TWI425069B - Adhesive film and semiconductor wafer processing tape - Google Patents

Description

Adhesive film and semiconductor wafer processing tape

The present invention relates to an adhesive film and a semiconductor wafer processing tape used for manufacturing a semiconductor device by dicing a semiconductor wafer into a semiconductor wafer.

For the semiconductor wafer processing tape used in the manufacturing process of the semiconductor device, a tape for semiconductor wafer processing having a structure in which an adhesive layer (granular film) is laminated on an adhesive film (grain film) has been proposed (for example, reference) Patent Document 1) has been put into practical use.

In the manufacturing process of the semiconductor device, after the semiconductor wafer processing tape is attached to the semiconductor wafer, a process of cutting (dicing) the semiconductor wafer into wafer units by a cutting blade, and expanding the semiconductor wafer processing are performed. The procedure of the tape, the process of picking up the diced wafer and the adhesive layer from the adhesive layer, the process of mounting the wafer to the substrate via the adhesive layer attached to the wafer, and the like, after sealing the wafer subsequent to the substrate or the like Let it pass the procedure of the reflow oven.

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 02-32181

However, in the tape for processing a semiconductor wafer described in the above Patent Document 1, when the contact time between the adhesive layer and the adhesive layer is long from the time of manufacture to use, the two layers are bonded to each other before use, and are picked up and cut. In the case of a wafer, the adhesive may be picked up while the adhesive is attached to the adhesive layer. In this state, when the wafer which is next to the substrate or the like is passed through the reflow furnace after sealing, there is a problem that reflow cracking occurs.

Therefore, an object of the present invention is to provide an adhesive film and a semiconductor wafer processing tape which can be picked up even when the adhesive is attached to the adhesive layer even when the adhesive layer is bonded to the adhesive layer and the wafer is picked up. Under the same, it can also reduce the reflow crack of the package.

In order to solve the above problems, the adhesive film of the present invention is an adhesive film for semiconductor wafer processing which is composed of a base film and an adhesive layer disposed on the base film, and is characterized by differential thermal analysis. The weight of the aforementioned adhesive layer at the reflow temperature was reduced by 1.5% or less.

In addition, an adhesive film for semiconductor wafer processing consisting of a base film and an adhesive layer disposed on the base film, characterized in that the adhesive is detected by differential thermal analysis at 260 ° C. The weight of the layer is reduced to less than 1.5%.

In addition, in order to solve the above problems, the tape for semiconductor wafer processing of the present invention has an adhesive film composed of a base film and an adhesive layer disposed on the base film, and is disposed on the adhesive. The wafer processing tape of the adhesive layer on the layer was examined by differential thermal analysis, and the weight of the adhesive layer at the reflow temperature was reduced to 1.5% or less.

Further, the tape for processing a semiconductor wafer of the present invention has an adhesive film composed of a base film and an adhesive layer disposed on the base film, and an adhesive disposed on the adhesive layer. The layer of wafer processing tape was examined by differential thermal analysis, and the weight of the adhesive layer at 260 ° C was reduced to 1.5% or less.

Further, in the tape for semiconductor wafer processing of the present invention, the weight average molecular weight of the adhesive layer is 1,000,000 or more.

Further, the tape for semiconductor wafer processing of the present invention is characterized in that the adhesive layer contains a photopolymerization initiator, and the thermal decomposition initiation temperature of the photopolymerization initiator is 260 ° C or higher.

In the adhesive film and the semiconductor wafer processing tape of the present invention, when the wafer is picked up, even when the adhesive is attached to the adhesive layer, the solder reflow crack can be reduced.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

As shown in Fig. 1, the tape for processing a semiconductor wafer according to the present embodiment has an adhesive film 14 on which an adhesive layer 12 is laminated on a base film 11, and an adhesive layer is laminated on the adhesive layer 12. 13 cut pellets. Further, the adhesive layer 12 and the adhesive layer 13 may be combined with a program and a device to be pre-cut (precut) into a specific shape. When the adhesive layer 13 (see FIG. 2(a)) is pre-cut, the adhesive layer 13 is bonded to the wafer W, and the adhesive layer 13 is bonded to the dicing ring frame 20 (see In the portion of Fig. 2(a), there is no adhesive layer 13 and only the adhesive layer 12 is present. In general, since the adhesive layer 13 is not easily peeled off from the adherend, the pre-cut adhesive layer 13 can be used to bond the ring frame 20 to the adhesive layer 12, and the ring frame 20 after use is less likely to generate residual glue. The effect. Further, the tape 15 for semiconductor wafer processing of the present invention includes a form in which one wafer is diced and laminated, and a strip having a plurality of wafers is wound into a roll shape. Hereinafter, the base film 11, the adhesive layer 12, and the adhesive layer 13 will be described in detail.

