CN108137793A - Composition epoxy resin, membranaceous composition epoxy resin and electronic device - Google Patents
Composition epoxy resin, membranaceous composition epoxy resin and electronic device Download PDFInfo
- Publication number
- CN108137793A CN108137793A CN201680058152.4A CN201680058152A CN108137793A CN 108137793 A CN108137793 A CN 108137793A CN 201680058152 A CN201680058152 A CN 201680058152A CN 108137793 A CN108137793 A CN 108137793A
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- Prior art keywords
- epoxy resin
- resin
- composition epoxy
- membranaceous
- hydroxyl
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- 0 CC*(C)(C=C)C=CC*C(C)(C(C)C)NC Chemical compound CC*(C)(C=C)C=CC*C(C)(C(C)C)NC 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
Abstract
The present invention relates to a kind of composition epoxy resins, contain：(A) epoxy resin, (B) there is the resin of aromatic rings and hydroxyl, (C) organosilicon powder, (D) curing accelerator, and (E) inorganic filler, (A) epoxy resin when epoxy resin is included in 25 DEG C for liquid, (B) resin with aromatic rings and hydroxyl includes the resin with naphthalene nucleus and hydroxyl, on the basis of (A) epoxy resin and (B) have the total amount of resin of aromatic rings and hydroxyl, the content at 25 DEG C being the epoxy resin of liquid is more than or equal to 32 mass %, with the total amount of composition epoxy resin (wherein, when composition epoxy resin contains solvent, do not include solvent.) on the basis of, the content of (C) organosilicon powder is 0.80~7.30 mass %.
Description
Technical field
The present invention relates to a kind of composition epoxy resin, membranaceous composition epoxy resin and electronic devices.The present invention relates to
It can carry out the embedment of electronic unit or electronic device (for example, being configured at the electronic unit or electronic device of printed wiring board)
Or sealing etc. composition epoxy resin and membranaceous composition epoxy resin and use their electronic device.
Background technology
With light and shortization of electronic equipment, the miniaturization and slimming of semiconductor device are being in progress.Using with half
The form of the semiconductor device of the almost the same size of conductor element or the installation shape for accumulating semiconductor device on semiconductor devices
State (Package on Package, stacked package) is just prevailing, it is contemplated that the miniaturization and slimming of semiconductor device from now on
Can further it be in progress.
If the further development that becomes more meticulous of semiconductor element, number of terminals increases, then is difficult to set on semiconductor element
Whole external connection terminals (terminal of external connection).For example, external connection terminals are arranged on semiconductor element by force
When upper, the spacing between terminal can narrow, and terminal height can be lower, it is difficult to ensure the connection after installation semiconductor device is reliable
Property.Therefore, in order to realize the miniaturization of semiconductor device and slimming, it is proposed that many new installation methods.
Such as, it is proposed that following installation method and the semiconductor device made using the installation method, the installation method
For：The semiconductor element that singualtion is carried out by semiconductor wafer and is made is reconfigure in a manner of with appropriate intervals
Afterwards, using liquid or solid resin-sealing material by semiconductor element encapsulation, and further by semiconductor element encapsulation
Part setting external connection terminals (for example, referring to following patent literature 1~4).
The sealing of semiconductor element through reconfiguration is for example by using mold by liquid or solid resin-sealing material
Carry out molding molded carry out.It when being sealed molding, is molded sometimes using transfer molding by molded, institute
State transfer molding molding be in the resin-cast to mold obtained by the way that the melting of granular resin-sealing material will be made come into
Row sealing.However, since the resin-cast for melting and obtaining being molded, in the situation for being sealed large area
Under, there is the possibility that generation is not filled by portion.Therefore, begin to use in recent years in advance by resin-sealing material be supplied to mold or by
Molding compression molding molding is carried out after seal.In compression molding molding, since resin-sealing material being supplied directly to
Mold or by seal, even therefore the sealing that has large area be not easy to produce the advantages of being not filled by portion.Compression molding into
In type, in the same manner as transfer molding molding, liquid or solid resin-sealing material are used.
Existing technical literature
Patent document
Patent document 1：No. 3616615 bulletins of Japanese Patent No.
Patent document 2：Japanese Unexamined Patent Publication 2001-244372 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2001-127095 bulletins
Patent document 4：No. 2007/205513 specification of U.S. Patent Application Publication No.
Invention content
Problem to be solved by the invention
In addition, following research has been carried out in recent years：Liquid or solid-state are replaced by using membranaceous resin-sealing material
Resin-sealing material, so as to be sealed using the forming method (lamination, suppress etc.) for not needing to mold.Such case
Under, from the viewpoint of avoiding membranaceous resin-sealing material damaged and becoming difficult to be sealed, for resin-sealing material,
It is required that excellent treatability (bendability etc.).
In addition, when large area is sealed, although since the area that can once seal increases and can shorten operation
Time, but warpage can occur for sealing moulding object sometimes.It is bad that the warpage of sealing moulding object can become induction in subsequent process
The factor of situation, therefore it is required that reducing the warpage of sealing moulding object.
The present invention complete in view of the above problems, its purpose is to provide it is a kind of obtain it is (curved with excellent treatability
Song etc.) membranaceous composition epoxy resin (membranaceous resin-sealing material) and can inhibit sealing after warpage epoxy
Resin combination.In addition, with excellent treatability and sticking up after sealing can be inhibited the purpose of the present invention is to provide a kind of
Bent membranaceous composition epoxy resin.It is a further object of the invention to provide a kind of used these epoxy composites
Object or the electronic device of its solidfied material or membranaceous composition epoxy resin.
The method for solving problem
The present invention provides a kind of composition epoxy resin, contains：(A) epoxy resin, (B) have aromatic rings and hydroxyl
Resin, (C) organosilicon powder, (D) curing accelerator and (E) inorganic filler, aforementioned (A) epoxy resin are included in 25 DEG C
When epoxy resin for liquid, the aforementioned resin of (B) with aromatic rings and hydroxyl includes the resin with naphthalene nucleus and hydroxyl, in the past
It states (A) epoxy resin and on the basis of the total amount of the resin of aforementioned (B) with aromatic rings and hydroxyl, aforementioned is liquid at 25 DEG C
Epoxy resin content be more than or equal to 32 mass %, with the total amount of composition epoxy resin (wherein, when epoxy resin group
When conjunction object contains solvent, not including solvent.It is similary below) on the basis of, the content of aforementioned (C) organosilicon powder is 0.80~7.30
Quality %.
According to composition epoxy resin of the present invention, by the composition epoxy resin be shaped to it is membranaceous in the case of,
The membranaceous composition epoxy resin with excellent treatability (bendability etc.) can be obtained.In addition, according to ring of the present invention
Epoxy resin composition can inhibit the warpage after sealing, and especially when large area is being sealed can inhibit to seal
Warpage afterwards.Further, composition epoxy resin of the present invention also is able to obtain excellent heat resistance and anti-flammability.
The aforementioned resin with naphthalene nucleus and hydroxyl can also include the compound represented by the following general formula (I).
[changing 1]
In formula (I), R11、R12、R13、R14And R15Each independently represent hydrogen atom, the alkyl of carbon number 1~6 or carbon number 1~
2 alkoxy；M1, m2, m3, m4, m5, m6, m7 and m8 each independently represent 0~2 integer (wherein, not including m1, m2,
The situation of m3, m4, m5, m6, m7 and m8 all 0)；N1 represents 0~10 integer.
On the basis of the total amount of composition epoxy resin, the content of aforementioned (C) organosilicon powder may be 2~7 matter
Measure %.
Aforementioned (C) organosilicon powder can also have siloxanes key to be cross-linked into three-dimensional netted structure.
In addition, the present invention provides a kind of membranaceous epoxy composite comprising aforementioned epoxy resins composition or its solidfied material
Object.Membranaceous composition epoxy resin of the present invention has excellent treatability (bendability etc.), and after can inhibiting sealing
Warpage, and with excellent heat resistance and anti-flammability.
