JPH09187884 | ORGANIC COMPOSITE COATED STEEL PLATE |
JPH1077391 | RESIN COMPOSITION FOR REFRIGERATING-MACHINE MOTOR |
WO/2010/144971 | SELF HEALING POLYMER MATERIALS |
KIM DO-HYUN (KR)
LEE JAE-WON (KR)
KIM YOUNG-IL (KR)
JEONG SEON-ROON (KR)
KIM DO-HYUN (KR)
LEE JAE-WON (KR)
KIM YOUNG-IL (KR)
US6342577B1 | 2002-01-29 | |||
US20020106515A1 | 2002-08-08 | |||
US6180696B1 | 2001-01-30 | |||
US20020142167A1 | 2002-10-03 |
[CLAIMS]
[Claim 1]
An epoxy resin composition comprising :
100 parts by weight of an epoxy resin which is a liquid phase at room
temperature and has 2 or more glycidyl groups in a molecule;
10-50 parts by weight of a reactive diluent having one or more glycidyl groups
in a molecule;
50-200 parts by weight of an anhydride curing agent which is a liquid phase at
room temperature with respect to 100 parts by weight of the epoxy resin and the
reactive diluent; and
1-20 parts by weight of a latent curing accelerator with respect to 100 parts by
weight of the epoxy resin, the reactive diluent, and the anhydride curing agent,
wherein a viscosity of the epoxy composition at 25 ° C is 250-500cps and
gelation time at 150 ° C is 120 seconds or below.
[Claim 2]
The epoxy resin composition of claim 1 , wherein the epoxy resin is selected
from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy
resin and mixtures thereof. [Claim 3]
The epoxy resin composition of claim 1, wherein the reactive diluent has one
glycidyl goup in a molecure.
[Claim 4]
The epoxy resin composition of claim 1, wherein the anhydride curing agent is
produced by reaction of a triene or a diene with an anhydrous maleic acid.
[Claim 5]
The epoxy resin composition of claim 1 , wherein the latent curing accelerator
is micro-capsulated compound that is selected from the group consisting of amine
compounds, imidazole compounds, modified amine compounds and modified imidazole
compounds. |
[DESCRIPTION]
[Invention Title]
EPOXY RESIN COMPOSITION
[Technical Field]
The present invention relates to an epoxy resin composition, in particular, to an
epoxy resin composition suitable for use as an encapsulant for electrical parts such as
driver-ICs mounted on a circuit board.
[Background Art]
Recently, in response to the trends of miniaturized, light-weighted and slim
electrical/electronic devices such as cellular phones, notebook computers and wall
hanging TVs, flat panel displays such as LCD display, plasma display,
electroluminescent(EL) device have been mainly used for image display devices, and
the miniaturization of driver-IC(Integrated Circuit) that drives these electric components
is required. Serial steps to mount bare chips like driver- IC on a circuit board are referred
to as packaging. As for the packaging method, the tape carrier package (TCP) process
which includes forming circuits on a polyimide film, mounting a bare chip, turning the
bare chip downward and injecting a resin into a hole of the circuit board, was used
previously.
[Disclosure]
[Technical Problem]
However, the TCP process has shortcomings that the package components have
low flexibility and has limitation to reduce weight, thickness, length and size of the
package components, because after processing a circuit board where a thick polyimide
film and copper foil are attached by an epoxy-based adhesive, the chip was mounted on
the circuit board.
To address this problem, a COF(CMp On Film) underfill process that includes
forming an insulating film having superior flexibility by coating a thin polyimide on the
upper portion of a thin copper foil or sputtering copper layer on the surface of thin
polyimide film, producing a flexible circuit board by forming a lead wiring on the
insulating film, mounting a bare chip on the flexible circuit board, filling the gap
between the board and the bare chip with resin has been developed and is used recently.
In such a COF process, since the gap between the board and the bare chip is less than
several tens of micrometers, there is a problem that the existing resin for TCP process
including a large amount of inorganic fillers and solvents can not be directly applied to
the COF underfill process. Further, because the gap between the board and the bare chip
is narrowed down to 10 um and the size of the chip is getting larger, needs for
encapsulation composition which has better Suability and is uniformly cured is on the
πse.
