CN103571412B - Adhesive composition having improved reliability at high voltage condition and adhesive tape for semiconductor packaging using the same - Google Patents
Adhesive composition having improved reliability at high voltage condition and adhesive tape for semiconductor packaging using the same Download PDFInfo
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- CN103571412B CN103571412B CN201310282858.7A CN201310282858A CN103571412B CN 103571412 B CN103571412 B CN 103571412B CN 201310282858 A CN201310282858 A CN 201310282858A CN 103571412 B CN103571412 B CN 103571412B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Lead Frames For Integrated Circuits (AREA)
Abstract
The present invention relates to an adhesive composition having an improved reliability at a high voltage condition and an adhesive tape for semiconductor packaging using the same. In the adhesive composition of the present invention, an epoxy resin comprises an epoxy curing agent of an optimum amount, so that the fracture toughness can be enhanced by enhancing a crosslinking density, and accordingly, the electrical reliability under a high voltage of 30V or greater is guaranteed. The molecules are crosslinked intensively in a curing network, thereby satisfying an excellent high temperature adhesiveness under the temperature of 200 DEG C or greater. Therefore, the adhesive composition of the present invention can be used for the adhesive tape which is very useful in the semiconductor packaging field, the semiconductor packaging field is accompanied by the high temperature technologies of more than 200 DEG C, such as the lead bonding, the tin soldering, etc. Moreover, the adhesive composition also can be used in the high voltage field effectively, such as the elevator, vehicle, semiconductor packaging, etc.
Description
Technical field
The present invention relates to have the enhancing adhesive of electrical reliability and being used for using this adhesive under high pressure
The adhesive tape of semiconductor packages.More specifically under high pressure with electrical reliability（electrical
reliability）Adhesive and using this adhesive the adhesive tape for semiconductor packages, wherein in epoxy
Epoxy hardener containing the optimum mix amount, fracture toughness is strengthened will pass through enhancing crosslink density, so as in 30V or more height
Pressure ensure that electrical reliability, because molecule is firmly crosslinked in curing network, therefore in 200 DEG C or more high temperature
Under obtain outstanding high temperature adhesivity.
Background technology
According to factors such as width, thickness, semiconductor packages area, wire length, chip bonding pad areas, various being used for is manufactured
The lead frame of semiconductor is installed.The typical structure of lead frame draws including lead frame main body, the outside extended from main body
Center is used to install semiconductor chip in line, the inner lead that body interior is extended to from outside lead, internally positioned lead
Chip bonding pad to its top surface, the tie-rod for being connected to chip bonding pad.
Efficiently integrated and packaging technology cost reduces this main trend to comply with semiconductor, and lead frame becomes to be directed to partly leads
The multiplicity of body encapsulation.
Although however, leadframe-type becomes variation, the lead in lead frame according to different encapsulating structures
What would generally be formed is very thin, so just needs to perform the various techniques such as lead welding, further, since external factor and make lead
It is easy to electrical connection failure when rocking.Accordingly, it would be desirable to lead fixation adhesive tape is bonded, to securely fix lead.
Brief summary is welded in technique for sticking of the lead frame with lead fixation adhesive tape by lead and partly led below
The step of wiring being formed between body and lead frame.First, lead fixation adhesive tape is cut off by punching press, and at 130 to 260 DEG C
Be adhered to lead fixation adhesive tape on lead frame after 0.1 to 1.0 second by punching press under compression temperature.
Second, using die bonding film by the chip of semiconductor chip agglutination to the lead frame for being stained with lead fixation adhesive tape
On pad.
3rd, the heat treatment of 5 to 90 minutes is carried out generally at a temperature of 130 to 180 DEG C, to solidify bonding semiconductor
The die bonding film of chip and lead frame.
Last 4th, welded by lead, complete the lead of the semiconductor chip and lead-frame packages through Overheating Treatment
Wiring between framework.At this moment, line lead welding is entered at a high temperature of 200 to 260 DEG C.
Due to lead fixation adhesive tape should in lead welding procedure anchor leg, although lead fixation adhesive tape is in nature
Lead frame is adhered under temperature and pressure, but lead welding procedure is carried out under 200 DEG C or higher temperature, and lead is fixed
Adhesive tape is typically the product of B-stage, therefore after being adhered on lead frame under the natural temperature and pressure, it is intended to by 130
Heat treatment to 180 DEG C reaches C-stage.
Although however, the lead in lead frame is bonded using lead fixation adhesive tape, being welded due to entering line lead
High temperature during technique, the viscosity of lead fixation adhesive tape becomes rubbery state, therefore the resistance to migration of lead is reduced.
Therefore, lead migration can bring electrical connection problem, so when the wire widths of lead frame are thinner, very may be used
Problems can occur.
Material typically can be sealed by coating epoxy resin to lead-frame packages（EMC）, after making pressure be adapted to complete to encapsulate
Operation, if lead frame is made up of copper product, then the insulating reliability between lead is major issue because
Electric short circuit can sometimes occur.
The mechanism of electric short circuit is illustratively produced, first, copper ion flows out from lead, be then applied to lead frame envelope
The pressure loaded onto shifts to another lead as driving force, the copper ion of precipitation.
At this moment, the copper ion for reaching another lead is precipitated as copper, and then cement copper is assembled and develops into dendron.
Finally, dendron reaches another lead, and electric short circuit is occurred because lead is electrically connected by copper.
That is, the driving force of copper ion migration is used as by the voltage for being applied, therefore electrical short occurs.Especially
It is such as elevator, vehicle, semiconductor packages in the case where high pressure is applied, this problem can be more serious.
Therefore, after completion lead-frame packages, it is desirable that migrated with high resistance lead in lead welding procedure
The adhesive of performance and under high pressure have safe insulation reliability and at high temperature have adhesivity.
But, high temperature adhesivity and insulating reliability are generally difficult to presence simultaneously.
That is, in order to improve high temperature adhesivity and insulating reliability, use the thermosetting resin meeting containing relatively small molecular weight
Increase reflection speed, and can improve crosslink density using the thermosetting resin containing smaller equivalent.However, due to only by containing compared with
The thermoset network that the thermosetting resin of small equivalent is constituted is enbrittled, and adhesivity is poor at high temperature.
Therefore, by making great efforts to improve the problem in prior art, the present inventor provides a kind of adhesive, this
Adhesive strengthens crosslink density by a kind of special epoxy hardener included in the curing network based on epoxy, from
And strengthen electrical reliability, the adhesive mobility under high temperature is improved by strengthening the fracture toughness of curing network, it is determined that with
There is high resistance lead migration performance in lead welding procedure in the adhesive tape of the semiconductor packages using adhesive, and complete
The adhesivity under the insulating reliability and high temperature under high pressure is met after into lead-frame packages simultaneously.
