U.S. patent application number 16/206511 was filed with the patent office on 2020-04-09 for resin composition and article made therefrom.
The applicant listed for this patent is Elite Material Co., Ltd.. Invention is credited to Ching-Hsien HSU, Kok-Sheng TAN.
Application Number | 20200109282 16/206511 |
Document ID | / |
Family ID | 69951724 |
Filed Date | 2020-04-09 |
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United States Patent
Application |
20200109282 |
Kind Code |
A1 |
HSU; Ching-Hsien ; et
al. |
April 9, 2020 |
RESIN COMPOSITION AND ARTICLE MADE THEREFROM
Abstract
A resin composition and an article made from the resin
composition are disclosed. The resin composition comprises: a first
vinyl-containing polyphenylene oxide resin, a prepolymer thereof or
both; and a second vinyl-containing polyphenylene oxide resin or a
prepolymer thereof; wherein the first vinyl-containing
polyphenylene oxide resin has a number average molecular weight of
between 500 and 1500, and the second vinyl-containing polyphenylene
oxide resin has a number average molecular weight of between 1600
and 3500.
Inventors: |
HSU; Ching-Hsien; (Taoyuan
City, TW) ; TAN; Kok-Sheng; (Taoyuan City,
TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Elite Material Co., Ltd. |
Taoyuan City |
|
TW |
|
|
Family ID: |
69951724 |
Appl. No.: |
16/206511 |
Filed: |
November 30, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01B 3/427 20130101;
C09D 171/12 20130101; C08K 3/013 20180101; C08K 5/0025 20130101;
C08L 2203/206 20130101; H05K 1/0373 20130101; C08G 65/485 20130101;
C08G 2650/36 20130101; C08L 71/126 20130101; C08L 71/126 20130101;
C08L 71/126 20130101; C09D 171/12 20130101; C08L 71/126
20130101 |
International
Class: |
C08L 71/12 20060101
C08L071/12; H05K 1/03 20060101 H05K001/03; C08G 65/48 20060101
C08G065/48; H01B 3/42 20060101 H01B003/42; C08K 3/013 20060101
C08K003/013; C08K 5/00 20060101 C08K005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 4, 2018 |
TW |
107135003 |
Claims
1. A resin composition, comprising: a first vinyl-containing
polyphenylene oxide resin, a prepolymer thereof or both; and a
second vinyl-containing polyphenylene oxide resin or a prepolymer
thereof; wherein the first vinyl-containing polyphenylene oxide
resin has a number average molecular weight of between 500 and
1500, and the second vinyl-containing polyphenylene oxide resin has
a number average molecular weight of between 1600 and 3500.
2. The resin composition of claim 1, comprising: 5 to 80 parts by
weight of the first vinyl-containing polyphenylene oxide resin, the
prepolymer thereof or both; and 5 to 80 parts by weight of the
second vinyl-containing polyphenylene oxide resin or the prepolymer
thereof.
3. The resin composition of claim 1, comprising: 10 to 50 parts by
weight of the first vinyl-containing polyphenylene oxide resin and
10 to 80 parts by weight of the prepolymer of the second
vinyl-containing polyphenylene oxide resin; or 10 to 50 parts by
weight of the second vinyl-containing polyphenylene oxide resin and
10 to 80 parts by weight of the prepolymer of the first
vinyl-containing polyphenylene oxide resin.
4. The resin composition of claim 1, wherein at least one of the
first vinyl-containing polyphenylene oxide resin and the second
vinyl-containing polyphenylene oxide resin is present as a
prepolymer.
5. The resin composition of claim 4, wherein the prepolymer present
is formed by prepolymerization of the first vinyl-containing
polyphenylene oxide resin or the second vinyl-containing
polyphenylene oxide resin and any one or more of a cyanate ester
resin, a small molecule vinyl compound, a maleimide resin, an
acrylate and a polyolefin.
6. The resin composition of claim 1, wherein the first
vinyl-containing polyphenylene oxide resin comprises a
vinylbenzyl-containing polyphenylene oxide resin, and the second
vinyl-containing polyphenylene oxide resin comprises a
vinylbenzyl-containing polyphenylene oxide resin, a
methacrylate-containing polyphenylene oxide resin, an
allyl-containing polyphenylene oxide resin, a vinylbenzyl-modified
bisphenol A polyphenylene oxide resin, a chain-extended
vinyl-containing polyphenylene oxide resin or a combination
thereof.
7. The resin composition of claim 1, wherein the first
vinyl-containing polyphenylene oxide resin has a number average
molecular weight of between 800 and 1400, and the second
vinyl-containing polyphenylene oxide resin has a number average
molecular weight of between 1800 and 3000.
8. The resin composition of claim 1, wherein the first
vinyl-containing polyphenylene oxide resin comprises a structure of
Formula (1-1): ##STR00010## wherein b1 is a natural number of 0 to
2; X.sub.1 comprises a structure of any one of Formula (2) to
Formula (4): ##STR00011## Y.sub.1 and Y.sub.2 individually comprise
a structure of Formula (5-1): ##STR00012## wherein m1 and n1
independently represent an integer of 1 to 15; R.sub.1 to R.sub.16
are independently selected from H, --CH.sub.3 and a halogen atom;
and A.sub.1 is selected from a covalent bond, --CH.sub.2--,
--CH(CH.sub.3)--, --C(CH.sub.3).sub.2--, --O--, --S--, --SO.sub.2--
and a carbonyl group; Z.sub.1 and Z.sub.2 individually comprise a
structure of Formula (6-1): ##STR00013## wherein R.sub.17 to
R.sub.23 are individually selected from H, --CH.sub.3 and a halogen
atom, and W.sub.1 is a C.sub.1 to C.sub.3 bivalent aliphatic
group.
9. The resin composition of claim 1, wherein the second
vinyl-containing polyphenylene oxide resin comprises a structure of
Formula (1-2): ##STR00014## wherein b2 is a natural number of 0 to
8; X.sub.2 comprises a structure of Formula (2) to Formula (4) or a
combination thereof: ##STR00015## Y.sub.3 and Y.sub.4 individually
comprise a structure of Formula (5-2): ##STR00016## wherein m2 and
n2 independently represent an integer of 1 to 30; R.sub.24 to
R.sub.39 are independently selected from H, --CH.sub.3 and a
halogen atom; A.sub.2 is selected from a covalent bond,
--CH.sub.2--, --CH(CH.sub.3)--, --C(CH.sub.3).sub.2--, --O--,
--S--, --SO.sub.2-- and a carbonyl group; Z.sub.3 and Z.sub.4
individually comprise a structure of Formula (6-2), Formula (6-3)
or Formula (6-4): ##STR00017## wherein R.sub.40 to R.sub.49 are
individually selected from H, --CH.sub.3 or a halogen atom, and
W.sub.2 and Q are individually a C.sub.1 to C.sub.3 bivalent
aliphatic group.
10. The resin composition of claim 1, further comprising an epoxy
resin, another polyphenylene oxide resin, a cyanate ester resin, a
small molecule vinyl compound, a maleimide resin, an acrylate, a
phenolic resin, a benzoxazine resin, a styrene maleic anhydride, a
polyolefin, a polyester resin, an amine curing agent, a polyamide
resin, a polyimide resin or a combination thereof.
11. The resin composition of claim 1, further comprising flame
retardant, inorganic filler, curing accelerator, solvent, silane
coupling agent, coloring agent, toughening agent or a combination
thereof.
12. An article made from the resin composition of claim 1,
comprising a prepreg, a resin film, a resin film with copper foil,
a laminate or a printed circuit board.
13. The article of claim 12, having a coefficient of thermal
expansion of less than 35.0 ppm/.degree. C. as measured with a
thermomechanical analyzer by reference to IPC-TM-650 2.4.24.5.