Further, the present invention provides one kind and includes aforementioned epoxy resins composition or its solidfied material or aforementioned membranaceous ring
The electronic device of epoxy resin composition has by seal and by the aforementioned sealing being sealed by seal, aforementioned quilt
Seal is to be selected from least one of group being made of electronic unit and electronic device.
Invention effect
According to the present invention it is possible to provide a kind of composition epoxy resin, can obtain with excellent treatability (bending
Property etc.) membranaceous composition epoxy resin, and the warpage after sealing can be inhibited, and with excellent heat resistance and anti-flammability.
In addition, according to the present invention it is possible to provide a kind of membranaceous composition epoxy resin, with excellent treatability (bendability etc.),
And the warpage after sealing can be inhibited, and with excellent heat resistance and anti-flammability.Further, according to the present invention it is possible to provide
It is a kind of to have used these composition epoxy resins or the electronic device of its solidfied material or membranaceous composition epoxy resin.
Membranaceous composition epoxy resin of the present invention can be suitably used for electronic unit or electronic device (for example,
The electronic unit or electronic device being configured on printed wiring board) embedment or sealing etc..Moreover, it relates to it is membranaceous
Composition epoxy resin can not only be suitably used for molded, additionally it is possible to be suitably used for not needing to the forming method of mold
(lamination, compacting etc.).
According to the present invention it is possible to provide a kind of application of membranaceous composition epoxy resin as sealing material.According to this hair
It is bright, a kind of application of membranaceous composition epoxy resin in the embedment or sealing of electronic unit can be provided.It, can according to the present invention
To provide a kind of application of membranaceous composition epoxy resin in the embedment or sealing of electronic device.According to the present invention it is possible to it carries
A kind of embedment or close for electronic unit or electronic device of membranaceous composition epoxy resin on printed wiring board is configured at
Application in envelope.According to the present invention it is possible to provide a kind of application of membranaceous composition epoxy resin in molded.According to this
Invention can provide a kind of membranaceous composition epoxy resin answering in the forming method (lamination, compacting etc.) for not needing to mold
With.
Description of the drawings
Fig. 1 is the plan view for representing the test film for evaluating amount of warpage.
Specific embodiment
Hereinafter, it is explained in detail for for implementing the preferred embodiment of the present invention.
In addition, in this specification, the numberical range represented by "~" is used to represent comprising the numerical value being recorded in before and after "~"
Respectively as minimum value and the range of maximum value.In addition, the amount about ingredient each in composition, there are a variety of phases in the composition
When in the substance of each ingredient, unless otherwise specified, just refer to the total amount for many kinds of substance being present in composition.
Further, in this specification, on the basis of the so-called total amount by composition epoxy resin, refer to contained by composition epoxy resin
Ingredient in ingredient in addition to organic solvent equal solvent total amount (total amount of solid constituent) on the basis of.That is, work as epoxy resin
When composition contains solvent, the total amount of the ingredient in addition to solvent becomes the total amount of composition epoxy resin.
<Composition epoxy resin>
Composition epoxy resin of the present embodiment contains (A) epoxy resin, (B) has the tree of aromatic rings and hydroxyl
Fat, (C) organosilicon powder, (D) curing accelerator and (E) inorganic filler are as essential component.It is related in present embodiment
Composition epoxy resin in, epoxy resin for liquid when aforementioned (A) epoxy resin is included in 25 DEG C, aforementioned (B) has virtue
The resin of fragrant ring and hydroxyl includes the resin with naphthalene nucleus and hydroxyl, has aromatic rings with aforementioned (A) epoxy resin and aforementioned (B)
On the basis of the total amount of the resin of hydroxyl, the content of the aforementioned epoxy resin at 25 DEG C being liquid is more than or equal to 32 matter
% is measured, on the basis of the total amount of composition epoxy resin, the content of aforementioned (C) organosilicon powder is 0.80~7.30 mass %.
Wherein, when above-mentioned composition epoxy resin contains solvent, the total amount of composition epoxy resin refers to the amount for not including solvent.
As the shape of composition epoxy resin of the present embodiment, membranaceous, liquid, solid-state (particle, powder can be enumerated
Body etc.) etc..Composition epoxy resin of the present embodiment can using molded progress sealing, using not needing to
It is used in sealing that the forming method (lamination, compacting etc.) of mold carries out etc..Composition epoxy resin of the present embodiment
It can be used in embedment or sealing of electronic unit or electronic device etc..As electronic unit, such as the filters such as SAW filter can be enumerated
Wave device；The passive components such as sensor.As electronic device, such as semiconductor element, integrated circuit, semiconductor devices can be enumerated
Deng.In addition, composition epoxy resin of the present embodiment also can be used in except them by the embedment of seal or close
Envelope.So-called " embedment " refers to sealing material being supplied to gap, difference of height etc..So-called " sealing ", refers to be coated with sealing material
Extraneous air is touched to avoid by seal by seal.
Hereinafter, each constituent to composition epoxy resin of the present embodiment illustrates.
((A) epoxy resin)
In order to assign flexibility to membranaceous composition epoxy resin, (A) epoxy resin is at 25 DEG C comprising at least one
The epoxy resin (hereinafter referred to as " epoxy resin (a1) ") of liquid.Herein, so-called " epoxy resin at 25 DEG C for liquid ", table
Show that value obtained from being measured using E types viscosimeter or Brookfield viscometer to the viscosity for being maintained at 25 DEG C of the epoxy resin is
The epoxy resin of below 400Pas.
It as epoxy resin (a1), is not particularly limited, such as can use in 1 molecule with more than two glycidols
The epoxy resin of base.As epoxy resin (a1), bisphenol A type epoxy resin, bisphenol f type epoxy resin, naphthalene type ring oxygen can be enumerated
Resin etc..From the viewpoint of being assigned heat resistance, epoxy resin (a1) also may include readily available high glass-transition temperature
(Tg) naphthalene type epoxy resin.
As epoxy resin (a1), it is possible to use commercially available product.As the commercially available product of epoxy resin (a1), Mitsubishi can be enumerated
Learn trade name " jER825 " (bisphenol A type epoxy resin, epoxide equivalent of Co., Ltd.'s manufacture：175), Mitsubishi chemical Co., Ltd
Trade name " jER806 " (bisphenol f type epoxy resin, epoxide equivalent of manufacture：160), the trade name of Dainippon Ink Chemicals's manufacture
" HP-4032D " (2 function naphthalene type epoxy resin) etc..Epoxy resin (a1) can be used alone one kind, also can and with two or more.
From the viewpoint of being obtained excellent treatability (bendability etc.), with (A) epoxy resin and (B) have aromatic rings and
On the basis of the total amount of the resin of hydroxyl, the content of epoxy resin (a1) is more than or equal to 32 mass %.It is more excellent from obtaining
Treatability (bendability etc.) from the perspective of, the content of epoxy resin (a1) can be more than or equal to 35 mass %, also may be used
Think more than or equal to 40 mass %, or more than or equal to 45 mass %, or more than or equal to 50 mass %.
The fissility of protective layer is good when as diaphragm seal equipped with protective layer, the content of epoxy resin (a1) can be with
To be less than or equal to 70 mass %, or less than or equal to 65 mass %.The treatability (bendability etc.) excellent from maintenance,
And as equipped with protective layer diaphragm seal when protective layer fissility it is good from the perspective of, the content of epoxy resin (a1) also may be used
Think 32~70 mass %, or 32~65 mass %.
From the viewpoint of being obtained superior treatability (bendability etc.), on the basis of the total amount of (A) epoxy resin, ring
The content of oxygen resin (a1) can be more than or equal to 60 mass %, or more than or equal to 65 mass %, or
More than or equal to 70 mass %.From the viewpoint of being obtained superior treatability (bendability etc.), with the total of (A) epoxy resin
On the basis of amount, the content of epoxy resin (a1) can be less than or equal to 100 mass %, or less than or equal to 95 matter
Measure %, or less than or equal to 90 mass %.
