WO2017145979A1 - Film-shaped adhesive composite sheet and method for producing semiconductor device - Google Patents

Abstract

This film-shaped adhesive composite sheet is equipped, on a support sheet having a substrate, with a curable film-shaped adhesive having a thickness of 1-50 µm, and satisfies formula (1) where the adhesion strength of the film-shaped adhesive before curing to a semiconductor wafer is expressed as adhesion force A (N/24 mm), the elongation at break of a laminate body obtained by laminating said film-shaped adhesive before curing such that the total thickness is 200 µm is expressed as elongation at break B (%), and the breaking strength of said laminate is expressed as breaking strength C (MPa). (1): A/(B×C)≥0.0005

Description

Film adhesive composite sheet and method for manufacturing semiconductor device

The present invention relates to a film-like adhesive composite sheet and a method for manufacturing a semiconductor device.
This application claims priority based on Japanese Patent Application No. 2016-031641 filed in Japan on February 23, 2016, the contents of which are incorporated herein by reference.

In the manufacturing process of a semiconductor device, a semiconductor chip to which a film adhesive for use in die bonding is attached may be used. As one of methods for obtaining such a semiconductor chip with a film adhesive, the film adhesive is applied to a plurality of semiconductor chips that have been divided in advance by dicing a semiconductor wafer, and then the film adhesive is applied. Is cut at a position corresponding to the arrangement position of the semiconductor chip. In this method, usually, one film adhesive is stuck to a plurality of semiconductor chips using a film adhesive composite sheet in which a film adhesive is provided on a support sheet. The semiconductor chip is manufactured by, for example, forming a groove from the front surface of the semiconductor wafer and then grinding the back surface side until reaching the groove, but this is an example, and the semiconductor chip is also manufactured by other methods. The The semiconductor chip to which the film adhesive after cutting is attached is separated (pick up) from the support sheet together with the film adhesive and used for die bonding.

In the above method, as a method of cutting the film adhesive, for example, a method of cutting the film adhesive by irradiating a laser, or a method of cutting the film adhesive by expanding is known. . However, the laser irradiation method requires a laser irradiation device and has a problem that it cannot be efficiently cut in a short time. In addition, the expanding method requires an expanding device and has a problem that the cut surface may be roughened. Further, since the expand works only in the same plane direction as the film adhesive, the film adhesive may only be stretched with the support sheet and not cut. For this reason, the film-like adhesive may be cooled to be easily cut and expanded, but in this case, a cooling step is required, resulting in poor productivity.

As a method for solving these problems, a film adhesive having a specific thickness and tensile elongation at break is used, and the semiconductor chip is picked up together with the uncut film adhesive immediately before the semiconductor chip is picked up. A method of cutting a film adhesive using a shearing force generated by lifting in the direction is disclosed (see Patent Document 1).

JP 2013-179317 A

However, in the method disclosed in Patent Document 1, it is not clear whether the semiconductor chip to which the cut film adhesive is attached can be picked up from the support sheet while suppressing the occurrence of process abnormality.

The present invention has been made in view of the above circumstances, and at the time of manufacturing a semiconductor device, a semiconductor chip to which a film-like adhesive is applied is suppressed by a simplified method, while suppressing the occurrence of process abnormality. It is an object of the present invention to provide a film-like adhesive composite sheet in which a film-like adhesive is provided on a support sheet that can be separated from the support sheet, and a method for manufacturing a semiconductor device using the composite sheet.

In order to solve the above-mentioned problems, the present invention provides a film-like adhesive composite sheet in which a curable film-like adhesive having a thickness of 1 to 50 μm is provided on a support sheet having a base material, and The adhesive strength A (N / 24 mm) of the film adhesive to the semiconductor wafer, the breaking elongation B (%) of the laminate obtained by laminating the film adhesive before curing to a total thickness of 200 μm And the breaking strength C (MPa) of the said laminated body provides the film-form adhesive composite sheet with which the relationship of following formula (1) is satisfy | filled.
A / (B × C) ≧ 0.0005 (1)