The content of the invention
Therefore, in view of the above mentioned problem occurred in prior art is made that the present invention, it is an object of the invention to provide one
Adhesive is planted, this adhesive has high resistance lead migration performance in lead welding procedure, and completes lead frame
After encapsulation, it is ensured that the adhesivity under insulating reliability and high temperature under high pressure.
It is a further object to provide a kind of adhesive, wherein the epoxy for carrying out curing reaction with epoxy resin is consolidated
Agent is included in epoxy, and the fracture toughness of curing network is strengthened will pass through enhancing crosslink density.
A further object of the present invention is directed to the semiconductor packages a kind of adhesive tape of offer for using adhesive.
To achieve these goals, according to an aspect of the invention, there is provided a kind of adhesive, including：（a）
The epoxy of 100 weight portions（epoxy base resin）,（b）30 to 100 weight portions contain polyfunctional phenolic resin
（multi-functional phenolic resin）The first epoxy hardener,（c）20 to 250 weight portions contain amine
Base epoxy hardener（amine-based epoxycuring agent）, anhydride group epoxy hardener（anhydride-based
epoxy curing agent）Or two kinds of second epoxy hardeners of mixing,（d）The curing accelerator of 0.1 to 10 weight portion,
And（e）The modifying agent being made up of thermoplastic resin of 30 to 150 weight portions（thermoplastic resin）.
In adhesive of the invention, component（b）The first epoxy hardener and component（c）Second curable epoxide
Agent preferably has 300 or less epoxy reaction equivalent.Additionally, for number-average molecular weight, component（b）The first epoxy
Curing agent and component（c）Second epoxy hardener preferably have 3,000 or more molecular weight.
At this point, in adhesive of the invention, component（b）In polyfunctional phenolic resin in the molecule have two
Individual or two or more phenolic hydroxyl group, hydroxyl equivalent is 100 to 300, and this can meet component（b）And component（c）Condition, component
（c）Anhydride group epoxy hardener be vinyl acetate-maleic anhydride copolymer（vinyl acetate-maleic anhydride
copolymer）Or styrene-maleic anhydride copolymer（styrene-maleic anhydride copolymer）.
In adhesive of the invention, component（e）Thermoplastic resin be single resin or from by polyester polyol
（polyester polyol）, dispersion acrylic rubber in the epoxy（acrylic rubber）, core shell rubbers（core
shell rubber）, carboxyl end group butyronitrile（carboxy terminated butadiene nitrile）, acrylonitrile-butadiene-
Styrene（acrylonitrile-butadiene-styrene）, polysiloxanes（polymethyl siloxane）And phenoxy group
Resin（phenoxy resin）The hybrid resin selected in the group of composition.
Additionally, adhesive of the invention may be included also（f）The fluorine surfactant of 0.001 to 1 weight portion.
The varnish of adhesive preferably contains the solids content of 10 to 50% weight in organic solvent.
The present invention provides a kind of adhesive tape for the semiconductor packages using adhesive.
As preferred first embodiment, the invention provides a kind of adhesive linkage for having on basement membrane and being made up of adhesive
Lead fixation adhesive tape.
Additionally, as second preferred embodiment, the invention provides a kind of with being formed by the adhesive on mould release membrance
Adhesive-layer two-sided tape.
When adhesive linkage is made into 20 μ m thick, adhesive tape of the invention has（a）Accelerate to answer the high of 30V or more is carried out
The insulating properties of wire short-circuiting resistance 500 hours or more are kept when power is tested,（b）When the copper of adhesive tape bonding to printed circuit board (PCB)
Paper tinsel mat surface and when being peeled off in 180 ° of angles under 200 DEG C or higher temperature, meets the tough of 1.0 to 2.5N/cm high temperature adhesivities
Property.
The invention provides a kind of adhesive, wherein the epoxy hardener containing optimum content in epoxy, with
Will pass through enhancing crosslink density to strengthen the fracture toughness of curing network, electrically may be used so as to be ensure that under 30V or more high pressures
By property, outstanding high temperature adhesivity is obtained under 200 DEG C or more high temperature.
Further, since the adhesive with high temperature adhesivity and high pressure reinforced insulation reliability is highly suitable for semiconductor
The adhesive tape of encapsulation, therefore can provide lead fixation adhesive tape or two-sided tape using this adhesive.
Lead fixation adhesive tape of the invention or two-sided tape have high resistance lead migration performance in lead welding procedure,
And after lead-frame packages are completed, the adhesivity under the insulating reliability and high temperature under high pressure can be met.
Brief description of the drawings
Fig. 1 shows the sample of the High-Voltage Insulation reliability of lead fixation adhesive tape in the test present invention, wherein in polyamide
Copper circuit is formd on film.
Fig. 2 is shown and lead fixation adhesive tape is bonded in the copper circuit of Fig. 1 samples in adhesive direction by thermal means
The sample being made.
Fig. 3 shows the High-Voltage Insulation reliability test result carried out for lead fixation adhesive tape of the invention.
Fig. 4 is shown after High-Voltage Insulation reliability testing is carried out to lead fixation adhesive tape of the invention, using micro-
The result of sem observation sampler unit.
Fig. 5 shows a kind of method for measuring toughness at high temperature, to test the height of lead fixation adhesive tape in the present invention
Warm reliability.
Description of reference numerals
1：Kapton
2：Aluminium sheet
3：Adhesive-layer
4：Slide and separate section
Specific embodiment
The invention provides a kind of adhesive, wherein including（a）The epoxy of 100 weight portions,（b）30 to 100 weights
The first epoxy hardener containing polyfunctional phenolic resin of part is measured,（c）20 to 250 weight portions contain amido curable epoxide
Agent, anhydride group epoxy hardener or two kinds of second epoxy hardeners of mixing,（d）The curing accelerator of 0.1 to 10 weight portion, with
And（e）The modifying agent being made up of thermoplastic resin of 30 to 150 weight portions.
Adhesive of the invention has 300 or less reaction equivalents and HMW comprising a kind of in epoxy
Special epoxy hardener, as the curing agent for carrying out with epoxy resin curing reaction, is strengthened with will pass through enhancing crosslink density
The fracture toughness of curing network.Therefore, the crosslink density of B-stage is strengthened, and is increased by improving the fragility of thermosetting network
Strong fracture toughness.
Additionally, thermosetting network can obtain toughness comprising thermoplastic resin by adding wherein, or can pass through
Thermosetting resin containing larger equivalent adjusts the adhesive mobility under high temperature.
Every kind of component of adhesive in the present invention is hereinafter described.