(A) epoxy resin also can further include at 25 DEG C as the epoxy resin other than the epoxy resin (a1) of liquid
(hereinafter referred to as " epoxy resin (a2) ".For example, being not the epoxy resin of liquid at 25 DEG C).It, can as epoxy resin (a2)
Enumerate naphthalene type epoxy resin (4 function naphthalene type epoxy resins, 3 function naphthalene type epoxy resins etc.), anthracene type epoxy resin, triphenylmenthane
Type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl aralkyl-type epoxy resin, phenol novolak type epoxy resin,
Cresol novolak type epoxy resin (o-cresol phenolic epoxy varnish etc.), dihydroxy benzenes nobolak type epoxy tree
Fat, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanurate type
Epoxy resin etc..Can be naphthalene type from the viewpoint of being obtained superior heat resistance and anti-flammability as epoxy resin (a2)
Epoxy resin.Epoxy resin (a2) can be used alone one kind, also can and with two or more.
As epoxy resin (a2), it is possible to use commercially available product.As the commercially available product of epoxy resin (a2), DIC plants can be enumerated
The trade name " HP-4700 " (4 function naphthalene type epoxy resin) of formula commercial firm manufacture, trade name " HP-4750 " (3 function naphthalene type ring oxygen
Resin), trade name " HP-4710 " (4 function naphthalene type epoxy resin), trade name " EPICLON N-770 " (phenol novolak type
Epoxy resin), trade name " EPICLON N-660 " (cresol novolak type epoxy resin) and trade name " EPICLON HP-
7200H " (dicyclopentadiene type epoxy resin)；Trade name " EPPN-502H " (triphenylmenthane of Nippon Kayaku K. K's manufacture
Type epoxy resin) and trade name " NC-3000 " (biphenyl aralkyl-type epoxy resin)；Nippon Steel ＆ Sumitomo Metal Corporation manufactures
Trade name " ESN-355 " (naphthalene type epoxy resin)；Trade name " YX-8800 " (anthracene type ring of Mitsubishi chemical Co., Ltd's manufacture
Oxygen resin)；Trade name " ESCN-190-2 " (o-cresol phenolic epoxy varnish) of Sumitomo Chemical Co's manufacture etc..
From the treatability (bendability etc.) of the membranaceous composition epoxy resin of heat resistance, anti-flammability and B ranks (semi-solid preparation)
From the perspective of more improving, (A) epoxy resin also may include the epoxy represented in epoxy resin (a2) by the following general formula (III)
Resin.In formula (III), from the viewpoint of being obtained superior heat resistance, n31+n32+n33+n34 can be more than or equal to
2, or more than or equal to 3.From the viewpoint of being obtained superior treatability (bendability etc.), n31+n32+n33+
N34 can be less than or equal to 4, or less than or equal to 3.
[changing 2]
In formula (III), n31~n34 each independently represent 0 or 1, n31+n32+n33+n34 represent be greater than or equal to 2
(n31+n32+n33+n34≥2)。
As the epoxy resin represented by formula (III), the epoxy resin represented by following formula (IV)s can be enumerated, by following formula
(V) epoxy resin represented etc..As the epoxy resin represented by formula (III), it is possible to use commercially available product.As by formula (IV) table
The commercially available product of the epoxy resin shown, such as trade name " HP-4750 " (epoxide equivalent of Dainippon Ink Chemicals's manufacture can be enumerated：
182).As the commercially available product of the epoxy resin represented by formula (V), such as the trade name " HP- of Dainippon Ink Chemicals's manufacture can be enumerated
4700 " (epoxide equivalents：166).
[changing 3]
[changing 4]
From the viewpoint of being obtained superior heat resistance, on the basis of the total amount of (A) epoxy resin, epoxy resin (a2)
Content can be more than or equal to 10 mass %, or more than or equal to 15 mass %, or be greater than or equal to
20 mass %.From the viewpoint of being obtained superior treatability (bendability etc.), on the basis of the total amount of (A) epoxy resin,
The content of epoxy resin (a2) can be less than or equal to 45 mass %, or, can also less than or equal to 42 mass %
To be less than or equal to 40 mass %.
((B) has the resin of aromatic rings and hydroxyl)
(B) resin with aromatic rings and hydroxyl include it is at least one with naphthalene nucleus (naphthalene skeleton) and hydroxyl resin (with
It is known as " resin (b1) " down).By using resin (b1), can reduce because (A) epoxy resin and (B) have aromatic rings and hydroxyl
Resin reaction and the contraction (reaction shrink) that generates, therefore speculate the warpage after can inhibiting sealing.In addition, by burning
When naphthalene skeleton formed carburization zone, so as to assign anti-flammability.There is the hydroxyl in the resin of aromatic rings and hydroxyl as (B),
Such as phenolic hydroxyl group (hydroxyl of the Direct Bonding on aromatic rings) etc. can be enumerated.As phenolic hydroxyl group, such as Direct Bonding can be enumerated and existed
The hydroxyl of hydroxyl, Direct Bonding on phenyl ring on naphthalene nucleus etc..
From the viewpoint of the warpage after more inhibiting sealing, resin (b1) also may include what is represented by the following general formula (I)
Compound.
[changing 5]
In formula (I), R11、R12、R13、R14And R15Each independently represent hydrogen atom, the alkyl of carbon number 1~6 or carbon number 1~
2 alkoxy；M1, m2, m3, m4, m5, m6, m7 and m8 each independently represent 0~2 integer (wherein, not including m1, m2,
The situation of m3, m4, m5, m6, m7 and m8 all 0)；N1 represents 0~10 integer.
It, can be with R from the viewpoint of being obtained superior anti-flammability11、R12、R13、R14And R15At least one of be hydrogen
Atom, can also R11、R12、R13、R14And R15Entirely hydrogen atom.It, can from the viewpoint of the warpage after more inhibiting sealing
It is 1 at least one of m1, m2, m3, m4, m5, m6, m7 and m8, it can also m1, m2, m3, m4, m5, m6, m7 and m8 whole
It is 1.Can be 2 at least one of m1, m2, m3, m4, m5, m6, m7 and m8 from the viewpoint of heat resistance is more excellent,
Can be entirely 2 with m1, m2, m3, m4, m5, m6, m7 and m8.Go out from mouldability, mobility and the more excellent viewpoint of anti-flammability
Hair, n1 can be 0~10 integer or 0~6 integer.
The viewpoint of warpage after sealing is more inhibited and obtaining superior heat resistance, by formula (I)
The compound of expression can also have the naphthalene nucleus that hydroxyl is bonded in 1 and 6.1 and 6 of naphthalene nucleus is bonded in by hydroxyl, energy
It is enough effectively to be reacted with (A) epoxy resin.From the viewpoint for more inhibiting the warpage after sealing and obtain superior resistance to
From the perspective of hot, the compound represented by formula (I) also may include the compound represented by the following general formula (II).
[changing 6]
In formula (II), R21、R22And R23Each independently represent the alkane of hydrogen atom, the alkyl of carbon number 1~6 or carbon number 1~2
Oxygroup mutually may be the same or different.N2 represents 0~10 integer.
In addition, from the viewpoint of being obtained superior anti-flammability, it can be with R21、R22And R23At least one of be hydrogen original
Son, can also R21、R22And R23Entirely hydrogen atom.From the viewpoint of mouldability, mobility and anti-flammability it is more excellent, n2
Can be 0~10 integer or 0~6 integer.
As the compound represented by formula (I), it is possible to use commercially available product.As the commercially available of the compound represented by formula (I)
Product can enumerate trade name " SN-180 ", " SN-395 ", " SN-475N " and " SN- of Nippon Steel ＆ Sumitomo Metal Corporation's manufacture
485 " etc..The compound represented by formula (I) can be used alone one kind, also can and with two or more.
