U.S. patent application number 13/239914 was filed with the patent office on 2013-03-28 for resin composition and prepreg, laminate and circuit board thereof.
The applicant listed for this patent is Tse-An LEE, Yu-Te LIN, Yih-Rern PENG, Jen-Chun WANG, Li-Chih YU. Invention is credited to Tse-An LEE, Yu-Te LIN, Yih-Rern PENG, Jen-Chun WANG, Li-Chih YU.
Application Number | 20130075136 13/239914 |
Document ID | / |
Family ID | 47892286 |
Filed Date | 2013-03-28 |
United States Patent
Application |
20130075136 |
Kind Code |
A1 |
YU; Li-Chih ; et
al. |
March 28, 2013 |
RESIN COMPOSITION AND PREPREG, LAMINATE AND CIRCUIT BOARD
THEREOF
Abstract
A resin composition comprises (A) 100 parts by weight of cyanate
ester resin; (B) 5 to 25 parts by weight of nitrogen and oxygen
containing heterocyclic compound; (C) 5 to 75 parts by weight of
polyphenylene oxide resin; and (D) 5 to 100 parts by weight of
oligomer of phenylmethane maleimide. By using specific components
at specific proportions, the resin composition of the invention
offers the features of low dielectric constant and low dissipation
factor and can be made into prepreg that may be used in printed
circuit board.
Inventors: |
YU; Li-Chih; (Tao-Yuan
Hsien, TW) ; LEE; Tse-An; (Tao-Yuan Hsien, TW)
; WANG; Jen-Chun; (Tao-Yuan Hsien, TW) ; LIN;
Yu-Te; (Tao-Yuan Hsien, TW) ; PENG; Yih-Rern;
(Tao-Yuan Hsien, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
YU; Li-Chih
LEE; Tse-An
WANG; Jen-Chun
LIN; Yu-Te
PENG; Yih-Rern |
Tao-Yuan Hsien
Tao-Yuan Hsien
Tao-Yuan Hsien
Tao-Yuan Hsien
Tao-Yuan Hsien |
|
TW
TW
TW
TW
TW |
|
|
Family ID: |
47892286 |
Appl. No.: |
13/239914 |
Filed: |
September 22, 2011 |
Current U.S.
Class: |
174/255 ;
524/115; 524/141; 524/540; 525/392 |
Current CPC
Class: |
C08K 5/315 20130101;
C08K 5/357 20130101; C08K 5/3415 20130101; C08K 5/357 20130101;
C08K 5/49 20130101; C08L 71/12 20130101; C08L 71/12 20130101; C08L
71/12 20130101; C08K 5/315 20130101; C08K 5/3415 20130101 |
Class at
Publication: |
174/255 ;
525/392; 524/141; 524/115; 524/540 |
International
Class: |
H05K 1/03 20060101
H05K001/03; C08K 5/521 20060101 C08K005/521; C08K 5/5399 20060101
C08K005/5399; C08L 71/02 20060101 C08L071/02 |
Claims
1. A resin composition, comprising: (A) 100 parts by weight of
cyanate ester resin; (B) 5 to 25 parts by weight of nitrogen and
oxygen containing heterocyclic compound; (C) 5 to 75 parts by
weight of polyphenylene oxide (PPO) resin; and (D) 5 to 100 parts
by weight of oligomer of phenylmethane maleimide.
2. The composition according to claim 1, wherein the cyanate ester
resin comprises at least one selected from a group consisting of
the following: ##STR00026## where X.sub.1 and X.sub.2 each
independently represents at least R, Ar, SO.sub.2 or O; R is
selected from the group consisting of --C(CH.sub.3).sub.2--,
--CH(CH.sub.3)--, --CH.sub.2, substituted dicyclopentadienyl and
unsubstituted dicyclopentadienyl; Ar is selected from the group
consisting of substituted benzene and unsubstituted benzene,
biphenyl, naphthalene, phenol novolac, bisphenol A, bisphenol A
novolac, bisphenol F and bisphenol F novolac functional group; n is
an integer greater than or equal to 1; and Y is hydrogen, an
aliphatic functional group or an aromatic functional group.
3. The composition according to claim 1, wherein the nitrogen and
oxygen containing heterocyclic compound comprises at least one
selected from a group consisting of the following: ##STR00027##
where X.sub.3 is R' or Ar; R' is selected from the group consisting
of --C(CH.sub.3).sub.3, --CH.sub.2(CH.sub.3), --CH.sub.3,
substituted dicyclopentadienyl and unsubstituted
dicyclopentadienyl; Ar is selected from the group consisting of
substituted benzene and unsubstituted benzene, biphenyl,
naphthalene, phenol novolac, bisphenol A, bisphenol A novolac,
bisphenol F and bisphenol F novolac; X.sub.4 and X.sub.5 each
independently represents R, Ar or --SO.sub.2--; R is selected from
the group of --C(CH.sub.3).sub.2--, --CH(CH.sub.3)--, --CH.sub.2--
and substituted or unsubstituted dicyclopentadienyl; n is an
integer greater than or equal to 1; and Y is hydrogen, an aliphatic
functional group or an aromatic functional group.