In adhesive of the invention, component（a）Epoxy be not particularly limited, but with 200 or more
It is preferential using in a molecule in the annular of molecular weight or the serial molecule of the aliphatic of linear backbone, alicyclic or aromatic series
In have two or more glycidol groups two or more epoxy resin.
For example, epoxy can include the epoxy resin with single main chain glycidol group, such as bisphenol-A epoxy tree
Fat, bisphenol F epoxy resin, bisphenol-A D epoxy resin, bisphenol-s epoxy resin, alicyclic ring epoxide resin, alicyclic ring chain epoxy resin, benzene
Phenol novolak epoxy, cresol novolak epoxy, Naphthol-based Epoxy Resin, fluorine-based epoxy resin, imide epoxy resin etc.
Deng, or reacted and the epoxy resin of acquisition by the resin or rubber with different physical properties and main chain, such as epihalohydrin changes
Property epoxy resin, acrylic modified epoxy resin, ethylene modified epoxy resin, Modified Epoxy Resin by Elastomers, amine modified epoxy
Resin etc..
At this point, epoxy preferably 470 or less equivalents, preferably 300 or less equivalents, so as in solidification
Ensure glass transition temperature and mechanical strength afterwards.Additionally, in terms of preferred physical characteristic or cured article, aromatic epoxy resin is excellent
From making epoxy.
In the present invention, aromatic epoxy resin is the epoxy resin with fragrant ring skeleton, such component in molecule（a）
There are two or more epoxy radicals in a molecule, and use the aromatic epoxy resin with 470 or smaller equivalents.
In addition it is possible to use a kind of epoxy resin or two or more epoxy resin compositions.
In adhesive of the invention, component（b）It is the first epoxy hardener, its first-selection has two in a molecule
Individual or two or more phenolic hydroxyl group phenolic resin, it is preferable to have the polyfunctional phenolic resin of 100 to 300 hydroxyl equivalents.
On this point, if the hydroxyl equivalent of phenolic resin is less than 100, will be made due to the fragility of the cured article of epoxy
The pooling feature of semiconductor packages declines, if hydroxyl equivalent is more than 300, the insulating reliability and heat resistance of synthetic will be
Degenerated under high pressure, because crosslink density is reduced.
Therefore, first-selection is used as component（b）The polyfunctional phenolic resin of the first epoxy hardener can be single resin
Or by biphenyl type phenolic resin, linear phenol-aldehyde resin, bisphenol F phenolic varnish gum, bisphenol F resin, bisphenol a resin, phenolic aldehyde
Varnish gum, cresol novolac resin, bisphenol A phenolic resin, phenolic aldehyde aralkyl resin, multi-functional novolac resin, dicyclopentadiene line
Selected in the group that type novolac resin, amino triazine novolac resin and polybutadiene phenol resol resins are constituted
Two or more hybrid resin.
Additionally, for number-average molecular weight, polyfunctional phenolic resin use molecular weight for 3000 or more component, therefore
Adhesive of the invention can keep adhesivity under 200 DEG C or more high temperature.At this point, molecular weight be 3000 or with
On polymer promote to tangle between polymer chains, therefore keep adhesivity under 200 DEG C or higher temperature.
Therefore, although bisphenol A novolac resin（It is Mai Tu company（The U.S.）SD-1508 phenolic resin products）It is used as
Polyfunctional phenolic resin, can meet the above-mentioned condition in the embodiment of the present invention, but it is also possible to use the business for meeting above-mentioned condition
Industry product or synthesis compound.
In adhesive of the invention, work as component（b）Polyfunctional phenolic resin be used as epoxy hardener when, it is epoxy functionalized
Equivalent proportion between group and phenolic hydroxyl group group is generally 1:1.2 and 1:It is adjusted between 0.6.However, due in the present invention
Use second epoxy curing agent component（c）, therefore phenolic resin amount is preferably reduced, to limit the curing reaction of phenol, from
And strengthen the crosslink density of B-stage.
Therefore, equivalent proportion is preferably regulated as 1:0.6 or lower, from the perspective of than in terms of from weight, with regard to component（a）In 100 weight portions
Epoxy for, preferably comprise the polyfunctional phenolic resin of 30 to 100 weight portions, this is component（b）The first ring
Oxygen curing agent.If at this point, the content of polyfunctional phenolic resin is less than 30 weight portions, epoxy resin or unreacted
Curing agent is retained in whole adhesive, this reduces crosslinking.If the content of polyfunctional phenolic resin is more than 100 weight
Part, then in adhesive it may happen that side reaction, rather than expected curing reaction and decomposition reaction.
In adhesive of the invention, component（c）It is second epoxy hardener, it is any to be carried out with epoxy-functional
The epoxy hardener of curing reaction can be used.It is therefore preferable that using amine based curative or anhydride group curing agent.
Anhydride group curing agent is preferably used, the polyimides of lead fixation adhesive tape basement membrane is used as in anhydride group curing agent and the present invention
（PI）There is stickiness very high between film.When anhydride group curing agent is used as the adhesive of lead fixation adhesive tape（This is
The first purpose of adhesive in the present invention）, it is less sensitive for change in size, and because initial reaction temperature is higher,
So with outstanding insulating properties.
Although anhydride group curing agent has initial reaction temperature and relatively low curing reaction speed higher, can be by bag
Component containing adhesive in the present invention（d）In the reaction of curing accelerator improve curing reaction speed.
Therefore, it can by comprising component（d）Curing accelerator adjust solidification temperature and speed.Anhydride group curing agent is more
Well with adhesive working life more long, and can be from by methyl hexahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, 1,2,4,5- equal benzene
Its preferred exemplary is selected in the group that tetracarboxylic acid dianhydride, benzophenone tetracarboxylic dianhydride (BTDA) and phthalic anhydride are constituted.
The component included in adhesive of the invention（c）Second epoxy hardener for number-average molecular weight using point
Son amount is 3000 or more component, with component（b）Polyfunctional phenolic resin ratio it is identical, so as to keep at high temperature compared with
Adhesivity high.
Unimolecule epoxy hardener from above-mentioned illustration is different, number-average molecular weight be 3000 or more epoxy hardener lead to
Increase molecular weight usually through the copolymerisation with other polymers.
Meeting the preferred exemplary of anhydride group curing agent that number-average molecular weight in the present invention is 3000 or more can be from acetic acid second
Selected in alkene ester-copolymer-maleic anhydride and styrene-maleic anhydride copolymer, but be not limited to this.
Styrene-maleic anhydride copolymer is preferably used as second epoxy hardener.Because with similar molecule
In the curing agent of amount, due to the space steric effect of the polymer chain with large volume side-chain structure, phenylethylene-maleic anhydride
Good entanglement is formed between each chain, so it can effectively control the mobility of adhesive under high temperature.It is therefore preferable that using benzene
Ethylene maleic acid anhydride copolymer is used as second epoxy hardener.