<Substrate film>

The material for constituting the base film is not particularly limited, however, it is preferably selected from the group consisting of polyolefin and polyvinyl chloride. Further, the surface roughness Ra of the surface in contact with the adhesive is preferably 1 μm or less, more preferably 0.5 μm or less. When the surface roughness Ra is 1 μm or less, the contact area with the adhesive can be increased, and the peeling of the adhesive from the base film can be suppressed.

The above polyene may be polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, poly-4-methylpentene-1, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, A homopolymer or copolymer of an α-olefin such as an ethylene-methyl acrylate copolymer, an ethylene-acrylic acid copolymer, a polyionic polymer, or the like, or a mixture thereof.

When the adhesive layer to be described later is cured by radiation irradiation to reduce the adhesive force, the base film should have radioelasticity. The thickness of the base film is preferably from 50 to 300 μm from the viewpoint of strength and ensuring wafer pick-up property. Further, the base film may be composed of a single layer or a plurality of layers.

<Adhesive layer>

The adhesive layer can also be produced by applying an adhesive to a substrate film. The adhesive layer is not particularly limited as long as it has such a property that the adhesive layer and the semiconductor wafer do not peel off when expanded, and the properties of the adhesive layer are easily peeled off at the time of pick-up. In order to improve the pick-up property, the adhesive layer is preferably radiation curable.

For example, a chlorinated polypropylene resin, an acrylic resin, a polyester resin, a polyurethane resin, an epoxy resin, an addition reaction type organic polyoxyalkylene resin, a polyfluorene-based alkane which are well known for use in an adhesive. Silicon acrylate resin, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, polyisoprene or styrene ‧ butadiene copolymer It is preferred to prepare the adhesive by appropriately blending the radiation-polymerizable compound with various elastomers or the like of the substance or its hydrogen additive or the like. In addition, various surfactants and surface smoothing agents can also be added. The thickness of the adhesive layer is not particularly limited and may be appropriately set. However, it is preferably 1 to 30 μm.

The polymerizable compound is, for example, a low molecular weight compound having at least two photopolymerizable carbon-carbon double bonds in a molecule which causes three-dimensional network formation by light irradiation, or a photopolymerizable carbon-carbon double bond group. A polymer or oligomer that is a substituent. Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butanediol diacrylate, 1,6 hexanediol diacrylate, polyethylene glycol diacrylate or oligoester acrylate, etc., polyfluorene alkacrylate or the like, acrylic acid or a copolymer of various acrylates.

Further, in addition to the above acrylate-based compound, an urethane acrylate-based oligomer can be used. The urethane acrylate oligomer is a polyvalent isocyanate compound such as a polyester or a polyether, and a polyvalent isocyanate compound (for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1, A terminal isocyanate urethane prepolymer obtained by the reaction of 3-phenyldimethyl diisocyanate, 1,4- phenyldimethyl diisocyanate, diphenylmethane 4,4-diisocyanate or the like, and an acrylate having a hydroxyl group Or methacrylate (for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, polyethylene glycol acrylate, polyethylene A diol methacrylate or the like is obtained by a reaction. Further, the adhesive layer may be a mixture of two or more selected from the above resins. Further, in addition to the surface free energy of 40 mJ/m ² or less, the above-mentioned adhesive material preferably has a polar group containing a large amount of a trifluoro group, a dimethylformyl group, a long-chain hydrocarbon group or the like in the molecular structure. .

Further, it is also possible to adjust the adhesion of the resin of the adhesive layer to a radiation-polymerizable compound which irradiates the base film with radiation to harden the adhesive layer, and a propylene-based adhesive, a photopolymerization initiator, a curing agent, and the like. Agent.

When a photopolymerization initiator is used, for example, isopropyl benzoin ether, isobutyl benzoin ether, diphenyl ketone, octyl ketone, chlorothioxanthone, dodecane can be used. Dodecyl chlorothioxanthone, dimethyl thioxanthone, diethyl thioxanthone, benzylic diethyl acetal, α-hydroxycyclohexyl phenyl ketone, 2-hydroxyl Methyl phenylpropane and the like. The blending amount of the photopolymerization initiator is preferably 0.01 to 30 parts by mass, more preferably 1 to 10 parts by weight, per 100 parts by mass of the propylene-based copolymer.