In the film adhesive composite sheet of the present invention, the breaking elongation B is preferably 500% or less.
In the film-like adhesive composite sheet of the present invention, the support sheet is preferably made of the base material, and the film-like adhesive is provided in direct contact with the base material.
The present invention is also a method for manufacturing a semiconductor device using the film-like adhesive composite sheet, wherein the film-like adhesive composite sheet is divided into a plurality of semiconductor chips that have been divided through the film-like adhesive. Applying a force from the side opposite to the side where the film adhesive is provided to the support sheet of the film adhesive composite sheet affixed to the semiconductor chip, over the support sheet Applying a force to the film adhesive to cut the film adhesive, and separating the semiconductor chip and the film adhesive after cutting attached thereto from the support sheet. A method for manufacturing a semiconductor device is provided.

That is, the present invention includes the following aspects.
[1] A film-like adhesive composite sheet,
The film-like adhesive composite sheet is provided with a curable film-like adhesive having a thickness of 1 to 50 μm on a support sheet having a substrate;
The adhesive strength of the film adhesive before curing to a semiconductor wafer is defined as adhesive strength A (N / 24 mm), and the film adhesive before curing is laminated so that the total thickness becomes 200 μm. A film-like adhesive composite sheet satisfying the relationship of the following formula (1) when the breaking elongation is B (%) and the breaking strength of the laminate is C (MPa).
A / (B × C) ≧ 0.0005 (1)
[2] The film adhesive composite sheet according to [1], wherein the breaking elongation B is 500% or less.
[3] The film adhesive composite sheet according to [1] or [2], wherein the support sheet is made of the substrate, and the film adhesive is provided in direct contact with the substrate.
[4] A method of manufacturing a semiconductor device,
Attaching the film-like adhesive composite sheet according to any one of [1] to [3] to a plurality of divided semiconductor chips via the film-like adhesive;
By applying a force from the side opposite to the side on which the film-like adhesive is provided to the support sheet in the film-like adhesive composite sheet attached to the semiconductor chip, the film-like shape is passed through the support sheet. Applying a force to the adhesive to cut the film adhesive;
A step of separating the semiconductor adhesive and the film adhesive after cutting attached to the semiconductor chip from the support sheet;
A method for manufacturing a semiconductor device, comprising:

According to the present invention, at the time of manufacturing a semiconductor device, the semiconductor chip to which the film adhesive is stuck can be separated from the support sheet while suppressing the occurrence of process abnormality by a simplified method. There are provided a film-like adhesive composite sheet in which a film-like adhesive is provided on a support sheet, and a method of manufacturing a semiconductor device using the composite sheet.

It is sectional drawing which shows typically one Embodiment from the cutting | disconnection of a film adhesive to the separation from the support sheet of a semiconductor chip in the manufacturing method of the semiconductor device of this invention. In the manufacturing method of the semiconductor device of this invention, it is sectional drawing for demonstrating other embodiment which applies force to a film adhesive and cut | disconnects this. It is sectional drawing which shows typically the one aspect | mode of a film adhesive composite sheet and a semiconductor chip in the manufacture process of a semiconductor device at the time of using the conventional film adhesive composite sheet. It is sectional drawing which shows typically the film adhesive composite sheet and the other aspect of a semiconductor chip in the manufacture process of a semiconductor device at the time of using the conventional film adhesive composite sheet.

<< Film adhesive composite sheet >>
The film-like adhesive composite sheet of the present invention is a film-like adhesive composite sheet in which a curable film-like adhesive having a thickness of 1 to 50 μm is provided on a support sheet having a base material, and before being cured. The adhesive strength of the film adhesive to the semiconductor wafer is defined as adhesive strength A (N / 24 mm), and the elongation at break of the laminate in which the film adhesive before curing is laminated to a total thickness of 200 μm. Is the breaking elongation B (%), and the breaking strength of the laminate is the breaking strength C (MPa), A, B and C satisfy the relationship of the following formula (1).
A / (B × C) ≧ 0.0005 (1)

The film-like adhesive composite sheet is attached to one surface (mainly, the back surface opposite to the circuit surface) of the semiconductor chip with the film-like adhesive when the semiconductor device is manufactured. In a later process, the semiconductor chip is separated (picked up) from the support sheet with the film adhesive applied.
At this time, when the film adhesive provided on the film adhesive composite sheet satisfies the relationship of the formula (1), the semiconductor chip to which the film adhesive is applied is treated as a process abnormality. Can be separated from the support sheet. More specifically, it is as follows.

