CN101230177A - Composition for pressure sensitive adhesive film, pressure sensitive adhesive film, and dicing die bonding film including the same - Google Patents

Composition for pressure sensitive adhesive film, pressure sensitive adhesive film, and dicing die bonding film including the same Download PDF

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Publication number
CN101230177A
CN101230177A CN 200710307124 CN200710307124A CN101230177A CN 101230177 A CN101230177 A CN 101230177A CN 200710307124 CN200710307124 CN 200710307124 CN 200710307124 A CN200710307124 A CN 200710307124A CN 101230177 A CN101230177 A CN 101230177A
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acrylate
cured
weight
resin
film
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黄龙河
宋珪锡
奇喜莲
河京珍
赵宰贤
丁畅范
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Cheil Industries Inc
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Cheil Industries Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/2919—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/831—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus
    • H01L2224/83101—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus as prepeg comprising a layer connector, e.g. provided in an insulating plate member
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01005—Boron [B]
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/01006—Carbon [C]
    • 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
    • H01L2924/06—Polymers
    • H01L2924/0665—Epoxy resin
    • 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
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/146—Mixed devices
    • H01L2924/1461—MEMS

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  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Dicing (AREA)

Abstract

A composition, including a polymer binder resin A, a UV-curing acrylate B, a heat curing agent C, and a photopolymerization initiator D. The composition includes about 20 to about 150 parts by weight of the UV-curing acrylate B per 100 parts by weight of the polymer binder resin A, and the UV-curing acrylate B is a solid or near-solid at room temperature and has a viscosity of about 10,000 cps or more at 40 DEG C.

Description

Composition for pressure sensitive adhesive film, pressure-sensitive adhesive film and the dicing die bonding that comprises this film
Technical field
The dicing die bonding that the present invention relates to composition for pressure sensitive adhesive film, pressure-sensitive adhesive film and comprise this film.
Background technology
In semiconductor fabrication, large diameter wafer (being built with circuit on it) is cut into little chip (being wafer) in cutting operation.For carrying out cutting operation, the cutting film can be attached on the wafer.Can carry out pick-up operation then, isolating chip is then adhered to is used for encapsulation.Each independent chip all is adhered to a support component for example on another active part, printed circuit board (pcb), the lead frame etc. by adhesive bonds.This method comprises two steps (cutting and adhesion), all is being disadvantageous aspect cost and the productivity therefore.
The other method that is called as " wafer rear adhesion chip " is used cutting belt and the incorporate single film of pressure-sensitive adhesive (PSA).This film comprises: first kind of film, independent PSA and adhesive layer wherein is provided, and PSA is used for cutting, and tackiness agent is used for adhesive die attachment to support component; Second kind of film wherein provides to be used for cutting and adherent simple layer simultaneously.In first kind of film, the PSA film can be the photocuring film, and as the UV cured film, thereby it demonstrates strong initial adherence power keep chip firmly in processes such as cutting, drying, and it demonstrates the adhesive power of reduction after the UV radiation, thereby helps to guarantee to transmit in pick-up operation.But usually when the known PSA composition of use, the UV curing low molecular weight material among the PSA can be moved on the adhesive layer that closes on, and this can cause picking up the complicated of step.
Summary of the invention
Therefore, the dicing die bonding that the present invention is devoted to a kind of composition for pressure sensitive adhesive film, pressure-sensitive adhesive film and comprises this film, they have solved one or more problems that cause owing to the limitation of association area and shortcoming substantially.
Therefore, one of the present invention is characterised in that a kind of dicing die bonding is provided.
Therefore, of the present invention another is characterised in that provides a kind of demonstration to go to sea-pressure-sensitive adhesive film of island (sea-island) structure.
Therefore, of the present invention another is characterised in that provides a kind of composition for pressure sensitive adhesive film.
At least one above-mentioned feature of the present invention and other feature and advantage can realize that said composition comprises polymer bonding Resin A, UV cured acrylate B, thermal curing agents C and Photoepolymerizationinitiater initiater D by a kind of composition is provided.It is the about 20 UV cured acrylate B to about 150 weight parts that said composition can comprise with respect to 100 parts by weight polymer binding resin A, UV cured acrylate B at room temperature can be solid or near solid and its viscosity 40 ℃ down for about 10,000cps or higher.It is the about 0.1 thermal curing agents C to about 10 weight parts that said composition can comprise with respect to 100 parts by weight polymer binding resin A, and said composition can to comprise with respect to 100 weight part UV cured acrylate B be the about 0.1 Photoepolymerizationinitiater initiater D to about 5 weight parts.Thermal curing agents C can comprise one or more in polymeric polyisocyanate, melamine/formaldehyde resin or the Resins, epoxy.Photoepolymerizationinitiater initiater D can comprise one or more in benzophenone cpd, acetophenone compound or the anthraquinone compounds.The polymer bonding Resin A can be have hydroxy functional group, the acrylic resin of one or more functional groups in carboxyl functional group, epoxy-functional or the amine functional group.The second-order transition temperature of this acrylic resin can be-60 ℃ to about 0 ℃ approximately, and weight-average molecular weight is about 100,000 to about 2,000,000.UV cured acrylate B can be the urethanum origoester acrylate.
At least one above-mentioned feature of the present invention and other feature and advantage can realize that said composition comprises polymer bonding Resin A, UV cured urethane origoester acrylate B1, UV cured acrylate B2, thermal curing agents C and Photoepolymerizationinitiater initiater D by a kind of composition is provided.It is the about 20 UV cured urethane origoester acrylate B1 to about 150 weight parts that said composition can comprise with respect to 100 parts by weight polymer binding resin A, it is the about 5 UV cured acrylate B2 to about 50 weight parts that said composition can comprise with respect to 100 parts by weight polymer binding resin A, UV cured urethane origoester acrylate B1 at room temperature can be solid or near solid and have at 40 ℃ and down be about 10,000cps or higher viscosity, and UV cured acrylate B2 can be solid or wax and can have and is higher than 25 ℃ fusing point.UV cured urethane origoester acrylate B1 can comprise the multipolymer that last isocyanic ester urethane prepolymer of end and hydroxy acrylate form.UV cured acrylate B2 can comprise one or more in trimethylolpropane tris (methyl) acrylate, tetramethylol methane tetraacrylate, three (2-acrylyl oxy-ethyl) isocyanuric acid ester (isocyanulate), methoxy poly (ethylene glycol) 1000 methacrylic esters, methoxy poly (ethylene glycol) 1000 acrylate, vinylformic acid mountain Yu ester, cetomacrogol 1000 dimethacrylate, cetomacrogol 1000 diacrylate or the tetramethylol methane tetraacrylate.UV cured acrylate B2 can comprise one or more acrylate, and each in them all can be solid or near solid and have and be higher than 25 ℃ fusing point.The polymer bonding Resin A can be have hydroxy functional group, the acrylic resin of one or more functional groups in carboxyl functional group, epoxy-functional or the amine functional group.
At least one above-mentioned feature of the present invention and other feature and advantage can realize by a kind of dicing die bonding is provided, and this film comprises support membrane, be positioned at the adhesive layer on this support membrane and be positioned at pressure-sensitive adhesive film on this adhesive layer.This pressure-sensitive adhesive film can comprise polymer bonding Resin A, UV cured acrylate B, thermal curing agents C and Photoepolymerizationinitiater initiater D.It is the about 20 UV cured acrylate B to about 150 weight parts that this pressure-sensitive adhesive film can comprise with respect to 100 parts by weight polymer binding resin A, UV cured acrylate B at room temperature can be solid or near solid and its viscosity 40 ℃ down for about 10,000cps or higher.The polymer bonding Resin A can be have hydroxy functional group, the acrylic resin of one or more functional groups in carboxyl functional group, epoxy-functional or the amine functional group.The second-order transition temperature of this acrylic resin can be-60 ℃ to about 0 ℃ approximately, and weight-average molecular weight is about 100,000 to about 2,000,000.UV cured acrylate B can be the urethanum origoester acrylate.This adhesive layer can comprise acrylic resin.This pressure-sensitive adhesive film can have sea-island structure, and wherein the mean sizes of island part is that about 1 μ m is to about 10 μ m.
At least one above-mentioned feature of the present invention and other feature and advantage can realize by a kind of dicing die bonding is provided, and this film comprises support membrane, be positioned at the adhesive layer on this support membrane and be positioned at pressure-sensitive adhesive film on this adhesive layer.This pressure-sensitive adhesive film can comprise polymer bonding Resin A, UV cured urethane origoester acrylate B1, UV cured acrylate B2, thermal curing agents C and Photoepolymerizationinitiater initiater D.It is the about 20 UV cured urethane origoester acrylate B1 to about 150 weight parts that this pressure-sensitive adhesive film can comprise with respect to 100 parts by weight polymer binding resin A, it is the about 5 UV cured acrylate B2 to about 50 weight parts that this pressure-sensitive adhesive film can comprise with respect to 100 parts by weight polymer binding resin A, UV cured urethane origoester acrylate B1 at room temperature can be solid or near solid and have at 40 ℃ and down be about 10,000cps or higher viscosity, and UV cured acrylate B2 can be solid or wax and can have and is higher than 25 ℃ fusing point.UV cured urethane origoester acrylate B1 can comprise the multipolymer that last isocyanic ester urethane prepolymer of end and hydroxy acrylate form.UV cured acrylate B2 can comprise one or more in trimethylolpropane tris (methyl) acrylate, tetramethylol methane tetraacrylate, three (2-acrylyl oxy-ethyl) isocyanuric acid ester, methoxy poly (ethylene glycol) 1000 methacrylic esters, methoxy poly (ethylene glycol) 1000 acrylate, vinylformic acid Shan Yu ester, cetomacrogol 1000 dimethacrylate, cetomacrogol 1000 diacrylate or the tetramethylol methane tetraacrylate.This adhesive layer can comprise acrylic resin.This pressure-sensitive adhesive film can have sea-island structure, and wherein the mean sizes of island part is that about 1 μ m is to about 10 μ m.