In addition, when a low molecular component is present in the adhesive, the low molecular component may move to the surface of the adhesive layer and the adhesive property may be impaired during the long-term storage after the base film is produced. The higher the colloid fraction, the better. It is usually 60% or more, preferably 70% or more. Here, the colloid fraction is calculated by the following method. Approximately 0.05 g of the adhesive layer was weighed and immersed in 50 ml of xylene at 120 ° C for 24 hours, then filtered through a 200 mesh stainless steel metal mesh, and the insoluble component of the metal mesh was dried at 110 ° C for 120 minutes. . Next, the mass of the dried insoluble component is weighed, and the colloidal fraction is calculated by the following formula 1.

Colloid fraction (%) = (quality of insoluble components / mass of adhesive layer) × 100 (Formula 1)

The adhesive layer has a weight reduction of 1.5% or less in the reflow temperature by the differential thermal analysis (TG-DTA). Here, the reflow temperature is the highest package body temperature (Tp: peak package body temperature), and the JEDEC: Joint Electron Device Engineering Council has a classification temperature (Tc: classification temperature) at which the classification temperature is As the highest temperature. The weight reduction of the adhesive layer is a reduction in the weight of the adhesive layer in the state where the reflow is performed. In other words, in the case of the radiation curable adhesive layer, since the reflow is performed after the radiation is irradiated and hardened, the weight of the adhesive in this state is reduced by 1.5% or less when heated at the reflow temperature for a necessary period of time. When the weight is reduced by 1.5% or less when the reheating temperature of the adhesive layer is performed for a necessary period of time, even if the reflow is performed while the adhesive adheres to the adhesive layer, the thermal decomposition of the adhesive can be suppressed at the same time. The occurrence of gas. As a result, the occurrence of reflow cracks can be reduced. Since the reflow temperature of the lead-free solder is about 260 ° C, the weight reduction of 260 ° C of the adhesive layer detected by differential thermal analysis (TG-DTA) is preferably 1.5% or less.

In order to suppress the weight loss of the adhesive due to heating, the glass transition temperature Tg of the base polymer of the adhesive should be -50 ° C or higher, or the weight average molecular weight of the adhesive layer should be 1,000,000 or more. Further, the photopolymerization initiator may be combined in such a manner that the decomposition temperature is 260 ° C or higher.

<Binder layer>

The adhesive layer has the following functions, that is, when the semiconductor wafer is bonded and cut and the wafer is picked up, the dicing adhesive layer is peeled off from the adhesive layer and attached to the wafer, as the wafer is fixed on the package substrate or The bonding film is used when the lead frame is fixed.

The subsequent layer is obtained by previously thinning the adhesive. For example, a polyimide resin, a polyamide resin, a polyether phthalimide resin, or a polyamidamine which is well known as an adhesive can be used. Amine resin, polyester resin, polyester phthalimide resin, phenoxy resin, polyfluorene resin, polyether oxime resin, polyphenylene sulfide resin, polyether ketone resin, chlorinated polypropylene resin, acrylic resin, polyurethane resin. Epoxy resin, polypropylene decylamine resin, melamine resin, or the like, or a mixture thereof. However, in order to impart good detachability to the adhesive layer 13, the propylene-based copolymer and the epoxy resin are contained, and the Tg of the propylene-based copolymer is 10 Above °C is preferred. Further, it is preferred to contain more than 50% of an inorganic filler. In addition, in order to enhance the adhesion to the wafer and the lead frame, a decane coupling agent or a titanate coupling agent should be added as an additive to the aforementioned materials or a mixture thereof. The thickness of the subsequent layer is not particularly limited, but is usually about 5 to 100 μm.

The epoxy resin is not particularly limited as long as it can be cured by curing. However, an epoxy resin having a molecular weight of at least 5,000 or more, preferably less than 3,000, should be used. Further, an epoxy resin having a molecular weight of 500 or more, preferably 800 or more, should be used.