[Technical solution]
Therefore, the present invention provides an epoxy resin composition which
has better penetrability and underfill ability into the gap between a board and a bare
chip, and which can be uniformly cured over the whole surface area of the chip. The
present invention further provides an epoxy resin composition having superior
productivity achieved by short thermosetting time, and excellent workability achieved
by forming less bubbles and volatile components. The invention further provides an
epoxy resin composition, not only having superior fillet forming ability and adhesion so
that it firmly connects a circuit board and a bare chip, but also having superior
temperature cycling ability and properties under high temperature and high humidity, so
that it can produce chip packages having high reliability.
To achieve the objectives, the present invention provides an epoxy composition
which is a liquid phase at room temperature and includes 100 parts by weight of an
epoxy resin having 2 or more glycidyl groups in the molecule, 10-50 parts by weight of
a reactive diluent having one or more glycidyl groups in the molecule, 50-200 parts by
weight of an anhydride curing agent which is a liquid phase at room temperature with
respect to 100 parts by weight of the epoxy resin and the reactive diluent, and 1-20 parts
by weight of a latent curing accelerator with respect to 100 parts by weight of the epoxy
resin, the reactive diluent, and the anhydrous curing agent, and whose viscosity at 25 °C
is 250-500cps, gelation time at 150 ° C is 120 seconds or below.
Hereinafter, more detailed descriptions will be given.
The inventors completed this invention by controlling the gelation time and
viscosity of a composition by adjusting components and contents of an epoxy resin
composition as a result of broad researches for an epoxy resin composition which is
useful for an underfill composition of the COF process. Main components of the epoxy
resin composition according to the invention include an epoxy resin, a reactive diluent,
an anhydrous curing agent and a latent curing accelerator.
The epoxy resin used in the invention, which is liquid at room temperature, has
2 or more glycidyl groups in a molecule, and a variety of curable epoxy resins may be
used, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin may be
used individually or together with. Specific examples of the bisphenol A type(diglycidyl
ether) epoxy resin include EpikoteYL-980(JAPAN EPOXY RESIN CO. LTD.), RE-
310(NIPPON KAYAKU CO. LTD.), DER-332(The Dow Chemical Company), etc., and
specific examples of the bisphenol F type(diglycidyl ether) epoxy resin include Epikote
YL-983U(JAPAN EPOXY RESIN CO. LTD.), RE-304(NIPPON KAYAKU CO. LTD.),
RE-404(NIPPON KAYAKU CO. LTD.), RE-303S(NIPPON KAYAKU CO. LTD.), etc.
The reactive diluent used in the invention functions to decrease viscosity of the
composition, a variety of compounds having one or more glycidyl groups in the
molecule may be used, for example, alkyl monoglycidyl ether, butyl phenyl glycidyl
ether, alkyl phenol monoglycidyl ether, polyglycol diglycidyl ether, alkyl diglycidyl
ether, etc. may be used individually or together with. Here, the carbon number of the
alkyl group is preferably 1-10, more preferably 1-4. Specific examples of mono-
functional reactive diluent having one glycidyl group in the molecule include YED-
11 IE(JAPAN EPOXY RESIN CO. LTD.), YED- 122(JAPAN EPOXY RESIN CO.
LTD.), ED-SOI(ADEKA CORPORATION), ED-502(ADEKA CORPORATION), ED-
509S(ADEKA CORPORATION), ED-529(ADEKA CORPORATION), ED-
518(ADEKA CORPORATION), etc., specific examples of di-functional reactive diluent
having two glycidyl groups in the molecule include YED-216(JAPAN EPOXY RESIN
CO. LTD.), ED-503(ADEKA CORPORATION), ED-506(ADEKA CORPORATION),
ED-523T(ADEKA CORPORATION), ED-515(ADEKA CORPORATION), etc.,
specific examples of multi-functional reactive diluent include YED-205(JAPAN
EPOXY RESIN CO. LTD.), ED-505R(ADEKA CORPORATION), etc. The amount of
the reactive diluent is preferably added by 10-50 parts by weight with respect to 100
pars by weight of the epoxy resin, more preferably 20-40 parts by weight. If the reactive
diluent is added by less than 10 parts by weight, viscosity of the composition may not
decrease sufficiently, if more than 50 parts by weight, glass transition temperature(Tg)
and mechanical property of the composition may be deteriorated.
