CN103571412A - 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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- CN103571412A CN103571412A CN201310282858.7A CN201310282858A CN103571412A CN 103571412 A CN103571412 A CN 103571412A CN 201310282858 A CN201310282858 A CN 201310282858A CN 103571412 A CN103571412 A CN 103571412A
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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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- 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
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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
- 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
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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- 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
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- 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
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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
- 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
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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
- 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
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- 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 under high pressure there is the glue paste of the electric reliability of enhancing and the adhesive tape for semiconductor packages that uses this glue paste.More particularly, relate under high pressure the there is electric reliability glue paste of (electrical reliability) and the adhesive tape for semiconductor packages that uses this glue paste, wherein in epoxy, contain the epoxy hardener of the optimum mix amount, to strengthen fracture toughness by strengthening cross-linking density, thereby guaranteed electric reliability under 30V or above high pressure, therefore because molecule is firmly cross-linked in curing network, under 200 ℃ or above high temperature, obtained outstanding high-temp glue viscosity.
Background technology
According to factors such as width, thickness, semiconductor packages area, wire length, chip bonding pad areas, manufacture various for semi-conductive lead frame is installed.The typical structure of lead frame comprise lead frame main body, from the extended outside lead of main body, from outside lead extend to body interior inner lead, be positioned at inner lead center for semi-conductor chip is installed to its end face chip bonding pad, be connected to the tie-rod of chip bonding pad.
Comply with efficient integrated and this megatrend of packaging process cost of semi-conductor, lead frame has become the diversified structure for semiconductor packages.
Yet; although leadframe-type becomes diversified according to different encapsulating structures, it is very thin that the lead-in wire in lead frame can form conventionally, so just needs to carry out the various techniques such as wire bonds; while in addition, lead-in wire being rocked due to external factor, be easy to occur electrical connection fault.Therefore, need bonding lead-in wire fixation adhesive tape, to firmly fix lead-in wire.
Below brief summary in the technique for sticking of lead frame and lead-in wire fixation adhesive tape, by wire bonds, between semi-conductor and lead frame, forms the step connecting up.First, by punching press, cut off lead-in wire fixation adhesive tape, and punching press bonded to lead-in wire fixation adhesive tape on lead frame after 0.1 to 1.0 second under the compression temperature of 130 to 260 ℃.
The second, use die bonding film by semiconductor chip agglutination to being stained with on the chip bonding pad of lead frame of lead-in wire fixation adhesive tape.
The 3rd, conventionally at the temperature of 130 to 180 ℃, carry out the thermal treatment of 5 to 90 minutes, to solidify the die bonding film of bonding semi-conductor chip and lead frame.
Last the 4th, by wire bonds, complete through the wiring between heat treated semi-conductor chip and the lead frame of lead-frame packages.At this moment, under the high temperature of 200 to 260 ℃, carry out wire bonds.
Due to lead-in wire fixation adhesive tape should be in wire bonds technique anchor leg, although lead-in wire fixation adhesive tape is to bond to lead frame under natural temperature and pressure, but wire bonds technique is carried out under 200 ℃ or higher temperature, lead-in wire fixation adhesive tape is the product in B stage normally, therefore, after bonding on lead frame under natural temperature and pressure, the thermal treatment being intended to by 130 to 180 ℃ makes it reach the C stage.
Yet, bonding although the lead-in wire in lead frame adopts lead-in wire fixation adhesive tape to carry out, the high temperature owing to carrying out wire bonds technique, the viscosity of lead-in wire fixation adhesive tape has become rubbery state, and therefore the anti-transport property of lead-in wire reduces.
Therefore, lead-in wire migration can bring electrical connection problem, so when the wire widths of lead frame is thinner, very may there is problems.
Generally can be by applying epoxy resin envelope material (EMC) to lead-frame packages, make pressure be applicable to encapsulation operation afterwards, if lead frame consists of copper product, the insulating reliability between lead-in wire is a major issue so, because sometimes can there is electric short circuit.
The mechanism that produces electric short circuit is once described, first, cupric ion flows out from lead-in wire, is then applied to pressure in lead-frame packages as motivating force, and the cupric ion of precipitation is shifted to another lead-in wire.
At this moment, the cupric ion that arrives another lead-in wire is precipitated as copper, and then precipitated copper is assembled and developed into dendron.
Finally, dendron arrives another lead-in wire, because lead-in wire is electrically connected electric short circuit is occurred by copper.
In other words, because applied voltage has been used as the motivating force of copper ion migration, so there is electrical short.Particularly, in the situation that applying high pressure, as elevator, vehicle, semiconductor packages etc., this problem can be more serious.
Therefore,, after completing lead-frame packages, what need is in wire bonds technique, have the glue paste of high resistance lead-in wire migration performance and under high pressure have safe insulation reliability and at high temperature have tackiness.
But high-temp glue viscosity and insulating reliability are difficult to exist conventionally simultaneously.
In other words,, in order to improve high-temp glue viscosity and insulating reliability, using to contain compared with the thermosetting resin of small molecules amount to increase reflection speed, and uses the thermosetting resin that contains less equivalent can improve cross-linking density.Yet because the thermoset network only consisting of the thermosetting resin that contains less equivalent is enbrittled, at high temperature tackiness is poor.
Therefore, by making great efforts to improve the problem in prior art, the present inventor provides a kind of glue paste, this glue paste strengthens cross-linking density by a kind of special epoxy hardener comprising in the curing network based on epoxy, thereby strengthen electric reliability, by strengthening the fracture toughness of curing network, improve the glue paste mobility under high temperature, be identified for using the adhesive tape of the semiconductor packages of glue paste in wire bonds technique, to there is high resistance lead-in wire migration performance, and after completing lead-frame packages, meet insulating reliability under high pressure and the tackiness under high temperature simultaneously.
Summary of the invention
Therefore, in view of the problems referred to above that occur in prior art have been made the present invention, the object of this invention is to provide a kind of glue paste, this glue paste has high resistance lead-in wire migration performance in wire bonds technique, and after completing lead-frame packages, guarantee insulating reliability under high pressure and the tackiness under high temperature.