Amine based curative is preferably selected as from polyethyleneimine and polyetheramine and is included in adhesive of the invention
Component（c）Second epoxy hardener, and second epoxy hardener be preferably used in mixed way with above-mentioned anhydride group curing agent.
The content of second epoxy hardener included in adhesive of the invention is with regard to component（a）100 weight portions ring
20 to 250 weight portions are preferably for oxygen tree fat.If at this point, second content of epoxy hardener is less than 20 weight
Part, then epoxy resin and unreacted curing agent can be retained in whole adhesive, therefore can reduce crosslink density.If second
The content of epoxy hardener is planted more than 250 weight portions, then it may happen that side reaction, anti-rather than expected solidification in adhesive
Should and decomposition reaction.
The component included in adhesive of the invention（d）It is a kind of curing accelerator, for increasing component（a）Epoxy radicals
Resin and component（b）The first epoxy hardener and component（c）Second epoxy hardener solidification rate.
If adhesive of the invention is used as the adhesive tape such as lead fixation adhesive tape of semiconductor packages, by lead fixation adhesive tape
Hardening time can be shortened when being bonded on printed circuit board (PCB) or electronic element assembly, because including component in adhesive（d）'s
Curing accelerator.
Although the solidification acceleration of curing agent is limited under the conditions of 100 DEG C or temperature below in the present invention, in order to avoid to glue
Stick working life produces harmful effect.But accelerate curing reaction at a temperature of 100 DEG C or more, to improve crosslink density.
Organic phosphine based compound such as triphenylphosphine, imidazole-based compounds such as 2-ethyl-4-methylimidazole or tertiary amine can be used as
Preferred consolidation accelerator.
With regard to component（a）100 weight portions epoxy for, the present invention in component（d）Curing accelerator it is excellent
It is 0.1 to 10 weight portion to select content.If at this point, the content of curing accelerator is less than 0.1 weight portion, cannot be expected
The acceleration effect of curing reaction, if the content of curing accelerator is more than 10 weight portions, can be due to quick in a manufacturing process
There is curing reaction and make the ratio sufficient degree that adhesive-layer is formed more stiff, therefore be difficult the viscosity needed for being bonded, this
Harmful effect can be produced to dimensional stability.
The component included in adhesive of the invention（e）It is a kind of modifying agent formed by thermoplastic resin, it can improve
The fragility of epoxy resin, so as to strengthen fracture toughness and alleviate internal stress.
With regard to component（a）100 weight portions epoxy for, the component included in adhesive of the invention（e）'s
Modifying agent preferred content is 30 to 150 weight portions.If at this point, the content of modifying agent is less than 30 weight portions, be unfavorable for
Enhancing fracture toughness and alleviation internal stress, if the content of modifying agent is more than 150 weight portions, cure component contains in adhesive
Amount can be reduced suddenly, therefore may reduce mechanically and electrically reliability after hardening.
According to the type of other adhesive components, can be from polyester polyol, dispersion acrylic acid in the epoxy
Rubber, core shell rubbers, carboxyl end group nitrile rubber（Carboxy terminated butadiene nitrile rubber,
CTBN）, acrylonitrile-butadiene-styrene (ABS), be chosen for use as component in polymethyl siloxane and phenoxy resin（e）Modifying agent
Thermoplastic resin.
Preferably, when adhesive of the invention is used for the adhesive tape of semiconductor packages, bonding location should be flexible, therefore uses
Polyester polyol（polyester polyol）Or carboxyl end group nitrile rubber（CTBN）.
Further, since purpose of the invention, it is desirable at high temperature with very strong adhesion characteristics, therefore preferably use
The preferable phenoxy resin of epoxy resin or adaptability with of a relatively high glass transition temperature.
Preferably polyester polyol or carboxyl end group nitrile rubber can be used in combination with phenoxy resin.
The particle of core shell rubbers is the rubber particles with stratum nucleare and shell.For example, it is double-layer structure, wherein outer shell
It is glassy polymers, inner nuclear layer is rubber-like polymer, or is three-decker, and wherein outer shell is glassy polymers,
Intermediate layer is rubber-like polymer, and inner nuclear layer is glassy polymers.At this point, glassy polymers methyl methacrylate
Ester polymer, rubber-like polymer is made up of butyl acrylate thing.
In addition to above-mentioned synthetic component, adhesive of the invention can additionally comprise a kind of adhesive, and such as surface is lived
Property agent, coupling agent, inorganic filler etc..At this point, with regard to the component of 100 weight portions（a）Epoxy for, comprising
The fluorine surfactant of 0.001 to 1 weight portion is used as additive.
Especially it is possible to using the surfactant coating performance appropriate for basement membrane is provided, first-selection uses macromolecule silica
The FC-4430 of alkane, such as organic acrylic polymers, polyalcohol, or fluorine-based compound such as 3M Co..
Solid of the varnish of adhesive preferably in organic solvent containing the weight of above-claimed cpd 10 to 50% contains in the present invention
Amount.If at this point, solids content is less than 10% weight, being difficult to remove the organic solvent of residual in drying process,
If solids content is beyond 50% weight, it is difficult to ensure that there is sufficient compatibility between adhesive.
The adhesive of above-mentioned composition has outstanding insulating properties under 30V or more high pressures in the present invention, because even
Crosslink density higher is formed in B-stage, and adhesivity higher is kept under 200 DEG C or more high temperature, because
Molecule has carried out strong crosslinking in curing network.
Additionally, a kind of adhesive tape is provided present invention is alternatively directed to the semiconductor packages using adhesive, can be with 200 DEG C
Or more the field of semiconductor package of high-temperature technology such as lead welding, soldering etc. use.
In the present invention adhesive tape of semiconductor packages played between the component of semiconductor package connection, inserts and absolutely
The effect of edge layer, at this point, adhesive surface can be two-sided or one side.
, it is necessary to protect adhesive surface to exempt to be affected by or physical damage after formation adhesive surface, until inciting somebody to action
It is applied to semiconductor packaging process.Therefore, generally the diaphragm with peel property is stacked on adhesive surface, in this point
On, diaphragm can from polyolefin such as polyethylene, polyvinyl chloride, polypropylene etc., polyester such as polyethylene terephthalate etc. or from
Selected in type paper.
10 to 150 μm of the thickness first-selection of diaphragm, except grout technique and embossing technology, can be satisfied with by stripping technology
Ground processing diaphragm.Diaphragm can be removed before adhesion technique is carried out.
As the first first-selected embodiment of semiconductor packages adhesive tape, semiconductor packages basement membrane to be used for the invention provides one kind
On lead fixation adhesive tape, lead fixation adhesive tape has the adhesive-layer that is formed by adhesive.