Description of drawings
By the accompanying drawing that illustrative examples is described in detail and reference is enclosed, above-mentioned and other feature and advantage of the present invention will become more obvious for ordinary skill in the art personnel, wherein:
Fig. 1 shows the sectional view of dicing die bonding of the present invention;
Fig. 2～Fig. 5 shows the sectional view that the dicing die bonding that uses Fig. 1 cuts each step in the method with the anabolic process of wafer bonding;
Fig. 6 shows the sea-island surface tissue of pressure-sensitive adhesive film of the present invention;
Fig. 7 shows the component among embodiment 1-1 and 1-2 and the Comparative Examples 1-1 to 1-5 and the table of test result; And
Fig. 8 shows the component among embodiment 2-4 to 2-6 and the Comparative Examples 2-7 to 2-12 and the table of test result.
Embodiment
Respectively at being incorporated by reference in this on December 27th, 2006 and on December 28th, 2006 to 10-2006-0134916 number of Korea S Department of Intellectual Property submission and the full content of 10-2006-0136203 korean patent application (title is " Photocurable composition that the formation adhesive film is used and the dicing die bonding that comprises it ").
Below with reference to the accompanying drawing of enclosing embodiment is carried out more detailed description, but they only characterize by different way, should not be interpreted as being limited only example described herein.Or rather, it is more abundant in order to expose, complete that these examples are provided, and fully shows scope of the present invention to those skilled in the art.
In the accompanying drawings, each layer and each regional size have been exaggerated for knowing purpose of description.Should also be understood that when mention certain one deck or a certain element another layer or substrate " on " time, its can be directly on this another layer or substrate, perhaps can have the middle layer.In addition, should be appreciated that when mentioning certain one deck that can also can there be one or more middle layers in it directly at it down at another layer " below ".In addition, should also be understood that when mention certain one deck two-layer " between " time, it can be the unique one deck between two-layer, or also can have one or more middle layers.Identical Reference numeral is represented components identical all the time.
Statement " at least one/a kind of " as used herein, " one/a kind of or a plurality of/multiple " and " and/or " be open statement, it in use is connectivity and washability (disjunctive) simultaneously.For instance, among statement " at least one among A, B and the C ", " at least one among A, B or the C ", " among A, B and the C one or more ", " among A, B or the C one or more " and " A, B and/or C " each all comprises following implication: A is only arranged, B is only arranged, C is only arranged, A and B, A and C, B and C, and A, B and C three.In addition, remove in conjunction with use term " by ... constitute " to represent clearly outside the contrary that these statements are open.For instance, statement " at least one among A, B and the C " also can comprise n composition, and wherein n is greater than 3.On the contrary, statement " at least one that select from the group that is made of A, B and C " then is not like this.
Statement as used herein " or " be not " exclusiveness or ", unless itself and term " not being ... be exactly ... " are used in combination.For instance, statement " A, B or C " comprising: A is only arranged, B is only arranged, C is only arranged, A and B, A and C, B and C, and A, B and C three.On the contrary, statement " not being that A, B are exactly C " represents that then A is only arranged, and B is only arranged, and a kind of in these three kinds of situations of C is only arranged, and do not represent A and B, A and C, B and C, and in A, B and these situations of C three any.
Wording " one " and " a kind of " are open wording as used herein, its can with singular item or plural article coupling.For instance, single compound can be represented in term " a kind of Photoepolymerizationinitiater initiater ", as benzophenone, or represents multiple combination of compounds, as the benzophenone that mixes with methyl phenyl ketone.
Unless otherwise indicated, the molecular weight of macromolecular material is a weight-average molecular weight as used herein.
Unless otherwise indicated, statement " based on the weight part of the total amount of adhesive film composition " does not count solvent as used herein.That is, reference point " total amount of adhesive film composition " does not comprise solvent as used herein.For instance, when a kind of composition is made up of two component A and B, and the total amount A based on adhesive film composition is 35 weight parts, when B is 65 weight parts, add 10 parts by weight solvent and can produce following result in said composition: based on the total amount of this adhesive film composition, said composition still contains the A of 35 weight parts and the B of 65 weight parts.
Fig. 1 shows the sectional view of the dicing die bonding 1 of the present invention's first example, wherein PSA and tackiness agent are positioned on other layer of branch, and Fig. 2～Fig. 5 shows the sectional view that the dicing die bonding that uses Fig. 1 cuts each step in the method with the anabolic process of wafer bonding.PSA film 4 with reference to figure 1, the second example can be positioned on the one side of extensible support membrane 5, and this support membrane for example can be polyolefine.The adhesive layer 3 that is used to adhere to chip can be positioned at PSA film 4.Separatory membrane 2 can be positioned at and be used to protect adhesive layer 3 on the dicing die bonding 1.PSA film 4 in the dicing die bonding 1 can be formed by the PSA composition of the 3rd example, and details are described in down.
With reference to figure 2, in semiconductor fabrication, adhesive layer 3 can be stacked on the wafer 6 after peeling off separatory membrane 2.After being stacked in adhesive layer 3 on the wafer 6, by cutting chip 6a is cut off from wafer 6, the size of chip 6a is corresponding to the size of designed schematic circuit.With reference to figure 3, cutting can comprise cuts the degree of depth that is positioned at the top of support membrane 5 to being lower than PSA film 4 with dicing die bonding 1, and like this, cutting is cut into chip 6a with wafer 6, adhesive layer 3 is cut into adhesive layer part 3a, and PSA film 4 is cut into PSA membrane portions 4a.
After the cutting, by PSA membrane portions 4a is carried out the UV optical radiation, the interface peel intensity between PSA membrane portions 4a and the adhesive layer part 3a can reduce.The variation that is caused by UV light among the PSA membrane portions 4a can cause the stripping strength that reduces, and it makes picking up of independent chip 6a become possibility, allows chip 6a from PSA membrane portions 4a separation, thereby they can be attached on the support component 7.As seen in Figure 4, independent chip 6a (still being stained with adhesive layer part 3a on it) is for example available to pick up machine or collet picks up, and attaches on the support component 7, and this element for example can be (with reference to figure 5) such as another active part, PCB substrate, lead frames.
Support membrane 5
The support membrane 5 that various types of plastic films can be used as dicing die bonding 1 uses.Can use thermoplastic film as support membrane 5.Preferred support membrane 5 is extendible.When 6 pairs of UV light of wafer to be cut were opaque, support membrane 5 was preferably to the UV optical transparency, thereby the UV radiation is penetrated on psa layer part 3a, and thereby caused the reduction of stripping strength.For this situation, support membrane 5 can demonstrate the good transmissivity in the UV wavelength region, is used to solidify PSA membrane portions 4a.
The example that can be used as the polymeric film of support membrane 5 uses for example comprises the polyolefins film, as polyethylene, polypropylene, ethylene/propene copolymer, polybutene-1, ethylene/vinyl acetate copolymer, polyethylene/styrene butadiene rubbers mixture, polyvinyl chloride etc.In addition, also can use plastics, as polyethylene terephthalate, polycarbonate, poly-(methyl methacrylate) etc., and thermoplastic and high-elastic, as urethane, polymeric amide-polyol copolymer etc.These materials can use separately, also can their form of mixtures use.
Support membrane 5 can have multilayered structure, and it can make cutting off and/or extending in the cutting process become possibility.Support membrane 5 for example can form by polyolefin piece being mixed and extruding by inflation etc.The thermotolerance of support membrane 5 and mechanical characteristics depend on the blended polyolefin piece.
The haze value of support membrane 5 is about 85 or higher.Such haze value can obtain by for example using the embossing on the one side of polyolefin film of embossing cooling roller.If the haze value of support membrane 5 is about 85 or higher, when before support membrane 5 is cut, being stacked on the one side of wafer 6, discern the position of support membrane 5 easily, this can simplify and works continuously.5 embossing also help to make the roll-in of support membrane 5 become possibility by preventing to block in the manufacturing processed of film to support membrane.
PSA film 4 can be formed on the one side relative with embossed one side on the support membrane 5.For improving the adhesive power of PSA film 4, preferably surface treatment is simultaneously carried out in the not embossing of support membrane 5 with respect to support membrane 5.Surface treatment can comprise modification physics and/or chemistry that the surface is carried out.Physical method for example comprises corona treatment and Cement Composite Treated by Plasma, and chemical process for example comprises online coating, prime treatment etc.Corona discharge Treatment can be used to make surface modification, thereby makes the coating of PSA film 4 become easier.
The thickness of support membrane 5 can be about 30 μ m to about 300 μ m, is preferably about 50 μ m to about 200 μ m.Support membrane 5 with such thickness can provide good elongation, operation easness, UV transmissivity etc.Used thickness is that about 30 μ m or thicker support membrane 5 help avoid the processing difficulties of the support membrane 5 that is in the precut state, and helps avoid the distortion of the film that the heat that produces in the UV radiative process by PSA film 4 causes.Used thickness is that about 300 μ m or thinner support membrane 5 can use littler power in stretched operation, thereby reduces cost.
PSA film 4
PSA film 4 can be coated in by the composition with the 3rd example on the one side of support membrane 5 and prepare.PSA film 4 for example can be applied to PSA film 4 to the support membrane 5 first-class modes that shift gained on the separatory membrane then with the PSA composition and be formed on the support membrane 5 by the PSA composition is coated directly onto on the support membrane.The coating of PSA composition can use suitable coating process to carry out, as the coating of bar rod, photogravure coating, comma coating (commacoating), contrary roller coat cloth, applicator coating, spraying etc.