4. The composition according to claim 1, wherein the polyphenylene
oxide resin comprises at least one selected from a group consisting
of ##STR00028## where X.sub.6 is selected from the group of
covalent bond, --SO.sub.2--, --C(CH.sub.3).sub.2--,
--CH(CH.sub.3)--, --CH.sub.2--; Z.sub.1 to Z.sub.12 each
independently represents hydrogen or a methyl group; W represents
hydroxyl, ethylenyl, phenyl ethylenyl, propylenyl, butenyl,
butadienyl or epoxy function group; and n is an integer greater
than or equal to 1.
5. The composition according to claim 1, wherein the oligomer of
phenylmethane maleimide has the following structural formula:
##STR00029## where n and m each independently represents a positive
integer greater than or equal to 1; and Y is hydrogen, an aliphatic
functional group or an aromatic functional group.
6. The composition according to claim 1, further comprising at
least one compound or modification thereof selected from a group
consisting of bisphenol diphenyl phosphate, ammonium polyphosphate,
hydroquinone bis-(diphenyl phosphate), bisphenol A
bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine (TCEP),
tri(isopropylchloro)phosphate, trimethyl phosphate (TMP), dimethyl
methyl phosphonate (DMMP), resorcinol dixylenylphosphate (RDXP)
(ex.: PX-200), melamine polyphosphate, phosphazene (ex.: SPB-100),
phosphazo compound,
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), melamine
cyanurate, and tri-hydroxy ethyl isocyanurate.
7. The composition according to claim 1, further comprising at
least one compound or modifications thereof selected from a group
consisting of epoxy resin, phenolic resin, phenol novolac resin,
styrene resin, polybutadiene resin, anhydride crosslinker, and
amino crosslinker.
8. The composition according to claim 1, further comprising at
least one selected from a group consisting of inorganic filler,
surfactant, toughening agent, curing accelerator and solvent.
9. A prepreg comprising the resin composition according to claim
1.
10. A metal clad laminate comprising the prepreg according to claim
9.
11. A printed circuit board comprising the metal clad laminate
according to claim 10.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a resin composition, more
particularly, a thermosetting resin composition that can be used in
prepreg or the insulating layer of printed circuit board.
BACKGROUND OF THE INVENTION
[0002] As the communications and bandwidth application technologies
evolve rapidly, conventional materials used in the printed circuit
board (PCB) industry (e.g. FR-4 laminate) can no longer meet the
demands for advanced applications, particularly the demands for
high frequency PCB.
[0003] To achieve high-frequency and high-speed transmission of
high-frequency PCB while ensuring minimal data loss or interference
in the transmission process, the materials of laminate preferably
has the electrical properties, thermal resistance, hygroscopic
property, mechanical properties, dimensional stability, and
chemical resistance needed for the process technology and market
applications.
[0004] In terms of electrical properties, major consideration
should be given to the dielectric constant and dielectric loss
(also called "dissipation factor") of the material.
[0005] In general, signal transmission speed of the laminate is
inversely proportional to the square root of its dielectric
constant. That is why the smaller the dielectric constant of the
laminate material is better. On the other hand, lower dissipation
factor means less loss in signal transmission. Thus materials with
low dissipation factor provide better transmission quality.
[0006] Therefore, how to develop materials with low dielectric
constant and low dissipation factor and apply them to the
manufacturing of high-frequency PCB is a pressing problem that PCB
material suppliers need to address at the present time.
[0007] In light of the drawbacks of prior art, the inventor, based
on his many years of experience in the industry, develops a resin
composition that meet the objectives of low dielectric constant and
low dissipation factor.
SUMMARY OF THE INVENTION
[0008] The primary object of the invention is to provide a resin
composition, which, by using specific components at specific
proportions, can offer the properties of low electric constant and
low dissipation factor, and can be made into prepreg and used in
PCB.
[0009] To achieve the aforesaid object, the invention provides a
resin composition, comprising: (A) 100 parts by weight of cyanate
ester resin; (B) 5 to 25 parts by weight of nitrogen and oxygen
containing heterocyclic compound; (C) 5 to 75 parts by weight of
polyphenylene oxide (PPO) resin; and (D) 5 to 100 parts by weight
of oligomer of phenylmethane maleimide.
[0010] The aforesaid composition may be used in manufacturing
prepreg, laminate and PCB.
[0011] By using specific components at specific proportions, the
resin composition of the invention can offer the properties of low
electric constant and low dissipation factor, and can be made into
prepreg and used in PCB.
[0012] The component (A) cyanate ester resin in the resin
composition of the invention comprises at least one selected from a
group consisting of the following:
##STR00001##
[0013] where X.sub.1 and X.sub.2 each independently represents at
least R, Ar, SO.sub.2 or O; R is selected from the group of
--C(CH.sub.3).sub.2--, --CH(CH.sub.3)--, --CH.sub.2--, and
substituted or unsubstituted dicyclopentadienyl; Ar is selected
from the group of substituted or unsubstituted benzene, biphenyl,
naphthalene, phenol novolac, bisphenol A, bisphenol A novolac,
bisphenol F and bisphenol F novolac function groups; n is an
integer greater than or equal to 1; and Y represents hydrogen, an
aliphatic functional group or an aromatic functional group.