For example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a cycloaliphatic epoxy resin, an aliphatic lock epoxy resin, a phenol novolac type epoxy resin can be used. , cresol novolac resin epoxy resin, bisphenol A synthetic phenolic resin epoxy resin, bisphenol propylene oxide etherate, naphthalenediol propylene oxide etherate, phenolic propylene oxide etherate, ethanol A difunctional epoxy resin such as a propylene oxide etherate or a hydrocarbyl substituent, a halide or a hydrogen additive, or a synthetic phenol resin epoxy resin. Further, generally known as a polyfunctional epoxy resin or a heterocyclic group-containing epoxy resin can be used. They can be used singly or in combination of two or more types. In addition, impurities other than the epoxy resin may be contained within the range of non-destructive properties.

As the propylene-based copolymer, for example, an epoxy group-containing propylene copolymer can be used. The epoxy group-containing propylene copolymer contains 0.5 to 6% by weight of glycidyl acrylate having an epoxy group or glycidyl methacrylate. In order to obtain a high adhesion, it should be 0.5% by weight or more, and if it is 6% by weight or less, gelation can be suppressed.

The amount of the glycidyl acrylate or the glycidyl methacrylate used as the functional group monomer is from 0.5 to 6% by weight of the copolymer ratio. That is, in the present invention, the epoxy group-containing propylene copolymer means a copolymer of glycidyl acrylate or glycidyl methacrylate used as a raw material in an amount of 0.5 to 6% by weight based on the copolymer obtained. . The remainder may be a mixture of an alkyl acrylate having a hydrocarbon group having 1 to 8 carbon atoms such as methacrylate or methyl methacrylate, an alkyl methacrylate, and styrene or acrylonitrile. Among these, ethyl methacrylate and/or butyl methacrylate are preferred. The mixing ratio should be adjusted in consideration of the Tg of the copolymer. The polymerization method is not particularly limited, however, for example, a copolymer obtained by a method such as bead polymerization or solution polymerization. The weight average molecular weight of the epoxy group-containing propylene copolymer is 100,000 or more. When it is in this range, the adhesiveness and heat resistance are high, and it is more preferably 300,000 to 3,000,000, more preferably 500,000 to 2,000,000. When it is 3,000,000 or less, it is possible to reduce the possibility that the filling property of the wiring circuit formed by the supporting member to which the semiconductor element is attached is lowered due to the necessity of blending due to the decrease in fluidity.

Further, in the present specification, the weight average molecular weight is a value obtained by a gel permeation chromatography (GPC) using a polystyrene equivalent of a standard polystyrene.

The inorganic filler is not particularly limited, and for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate crystal, or the like can be used. Boron nitride, crystalline vermiculite, amorphous vermiculite, and the like. It is also possible to use one type or two or more types in combination. In order to improve thermal conductivity, alumina, aluminum nitride, boron nitride, crystalline vermiculite, amorphous vermiculite or the like is preferred. From the point of view of the balance of characteristics, it is preferable to use vermiculite.

The average particle diameter of the filler should be 0.002 to 2 μm, more preferably 0.008 to 0.5 μm, still more preferably 0.01 to 0.05 μm. When the average particle diameter of the filler is 0.002 μm or less, the wettability to the object is lowered and the adhesion is lowered. When the thickness exceeds 2 μm, the reinforcing effect by the addition of the filler is small, and the heat resistance tends to be lowered. Here, the average particle diameter means an average value obtained from the particle diameters of 100 fillers detected by TEM, SEM, or the like.

Next, a method of manufacturing a semiconductor wafer with an adhesive layer using the tape for semiconductor wafer processing of the present invention shown in Fig. 1 will be described with reference to Fig. 2 .

<Finishing procedure>

First, as shown in Fig. 2(a), the back surface of the semiconductor wafer W is bonded to the adhesive layer 13 of the semiconductor wafer processing tape 15, and the ring frame 20 is bonded to the specific layer of the adhesive layer 12. position.

<cutting procedure>

The wafer processing tape 15 is adsorbed and supported by the adsorption stage 22 from the surface of the base film 12, and the semiconductor wafer W is mechanically cut by a blade (not shown) to be divided into a plurality of semiconductor wafers C (second (b) Figure). Further, at this time, a part of the adhesive layer 13, the adhesive layer 12, and the base film 11 is also appropriately cut.

<Irradiation procedure>

Next, the adhesive layer 12 is irradiated with radiation from the underside of the base film 11 to harden the adhesive layer 12. Since the adhesive force of the hardened adhesive layer 12 is lowered, the adhesive layer 13 on the adhesive layer 12 can be peeled off. Further, when the adhesive layer is formed of a plurality of layers, in order to peel the adhesive layer 13 from the adhesive layer 12, it is not necessary to cure the entire adhesive layer, and only the adhesive layer of the corresponding wafer may be partially cured.