First, according to the film-like adhesive composite sheet of the present invention, by performing a normal operation of applying a force to the film-like adhesive through the support sheet, a process mainly intended for cutting the film-like adhesive is separately performed. Even if it does not provide, it can cut | disconnect at normal temperature in the location which aims at a film adhesive. Therefore, the separation (lifting) defect of the semiconductor chip due to the fact that the film adhesive is not cut is suppressed.
In addition, the part corresponding to the target semiconductor chip in the film adhesive is peeled off from the support sheet, and the phenomenon that the part corresponding to the non-target semiconductor chip in the film adhesive is peeled off from the support sheet is suppressed. The Accordingly, the film-like adhesive not only removes (lifts) the semiconductor chip due to the target site of the film-like adhesive not being peeled from the support sheet, but also the semiconductor chip adjacent to the target semiconductor chip simultaneously. At the same time, the occurrence of so-called double dies that are pulled away from the support sheet is suppressed.

Thus, by using the film-like adhesive composite sheet, it is possible to suppress the separation failure of the semiconductor chip and the generation of the double die. Furthermore, the process mainly intended for cutting the film adhesive as described above, for example, the process of cutting the film adhesive by irradiating the laser, the process of cutting the film adhesive by expanding, etc. Since it can be omitted, problems caused by performing these steps can be avoided, the film adhesive can be cut at room temperature, the number of steps can be reduced, and a semiconductor device can be manufactured by a simplified method.

On the other hand, in the above-mentioned “Japanese Unexamined Patent Application Publication No. 2013-179317” (Patent Document 1), the semiconductor chip is lifted together with the uncut film adhesive in the pickup direction immediately before the pickup of the semiconductor chip. A method of cutting a film adhesive using a shearing force generated at that time is disclosed. However, in this method, it is not certain whether the semiconductor chip to which the cut film adhesive is attached can be picked up from the support sheet while suppressing the occurrence of process abnormality. For example, it is not certain whether the semiconductor chip is pulled away from the support sheet while being normally provided with the cut film adhesive. In the examples of this document, although a film-like adhesive composite sheet in which a film-like adhesive is provided on a general dicing sheet (a support sheet having a base material and a pressure-sensitive adhesive layer) is specifically disclosed, It is not disclosed that the above-described effects of the present invention are achieved.

<Support sheet>
The said support sheet has a base material, may consist of a base material (it has only a base material), and may have a base material and other layers other than a base material. . As a support sheet which has the said other layer, what provided the adhesive layer on the base material is mentioned, for example.
The film adhesive described later is provided on the support sheet. Therefore, for example, when the support sheet is provided with a pressure-sensitive adhesive layer on the base material, a film-like adhesive is provided on the pressure-sensitive adhesive layer, and the support sheet is made of a base material. The film adhesive is provided in direct contact with the substrate.

[Base material]
The constituent material of the base material is preferably various resins. Specifically, for example, polyethylene (low density polyethylene (abbreviated as LDPE), linear low density polyethylene (abbreviated as LLDPE)) , High density polyethylene (such as HDPE)), polypropylene, polybutene, polybutadiene, polymethylpentene, styrene / ethylene butylene / styrene block copolymer, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate , Polybutylene terephthalate, polyurethane, polyurethane acrylate, polyimide, ethylene vinyl acetate copolymer, ionomer resin, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, polystyrene, polycarbonate Fluororesin, hydrogenated product of any of these resins, modified products, include cross-linked product or copolymer and the like.

In the present specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth) acrylic acid. For example, “(meth) acrylate” is a concept including both “acrylate” and “methacrylate”, and “(meth) acryloyl group” Is a concept including both an “acryloyl group” and a “methacryloyl group”.

The resin constituting the substrate may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily selected.