The PSA film 4 that uses in dicing die bonding 1 can provide the strong adhesive power to adhesive layer 3 and ring frame.PSA film 4 can demonstrate strong viscosity before the UV radiation, and after the UV radiation, because the cohesiveness of the increase of PSA membrane portions 4a, PSA film 4 and adhesive layer 3 between at the interface adhesive power demonstrate tangible reduction, like this, chip 6a and adhesive layer part 3a can easily be picked up and wafer bonding (diebond) to support component 7.In another embodiment, PSA film 4 can be a kind of like this film because other energy input, for example thermofixation etc., its and adhesive layer 3 between the reduction that demonstrates adhesive power at the interface.
PSA film 4 can use the composition of the 3rd example to prepare, and said composition comprises polymer bonding Resin A, UV cured acrylate B, thermal curing agents C and Photoepolymerizationinitiater initiater D.It is the about 20 UV cured acrylate B to about 150 weight parts that said composition can comprise with respect to 100 parts by weight polymer binding resin A, be about 0.1 to the thermal curing agents C of about 10 weight parts and be about 0.1 Photoepolymerizationinitiater initiater D with respect to 100 parts by weight polymer binding resin A to about 5 weight parts with respect to 100 weight part UV cured acrylate B.Said composition also can comprise one or more in for example organic filler, mineral filler, adhesionpromoter, tensio-active agent, the static inhibitor.
The polymer bonding Resin A can be given PSA film 4 with sensitive adhesive properties.The polymer bonding Resin A can be mixed with UV cured acrylate B and caused the crosslinked of PSA tackiness agent and acrylate, thereby after the UV radiation adhesive power is obviously descended.Can use acrylic resin as the polymer bonding Resin A, it can provide good cohesiveness and excellent thermotolerance, and allows easily to introduce functional group and/or low molecular weight side chains by chemical reaction.In addition, the use of acrylic resin makes second-order transition temperature and/or molecular weight to control by selecting suitable monomers.Equally, the introducing of functional group can be controlled by selecting suitable monomers on the side chain.Also can use other various resins, as polyester resin, urethane esters resin, silicone based resin and rubber resin as the polymer bonding Resin A.
In acrylic resin, the monomer that is used for copolymerization for example comprises butyl acrylate, 2-EHA, vinylformic acid, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) methyl acrylate, vinylbenzene, (methyl) glycidyl acrylate, Isooctyl acrylate monomer, stearyl methacrylate, dodecyl acrylate, decyl acrylate, vinyl acetate, vinyl cyanide etc.Acrylic resin through copolymerization can have-60 ℃ to about 0 ℃ approximately, preferred-40 ℃ to about-10 ℃ second-order transition temperature approximately.About-60 ℃ of adhesivityes (viscosity) that help to guarantee to want under the room temperature level to about 0 ℃ Tg.Approximately-40 ℃ or higher Tg help for PSA film 4 provides combining of good intensity and adhesive power, and-10 ℃ of pacts or lower Tg can provide adhesive power good under the room temperature.The second-order transition temperature of acrylic resin can be controlled by the monomeric relative proportion of regulating certain monomers and carrying out copolymerization.
Acrylic resin preferably has at least one polar functional group, as hydroxyl, carboxyl, epoxy group(ing), amine or the like.If support membrane 5 is non-polar materials, as polyolefin film, the film surface can be through modification to provide the good affinity to PSA film 4.But, by being incorporated in the acrylic resin that uses in the composition and/or with solidifying agent, functional group carries out crosslinking reaction, and the adhesive power that improves between PSA film 4 and the support membrane 5 is possible.
The example of polyester resin comprises the material Vylon that makes as by Toyobo Co.Ltd. (Japan) 200, Vylon 280 and Vylon 500.The resinoid example of urethanum comprises the material Vylon that makes as by Toyobo Co.Ltd. (Japan) UR-1350 and Vylon UR-2300.The resinoid example of organosilicon comprises material DPSA200, PSA518, PSA529 and the PSA595 that makes as by Dong Yang Silicone Co.Ltd. (Korea S).The example of rubber resin comprises the material Ni pol that makes as by Zeon Corp. (Japan) DN003, Nipol 1041 and Nipol 1043.
The weight-average molecular weight of polymer bonding Resin A is preferably about 100,000 to about 2,000,000.About 100,000 or bigger molecular weight can provide can with the PSA composition of support membrane 5 secure bond, help to reduce or eliminate undesirable separation of occurring in the chip during the cutting owing to film cohesiveness is not enough, chip rupture etc.About 2,000,000 or lower molecular weight help to guarantee solvability, its can make the coating and other process operation become easy.
UV cured acrylate B has (25 ℃) high immesurable viscosity under the room temperature, that is, it is a solid or near solid, and on-liquid, and the viscosity under 40 ℃ is about 10,000cps or higher.UV cured acrylate B can have can be by the carbon-carbon double bond of UV photocuring (C=C).UV cured acrylate B can be urethanum acrylate quasi-oligomer.In one embodiment, the urethanum origoester acrylate can prepare by making last isocyanic ester urethane prepolymer of end and the acrylate reactions with hydroxyl.Hold last isocyanic ester urethane prepolymer to obtain by polyester polyol compound or polyether polyol compound and polyisocyanate compounds are reacted.
Usually, when the polymer bonding resin mixes with UV curing low molecular weight material, move on the adhesive layer if solidify the back low molecular weight material at UV, adhesive power can obviously not descend.Particularly, traditional UV cured acrylate at room temperature exists with liquid form, and they tend to migration like this.On the contrary, in the present invention, can use UV cured acrylate B,, therefore suppress migration to such an extent as to this is because UV cured acrylate B at room temperature glues it for solid or near solid very much.
For instance, it is about 1,000 low molecular weight propylene acid esters that UV cured acrylate B can be molecular weight for example, thereby and at room temperature very sticking its as solid or near solid, and on-liquid, and have 40 ℃ down for about 10,000cps or higher viscosity.When mixing with fluoropolymer resin A and being coated on the support membrane 5, UV cured acrylate B can form the film of firm attaching.As a result, it can not moved on the adhesive layer 3 before the UV radiation, and can demonstrate tangible adhesive power reduce after the UV radiation, and this makes the possibility that becomes of picking up of chip 6a.
Thermal curing agents C can comprise one or more in for example polymeric polyisocyanate, melamine/formaldehyde resin or the Resins, epoxy.Thermal curing agents C can be used as linking agent and with the functional group reactions of polymer bonding Resin A.By crosslinked generation tridimensional network.Thermal curing agents C can form firm film on the support membrane 5 with polymer bonding Resin A and UV cured acrylate B, and its during cutting (before being the UV radiation) can not be stripped from.When support membrane 5 is when not having the polyolefin film of polar group, be difficult to apolar substance is attached on the film surface.Therefore, as mentioned above, must carry out corona treatment, prime treatment etc., it can increase surface polarity and surface tension.But the effect of these processing is limited, therefore wishes to adjust the basic polarity of resin.Therefore, preferred use polymer bonding Resin A with polar functional group such as hydroxyl or carboxyl with thermal curing agents C with by they being cross-linked to form firm film.
It is the about 0.1 thermal curing agents C to about 10 weight parts that said composition preferably comprises with respect to 100 parts by weight polymer binding resin A.Use about 0.1 weight part or more since very low degree maybe can ignore crosslinked (crosslinked meeting causes being coated with peeling off of back rete) of degree and can avoid and support membrane 5 between the reduction of adhesive power.Use about 10 weight parts or still less can avoid before the UV radiation reduction by the excessive crosslinked viscosity that causes, the reduction of this viscosity can reduce and ring frame between pressure-sensitive adhesive power, and cause that dicing die bonding separates from ring frame with wafer between extended peroid.
Photoepolymerizationinitiater initiater D can comprise for example benzophenone cpd, as benzophenone, 4, and 4 '-dimethylamino benzophenone, 4,4 '-diethylin benzophenone, 4,4 '-dichloro benzophenone etc.; Acetophenone compound is as methyl phenyl ketone, diethoxy acetophenone etc.; Anthraquinone compounds is as 2-ethyl-anthraquinone, tertiary butyl anthraquinone etc.It is the about 0.1 Photoepolymerizationinitiater initiater D to about 5 weight parts that said composition can comprise with respect to 100 weight part UV cured acrylate B.Use about 0.1 weight part or more generations that effective free radical can be provided when the UV radiation, cause when the UV radiation PSA film 4 and the adhesive power at the interface of adhesive layer 3 obviously to reduce, and can carry out chip pickup the chip of various size.Use about 5 weight parts or still less can avoid the waste of Photoepolymerizationinitiater initiater D, can reduce pungent smell, and can avoid migrating to the decline of adhesive layer reliability in the packaged piece that adhesive layer 3 causes owing to unreacted Photoepolymerizationinitiater initiater D.
The composition of the 3rd example can be used to produce the PSA film 4 of second example, and it can have " sea-island " structure on the surface, and as shown in Figure 6, it is the result of phase (phase) uncompatibility between polymer bonding Resin A and the UV cured acrylate B.With reference to figure 6, " sea " is the part that the polymer bonding Resin A exists, and " island " is the part that UV cured acrylate B exists.When solidifying being subjected to the UV optical radiation, island (being UV cured acrylate B) demonstrates physical change.For instance, when solidifying being subjected to the UV optical radiation, the island can demonstrate reduction on the volume (promptly shrinking) and/or demonstrate the variation of phase.But the sea part can not demonstrate considerable change because of the UV optical radiation.Therefore, total adhesive power of demonstrating of sea-island structure is lowered.The opticmicroscope that the sea-island structure of PSA film 4 can use FE-SEM for example or have about 3,000 times or a bigger magnification is observed.