<extension program>

After the irradiation process, the semiconductor wafer processing tape 15 holding the divided plurality of semiconductor wafers C is placed on the stage 21 of the expansion device. Then, as shown in Fig. 2(c), the top member 23 having a hollow cylindrical shape is raised from the lower surface side of the semiconductor wafer processing tape 15, and the base film 11 is oriented in the radial direction and the circumferential direction of the ring frame 20. Stretching.

<pickup procedure>

After the expansion program is implemented, the pickup process of picking up the wafer C is carried out while the adhesive film is expanded. Specifically, the wafer is topped by a pin (not shown) from the lower side of the adhesive film 14, and the wafer C is adsorbed from the upper side of the adhesive film 14 by an adsorption jig (not shown) to be singulated. The wafer C is picked up together with the adhesive layer 13.

<granulation procedure>

Next, after the picking process is implemented, the splicing process is performed. Specifically, the semiconductor wafer is attached to the lead frame, the package substrate, and the like by the adhesive layer picked up by the pick-up program together with the wafer C.

<Reflow procedure>

After the substrate or the like on which the semiconductor wafer is mounted is sealed with a sealing material, the solder is melted and placed on a semiconductor wafer solder ball or the like, and the semiconductor wafer and the substrate are electrically connected to each other to pass through a reflow furnace to obtain a semiconductor device. Here, since the weight of the adhesive layer of the adhesive layer is less than 1.5% by the reflow temperature detected by differential thermal analysis, the adhesive heat can be suppressed even if the adhesive is adhered to the adhesive layer and reflow is performed. Decomposition caused by the occurrence of exhaust.

As described above, when the wafer is picked up, even if the adhesive is attached to the adhesive layer, the occurrence of reflow cracks in the package can be reduced.

Next, an embodiment of the present invention will be described, however, the present invention is not limited to the implementation side.

First, after the adhesive compositions 1 to 9 were prepared, the adhesive composition was applied to the ethylene-vinyl acetate copolymer film (base film) having a thickness of 100 μm so that the thickness of the adhesive composition after drying was 10 μm. After ～9, it was dried at 110 ° C for 3 minutes, and then allowed to stand at 23 ± 5 ° C and 45% environment for 3 weeks to obtain an adhesive film. Next, the adhesive compositions 1 and 2 were prepared by applying a release liner composed of a polyethylene-terephthalate film of a release-treated adhesive composition to a thickness of 20 μm after drying. The composition 1 to 2 was dried at 110 ° C for 3 minutes to prepare a film. Next, the adhesive film and the adhesive film were respectively cut into a circular shape having a diameter of 370 mm and 320 mm, and the adhesive layer of the adhesive film was bonded to the adhesive layer side of the adhesive film in the combination shown in Table 1, and Examples 1 to 6 were produced. And the cut ‧ grain film of Comparative Examples 1 to 3. Hereinafter, the method of adjusting the adhesive compositions 1 to 8 and the adhesive compositions 1 to 2 will be employed.

(modulation of the adhesive composition) (Adhesive Composition 1)

Into the solvent toluene 400g, moderately adjust the amount of dripping to add 340g of isooctyl acrylate, 13g of methyl methacrylate, 60g of hydroxy acrylate, 0.5g of methacrylate, and benzamidine peroxide as a polymerization initiator The mixture was adjusted to adjust the reaction temperature and the reaction time to obtain a compound (1) solution having a weight average molecular weight of 800,000. The Tg of the compound (1) was measured by a differential scanning calorimetry (DSC) to -49 °C. Next, in the solution of the compound (1), 2 parts by weight of CORONATE L (manufactured by NIPPON POLYURETHANE INDUSTRY CO., LTD.) was added as a polyisocyanate, 300 parts by weight, based on 100 parts by weight of the compound (1) in the solution. The polyisocyanate was used as a solvent and stirred to obtain an adhesive composition 1.