[0014] The component (B) nitrogen and oxygen containing
heterocyclic compound in the resin composition of the invention
comprises a ring structure being simultaneously replaced by
nitrogen and oxygen, and preferably comprises at least one selected
from a group consisting of the following:
##STR00002##
[0015] where X.sub.3 represents R' or Ar; R' is selected from the
group of --C(CH.sub.3).sub.3, --CH.sub.2(CH.sub.3), --CH.sub.3 and
substituted or unsubstituted dicyclopentadienyl; Ar is selected
from the group of substituted or unsubstituted benzene, biphenyl,
naphthalene, phenol novolac, bisphenol A, bisphenol A novolac,
bisphenol F and bisphenol F novolac; X.sub.4 and X.sub.5 each
independently represents R, Ar or --SO.sub.2--; R is selected from
the group of --C(CH.sub.3).sub.2--, --CH(CH.sub.3)--, --CH.sub.2--
and substituted or unsubstituted dicyclopentadienyl; n is an
integer greater than or equal to 1; and Y is hydrogen, an aliphatic
functional group or an aromatic functional group.
[0016] Through research and experiments, the inventor finds that
nitrogen and oxygen containing heterocyclic compound can bond
directly with cyanate ester resin. In comparison with prior art
where cyanate ester resin could effectively bond with other types
of resin in the presence of a catalyst, the resin composition in
this invention could engage in crosslinking in the presence or
absence of a catalyst.
[0017] In the bonding reaction of nitrogen and oxygen containing
heterocyclic compound with cyanate ester resin, increasing
temperature could increase the rate of reaction. For example,
heating nitrogen and oxygen containing heterocyclic compound and
cyanate ester resin in an 150.about.190.degree. C. oven for 2 to 10
minutes could accelerate the bonding and form a composition in
semi-cured or fully curing state.
[0018] Given the low dielectric constant of cyanate ester resin and
the low dissipation factor of nitrogen and oxygen containing
heterocyclic compound, the resin composition of the invention
possesses the characteristics of low dielectric constant and low
dissipation factor. In addition, in the bonding process of nitrogen
and oxygen containing heterocyclic compound and cyanate ester
resin, the C atom and N atom in functional group --O--C.ident.N
bond directly with respectively O atom and C atom (C atom between O
atom and N atom) in the nitrogen-oxygen heterocyclic ring.
Therefore, hygroscopic hydroxyl group resulting from the bonding
with water molecules will not increase in this bonding process.
Consequently, the resin composition of the invention has low
hygroscopic property with more than 40% less moisture absorption as
compared to general FR4 materials.
[0019] The component (C) polyphenylene oxide resin in the resin
composition of the invention comprises at least one selected from a
group consisting of the following:
##STR00003##
[0020] where X.sub.6 is selected from the group of covalent bond,
--SO.sub.2--, --C(CH.sub.3).sub.2--, --CH(CH.sub.3)-- and
--CH.sub.2--; Z.sub.1 to Z.sub.12 each independently represents
hydrogen or a methyl group; W represents hydroxyl, ethylenyl,
phenyl ethylenyl, propylenyl, butenyl, butadienyl or epoxy function
group; and n is an integer greater than or equal to 1.
[0021] Because the polyphenylene oxide resin in this invention
could effectively improve the dielectric properties of resin
composition, the addition of polyphenylene oxide resin to nitrogen
and oxygen containing heterocyclic compound and cyanate ester resin
could further lower the dielectric constant and dissipation factor
of the resin composition, and its effect is more pronounced at high
frequency (e.g. 1GHz to 10 GHz). In addition, because of the
difficult flammability of polyphenylene oxide resin, the resin
composition of the invention could also meet the UL 94 V-1 fire
safety requirement.
[0022] The component (D) oligomer of phenylmethane maleimide in the
resin composition of the invention has the following structural
formula:
##STR00004##
[0023] where n and m each independently represents a positive
integer greater than or equal to 1, and Y is hydrogen, an aliphatic
functional group or an aromatic functional group.
[0024] The content of each component in the resin composition of
the invention is preferably: (A) 100 parts by weight of cyanate
ester resin; (B) 5 to 25 parts by weight of nitrogen and oxygen
containing heterocyclic compound; (C) 5 to 75 parts by weight of
polyphenylene oxide resin; and (D) 5 to 100 parts by weight of
oligomer of phenylmethane maleimide, wherein if the content of
nitrogen and oxygen containing heterocyclic compound is less than 5
parts by weight, its addition will not produce the effect of lower
moisture absorption; if the content of nitrogen and oxygen
containing heterocyclic compound is more than 25 parts by weight,
the laminate made from the resin composition will show poor thermal
resistance; the addition of less than 5 parts by weight of
polyphenylene oxide resin will not produce the desired effect,
whereas the addition of more than 75 parts by weight of
polyphenylene oxide resin will result in poor (ex. rough)
appearance of prepreg made from the resin composition; the addition
of less than 5 parts by weight of oligomer of phenylmethane
maleimide will not produce the desired effect, whereas the addition
of more than 100 parts by weight of oligomer of phenylmethane
maleimide will increase the costs of the resin composition. The
high costs of the resin composition, and prepreg and laminate made
thereof will reduce their competitive advantage.