The mean sizes on island is preferably about 1 μ m to about 10 μ m in the sea-island structure.The island district that forms by UV cured acrylate B after solidifying (UV radiation), be easy to being stripped from the interface of adhesive layer 3.On the contrary, do not solidified corresponding to the sea part of polymer binder A, so its structure can not change by the UV radiation.Therefore, suppose the situation that the area of sea part equates with the total area of island part, owing to the relative dimension of island part becomes bigger with respect to the size of sea part, the adhesive power of sea-island structure will demonstrate very big reduction when UV solidifies so.That is, along with the long-pending ratio increase of island area and sea, this structure demonstrates more obvious adhesive power decline when UV solidifies.The long-pending ratio in island area and sea can change according to amount and/or the composition of UV cured acrylate B.And the size on island depends on process parameter such as film-forming temperature, rate of drying, and the molecular weight of other parameter such as component.
If the sea-island structure of PSA film has the island district of mean sizes less than about 1 μ m, PSA film 4 and adhesive layer 3 are attached to together mutually with very high adhesion level.Therefore, need a large amount of UV radiation to reduce the adhesive power of 4 pairs of adhesive layers 3 of PSA film, this will produce heat.Excessive heat can be adhesive layer 3 liquefaction that is stacked on the PSA film 4, and difficulty becomes thereby make and pick up (that is the separation of PSA film 4 from the adhesive layer 3).If the mean sizes in island district surpasses about 10 μ m, PSA film 4 and adhesive layer 3 attach insecurely, PSA film 4 and adhesive layer 3 peeling off and can take place under very a spot of UV radiation at the interface.But because more weak attaching power also undesired peeling off can be taken place before the UV radiation, it can cause separation, the chip rupture during the cutting or the separation etc. of PSA film 4.Equally, if the mean sizes in island district surpasses about 10 μ m, before the UV radiation and the adhesive power between the ring frame can descend, thereby can take place when during wafer bonding, stretching (extension) dicing die bonding 1 and the separating of ring frame.Therefore, although a large amount of reductions of adhesive power when demonstrating UV and solidify by the structure with big island area (for the sea is long-pending), this structure can demonstrate low adhesive power before UV solidifies, and this can cause undesired separation, as with the separating of ring frame.
The thickness of PSA film 4 can be about 3 μ m to about 30 μ m, and preferred about 5 μ m are to about 20 μ m.About 3 μ m or thicker thickness help to guarantee that the cohesion of PSA film 4 after UV solidifies is enough high, thereby can cause that the adhesive power at the interface with adhesive layer 3 obviously reduces.About 30 μ m or thinner thickness help to reduce or eliminate undesired fine rule and fragment during the cutting.
Adhesive layer 3
As mentioned above, dicing die bonding 1 can be by being coated on PSA film 4 on the support membrane 5, and superimposed gel adhesive layer 3 forms thereon then.Chip 6a (as semi-conductor chip, optical chip, MEMS device etc.) can be attached on the adhesive layer 3.When film during, for example use pick-up method that chip 6a is separated from PSA film 4 with adhesive layer part 3a, and wafer bonding is to the surface of support component 7 by cutting.Adhesive layer 3 can for example attach on the one side (glass side) of wafer 6 under about 60 ℃, on it with design circuit figure.After cutting, chip 6a and adhesive layer part 3a can be bonded on the support component 7 (it can be lead frame, PCB or other devices) at for example about 120 ℃ of lower wafers, and use epoxy resin mold to encapsulate.Like this, even adhesive layer 3 is also stayed in the packaged piece, and can influence the reliability of packaged piece behind epoxy resin mold.
Adhesive layer 3 can form by having high-molecular weight film forming thermosetting resin.Adhesive layer 3 for example can comprise acrylic copolymer, Resins, epoxy etc.The example of acrylic copolymer comprises acrylate, methacrylic ester and acrylic rubber (it is the multipolymer of vinyl cyanide).Resins, epoxy can be the resin that can solidify and provide adhesive power, and can comprise two or more functional groups.The example of Resins, epoxy comprises bisphenol A epoxide resin, phenol phenolic resin varnish, cresols phenolic resin varnish etc.
Also can in adhesive layer 3, include curing catalyst to promote the curing of Resins, epoxy.Curing catalyst can be imidazoles, amine or the like.In addition, according to specific embodiment, can in adhesive layer 3, add organic filler, mineral filler, adhesionpromoter, tensio-active agent, static inhibitor etc.For instance, can in adhesive layer 3, use various silane coupling agents to strengthen the adhesive power of 3 pairs of wafers 6 of adhesive layer.In addition, mineral filler can comprise inorganic particle, as silicon-dioxide etc., is used to improve the dimensional stability and the thermotolerance of adhesive layer 3.
The thickness of adhesive layer coating can be about 5 μ m to about 100 μ m, is preferably about 10 μ m to about 80 μ m.When thickness increases, when chip 6a being bonded to another chip 6a, substrate 7 etc., keep homogeneous thickness to become more difficult, similar concave surface (fillet) defective when this will produce with the use liquid adhesive.About 5 μ m or thicker thickness help to guarantee and wafer 6 between the adhesive power of wanting level.About 100 μ m or thinner thickness can provide gently, thin and small-sized packaged piece.Similar with the coating process of PSA film 4, the coating process that is used for adhesive layer 3 can provide uniform film thickness.
Provide following embodiment to describe the special details of the one or more examples of the present invention.But, will be appreciated that these embodiments described here are not limited to described in an embodiment special details.
First group of embodiment
Preparation tackiness agent tunic is also pasted itself and various PSA film preparing dicing die bonding, and test dicing die bonding by wafer installation, cutting and wafer bonding.
The preparation of adhesive film
Mix following compound and prepare adhesive film (" adhesive film 1-3-a "):
400g acrylic resin (KLS-1046DR, hydroxyl value are 13mg KOH/g, and acid number is 63mg KOH/g, and Tg is 38 ℃, and molecular-weight average is 690,000, are made by Fujikura KaseiCo.Ltd. (Japan));
60g acrylic resin (WS-023, hydroxyl value or acid number are 20mg KOH/g, and Tg is-5 ℃, and molecular-weight average is 500,000, and hydroxyl or carboxyl-content are 20, are made by NagaseChemteX Corp. (Japan));
60g cresols phenolic resin varnish (YDCN-500-4P, molecular weight are 10,000 or lower, are made by Kukdo Chemical Co.Ltd. (Korea S));
40g cresols phenolic varnish solidifying agent (MEH-7800SS is made by Meiwa Plastic Industries (Japan));
0.1g imidazoles curing catalysts (2P4MZ is made by Shikoku Chemicals Corp. (Japan));
The Procuring additive of 3g alkyl isocyanate TriMethylolPropane(TMP) modification (L-45 is made by Nippon Polyurethane Industries (Japan));
(E-5XM is by Soken Chemical ﹠amp for the 1g epoxy additive; Engineering Co.Ltd. (Japan) makes);
0.5g mercaptosilane coupling agents (KBM-803 is made by Shin-Etsu Chemical Co.Ltd. (Japan));
0.5g epoxy silane coupling agent (KBM-303 is made by Shin-Etsu Chemical Co.Ltd. (Japan)); With
20g soft silica filler (OX-50 is made by Degussa GmbH (Germany)).
Mixture disperseed about 2 hours with 500rpm.After the dispersion, grind.The main inorganic particle that uses carries out the bead grinding.After the grinding, with solution coat on the one side of the thick polyethylene terephthalate separatory membrane of 38 μ m of drying to thickness be 20 μ m, to obtain adhesive film 1-3-a.Next, stacked thereon polyethylene terephthalate film is protected this adhesive film 1-3-a.
The preparation of PSA film
Embodiment 1-1
With the 300g solids content be 33%, Tg be 350,000 acrylic resin (PSA binding agent) for-30 ℃, weight-average molecular weight with the 80g room temperature under viscosity can not survey, 40 ℃ of following viscosity are 20, the U-324A of 000cps (Shin-Nakamura (Japan)) mixes.Next, the IC-651 (Ciba-Geigy, (Switzerland)) of the polyisocyanate curing agent (L-45, Nippon Polyurethane (Japan)) of interpolation 2g and 1g is with the preparation Photocurable composition.Use applicator that this Photocurable composition is coated on the one side of the thick PET separatory membrane of 38 μ m (MRF-38, Mitsubishi Polyester (Japan)).At 100 ℃ down after dry 2 minutes, by being heated to the thick polyolefin film (OGF-100, Osaka Godo (Japan)) of 60 ℃ of stacked 100 μ m to obtain PSA film 1-4-a.Prepared PSA film 1-4-a has the island district that mean sizes is 5 μ m.
Embodiment 1-2
With the 300g solids content be 33%, Tg is 290 for-28 ℃, weight-average molecular weight, viscosity can not be surveyed under 000 acrylic resin (PSA binding agent) and the 60g room temperature, 40 ℃ of following viscosity are 30, QU-1000 (the urethanum of 000cps, Mw 1,800, make by QNTOP (Korea S)) mix.Next, the IC-651 of the polyisocyanate curing agent (L-45) of interpolation 2g and 1g is with the preparation Photocurable composition.Use applicator that this Photocurable composition is coated on the one side of the thick PET separatory membrane (MRF-38) of 38 μ m.At 100 ℃ down after dry 2 minutes, by being heated to the thick polyolefin film (0GF-100) of 60 ℃ of stacked 100 μ m to obtain PSA film 1-4-b.Prepared PSA film 1-4-b has the island district that mean sizes is 6 μ m.