14. The article of claim 12, having at least one of the following
properties: a T288 thermal resistance as measured by reference to
IPC-TM-650 2.4.24.1 of greater than or equal to 70 minutes; an
interlayer bonding strength as measured by reference to IPC-TM-650
2.4.8 of greater than or equal to 2.85 lb/in; and a Z-axis
dimensional change ratio as measured by reference to IPC-TM-650
2.4.24.5 of less than or equal to 1.80%.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the priority benefits of Taiwan
Patent Application No. 107135003, filed on Oct. 4, 2018. The
entirety the above-mentioned patent application is hereby
incorporated by reference herein and made a part of this
specification.
BACKGROUND
1. Field of the Disclosure
[0002] The present disclosure relates to a resin composition and
more particularly to a resin composition comprising at least two
vinyl-containing polyphenylene oxide resins with different
molecular weight, which is used for making a prepreg, a resin film,
a resin film with copper foil, a laminate or a printed circuit
board.
2. Description of Related Art
[0003] With the rapid advancement of electronic technology,
information processing in mobile communication, servers, cloud
storage and other electronic products has been incessantly directed
toward high frequency signal transmission and high speed
digitalization, and low dielectric resin material has become the
mainstream for the development of laminates for high speed data
transmission in order to satisfy the demands of high speed
information transmission. The major requirements of resin materials
such as copper-clad laminates include several aspects such as low
dielectric constant (Dk), low dissipation factor (Df), high
reliability, high thermal resistance after moisture absorption and
high dimensional stability. Therefore, there is a need for
developing materials suitable for a high performance printed
circuit board.
[0004] Compared with other resin materials, polyphenylene oxide
resins (PPO resins), also known as polyphenylene ether resins (PPE
resins), are widely used in high frequency low dielectric printed
circuit boards due to their low dielectric constant and low
dissipation factor. However, currently available polyphenylene
oxide resins fail to perform well in dimensional stability, so
there is a need to propose a polyphenylene oxide resin composition
capable of achieving satisfactory dimensional stability.
SUMMARY
[0005] A primary object of the present disclosure is to provide a
resin composition, comprising: a first vinyl-containing
polyphenylene oxide resin, a prepolymer thereof or both; and a
second vinyl-containing polyphenylene oxide resin or a prepolymer
thereof; wherein the first vinyl-containing polyphenylene oxide
resin has a number average molecular weight of between 500 and
1500, and the second vinyl-containing polyphenylene oxide resin has
a number average molecular weight of between 1600 and 3500.
[0006] In one embodiment, the resin composition comprises 5 to 80
parts by weight of the first vinyl-containing polyphenylene oxide
resin, a prepolymer thereof or both; and 5 to 80 parts by weight of
the second vinyl-containing polyphenylene oxide resin or a
prepolymer thereof. In another embodiment, the resin composition
comprises 10 to 50 parts by weight of the first vinyl-containing
polyphenylene oxide resin and 10 to 80 parts by weight of the
prepolymer of the second vinyl-containing polyphenylene oxide
resin; or 10 to 50 parts by weight of the second vinyl-containing
polyphenylene oxide resin and 10 to 80 parts by weight of the
prepolymer of the first vinyl-containing polyphenylene oxide
resin.
[0007] In one embodiment, at least one of the first
vinyl-containing polyphenylene oxide resin and the second
vinyl-containing polyphenylene oxide resin is present as a
prepolymer. For example, the prepolymer is formed by
prepolymerization of the first vinyl-containing polyphenylene oxide
resin or the second vinyl-containing polyphenylene oxide resin and
any one or more of a cyanate ester resin, a small molecule vinyl
compound, a maleimide resin, an acrylate and a polyolefin.
[0008] In one embodiment, the first vinyl-containing polyphenylene
oxide resin comprises a vinylbenzyl-containing polyphenylene oxide
resin, and the second vinyl-containing polyphenylene oxide resin
comprises a vinylbenzyl-containing polyphenylene oxide resin, a
methacrylate-containing polyphenylene oxide resin, an
allyl-containing polyphenylene oxide resin, a vinylbenzyl-modified
bisphenol A polyphenylene oxide resin, a chain-extended
vinyl-containing polyphenylene oxide resin or a combination
thereof. In one embodiment, the first vinyl-containing
polyphenylene oxide resin has a number average molecular weight of
between 800 and 1400, and the second vinyl-containing polyphenylene
oxide resin has a number average molecular weight of between 1800
and 3000.
[0009] In one embodiment, in addition to the first vinyl-containing
polyphenylene oxide resin (and/or a prepolymer thereof) and the
second vinyl-containing polyphenylene oxide resin (or a prepolymer
thereof), the resin composition disclosed herein may further
comprise: an epoxy resin, another polyphenylene oxide resin, a
cyanate ester resin, a small molecule vinyl compound, a maleimide
resin, a phenolic resin, a benzoxazine resin, a styrene maleic
anhydride, a polyolefin, a polyester resin, an amine curing agent,
a polyamide resin, a polyimide resin or a combination thereof. In
another embodiment, the resin composition disclosed herein further
comprises the following ingredient: flame retardant, inorganic
filler, curing accelerator, solvent, silane coupling agent,
coloring agent, toughening agent or a combination thereof.
[0010] The resin compositions of various embodiments may be used
for making different articles, including but not limited to a
prepreg, a resin film, a resin film with copper foil, a laminate or
a printed circuit board.
[0011] Surprisingly, by the use of at least two vinyl-containing
polyphenylene oxide resins with different molecular weight, the
present disclosure achieves significant improvements in the
following one or more or all aspects: a coefficient of thermal
expansion of less than 35.0 ppm/.degree. C. as measured with a
thermomechanical analyzer by reference to IPC-TM-650 2.4.24.5; a
T288 thermal resistance as measured by reference to IPC-TM-650
2.4.24.1 of greater than or equal to 70 minutes; an interlayer
bonding strength as measured by reference to IPC-TM-650 2.4.8 of
greater than or equal to 2.85 lb/in; and a Z-axis dimensional
change ratio as measured by reference to IPC-TM-650 2.4.24.5 of
less than or equal to 1.80%.
DETAILED DESCRIPTION OF EMBODIMENTS
[0012] To enable those skilled in the art to further appreciate the
features and effects of the present disclosure, words and terms
contained in the specification and appended claims are described
and defined. Unless otherwise defined, all technical and scientific
terms used herein have the same meaning as commonly understood by
those of ordinary skill in the art to which this disclosure
pertains. In the case of conflict, the present document and
definitions contained herein will control.
[0013] As used herein, the term "comprises," "comprising,"
"includes," "including," "has," "having" or any other variant
thereof is construed as an open-ended transitional phrase intended
to cover a non-exclusive inclusion. For example, a composition or
article of manufacture that comprises a list of elements is not
necessarily limited to only those elements but may include other
elements not expressly listed or inherent to such composition or
article of manufacture. Further, unless expressly stated to the
contrary, the term "or" refers to an inclusive or and not to an
exclusive or. For example, a condition "A or B" is satisfied by any
one of the following: A is true (or present) and B is false (or not
present), A is false (or not present) and B is true (or present),
and both A and B are true (or present). In addition, whenever
open-ended transitional phrases are used, such as "comprises,"
"comprising," "includes," "including," "has," "having" or any other
variant thereof, it is understood that transitional phrases such as
"consisting essentially of" and "consisting of" are also disclosed
and included.
[0014] In this disclosure, features or conditions presented as a
numerical range or a percentage range are merely for convenience
and brevity. Therefore, a numerical range or a percentage range
should be interpreted as encompassing and specifically disclosing
all possible subranges and individual numerals or values therein,
particularly all integers therein. For example, a range of "1 to 8"
or "between 1 and 8" should be understood as explicitly disclosing
all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to
8 and so on, particularly all subranges defined by integers, as
well as disclosing all individual values such as 1, 2, 3, 4, 5, 6,
7 and 8. Unless otherwise defined, the aforesaid interpretation
rule should be applied throughout the present disclosure regardless
broadness of the scope.
[0015] Whenever amount, concentration or other numeral or parameter
is expressed as a range, a preferred range or a series of upper and
lower limits, it is understood that all ranges defined by any pair
of the upper limit or preferred value and the lower limit or
preferred value are specifically disclosed, regardless whether
these ranges are explicitly described or not. In addition, unless
otherwise defined, whenever a range is mentioned, the range should
be interpreted as inclusive of the endpoints and every integers and
fractions in the range.