[0025] The invention preferably and optionally includes at least
one specific flame retardant compound to further improve the flame
retardancy of the resin composition. The optional flame retardant
compound includes but is not limited to phosphate compound and
nitrogen-containing phosphate compound. More specifically, the
flame retardant compound preferably is at least one selected from a
group consisting of but not limited to bisphenol diphenyl
phosphate, ammonium polyphosphate, hydroquinone bis-(diphenyl
phosphate), bisphenol A bis-(diphenylphosphate),
tri(2-carboxyethyl)phosphine (TCEP), tri(isopropylchloro)phosphate,
trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP),
resorcinol dixylenylphosphate (RDXP) (ex.: PX-200), melamine
polyphosphate, phosphazene (ex.: SPB-100), phosphazo compound, 9,
10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and
derivatives or resins thereof, melamine cyanurate, and tri-hydroxy
ethyl isocyanurate.
[0026] For example, the flame retardant compound could be a DOPO
compound, DOPO resin (e.g. DOPO-HQ, DOPO-PN, DOPO-BPN), or
DOPO-based epoxy resin, in which DOPO-BPN could be DOPO-BPAN,
DOPO-BPFN, DOPO-BPSN, or other bisphenol novolac compounds with
structural formula as shown below:
##STR00005## ##STR00006##
[0027] where n is an integer greater than or equal to 1; X
represents DOPO functional group; Y is covalent bond, an aliphatic
functional group or an aromatic functional group; and Z is
hydrogen, an aliphatic functional group or an aromatic functional
group. In addition, X and Z could bind to any substituting group
position on the benzene ring structure and each benzene ring is not
limited to having one X or Z substituting group. For example, a
benzene ring can have two or more X substituting groups thereon, or
two or more Z substituting groups thereon. In addition, not every
benzene ring must have both X and Z substituting groups or some
benzene rings have respectively X or Z substituting group or have
simultaneously X and Z substituting groups, whereas some other
benzene rings have neither X nor Z substituting group.
[0028] Adding a flame retardant compound to the resin composition
of the invention could increase the flame retardancy of the resin
composition and cured products thereof up to UL 94 V-O fire safety
level. As such, laminates and PCBs that use the resin composition
would possess good flame retardancy.
[0029] On the basis of 100 parts by weight of cyanate ester resin,
the added flame retardant compound is preferably 10 to 200 parts by
weight. This preferred content markedly improves the flame
retardancy of resin composition and cured products thereof without
producing any adverse effect on their physical properties.
[0030] In addition, the resin composition of the invention
optionally includes at least one selected from a group consisting
of epoxy resin, phenolic resin, phenol novolac resin, styrene
resin, polybutadiene resin, anhydride crosslinker, and amino
crosslinker, and modifications and combinations thereof.
[0031] Wherein, the epoxy resin could be bisphenol A epoxy resin,
bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac
epoxy resin, bisphenol A novolac epoxy resin, o-cresol novolac
epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy
resin, multifunctional epoxy resin, dicyclopentadiene (DCPD) epoxy
resin, phosphorus-containing epoxy resin, p-xylene epoxy resin,
naphthalene-based epoxy resin, benzopyran-based epoxy resin,
biphenyl novolac epoxy resin, and phenol aralkyl novolac epoxy
resin. With the addition of epoxy resin, the crosslinking and
thermal resistance properties of the resin composition are further
enhanced.
[0032] Wherein, the anhydride crosslinker could be methyl
tetrahydro phthalic anhydride (MTHPA), phthalic anhydride (PA),
nadic methyl anhydride (NMA), or styrene maleic anhydride (SMA);
the amino crosslinker could be polyamide resin, dicyandiamide,
diamino diphenylsulfone, diamino diphenyl methane and amino
triazine novolac.
[0033] The resin composition of the invention optionally further
comprises inorganic filler, surfactant, toughening agent, curing
accelerator or solvent additive.
[0034] The main purpose of adding inorganic filler is to increase
the thermal conductivity of resin composition to improve its
thermal expansion and mechanical strength. The inorganic filler is
preferably evenly distributed in the resin composition. The main
purpose of adding surfactant is to enable even distribution of
inorganic fillers in the resin composition. The main purpose of
adding toughening agent is to improve the flexibility of the resin
composition. The main purpose of adding curing accelerator is to
increase the reaction rate of the resin composition. The main
purpose of adding solvent is to change the solid content of the
resin composition and modify its viscosity.