Comparative Examples 1-1
With the 300g solids content be 33%, Tg is that 380,000 acrylic resin (PSA binding agent) mixes with the U-324A of 100g for-32 ℃, weight-average molecular weight.Next, the IC-651 of the polyisocyanate curing agent (L-45) of interpolation 2g and 1g is with the preparation Photocurable composition.Use applicator that this Photocurable composition is coated on the one side of the thick PET separatory membrane (MRF-38) of 38 μ m.At 100 ℃ down after dry 2 minutes, by being heated to the thick polyolefin film (OGF-100) of 60 ℃ of stacked 100 μ m to obtain PSA film 1-4-c.Prepared PSA film 1-4-c has the island district that mean sizes is 14 μ m.
Comparative Examples 1-2
With the 300g solids content be 33%, second-order transition temperature is 310 for-25 ℃, weight-average molecular weight, 000 acrylic resin (PSA binding agent) is aqueous with 70g, at room temperature the viscosity of (25 ℃) is 2, and the UA-4400 of 000cps (Shin-Nakamura Chemical Co. (Japan)) mixes.Next, the IC-651 of the polyisocyanate curing agent (L-45) of interpolation 2g and 1g is with the preparation Photocurable composition.Use applicator that this Photocurable composition is coated on the one side of the thick PET separatory membrane (MRF-38) of 38 μ m.At 100 ℃ down after dry 2 minutes, by being heated to the thick polyolefin film (OGF-100) of 60 ℃ of stacked 100 μ m to obtain PSA film 1-4-d.Prepared PSA film 1-4-d has the island district that mean sizes is 7 μ m.
Comparative Examples 1-3
With the 300g solids content be 33%, Tg is that 380,000 acrylic resin (PSA binding agent) mixes with the U-324A of 70g for-32 ℃, weight-average molecular weight.Next, the IC-651 of the polyisocyanate curing agent (L-45) of interpolation 2g and 1g is with the preparation Photocurable composition.Use applicator that this Photocurable composition is coated on the one side of the thick PET separatory membrane (MRF-38) of 38 μ m.At 100 ℃ down after dry 2 minutes, by being heated to the thick polyolefin film (OGF-100) of 60 ℃ of stacked 100 μ m to obtain PSA film 1-4-e.Prepared PSA film 1-4-e has the island district that mean sizes is 0.5 μ m.
Comparative Examples 1-4
With the 300g solids content be 33%, Tg is that 380,000 acrylic resin (PSA binding agent) mixes with the U-324A of 170g for-32 ℃, weight-average molecular weight.Next, the IC-651 of the polyisocyanate curing agent (L-45) of interpolation 2g and 1g is with the preparation Photocurable composition.Use applicator that this Photocurable composition is coated on the one side of the thick PET separatory membrane (MRF-38) of 38 μ m.At 100 ℃ down after dry 2 minutes, by being heated to the thick polyolefin film (OGF-100) of 60 ℃ of stacked 100 μ m to obtain PSA film 1-4-f.Prepared PSA film 1-4-f has the island district that mean sizes is 5 μ m.
Comparative Examples 1-5
With the 300g solids content be 33%, Tg is that 380,000 acrylic resin (PSA binding agent) mixes with the U-324A of 15g for-32 ℃, weight-average molecular weight.Next, the IC-651 of the polyisocyanate curing agent (L-45) of interpolation 2g and 1g is with the preparation Photocurable composition.Use applicator that this Photocurable composition is coated on the one side of the thick PET separatory membrane (MRF-38) of 38 μ m.At 100 ℃ down after dry 2 minutes, by being heated to the thick polyolefin film (OGF-100) of 60 ℃ of stacked 100 μ m to obtain PSA film 1-4-g.Prepared PSA film 1-4-g has the island district that mean sizes is 5 μ m.
The physical properties test of dicing die bonding
Measure physical properties as follows by the PSA membrane prepare dicing die bonding of adhesive film 1-3-a and embodiment 1-1 and 1-2 (PSA film 1-4-a and 1-4-b) and Comparative Examples 1-1 to 1-5 (PSA film 1-4-c to 1-4-g).
The mean sizes in sea-island structure Zhong Dao district
Use FE-SEM S-4800 (Hitachi High Technologies America, Inc. (U.S.)) to take the surface picture of the PSA film that in first group of embodiment and Comparative Examples, prepares with 5,000 times enlargement ratio.Measure the mean sizes in island district by analyzing photo.
The weight-average molecular weight of polymer bonding Resin A
1% solution that dissolve polymer binding resin A in tetrahydrofuran (THF) is obtained carries out gel permeation chromatography (150-C ALC/GPC, Waters Corp. (U.S.)).From measurement result, calculate the weight-average molecular weight of polystyrene conversion.
The second-order transition temperature of polymer bonding Resin A
The binding resin A that uses about 5mg to have viscosity to about 10mg uses DSC2910 (TA Instruments (U.S.)), with 10 ℃/minute speed temperature is risen to 200 ℃ by-70 ℃, carries out the mensuration of second-order transition temperature.
180 ° of stripping strengths between PSA film and the adhesive layer (UV solidifies before with afterwards)
According to each PSA film of step measurements of JIS Z0237 and 180 ° of stripping strengths between the adhesive layer.The dicing die bonding sample for preparing in first group of embodiment and Comparative Examples is cut into 15mm * 100mm size.Use tensile strength tester (Series1X/s Automated Materials Tester 3343, Instron Corp. (U.S.)), with the load cell of 10N every kind of sample of rate test with 300mm/ minute.Use AR 08 UV equipment (making), with 70W/cm by AARON Co. 2Carry out the UV radiation in 2 seconds.The UV exposure is 140mJ/cm 2Before the UV radiation and afterwards, each embodiment and comparative example are carried out the test of 10 samples and average.
The viscosity of PSA film (UV solidifies before with afterwards)
Use probe tack tester (Chemilab Tack Tester is made by Chemilab (Korea S)), before UV solidifies and afterwards, to measuring by the PSA film of the dicing die bonding for preparing in first group of embodiment and the Comparative Examples.According to the step of ASTM D2979-71, the tip of cleaning probe is contacted 1.0+0.01 second with the surface of PSA, speed is 10+0.1mm/ second, contact load is 9.79+1.01kPa, measures required maximum, force.Use AR 08 UV, with 70W/cm 2Carry out the UV radiation in 2 seconds.The UV exposure is 140mJ/cm 2Before the UV radiation and afterwards, each embodiment and comparative example are carried out the test of 5 samples and average.
Pick up success ratio
Under 60 ℃, apply heat and 10 seconds of pressure, the thick Silicon Wafer of 80 μ m is attached on each the sheet dicing die bonding for preparing in first group of embodiment and Comparative Examples.Next, after using DFD-650 (DISCO Corp. (Japan)) to be cut to 16mm * 9mm size, use AR 08 UV, with 70W/cm 2Carry out the UV radiation in 2 seconds.The UV exposure is 140mJ/cm 2After the UV radiation, use loader (SDB-10M is made by Samsung Mechatronics (Korea S)), carry out the test of picking up of 200 chips in the center of Silicon Wafer.
Test result by the physical properties of estimating is as mentioned above listed in the table 1 of Fig. 7.For embodiment 1-1 and 1-2, obtained 100% the success ratio of picking up for the chip of 16mm * 9mm size.For Comparative Examples 1-1, owing between extended peroid, separate, pick up trial from ring frame at all, the mean sizes in island district surpasses 10 μ m, and stripping strength and viscosity before the UV radiation are very low.For Comparative Examples 1-2, UV cured acrylate B at room temperature is liquid.When forming PSA film 1-4-c, the liquid propene acid esters is moved on the adhesive layer, and adhesive power is constant substantially after the UV radiation, and picking up success ratio is 0%.For Comparative Examples 1-3, it is very low to pick up success ratio, and the mean sizes in island district is less than 1 μ m, and the adhesive power at the interface of PSA film and adhesive layer does not obviously reduce.In Comparative Examples 1-4 and 1-5, the content ratio of PSA polymeric binder A and UV cured acrylate B is respectively 100/170 and 100/15.In Comparative Examples 1-4, the content of UV cured acrylate B is 170 weight parts with respect to 100 weight part PSA polymeric binder A, stripping strength and viscosity before the UV radiation are very low, after the UV radiation decline of stripping strength also very low, and it is very low to pick up success ratio.For Comparative Examples 1-5, it picks up success ratio is 0%, and the content of UV cured acrylate B is very low, and the decline of stripping strength is also very low after the UV radiation.
Use the PSA film 4 ' of the 5th example can form the dicing die bonding 1 ' of the 4th example.Dicing die bonding 1 ' and PSA film 4 ' can have the structure identical with dicing die bonding shown in Figure 11 and PSA film 4, and are used in an identical manner in manufacture method.PSA film 4 ' can use the PSA composition of the 6th example to form, and now will describe its details.The details of the 4th to the 6th example have been described with the lower section.But, omitted the details with essentially identical material of above description and structure, thereby avoided repetition.
The PSA composition of the 6th example can comprise polymer bonding Resin A, UV cured urethane origoester acrylate B1, UV cured acrylate B2, thermal curing agents C and Photoepolymerizationinitiater initiater D.UV cured urethane origoester acrylate B1 can have at room temperature the high immesurable viscosity of viscosity, that is, they at room temperature are solid or near solid, and is 10 40 ℃ of following viscosity, 000cps or higher.UV cured acrylate B2 can be solid or wax and can have and is higher than 25 ℃ fusing point.
With the polymer bonding Resin A, UV cured acrylate B1 and B2 can cause crosslinked between polymer bonding Resin A and UV cured acrylate B1 and the B2, thereby cause that adhesive power obviously reduces after the UV radiation.