[0016] Given the intended purposes and advantages of this
disclosure are achieved, numerals or figures have the precision of
their significant digits. For example, 40.0 should be understood as
covering a range of 39.50 to 40.49.
[0017] As used herein, a Markush group or a list of items is used
to describe examples or embodiments of the present disclosure. A
skilled artisan will appreciate that all subgroups of members or
items and individual members or items of the Markush group or list
can also be used to describe the present disclosure. For example,
when X is described as being "selected from a group consisting of
X.sub.1, X.sub.2 and X.sub.3," it is intended to disclose the
situations of X is X.sub.1 and X is X.sub.1 and/or X.sub.2 and/or
X.sub.3. In addition, when a Markush group or a list of items is
used to describe examples or embodiments of the present disclosure,
a skilled artisan will understand that any subgroup or any
combination of the members or items in the Markush group or list
may also be used to describe the present disclosure. Therefore,
when X is described as being "selected from a group consisting of
X.sub.1, X.sub.2 and X.sub.3" and Y is described as being "selected
from a group consisting of Y.sub.1, Y.sub.2 and Y.sub.3," the
disclosure of any combination of X is X.sub.1 and/or X.sub.2 and/or
X.sub.3 and Y is Y.sub.1 and/or Y.sub.2 and/or Y.sub.3.
[0018] The following embodiments and examples are illustrative in
nature and are not intended to limit the present disclosure and its
application. In addition, the present disclosure is not bound by
any theory described in the background and summary above or the
following embodiments or examples.
[0019] As described above, a primary object of the present
disclosure is to provide a resin composition, comprising: a first
vinyl-containing polyphenylene oxide resin, a prepolymer thereof or
both; and a second vinyl-containing polyphenylene oxide resin or a
prepolymer thereof; wherein the first vinyl-containing
polyphenylene oxide resin has a number average molecular weight of
between 500 and 1500, and the second vinyl-containing polyphenylene
oxide resin has a number average molecular weight of between 1600
and 3500.
[0020] As used herein, "vinyl-containing" refers to the presence of
an ethylenic carbon-carbon double bond (C.dbd.C) or a functional
group derived therefrom in a compound. Therefore, examples of
"vinyl-containing" may include, but not limited to, a structure
containing a vinyl group, an allyl group, a vinylbenzyl group, a
methacrylate or the like. Unless otherwise specified, the position
of the aforesaid functional group is not particularly limited and
may be located at the terminal of a long chain structure.
[0021] As used herein, "polyphenylene oxide" refers to an aromatic
polymer having two or more "-(phenylene-oxy)-" structures. The
phenylene group may be optionally substituted or unsubstituted. For
example, the phenylene group may be substituted at position number
2, at position number 6 or at position number 2 and number 6 by a
C1 to C6 alkyl group. As used herein, "natural number" includes 0
and positive integers.
[0022] As used herein, "prepolymer" refers to the product of a
compound subject to preliminary or partial polymerization and
retaining a reactive functional group which may be subject to
further polymerization or crosslinking reaction.
[0023] Unless otherwise specified, the ratio or content of
different components in the resin composition is not particularly
limited. For example, the resin composition may comprise: 1 to 100
parts by weight of a first vinyl-containing polyphenylene oxide
resin, a prepolymer thereof or both; and 1 to 100 parts by weight
of a second vinyl-containing polyphenylene oxide resin or a
prepolymer thereof.
[0024] In one embodiment, the resin composition may comprise: 5 to
80 parts by weight of a first vinyl-containing polyphenylene oxide
resin, a prepolymer thereof or both; and 5 to 80 parts by weight of
a second vinyl-containing polyphenylene oxide resin or a prepolymer
thereof. In other words, relative to 5 to 80 parts by weight of a
first vinyl-containing polyphenylene oxide resin, a prepolymer
thereof or both, the resin composition may comprise 5, 10, 20, 30,
40, 50, 60, 70 or 80 parts by weight of a second vinyl-containing
polyphenylene oxide resin or a prepolymer thereof, but not limited
thereto; and relative to 5 to 80 parts by weight of a second
vinyl-containing polyphenylene oxide resin or a prepolymer thereof,
the resin composition may comprise 5, 10, 20, 30, 40, 50, 60, 70 or
80 parts by weight of a first vinyl-containing polyphenylene oxide
resin, a prepolymer thereof or both, but not limited thereto.
[0025] In one embodiment, the resin composition comprises 10 to 50
parts by weight of the first vinyl-containing polyphenylene oxide
resin and 10 to 80 parts by weight of the prepolymer of the second
vinyl-containing polyphenylene oxide resin.
[0026] In one embodiment, the resin composition comprises 10 to 50
parts by weight of the first vinyl-containing polyphenylene oxide
resin and 10 to 50 parts by weight of the prepolymer of the second
vinyl-containing polyphenylene oxide resin.
[0027] In one embodiment, the resin composition comprises 10 to 50
parts by weight of the second vinyl-containing polyphenylene oxide
resin and 10 to 80 parts by weight of the prepolymer of the first
vinyl-containing polyphenylene oxide resin.
[0028] In one embodiment, the resin composition comprises 10 to 30
parts by weight of the second vinyl-containing polyphenylene oxide
resin and 30 to 80 parts by weight of the prepolymer of the first
vinyl-containing polyphenylene oxide resin.
[0029] In one embodiment, the resin composition comprises 10 to 30
parts by weight of the second vinyl-containing polyphenylene oxide
resin and 60 to 80 parts by weight of the prepolymer of the first
vinyl-containing polyphenylene oxide resin.
[0030] Unless otherwise specified, the first vinyl-containing
polyphenylene oxide resin and/or the second vinyl-containing
polyphenylene oxide resin may be present as a prepolymer. For
example, the resin composition described herein may comprise the
prepolymer of the first vinyl-containing polyphenylene oxide resin
and the second vinyl-containing polyphenylene oxide resin. For
example, the resin composition described herein may comprise the
first vinyl-containing polyphenylene oxide resin and the prepolymer
of the second vinyl-containing polyphenylene oxide resin. For
example, the resin composition described herein may comprise the
prepolymer of the first vinyl-containing polyphenylene oxide resin
and the prepolymer of the second vinyl-containing polyphenylene
oxide resin.
[0031] The prepolymer may be formed by prepolymerization of the
first vinyl-containing polyphenylene oxide resin or the second
vinyl-containing polyphenylene oxide resin and any one or more of a
cyanate ester resin, a small molecule vinyl compound, a maleimide
resin, an acrylate and a polyolefin, as described in detail
below.
[0032] The cyanate ester resin may include any one or more cyanate
ester resins used for preparing a prepreg, a resin film, a resin
film with copper foil, a laminate or a printed circuit board, such
as a compound having an Ar--O--C.ident.N structure, wherein Ar may
be a substituted or unsubstituted aromatic group. Examples include
but are not limited to novolac cyanate ester resin, bisphenol A
cyanate ester resin, bisphenol F cyanate ester resin,
dicyclopentadiene-containing cyanate ester resin,
naphthalene-containing cyanate ester resin, phenolphthalein cyanate
ester resin, adamantane cyanate ester resin, fluorene cyanate ester
resin or a combination thereof. The novolac cyanate ester resin may
be bisphenol A novolac cyanate ester resin, bisphenol F novolac
cyanate ester resin or a combination thereof. For example, the
cyanate ester resin may be available under the tradename Primaset
PT-15, PT-30S, PT-60S, BA-200, BA-230S, BA-3000S, BTP-2500,
BTP-6020S, DT-4000, DT-7000, ULL950S, HTL-300, CE-320, LVT-50, or
LeCy sold by Lonza.