As the compound represented by formula (I), from the viewpoint of the warpage after more inhibiting water suction and sealing, Ke Yishi
(n6 represents the integer more than or equal to 1 to compound with the structure represented by the following general formula (VI).For example, gold is lived by Nippon Steel
The trade name " SN-180 " of Chemical Co., Ltd. manufacture) and with the compound (n7 of structure represented by the following general formula (VII)
Represent the integer more than or equal to 1.For example, the trade name " SN-475N " of Nippon Steel ＆ Sumitomo Metal Corporation's manufacture).
[changing 7]
[changing 8]
(B) resin with aromatic rings and hydroxyl also can further include the resin (hereinafter referred to as " resin without naphthalene nucleus
(b2) ") as the resin other than resin (b1).As resin (b2), can enumerate in encapsulating epoxy resin composition usually makes
Resin etc., is not particularly limited.
As resin (b2), can enumerate：Novolak type phenol resin (makes phenols contract under acidic catalyst with aldehydes
Close or cocondensation and resin for obtaining etc.)；Triphenyl methane type phenolic resin；Poly- 4-Vinyl phenol resin；Phenol-aralkyl
Resin (phenol-aralkyl resin with xyxylene synthesized by phenols and dimethoxy paraxylene etc.)；With biphenyl
Phenolic resin (biphenyl aralkyl-type phenol resin etc.) of skeleton etc..As foregoing phenolic, can enumerate：Phenol, cresols, dimethylbenzene
Phenol, resorcinol, catechol, bisphenol-A, Bisphenol F etc..As aforementioned aldehydes, can enumerate：Formaldehyde, acetaldehyde, propionic aldehyde, benzaldehyde,
Salicylide etc..From the viewpoint of being obtained superior anti-flammability, resin (b2) can be biphenyl aralkyl-type phenol resin, from
It obtains from the perspective of superior heat resistance or novolak phenolics.Resin (b2) can be used alone one
Kind, also can and with two or more.
As commercially available resin (b2), can enumerate：The trade name " PAPS-PN2 " of Asahi Organic Chem Ind's manufacture
(novolak phenolics)；Trade name " SK-Resin HE200C-7 " (the biphenyl virtue of AIR WATER Co., Ltd. manufacture
Alkyl type phenolic resin) and trade name " HE910-10 " (triphenyl methane type phenolic resin)；Bright and chemical conversion Co., Ltd. manufacture
Trade name " DL-92 ", " H-4 " and " HF-1M "；The trade name " LVR-8210DL " of Gunsaka Chem. Industry Co., Ltd.'s manufacture,
" ELP " series and " NC " series；The trade name " HP-850N " (novolak phenolics) of Hitachi Chemical Co., Ltd.'s manufacture
Deng.
From the viewpoint of resin that unreacted (B) is had to aromatic rings and hydroxyl be suppressed to it is less, (A) epoxy resin
Glycidyl equivalent (epoxide equivalent) have relative to (B) in resin of aromatic rings and hydroxyl with aforementioned glycidol
(shrink of (A) epoxy resin is sweet for the ratio of the equivalent (such as hydroxyl equivalent) for functional group's (such as phenolic hydroxyl group) that base is reacted
The equivalent of oil base/(B) has working as the functional group reacted with aforementioned glycidyl in the resin of aromatic rings and hydroxyl
Amount) can be more than or equal to 0.7, or more than or equal to 0.8, or more than or equal to 0.9.From by unreacted
(A) epoxy resin be suppressed to it is less from the perspective of, aforementioned ratio can be less than or equal to 2.0, or be less than or
Equal to 1.8, or less than or equal to 1.7.There is aromatic rings from by unreacted (A) epoxy resin and unreacted (B)
With the resin of hydroxyl be suppressed to it is less from the perspective of, aforementioned ratio can be 0.7~2.0, or 0.8~1.8, also may be used
Think 0.9~1.7.
From the viewpoint of unreacted resin (b2) is suppressed to it is less, the glycidyl of (A) epoxy resin work as
(epoxide equivalent) is measured relative to the functional group's (such as phenolic hydroxyl group) reacted with aforementioned glycidyl in resin (b2)
Equivalent (such as hydroxyl equivalent) ratio (in equivalent/resin (b2) of the glycidyl of (A) epoxy resin with aforementioned shrink
The equivalent for the functional group that glyceryl is reacted) can be more than or equal to 0.7, or it, can also more than or equal to 0.8
To be greater than or equal to 0.9.From the viewpoint of unreacted (A) epoxy resin is suppressed to it is less, aforementioned ratio can be small
In or equal to 2.0, or less than or equal to 1.8, or less than or equal to 1.7.From by unreacted (A) asphalt mixtures modified by epoxy resin
Fat and unreacted resin (b2) be suppressed to it is less from the perspective of, aforementioned ratio can be 0.7~2.0, or 0.8~
1.8, or 0.9~1.7.
((C) organosilicon powder)
Composition epoxy resin of the present embodiment is by containing (C) organosilicon powder, so as to effectively subtract
Warpage (such as amount of warpage of packaging body) and packaging body crackle after few sealing, can obtain excellent heat resistance and anti-flammability.
From the viewpoint of mobility is excellent, the shape of particle of (C) organosilicon powder can be spherical (spherical shape or substantially
It is spherical).As (C) organosilicon powder, it is, for example, possible to use surface of the shape of particle for spherical silicone rubber powder is used
Organic siliconresin envelope simultaneously carries out obtained substance of powdered etc..Such (C) organosilicon powder is by using organic siliconresin
Envelope, so as to be not easy to be aggregated, there is dispersion in resin, after sealing to the inhibition of warpage and the feature of excellent heat resistance.(C)
Organosilicon powder is cross-linked into three-dimensional netted structure by siloxanes key by having, so as to obtain heat resistance and anti-flammability more
Add excellent composition epoxy resin.(C) organosilicon powder can also have dimethyl polysiloxane to carry out being crosslinked obtained knot
Structure.
As the commercially available product of (C) organosilicon powder, the trade name of Shin-Etsu Chemial Co., Ltd's manufacture can be enumerated
" KMP597 ", " KMP590 ", " KMP600 ", " KMP601 ", " KMP602 ", " KMP605 ", " KMP701 ", " X-52-7042 " etc..
(C) organosilicon powder can be used alone one kind, also can and with two or more.
(C) lower limiting value of the average grain diameter of organosilicon powder can be more than or equal to 0.05 μm, or be more than or
Equal to 0.1 μm, or more than or equal to 2 μm, or more than or equal to 2.5 μm, or more than or equal to 3 μ
m.In addition, the upper limit value of the average grain diameter of (C) organosilicon powder can be less than or equal to 50 μm, or be less than or equal to
45 μm, or less than or equal to 30 μm, or less than or equal to 20 μm, or less than or equal to 10 μm.That is,
(C) average grain diameter of organosilicon powder can be 0.05~50 μm, or 0.1~45 μm, or 2~30 μm,
It can be 2.5~20 μm, or 3~10 μm.It is these ranges by the average grain diameter of (C) organosilicon powder, can presses down
The mobility of resin combination reduces during system melting.(C) average grain diameter of organosilicon powder can pass through particle size distribution device
To measure.
On the basis of the total amount of composition epoxy resin, the content of (C) organosilicon powder is 0.80~7.30 mass %.It is logical
The content for crossing (C) organosilicon powder is such range so that the treatability (bendability etc.) of film well, can efficiently reduce
Warpage after sealing, and can play excellent anti-flammability in burning.It is more good from the treatability (bendability etc.) of film, more
The warpage after sealing is efficiently reduced, and in burning from the perspective of the more excellent anti-flammability of performance, (C) organosilicon powder
Content can be 2~7 mass %, or 3~6 mass %.