Another object of the present invention is to provide a kind of glue paste, is wherein cured with epoxy resin the epoxy hardener reacting and is included in epoxy, to strengthen the fracture toughness of curing network by strengthening cross-linking density.
Another object of the present invention is for using the semiconductor packages of glue paste that a kind of adhesive tape is provided.
To achieve these goals, according to an aspect of the present invention, a kind of glue paste is provided, comprising: (a) epoxy of 100 weight parts (epoxy base resin), (b) the first epoxy hardener that contains polyfunctional phenolic resin (multi-functional phenolic resin) of 30 to 100 weight parts, (c) 20 to 250 weight parts contains amido epoxy hardener (amine-based epoxycuring agent), the second epoxy hardener of acid anhydride base epoxy hardener (anhydride-based epoxy curing agent) or two kinds of mixing, (d) curing catalyst of 0.1 to 10 weight part, and (e) properties-correcting agent being formed by thermoplastic resin of 30 to 150 weight parts (thermoplastic resin).
In glue paste of the present invention, the second epoxy hardener of the first epoxy hardener of component (b) and component (c) has 300 or following epoxy reaction equivalent better.In addition,, with regard to number-average molecular weight, the second epoxy hardener of the first epoxy hardener of component (b) and component (c) has 3,000 or above molecular weight better.
In this, in glue paste of the present invention, polyfunctional phenolic resin in component (b) has two or more phenol hydroxyls in molecule, hydroxyl equivalent is 100 to 300, this can meet the condition of component (b) and component (c), and the acid anhydride base epoxy hardener of component (c) is vinyl acetate between to for plastic-copolymer-maleic anhydride (vinyl acetate-maleic anhydride copolymer) or styrene-maleic anhydride copolymer (styrene-maleic anhydride copolymer).
In glue paste of the present invention, the thermoplastic resin of component (e) is single resin or from by polyester polyol (polyester polyol), be dispersed in the acrylic rubber (acrylic rubber) in epoxy resin, core shell rubbers (core shell rubber), carboxyl end group butyronitrile (carboxy terminated butadiene nitrile), acrylonitrile-butadiene-styrene (ABS) (acrylonitrile-butadiene-styrene), the hybrid resin of selecting in the group that polysiloxane (polymethyl siloxane) and phenoxy resin (phenoxy resin) form.
In addition, glue paste of the present invention may also comprise the fluorine surfactant of (f) 0.001 to 1 weight part.
The varnish of glue paste preferably contains the solids content of 10 to 50% weight in organic solvent.
The present invention is directed to and use the semiconductor packages of glue paste that a kind of adhesive tape is provided.
As preferred the first embodiment, the invention provides a kind of lead-in wire fixation adhesive tape on basement membrane with the adhesive linkage being formed by glue paste.
In addition,, as the second preferred embodiment, the invention provides a kind of double sticky tape with the adhesive-layer being formed by the glue paste on release film.
When adhesive linkage is made into 20 μ m thickness, adhesive tape of the present invention has (a) and keep wire short-circuiting resistance 500 hours or above insulating property when carrying out 30V or above high accelerated stress test, (b) when adhesive tape bonding to the Copper Foil uneven surface of printed circuit board (PCB) and under 200 ℃ or higher temperature when peel off at 180 ° of angles, meet the toughness of 1.0 to 2.5N/cm high-temp glue viscosity.
The invention provides a kind of glue paste, wherein in epoxy, contain the epoxy hardener of optimum content, to strengthen the fracture toughness of curing network by strengthening cross-linking density, thereby under 30V or above high pressure, guaranteed electric reliability, under 200 ℃ or above high temperature, obtained outstanding high-temp glue viscosity.
In addition, owing to thering is the glue paste of high-temp glue viscosity and high pressure reinforced insulation reliability, be suitable for very much the adhesive tape of semiconductor packages, so adopt this glue paste that lead-in wire fixation adhesive tape or double sticky tape can be provided.
Lead-in wire fixation adhesive tape of the present invention or double sticky tape have high resistance lead-in wire migration performance in wire bonds technique, and after completing lead-frame packages, can meet insulating reliability under high pressure and the tackiness under high temperature.
Accompanying drawing explanation
Fig. 1 has shown the sample of the High-Voltage Insulation reliability of the fixation adhesive tape that goes between in test the present invention, wherein on polyamide layer, has formed copper circuit.
Fig. 2 has shown the sample of making in glue paste direction is bonded in the copper circuit of Fig. 1 sample by lead-in wire fixation adhesive tape by thermal means.
Fig. 3 has shown the High-Voltage Insulation reliability testing result of carrying out for lead-in wire fixation adhesive tape of the present invention.
Fig. 4 has shown after lead-in wire fixation adhesive tape of the present invention is carried out to High-Voltage Insulation reliability testing, uses the result of microscopic examination sampler unit.
Fig. 5 has shown a kind of method of at high temperature measuring toughness, so that the high temperature reliability of the fixation adhesive tape that goes between in test the present invention.
Description of reference numerals
1: Kapton
2: aluminium sheet
3: adhesive-layer
4: slide and separate part
Embodiment
The invention provides a kind of glue paste, the epoxy that wherein comprises (a) 100 weight parts, (b) the first epoxy hardener that contains polyfunctional phenolic resin of 30 to 100 weight parts, (c) the second epoxy hardener that contains amido epoxy hardener, acid anhydride base epoxy hardener or two kinds of mixing of 20 to 250 weight parts, (d) curing catalyst of 0.1 to 10 weight part, and (e) properties-correcting agent being formed by thermoplastic resin of 30 to 150 weight parts.
Glue paste of the present invention comprises and a kind ofly in epoxy, has 300 or the special epoxy hardener of following reaction equivalent and high molecular, as being cured with epoxy resin the solidifying agent reacting, to strengthen the fracture toughness of curing network by strengthening cross-linking density.Therefore, the cross-linking density in B stage is enhanced, and strengthens fracture toughness by improving the fragility of thermosetting network.