(Adhesive Composition 2)

In the solution of the above compound (1), 2.5 g of isocyanatoethylmethacrylate is added as a compound having radioactive hardening carbon-carbon double bond and functional group, and as a compound The hydroquinone of the polymerization inhibitor is adjusted, and the reaction temperature and reaction time are adjusted to obtain a solution of the compound (2) having a radioactive hardenable carbon-carbon double bond. The Tg of the compound (2) was measured by DSC to -49 °C. Next, in the solution of the compound (2), 2 parts by weight of CORONATE L based on 100 parts by weight of the compound (2) in the solution is added as a polyisocyanate, and 1 part by weight of ILGACURE-184 (manufactured by NIHON CIBA-GEIGY) is added. As a photopolymerization initiator, 300 parts by weight of a polyisocyanate was added as a solvent, and the mixture was stirred to obtain an adhesive composition 2.

(Adhesive Composition 3)

In 400 g of toluene in a solvent, 340 g of isooctyl acrylate, 3 g of methyl methacrylate, 60 g of hydroxy acrylate, 0.5 g of methacrylate, and benzoic acid as a polymerization initiator were added as appropriate. A mixture of formazan, adjusting the reaction temperature and reaction time to obtain a compound having a weight average molecular weight of 500,000, and then appropriately adjusting the amount of dropwise addition to add 2.5 g of 2-cyanoethyl methacrylate as a radioactive hard carbon-carbon. A compound having a double bond and a functional group, and hydroquinone added as a polymerization inhibitor, the reaction temperature and the reaction time are adjusted to obtain a compound (3) solution having a radioactive hardenable carbon-carbon double bond. The Tg of the compound (3) was measured by DSC to -52 °C. Next, in the solution of the compound (3), 0.7 parts by weight of CORONATE L based on 100 parts by weight of the compound (3) in the solution is added as a polyisocyanate, and 1 part by weight of ILGACURE-184 is added as a photopolymerization initiator. 300 parts by weight of polyisocyanate was added as a solvent, and the mixture was stirred to obtain an adhesive composition 3.

(Adhesive Composition 4)

In 400 g of toluene, 443 g of n-butyl acrylate, 80 g of methyl methacrylate, 100 g of hydroxy acrylate, 7 g of methacrylate, and benzammonium peroxide as a polymerization initiator were added to the toluene in an appropriate amount. Mixing solution, adjusting reaction temperature and reaction time to obtain a compound having a weight average molecular weight of 200,000, and then appropriately adjusting the amount of dropwise addition to add 2-methacrylic acid isocyanide as a compound having a radioactive hardening carbon-carbon double bond and a functional group. 2.5 g of ethyl ethyl ester, hydroquinone as a polymerization inhibiting agent, and the reaction temperature and reaction time were adjusted to obtain a compound (4) solution having a radioactive hardenable carbon-carbon double bond. The Tg of the compound (4) was measured by DSC to -36 °C. Next, in the solution of the compound (4), 0.5 parts by weight of CORONATE L based on 100 parts by weight of the compound (4) in the solution is added as a polyisocyanate, and 1 part by weight of ILGACURE-184 is added as a photopolymerization initiator. 300 parts by weight of polyisocyanate was added as a solvent, and the mixture was stirred to obtain an adhesive composition 4.

(Adhesive Composition 5)

To the solution of the above compound (4), 0.7 parts by weight of CORONATE L relative to 100 parts by weight of the compound (4) in the solution is added as a polyisocyanate, and 1 part by weight of ILGACURE-2959 is added as a photopolymerization initiator. 300 parts by weight of polyisocyanate was added as a solvent, and the mixture was stirred to obtain an adhesive composition 5.

(Adhesive Composition 6)

In 400 g of toluene in a solvent, 200 g of lauryl acrylate, 100 g of ethylhexylacrylate, 10 g of methacrylate, and peroxidation as a polymerization initiator were added as appropriate. a mixture of benzamidine, adjusting the reaction temperature and reaction time to obtain a compound having a weight average molecular weight of 800,000, and then appropriately adjusting the amount of dropping to add a compound which is a compound having a radioactive hardening carbon-carbon double bond and a functional group. 2.5 g of isocyanoethyl acrylate and hydroquinone as a polymerization inhibitor, the reaction temperature and the reaction time were adjusted to obtain a compound (5) solution having a radioactive hardenable carbon-carbon double bond. The Tg of the compound (5) was measured by DSC to be -20 °C. Next, in the solution of the compound (5), 1 part by weight of CORONATE L based on 100 parts by weight of the compound (5) in the solution is added as a polyisocyanate, and 1 part by weight of ILGACURE-907 is added as a photopolymerization initiator. , the adhesive composition 6 was obtained.