[0033] The small molecule vinyl compound as used herein refers to a
vinyl-containing compound with a molecular weight of less than or
equal to 1000, preferably between 100 and 900 and more preferably
between 100 and 800. According to the present disclosure, the small
molecule vinyl compound may include, but not limited to,
divinylbenzene (DVB), bis(vinylbenzyl) ether (BVBE),
bis(vinylphenyl) ethane (BVPE), triallyl isocyanurate (TAIC),
triallyl cyanurate (TAC), 1,2,4-trivinyl cyclohexane (TVCH) or a
combination thereof.
[0034] The maleimide resin refers to a compound, monomer, mixture,
oligomer or polymer containing at least one maleimide group. Unless
otherwise specified, the maleimide resin used in the present
disclosure is not particularly limited and may include any one or
more maleimide resins used for preparing a prepreg, a resin film, a
resin film with copper foil, a laminate or a printed circuit board.
Examples include but are not limited to 4,4'-diphenylmethane
bismaleimide, oligomer of phenylmethane maleimide (a.k.a.
polyphenylmethane maleimide), m-phenylene bismaleimide, bisphenol A
diphenyl ether bismaleimide,
3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide,
4-methyl-1,3-phenylene bismaleimide,
1,6-bismaleimide-(2,2,4-trimethyl hexane), N-2,3-xylylmaleimide,
N-2,6-xylenemaleimide, N-phenylmaleimide, maleimide resin
containing aliphatic long chain structure, prepolymer thereof and a
combination thereof. The aforesaid prepolymer may for example be a
prepolymer of diallyl compound and maleimide resin, a prepolymer of
diamine and maleimide resin, a prepolymer of multi-functional amine
and maleimide resin or a prepolymer of acid phenol compound and
maleimide resin.
[0035] For example, the maleimide resin may include products such
as BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300,
BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BM-7000 and
BMI-7000H available from Daiwakasei Co., Ltd., or products such as
BMI-70 and BMI-80 available from K.I Chemical Industry Co.,
Ltd.
[0036] For example, the maleimide resin containing aliphatic long
chain structure may include products such as BMI-689, BMI-1400,
BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000 sold
by Designer Molecules Inc.
[0037] The acrylate may include, but not limited to, tricyclodecane
di(meth)acrylate, tri(meth)acrylate,
1,1'-[(octahydro-4,7-methano-1H-indene-5,6-diyl)bis(methylene)]ester
(e.g., SR833S, available from Sartomer) or a combination
thereof.
[0038] Examples of polyolefin include but are not limited to
styrene-butadiene-divinylbenzene terpolymer,
styrene-butadiene-maleic anhydride terpolymer,
vinyl-polybutadiene-urethane oligomer, styrene butadiene copolymer,
hydrogenated styrene butadiene copolymer, styrene isoprene
copolymer, hydrogenated styrene isoprene copolymer, hydrogenated
styrene-butadiene-divinylbenzene copolymer, polybutadiene
(homopolymer of butadiene), maleic anhydride-butadiene copolymer,
methyl styrene copolymer or a combination thereof.
[0039] The first vinyl-containing polyphenylene oxide resin or the
second vinyl-containing polyphenylene oxide resin may be
prepolymerized with any one or more components described above
under proper conditions, such as in the presence of peroxide and
solvent, so as to obtain the prepolymer of the first
vinyl-containing polyphenylene oxide resin or the prepolymer of the
second vinyl-containing polyphenylene oxide resin.
[0040] For example, the first vinyl-containing polyphenylene oxide
resin or the second vinyl-containing polyphenylene oxide resin may
be dissolved and mixed together with any one or more of a cyanate
ester resin, a small molecule vinyl compound, a maleimide resin, an
acrylate and a polyolefin, followed by the addition of a peroxide
if needed, then the temperature is increased to such as 70.degree.
C. to 110.degree. C., stirred and reacted for 4 to 10 hours, and
the solution thus obtained is purified to obtain the product, which
is the prepolymer of the first vinyl-containing polyphenylene oxide
resin or the prepolymer of the second vinyl-containing
polyphenylene oxide resin.
[0041] The solvent may be any solvent suitable for dissolving the
vinyl-containing polyphenylene oxide resin, cyanate ester resin,
small molecule vinyl compound, maleimide resin, acrylate and/or
polyolefin, and may comprise, but not limited to, methanol,
ethanol, ethylene glycol monomethyl ether, acetone, butanone
(methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone,
toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate,
propoxyethyl acetate, ethyl acetate, dimethylformamide,
dimethylacetamide, propylene glycol methyl ether, or a mixture
thereof.
[0042] The peroxide may be any peroxide suitable for initiating the
prepolymerization of the vinyl-containing polyphenylene oxide resin
and the cyanate ester resin, small molecule vinyl compound,
maleimide resin, acrylate and/or polyolefin, and may comprise, but
not limited to, dicumyl peroxide, tert-butyl peroxybenzoate,
dibenzoyl peroxide (BPO),
2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B),
bis(tert-butylperoxyisopropyl)benzene or a combination thereof.
[0043] For example, a first vinyl-containing polyphenylene oxide
resin (or a second vinyl-containing polyphenylene oxide resin), a
cyanate ester resin, a peroxide and a toluene solvent may be well
mixed, heated to 70.degree. C. to 110.degree. C. and reacted for 4
to 10 hours, and the product is purified to obtain a prepolymer of
the first vinyl-containing polyphenylene oxide resin (or of the
second vinyl-containing polyphenylene oxide resin).
[0044] For example, a first vinyl-containing polyphenylene oxide
resin (or a second vinyl-containing polyphenylene oxide resin), a
cyanate ester resin, a small molecule vinyl compound, a peroxide
and a toluene solvent may be well mixed, heated to 70.degree. C. to
110.degree. C. and reacted for 4 to 10 hours, and the product is
purified to obtain a prepolymer of the first vinyl-containing
polyphenylene oxide resin (or of the second vinyl-containing
polyphenylene oxide resin).
[0045] In one embodiment, the first vinyl-containing polyphenylene
oxide resin comprises a vinylbenzyl-containing polyphenylene oxide
resin, and the second vinyl-containing polyphenylene oxide resin
comprises a vinylbenzyl-containing polyphenylene oxide resin, a
methacrylate-containing polyphenylene oxide resin, an
allyl-containing polyphenylene oxide resin, a vinylbenzyl-modified
bisphenol A polyphenylene oxide resin, a chain-extended
vinyl-containing polyphenylene oxide resin or a combination
thereof.
[0046] For example, the first vinyl-containing polyphenylene oxide
resin may be a vinylbenzyl-containing polyphenylene oxide resin
with a number average molecular weight of about 1200 (such as
OPE-2st 1200, available from Mitsubishi Gas Chemical Co.,
Inc.).
[0047] For example, the second vinyl-containing polyphenylene oxide
resin may be a vinylbenzyl-containing polyphenylene oxide resin
with a number average molecular weight of about 2200 (such as
OPE-2st 2200, available from Mitsubishi Gas Chemical Co., Inc.), a
methacrylate-containing polyphenylene oxide resin with a number
average molecular weight of about 1900 to 2300 (such as SA-9000,
available from Sabic), a vinylbenzyl-modified bisphenol A
polyphenylene oxide resin with a number average molecular weight of
about 2400 to 2800, a chain-extended vinyl-containing polyphenylene
oxide resin with a number average molecular weight of between about
2200 and about 3000, or a combination thereof. The chain-extended
vinyl-containing polyphenylene oxide resin may include various
polyphenylene oxide resins disclosed in the US Patent Application
Publication No. 2016/0185904 A1, all of which are incorporated
herein by reference in their entirety.
[0048] According to the present disclosure, the first
vinyl-containing polyphenylene oxide resin has a number average
molecular weight of between 500 and 1500, such as between 800 and
1400.