When mixing with fluoropolymer resin A and being coated on the support membrane 5, UV cured acrylate B2 can form firm film in the adhesive bond agent, thereby the migration to adhesive layer 3 can not take place before the UV radiation.As a result, when the UV radiation, psa layer 4 ' can obviously descend with respect to the adhesive power of adhesive layer 3.In addition, because the high viscosity of UV cured urethane origoester acrylate B1 and UV cured acrylate B2 even they are low-molecular-weight materials, for example has about 1,000 molecular weight, also can prevent to move on the adhesive layer 3.Therefore, the adhesive power at the interface between PSA film 4 ' and the adhesive layer 3 can obviously descend when the UV radiation.
The PSA composition of the 6th example can be used to produce the PSA film 4 ' that has " sea-island structure " as shown in Figure 6 on the surface.This sea-island structure is because the generation of uncompatibility mutually between polymer bonding Resin A and the lower molecular weight UV cured acrylate.Particularly, with reference to figure 6, in the PSA of the 5th example film 4 ', " island " formed by UV cured urethane origoester acrylate B1, and " sea " district is formed by the polymer bonding Resin A.
The mean sizes on island can be about 1 μ m to about 10 μ m.Regard to as above that first example discusses like that, after the UV radiation, compare with the sea area, the island district that is formed by UV cured acrylate B1 demonstrates tangible contraction and viscosity decline, thereby make with the peeling off and become possibility at the interface of adhesive layer 3.When standing the UV radiation, the polymer bonding Resin A combines the reticulated structure that interpenetrates with formation with UV cured acrylate B2, and the Tg of polymer bonding Resin A is increased, and the viscosity of PSA film 4 ' is reduced.If the mean sizes on island is less than about 1 μ m, a large amount of UV radiation of needs reduces the adhesive power at the interface with adhesive layer 3, and this is because the contact area between PSA film 4 ' and the adhesive layer 3 can become big.If the mean sizes on island surpasses about 10 μ m, PSA film 4 ' demonstrate and ring frame and wafer bonding adhesive layer between the adhesive power of difference.The opticmicroscope that the sea-island structure of PSA film 4 ' can use FE-SEM for example or have about 3,000 times or a bigger magnification is observed.In one embodiment, the PSA composition of the 6th example can comprise the polymer bonding Resin A, be about 20 to the UV cured urethane origoester acrylate B 1 of about 150 weight parts and be the about 5 UV cured acrylate B2 to about 50 weight parts with respect to 100 parts by weight polymer binding resin A with respect to 100 parts by weight polymer binding resin A.UV cured urethane origoester acrylate B1 at room temperature is a solid or near solid, and its viscosity 40 ℃ down for about 10,000cps or higher.UV cured acrylate B2 can be solid or wax and can have and is higher than 25 ℃ fusing point.UV cured acrylate B2 can comprise one or more in trimethylolpropane tris (methyl) acrylate, tetramethylol methane tetraacrylate, three (2-acrylyl oxy-ethyl) isocyanuric acid ester, methoxy poly (ethylene glycol) 1000 methacrylic esters, methoxy poly (ethylene glycol) 1000 acrylate, vinylformic acid mountain Yu ester, cetomacrogol 1000 dimethacrylate, cetomacrogol 1000 diacrylate or the tetramethylol methane tetraacrylate.
When UV cured urethane origoester acrylate B1 was added with the amount that is less than about 20 weight parts, because very little by the absolute magnitude of UV photocuring, the reduction of adhesive power was also relatively very little.When UV cured urethane origoester acrylate B1 is added with the amount that surpasses about 150 weight parts, because the cohesion of very poor film can not form film (before the UV radiation).When UV cured acrylate B2 was added with the amount that is less than about 5 weight parts, because very little by the absolute magnitude of UV photocuring, the increase of the force of cohesion that is caused by UV light and the reduction meeting of viscosity were very low.When UV cured acrylate B2 is added with the amount that surpasses about 50 weight parts, can be fine by UV solidified absolute magnitude, but some unreacted UV cured acrylate B2 can be moved on the adhesive layer 3, it can obviously reduce the reduction of the adhesive power that is caused by UV light, or even can increase adhesive power after the UV radiation.
It is the about 0.1 thermal curing agents C to about 10 weight parts that the PSA composition can further comprise with respect to 100 parts by weight polymer binding resin A, and be the about 0.1 Photoepolymerizationinitiater initiater D to about 5 weight parts with respect to 100 parts by weight of acrylic acid ester B1 and B2 total amount, be about 0.1 to about 5 weight parts promptly based on the weight sum of the weight of UV cured urethane origoester acrylate B1 and UV cured acrylate B2.
Can use acrylic resin as the polymer bonding Resin A.Also can use other various resins, as vibrin, urethane resin, silicone resin and caoutchouc resin as the polymer bonding Resin A.In acrylic resin, the monomer that is used for copolymerization for example comprises one or more of butyl acrylate, 2-EHA, vinylformic acid, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) methyl acrylate, vinylbenzene, (methyl) glycidyl acrylate, Isooctyl acrylate monomer, stearyl methacrylate, dodecyl acrylate, decyl acrylate, vinyl acetate, vinyl cyanide etc.
UV cured acrylate B1 that is comprised in the PSA composition and B2 can have can be by the carbon-carbon double bond of UV photocuring (C=C), for example Viscoat 295, tetramethylol methane tetraacrylate, tetramethylolmethane six acrylate, tetramethylol methane tetraacrylate, Dipentaerythritol monohydroxy five acrylate, dipentaerythritol acrylate, 1,4-butylene glycol diacrylate, 1,6 hexanediol diacrylate, polyethyleneglycol diacrylate, origoester acrylate etc.
UV cured urethane origoester acrylate B1 can be at room temperature (25 ℃) and has full-bodied one or more acrylate, thereby they are as solid or near solid, and under 40 ℃, have about 10,000cps or higher viscosity.In one embodiment, UV cured urethane origoester acrylate B1 can prepare by making the reaction of last isocyanic ester urethane prepolymer of end and hydroxy acrylate (that is the acrylate that, has hydroxyl).Hold last isocyanic ester urethane prepolymer to obtain by polyester polyol compound or polyether polyol compound and polyisocyanate compounds are reacted.
UV cured acrylate B2 can be has full-bodied one or more acrylate under the room temperature, thereby they look like to have the solid or the wax of the fusing point that is higher than 25 ℃.The weight-average molecular weight of UV cured acrylate B2 can be about 100 to about 5,000.In one embodiment, UV cured acrylate B2 can be trimethylolpropane tris (methyl) acrylate UV cured acrylate, tetramethylol methane tetraacrylate, three (2-acrylyl oxy-ethyl) isocyanuric acid ester, methoxy poly (ethylene glycol) 1000 methacrylic esters, methoxy poly (ethylene glycol) 1000 acrylate, vinylformic acid Shan Yu ester, cetomacrogol 1000 dimethacrylate, cetomacrogol 1000 diacrylate or tetramethylol methane tetraacrylate.Between the UV radiation era, when being solidified separately, urethanum origoester acrylate B1 compares, and trimethylolpropane tris (methyl) acrylate UV cured acrylate B2 can increase curing efficiency.
Second group of embodiment
Preparation tackiness agent tunic is also pasted itself and various PSA film preparing dicing die bonding, and test dicing die bonding by wafer installation, cutting and wafer bonding.
The preparation of adhesive film
By being prepared as follows adhesive film (" adhesive film 2-3-a "):
With following compound, and disperseed about 2 hours with 500rpm:
400g acrylic resin KLS-1046DR (Tg=38 ℃, molecular-weight average=690,000 are made by Fujikura Kasei Co.Ltd. (Japan) for hydroxyl value=13mg KOH/g, acid number=63mg KOH/g);
The WS-023 of 60g (hydroxyl value or acid number=20mg KOH/g, Tg=-5 ℃, molecular-weight average=500,000, hydroxyl or carboxyl-content=20 are made by Nagase ChemteX Corp. (Japan));
60g cresols phenolic resin varnish YDCN-500-4P (molecular weight=10,000 or lower are made by Kukdo Chemical Co.Ltd. (Korea S));
40g cresols phenolic varnish solidifying agent MEH-7800SS (making) by Meiwa Plastic Industries (Japan);
0.1g imidazoles curing catalysts 2P4MZ (Saguk Chemical);
The Procuring additive L-45 of 3g alkyl isocyanate TriMethylolPropane(TMP) modification;
1g epoxy additive E-5XM is (by Soken Chemical ﹠amp; Engineering Co.Ltd. (Japan) makes);
0.5g mercaptosilane coupling agents KBM-803 (making) by Shin-Etsu Chemical Co.Ltd. (Japan);
0.5g epoxy silane coupling agent KBM-303 (making) by Shin-Etsu Chemical Co.Ltd. (Japan); With
20g soft silica filler (OX-50 is made by Degussa GmbH (Germany)).
Grind after the dispersion.Using inorganic particle to carry out bead grinds.After grinding was finished, being applied to thickness on the one side of the thick polyethylene terephthalate separatory membrane of 38 μ m was 20 μ m.Protect the surface by stacked polyethylene terephthalate film on coating layer, thereby obtain adhesive film 2-3-a.
The PSA preparation of compositions
Embodiment 2-1: the preparation of Photocurable composition
By mix the following one-tenth Photocurable composition of assigning to prepare in the beaker of 1L: the 300g solids content is 33%, the Tg temperature for-35 ℃, weight-average molecular weight is 400,000 adhesive bond agent; The viscosity height can not be surveyed under the 60g room temperature, 40 ℃ of following viscosity are 20, the U-324A of 000cps (Shin-Nakamura Chemical (Japan)); With under the 25g room temperature for solid-state and have an A-1000 (Shin-Nakamura Chemical) of about 38 ℃ fusing point.Next, add the polyisocyanate curing agent L-45 (Nippon Polyurethane Industry (Japan)) of 2g and the IC-184 (Ciba-Geigy (Switzerland)) of 1g.