(Adhesive Composition 7)

In 400 g of toluene in a solvent, the amount of dripping was adjusted appropriately, and 340 g of n-butyl acrylate, 70 g of hydroxy acrylate, 3.5 g of methacrylate, and a mixture of benzammonium peroxide as a polymerization initiator were added and adjusted. After the reaction temperature and the reaction time are obtained, a compound having a weight average molecular weight of 900,000 is obtained, and the amount of the dropwise addition is appropriately adjusted to add 2-isocyanoethyl 2-methacrylate as a compound having a radioactive hardening carbon-carbon double bond and a functional group. g. Hydroquinone as a polymerization inhibitor, adjusting the reaction temperature and reaction time to obtain a compound (6) solution having a radioactive hardening carbon-carbon double bond. The Tg of the compound (6) was measured by DSC to -49 °C. Next, in the solution of the compound (6), 1 part by weight of ILGACURE-651 is added as a photopolymerization initiator to 100 parts by weight of the compound (6) in the solution to obtain an adhesive composition 7.

(Adhesive Composition 8)

In 400 g of toluene in a solvent, 340 g of n-butyl acrylate, 13 g of methyl methacrylate, 7 g of hydroxy acrylate, 0.5 g of methacrylate, and benzoyl peroxide as a polymerization initiator were added as appropriate. The mixture of hydrazine was adjusted to the reaction temperature and the reaction time to obtain a solution of the compound (7) having a weight average molecular weight of 50,000. The Tg of the compound (7) was measured by DSC to -52 °C. Next, in the solution of the compound (7), 2 parts by weight of CORONATE L based on 100 parts by weight of the compound (7) in the solution is added as a polyisocyanate, 300 parts by weight of polyisocyanate is added as a solvent, and stirring is carried out to obtain an adhesive. Composition 8.

The thermal decomposition onset temperature of each photopolymerization initiator was only 260 ° C or higher for ILGACURE-2959, and less than 260 ° C for ILGACURE-907, 651, and 184.

(Production of adhesive composition) (adhesive composition 1)

A part of the cresol novolac type epoxy resin (epoxide equivalent 197, molecular weight 1200, softening point 70 ° C) as an epoxy resin is 15 parts by weight, and an acrylic resin (mass average molecular weight: 800,000, glass transition temperature - 17 parts by weight of a phenolic phenol resin resin (hydroxyl group equivalent 104, softening point 80 ° C) as a curing agent, 15 parts by weight of CUREZOL 2PZ (manufactured by SHIKOKU CHEMICALS CORPORATION, trade name: 2-benzimidazole) (phenylimidazole)) was stirred in an organic solvent to obtain an adhesive composition 1.

(Binder composition 2)

A part of a cresol novolac type epoxy resin (epoxide equivalent 197, molecular weight 1200, softening point 70 ° C) as an epoxy resin, 5 parts by weight as a decane coupling agent, 3-glycidylpropyltrimethoxy group 0.5 parts by mass of glycidoxypropyltrimethoxysilane, 50 parts by mass of vermiculite filler having an average particle diameter of 1.0 μm, 2,2′-bis[4-(4-aminophenoxy)phenyl]propane, and 3,3′, 40 parts by mass of a polyamidene resin having a mass average molecular weight of 50,000 synthesized by 4,4'-diphenyltetracarboxylic dianhydride and pyromellitic anhydride, and a phenol novolac resin as a hardener 5 parts by weight of a hydroxyl group equivalent 104, a softening point of 80 ° C), and 1 part of CUREZOL 2PZ as a promoter were stirred in an organic solvent to obtain an adhesive composition 2.

The evaluation of the examples and comparative examples was carried out in the following manner.

(Detection of average molecular weight of adhesive)

Using an adhesive film made of an adhesive composition, only the adhesive was scraped off, and a standard polystyrene calibration line was used for gel permeation chromatography (GPC) and detected in terms of polystyrene. The detection conditions are as follows.

GPC device: HLC-8120GPC manufactured by TOSOH CORPORATION

Column: TSK gel SuperH5000, flow: 0.6ml/min

Concentration: 0.3% by mass, injection amount: 20 μl

Column temperature: 40 ° C, eluent: tetrahydrofuran.