[0049] In one embodiment, the first vinyl-containing polyphenylene
oxide resin may comprise a structure of Formula (1-1):
##STR00001## [0050] wherein b1 is a natural number of 0 to 2;
[0051] X.sub.1 comprises a structure of any one of Formula (2) to
Formula (4):
[0051] ##STR00002## [0052] Y.sub.1 and Y.sub.2 individually
comprise a structure of Formula (5-1):
[0052] ##STR00003## [0053] wherein m1 and n1 independently
represent an integer of 1 to 15, such as 1, 5, 10 or 15; [0054]
R.sub.1 to R.sub.16 are independently selected from H, --CH.sub.3
and a halogen atom (e.g., chlorine, bromine, or iodine); A.sub.1 is
selected from a covalent bond, --CH.sub.2--, --CH(CH.sub.3)--,
--C(CH.sub.3).sub.2--, --O--, --S--, --SO.sub.2-- and a carbonyl
group; [0055] Z.sub.1 and Z.sub.2 individually comprise a structure
of Formula (6-1):
[0055] ##STR00004## [0056] wherein R.sub.17 to R.sub.23 are
individually selected from H, --CH.sub.3 or a halogen atom, and
W.sub.1 is a C1 to C3 bivalent aliphatic group, such as methylene,
ethylene, or propylene.
[0057] For example, the first vinyl-containing polyphenylene oxide
resin may comprise a structure below:
##STR00005## [0058] wherein m3 and n3 independently represent an
integer of 1 to 15; R.sub.50 to R.sub.65 are independently selected
from H, --CH.sub.3 and a halogen atom; and A.sub.3 is selected from
a covalent bond, --CH.sub.2--, --CH(CH.sub.3)--,
--C(CH.sub.3).sub.2--, --O--, --S--, --SO.sub.2-- and a carbonyl
group;
[0059] According to the present disclosure, the second
vinyl-containing polyphenylene oxide resin has a number average
molecular weight of between 1600 and 3500, such as between 1800 and
3000. In addition, in one embodiment, the second vinyl-containing
polyphenylene oxide resin may comprise a structure of Formula
(1-2):
##STR00006## [0060] wherein b2 is a natural number of 0 to 8;
[0061] X.sub.2 comprises a structure of Formula (2) to Formula (4)
or a combination thereof:
[0061] ##STR00007## [0062] Y.sub.3 and Y.sub.4 individually
comprise a structure of Formula (5-2):
[0062] ##STR00008## [0063] wherein m2 and n2 independently
represent an integer of 1 to 30, such as 1, 5, 10, 15, 20, 25 or
30; R.sub.24 to R.sub.39 are independently selected from H,
--CH.sub.3 and a halogen atom (e.g., chlorine, bromine, or iodine);
A.sub.2 is selected from a covalent bond, --CH.sub.2--,
--CH(CH.sub.3)--, --C(CH.sub.3).sub.2--, --O--, --S--, --SO.sub.2--
and a carbonyl group; [0064] Z.sub.3 and Z.sub.4 individually
comprise a structure of Formula (6-2), Formula (6-3) or Formula
(6-4):
[0064] ##STR00009## [0065] wherein R.sub.40 to R.sub.49 are
individually selected from H, --CH.sub.3 or a halogen atom, and
W.sub.2 and Q are individually a C.sub.1 to C.sub.3 bivalent
aliphatic group (e.g., methylene, ethylene, or propylene).
[0066] In one embodiment, in addition to the first vinyl-containing
polyphenylene oxide resin (and/or a prepolymer thereof) and the
second vinyl-containing polyphenylene oxide resin (or a prepolymer
thereof), the resin composition disclosed herein may further
comprise the following component as a crosslinking agent: an epoxy
resin, another polyphenylene oxide resin, a cyanate ester resin, a
small molecule vinyl compound, a maleimide resin, an acrylate, a
phenolic resin, a benzoxazine resin, a styrene maleic anhydride, a
polyolefin, a polyester resin, an amine curing agent, a polyamide
resin, a polyimide resin or a combination thereof. Examples of the
cyanate ester resin, small molecule vinyl compound, maleimide
resin, acrylate and polyolefin are as described above.
[0067] Amount of the aforesaid crosslinking agent is not
particularly limited; for example, relative to a total of 60 parts
by weight of the first vinyl-containing polyphenylene oxide resin
(and/or a prepolymer thereof) and the second vinyl-containing
polyphenylene oxide resin (or a prepolymer thereof), one or more of
the crosslinking agents above may be used at an amount of 1 to 200
parts by weight, preferably 5 to 150 parts by weight, more
preferably 10 to 100 parts by weight and even more preferably 10 to
50 parts by weight. The total amount of the crosslinking agent(s)
may be 1 to 200 parts by weight, preferably 5 to 150 parts by
weight, more preferably 10 to 100 parts by weight, and even more
preferably 20 to 80 parts by weight.
[0068] For example, the epoxy resin may be any epoxy resins known
in the field to which this disclosure pertains, including but not
limited to bisphenol A epoxy resin, bisphenol F epoxy resin,
bisphenol S epoxy resin, bisphenol AD epoxy resin, novolac epoxy
resin, trifunctional epoxy resin, tetrafunctional epoxy resin,
multifunctional novolac epoxy resin, dicyclopentadiene (DCPD) epoxy
resin, phosphorus-containing epoxy resin, p-xylene epoxy resin,
naphthalene epoxy resin (e.g., naphthol epoxy resin), benzofuran
epoxy resin, isocyanate-modified epoxy resin, or a combination
thereof. The novolac epoxy resin may be phenol novolac epoxy resin,
bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin,
biphenyl novolac epoxy resin, phenol benzaldehyde epoxy resin,
phenol aralkyl novolac epoxy resin or o-cresol novolac epoxy resin,
wherein the phosphorus-containing epoxy resin may be DOPO
(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin,
DOPO-HQ epoxy resin or a combination thereof. The DOPO epoxy resin
may be any one or more selected from DOPO-containing phenolic
novolac epoxy resin, DOPO-containing cresol novolac epoxy resin and
DOPO-containing bisphenol-A novolac epoxy resin; the DOPO-HQ epoxy
resin may be any one or more selected from DOPO-HQ-containing
phenolic novolac epoxy resin, DOPO-HQ-containing cresol novolac
epoxy resin and DOPO-HQ-containing bisphenol-A novolac epoxy
resin.
[0069] For example, as a crosslinking agent, the aforesaid another
polyphenylene oxide resin may comprise, other than the first
vinyl-containing polyphenylene oxide resin and the second
vinyl-containing polyphenylene oxide resin, another polyphenylene
oxide resin, such as a maleimide-terminated polyphenylene oxide
resin, an anhydride-terminated polyphenylene oxide resin, a
cyanate-terminated polyphenylene oxide resin or a
hydroxyl-terminated polyphenylene oxide resin. For example, unless
otherwise specified, the polyphenylene oxide resin used in the
present disclosure is not particularly limited and may be any
commercial product, product synthesized by Applicant or a
combination thereof.
[0070] For example, the phenolic resin may comprise but not limited
to mono-functional, bifunctional or multifunctional phenolic resin,
comprising phenolic resin of a resin composition conventionally
used for making prepregs, such as phenoxy resin, phenol novolac
resin, etc.
[0071] For example, the benzoxazine resin includes, but not limited
to, bisphenol A benzoxazine resin, bisphenol F benzoxazine resin,
phenolphthalein benzoxazine resin, dicyclopentadiene benzoxazine
resin, phosphorus-containing benzoxazine resin, oxydianiline
benzoxazine resin, or unsaturated bond-containing benzoxazine
resin, such as but not limited to LZ-8270, LZ-8280, LZ-8290 or
LZ-8298 available from Huntsman, HFB-2006M available from Showa
High Polymer, or KZH-5031 available from Kolon Industries Inc.
[0072] For example, in the styrene maleic anhydride, the ratio of
styrene (S) and maleic anhydride (MA) may be for example 1/1, 2/1,
3/1, 4/1, 6/1, 8/1 or 12/1, including styrene maleic anhydride
copolymers such as SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40,
EF-60 and EF-80 available from Cray Valley.
[0073] For example, the polyester resin may be prepared by
esterification of dicarboxylic aromatic compounds with dihydroxyl
aromatic compounds. Examples include, but not limited to, HPC-8000,
HPC-8150 or HPC-8200 available from D.I.C. Corporation.