Embodiment 2-2: the preparation of Photocurable composition
By mix the following one-tenth Photocurable composition of assigning to prepare in the beaker of 1L: the 300g solids content is 33%, the Tg temperature for-32 ℃, weight-average molecular weight is 380,000 adhesive bond agent; The U-324A of 60g; With under the 25g room temperature for solid-state and have a Miramer M420 (Miwon Commercial Co.Ltd. (Korea S)) of about 37 ℃ fusing point.Next, add the polyisocyanate curing agent L-45 of 2g and the IC-184 of 1g.
Embodiment 2-3: the preparation of Photocurable composition
By mix the following one-tenth Photocurable composition of assigning to prepare in the beaker of 1L: the 300g solids content is 33%, the Tg temperature for-28 ℃, weight-average molecular weight is 290,000 adhesive bond agent; The viscosity height can not be surveyed under the 70g room temperature, 40 ℃ of following viscosity are 30, the QU-1000 of 000cps (Q ﹠amp; Top); With under the 10g room temperature be solid-state A-1000 (Shin-NakamuraChemical (Japan)).Next, add the polyisocyanate curing agent L-45 of 2g and the IC-184 of 1g.
Comparative Examples 2-1: the preparation of Photocurable composition
By mix the following one-tenth Photocurable composition of assigning to prepare in the beaker of 1L: the 300g solids content is 33%, the Tg temperature for-35 ℃, weight-average molecular weight is 400,000 adhesive bond agent; U-324A with 60g.Next, add the polyisocyanate curing agent L-45 of 2g and the IC-184 of 1g.
Comparative Examples 2-2: the preparation of Photocurable composition
By mix the following one-tenth Photocurable composition of assigning to prepare in the beaker of 1L: the 300g solids content is 33%, the Tg temperature for-40 ℃, weight-average molecular weight is 350,000 adhesive bond agent; The QU-1000 of 100g; A-1000 with 25g.Next, add the polyisocyanate curing agent L-45 of 2g and the IC-184 of 1g.
Comparative Examples 2-3: the preparation of Photocurable composition
By mix the following one-tenth Photocurable composition of assigning to prepare in the beaker of 1L: the 300g solids content is 33%, the Tg temperature for-32 ℃, weight-average molecular weight is 380,000 adhesive bond agent; (that is, 25 ℃ of following viscosity are 2, UA-4400 000cps) (Shin-Nakamura Chemical (Japan)) but 60g has viscosimetric under the room temperature; Miramer M420 with 25g.Next, add the polyisocyanate curing agent L-45 of 2g and the IC-184 of 1g.
Comparative Examples 2-4: the preparation of Photocurable composition
By mix the following one-tenth Photocurable composition of assigning to prepare in the beaker of 1L: the 300g solids content is 33%, the Tg temperature for-25 ℃, weight-average molecular weight is 310,000 adhesive bond agent; The U-324A of 50g; A-1000 with 25g.Next, add the polyisocyanate curing agent L-45 of 2g and the IC-184 of 1g.
Comparative Examples 2-5: the preparation of Photocurable composition
By mix the following one-tenth Photocurable composition of assigning to prepare in the beaker of 1L: the 300g solids content is 33%, the Tg temperature for-35 ℃, weight-average molecular weight is 400,000 adhesive bond agent; The U-324A of 60g; A-1000 with 3g.Next, add the polyisocyanate curing agent L-45 of 2g and the IC-184 of 1g.
Comparative Examples 2-6: the preparation of Photocurable composition
By mix the following one-tenth Photocurable composition of assigning to prepare in the beaker of 1L: the 300g solids content is 33%, the Tg temperature for-35 ℃, weight-average molecular weight is 400,000 adhesive bond agent; The U-324A of 60g; A-1000 with 70g.Next, add the polyisocyanate curing agent L-45 of 2g and the IC-184 of 1g.
The preparation of dicing die bonding
Embodiment 2-4: the preparation of dicing die bonding
Be coated on the one side of polyolefin film by the photocuring PSA composition that will prepare among the embodiment 2-1 and the dry thick PSA film 2-4-a of 10 μ m for preparing.By on the one side of adhesive film 2-3-a, peeling off polyethylene terephthalate film and with adhesive film 2-3-a and the at room temperature stacked dicing die bonding for preparing of PSA film 2-4-a, as shown in Figure 1.
Embodiment 2-5: the preparation of dicing die bonding
Press the as above described preparation dicing die bonding of embodiment 2-4, difference is to use the Photocurable composition for preparing among the embodiment 2-2 to prepare PSA film 2-4-b.
Embodiment 2-6: the preparation of dicing die bonding
Press the as above described preparation dicing die bonding of embodiment 2-4, difference is to use the Photocurable composition for preparing among the embodiment 2-3 to prepare PSA film 2-4-c.
Comparative Examples 2-7: the preparation of dicing die bonding
Press the as above described preparation dicing die bonding of embodiment 2-4, difference is to use the Photocurable composition for preparing among the Comparative Examples 2-1 to prepare PSA film 2-4-d.
Comparative Examples 2-8: the preparation of cutting product sheet adhesive film
Press the as above described preparation dicing die bonding of embodiment 2-4, difference is to use the Photocurable composition for preparing among the Comparative Examples 2-2 to prepare PSA film 2-4-e.
Comparative Examples 2-9: the preparation of dicing die bonding
Press the as above described preparation dicing die bonding of embodiment 2-4, difference is to use the Photocurable composition for preparing among the Comparative Examples 2-3 to prepare PSA film 2-4-f.
Comparative Examples 2-10: the preparation of dicing die bonding
Press the as above described preparation dicing die bonding of embodiment 2-4, difference is to use the Photocurable composition for preparing among the Comparative Examples 2-4 to prepare PSA film 2-4-g.
Comparative Examples 2-11: the preparation of dicing die bonding
Press the as above described preparation dicing die bonding of embodiment 2-4, difference is to use the Photocurable composition for preparing among the Comparative Examples 2-5 to prepare PSA film 2-4-h.
Comparative Examples 2-12: the preparation of dicing die bonding
Press the as above described preparation dicing die bonding of embodiment 2-4, difference is to use the Photocurable composition for preparing among the Comparative Examples 2-6 to prepare PSA film 2-4-i.
The physical properties test of dicing die bonding
The mean sizes in sea-island structure Zhong Dao district
The surface picture of using FE-SEM S-4800 (Hitachi (Japan)) to take the PSA film of preparation in second group of embodiment and Comparative Examples (being embodiment 2-4 to 2-6 and Comparative Examples 2-7 to 2-12) with 5,000 times enlargement ratio, the mean sizes on mensuration island.The result provides in the table 2 of Fig. 8.
The weight-average molecular weight of polymer bonding Resin A
The polymer bonding Resin A that will prepare in the Photocurable composition preparation of embodiment 2-1 to 2-3 and Comparative Examples 2-1 to 2-6 is dissolved in and obtains 1% solution in the tetrahydrofuran (THF).Carry out gel permeation chromatography (150-C ALC/GPC, Waters (U.S.)), and calculate the weight-average molecular weight of polystyrene conversion.The result provides in table 2.
The second-order transition temperature of polymer bonding Resin A
To the every kind polymer bonding Resin A of about 5mg, use DSC2910 (TA) to measure Tg from-70 ℃ to 200 ℃ up to scanning for the second time with 10 ℃/minute heating rate to about 10mg preparation in the Photocurable composition preparation of embodiment 2-1 to 2-3 and Comparative Examples 2-1 to 2-6.The result provides in table 2.
180 ° of stripping strengths between PSA film and the adhesive layer (UV solidifies before with afterwards)
According to 180 ° of stripping strengths between JIS Z0237 mensuration PSA film and the adhesive layer.The dicing die bonding sample for preparing among embodiment 2-4 to 2-6 and the Comparative Examples 2-7 to 2-12 is cut to 15mm * 100mm size.Use Instron Series 1X/s AutomatedMaterials Tester-3343, peel off every kind of sample with 300mm/ minute speed with the load cell of 10N.Mensuration is peeled off required load.The result provides in table 2.
Use AR 08 UV (Aaron), with 70W/cm 2Brightness carry out the UV radiation in 2 seconds, radiation quantity is 140mJ/cm 2Before the UV radiation and afterwards, each sample being carried out ten times (10) tests and averages.
The viscosity of PSA film (UV solidifies before with afterwards)
For the dicing die bonding for preparing among embodiment 2-4 to 2-6 and the Comparative Examples 2-7 to 2-12, use probe tack tester (Chemilab Tack Tester), before UV solidifies and measure viscosity (only to the PSA film) afterwards.Step according to ASTM D2979-71 is measured.The tip of cleaning probe is contacted 1.0+0.1 second with the surface of PSA, and speed is 10+0.1mm/ second, and contact is pressed and is 9.79+1.01kPa, measures from the required power of surface isolation.The result provides in table 2.
Use AR 08 UV (Aaron), with 70W/cm 2Brightness carry out the UV radiation in 2 seconds, radiation quantity is 140mJ/cm 2Before the UV radiation and afterwards, each sample being carried out five times (5) tests and averages.
Pick up success ratio
Used for 10 seconds down at 60 ℃, the thick Silicon Wafer of 80 μ m is thermally bonded on each the sheet dicing die bonding for preparing in embodiment 2-4 to 2-6 and Comparative Examples 2-7 to 2-12.Next, use DFD-650 (DISCO Corp. (Japan)) to be cut to 16mm * 9mm size.Then, use AR 08 UV (Aaron), with 70W/cm 2Brightness carry out the UV radiation in 2 seconds, radiation quantity is 140mJ/cm 2After the UV radiation, use loader (SDB-10M, Samsung Mechatronics (Korea S)), carry out picking up of 200 chips and measure success ratio (%) in the center of Silicon Wafer.The result provides in table 2.