By and with resin (b1) and (C) organosilicon powder, so as to can more effectively play excellent resistance in burning
Combustion property.This, it can be said that in burning, by the carburization zone of the naphthalene nucleus generation by be used as condensation aromatic rings in resin (b1) with by wrapping
The composite bed for inorganic system's combustion residue that the complex of siloxanes containing (C) organosilicon powder generates, shows excellent thermal insulation
Effect and oxygen barrier effect, it is thus possible to play high fire-retardance effect.
In addition, in recent years, from the viewpoint of environmental protection, with twoThe problem of English is the beginning, is existed to ten bromines two
The trend that halogenated resin headed by phenylate limits, similarly, from toxicity aspect, to antimonial (antimony containing compounds)
There is also the trend limited, therefore there is non-halogen (no bromination etc.) for resin-sealing material and wanted without antimony
It asks.Additionally, it is known that bromine compounds (bromine-containing compound) can bring harmful effect to the high-temperature standing properties of plastic seal IC, so as to
It is expected to reduce bromine compounds.Composition epoxy resin of the present embodiment can be suitable for due to excellent in flame retardance
Meet the sealing material of requirement non-halogen and without antimony.Therefore, composition epoxy resin of the present embodiment can carry
For non-halogen and without the application in the flame resistant sealing material of antimony.
((D) curing accelerator)
It as (D) curing accelerator, is not particularly limited, such as can be selected from curing accelerator, the miaow by amine system
At least one of group of curing accelerator composition of the curing accelerator of azoles system, the curing accelerator of urea system and phosphorus system.As
The curing accelerator of amine system can be enumerated：1,8- diazabicyclos [5.4.0] -7- hendecenes, 1,5- diazabicyclos [4.3.0] -
5- nonenes etc..As the curing accelerator of imidazoles system, can enumerate：2- phenyl -4-methylimidazole, 2-ethyl-4-methylimidazole, 1-
Cyanoethyl -2-ethyl-4-methylimidazole etc..As the curing accelerator of urea system, can enumerate：3- phenyl -1,1- dimethyl ureas etc..
As the curing accelerator of phosphorus system, can enumerate：Triphenylphosphine and its addition reaction, (4- hydroxy phenyls) diphenylphosphine, bis- (4-
Hydroxy phenyl) Phenylphosphine, three (4- hydroxy phenyls) phosphines etc..
As (D) curing accelerator, the viewpoint enriched from the type of derivative and be easily obtained desired active temperature goes out
Hair can be the curing accelerator of imidazoles system.As the curing accelerator of imidazoles system, commercially available product can be used.As imidazoles system
The commercially available product of curing accelerator, such as trade name " the CUREZOL 2PHZ- of Shikoku Chem's manufacture can be enumerated
PW " and " CUREZOL 2P4MZ " etc..(D) curing accelerator can be used alone one kind, also can and with two or more.
From the viewpoint that can be readily available sufficient curing facilitation effect and making membranaceous composition epoxy resin
When process (coating and dry etc.) in or curing can be inhibited to carry out, and easily in the keeping of membranaceous composition epoxy resin
From the perspective of the rupture for preventing membranaceous composition epoxy resin and the molding generated as melt viscosity rises are bad,
(D) content of curing accelerator can be following ranges.There is the resin of aromatic rings and hydroxyl with (A) epoxy resin and (B)
On the basis of total amount, the content of (D) curing accelerator can be more than or equal to 0.01 mass %, or be greater than or equal to
0.1 mass %, or more than or equal to 0.3 mass %.There is the tree of aromatic rings and hydroxyl with (A) epoxy resin and (B)
On the basis of the total amount of fat, the content of (D) curing accelerator can be less than or equal to 5 mass %, or be less than or wait
In 3 mass %, or less than or equal to 1.5 mass %.From these viewpoints, there is virtue with (A) epoxy resin and (B)
On the basis of the total amount of the resin of fragrant ring and hydroxyl, the content of (D) curing accelerator can be 0.01~5 mass %, can also
For 0.1~3 mass %, or 0.3~1.5 mass %.
((E) inorganic filler)
As (E) inorganic filler, known inorganic filler can be used, is not limited specifically.As (E)
Inorganic filler can be enumerated：Barium sulfate；Barium titanate；Amorphous silica, crystallinity silica, fused silica, ball
Shape silica etc. is silica-based；Talcum；Clay；Magnesium carbonate；Calcium carbonate；Aluminium oxide；Aluminium hydroxide；Silicon nitride；Aluminium nitride
Deng.Inhibit effect from being modified by surface etc. to be easy to get the improvement effect of the dispersibility in resin and the sedimentation in varnish
The viewpoint of fruit and due to being easy to get desired cured film characteristic with smaller coefficient of thermal expansion from the perspective of, (E) nothing
Machine filler can be silica-based.(E) inorganic filler can be used alone one kind, also can and with two or more.
(E) inorganic filler may also pass through surface modification.As the method that surface is modified, it is not particularly limited, but conform to the principle of simplicity
Just and the type of functional group is enriched, is easy to assign desired characteristic and set out, and can be that the surface of silane coupling agent has been used to be modified.
As silane coupling agent, alkyl silane, alkoxy silane, vinyl silanes, epoxy silane, amino silane, acryloyl can be enumerated
Base silane, methacryl base silane, hydrosulphonyl silane, thioether silane, isocynate silane, polysulfur silane, styryl silane, alkane
Base chlorosilane etc..Silane coupling agent can be used alone one kind, also can and with two or more.
Can be fully dispersed from easy be suppressed of aggegation of inorganic filler, and in membranaceous composition epoxy resin
From the perspective of sedimentation of the particle in varnish is easily suppressed in making, under the average grain diameter of (E) inorganic filler can be
State range.(E) average grain diameter of inorganic filler can be more than or equal to 0.01 μm, or more than or equal to 0.1 μm,
Or more than or equal to 0.3 μm.(E) average grain diameter of inorganic filler can be less than or equal to 50 μm, or
Less than or equal to 25 μm, or less than or equal to 10 μm.From these viewpoints, the average grain diameter of (E) inorganic filler
It can be 0.01~50 μm, or 0.1~25 μm, or 0.3~10 μm.
From can be easily prevented from due to by the thermal expansion of seal (electronic devices such as semiconductor element etc.) and sealing
The difference of rate causes the warpage of electronic device (semiconductor device etc.) to become larger, and can easily inhibit making membranaceous asphalt mixtures modified by epoxy resin
Rupture is generated in drying process and made due to the rising of the melt viscosity of membranaceous composition epoxy resin during oil/fat composition
Into become by seal can not be sufficiently sealed undesirable condition from the perspective of, the content of (E) inorganic filler can be following
Range.On the basis of the total amount of composition epoxy resin, the content of (E) inorganic filler can be more than or equal to 50 matter
Measure %, or more than or equal to 60 mass %, or more than or equal to 70 mass %.With composition epoxy resin
On the basis of total amount, the content of (E) inorganic filler can be less than or equal to 95 mass %, or less than or equal to 90 matter
Measure %.From these viewpoints, on the basis of the total amount of composition epoxy resin, the content of (E) inorganic filler can be big
In or equal to 50 mass %, or 60~95 mass %, or 70~90 mass %.
(other compositions)
Composition epoxy resin of the present embodiment also can be further containing other additives.Add as such
Add agent, pigment, dyestuff, releasing agent, antioxidant, stress relaxation agent, coupling agent, surface tension regulator, ion can be enumerated and handed over
Change body, colorant, fire retardant etc..But additive is not limited to these, composition epoxy resin of the present embodiment
Also it can contain various additives known in the technical field as needed.