In addition, thermosetting network can obtain toughness containing thermoplastic resin by additional packet therein, or can adjust the glue paste mobility under high temperature by the thermosetting resin that contains larger equivalent.
Below every kind of component of glue paste in the present invention will be introduced in detail.
In glue paste of the present invention, the epoxy of component (a) is not particularly limited, but having 200 or more in the annular of polymolecular amount or the aliphatics of linear backbone, the molecule that alicyclic or aromatic series is serial, preferentially adopt and in a molecule, there is two or more epoxy resin of two or more Racemic glycidol groups.
For example, epoxy can comprise the epoxy resin with single main chain Racemic glycidol group, as bisphenol A epoxide resin, bisphenol F epoxy resin, dihydroxyphenyl propane D epoxy resin, bisphenol-s epoxy resin, alicyclic ring epoxide resin, alicyclic ring chain epoxy resin, phenol novolac epoxy resins, cresol novolak epoxy, Naphthol-based Epoxy Resin, fluorine-based epoxy resin, imide epoxy resin etc., or react by thering is resin or the rubber of different physical properties the epoxy resin obtaining with main chain, as epihalohydrin modified epoxy, acrylic modified epoxy resin, ethene modified epoxy, Modified Epoxy Resin by Elastomers, amine-modified epoxy resin etc.
In this, epoxy preferably 470 or equivalent still less, preferably 300 or equivalent still less, to guarantee second-order transition temperature and physical strength after solidifying.In addition,, from preferred physical property or solidifying product aspect, aromatic epoxy resin is preferably used as epoxy.
In the present invention, aromatic epoxy resin is the epoxy resin in molecule with aromatic nucleus skeleton, and component (a) has two or more epoxy group(ing) in a molecule like this, and uses and to have 470 or the aromatic epoxy resin of less equivalent.In addition, can use a kind of epoxy resin or two or more epoxy resin composition.
In glue paste of the present invention, component (b) is the first epoxy hardener, and its first-selection has the resol of two or more phenol hydroxyls in a molecule, preferably has the polyfunctional phenolic resin of 100 to 300 hydroxyl equivalents.In this, if the hydroxyl equivalent of resol is less than 100, will make due to the fragility of the solidifying product of epoxy the pooling feature of semiconductor packages decline, if hydroxyl equivalent surpasses 300, the insulating reliability of synthetics and thermotolerance will under high pressure be degenerated, because cross-linking density has reduced.
Therefore, the polyfunctional phenolic resin of first-selected the first epoxy hardener as component (b) can be two or more hybrid resin of selecting in single resin or the group consisting of biphenyl type resol, lacquer resins, bisphenol F phenolic varnish resin, Bisphenol F resin, bisphenol a resin, novolac resin, cresol novolac resin, bisphenol A phenolic resin, phenolic aldehyde aralkyl resin, multi-functional novolac resin, dicyclopentadiene phenolic novolac, aminotriazine novolac resin and polyhutadiene phenol novolac resin.
In addition, with regard to number-average molecular weight, it is 3000 or above component that polyfunctional phenolic resin adopts molecular weight, and therefore glue paste of the present invention can keep tackiness under 200 ℃ or above high temperature.In this, molecular weight be 3000 or above polymkeric substance impel between polymer chain and tangle, therefore under 200 ℃ or higher temperature, keep tackiness.
Therefore, although bisphenol-A phenolic varnish resin (the SD-1508 resol product of Shi Maitu company (U.S.)) is as polyfunctional phenolic resin, can meet the above-mentioned condition in the embodiment of the present invention, but also can use commerical prod or the synthetic compound that meets above-mentioned condition.
In glue paste of the present invention, when the polyfunctional phenolic resin of component (b) is used as epoxy hardener, the equivalence ratio between epoxy-functional and phenol hydroxyl groups is adjusted conventionally between 1:1.2 and 1:0.6.Yet, owing to using in the present invention the second epoxy hardener component (c), therefore preferably reduce resol amount, so that the curing reaction of restriction phenol, thereby the cross-linking density in B stage strengthened.
Therefore, equivalence ratio is preferably adjusted into 1:0.6 or lower, from weight ratio aspect, with regard to the epoxy of 100 weight parts in component (a), preferably comprises the polyfunctional phenolic resin of 30 to 100 weight parts, and this is the first epoxy hardener of component (b).In this, if the content of polyfunctional phenolic resin is less than 30 weight parts, epoxy resin or unreacted solidifying agent are retained in whole glue paste, have so just reduced crosslinked.If the content of polyfunctional phenolic resin surpasses 100 weight parts, in glue paste, may there is side reaction, rather than curing reaction and the decomposition reaction of expection.
In glue paste of the present invention, component (c) is the second epoxy hardener, anyly can be cured the epoxy hardener reacting with epoxy-functional and can use.Therefore, preferably use amido solidifying agent or acid anhydride base solidifying agent.
Preferably use acid anhydride base solidifying agent, in acid anhydride base solidifying agent and the present invention, be used as between polyimide (PI) film of the fixation adhesive tape basement membrane that goes between and there is very high stickiness.When acid anhydride base solidifying agent is used as the glue paste of lead-in wire fixation adhesive tape (this is one of object of glue paste in the present invention), it is less sensitive for dimensional change, and because initial reaction temperature is higher, so there is outstanding insulativity.
Although acid anhydride base solidifying agent has higher initial reaction temperature and lower curing reaction speed, can improve curing reaction speed by the reaction that comprises the curing catalyst in the component of glue paste (d) in the present invention.
Therefore, can adjust solidification value and speed by the curing catalyst that comprises component (d).Acid anhydride base solidifying agent has longer tackiness agent working life better, and can be from by methyl hexahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, 1, in the group that 2,4,5-pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride and Tetra hydro Phthalic anhydride form, select its preferred exemplary.
It is 3000 or above component that the second epoxy hardener of the component comprising in glue paste of the present invention (c) is used molecular weight with regard to number-average molecular weight, identical with the ratio of the polyfunctional phenolic resin of component (b), at high temperature keep higher tackiness.