As shown in table 2, for the Photocurable composition of the embodiment 2-4 to 2-6 that comprises polymeric binder A, lower molecular weight UV cured acrylate B1 and B2, thermal curing agents C and Photoepolymerizationinitiater initiater D, the chip of 16mm * 9mm size has obtained 100% the success ratio of picking up.
On the contrary, the Comparative Examples 2-7 that does not comprise UV cured acrylate B2 does not obtain 100% the success ratio of picking up, and this is because stripping strength and viscosity after the UV radiation are higher than embodiment 2-4 to 2-6.The Comparative Examples 2-8 that average island size surpasses 10 μ m demonstrates 0% the success ratio of picking up, this be because before the UV radiation and afterwards stripping strength and viscosity all very high.Have under the room temperature can viscosimetric UV cured acrylate B2 Comparative Examples 2-9 demonstrate 0% the success ratio of picking up, this is because because acrylate migrates to adhesive layer from the PSA film, adhesive power does not descend after the UV radiation at all.Average island size demonstrates the low success ratio of picking up less than the Comparative Examples 2-10 of 1 μ m, and this is because in the unobvious decline of the adhesive power at the interface of PSA film and adhesive layer.The Comparative Examples 2-11 that contains the lower molecular weight UV cured acrylate B2 of 3 weight parts with respect to 100 parts by weight polymer binding resin A demonstrates the similar result with Comparative Examples 2-7 (wherein having removed lower molecular weight UV cured acrylate B2), this is because because very little by the absolute magnitude of UV photocuring, the reduction of the increase of force of cohesion and viscosity is all not obvious after the UV radiation.The Comparative Examples 2-12 that contains 70 weight part lower molecular weight UV cured acrylate B2 with respect to 100 parts by weight polymer binding resin A demonstrates 0% the success ratio of picking up, and this is because stripping strength and not obviously decline of viscosity after the UV radiation.
As mentioned above, can use composition of the present invention to form the PSA film of dicing die bonding.Can not take place or rare migration to adhesive layer, and after the UV radiation between PSA film and the adhesive layer at the interface adhesive power can obviously descend.In one embodiment, composition can comprise vinylformic acid PSA binding agent and UV cured acrylate.Even can be used to preparation, said composition also can provide excellence to pick up the dicing die bonding of characteristic for large-sized chip (for example 10mm * 10mm or bigger).
Embodiments of the invention are open at this, although used specific term, they should be only use on general descriptive sense and explain and be not used in restriction.Therefore, those skilled in the art will appreciate that under the situation of the spirit and scope of the present invention of in not deviating from the claims of enclosing, describing, can carry out the various changes on form and the details.

Claims (23)

1. composition comprises:
The polymer bonding Resin A;
UV cured acrylate B;
Thermal curing agents C; With
Photoepolymerizationinitiater initiater D, wherein:
It is the about 20 UV cured acrylate B to about 150 weight parts that said composition comprises with respect to 100 parts by weight polymer binding resin A, and
This UV cured acrylate B at room temperature is a solid or near solid, and its viscosity 40 ℃ down for about 10,000cps or higher.
2. the described composition of claim 1, wherein:
It is the about 0.1 thermal curing agents C to about 10 weight parts that said composition comprises with respect to 100 parts by weight polymer binding resin A, and
It is the about 0.1 Photoepolymerizationinitiater initiater D to about 5 weight parts that said composition comprises with respect to 100 weight part UV cured acrylate B.
3. the described composition of claim 2, wherein this thermal curing agents C comprises one or more in polymeric polyisocyanate, melamine/formaldehyde resin or the Resins, epoxy.
4. the described composition of claim 3, wherein this Photoepolymerizationinitiater initiater D comprises one or more in benzophenone cpd, acetophenone compound or the anthraquinone compounds.
5. the described composition of claim 1, wherein this polymer bonding Resin A is the acrylic resin with one or more functional groups in hydroxy functional group, carboxyl functional group, epoxy-functional or the amine functional group.
6. the described composition of claim 5, wherein the second-order transition temperature of this acrylic resin is-60 ℃ to about 0 ℃ approximately, weight-average molecular weight is about 100,000 to about 2,000,000.
7. the described composition of claim 5, wherein this UV cured acrylate B is the urethanum origoester acrylate.
8. composition comprises:
The polymer bonding Resin A;
UV cured urethane origoester acrylate B1;
UV cured acrylate B2;
Thermal curing agents C; With
Photoepolymerizationinitiater initiater D, wherein:
It is the about 20 UV cured urethane origoester acrylate B1 to about 150 weight parts that said composition comprises with respect to 100 parts by weight polymer binding resin A,
It is the about 5 UV cured acrylate B2 to about 50 weight parts that said composition comprises with respect to 100 parts by weight polymer binding resin A,
This UV cured urethane origoester acrylate B1 at room temperature is a solid or near solid, and viscosity 40 ℃ down for about 10,000cps or higher, and
This UV cured acrylate B2 is solid or wax and has and be higher than 25 ℃ fusing point.
9. the described composition of claim 8, wherein this UV cured urethane origoester acrylate B1 comprises the multipolymer of the last isocyanic ester urethane prepolymer of end and hydroxy acrylate formation.
10. the described composition of claim 9, wherein this UV cured acrylate B2 comprises one or more in trimethylolpropane tris (methyl) acrylate, tetramethylol methane tetraacrylate, three (2-acrylyl oxy-ethyl) isocyanuric acid ester, methoxy poly (ethylene glycol) 1000 methacrylic esters, methoxy poly (ethylene glycol) 1000 acrylate, vinylformic acid Shan Yu ester, cetomacrogol 1000 dimethacrylate, cetomacrogol 1000 diacrylate or the tetramethylol methane tetraacrylate.
11. the described composition of claim 10, wherein this UV cured acrylate B2 comprises one or more acrylate, and each in them at room temperature is solid or wax and has and is higher than 30 ℃ fusing point.
12. the described composition of claim 8, wherein this polymer bonding Resin A is the acrylic resin with one or more functional groups in hydroxy functional group, carboxyl functional group, epoxy-functional or the amine functional group.
13. a dicing die bonding, this film comprises:
Support membrane;
Be positioned at the adhesive layer on this support membrane; With
Be positioned at the pressure-sensitive adhesive film on this adhesive layer, wherein:
This pressure-sensitive adhesive film comprises:
The polymer bonding Resin A;
UV cured acrylate B;
Thermal curing agents C; With
Photoepolymerizationinitiater initiater D,
It is the about 20 UV cured acrylate B to about 150 weight parts that this pressure-sensitive adhesive film comprises with respect to 100 parts by weight polymer binding resin A, and
This UV cured acrylate B at room temperature is a solid or near solid, and its viscosity 40 ℃ down for about 10,000cps or higher.
14. the described dicing die bonding of claim 13, wherein this polymer bonding Resin A is the acrylic resin with one or more functional groups in hydroxy functional group, carboxyl functional group, epoxy-functional or the amine functional group.
15. the described dicing die bonding of claim 14, wherein the second-order transition temperature of this acrylic resin is-60 ℃ to about 0 ℃ approximately, and weight-average molecular weight is about 100,000 to about 2,000,000.
16. the described dicing die bonding of claim 14, wherein this UV cured acrylate B is the urethanum origoester acrylate.
17. the described dicing die bonding of claim 14, wherein this adhesive layer comprises acrylic resin.
18. the described dicing die bonding of claim 13, wherein this pressure-sensitive adhesive film has sea-island structure, and wherein the mean sizes of island part is that about 1 μ m is to about 10 μ m.
19. a dicing die bonding, this film comprises:
Support membrane;
Be positioned at the adhesive layer on this support membrane; With
Be positioned at the pressure-sensitive adhesive film on this adhesive layer, wherein:
This pressure-sensitive adhesive film comprises:
The polymer bonding Resin A;
UV cured urethane origoester acrylate B1;
UV cured acrylate B2;
Thermal curing agents C; With
Photoepolymerizationinitiater initiater D,
It is the about 20 UV cured urethane origoester acrylate B1 to about 150 weight parts that this pressure-sensitive adhesive film comprises with respect to 100 parts by weight polymer binding resin A,
It is the about 5 UV cured acrylate B2 to about 50 weight parts that this pressure-sensitive adhesive film comprises with respect to 100 parts by weight polymer binding resin A,
This UV cured urethane origoester acrylate B1 at room temperature is a solid or near solid, and viscosity 40 ℃ down for about 10,000cps or higher, and
This UV cured acrylate B2 is solid or wax and has and be higher than 25 ℃ fusing point.
20. the described dicing die bonding of claim 19, wherein this UV cured urethane origoester acrylate B1 comprises the multipolymer that last isocyanic ester urethane prepolymer of end and hydroxy acrylate form.
21. the described dicing die bonding of claim 20, wherein this UV cured acrylate B2 comprises one or more in trimethylolpropane tris (methyl) acrylate, tetramethylol methane tetraacrylate, three (2-acrylyl oxy-ethyl) isocyanuric acid ester, methoxy poly (ethylene glycol) 1000 methacrylic esters, methoxy poly (ethylene glycol) 1000 acrylate, vinylformic acid mountain Yu ester, cetomacrogol 1000 dimethacrylate, cetomacrogol 1000 diacrylate or the tetramethylol methane tetraacrylate.
22. the described dicing die bonding of claim 21, wherein this adhesive layer comprises acrylic resin.
23. the described dicing die bonding of claim 19, wherein this pressure-sensitive adhesive film has sea-island structure, and wherein the mean sizes of island part is that about 1 μ m is to about 10 μ m.
CN 200710307124 2006-12-27 2007-12-27 Composition for pressure sensitive adhesive film, pressure sensitive adhesive film, and dicing die bonding film including the same Pending CN101230177A (en)

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