In an embodiment of the present invention, by the physical characteristic of test lead fixation adhesive tape, demonstrate and go out under normal temperature
The adhesivity of color, and tested by the Resin Flow shown in table 1, it is determined that even if being pressed under 180 to 230 DEG C of high temperature
Lead fixation adhesive tape, the mobility of adhesive resin is still restricted.
Additionally, carrying out accelerated stress test high by lead fixation adhesive tape of the invention（HAST）, i.e., such as the institutes of Fig. 1 to 3
Show and measure resistance per hour under 30V or more high pressures, as a result show, electrical shorting issues under high pressure can be solved
Certainly, because up to resistance drop is not observed in the experiment condition of 500 hours.
Fig. 4 shown after accelerated stress test high is performed, using the result of micro- sem observation lead fixation adhesive tape, by
Dendron will not be produced in copper circuit in lead fixation adhesive tape of the invention, thus may determine that lead fixation adhesive tape under high pressure
Insulation characterisitic.
Additionally, measuring high temperature reliability by for lead fixation adhesive tape of the invention, as a result determine outstanding anti-skidding
Property [table 2] and high temperature adhesivity（Strength of glass）[table 3], it is determined that by controlling mobility at high temperature, it can be ensured that this hair
Bright adhesive has sufficient toughness.
In the present invention in first of the semiconductor packages adhesive tape lead fixation adhesive tape of first-selected embodiment, basement membrane can be by
Engineering plastics comprising polyphenylene sulfide or polyimides are constituted, it is contemplated that electric insulating quality and physical toughness, first-selection use polyamides
Imines film.At this point, 10 to 150 μm of the thickness first-selection of polyimide film.In addition to grout technique and corona technique, may be used also
Additionally process of surface treatment is carried out with basement membrane.Particularly, if by applying adhesive varnish of the invention on basement membrane
And varnish is dried and adhesive-layer is formed, the adhesive tape of semiconductor packages B-stage can be manufactured.At this point, obtaining
In the technique of adhesive varnish, it is possible to use organic solvent, to obtain the mixing of various components easily, can preferably use and appoint
A kind of or Conventional solvents and chlorine solvent（Such as dichloromethane）Mixing.Conventional solvents include ketone such as acetone, MEK, hexamethylene
Ketone etc., acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol methyl ether acetate etc., aromatic hydrocarbon such as toluene, two
Toluene etc..Additionally, after the varnish of adhesive is coated on basement membrane, by heating, dry and aging can form viscose glue
Layer, adhesive-layer does not receive organic solvent and volatile matter（Such as by the moisture of moisture absorption generation）Influence.Heating and drying are 200
DEG C or less（It is preferred that 180 DEG C or less）The high temperature drying processes for carrying out, when using organic solvent, can be made by heating
Organic solvent in adhesive is vapored away.Aging is at 70 DEG C or less（It is preferred that 50 DEG C or less）The low temperature drying work for carrying out
Skill, by aging technique, can further reduce the volatile matter produced by the moisture absorption.
Additionally, as second preferred embodiment of semiconductor packages adhesive tape, semiconductor to be used for the invention provides one kind
The two-sided tape of encapsulation, this two-sided tape has the adhesive-layer formed by the adhesive on mould release membrance.
Different from the above-mentioned lead fixation adhesive tape for semiconductor packages, the mould release membrance with peel property is used as basement membrane,
Mould release membrance preferably from polyolefin such as polyethylene, polyvinyl chloride, polypropylene etc., polyester such as polyethylene terephthalate etc. or release liners
Middle selection.Do not reached five minutes by the way that the pressure for applying 8Mpa under 100 DEG C or lower temperature is long, machinery is carried out to two-sided tape
Compression, the mould release membrance as basement membrane is separated, and finally uses the adhesive surface being tightly bonded on mould release membrance.
Although present only the physical characteristic of lead fixation adhesive tape in embodiments of the invention, these physics are specific to be based on
The characteristic of adhesive, due to two-sided tape（The model usage of semiconductor packages adhesive tape in the present invention）Also adhesive is used, can be with
Naturally it is understood that two-sided tape can ensure the adhesivity under outstanding insulating properties and high temperature under high pressure.
That is, when adhesive linkage is made into 20 μm of thickness, the adhesive tape in the present invention for semiconductor packages meets（a）
When the accelerated stress test high of 30V or more is carried out using 200 μm of test specimen, in 85% relative humidity and 130 DEG C of high temperature
The lower insulating properties for keeping short-circuit resistance 500 hours or more,（b）By the Copper Foil mat surface of adhesive tape bonding to printed circuit board (PCB)
Afterwards, when being peeled off in 180 ° of angles under 200 DEG C or higher temperature, the toughness of 1.0 to 2.5N/cm high temperature adhesivities is met.
Additionally, it is used for the adhesive tape of semiconductor packages in the present invention, as 5mm in adhesive tape bonding to aluminium sheet and at 200 DEG C or more
When being torn in 180 ° of angles under high-temperature, the skid resistance of 20 to 35N is met.
Hereinafter, the present invention will be more fully described by embodiment.
This is that, in order to more specifically describe the present invention, the scope of the present invention is not limited to these embodiments.
Embodiment 1 manufactures adhesive
Just as component（a）Epoxy 100 weight portions dicyclopentadiene epoxy resin（Japanese Nippon Kayaku
XD-1000）For, the bisphenol A novolac resin of 50 weight portions（The SD1508 of Mai Tu company of the U.S., number-average molecular weight is
3100th, epoxide equivalent is 120）As component（b）The first epoxy hardener, the phenylethylene-maleic anhydride of 40 weight portions（Number
Average molecular weight is 4500, and epoxide equivalent is 260）As component（c）Second epoxy hardener, the 2- methyl of 0.1 weight portion
Imidazoles is used as component（d）Curing accelerator, the nitrile rubber of 80 weight portions as by component（e）Thermoplastic resin formed change
Property agent, the component of 0.1 weight portion（f）Fluorine surfactant（The FC4430 of U.S. 3M）It is added to MEK as additive molten
In agent, by room temperature and pressure mixing them five hours, so as to manufacture solids content concn for the weight of total composition 28%
The adhesive varnish of amount.
Embodiment 2 manufactures adhesive
Just as component（a）Epoxy 100 weight portions bisphenol A epoxide resin（Kukdo Chemical
Co. KDS-8128）For, the novolac resin of 50 weight portions（The MEH- of Japanese Myungsung Hwasung Co.