[0035] Wherein, the inorganic filler is at least one of the
following: silica (fused or non-fused), aluminum oxide, magnesium
oxide, magnesium hydroxide, calcium carbonate, talc, clay, aluminum
nitride, boron nitride, aluminum hydroxide, aluminum silicon
carbide, silicon carbide, sodium carbonate, titanium dioxide, zinc
oxide, zirconium oxide, quartz, diamond powder, diamond-like
powder, graphite, or calcined kaolin, and the inorganic filler is
spherical or irregular in shape, and can be optionally pretreated
with surfactant. The inorganic filler is granular powder under 100
.mu.m in size, preferably 1-20 .mu.m in size, and most preferably
nanogranular powder under 1 .mu.m in size.
[0036] The aforesaid surfactant could be silane, siloxane, amino
silane or polymer thereof.
[0037] The aforesaid toughening agent could be rubber resin,
polybutadiene or core-shell polymer.
[0038] The curing accelerator is a catalyst such as Lewis base or
Lewis acid, wherein Lewis base includes one or the combination of
imidazole, boron trifluoride-amine complex, ethyltriphenyl
phosphonium chloride, 2-methylimidazole (2MI),
2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MZ),
triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP), and
Lewis acid include metal salt compound, such as the metal salt
compound of manganese, iron, cobalt, nickel, copper and zinc.
[0039] The resin composition of the invention optionally further
comprises other types of resin in addition to cyanate ester resin
and nitrogen and oxygen containing heterocyclic compound. Under the
circumstances, the resin composition could be further added with a
curing accelerator to facilitate the bonding between said resin and
cyanate ester resin and nitrogen and oxygen containing heterocyclic
compound. For example, the resin composition further includes an
epoxy resin and at least a curing accelerator. The curing
accelerator could effectively promote the ring opening of epoxy
resin and bonding with cyanate ester resin and nitrogen and oxygen
containing heterocyclic compound.
[0040] The aforesaid solvent includes methanol, ethanol, ethylene
glycol mono methylether, acetone, methyl ethyl ketone, methyl
isobutyl ketone, cyclohexanone, toluene, dimethylbenzene,
methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate,
ethyl acetate, dimethyl formamide, propylene glycol methyl ether,
or mixtures thereof.
[0041] Another object of the invention is to disclose a resin film
having the properties of low dielectric constant, flame retardancy,
low moisture absorption, and halogen-free that can be used as
insulating material for laminate and PCB.
[0042] The resin film of the invention comprises the aforementioned
resin composition, wherein the resin composition is heated to
become semi-cured. For example, the resin composition coated on a
polyethylenyl terephthalate (PET) film and heated to form resin
film.
[0043] Yet another object of the invention is to disclose a
laminate, comprising at least a metal foil layer and at least an
insulating layer, wherein the metal foil layer is made of copper,
aluminum, nickel, platinum, silver, gold or alloy thereof, and
preferably copper foil. By laminating the resin film disclosed in
the invention to at least one sheet of metal foil and then removing
the aforesaid PET film and heat curing the resin film and the metal
foil under high temperature and high pressure, an insulating layer
that adheres closely to the metal foil layer is formed.
[0044] A further object of the invention is to disclose a prepreg
having the properties of high mechanical strength, low dielectric
constant and low dissipation factor, flame retardancy, low moisture
absorption, and halogen-free. The prepreg comprises a reinforcement
material and the aforementioned resin composition, wherein the
reinforcement material is impregnated with the resin composition,
which becomes semi-cured under high temperature heating. The
reinforcement material can be fiber material, woven fabric and
non-woven fabric, such as fiberglass cloth, which can increase the
mechanical strength of the prepreg. In addition, the reinforcement
material can be optionally pre-treated by silane coupling agent or
siloxane coupling agent, such as fiberglass cloth pretreated by
silane coupling agent.
[0045] The aforementioned prepreg can be cured to form a cured
sheet or solid insulating layer under high temperature heating or
under high temperature and high pressure condition. If the resin
composition contains solvent, the solvent will evaporate in the
process of high-temperature heating.
[0046] Yet another object of the invention is to disclose a
laminate having the properties of low dielectric constant, flame
retardancy, low moisture absorption, high mechanical strength, and
halogen-free, and is particularly suitable for use in PCB capable
of high-speed, high-frequency signal transmission. As such, the
invention provides a laminate, comprising two or more metal foil
layers and at least an insulating layer, wherein the metal foil is
made of copper, aluminum, nickel, platinum, silver, gold or alloy
thereof; the insulating layer is formed by curing the
aforementioned prepreg under high temperature and high pressure, or
by laminating the aforementioned prepreg between two metal foil and
then pressing under high temperature and high pressure.
[0047] The laminate described above offers at least once of the
following advantages: good flame retardancy, low moisture
absorption, low dielectric constant and low dissipation factor,
higher thermal conduction, lower thermal expandability, better
mechanical strength, and environmentally friendly without
containing halogen. The laminate may be further formed into a
printed circuit board after the circuit fabrication process.
[0048] Yet another object of the invention is to disclose a printed
circuit board having the properties of low dielectric constant,
flame retardancy, low moisture absorption, high mechanical
strength, and halogen-free and is particularly suitable for use in
high-speed, high-frequency signal transmission. Wherein the printed
circuit board comprises at least a laminate described above and is
fabricated using standard printed circuit board fabrication
process.
