Admatechs Co., Ltd.
[0066] An S glass fiber woven fabric is impregnated with the
thermosetting resin composition and the thermosetting resin
composition is heated at 160.degree. C. for 300 seconds, and
accordingly, a prepreg having a thickness of 100 .mu.m and a resin
content of 45% by mass is obtained.
[0067] A laminate obtained by laminating two sheets of this prepreg
is interposed between two sheets of copper foil having a thickness
of 12 .mu.m and heat-pressed under the conditions of a heating
temperature of 200.degree. C., a pressing pressure of 30 MPa, and a
treatment time of 120 minutes. Therefore, a metal-clad laminated
plate is obtained.
[0068] Evaluation Test
[0069] The following evaluation test is performed with respect to
the metal-clad laminated plate obtained in the respective examples
and comparative examples.
[0070] (1) Resistance to Desmear
[0071] The copper foil is etched and removed from the metal-clad
laminated plate to obtain an unclad material formed of the
insulating layer. A sample having a length of 100 mm and a width of
100 mm is cut from the unclad material, this sample is subjected to
the desmear treatment, and an amount decreased in weight of the
sample generated by the desmear treatment is measured. The desmear
treatment is performed under the standard conditions for FR-4
manufactured by Rohm and Haas Company.
[0072] (2) Evaluation of adhesiveness at the time of heating
[0073] The adhesive strength of the copper foil in the metal-clad
laminated plate at 150.degree. C. is measured based on IPC TM650
2.4.8.
[0074] (3) CTE measurement
[0075] The copper foil is etched and removed from the metal-clad
laminated plate to obtain an unclad material formed of the
insulating layer. The CTE of the unclad material in a direction
orthogonal to the thickness direction in a temperature range of
50.degree. C. to 250.degree. C. is measured. The measurement is
performed by a thermal mechanical analysis method (TMA method)
based on IPC TM650 2.4.41.
[0076] (4) Modulus of Elasticity
[0077] The copper foil is etched and removed from the metal-clad
laminated plate to obtain an unclad material formed of the
insulating layer. A sample having a length of 100 mm and a width of
25 mm is cut from the unclad material and a modulus of elasticity
(bending elastic modulus) of this sample at 250.degree. C. is
measured based on JIS C6481.
[0078] (5) Formability
[0079] The metal-clad laminated plate is cut and a cross section is
observed by an SEM, and accordingly the presence or absence of
voids and scratches in the insulating layer is checked. As a
result, a case where no voids and scratches are observed is
evaluated as "A" and a case where at least one of voids and
scratches is observed is evaluated as "B".
[0080] (6) Via shape
[0081] Holes are formed in the metal-clad laminated plate by laser
beam machining under conditions of output of 13 W per operation and
performing irradiation at 10 .mu.s five times. Then, the metal-clad
laminated plate is cut so as to bisect the hole, the inner wall of
the hole is observed, and the presence or absence of abnormal
irregularities on the inner wall is observed. As a result, a case
where no abnormal irregularities are observed is evaluated as "A"
and a case where abnormal irregularities are observed is evaluated
as "B".
TABLE-US-00001 TABLE 1 Comparative Examples Examples 1 2 3 4 5 6 7
8 9 10 1 2 3 4 Composition Epoxy resin 1 (tetrafunctional 60 60 60
60 60 60 60 60 60 60 60 60 60 60 (parts by mass) naphthalene type)
Hardener (phenol novolac) 40 40 40 40 40 40 40 40 40 40 40 40 40 40
Hardening accelerator (2E4MZ) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
0.1 0.1 0.1 0.1 0.1 Core shell rubber (silicone-acryl -- 50 18 22
78 83 50 50 50 50 50 50 50 50 composite rubber) Acryl 50 -- -- --
-- -- -- -- -- -- -- -- -- -- Silica 1 (isocyanate-treated -- -- --
-- -- -- -- -- -- -- 100 -- -- -- product having particle diameter
of 0.1 .mu.m) Silica 2 (isocyanate-treated -- -- -- -- -- -- -- 100
-- -- -- -- -- -- product having particle diameter of 0.2 .mu.m)
Silica 3 (isocyanate-treated 100 100 100 100 100 100 -- -- 40 320
-- -- -- -- product having particle diameter of 2 .mu.m) Silica 4
(isocyanate-treated -- -- -- -- -- -- 100 -- -- -- -- -- -- --
product having particle diameter of 12 .mu.m) Silica 5
(epoxy-treated product -- -- -- -- -- -- -- -- -- -- -- 100 -- --
having particle diameter of 2 .mu.m) Silica 6 (amino-treated
product -- -- -- -- -- -- -- -- -- -- -- -- 100 -- having particle
diameter of 2 .mu.m) Silica 7 (vinyl-treated product -- -- -- -- --
-- -- -- -- -- -- -- -- 100 having particle diameter of 2 .mu.m)
Evaluation Resistance to besmear 0.25 0.25 0.25 0.25 0.25 0.25 0.2
0.35 0.25 0.25 0.5 0.8 0.8 0.8 (mg/cm.sup.2) Adhesiveness at the
time of 0.1 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6
heating (kN/m) CTE(ppm/.degree. C.) 3 3 5 3 2 2 3 3 3 3 3 3 3 3
Modulus of elasticity (GPa) 30 30 35 33 25 25 30 30 20 40 30 30 30
30 Formability A A A A A B A A A B A A A A Via shape A A A A A A B
A A A A A A A
* * * * *