<Membranaceous composition epoxy resin>
Membranaceous composition epoxy resin of the present embodiment includes composition epoxy resin of the present embodiment
Or its solidfied material.Membranaceous composition epoxy resin of the present embodiment can use the sealing of molded progress, adopt
It is used in sealing carried out with the forming method (lamination, compacting etc.) for not needing to mold etc..
The membranaceous composition epoxy resin being related to according to the present embodiment, even if in the case where being maximized by seal,
Compared with the resin-sealing material of liquid or solid-state (particle, powder etc.), sealing resin can be also supplied uniformly across in close
It seals on body, will easily and well can be sealed by seal.In addition, in the resin-sealing material for having used particle or powder
When, resin-sealing material can become dust production resource, sometimes polluting device or dust free room, in contrast, relating to according to the present embodiment
And membranaceous composition epoxy resin, sealing moulding object is made to maximize while can be reduce dust the problem of.
In molded, due in in-mold molding sealing resin, when sealing moulding object is made to maximize, needing
The enlargement of mold.The enlargement of mold is improved due to requiring high mould and die accuracy in the difficulty of technical aspect, and
The manufacture cost of mold is significantly increased sometimes.In contrast, membranaceous composition epoxy resin of the present embodiment is not only
It can be suitably used for that previous sealing moulding method is i.e. molded, also can be suitably used for not needing to forming method (lamination, the compacting of mold
Deng).
From the viewpoint of being easy to prevent membranaceous composition epoxy resin from rupturing, membranaceous asphalt mixtures modified by epoxy resin of the present embodiment
The thickness of oil/fat composition can be more than or equal to 25 μm, or more than or equal to 50 μm.From the membranaceous epoxy resin of inhibition
From the perspective of the thickness deviation of composition, the thickness of membranaceous composition epoxy resin of the present embodiment can be less than
Or equal to 500 μm, or less than or equal to 300 μm.
Membranaceous composition epoxy resin of the present embodiment for example can be by by epoxy of the present embodiment
Resin combination or its solidfied material are shaped to membranaceous and obtain.The system of membranaceous composition epoxy resin that first embodiment is related to
The method of making is varnish rubbing method, such as is had：Use the tree at least containing (A) epoxy resin, (B) with aromatic rings and hydroxyl
Fat, (C) organosilicon powder, (D) curing accelerator and (E) inorganic filler varnish, the work of film is formed on supporter
Sequence；And the process that aforementioned film is thermally dried and obtains membranaceous composition epoxy resin.Second embodiment is related to
The manufacturing method of membranaceous composition epoxy resin have：(A) epoxy resin will at least be contained, (B) has aromatic rings and hydroxyl
Resin, (C) organosilicon powder, (D) curing accelerator and (E) inorganic filler solid resin composition molding be sheet
And the process for obtaining membranaceous composition epoxy resin.Can be aforementioned varnish from the viewpoint of it easily can control thickness
Rubbing method.
Membranaceous composition epoxy resin of the present embodiment can for example have by mixing (A) epoxy resin, (B)
The resin of aromatic rings and hydroxyl, (C) organosilicon powder, (D) curing accelerator, (E) inorganic filler and use as needed
Various any ingredients make.As mixed method, as long as can by each gradation composition dispersion mixing as long as be not particularly limited,
Grinder, mixing machine, stirring blade etc. can be used.As needed, solvent can be dissolved in by using by each gradation composition
It is film-made etc. the varnish rubbing method of obtained varnish.In addition, membranaceous composition epoxy resin of the present embodiment also may be used
To be obtained as below：Each gradation composition is kneaded by using kneader, dual-screw-stem machine, continuous mixing device etc. and is made solid
The solid resin composition is squeezed out slabbing and is filmed by state resin combination.
As solvent, known organic solvent can be used.As organic solvent, aliphatic hydrocarbon, fragrance can be enumerated
Race's hydro carbons, terpenes, halogen, esters, ketone, alcohols, aldehydes etc..Organic solvent can be used alone one kind, also can and with two
Kind or more.
As organic solvent, there is fragrance from the small viewpoint of carrying capacity of environment and (A) epoxy resin easy to dissolve and (B)
From the perspective of the resin of ring and hydroxyl or esters, ketone and alcohols.As organic solvent, from being especially susceptible to dissolve
(A) can be ketone from the perspective of epoxy resin and (B) have the resin of aromatic rings and hydroxyl.As organic solvent, from
Can be acetone, methyl ethyl ketone and methyl tert-butyl from the perspective of the volatilization of room temperature (25 DEG C) is easily removed less and when drying
Base ketone.
About for manufacturing the content of the organic solvent in the varnish of membranaceous composition epoxy resin, with the total amount of the varnish
On the basis of meter can be 2~30 mass %, or 5~25 mass %.By being in such range, can easily prevent
Only the undesirable conditions such as rupture occur for film, and are easily obtained sufficient lowest melt viscosity.In addition, it can be easily prevented from adhering
Property become too strong and when undesirable condition that treatability reduces and heat cure such as foams at the bad shape with the volatilization of organic solvent
Condition.
In varnish rubbing method, can by supporter be coated with the obtained film of varnish blow hot wind etc. come into
Row heat drying, so as to make membranaceous composition epoxy resin.As painting method used in coating, there is no especially limits
It is fixed, die coating method, unfilled corner wheel rubbing method etc. can be enumerated.
It as supporter, is not particularly limited, polymeric membrane, metal foil etc. can be enumerated.As polymeric membrane, can enumerate：
The polyolefin films such as polyethylene film, polypropylene screen；The polyester films such as polyethylene terephthalate；Polychloroethylene film；Makrolon
Film；Acetylcellulose film；Polyimide film；PA membrane；Tetrafluoroethylene etc..As metal foil, copper foil, aluminium foil can be enumerated
Deng.
The thickness of supporter is not particularly limited, and can be 2~200 μ from the viewpoint of operability and drying property are excellent
m.If such thickness, then supporter undesirable condition for being broken and because the weight of varnish is led in coating can be prevented
The undesirable condition that supporter is caused to be bent in coating.In addition, using drying that hot wind is blowed from the two sides at coated face and the back side
During machine, it can also inhibit to occur the solvent seasoning in varnish by the undesirable condition interfered.
As the heat drying of aforementioned film, can in 25% time more than or equal to whole drying times, with
The temperature heating film of boiling point ± 10 DEG C of organic solvent.Heat drying can be with 2 different the work more than stage of heating temperature
Sequence carries out.At this time it is also possible to proceed by heat drying from low temperature, the heating temperature of next stage can be set as preceding rank
Within+30 DEG C of the heating temperature of section.
In the present embodiment, it on membranaceous composition epoxy resin that can also be on supporter is set to, is configured to protect
Protective layer (such as protective film) for the purpose of shield.By the way that protective layer is configured so that treatability more improves, and can avoid winding
When membranaceous composition epoxy resin be adhered to supporter the back side undesirable condition.
It as protective layer, is not particularly limited, polymeric membrane, metal foil etc. can be enumerated.As polymeric membrane, can enumerate：
The polyolefin films such as polyethylene film, polypropylene screen；The polyester films such as polyethylene terephthalate；Polychloroethylene film；Makrolon
Film；Acetylcellulose film；Tetrafluoroethylene etc..As metal foil, copper foil, aluminium foil etc. can be enumerated.
The thickness of protective layer is not particularly limited, but will be membranaceous from the viewpoint and reduction for obtaining sufficient protecting effect
From the perspective of thickness during composition epoxy resin wound into rolls, or 12~100 μm.
According to the present embodiment, a kind of diaphragm seal is capable of providing, have supporter and is configured on the supporter
Membranaceous composition epoxy resin.Diaphragm seal also can further have in membranaceous composition epoxy resin and support side opposite side
Standby protective layer.
<Electronic device>
Electronic device of the present embodiment has by seal and by the aforementioned sealing being sealed by seal,
Aforementioned by seal is to be selected from least one of group for being made of electronic unit and electronic device, and aforementioned seal portion includes this reality
The composition epoxy resin or its solidfied material or membranaceous composition epoxy resin of the present embodiment that the mode of applying is related to.