[0049] To further disclose the invention for implementation by
people with common knowledge in the field, a few examples are cited
below. However it should be noted that the examples below are meant
to further explain the invention and should not be construed as a
limitation on the actual applicable scope of the invention, and as
such, all modifications and alterations without departing from the
spirits of the invention shall remain within the protected scope
and claims of the invention.
[0050] The objects, features and effects of the invention are
described in detail below with embodiments in reference to the
accompanying diagrams.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0051] The components of resin composition in Examples
2-1.about.2-4 are depicted in Table 1, while those of Comparative
Examples 1.about.6 are depicted in Table 3.
EXAMPLE 1 (E1)
[0052] A resin composition comprising:
[0053] (A) 100 parts by weight of cyanate ester resin as shown
below;
##STR00007##
[0054] (B) 20 parts by weight of nitrogen and oxygen containing
heterocyclic compound as shown below, where X.sub.5 is defined the
same as above;
##STR00008##
[0055] (C) 50 parts by weight of polyphenylene oxide resin, where n
is an integer greater than or equal to 1; and
##STR00009##
[0056] (D) 50 parts by weight of oligomer of phenylmethane
maleimide, where n and m each independently represents an integer
greater than or equal to 1 as shown below (product name:
BMI-2300).
##STR00010##
EXAMPLE 2-1 (E2-1)
[0057] A resin composition comprising:
[0058] (A) 100 parts by weight of cyanate ester resin (product
name: BA-230S) as shown below;
##STR00011##
[0059] (B) 25 parts by weight of nitrogen and oxygen containing
heterocyclic compound (Benzoxazine) as shown below;
##STR00012##
[0060] (C) 75 parts by weight of polyphenylene oxide resin (PPO) as
shown below, where n is an integer greater than or equal to 1;
##STR00013##
[0061] (D) 50 parts by weight of oligomer of phenylmethane
maleimide as shown below, where n and m each independently
represents an integer greater than or equal to 1 (product name:
BMI-2300).
##STR00014##
[0062] (E) 100 parts by weight of dicyclopentadiene (DCPD) epoxy
resin;
[0063] (F) 50 parts by weight of flame retardant (RDXP);
[0064] (G) 0.1 parts by weight of cobalt salt compound (cobalt
octanoate);
[0065] (H) 0.2 parts by weight of 2-phenylimidazole (2PZ);
[0066] (I) 50 parts by weight of fused silica;
[0067] (J) 0.4 parts by weight of siloxane; and
[0068] (K) 50 parts by weight of methyl ethyl ketone (MEK).
[0069] Example 2-2.about.2-4 (E2-2.about.E2-4) Examples
2-2.about.2-4 (E2-2.about.E2-4) are basically the same as E2-1. The
difference is E2-2 used 5 parts by weight of nitrogen and oxygen
containing heterocyclic compound; E2-3 used 5 parts by weight of
polyphenylene oxide resin; and E2-4 used 5 parts by weight of
oligomer of phenylmethane maleimide.
EXAMPLE 3 (E3)
[0070] A resin composition comprising:
[0071] (A) 100 parts by weight of cyanate ester resin as shown
below;
##STR00015##
[0072] (B) 25 parts by weight of nitrogen and oxygen containing
heterocyclic compound as shown below;
##STR00016##
[0073] (C) 75 parts by weight of polyphenylene oxide resin as shown
below, where n is an integer greater than or equal to 1;
##STR00017##
[0074] (D) 50 parts by weight of oligomer of phenylmethane
maleimide as shown below, where n and m each independently
represents an integer greater than or equal to 1;
##STR00018##
[0075] (E) 100 parts by weight of DOPO-BPAN resin;
[0076] (F) 50 parts by weight of phosphazene;
[0077] (G) 50 parts by weight of spherical silica;
[0078] (H) 1 parts by weight of siloxane; and
[0079] (I) 50 parts by weight of MEK.
EXAMPLE 4 (E4)
[0080] A resin composition comprising:
[0081] (A) 100 parts by weight of PPO-modified cyanate ester resin
as shown below:
##STR00019##
[0082] (B) 25 parts by weight of nitrogen and oxygen containing
heterocyclic compound as shown below;
##STR00020##
[0083] (C) 50 parts by weight of oligomer of phenylmethane
maleimide as shown below, where n and m each independently
represents an integer greater than or equal to 1; and
##STR00021##
[0084] (D) 50 parts by weight of flame retardant (RDXP).
EXAMPLE 5 (E5)
[0085] A resin film was prepared by mixing uniformly the resin
composition disclosed in E2 in a blender and then coating it on a
PET sheet, and heating the resin composition into semi-cured
state.
EXAMPLE 6 (E6)
[0086] A prepreg (PP) was prepared in the following manner: Mix
respectively the resin composition disclosed in E2-1.about.2-4
uniformly and then place it in an impregnator. Pass a fiberglass
cloth through the aforesaid impregnator to impregnate the resin
composition thereon, and then heat the resin composition into
semi-cured state.