Different from the unit molecule epoxy hardener of above-mentioned illustration, number-average molecular weight be 3000 or above epoxy hardener conventionally by increasing molecular weight with the interpolymerization of other polymkeric substance.
Meet number-average molecular weight in the present invention and be 3000 or the preferred exemplary of above acid anhydride base solidifying agent can from vinyl-acetic ester-copolymer-maleic anhydride and styrene-maleic anhydride copolymer, select, but be not limited to this.
Preferably use styrene-maleic anhydride copolymer as the second epoxy hardener.Because in having the solidifying agent of similar molecular weight, owing to having the space steric effect of the polymer chain of large volume side-chain structure, phenylethylene-maleic anhydride forms good entanglement between each chain, so it can effectively control the mobility of glue paste under high temperature.Therefore, preferably use styrene-maleic anhydride copolymer as the second epoxy hardener.
Amido solidifying agent is preferably selected as the second epoxy hardener that is included in the component (c) in glue paste of the present invention from polymine and polyetheramine, and the second epoxy hardener preferably mixes use with above-mentioned acid anhydride base solidifying agent.
The content of the second epoxy hardener comprising in glue paste of the present invention is preferably 20 to 250 weight parts with regard to the epoxy resin of 100 weight parts of component (a).In this, if the content of the second epoxy hardener is less than 20 weight parts, epoxy resin and unreacted solidifying agent can be retained in whole glue paste, therefore can reduce cross-linking density.If the content of the second epoxy hardener surpasses 250 weight parts, in glue paste, may there is side reaction, rather than curing reaction and the decomposition reaction of expection.
The component comprising in glue paste of the present invention (d) is a kind of curing catalyst, for increasing the solidification rate of the second epoxy hardener of the epoxy of component (a) and the first epoxy hardener of component (b) and component (c).
If glue paste of the present invention is used as the adhesive tape of semiconductor packages as lead-in wire fixation adhesive tape, when being bonded on printed circuit board (PCB) or electronic element assembly, lead-in wire fixation adhesive tape can shorten set time, because comprise the curing catalyst of component (d) in glue paste.
Although the curing booster action of solidifying agent is limited under 100 ℃ or following temperature condition in the present invention, in order to avoid tackiness agent is produced to detrimentally affect working life.But at 100 ℃ or above temperature, accelerate curing reaction, to improve cross-linking density.
Organic phosphine based compound can be used as preferred consolidation promotor as 2-ethyl-4-methylimidazole or tertiary amine as triphenylphosphine, imidazole-based compounds.
With regard to the epoxy of 100 weight parts of component (a), the preferred content of the curing catalyst of component in the present invention (d) is 0.1 to 10 weight part.In this, if the content of curing catalyst is less than 0.1 weight part, cannot expect the acceleration effect of curing reaction, if the content of curing catalyst surpasses 10 weight parts, can make the ratio sufficient degree of adhesive-layer formation more stiff owing to there is fast curing reaction in manufacturing process, therefore be difficult to obtain bonding required viscosity, this can produce detrimentally affect to dimensional stability.
The component comprising in glue paste of the present invention (e) is a kind of properties-correcting agent being formed by thermoplastic resin, and it can improve the fragility of epoxy resin, thereby strengthens fracture toughness and alleviate internal stress.
With regard to the epoxy of 100 weight parts of component (a), the properties-correcting agent preferred content of the component comprising in glue paste of the present invention (e) is 30 to 150 weight parts.In this, if the content of properties-correcting agent is less than 30 weight parts, is unfavorable for strengthening fracture toughness and alleviates internal stress, if the content of properties-correcting agent surpasses 150 weight parts, in glue paste, the content of cure component can reduce suddenly, therefore after solidifying, may reduce machinery and electric reliability.
According to the type of other glue paste components, can be from polyester polyol, be dispersed in acrylic rubber, core shell rubbers, carboxyl end group paracril (carboxy terminated butadiene nitrile rubber, CTBN), acrylonitrile-butadiene-styrene (ABS), polymethyl siloxane and the phenoxy resin epoxy resin the thermoplastic resin of selecting as the properties-correcting agent of component (e).
Preferably, when glue paste of the present 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 paracril (CTBN).
In addition, due to object according to the present invention, require at high temperature to have very strong adhesion characteristics, therefore preferably use and there is relatively epoxy resin or the good phenoxy resin of adaptability of high glass transition temperature.
Preferably polyester polyol or carboxyl end group paracril can be combined 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, and wherein outer shell is glassy polymers, and inner nuclear layer is rubbery polymer, or is three-decker, and wherein outer shell is glassy polymers, and middle layer is rubbery polymer, and inner nuclear layer is glassy polymers.In this, glassy polymers methyl methacrylate polymer, rubbery polymer consists of butyl acrylate thing.
Except above-mentioned synthetics component, glue paste of the present invention can comprise a kind of glue paste in addition, as tensio-active agent, coupling agent, mineral filler etc.In this, with regard to the epoxy of the component (a) of 100 weight parts, the fluorine surfactant that comprises 0.001 to 1 weight part is as additive.
Particularly, can use tensio-active agent to provide suitable coating performance for basement membrane, the first-selected high molecular weight siloxane that uses, as organic propene polymer, polyvalent alcohol etc., or fluorine-based compound is as the FC-4430 of 3M Co..
In the present invention, the varnish of glue paste preferably contains the solids content of above-claimed cpd 10 to 50% weight in organic solvent.In this, if solids content is less than 10% weight, in drying process, be difficult to remove residual organic solvent, if solids content exceeds 50% weight, being difficult to guarantee has sufficient compatibility between glue paste.
In the present invention, the glue paste of above-mentioned formation has outstanding insulating property under 30V or above high pressure, because even just formed higher cross-linking density in the B stage, and under 200 ℃ or above high temperature, keep higher tackiness, because molecule has carried out strong crosslinked in curing network.
In addition, the present invention is also for using the semiconductor packages of tackiness agent that a kind of adhesive tape is provided, and can follow 200 ℃ or above high-temperature technology as used in the semiconductor packages field of wire bonds, soldering etc.