Electronic device of the present embodiment is using composition epoxy resin or its solidfied material or membranaceous composition epoxy resin
By what is be sealed to form by seal.As the electronic device for having electronic device, such as it can enumerate and have the half of semiconductor element
Conductor device.
The manufacturing method of electronic device of the present embodiment can have：Utilize epoxy resin of the present embodiment
Composition (membranaceous composition epoxy resin etc.) will be selected from least one of the group being made of electronic unit and electronic device quilt
The sealing process that seal is sealed；And the process for curing aforementioned epoxy resins composition and obtaining sealing.Sealing
Process is, for example, by the way that press composition epoxy resin (membranaceous composition epoxy resin etc.) under heating will be by seal
The process that (such as be set on substrate by seal) is sealed.The manufacturing method of electronic device of the present embodiment
Such as can also have：By under heating by membranaceous composition epoxy resin be pressed by seal so as to utilize membranaceous epoxy
The process that resin combination will be sealed by seal；And make the membranaceous composition epoxy resin after being sealed by seal
The process for being cured and obtaining sealing.
More than, it is illustrated, but the present invention is not limited to above-mentioned implementations for the suitable embodiment of the present invention
Mode can be also carried out within the scope of its spirit suitable for change.
Embodiment
Hereinafter, the present invention is further illustrated, but the scope of the present invention is not limited to these implementations by embodiment
Example.
<Examples 1 to 5 and comparative example 1~4,6>
(making of membranaceous composition epoxy resin)
As the ingredient for forming membranaceous composition epoxy resin, prepare 2 compound represented of table 1 and table.Each ingredient it is detailed
Thin content is as follows.
(A) epoxy resin
[ingredient at 25 DEG C for liquid]
A1：Bisphenol f type epoxy resin (epoxide equivalent：160, Mitsubishi chemical Co., Ltd's manufacture, trade name " jER806 ")
A2：2 function naphthalene type epoxy resin (epoxide equivalents：141, Dainippon Ink Chemicals's manufacture, trade name " HP-4032D ", by
The compound that following formula represents)
[changing 9]
[being not the ingredient of liquid at 25 DEG C]
A3：3 function naphthalene type epoxy resin (epoxide equivalents：182, Dainippon Ink Chemicals's manufacture, trade name " HP-4750 ", by
The compound that formula (IV) represents)
(B) there is the resin of aromatic rings and hydroxyl
[resin with naphthalene nucleus and hydroxyl]
B1：Compound (the hydroxyl equivalent represented by following formula：110, Nippon Steel ＆ Sumitomo Metal Corporation's manufacture, commodity
Name " SN-395 ")
[changing 10]
In formula, n represents the integer more than or equal to 1.
B2：Compound (hydroxyl equivalent with the structure represented by formula (VII)：205, aurification strain formula meeting is lived by Nippon Steel
Society manufactures, trade name " SN-475N ")
[phenolic resin for not having naphthalene nucleus]
B3：Novolak phenolics (hydroxyl equivalent：104, Asahi Organic Chem Ind's manufacture, trade name
“PAPS-PN2”)
(C) organosilicon powder
C1：Shin-Etsu Chemial Co., Ltd manufactures, trade name " KMP605 ", average grain diameter：2μm
C2：Shin-Etsu Chemial Co., Ltd manufactures, trade name " KMP600 ", average grain diameter：5μm
C3：Shin-Etsu Chemial Co., Ltd manufactures, trade name " KMP701 ", average grain diameter：3.5μm
(D) curing accelerator
Shikoku Chem manufactures, trade name " CUREZOL 2P4MZ "
(E) inorganic filler
(Co., Ltd. Admatechs is manufactured silica, trade name " SX-E2 ", phenyl amino silane treatment, average grain
Diameter：5.8μm)
Organic solvent
Methyl ethyl ketone (Co., Ltd. GODO manufactures)
By the use level (unit shown in table 1 and table 2：Mass parts) each ingredient add in 1L polyethylene can in after,
Stirring is disperseed and is mixed for 3 hours, so as to obtain mixed liquor.By the #200 mesh screen (opening diameters of mixed liquor nylon：
75 μm) filtering, acquisition filtrate is as varnish shape composition epoxy resin.Using coating machine by the varnish shape composition epoxy resin
It is made it dry after being coated on supporter (polyethylene terephthalate of 38 μ m-thicks, the manufacture of prince F-Tex Co., Ltd.),
So as to make the laminated body (total thickness of supporter and membranaceous composition epoxy resin：188 μm, the thickness of resin composition layer：150μ
m).In addition, coating and dry condition are as described below.
Coating method：Unfilled corner wheel is coated with
Rate of drying：1m/ minutes
Drying condition (temperature/furnace superintendent)：110℃/3.3m、130℃/3.3m、140℃/3.3m
<Comparative example 5>
Using 2 compound represented of table, varnish shape composition epoxy resin is coated on supporter similarly to Example 1
It is made it dry, but the membranization of resin combination fails to carry out after upper, fails to obtain membranaceous composition epoxy resin.
<Evaluation>
It is conducted the following evaluation using the membranaceous composition epoxy resin of Examples 1 to 5 and comparative example 1~4,6.In addition,
For comparative example 3, the evaluation of amount of warpage and heat resistance is not carried out.For failing to obtain the comparison of membranaceous composition epoxy resin
Treatability is denoted in the table as " B " by example 5.
(evaluation of treatability (bendability))
The bendability of membranaceous composition epoxy resin is using Apparatus for Bending at low-temp and follows the steps below evaluation.As examination
Machine is tested, prepares the Apparatus for Bending at low-temp (JIS type type1, cylinder spindle method) of YOSHIMITSU Jing Ji Co., Ltd. manufacture.It will branch
The laminated body of support body and membranaceous composition epoxy resin is cut into 5cm square, prepares test film.Make the supporter side contacts of test film
The cylinder spindle of diameter 2mm, evaluate has crack-free by membranaceous composition epoxy resin during 180 ° of test film bending.It will not send out
It is good that the situation of raw rupture is set as bendability, is denoted in the table as " A ".It is bad that situation about being ruptured is set as bendability,
It is denoted as in table " B ".By treatability (bendability) evaluation result is shown in table 1 and table 2.
(evaluation of amount of warpage)
[making of evaluation sample]
Prepare the NAFLON of NICHIAS Co., Ltd. manufacture of length 200mm × width 200mm × thickness 1.0mm
Sheet (trade names：TOMBO 9000-S).The central part of NAFLON sheet is cut into length 120mm × width 10mm × thickness
1.0mm is spent, as shown in Figure 1, obtaining the test film 10 with opening 10a.Length 120mm × width is put into being open in 10a
Silicon (Si) substrate of 10mm × thickness 0.725mm, with being cut into length 140mm × width 25mm × thickness 0.025mm's
The polyamide tape of NICHIBAN Co., Ltd. manufacture is from the lower surface of NAFLON sheet by the whole face and NAFLON of silicon substrate
Sheet is fixed, to avoid silicon substrate activity.In the upper surface not being fixed with polyamide tape, to cover silicon substrate
The membranaceous composition epoxy resin of 2 150 μm of thickness is configured (using being cut into length 120mm × width in entire mode on plate
The film of 10mm).It will be under the membranaceous composition epoxy resin that be configured under vacuum (0.1kPa), 110 DEG C of temperature, pressure 0.1MPa
Suppress within 5 minutes.Then, the pressure recovery of compacting is made to obtain the membranaceous epoxy resin group of bonding on a silicon substrate to normal pressure
Close object.Membranaceous asphalt mixtures modified by epoxy resin is ground in a manner that the total thickness of silicon substrate and the laminated body of membranaceous composition epoxy resin becomes 1.00mm
Oil/fat composition.After the laminated body of total thickness 1.00mm being made to cure 2 hours with 140 DEG C of oven, it is made to naturally cool to 25 DEG C, so as to
Obtain warpage piece sample for evaluation.