EXAMPLE 7 (E7)
[0087] A laminate comprising a resin film, a copper foil sheet and
a circuit board was prepared in the following manner: Superimpose
the PET-free surface of resin film as described in E5 on the
circuit board; remove the PET sheet, and then superimpose the
surface of resin film with PET sheet removed on the copper foil;
cure the resin composition under high temperature and high pressure
into an insulating layer between the copper foil and the circuit
board.
EXAMPLE 8 (E8)
[0088] A laminate comprising four sheets of prepreg as described in
E6 and two sheets of copper foil was prepared in the following
manner: Laminate in sequence copper foil, four sheets of prepreg
and copper foil; cure the four prepreg sheets under high
temperature and high pressure into an insulating layer between the
two copper foil sheets.
[0089] Use respectively resin compositions in E2-1.about.E2-4 to
fabricate laminates according to the process described in E6 and
E8. The physical property testing results of the laminates are
shown in Table 2 below.
EXAMPLE 9 (E9)
[0090] A printed circuit board comprising a multilayer laminates
and a plurality of prepregs was prepared, wherein the laminates are
those as described in E8 which form surface circuit through
lithography and etching process, and the prepregs are those as
described in E6. The plurality of laminates and plurality of
prepregs were alternately superimposed onto each other between two
sheets of copper foil. The laminated structure was then pressed
under high temperature and high pressure to form a circuit board,
which is then made into a printed circuit board using standard
printed circuit board process.
EXAMPLE 10 (E10)
[0091] A printed circuit board with main structure as described in
Example 9 was prepared, where the difference is that the laminates
are bored to form blind holes.
COMPARATIVE EXAMPLE 1 (C1)
[0092] A resin composition comprising:
[0093] (A) 100 parts by weight of cyanate ester resin as shown
below (product name: BA-230S);
##STR00022##
[0094] (B) 2 parts by weight of nitrogen and oxygen containing
heterocyclic compound as shown below;
##STR00023##
[0095] (C) 75 parts by weight of polyphenylene oxide resin as shown
below, where n is an integer greater than or equal to 1;
##STR00024##
[0096] (D) 50 parts by weight of oligomer of phenylmethane
maleimide as shown below, where n and m each independently
represents an integer greater than or equal to 1 (product name:
BMI-2300);
##STR00025##
[0097] (E) 100 parts by weight of dicyclopentadiene epoxy
resin;
[0098] (F) 50 parts by weight of flame retardant (RDXP);
[0099] (G) 0.1 parts by weight of cobalt salt compound;
[0100] (H) 0.2 parts by weight of 2-phenylimidazole;
[0101] (I) 50 parts by weight of fused silica;
[0102] (J) 0.4 parts by weight of siloxane; and
[0103] (K) 50 parts by weight of MEK.
COMPARATIVE EXAMPLES 2.about.6 (C2.about.C6)
[0104] Comparative Examples 2.about.6 (C2.about.C6) are basically
the same as C1. The difference is C2 used 30 parts by weight of
nitrogen and oxygen containing heterocyclic compound; C3 used 2
parts by weight of polyphenylene oxide resin; C4 used 80 parts by
weight of polyphenylene oxide resin; C5 used 2 parts by weight of
oligomer of phenylmethane maleimide;; and C6 used 105 parts by
weight of oligomer of phenylmethane maleimide
[0105] Use respectively the resin compositions in C1.about.C6 to
prepare copper clad laminates with the methods described in E6 and
E8. Subject the aforesaid copper clad laminates and copper-free
laminates after copper foil etching to physical property testing.
The tested items included glass transition temperature (Tg), heat
resistance (T288), decomposition temperature of laminate (Td),
solder dip test of copper-containing laminate (S/D, solder dip
288.degree. C., 10 seconds, test the number of dip cycles to
thermal delamination), solder dip test of copper-free laminate
after pressure cooking test (PCT) (pressure cooking at 121.degree.
C., 1 hr, then solder dip 288.degree. C., 20 seconds to observe the
presence of delamination), moisture absorption (measure the
difference between the weights of copper-free laminate before and
after PCT (1 hr) to obtain moisture absorption), peeling strength
between copper foil and laminate (P/S, half ounce copper foil),
dielectric constant (Dk), dissipation factor (Df), flaming test
(UL94). The test results are shown in Table 4.
[0106] The test results of E2-1 and E2-2 show that increasing the
amount of nitrogen and oxygen containing heterocyclic compound
could effectively reduce the moisture absorption of the laminate.
The test results of C1 show that when the content of nitrogen and
oxygen containing heterocyclic compound is below 5 parts by weight,
the moisture absorption of the laminate is increased to 0.4%. The
test results of C2 show that when the content of nitrogen and
oxygen containing heterocyclic compound is more than 25 parts by
weight, the laminate displays poorer heat resistance (as indicated
by poorer T288, Td and S/D, and delamination occurs in PCT
test).