In the present invention, the adhesive tape of semiconductor packages plays the effect of connection, stopping composition and insulation layer between the component of semiconductor package, and in this, adhesive surface can be two-sided or one side.
After forming adhesive surface, the adhesive surface that needs protection is avoided impact or the physical damage of outside atmosphere, until apply it to semiconductor packaging process.Therefore, the protective membrane conventionally with peel property is stacked on adhesive surface, and in this, protective membrane can be from polyolefine if polyethylene, polyvinyl chloride, polypropylene etc., polynary ester be as selected polyethylene terephthalate etc. or separate-type paper.
Thickness first-selection 10 to the 150 μ m of protective membrane, except mud technique and embossing technology, can process protective membrane satisfactorily by stripping technology.Before carrying out adhesion technique, can remove protective membrane.
As the first first-selected embodiment of semiconductor packages adhesive tape, the invention provides a kind of for the epilamellar lead-in wire fixation adhesive tape of semiconductor packages, lead-in wire fixation adhesive tape there is the adhesive-layer being formed by glue paste.
In an embodiment of the present invention, by the physical property of test lead fixation adhesive tape, proved tackiness outstanding under normal temps, and test by the Resin Flow showing in table 1, even if determined that under 180 to 230 ℃ of high temperature, by voltage lead wires fixation adhesive tape, the mobility of adhesive resin is still restricted.
In addition, by lead-in wire fixation adhesive tape of the present invention is carried out to high accelerated stress test (HAST), i.e. measuring resistance per hour under 30V or above high pressure as shown in Figures 1 to 3, result shows, electric short circuit problem under high pressure can be resolved, because do not observe resistance drop in reaching the experiment condition of 500 hours.
Fig. 4 has shown after carrying out high accelerated stress test, uses the result of microscopic examination lead-in wire fixation adhesive tape, because lead-in wire fixation adhesive tape of the present invention can not produce dendron in copper circuit, therefore can determine the insulation characterisitic of the fixation adhesive tape that goes between under high pressure.
In addition, by measuring high temperature reliability for lead-in wire fixation adhesive tape of the present invention, result has been determined outstanding anti-skid [table 2] and high-temp glue viscosity (strength of glass) [table 3], has determined by high temperature controlling mobility, can guarantee that glue paste of the present invention has sufficient toughness.
In the lead-in wire fixation adhesive tape of first first-selected embodiment of semiconductor packages adhesive tape, basement membrane can consist of the engineering plastics that comprise polyphenylene sulfide or polyimide in the present invention, considers electric insulating quality and physics rigidity, the first-selected polyimide film that uses.In this, thickness first-selection 10 to the 150 μ m of polyimide film.Except mud technique and corona technique, can also on basement membrane, additionally carry out process of surface treatment.Particularly, if by applying glue paste varnish of the present invention and varnish is dried and forms adhesive-layer on basement membrane, can manufacture the adhesive tape in semiconductor packages B stage.In this, in obtaining the technique of glue paste varnish, can be with an organic solvent, to obtain easily the mixing of various components, preferably can use mixing of any or conventional solvent and chlorine solvent (as methylene dichloride etc.).Conventional solvent comprises that ketone is as acetone, methylethylketone, pimelinketone etc., and acetic ester is as ethyl acetate, butylacetate, cellosolve acetate, 1-Methoxy-2-propyl acetate etc., and aromatic hydrocarbon is as toluene, dimethylbenzene etc.In addition,, after the varnish of glue paste is coated on basement membrane, by heating, dry and agingly can form adhesive-layer, adhesive-layer is not subject to the impact of organic solvent and volatile matter (as the moisture producing by the moisture absorption etc.).Heating and dry be at 200 ℃ or following (preferably 180 ℃ or following), carry out high temperature drying technique, when with an organic solvent, can the organic solvent in glue paste be vapored away by heating.Aging is the low temperature drying technology carrying out at 70 ℃ or following (preferably 50 ℃ or following), by aging technique, can further reduce the volatile matter producing by the moisture absorption.
In addition, as the second preferred embodiment of semiconductor packages adhesive tape, the invention provides a kind of double sticky tape for semiconductor packages, this double sticky tape has the adhesive-layer being formed by the glue paste on release film.
Different from the above-mentioned lead-in wire fixation adhesive tape for semiconductor packages, the release film with peel property is as basement membrane, release film preferably from polyolefine as polyethylene, polyvinyl chloride, polypropylene etc., polynary ester is as selected in polyethylene terephthalate etc. or separate-type paper.By apply the pressure of 8Mpa under 100 ℃ or lower temperature, reach less than five minutes, double sticky tape is carried out to mechanically compress, separated as the release film of basement membrane, finally use and be tightly bonded in the adhesive surface on release film.
Although only presented the physical property of lead-in wire fixation adhesive tape in embodiments of the invention, but the specific characteristic based on glue paste of these physics, because double sticky tape (the model usage of semiconductor packages adhesive tape in the present invention) is also used glue paste, can naturally understand, double sticky tape can guarantee outstanding insulativity under high pressure and the tackiness under high temperature.
In other words, when adhesive linkage is made into the thickness of 20 μ m, in the present invention, for the adhesive tape of semiconductor packages, meet (a) when the test specimen that uses 200 μ m carries out 30V or above high accelerated stress test, under the high temperature of the relative humidity 85% and 130 ℃, keep short circuited resistance 500 hours or above insulating property, (b) adhesive tape bonding is arrived after the Copper Foil uneven surface of printed circuit board (PCB), under 200 ℃ or higher temperature, when peel off at 180 ° of angles, meet the toughness of 1.0 to 2.5N/cm high-temp glue viscosity.
In addition, in the present invention for the adhesive tape of semiconductor packages, when adhesive tape bonding to 5mm on aluminium sheet and under 200 ℃ or higher temperature when tear in 180 ° of angles, meet 20 to 35N anti-skid.
Hereinafter, will the present invention be described in more detail by embodiment.
This is that scope of the present invention is not limited to these embodiment in order more specifically to describe the present invention.