7500H, number-average molecular weight is that 290, epoxide equivalent is 97）As component（b）The first epoxy hardener, the benzene of 40 weight portions
Ethylene-maleic acid（Number-average molecular weight is 4500, and epoxide equivalent is 260）As component（c）Second epoxy hardener,
The 2-methylimidazole of 0.1 weight portion is used as component（d）Curing accelerator, the nitrile rubber of 70 weight portions and 10 weight portions benzene
Epoxide resin is used as by component（e）Thermoplastic resin formed modifying agent, the component of 0.1 weight portion（f）Fluorine surfactant
（The FC4430 of U.S. 3M）It is added in methyl ethyl ketone solvent as additive, by room temperature and pressure mixing them
Five hours, so as to manufacture the adhesive varnish that solids content concn is the weight of total composition 28%.
Embodiment 3 manufactures adhesive
Just as component（a）Epoxy 100 weight portions bisphenol A epoxide resin（Kukdo Chemical
Co. KDS-8128）For, the novolac resin of 60 weight portions（The MEH- of Japanese Myungsung Hwasung Co.
7500H, number-average molecular weight is that 290, epoxide equivalent is 97）As component（b）The first epoxy hardener, the weight of 40 weight portions
Amount is than being 1:The polyetheramine of 1 mixing（The T-5000 of U.S. Huntsman Co.）And phenylethylene-maleic anhydride（Number-average molecular weight is
4500, epoxide equivalent is 260）Mixture as component（c）Second epoxy hardener, the 2- methyl miaows of 0.1 weight portion
Azoles is used as component（d）Curing accelerator, the nitrile rubber of 70 weight portions and 10 weight portions phenoxy resin as by component
（e）Thermoplastic resin formed modifying agent, the component of 0.1 weight portion（f）Fluorine surfactant（The FC4430 of U.S. 3M）Make
For additive is added in methyl ethyl ketone solvent, by room temperature and pressure mixing them five hours, so as to manufacture solid
Body content concn is the adhesive varnish of the weight of total composition 28%.
Comparative example 1 manufactures adhesive
Just as component（a）Epoxy 100 weight portions dicyclopentadiene epoxy resin（Japanese Nippon Kayaku
XD-1000）For, the MDA of 60 weight portions（Molecular weight is that 198.2, epoxide equivalent is 49.6）As single point
Sub- epoxy hardener, 100 weight portion nitrile rubbers are used as by component（e）The thermoplastic resin modifying agent, 0.1 weight portion that are formed
Fluorine surfactant（The FC4430 of U.S. 3M）It is added in methyl ethyl ketone solvent as additive, by room temperature and atmospheric pressure
It is lower to mix them five hours, so as to manufacture the adhesive varnish that solids content concn is the weight of total composition 28%.
Comparative example 2 manufactures adhesive
Just as component（a）Epoxy 100 weight portions dicyclopentadiene epoxy resin（Japanese Nippon Kayaku
XD-1000）For, except the novolac resin of 50 weight portions（The MEH- of Japanese Myungsung Hwasung Co.
7500H, number-average molecular weight is that 290, epoxide equivalent is 97）As component（b）The first epoxy hardener outside, comprising 60 weight
The phthalic anhydride of part（Molecular weight is 148.1, and epoxide equivalent is 79.1）As component（c）Second curable epoxide of unimolecule
Agent, adhesive varnish is manufactured using component in the same manner as in Example 1 and content.
Embodiment 4 manufactures lead fixation adhesive tape
After the adhesive of 20 μ m-thicks manufactured in embodiment 1 is coated on the polyamide basement membrane of 50 μ m-thicks, will be thin
Film dries in the air ten minutes at being placed on 50 DEG C.Then, heated three minutes at 170 DEG C in convective oven, form viscous with 20 μ m-thicks
The lead fixation adhesive tape of the semiconductor packages of glue-line.
Embodiment 5 manufactures lead fixation adhesive tape
Technique manufacture is carried out by method in the same manner as in Example 4, difference is that the adhesive that will be manufactured in embodiment 2 is applied
It is applied on the polyamide basement membrane of 50 μ m-thicks, forms the lead fixation adhesive tape of the semiconductor packages of the adhesive-layer with 20 μ m-thicks.
Embodiment 6 manufactures lead fixation adhesive tape
Technique manufacture is carried out by method in the same manner as in Example 4, difference is that the adhesive that will be manufactured in embodiment 3 is applied
It is applied on the polyamide basement membrane of 50 μ m-thicks, forms the lead fixation adhesive tape of the semiconductor packages of the adhesive-layer with 20 μ m-thicks.
Comparative example 3 and 4 manufactures lead fixation adhesive tape
Manufacturing process is carried out by method in the same manner as in Example 4, difference is the viscose glue that will be manufactured in comparative example 1 or 2
Agent is coated on the polyamide basement membrane of 50 μ m-thicks, forms the lead fixing glue of the semiconductor packages of the adhesive-layer with 20 μ m-thicks
Band.
Experimental example 1 tests Resin Flow
The lead fixation adhesive tape manufactured in embodiment 4 to 6 and comparative example 3 and 4 is adhered on the thick aluminium sheets of 1mm, wherein
Lead fixation adhesive tape is cut into 10mm（It is wide）×100mm（It is high）Size, and by viscose glue be placed in face of 1mm thickness aluminium sheet position
Put.Then it is up to 1 second by applying the pressure of 8Mpa at a temperature of 180 DEG C, 210 DEG C and 230 DEG C respectively, by lead fixing glue
Band is compressed on aluminium sheet.Sample is manufactured under above-mentioned contractive condition, and measures the width of the adhesive flowed out from lead fixation adhesive tape
Degree.Measured altogether ten times in vertical direction, i.e., measured five times in left side and right side respectively, then calculate its average value.
[table 1]
Test the result of Resin Flow
| Compression temperature | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 3 | Comparative example 4 |
| 180℃ | 140μm | 150μm | 130μm | 190μm | 210μm |
| 210℃ | 190μm | 210μm | 180μm | 400μm | 420μm |
| 230℃ | 230μm | 280μm | 210μm | 650μm | 700μm |
By the Resin Flow test result shown in table 1, what is manufactured in embodiment 4 to 6 and comparative example 3 and 4 is all
Lead fixation adhesive tape shows that Resin Flow increases with the increase of pressing temperature.However, with comparative example 3 to 4 in lead
Fixation adhesive tape is compared, and the lead fixation adhesive tape manufactured in embodiment 4 to 6 all shows relatively restricted under every kind of temperature conditionss
Resin Flow.
The accelerated stress test high of experimental example 2（HAST）
In order to test the electricity of the lead fixation adhesive tape of the semiconductor packages manufactured in embodiment 4 to 6 and comparative example 3 and 4
Gas reliability, accelerated stress test high has been carried out by method shown in Fig. 1 and 2.
Fig. 1 shows the sample of the electrical reliability of lead fixation adhesive tape in the test present invention, wherein in polyamide film
On form copper circuit, and earth electrode unit is placed on two ends.It it is 200 μm by the space allocation between copper circuit.