(Detection of weight reduction)

The adhesive layers of the ‧ granule films of Examples 1 to 6 and Comparative Examples 1 to 3 were irradiated with ultraviolet rays by an air-cooled high-pressure mercury lamp (80 W/cm, irradiation distance: 10 cm) and 200 mJ/cm ² . With respect to Example 1 and Examples 2 to 6 and Comparative Examples 1 to 3 after ultraviolet irradiation, differential thermal analysis (TG-DTA) was performed by thermogravimetric detection, and the temperature in the detection container was changed from room temperature to 300 ° C. The weight reduction test was performed to obtain a weight loss of 220 ° C and 260 ° C. The sample size was about 10 mg and was varied at a rate of 10 ° C/min. The results are shown in Table 1.

<Reflow resistance>

On the back surface of the wafer having a thickness of 200 μm, the adhesive layer of the ‧ grain film of the embodiment and the comparative example was attached, and cut into 7.5 mm × 7.5 mm, and the wafer with the adhesive layer was peeled off from the adhesive layer and picked up. Then, XPS (X-ray photoelectron spectroscopy) is used to compare the carbon increase blanks of the transfer contaminants from the adhesive, and select 20 wafers of 5 Atomic% or more, at 180 ° C, 10 N, 5 seconds. The conditions are fixed on the glass epoxy substrate. Further, a reflowed sample was produced by molding with a sealing material (manufactured by KYOCERA CHEMICAL CORPORATION). The sample of the sealing material is treated with a constant temperature and humidity layer of 85 ° C / 85% RH for 168 hours, and then heated at 220 ° C for 60 seconds corresponding to the eutectic solder treatment, or heated at 260 ° C for 60 seconds corresponding to the lead-free solder treatment. The ultrasonic imager (SAT) manufactured by Hitachi Construction Machinery Co., Ltd. was observed to investigate the presence or absence of cracks in the package. The number of packages of package cracks observed for all 20 packages is shown in Table 1.

In the comparative example, since the weight loss at 220 ° C and 260 ° C exceeded 1.5%, cracks were observed in most of the packages. On the other hand, in Examples 1 to 6, the weight loss at 220 ° C and 260 ° C was 1.5% or less, and no crack was observed in all of the packages.

As described above, when the wafer is picked up, even if the adhesive is attached to the adhesive layer and picked up, the reflow crack of the package can be reduced.

11. . . Substrate film

12. . . Adhesive layer

13. . . Subsequent layer

14. . . Adhesive film

15. . . Semiconductor wafer processing tape

20. . . Ring frame

twenty one. . . Workbench

twenty two. . . Adsorption station

twenty three. . . Top member

Fig. 1 is a cross-sectional view showing an example of a tape for processing a semiconductor wafer of the present invention.

Fig. 2(a) is a cross-sectional view showing a state in which a semiconductor wafer W and a ring frame are bonded to a semiconductor wafer processing tape, and (b) a sectional view of the semiconductor wafer processing tape and the semiconductor wafer after the dicing (c) is a cross-sectional view of the expanded semiconductor wafer processing tape and the semiconductor wafer.

11. . . Substrate film

12. . . Adhesive layer

13. . . Subsequent layer

14. . . Adhesive film

15. . . Semiconductor wafer processing tape

Claims (3)

An adhesive tape for processing a semiconductor wafer, comprising: an adhesive film comprising a base film and an adhesive layer disposed on the base film; and an adhesive layer disposed on the adhesive layer, wherein the adhesive tape is characterized For the detection by differential thermal analysis, the weight of the adhesive layer at the reflow temperature is reduced to 1.5% or less, the weight average molecular weight of the adhesive layer is 1,000,000 or more, and the weight of the binder of the adhesive layer is the weight of the base polymer. The average molecular weight is 200,000 or more. An adhesive tape for processing a semiconductor wafer, comprising: an adhesive film comprising a base film and an adhesive layer disposed on the base film; and an adhesive layer disposed on the adhesive layer, wherein the adhesive tape is characterized For the detection by differential thermal analysis, the weight of the adhesive layer at 260 ° C is reduced to 1.5% or less, the weight average molecular weight of the adhesive layer is 1,000,000 or more, and the weight of the raw material polymer of the adhesive layer of the adhesive layer is average. The molecular weight is 200,000 or more. The tape for semiconductor wafer processing according to any one of claims 1 to 2, wherein the adhesive layer contains a photopolymerization initiator, and the thermal decomposition initiation temperature of the photopolymerization initiator is 260 ° C or higher. .