With regard to the dicyclopentadiene epoxy resin (XD-1000 of Japanese Nippon Kayaku) of 100 weight parts of the epoxy as component (a), the bisphenol-A phenolic varnish resin of the 50 weight parts (SD1508 of U.S. Mai Tu company, number-average molecular weight is 3100, epoxy equivalent (weight) is 120) as the first epoxy hardener of component (b), (number-average molecular weight is 4500 to the phenylethylene-maleic anhydride of 40 weight parts, epoxy equivalent (weight) is 260) as the second epoxy hardener of component (c), the glyoxal ethyline of 0.1 weight part is as the curing catalyst of component (d), the properties-correcting agent that the paracril of 80 weight parts forms as the thermoplastic resin by component (e), the fluorine surfactant of the component of 0.1 weight part (f) (FC4430 of U.S. 3M) adds in methyl ethyl ketone solvent as additive, by they being mixed five hours under room temperature and barometric point, thereby manufacturing solids content concn is the glue paste varnish of total composition 28% weight.
With regard to the bisphenol A epoxide resin (KDS-8128 of Kukdo Chemical Co.) of 100 weight parts of the epoxy as component (a), the novolac resin of the 50 weight parts (MEH-7500H of Japanese Myungsung Hwasung Co., number-average molecular weight is 290, epoxy equivalent (weight) is 97) as the first epoxy hardener of component (b), (number-average molecular weight is 4500 to the phenylethylene-maleic anhydride of 40 weight parts, epoxy equivalent (weight) is 260) as the second epoxy hardener of component (c), the glyoxal ethyline of 0.1 weight part is as the curing catalyst of component (d), the properties-correcting agent that the phenoxy resin of the paracril of 70 weight parts and 10 weight parts forms as the thermoplastic resin by component (e), the fluorine surfactant of the component of 0.1 weight part (f) (FC4430 of U.S. 3M) adds in methyl ethyl ketone solvent as additive, by they being mixed five hours under room temperature and barometric point, thereby manufacturing solids content concn is the glue paste varnish of total composition 28% weight.
With regard to the bisphenol A epoxide resin (KDS-8128 of Kukdo Chemical Co.) of 100 weight parts of the epoxy as component (a), the novolac resin of the 60 weight parts (MEH-7500H of Japanese Myungsung Hwasung Co., number-average molecular weight is 290, epoxy equivalent (weight) is 97) as the first epoxy hardener of component (b), the weight ratio of 40 weight parts is that (number-average molecular weight is 4500 for the polyetheramine (T-5000 of U.S. Huntsman Co.) that mixes of 1:1 and phenylethylene-maleic anhydride, epoxy equivalent (weight) is 260) mixture as the second epoxy hardener of component (c), the glyoxal ethyline of 0.1 weight part is as the curing catalyst of component (d), the properties-correcting agent that the phenoxy resin of the paracril of 70 weight parts and 10 weight parts forms as the thermoplastic resin by component (e), the fluorine surfactant of the component of 0.1 weight part (f) (FC4430 of U.S. 3M) adds in methyl ethyl ketone solvent as additive, by they being mixed five hours under room temperature and barometric point, thereby manufacturing solids content concn is the glue paste varnish of total composition 28% weight.
Comparative example 1 is manufactured glue paste
With regard to the dicyclopentadiene epoxy resin (XD-1000 of Japanese Nippon Kayaku) of 100 weight parts of the epoxy as component (a), (molecular weight is 198.2 to the diaminodiphenylmethane of 60 weight parts, epoxy equivalent (weight) is 49.6) as unit molecule epoxy hardener, the properties-correcting agent that 100 weight part paracrils form as the thermoplastic resin by component (e), the fluorine surfactant of 0.1 weight part (FC4430 of U.S. 3M) adds in methyl ethyl ketone solvent as additive, by they being mixed five hours under room temperature and barometric point, thereby manufacturing solids content concn is the glue paste varnish of total composition 28% weight.
Comparative example 2 is manufactured glue paste
With regard to the dicyclopentadiene epoxy resin (XD-1000 of Japanese Nippon Kayaku) of 100 weight parts of the epoxy as component (a), novolac resin (the MEH-7500H of Japanese Myungsung Hwasung Co. except 50 weight parts, number-average molecular weight is 290, epoxy equivalent (weight) is 97) outside the first epoxy hardener as component (b), (molecular weight is 148.1 to the phthalic anhydride that comprises 60 weight parts, epoxy equivalent (weight) is 79.1) as unit molecule the second epoxy hardener of component (c), use component in the same manner as in Example 1 and content to manufacture glue paste varnish.
Embodiment 4 manufactures lead-in wire fixation adhesive tape
After the thick glue paste of 20 μ m of manufacturing in embodiment 1 is coated in the polyamide based that 50 μ m are thick, film is placed at 50 ℃ and is dried in the air ten minutes.Then, in convection oven, at 170 ℃, heat three minutes, form the lead-in wire fixation adhesive tape of the semiconductor packages with the thick adhesive-layer of 20 μ m.
Embodiment 5 manufactures lead-in wire fixation adhesive tape
By method in the same manner as in Example 4, carry out technique manufacture, difference is that the glue paste of manufacturing in embodiment 2 is coated in the polyamide based that 50 μ m are thick, forms the lead-in wire fixation adhesive tape of the semiconductor packages with the adhesive-layer that 20 μ m are thick.
Embodiment 6 manufactures lead-in wire fixation adhesive tape
By method in the same manner as in Example 4, carry out technique manufacture, difference is that the glue paste of manufacturing in embodiment 3 is coated in the polyamide based that 50 μ m are thick, forms the lead-in wire fixation adhesive tape of the semiconductor packages with the adhesive-layer that 20 μ m are thick.
Comparative example 3 and 4 is manufactured lead-in wire fixation adhesive tape
By method in the same manner as in Example 4, carry out manufacturing process, difference is that the glue paste of manufacturing in comparative example 1 or 2 is coated in the polyamide based that 50 μ m are thick, forms the lead-in wire fixation adhesive tape of the semiconductor packages with the adhesive-layer that 20 μ m are thick.