[0074] For example, the amine curing agent may include, but not
limited to, any one or a combination of diamino diphenyl sulfone,
diamino diphenyl methane, diamino diphenyl ether, diamino diphenyl
sulfide and dicyandiamide (DICY).
[0075] For example, the polyamide resin may be any polyamide resin
known in the field to which this disclosure pertains, including but
not limited to various commercially available polyamide resin
products.
[0076] For example, the polyimide resin may be any polyimide resin
known in the field to which this disclosure pertains, including but
not limited to various commercially available polyimide resin
products.
[0077] In addition, the resin composition may optionally further
comprise: flame retardant, inorganic filler, curing accelerator,
solvent, silane coupling agent, coloring agent, toughening agent or
a combination thereof.
[0078] The flame retardant used herein may be any one or more flame
retardants used for preparing a prepreg, a resin film, a resin film
with copper foil, a laminate or a printed circuit board; examples
of the flame retardant include but are not limited to
phosphorus-containing flame retardant, preferably any one, two or
more selected from the following group: ammonium polyphosphate,
hydroquinone bis-(diphenyl phosphate), bisphenol A
bis-(diphenylphosphate), tri(2-carboxyethyl) phosphine (TCEP),
phosphoric acid tris(chloroisopropyl) ester, trimethyl phosphate
(TMP), dimethyl methyl phosphonate (DMMP), resorcinol bis(dixylenyl
phosphate) (RDXP, such as commercially available PX-200, PX-201,
and PX-202), phosphazene (such as commercially available SPB-100,
SPH-100, and SPV-100), melamine polyphosphate, DOPO and its
derivatives or resins, DPPO (diphenylphosphine oxide) and its
derivatives or resins, melamine cyanurate, tri-hydroxy ethyl
isocyanurate and aluminium phosphinate (e.g., commercially
available OP-930 and OP-935).
[0079] For example, the flame retardant may be a DPPO compound
(e.g., di-DPPO compound), a DOPO compound (e.g., di-DOPO compound),
a DOPO resin (e.g., DOPO-HQ, DOPO-NQ, DOPO-PN, and DOPO-BPN) and a
DOPO-containing epoxy resin, wherein DOPO-PN is a DOPO phenol
novolac compound, and DOPO-BPN may be a bisphenol novolac compound,
such as DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN
(DOPO-bisphenol F novolac) and DOPO-BPSN (DOPO-bisphenol S
novolac).
[0080] For example, the inorganic filler may be any one or more
inorganic fillers used for preparing a prepreg, a resin film, a
resin film with copper foil, a laminate or a printed circuit board;
examples of inorganic filler include but are not limited to silica
(fused, non-fused, porous or hollow type), aluminum oxide, aluminum
hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate,
aluminum nitride, boron nitride, aluminum silicon carbide, silicon
carbide, titanium dioxide, zinc oxide, zirconium oxide, mica,
boehmite (AlOOH), calcined talc, talc, silicon nitride and calcined
kaolin. Moreover, the inorganic filler can be spherical, fibrous,
plate-like, particulate, sheet-like or whisker-like in shape and
can be optionally pretreated by a silane coupling agent.
[0081] For example, the curing accelerator (including curing
initiator) may comprise a catalyst, such as a Lewis base or a Lewis
acid. The Lewis base may comprise any one or more of imidazole,
boron trifluoride-amine complex, ethyltriphenyl phosphonium
chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ),
2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP) and
4-dimethylaminopyridine (DMAP). The Lewis acid may comprise metal
salt compounds, such as those of manganese, iron, cobalt, nickel,
copper and zinc, such as zinc octanoate or cobalt octanoate. The
curing accelerator also includes a curing initiator, such as a
peroxide capable of producing free radicals, examples of curing
initiator including but not limited to dicumyl peroxide, tert-butyl
peroxybenzoate, dibenzoyl peroxide (BPO),
2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B),
bis(tert-butylperoxyisopropyl)benzene or a combination thereof.
[0082] For example, the solvent may comprise, but not limited to,
methanol, ethanol, ethylene glycol monomethyl ether, acetone,
butanone (methyl ethyl ketone), methyl isobutyl ketone,
cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl
acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide,
dimethylacetamide, propylene glycol methyl ether, or a mixture
thereof.
[0083] For example, the silane coupling agent may comprise silane
(such as but not limited to siloxane) and may be further
categorized according to the functional groups into amino silane,
epoxide silane, vinyl silane, acrylate silane, methacrylate silane,
hydroxyl silane, isocyanate silane, methacryloxy silane and
acryloxy silane.
[0084] For example, the coloring agent may comprise but not limited
to dye or pigment.
[0085] The purpose of adding toughening agent is to improve the
toughness of the resin composition. The toughening agent may
comprise, but not limited to, rubber resin, carboxyl-terminated
butadiene acrylonitrile rubber (CTBN rubber), core-shell rubber, or
a combination thereof.
[0086] The resin compositions of various embodiments may be used
for making different articles, including but not limited to a
prepreg, a resin film, a resin film with copper foil, a laminate or
a printed circuit board.
[0087] For example, the resin composition according to each of the
various embodiments may be coated on a polyester (PET) film or a
polyimide (PI) film, followed by baking and heating to the
semi-cured state (B-Stage) to obtain a resin film.
[0088] For example, the resin composition according to each of the
various embodiments may be coated on a copper foil, followed by
baking and heating to the semi-cured state to obtain the resin film
with copper foil, such as a resin coated copper (RCC).
[0089] For example, the resin composition according to each of the
various embodiments may be used to make a prepreg, which has a
reinforcement material and a layered structure (e.g., insulation
layer) formed thereon, wherein the layered structure is made by
heating the resin composition to a semi-cured state (B-Stage) at a
temperature for example between 120.degree. C. and 160.degree. C.
For example, the reinforcement material may be any one of a fiber
material, woven fabric, and non-woven fabric, and the woven fabric
preferably comprises fiberglass fabrics. Types of fiberglass
fabrics are not particularly limited and may be any commercial
fiberglass fabric used for various printed circuit boards, such as
E-glass fabric, D-glass fabric, S-glass fabric, T-glass fabric,
L-glass fabric or Q-glass fabric, wherein the fiber may comprise
yarns and rovings, in spread form or standard form. Non-woven
fabric preferably comprises liquid crystal polymer non-woven
fabric, such as polyester non-woven fabric, polyurethane non-woven
fabric and so on, but not limited thereto. Woven fabric may also
comprise liquid crystal polymer woven fabric, such as polyester
woven fabric, polyurethane woven fabric and so on, but not limited
thereto. The reinforcement material may increase the mechanical
strength of the prepreg. In one preferred embodiment, the
reinforcement material can be optionally pre-treated by a silane
coupling agent. The prepreg may be further heated and cured to the
C-stage to form an insulation layer.
[0090] For example, resin compositions of various embodiments of
the present disclosure may be made into a laminate, such as a
copper-clad laminate, which comprises two copper foils and an
insulation layer disposed between the copper foils, wherein the
insulation layer is made by curing the resin compositions at high
temperature and high pressure, a suitable curing temperature being
for example between 190.degree. C. and 220.degree. C. and
preferably between 200.degree. C. and 215.degree. C. and a suitable
curing time being 90 to 180 minutes and preferably 110 to 150
minutes. The insulation layer may be obtained by curing the
aforesaid prepreg, resin film with copper foil or resin film. In
one preferred embodiment, the laminate is a copper-clad
laminate.
[0091] In one embodiment, the laminate may be further processed by
trace formation processes to provide a printed circuit board.
[0092] The resin composition according to the present disclosure
has one or more preferred properties including lower coefficient of
thermal expansion, better dimensional stability, better interlayer
bonding strength, better T288 thermal resistance, etc.
[0093] For example, the resin composition according to the present
disclosure may achieve one, more or all of the following
properties: [0094] a coefficient of thermal expansion of less than
35.0 ppm/.degree. C. as measured with a thermomechanical analyzer
by reference to IPC-TM-650 2.4.24.5, such as between 25.0
ppm/.degree. C. and 35.0 ppm/.degree. C., between 26.0 ppm/.degree.