Fig. 2 is shown and be bonded by the lead fixation adhesive tape that will be manufactured in embodiment 4 to 6 and comparative example 3 and 4 with thermal means
The sample manufactured in the copper circuit of Fig. 1 test specimens, wherein carrying out hot compression to lead fixation adhesive tape with adhesive side
To the copper circuit of covering test specimen, compression temperature, compression time and pressure are adjusted to 200 DEG C, 1 second and 8Mpa respectively.Next, making
Test specimen with convective oven to being stained with lead fixation adhesive tape at a temperature of 180 DEG C carries out the solidification of a hour.Make electrode list
After unit's contact positive electrode and negative electrode, at 130 DEG C of temperature and 85% relative humidity, the test specimen to solidifying applies 30V electricity
Pressure, measures a change for resistance per hour.
Fig. 3 shows the test result of the High-Voltage Insulation reliability of lead fixation adhesive tape in the present invention, in embodiment 4 to 6
The lead fixation adhesive tape of middle manufacture under the experiment condition of 500 hours up to not showing resistance drop.However, in comparative example 3 and 4
The lead fixation adhesive tape of middle manufacture just showed resistance drop before 100 hours.
Fig. 4 is shown after High-Voltage Insulation reliability testing is carried out to lead fixation adhesive tape of the invention, using micro-
The result of sem observation sampler unit.If in the lead fixation adhesive tape manufactured in comparative example 3 and 4, dendron is determined
Growth reaches comparative electrode, so as to produce electric short circuit.However, if in the lead fixing glue manufactured in embodiment 4 to 6
Band, it was observed that the electrode surface of cleaning, it is thus determined that not producing dendron.
The accelerated stress test high of experimental example 3
The high pressure that be shown below is carried out for the lead fixation adhesive tape manufactured in embodiment 4 to 6 and comparative example 3 and 4 can
By property test.
As shown in figure 5, by embodiment 4 to 6 and comparative example 3 and 4 manufacture lead fixation adhesive tape be adhered to aluminium sheet 2 it
Afterwards, wherein forming adhesive-layer 3 on basement membrane 1, measurement is brought from both direction lead fixing glue of tearing by a temperature of 200 DEG C
Skid resistance, and measure the toughness under high temperature.
As described above after each layer is stacked, it is up to 1 second by compressing storehouse at 180 DEG C of temperature and 8MP pressure, from
And manufacture test sample.If using the universal testing machine with high temperature chamber（UTM）With 10 DEG C per minute of increment temperature
Increase to 200 DEG C afterwards, test sample is torn towards the direction of arrow, the bonding plane of the relative narrower of the adhesive surface of test sample will
Slide, be then finally recovered.Record the time point institute being finally recovered from the time point to test sample applying power to bonding plane
The time for needing and the maximum, force when bonding plane is separate.Measurement result is shown in table 2.
[table 2]
Skid resistance measurement result
| Test event | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 3 | Comparative example 4 |
| Force time | 2.5 seconds | 2.5 seconds | 2.5 seconds | 2.5 seconds | 2.5 seconds |
| Maximum, force during fracture | 35 Ns | 32 Ns | 28 Ns | 17 Ns | 14 Ns |
Although it was determined that in embodiment 4 to 6 and comparative example 3 and 4 from the result of the measurement skid resistance shown in table 2
The duration of the lead fixation adhesive tape force of manufacture is identical, but when bonding plane is slided and is separated, to being made in embodiment 4 to 6
The maximum, force that the lead fixation adhesive tape made applies is than big 10N of lead fixation adhesive tape of manufacture or more in comparative example 3 and 4.
Additionally, the lead fixation adhesive tape manufactured in embodiment 4 to 6 and comparative example 3 and 4 is bonded on the Copper Foil of 1/20z,
Lead fixation adhesive tape is wherein cut into 10mm（It is wide）×100mm（It is high）Size, by viscose glue be placed on contact Copper Foil position, and
The pressure for applying 8Mpa under by being spent at 180 DEG C is up to 1 second, is adhered on Copper Foil.Using with the omnipotent of high temperature chamber
Testing machine is increased temperature to 200 DEG C with 10 DEG C per minute of increment, and the stripping for then measuring the sample being adhered on Copper Foil is strong
Degree, while PI faces of tearing.Measurement result is shown in table 3.
[table 3]
The measurement result of high temperature peel strength
| Test event | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 3 | Comparative example 4 |
| Peel strength | 1.8 Ns | 1.6 Ns | 1.8 Ns | 0.3 N | 0.4 N |
Additionally, observed from the peel strength measurement result of the display of table 3, due to the lead manufactured in embodiment 4 to 6
The peel strength of fixation adhesive tape than four times high of the lead fixation adhesive tape or more manufactured in comparative example 3 and 4, it is determined that at 200 DEG C
Or more there is under high temperature outstanding adhesivity.
As described above, the invention provides a kind of adhesive, wherein the epoxy containing optimised quantity is consolidated in epoxy
Agent, fracture toughness is strengthened will pass through enhancing crosslink density, so that adhesive can under high pressure have insulating reliability,
There is outstanding skid resistance and adhesivity at high temperature.
In the present invention, being manufactured using adhesive can securely fix lead frame while having under elevated pressure conditions outstanding
The lead fixation adhesive tape of insulating properties, and adhesive of the invention can be used as double-sided adhesive jelly in semiconductor fab technique,
Semiconductor fab technique generally includes 200 DEG C or more of high temperature assembly technology.
Particularly, above-mentioned adhesive of the invention is due to even in B-stage just foring high crosslink density, therefore in 30V
Or more there are under high pressure outstanding insulating properties, and due to carrying out intensity crosslinking to molecule in curing network, thus
Adhesivity high is kept under 200 DEG C or more high temperature, therefore in the case of applying is high-tension, such as elevator, vehicle, semiconductor packages
Deng it can be highly useful.
Although according to specific illustrative embodiment, invention has been described, and the present invention is not limited by these embodiments
System, is only limited by accessory claim.It is to be understood that those skilled in the art change or improve these embodiments, also not
Depart from the scope of the present invention and spirit.
Claims (9)
1. a kind of adhesive, including：
The epoxy of (a) 100 weight portion,
The first epoxy hardener comprising polyfunctional phenolic resin of (b) 30 to 100 weight portion,
The anhydride group epoxy hardener of (c) 20 to 250 weight portion,
The curing accelerator of (d) 0.1 to 10 weight portion,
The modifying agent formed by thermoplastic resin of (e) 30 to 150 weight portion；
Wherein the anhydride group epoxy hardener of component (c) is vinyl acetate-maleic anhydride copolymer or styrene-maleic anhydride copolymer
Thing；
There are two or more phenolic hydroxyl group, hydroxyl equivalent is 100 wherein in the polyfunctional phenolic resin molecule of component (b)
To 300.