Experimental example 1 testing tree Membranous lipid fluidity
The lead-in wire fixation adhesive tape of manufacturing in embodiment 4 to 6 and comparative example 3 and 4 is bonded on the aluminium sheet that 1mm is thick, wherein lead-in wire fixation adhesive tape is cut into 10mm(wide) * 100mm(is high) size, and adhesive-layer is placed in to the position in the face of the thick aluminium sheet of 1mm.Then by apply respectively the pressure of 8Mpa at 180 ℃, 210 ℃ and 230 ℃ of temperature, reached for 1 second, lead-in wire fixation adhesive tape is compressed on aluminium sheet.Under above-mentioned contractive condition, manufacture sample, and measure the width of the glue paste flowing out from lead-in wire fixation adhesive tape.Altogether measure in the vertical direction ten times, in left side and right side, measure five times respectively, then calculate its mean value.
[table 1]
The result of testing tree Membranous lipid fluidity
| 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, in embodiment 4 to 6 and comparative example 3 and 4, the leaded fixation adhesive tape of manufacture all shows, Resin Flow increases with the increase of pressing temperature.Yet, to compare with the lead-in wire fixation adhesive tape in comparative example 3 to 4, the lead-in wire fixation adhesive tape of manufacturing in embodiment 4 to 6 all demonstrates the Resin Flow of relative restriction under every kind of temperature condition.
The high accelerated stress test of experimental example 2 (HAST)
In order to test the electric reliability of the lead-in wire fixation adhesive tape of the semiconductor packages of manufacturing in embodiment 4 to 6 and comparative example 3 and 4, by method shown in Fig. 1 and 2, carried out high accelerated stress test.
Fig. 1 has shown the sample of the electric reliability of the fixation adhesive tape that goes between in test the present invention, wherein on polyamide layer, has formed copper circuit, and ground-electrode unit is placed on to two ends.By the space allocation between copper circuit, be 200 μ m.
Fig. 2 has shown by the lead-in wire fixation adhesive tape of manufacturing in embodiment 4 to 6 and comparative example 3 and 4 being bonded to a sample of manufacturing in the copper circuit of Fig. 1 test specimen with thermal means, wherein lead-in wire fixation adhesive tape is carried out to thermo compression to cover the copper circuit of test specimen in glue paste direction, compression temperature, compression time and pressure are adjusted into respectively 200 ℃, 1 second and 8Mpa.Next, use convection oven to being stained with the test specimen of lead-in wire fixation adhesive tape, to carry out one hour solidifying at 180 ℃ of temperature.After making electrode unit contact positive electrode and negative potential, under the relative humidity of the temperature of 130 ℃ and 85%, curing test specimen is applied to 30V voltage, the variation of a resistance of measurement per hour.
Fig. 3 has shown the test result of the High-Voltage Insulation reliability of the fixation adhesive tape that goes between in the present invention, and the lead-in wire fixation adhesive tape of manufacturing in embodiment 4 to 6 is reaching under the experiment condition of 500 hours and do not showing resistance drop.Yet the lead-in wire fixation adhesive tape of manufacturing in comparative example 3 and 4 had just shown resistance drop before 100 hours.
Fig. 4 has shown after lead-in wire fixation adhesive tape of the present invention is carried out to High-Voltage Insulation reliability testing, uses the result of microscopic examination sampler unit.If the lead-in wire fixation adhesive tape of manufacturing determines that the growth of dendron has arrived comparative electrode, thereby produce electric short circuit in comparative example 3 and 4.Yet, if the lead-in wire fixation adhesive tape of manufacturing in embodiment 4 to 6 is observed clean electrode surface, therefore determine and do not produce dendron.
The high accelerated stress test of experimental example 3
Shown the high voltage reliability test of carrying out for the lead-in wire fixation adhesive tape of manufacturing in embodiment 4 to 6 and comparative example 3 and 4 below.
As shown in Figure 5, after the lead-in wire fixation adhesive tape of manufacturing in embodiment 4 to 6 and comparative example 3 and 4 is bonded to aluminium sheet 2, wherein on basement membrane 1, form adhesive-layer 3, by bring measurement anti-skid from the both direction lead-in wire fixing glue of tearing at 200 ℃ of temperature, and measure the toughness under high temperature.
As mentioned above after stacking each layer, by reaching for 1 second in 180 ℃ of temperature and 8MP pressure lower compression storehouse, thus manufacturing test sample.If the universal testing machine (UTM) that has a high temperature chamber in use after increase in temperature to 200 ℃, tears test sample book towards the direction of arrow with the increment of 10 ℃ of per minutes, the bonding plane of the relative narrower of the adhesive surface of test sample book will slide, then final separated.Record time point from test sample book being applied to power to required time of the final separated time point of bonding plane and the maximum, force when the bonding plane separation.In table 2, shown measuring result.
[table 2]
Anti-skid measuring result
| Test event | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 3 | Comparative example 4 |
| Force time | 2.5 second | 2.5 second | 2.5 second | 2.5 second | 2.5 second |
| Maximum, force during fracture | 35 Ns | 32 Ns | 28 Ns | 17 |
14 Ns |
From the result of the measurement anti-skid shown in table 2, can determine, although identical with the time length of the lead-in wire fixation adhesive tape application of force of manufacturing in 4 with comparative example 3 to embodiment 4 to 6, but when bonding plane slides and is separated, the maximum, force that the lead-in wire fixation adhesive tape of manufacturing in embodiment 4 to 6 is applied than the large 10N of lead-in wire fixation adhesive tape manufacturing in comparative example 3 and 4 or more than.
In addition, the lead-in wire fixation adhesive tape of manufacturing in embodiment 4 to 6 and comparative example 3 and 4 is bonded on the Copper Foil of 1/20z, wherein by lead-in wire fixation adhesive tape, to be cut into 10mm(wide) * 100mm(is high) size, adhesive-layer is placed in to the position of contact Copper Foil, and reached for 1 second by apply the pressure of 8Mpa under 180 ℃ of degree, bonded on Copper Foil.The universal testing machine that use has a high temperature chamber increase in temperature to 200 ℃, is then measured the stripping strength that bonds to the sample on Copper Foil, the PI face of simultaneously tearing with the increment of 10 ℃ of per minutes.In table 3, shown measuring result.