C. and 34.0 ppm/.degree. C. or between 26.0 ppm/.degree. C. and
32.0 ppm/.degree. C.; [0095] a T288 thermal resistance as measured
by reference to IPC-TM-650 2.4.24.1 of greater than or equal to 70
minutes, such as greater than or equal to 90 minutes, 120 minutes,
150 minutes, 180 minutes, or 240 minutes; [0096] an interlayer
bonding strength as measured by reference to IPC-TM-650 2.4.8 of
greater than or equal to 2.85 lb/in, such as between 2.85 lb/in and
3.20 lb/in; and [0097] a Z-axis dimensional change ratio as
measured by reference to IPC-TM-650 2.4.24.5 of less than or equal
to 1.80%, such as between 1.30% and 1.80%.
[0098] Specifically, the resin compositions according to the
present disclosure and articles made therefrom may achieve one,
more or all of the following features: [0099] by using a first
vinyl-containing polyphenylene oxide resin with a number average
molecular weight of 500-1500 in conjunction with a second
vinyl-containing polyphenylene oxide resin with a number average
molecular weight of 1600-3500, in contrast to the use of a single
polyphenylene oxide resin with a number average molecular weight of
500-1500 (e.g., a vinylbenzyl-containing polyphenylene oxide
resin), laminates made from the resin composition according to the
present disclosure have better (lower) coefficient of thermal
expansion, higher interlayer bonding strength and better T288
thermal resistance; [0100] by using a first vinyl-containing
polyphenylene oxide resin with a number average molecular weight of
500-1500 in conjunction with a second vinyl-containing
polyphenylene oxide resin with a number average molecular weight of
1600-3500, in contrast to the use of a single polyphenylene oxide
resin with a number average molecular weight of 1600-3500 (e.g., a
vinylbenzyl-containing polyphenylene oxide resin or a methyl
methacrylate-containing polyphenylene oxide resin), laminates made
from the resin composition according to the present disclosure have
better (lower) coefficient of thermal expansion, better (lower)
dimensional change ratio and better T288 thermal resistance; and
[0101] the combination of a first vinyl-containing polyphenylene
oxide resin with a number average molecular weight of 500-1500 and
a second vinyl-containing polyphenylene oxide resin with a number
average molecular weight of 1600-3500 according to the present
disclosure unexpectedly achieves better (lower) coefficient of
thermal expansion, better (lower) dimensional change ratio, higher
interlayer bonding strength, and better T288 thermal
resistance.
[0102] Materials and reagents used in Preparation Examples,
Examples and Comparative Examples disclosed herein are listed
below: [0103] OPE-2st 1200: vinylbenzyl-terminated polyphenylene
oxide resin with a number average molecular weight (Mn) of about
1200 (used as a first vinyl-containing polyphenylene oxide resin),
available from Mitsubishi Gas Chemical Co., Inc.; [0104] OPE-2st
2200: vinylbenzyl-terminated polyphenylene oxide resin with a
number average molecular weight (Mn) of about 2200 (used as a
second vinyl-containing polyphenylene oxide resin), available from
Mitsubishi Gas Chemical Co., Inc.; [0105] SA-9000:
methacrylate-terminated polyphenylene oxide resin with a number
average molecular weight (Mn) of about 1900-2300 (used as a second
vinyl-containing polyphenylene oxide resin), available from SABIC;
[0106] TAIC: triallyl isocyanurate, available from Sigma Aldrich;
[0107] BA-230S: bisphenol A type cyanate ester resin (BPA-CE),
available from LONZA; [0108] BPO: benzoyl peroxide, available from
NOF Corporation; [0109] BMI-5100:
3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide,
available from Daiwakasei Industry Co., Ltd.; [0110] 25B:
2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, available from NOF
Corporation; SC-2500-SMJ: spherical silica pre-treated by
methacrylate silane coupling agent, available from Admatechs;
[0111] Toluene: available from Chambeco Group. [0112] MEK: methyl
ethyl ketone, source not limited.
Prepolymer Preparation Example 1
[0113] 30 parts by weight of OPE-2st 1200, 20 parts by weight of
BA-230S, 10 parts by weight of TAIC and 0.3 part by weight of BPO
were added to 40 parts by weight of methyl ethyl ketone solvent,
stirred in a stirred tank until the powders were fully dissolved
and then gradually heated to a temperature of 85.degree. C., and
stirred for another 4 hours so as to obtain a solution which was
subject to purification to obtain a prepolymer P1 of the first
vinyl-containing polyphenylene oxide resin.
Prepolymer Preparation Example 2
[0114] 50 parts by weight of OPE-2st 1200, 20 parts by weight of
BA-230S, 10 parts by weight of TAIC and 0.3 part by weight of BPO
were added to 40 parts by weight of methyl ethyl ketone solvent,
stirred in a stirred tank until the powders were fully dissolved
and then gradually heated to a temperature of 85.degree. C., and
stirred for another 4 hours so as to obtain a solution which was
subject to purification to obtain a prepolymer P2 of the first
vinyl-containing polyphenylene oxide resin.
Prepolymer Preparation Example 3
[0115] 30 parts by weight of OPE-2st 2200, 20 parts by weight of
BA-230S, 10 parts by weight of TAIC and 0.3 part by weight of BPO
were added to 40 parts by weight of methyl ethyl ketone solvent,
stirred in a stirred tank until the powders were fully dissolved
and then gradually heated to a temperature of 85.degree. C., and
stirred for another 4 hours so as to obtain a solution which was
subject to purification to obtain a prepolymer P3 of the second
vinyl-containing polyphenylene oxide resin.
[0116] Samples (specimens) were prepared as described below and
tested and analyzed under specified conditions below. [0117] 1.
Prepreg: Resin composition from each Example and each Comparative
Example (in part by weight) was separately well-mixed to form a
varnish, which was then loaded to an impregnation tank; a
fiberglass fabric (e.g., 2116 E-glass fiber fabric, available from
Asahi) was impregnated into the impregnation tank to adhere the
resin composition onto the fiberglass fabric, followed by heating
and baking at 130.degree. C. for about 4 minutes to obtain a
prepreg. [0118] 2. Copper-containing laminate (e.g., copper-clad
laminate, 5-ply, formed by lamination of five prepregs): Two 18
.mu.m RTF (reverse-treated foils) copper foils and five prepregs
obtained from 2116 E-glass fiber fabrics impregnated with each
Example or Comparative Example and having a resin content of about
55% were prepared and stacked in the order of one copper foil, five
prepregs and one copper foil, followed by lamination under vacuum
at 30 kgf/cm.sup.2 pressure and 200.degree. C. for 120 minutes to
form a copper-containing laminate. Insulation layers were formed by
laminating five sheets of prepreg between the two copper foils, and
the resin content of the insulation layers is about 55%. [0119] 3.
Copper-free laminate (5-ply, formed by lamination of five
prepregs): Each aforesaid copper-containing laminate (5-ply) was
etched to remove the two copper foils to obtain a copper-free
laminate (5-ply) formed by laminating five sheets of prepreg and
having a resin content of about 55%.
[0120] Test items and test methods are described below.
[0121] Coefficient of Thermal Expansion (CTE)
[0122] The copper-free laminate (obtained by laminating five
prepregs) specimen was subject to coefficient of thermal expansion
(Z-axis) measurement. A thermomechanical analyzer (TMA) was used
for measurement (unit: ppm/.degree. C.) by reference to IPC-TM-650
2.4.24.5 at a temperature range from 50.degree. C. to 110.degree.
C. at an increase rate of 10.degree. C./minute. Lower coefficient
of thermal expansion represents lower expansion of the specimen
under heat, indicating the resin composition may have a better
property when being used for a printed circuit board. Lower
coefficient of thermal expansion is more preferred; in general, a
difference of 0.1 ppm/.degree. C. in the coefficient of thermal
expansion represents a significant difference.