2. adhesive according to claim 1, wherein the second of the first epoxy hardener of component (b) and component (c)
Planting epoxy hardener has 300 or less epoxy reaction equivalent.
3. adhesive according to claim 1, wherein for number-average molecular weight, the first curable epoxide of component (b)
Second epoxy hardener of agent and component (c) has 3,000 or more molecular weight.
4. adhesive according to claim 1, the thermoplastic resin of wherein component (e) is from by polyester polyol, dispersion
Acrylic rubber in the epoxy, core shell rubbers, end carboxyl butyronitrile, acrylonitrile-butadiene-styrene (ABS), methyl polysilicone
The single resin or hybrid resin selected in the group that alkane and phenoxy resin are constituted.
5. adhesive according to claim 1, further comprising the fluorine surfactant of (f) 0.001 to 1 weight portion.
6. adhesive according to claim 1, the wherein varnish of adhesive contain 10 to 50% weight in organic solvent
Solids content.
7. a kind of adhesive tape for semiconductor packages, is had as the adhesive according to claim any one of 1-6 in base
The lead fixation adhesive tape of adhesive-layer is formed on film.
8. a kind of adhesive tape for semiconductor packages, be have as the adhesive according to claim any one of 1-6 from
The two-sided tape of adhesive-layer is formed on type film.
9. the adhesive tape according to claim 7 or 8, wherein when the thickness of adhesive-layer is 20 μm, described adhesive tape has：
A () keeps insulating properties of the short-circuit resistance up to 500 hours when 30V or more accelerated stress test high is carried out,
B () peels off at a temperature of 200 DEG C or more after the Copper Foil mat surface of adhesive tape bonding to printed circuit board (PCB) in 180 ° of angles
When, meet the toughness of 1.0 to 2.5N/cm high temperature adhesivities.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2012-0078113 | 2012-07-18 | ||
| KR20120078113 | 2012-07-18 |
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| CN103571412A CN103571412A (en) | 2014-02-12 |
| CN103571412B true CN103571412B (en) | 2017-05-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310282858.7A Expired - Fee Related CN103571412B (en) | 2012-07-18 | 2013-07-05 | Adhesive composition having improved reliability at high voltage condition and adhesive tape for semiconductor packaging using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5799056B2 (en) |
| KR (1) | KR101395322B1 (en) |
| CN (1) | CN103571412B (en) |
| TW (1) | TWI500734B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AU2015362688B2 (en) * | 2014-12-18 | 2021-01-21 | Cytec Industries Inc. | Modified resin systems suitable for liquid resin infusion |
| CN104974471B (en) * | 2015-07-14 | 2017-12-05 | 江苏兆鋆新材料股份有限公司 | A kind of high heat-resisting, high-toughness epoxy resin carbon fibre composite preparation method |
| CN106281175A (en) * | 2016-09-22 | 2017-01-04 | 佛山慧创正元新材料科技有限公司 | A kind of PET film epoxyn |
| JP6739390B2 (en) * | 2017-03-30 | 2020-08-12 | 富士フイルム株式会社 | Method for manufacturing organic EL image display device |
| TWI719419B (en) * | 2019-03-11 | 2021-02-21 | 台光電子材料股份有限公司 | Epoxy resin composition and articles made therefrom |
| JP2021161274A (en) * | 2020-03-31 | 2021-10-11 | 株式会社有沢製作所 | Adhesive tape |
| CN114806432A (en) * | 2022-03-23 | 2022-07-29 | 东莞市穗滢新型材料科技有限公司 | Anti-aging high-temperature-resistant polyimide adhesive tape and preparation method thereof |
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|---|---|---|---|---|
| US5863988A (en) * | 1995-12-25 | 1999-01-26 | Tomoegawa Paper Co., Ltd. | Liquid adhesive for electronic parts and adhesive tape |
| CN101210162A (en) * | 2006-12-28 | 2008-07-02 | 西安西电变压器有限责任公司 | Semi-conductor adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3118420B2 (en) * | 1996-06-12 | 2000-12-18 | 株式会社巴川製紙所 | Liquid adhesives and adhesive tapes for electronic components |
| JP4577716B2 (en) * | 2005-01-21 | 2010-11-10 | 日本化薬株式会社 | Heat curable epoxy resin composition and article having a cured adhesive layer thereof |
| JP2008074891A (en) * | 2006-09-19 | 2008-04-03 | Daicel-Cytec Co Ltd | Thermosetting or active energy ray curing composition and film |
| JP2010510653A (en) * | 2006-11-16 | 2010-04-02 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Board-on-chip package and manufacturing method thereof |
| JP4352282B1 (en) * | 2008-10-24 | 2009-10-28 | 住友ベークライト株式会社 | Adhesive composition for semiconductor and semiconductor device manufactured using the same |
| JP5670048B2 (en) * | 2009-12-21 | 2015-02-18 | 株式会社Ｄｎｐファインケミカル | Adhesive composition and method for producing curable adhesive sheet |
| KR101045262B1 (en) * | 2009-12-21 | 2011-06-29 | 제일모직주식회사 | Semiconductor adhesive composition for stealth dicing and adhesive film using it |
| KR101374364B1 (en) * | 2010-12-27 | 2014-03-17 | 제일모직주식회사 | Adhesive composition for semiconductor, adhesive film comprising the same |
| CN103282456B (en) * | 2010-12-27 | 2016-12-14 | 第一毛织株式会社 | For the adhesive composition of quasiconductor and the binder film comprising it |
-
2012
- 2012-12-12 KR KR1020120144111A patent/KR101395322B1/en active IP Right Grant
-
2013
- 2013-06-14 TW TW102121144A patent/TWI500734B/en not_active IP Right Cessation
- 2013-06-14 JP JP2013125152A patent/JP5799056B2/en active Active
- 2013-07-05 CN CN201310282858.7A patent/CN103571412B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5863988A (en) * | 1995-12-25 | 1999-01-26 | Tomoegawa Paper Co., Ltd. | Liquid adhesive for electronic parts and adhesive tape |
| CN101210162A (en) * | 2006-12-28 | 2008-07-02 | 西安西电变压器有限责任公司 | Semi-conductor adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014019869A (en) | 2014-02-03 |
| TW201404857A (en) | 2014-02-01 |
| KR20140011906A (en) | 2014-01-29 |
| CN103571412A (en) | 2014-02-12 |
| KR101395322B1 (en) | 2014-05-16 |
| TWI500734B (en) | 2015-09-21 |
| JP5799056B2 (en) | 2015-10-21 |
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