The anhydride curing agent is what reacts with the epoxy resin and cures, so
that the viscosity of the epoxy resin composition becomes 250-500cps, it is preferable
that a liquid phase anhydride curing agent be used, among them, an anhydride curing
agent that generates less carbon dioxide during the curing, for example, an anhydride
curing agent produced by reaction of triene or diene of C 10 with anhydride maleic acid,
is preferable. Specific examples of the anhydride curing agent are 3,4-dimethyl-6-(2-
methyl-l-prophenyl)-4-cyclohexene-l,2-dicarboxylic acid anhydride or its mixture with
l-isopropyl-4-methylbicyclo[2.2.2]octa-5-ene-2,3-dicarbox ylic anhydride. YH-
306(JAPAN EPOXY RESIN CO. LTD.), YH-307(JAPAN EPOXY RESIN CO. LTD.) is
commercially available. Appropriate adding amount of the anhydride curing agent is 50-
200 parts by weight with respect to 100 parts by weight of the epoxy resin and the
reactive diluent, preferably, 100-150 parts by weight. If the anhydride curing agent is
added by less than 50 parts by weight or more than 200 parts by weight, unreacted
epoxy resin or unreacted anhydrous curing agent remains behind and can cause
deterioration of glass transition temperature(Tg) and mechanical property.
The latent curing accelerator used in the invention may be preserved in a
mixture with the epoxy resin and the anhydride curing agent and function to cure the
composition when the reaction of the anhydride curing agent is initiated by means of
heating and so on. For example, micro-encapsulated amine compounds, imidazole
compounds and modified amine compounds and modified imidazole compounds may
be used. Examples of commercialized products of the latent curing accelerator are MY-
24, MY-H, MY-D(the foregoing available from AJINOMOTO-FINE-TECHNO
CO.,INC), Fujicure FXR-1020, FXR-1030, FXR-1080, FXR-1110(the foregoing
available from FUJI KASEI CO., INC.), novacure HX-3088, HX-3722, HX3748, HX-
3921 , HX-3941HP(the foregoing available from ASAHI KASEI CHEMICALS
CORPORATION). The adding amount of the latent curing accelerator is 1-20 parts by
weight, preferably 2-10 parts by weight with respect to 100 parts by weight of the
anhydrous curing agent. If the curing accelerator is added by less than 1 part by weight,
the curing rate increasing effect is low. On the other hand, if it is added by more than 20
parts by weight, viscosity of the composition increases and the mechanical property
may be deteriorated. The liquid epoxy resin composition for encapsulation according to
the invention has a low viscosity of 250-500cps at 25 ° C , and gelation time of below 120
seconds at 150 ° C , preferably 80-120 seconds. Any general inorganic filler, coupling
agent, antifoaming agent, pigment, dye, curing accelerator, etc may be added within a
scope apparent to those skilled in the art. The liquid epoxy resin composition according
to the invention may be produced by sufficiently mixing each compound by generally
known methods, for example, uniformly mixing each compound using a spiral mixer, a
universal mixer, etc. under a vacuum condition. A thermosetting one-pack type epoxy
resin composition according to the invention, for example, in case of producing a
semiconductor device by mounting a bare chip such as flip chip on a flexible circuit
board of polyimide by COF packaging method, is particularly useful for an underfill
composition for the flip chip.
[Mode for Invention]
Hereinafter, explanations will be given in greater detail with specific examples.
The invention is not limited to the examples stated below and it is also apparent that
more changes may be made by those skilled in the art without departing from the
principles and spirit of the present invention.
[Example 1]
70 parts by weight of a bisphenol F type epoxy resin (JAPAN EPOXY RESIN
CO. LTD., Product name: Epikote YL983U), 30 parts by weight of a mono-functional
reactive diluent (JAPAN EPOXY RESIN CO. LTD., Product name: YED-I HE), 120
parts by weight of a liquid anhydrous curing agent (JAPAN EPOXY RESIN CO. LTD.,
Product name: YH-306), 5 parts by weight of a curing accelerator (AJINOMOTO FINE
TECHNO CO. LTD., Product name: MY-24) and 2.0 parts by weight of a silane
coupling agent (JAPAN UNIKASA, Product name: A-187) were mixed to produce a
liquid resin composition for encapsulation.