[0123] Dimensional Change Ratio (or Thermal Expansion Ratio)
[0124] The copper-free laminate (obtained by laminating five
prepregs) specimen was subject to thermomechanical analysis (TMA)
during dimensional change ratio measurement. Each specimen was
heated from 50.degree. C. to 260.degree. C. at an increase rate of
10.degree. C./minute and then subject to the measurement of
dimensional change ratio (%) in Z-axis by reference IPC-TM-650
2.4.24.5, wherein lower dimensional change ratio (%) is more
preferred, and in general a difference of greater than or equal to
0.1% represents significant difference.
[0125] Interlayer Bonding Strength
[0126] The copper-containing laminate (obtained by laminating five
prepregs) was cut into a rectangle with a width of 12.7 mm and a
length of greater than 60 mm and tested by using a tensile strength
tester by reference to IPC-TM-650 2.4.8 with the proviso that the
surface copper foil was not etched off and the measurement position
was set at the interface between the second prepreg layer and the
third prepreg layer; under room temperature (about 25.degree. C.),
the cured insulation laminate was tested to measure the force
(lb/in) required to separate the two layers. In general, a
difference in interlayer bonding strength of greater than 0.1 lb/in
represents a significant difference.
[0127] T288 Thermal Resistance
[0128] The copper-containing laminate (obtained by laminating five
prepregs) specimen was used in the T288 thermal resistance test. At
a constant temperature of 288.degree. C., a thermomechanical
analyzer (TMA) was used by reference to IPC-TM-650 2.4.24.1 "Time
to Delamination (TMA Method)" to measure each specimen and record
the time to delamination.
[0129] Compositions and test results of Examples and Comparative
Examples are listed in Table 1 to Table 3.
TABLE-US-00001 TABLE 1 Resin compositions of Examples (in part by
weight) and test results component name E1 E2 E3 E4 E5 E6 E7 first
vinyl-containing PPO OPE-2st 1200 30 20 50 10 55 second
vinyl-containing PPO OPE-2st 2200 30 20 10 50 30 10 5 prepolymer P1
60 P2 80 P3 methacrylate-containing PPO SA-9000 20 TAIC TAIC 10 10
10 10 10 BPA-CE BA-230S 20 20 20 20 20 BMI BMI-5100 20 20 20 20 20
20 20 peroxide 25B 1 1 1 1 1 1 1 fused silica SC-2500-SMJ 110 110
110 110 110 110 110 solvent toluene 30 30 30 30 30 30 30 MEK 50 50
50 50 50 50 50 property unit E1 E2 E3 E4 E5 E6 E7 CTE (Z-axis)
ppm/.degree. C. 28.5 29.3 30.1 31.5 24.7 25.3 31.2 dimensional
change ratio % 1.48 1.51 1.64 1.78 1.31 1.35 1.68 (Z-axis)
interlayer bonding strength lb/in 3.05 2.97 2.99 3.03 3.14 3.10
2.89 T288 thermal resistance minute >70 >70 >70 >70
>70 >70 68
TABLE-US-00002 TABLE 2 Resin compositions of Examples (in part by
weight) and test results component name E8 E9 E10 E11 E12 E13 first
vinyl-containing PPO OPE-2st 1200 5 30 30 35 30 15 second
vinyl-containing PPO OPE-2st 2200 55 30 15 30 prepolymer P1 30 P2
P3 60 methacrylate-containing PPO SA-9000 30 10 TAIC TAIC 10 10 10
10 5 BPA-CE BA-230S 20 20 20 10 BMI BMI-5100 20 20 20 20 20 20
peroxide 25B 1 1 1 1 1 1 fused silica SC-2500-SMJ 110 110 110 110
110 110 solvent toluene 30 30 30 30 30 30 MEK 50 50 50 50 50 50
property unit E8 E9 E10 E11 E12 E13 CTE (Z-axis) ppm/.degree. C.
33.4 29.2 29.8 28.8 31.2 25.7 dimensional change ratio % 1.80 1.59
1.54 1.41 1.68 1.40 (Z-axis) interlayer bonding strength lb/in 2.95
3.07 2.98 3.07 2.99 3.07 T288 thermal resistance minute 63 >70
>70 >70 >70 >70
TABLE-US-00003 TABLE 3 Resin compositions of Comparative Examples
(in part by weight) and test results component name C1 C2 C3 C4 C5
C6 C7 first vinyl-containing PPO OPE-2st 1200 60 second
vinyl-containing PPO OPE-2st 2200 60 30 30 50 prepolymer P1 P2 P3
methacrylate-containing PPO SA-9000 60 30 30 10 TAIC TAIC 10 10 10
10 10 10 10 BPA-CE BA-230S 20 20 20 20 20 20 BMI BMI-5100 20 20 20
20 20 20 20 peroxide 25B 1 1 1 1 1 1 1 fused silica SC-2500-SMJ 110
110 110 110 110 110 110 solvent toluene 30 30 30 30 30 30 30 MEK 50
50 50 50 50 50 50 property unit C1 C2 C3 C4 C5 C6 C7 CTE (Z-axis)
ppm/.degree. C. 35.7 40.0 41.1 37.8 39.2 40.3 38.8 dimensional
change ratio % 1.77 1.95 2.11 1.55 2.01 2.04 1.99 (Z-axis)
interlayer bonding strength lb/in 2.77 2.91 2.81 2.55 2.86 2.75
2.88 T288 thermal resistance minute 66 62 63 >70 65 64 62
[0130] The following observations can be made according to the test
results above.
[0131] Comparison of Examples E1 to E4 and E7 to Ell with
Comparative Examples C1 to C4 indicates that the combination of a
first vinyl-containing polyphenylene oxide resin and a second
vinyl-containing polyphenylene oxide resin in the resin
composition, relative to the use of only one or absence of
vinyl-containing polyphenylene oxide resin in the resin
composition, achieves lower coefficient of thermal expansion, lower
dimensional change ratio, and higher interlayer bonding
strength.
[0132] Comparison of Examples E1 to E4 and E7 to Ell with
Comparative Examples C5 to C7, which contain two different
vinyl-containing polyphenylene oxide resins, indicates that the
combination of a first vinyl-containing polyphenylene oxide resin
and a second vinyl-containing polyphenylene oxide resin according
to the present disclosure in the resin composition, relative to the
use of two different second vinyl-containing polyphenylene oxide
resins in the resin composition, achieves lower coefficient of
thermal expansion, lower dimensional change ratio, higher
interlayer bonding strength and better T288 thermal resistance.
[0133] On the other hand, comparison of Examples E1 to E4 with E7
and E8 indicates that the use of 10 to 50 parts by weight of the
first vinyl-containing polyphenylene oxide resin and 10 to 50 parts
by weight of the second vinyl-containing polyphenylene oxide resin
in the resin composition, relative to other greater or less use
amount, may achieve higher interlayer bonding strength and better
T288 thermal resistance.
[0134] Moreover, by contrast between Examples E5 and E1 and between
Examples E6 and E3, it can be observed that the use of a prepolymer
of the first vinyl-containing polyphenylene oxide resin, relative
to a non-prepolymerized first vinyl-containing polyphenylene oxide
resin, achieves lower coefficient of thermal expansion, lower
dimensional change ratio, and higher interlayer bonding
strength.
[0135] The above detailed description is merely illustrative in
nature and is not intended to limit the embodiments of the subject
matter or the application and uses of such embodiments. As used
herein, the term "exemplary" means "serving as an example,
instance, or illustration." Any implementation described herein as
exemplary is not necessarily to be construed as preferred or
advantageous over other implementations.
[0136] Moreover, while at least one exemplary example or
comparative example has been presented in the foregoing detailed
description, it should be appreciated that a vast number of
variations exist. It should also be appreciated that the exemplary
one or more embodiments described herein are not intended to limit
the scope, applicability, or configuration of the claimed subject
matter in any way. Rather, the foregoing detailed description will
provide those skilled in the art with a convenient guide for
implementing the described one or more embodiments. Also, various
changes can be made in the function and arrangement of elements
without departing from the scope defined by the claims, which
include known equivalents and foreseeable equivalents at the time
of filing this patent application.
* * * * *