[assay method of amount of warpage]
Using three-dimensional laser shape measuring apparatus, (Co., Ltd. KEYENCE is manufactured, trade name：LK-030), measure by preceding
State maximum amount of warpage of the warpage sample for evaluation of acquisition at room temperature (25 DEG C).By scanning range be set as 140mm × 20mm,
Sweep span is set as 1.0mm, sweep speed is set as 20mm/s to be measured.Measurement result is shown in table 1 and table 2.
(evaluation of heat resistance)
The laminated body of supporter and membranaceous composition epoxy resin is cut into length 30mm × width 5mm × thickness
0.18mm.Then, the vacuum pressed laminating machine MVLP-500 manufactured using Co., Ltd. Mingji Koito in 90 DEG C of temperature, is taken out
Vacuum time 30 seconds, pressure 0.5MPa, under conditions of 40 seconds pressing times, membranaceous composition epoxy resin face is made to face length
NAFLON sheet (the trade names of NICHIAS Co., Ltd. manufacture of 100mm × width 100mm × thickness 2mm：TOMBO
9000-S) face and be laminated.It later, will be by NAFLON after the supporter for supporting membranaceous composition epoxy resin is removed
The oven that the laminated body that sheet and membranaceous composition epoxy resin are formed is put into 140 DEG C is cured for 2 hours, is laminated
In the cured film of NAFLON sheet.Then, cured film is removed from NAFLON sheet, obtains test sample.Using dynamic
State determination of viscoelasticity device E-4000 (Co., Ltd. UBM manufactures), in stretch mode, fixture spacing 20mm, frequency 10Hz, heating
It is measured under conditions of speed 5/min, the peak value of tan δ when obtaining the measure is as glass transition temperature (Tg).It will be resistance to
Hot (glass transition temperature [DEG C]) evaluation result is shown in table 1 and table 2.
(evaluation of anti-flammability)
Supporter is removed from the laminated body of supporter and membranaceous composition epoxy resin, obtains membranaceous epoxy composite
Object using the mold of the test film for 1/8 inch of molding thickness, is existed the membranaceous composition epoxy resin using compacting is transmitted
140 DEG C of mold temperature, briquetting pressure 1.0MPa, molding time are molded under conditions of 10 minutes.Later, it takes out and cures from mold
Object.Further, using 140 DEG C of oven cure within 2 hours, obtain the test film of 1/8 inch of thickness.Evaluation method according to
UL-94 test method(s)s.In the case where evaluation result reaches " V-1 ", " A " is denoted in the table as, is not up to " V-1 " in evaluation result
In the case of, it is denoted in the table as " B ".By anti-flammability evaluation result is shown in table 1 and table 2.
[table 1]
[table 2]
As known by the foregoing results, the composition epoxy resin of embodiment either treatability, amount of warpage, heat resistance and fire-retardant
Property is good.And in contrast, for Comparative Examples 1 and 2 and 6, although treatability is excellent, substrate after resin seal
Warpage is big, and amount of warpage is poor, and anti-flammability is also poor.For comparative example 3, although excellent in flame retardance, flexibility is low and handles
Property is poor.For comparative example 4, although treatability and excellent in flame retardance, the warpage of the substrate after resin seal is big, amount of warpage
Difference.For comparative example 5, fail membranization, treatability is poor.
Symbol description
10 ... test films, 10a ... openings.
Claims (6)
1. a kind of composition epoxy resin, contains：(A) resin, (C) with aromatic rings and hydroxyl of epoxy resin, (B) are organic
Si powder, (D) curing accelerator and (E) inorganic filler,
Epoxy resin when (A) epoxy resin is included in 25 DEG C for liquid,
The resin of (B) with aromatic rings and hydroxyl includes the resin with naphthalene nucleus and hydroxyl,
It is described at 25 DEG C on the basis of (A) epoxy resin and (B) have the total amount of resin of aromatic rings and hydroxyl
When be liquid epoxy resin content be more than or equal to 32 mass %,
On the basis of the total amount of composition epoxy resin, the content of (C) organosilicon powder is 0.80~7.30 mass %,
In, when the composition epoxy resin contains solvent, the total amount of composition epoxy resin does not include the solvent.
2. composition epoxy resin as described in claim 1, the resin with naphthalene nucleus and hydroxyl is included by the following general formula
(I) compound represented,
[changing 1]
In formula (I), R11、R12、R13、R14And R15Each independently represent the alkane of hydrogen atom, the alkyl of carbon number 1~6 or carbon number 1~2
Oxygroup；M1, m2, m3, m4, m5, m6, m7 and m8 each independently represent 0~2 integer, wherein, not including m1, m2, m3, m4,
The situation of m5, m6, m7 and m8 all 0；N1 represents 0~10 integer.
3. composition epoxy resin as claimed in claim 1 or 2, on the basis of the total amount of composition epoxy resin, (C)
The content of organosilicon powder is 2~7 mass %, wherein, when the composition epoxy resin contains solvent, epoxy composite
The total amount of object does not include the solvent.
4. composition epoxy resin according to any one of claims 1 to 3, (C) organosilicon powder has siloxanes
Key is cross-linked into three-dimensional netted structure.
5. a kind of membranaceous composition epoxy resin, it includes composition epoxy resin according to any one of claims 1 to 4 or
Its solidfied material.
6. a kind of electronic device, have by seal and by the sealing being sealed by seal, it is described to be sealed
Body is to be selected from least one of group being made of electronic unit and electronic device,
The sealing includes composition epoxy resin according to any one of claims 1 to 4 or its solidfied material or right
It is required that the membranaceous composition epoxy resin described in 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015153457 | 2015-08-03 | ||
| JP2015-153457 | 2015-08-03 | ||
| PCT/JP2016/072537 WO2017022721A1 (en) | 2015-08-03 | 2016-08-01 | Epoxy resin composition, film-shaped epoxy resin composition, and electronic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108137793A true CN108137793A (en) | 2018-06-08 |
| CN108137793B CN108137793B (en) | 2021-12-24 |
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|---|---|
| JP (1) | JP6801659B2 (en) |
| KR (1) | KR102477938B1 (en) |
| CN (1) | CN108137793B (en) |
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| CN113604184A (en) * | 2021-10-09 | 2021-11-05 | 武汉市三选科技有限公司 | Chip packaging material, chip packaging structure and packaging method |
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| CN108864654B (en) * | 2017-05-10 | 2023-07-14 | 味之素株式会社 | Resin composition layer |
| TWI787295B (en) * | 2017-06-29 | 2022-12-21 | 日商昭和電工材料股份有限公司 | Resin composition for encapsulation, semiconductor package and method of producing semiconductor package |
| JP6815293B2 (en) * | 2017-08-16 | 2021-01-20 | 信越化学工業株式会社 | Thermosetting epoxy resin sheet for semiconductor encapsulation, semiconductor device, and its manufacturing method |
| JP7184002B2 (en) * | 2019-09-13 | 2022-12-06 | 味の素株式会社 | resin composition |
| CN113292957B (en) * | 2021-07-27 | 2021-10-26 | 武汉市三选科技有限公司 | Underfill adhesive for chip packaging and chip packaging structure |
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| Publication number | Publication date |
|---|---|
| CN108137793B (en) | 2021-12-24 |
| KR102477938B1 (en) | 2022-12-14 |
| JPWO2017022721A1 (en) | 2018-05-24 |
| JP6801659B2 (en) | 2020-12-16 |
| WO2017022721A1 (en) | 2017-02-09 |
| TW201716501A (en) | 2017-05-16 |
| TWI728992B (en) | 2021-06-01 |
| KR20180037017A (en) | 2018-04-10 |
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