[0107] Based on the test results of E2-1 and E2-3, increasing the
amount of polyphenylene oxide resin could lower the Df value. The
test results of C3 show that when the content of PPO is below 5
parts by weight, the Df of laminate would increase to an unexpected
level. The test results of C4 show that when the content of PPO is
more than 75 parts by weight, the prepreg displays poor (ex. rough)
external appearance, thereby resulting in lower process yield, and
the S/D testing is also failed.
[0108] Based on the test results of E2-1 and E2-4, increasing the
amount of oligomer of phenylmethane maleimide could increase the Tg
value of the laminate. According to the test results of C5, when
the content of oligomer of phenylmethane maleimide is below 5 parts
by weight, the Tg value of the laminate will drop below the
expected value. According to the test results of C6, the Tg value
of the laminate will increase significantly when the content of
oligomer of phenylmethane maleimide exceeds 100 parts by weight.
But it will also jack up the costs of the resin composition and the
laminate that the products will not be cost competitive.
TABLE-US-00001 TABLE 1 Components E2-1 E2-2 E2-3 E2-4 Cyanate ester
resin BA-230S 100 100 100 100 Nitrogen and Benzoxazine 25 5 25 25
oxygen containing heterocyclic compound Polyphenylene PPO 75 75 5
75 oxide resin Maleimide BMI-2300 50 50 50 5 Flame retardant RDXP
50 50 50 50 Epoxy resin DCPD-epoxy 100 100 100 100 Inorganic filler
fused silica 50 50 50 50 Siloxane compound Siloxane 0.4 0.4 0.4 0.4
Catalyst Cobalt octanoate 0.1 0.1 0.1 0.1 2PZ 0.2 0.2 0.2 0.2
Solvent MEK 50 50 50 50
TABLE-US-00002 TABLE 2 Property test Test method E2-1 E2-2 E2-3
E2-4 Tg DSC 181 178 184 173 (.degree. C.) T288 TMA >70 >70
>70 >70 (min) Td TGA (.degree. C.) 391 394 396 392 S/D dip
cycles >40 >40 >40 >40 (288.degree. C.) PCT (1 hr) dip
288.degree. C., Pass pass pass pass 20 s Moisture after PCT 0.25
0.38 0.25 0.25 absorption (1 hr) (%) P/S Hoz Cu 6.5 6.6 6.9 6.5
foil Dk 1 GHz 3.75 3.73 3.75 3.75 Df 1 GHz 0.0055 0.0055 0.0063
0.0055 Flaming UL94 V-0 V-0 V-0 V-0 test Cost normal normal normal
low Others PP smooth smooth smooth smooth appearance
TABLE-US-00003 TABLE 3 Component C1 C2 C3 C4 C5 C6 Cyanate BA-230S
100 100 100 100 100 100 ester resin Nitrogen and Benzoxazine 2 30
25 25 25 25 Oxygen containing heterocyclic compound Polyphenylene
PPO 75 75 2 80 75 75 oxide resin Maleimide BMI-2300 50 50 50 50 2
105 Flame retardant RDXP 50 50 50 50 50 50 Epoxy resin DCPD- 100
100 100 100 100 100 epoxy Inorganic filler Fused silica 50 50 50 50
50 50 Siloxane Siloxane 0.4 0.4 0.4 0.4 0.4 0.4 compound Catalyst
Cobalt 0.1 0.1 0.1 0.1 0.1 0.1 octanoate 2PZ 0.2 0.2 0.2 0.2 0.2
0.2 Solvent MEK 50 50 50 50 50 50
TABLE-US-00004 TABLE 4 Property test Test method C1 C2 C3 C4 C5 C6
Tg DSC(.degree. C.) 178 183 186 175 171 191 T288 TMA (min) >70
24 >70 >70 >70 >70 Td TGA(.degree. C.) 390 381 396 383
390 390 S/D dip cycles(288.degree. C.) >40 13 >40 23 >40
>40 PCT (1 hr) dip 288.degree. C., 20 s pass fail pass pass pass
pass Moisture after PCT (1 hr) 0.40 0.25 0.25 0.26 0.25 0.25
absorption (%) P/S Hoz Cu foil 6.6 6.4 6.9 6.2 6.5 6.5 Dk 1 GHz
3.73 3.81 3.86 3.76 3.75 3.75 Df 1 GHz 0.0055 0.0055 0.0064 0.0053
0.0055 0.0055 Flaming test UL94 V-0 V-0 V-0 V-0 V-0 V-0 Cost normal
normal normal normal Low High Others PP appearance smooth smooth
smooth rough smooth smooth
[0109] As described above, the invention meets the three criteria
of patentability, i.e. novelty, inventive step and usefulness. In
terms of novelty and inventive step, the resin composition of the
invention offers the features of low dielectric constant and low
dissipation factor by using specific components at specific
proportions, and can be made into prepreg or resin film for
application in the printed circuit board. In terms of usefulness,
using the products derived from the invention could fully meet the
current market demands.
[0110] The preferred embodiments of the present invention have been
disclosed in the examples. However the examples should not be
construed as a limitation on the actual applicable scope of the
invention, and as such, all modifications and alterations without
departing from the spirits of the invention shall remain within the
protected scope and claims of the invention.
* * * * *