[Example 2]
70 parts by weight of a bisphenol F type eρoxy(NIPPON KAYAKU CO. LTD.,
Product name: RE-303S), 30 parts by weight of a multi-functional reactive
diluent(ASAHI DENKA CO. LTD., Product name: ED-505R), 130 parts by weight of a
liquid anhydrous curing agent(JAPAN EPOXY RESIN CO. LTD., Product name: YH-
307), 2.0 parts by weight of a silane coupling agent (GE TOSHIBA SILICONES,
Product name: A- 187), and 5 parts by weight of a curing accelerator (FUJI KASEI CO.
LTD, Product name: FXR-1020) were mixed to produce a liquid resin composition for
encapsulation.
[Comparison Example 1]
100 parts by weight of a bisphenol F type epoxy resin (JAPAN EPOXY RESIN
CO. LTD., Product name: Epikote YL983U), 90 parts by weight of a liquid anhydrous
curing agent (JAPAN EPOXY RESIN CO. LTD., Product name: YH-306), 0.5 parts by
weight of a curing accelerator (FUJIKASEI CO. LTD, Product name: FXR- 1040) and
2.0 parts by weight of a silane coupling agent (GE TOSHIBA SILICONES, Product
name: A- 187) were mixed to produce a liquid resin composition for encapsulation.
[Comparison Example 2]
70 parts by weight of a bisphenol F type epoxy(NIPPON KAYAKU CO. LTD.,
Product name: RE-303S), 30 parts by weight of a multi-functional reactive
diluent( ADEKA CORPORATION, Product name: ED-505R), 210 parts by weight of a
liquid anhydrous curing agent(JAPAN EPOXY RESIN CO. LTD., Product name: YH-
307), 2.0 parts by weight of a silane coupling agent (GE TOSHIBA SILICONE, Product
name: A-187) and 0.9 parts by weight of a curing accelerator (AJINOMOTO FINE
TECHNO CO. LTD., Product name: MY-H) were mixed to produce a liquid resin
composition for encapsulation.
The viscosity of the one-pack type liquid epoxy resin composition for
encapsulation, which were produced according to examples 1 and 2, and comparison
examples 1 and 2, was determined at 25 °C with Haake cone and plate type viscometer,
the gelation time at 150 " C was determined by dropping one drop of the composition on
a micro-slide glass, stirring the composition with a wood stick, and monitoring the time
when it has become impossible to stir the composition with melting point measuring
apparatus from FISHER SCIENTIFIC CO. LTD., and decrease of weight for 15 minutes
were estimated with TGA(Thermogravimetric analysis). The results are shown in table
1. Also, 2 glass plates of 2x2cm size in which a spacer was incorporated were placed on
a heat plate of 130 ° C so that a 20 micron size gap is maintained, then the fillability of
the resin was evaluated by dropping the resin composition on one glass plate and
estimating the time for filling to the opposite side glass plate. If the gelation time was
below 10 seconds, it was decided as 'good' and if more than 10 seconds, 'defective',
and the results are shown in Table 1.
Table 1.
Referring to Table 1, it is shown that the liquid epoxy resin composition for
encapsulation of the examples have superior resin viscosity and gelation time in
comparison with epoxy resin composition of the comparison examples. Also, when the
gelation time is longer, it is shown that the decrease of weight is getting higher because
of evaporation of the liquid anhydride that occurs before the epoxy resin cures by the
reaction, in this case, it is highly expected that bubbles are generated between chips and
boards. Further, it is shown that in case of the viscosity is more than 500cps, it takes a
long period of time to fill the gap between chips and boards with the epoxy resin, or
incomplete filling of the gap occurs.
[Industrial Applicability]
As previously mentioned, the epoxy resin composition according to the
invention has better penetrability and underfill ability into the gap between a film and a
bare chip, and can be uniformly cured over the whole surface area of the chip. Further,
the epoxy resin composition has superior productivity achieved by short thermosetting
time, excellent workability achieved by forming less bubbles and volatile components,
and advantage to produce chip packages having high reliability.