[table 3]
The measuring result of high temperature stripping strength
| Test event | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 3 | Comparative example 4 |
| Stripping strength | 1.8 ox | 1.6 ox | 1.8 ox | 0.3 N | 0.4 N |
In addition, the stripping strength measuring result showing from table 3, observe, due to the stripping strength of the lead-in wire fixation adhesive tape of manufacturing in embodiment 4 to 6 than the lead-in wire fixation adhesive tape of manufacturing in comparative example 3 and 4 high four times or more than, determine under 200 ℃ or above high temperature and there is outstanding tackiness.
As mentioned above, the invention provides a kind of glue paste, wherein in epoxy, contain the epoxy hardener of optimum quantity, to strengthen fracture toughness by strengthening cross-linking density, thereby glue paste can under high pressure have insulating reliability, at high temperature has outstanding anti-skid and tackiness.
In the present invention, use glue paste manufacture firmly anchor leg framework under condition of high voltage, there is the lead-in wire fixation adhesive tape of outstanding insulating property simultaneously, and glue paste of the present invention can be used as double-sided adhesive jelly in semiconductor fab technique, semiconductor fab technique generally includes 200 ℃ or above high temperature assembly technology.
Particularly, above-mentioned glue paste of the present invention is owing to even just having formed high crosslink density in the B stage, therefore under 30V or above high pressure, there are outstanding insulating property, and be cross-linked owing to molecule being carried out to intensity in curing network, therefore under 200 ℃ or above high temperature, keep high tackiness, therefore applying in high-tension situation, as elevator, vehicle, semiconductor packages etc., it can be very useful.
Although invention has been described according to specific illustrative embodiment, the present invention is not subject to the restriction of these embodiment, is only subject to the restriction of accessory claim.Will be appreciated that, those skilled in the art change or improve these embodiment, also do not depart from the scope of the present invention and spirit.
Claims (11)
1. a glue paste, comprising:
(a) epoxy of 100 weight parts,
(b) the first epoxy hardener that comprises polyfunctional phenolic resin of 30 to 100 weight parts,
(c) the second epoxy hardener that comprises amido epoxy hardener, acid anhydride base epoxy hardener or both mixing of 20 to 250 weight parts,
(d) curing catalyst of 0.1 to 10 weight part,
(e) properties-correcting agent being formed by thermoplastic resin of 30 to 150 weight parts.
2. glue paste according to claim 1, wherein the second epoxy hardener of the first epoxy hardener of component (b) and component (c) has 300 or following epoxy reaction equivalent.
3. glue paste according to claim 1, wherein with regard to number-average molecular weight, the second epoxy hardener of the first epoxy hardener of component (b) and component (c) has 3,000 or above molecular weight.
4. glue paste according to claim 1, wherein has two or more phenol hydroxyls in the polyfunctional phenolic resin molecule of component (b), and hydroxyl equivalent is 100 to 300.
5. glue paste according to claim 1, wherein the acid anhydride base epoxy hardener of component (c) is vinyl acetate between to for plastic-copolymer-maleic anhydride multipolymer or styrene-maleic anhydride copolymer.
6. glue paste according to claim 1, wherein the thermoplastic resin of component (e) be from by polyester polyol, be dispersed in single resin or the hybrid resin in the group that acrylic rubber, core shell rubbers, carboxyl end group butyronitrile, acrylonitrile-butadiene-styrene (ABS), polymethyl siloxane and phenoxy resin in epoxy resin form, selected.
7. glue paste according to claim 1, further comprises the fluorine surfactant of (f) 0.001 to 1 weight part.
8. glue paste according to claim 1, wherein the varnish of glue paste contains the solids content of 10 to 50% weight in organic solvent.
9. for an adhesive tape for semiconductor packages, be to have by form the lead-in wire fixation adhesive tape of adhesive-layer on basement membrane according to the glue paste described in claim 1-8 any one.
10. for an adhesive tape for semiconductor packages, be to have by form the double sticky tape of adhesive-layer on release film according to the glue paste described in claim 1-8 any one.
11. according to the adhesive tape described in claim 9 or 10, and wherein the thickness when adhesive-layer is 20
μduring m, described adhesive tape has:
(a) when carrying out 30V or above high accelerated stress test, keep short circuited resistance to reach the insulating property of 500 hours,
(b) when adhesive tape bonding to after the Copper Foil uneven surface of printed circuit board (PCB) at 200 ℃ or above temperature when peel off at 180 ° of angles, meet the toughness of 1.0 to 2.5N/cm high-temp glue viscosity.
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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| 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 |
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| Country | Link |
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| JP (1) | JP5799056B2 (en) |
| KR (1) | KR101395322B1 (en) |
| CN (1) | CN103571412B (en) |
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| CN104974471A (en) * | 2015-07-14 | 2015-10-14 | 江苏兆鋆新材料股份有限公司 | Preparation method of high-heat-resistance high-toughness epoxy resin carbon-fiber composite material |
| CN109929092A (en) * | 2019-03-11 | 2019-06-25 | 台光电子材料股份有限公司 | Composition epoxy resin and the product being made from it |
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| AU2015362688B2 (en) * | 2014-12-18 | 2021-01-21 | Cytec Industries Inc. | Modified resin systems suitable for liquid resin infusion |
| 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 |
| WO2021200405A1 (en) * | 2020-03-31 | 2021-10-07 | 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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Also Published As
| Publication number | Publication date |
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| TWI500734B (en) | 2015-09-21 |
| JP5799056B2 (en) | 2015-10-21 |
| TW201404857A (en) | 2014-02-01 |
| JP2014019869A (en) | 2014-02-03 |
| KR101395322B1 (en) | 2014-05-16 |
| CN103571412B (en) | 2017-05-24 |
| KR20140011906A (en) | 2014-01-29 |
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