The substrate may be composed of one layer (single layer) or may be composed of two or more layers. When a base material consists of multiple layers, these multiple layers may be mutually the same or different, and the combination of these multiple layers is not particularly limited as long as the effects of the present invention are not impaired.
In the present specification, not limited to the case of a base material, “a plurality of layers may be the same or different from each other” means “all layers may be the same or all layers are different. Means that only some of the layers may be the same ”, and“ a plurality of layers are different from each other ”means that“ at least one of the constituent materials and thickness of each layer is different from each other ”. Means.

The thickness of the substrate can be appropriately selected depending on the purpose, but is preferably 50 to 300 μm, more preferably 60 to 100 μm.
Here, “the thickness of the substrate” means the thickness of the entire substrate. For example, the thickness of the substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate. means.
In the present specification, “thickness” means a value represented by an average of thicknesses measured with a contact-type thickness meter at any five locations.

In order to improve the adhesion with other layers such as a pressure-sensitive adhesive layer provided on the substrate, the substrate is subjected to a roughening treatment such as sandblast treatment, solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment. The surface may be subjected to oxidation treatment such as ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment.
The base material may have a surface subjected to primer treatment.
In addition, the base material prevents the base material from adhering to other sheets or the base material from adhering to the adsorption table when the antistatic coat layer and the film-like adhesive composite sheet are stored in an overlapping manner. It may have a layer or the like.
Among these, the substrate preferably has a surface subjected to electron beam irradiation treatment from the viewpoint that generation of fragments of the substrate due to blade friction during dicing is suppressed.

[Adhesive layer]
A well-known thing can be used suitably for the said adhesive layer.
An adhesive layer can be formed using the adhesive composition containing the various components for comprising this. The ratio of the content of components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the content of the components of the pressure-sensitive adhesive layer. In the present specification, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

When the pressure-sensitive adhesive layer contains an energy ray-curable component, the semiconductor chip can be easily picked up by irradiating the energy ray to reduce its adhesiveness. The treatment for reducing the adhesiveness by irradiating the adhesive layer with the energy ray may be performed after the film-like adhesive composite sheet has been applied to the adherend, or in advance before being applied to the adherend. May be.

In the present invention, “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, or a xenon lamp as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
In the present invention, “energy ray curable” means the property of being cured by irradiation with energy rays, and “non-energy ray curable” means the property of not being cured even when irradiated with energy rays. .

Preferred examples of the pressure-sensitive adhesive composition include those containing an acrylic polymer and an energy beam polymerizable compound (pressure-sensitive adhesive composition (i); having a hydroxyl group and having a polymerizable group in the side chain. An acrylic polymer (for example, one having a hydroxyl group and having a polymerizable group in the side chain via a urethane bond) and an isocyanate-based crosslinking agent (adhesive composition (ii)) are mentioned. Further, those containing a solvent are preferred.

In addition to the above-mentioned components, the pressure-sensitive adhesive composition further comprises various additives such as a photopolymerization initiator, a colorant (pigment, dye), a deterioration inhibitor, an antistatic agent, a flame retardant, a silicone compound, and a chain transfer agent. Any of these may be contained.

The pressure-sensitive adhesive composition may contain a reaction retarder for suppressing the progress of an undesired crosslinking reaction during storage. Examples of the reaction retarder include those that inhibit the action of a component that serves as a catalyst for advancing the crosslinking reaction, and preferable examples include those that form a chelate complex by chelation with respect to the catalyst. More preferable examples of the reaction retardant include those having two or more carbonyl groups (—C (═O) —) in the molecule, and those having two carbonyl groups in the molecule. For example, dicarboxylic acid, keto acid, diketone and the like can be mentioned.

The thickness of the pressure-sensitive adhesive layer can be appropriately selected depending on the purpose, but is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.

The pressure-sensitive adhesive composition is obtained by blending each component for constituting the pressure-sensitive adhesive layer such as an acrylic polymer. For example, except that the blending components are different, the same as in the case of the adhesive composition described later. Obtained by the method.

The pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive composition to the surface of the substrate and drying it.
At this time, you may bridge | crosslink by heating the applied adhesive composition as needed. The heating condition can be, for example, 100 to 130 ° C. for 1 minute to 5 minutes, but is not limited thereto. Alternatively, the pressure-sensitive adhesive layer formed by applying the pressure-sensitive adhesive composition to the release-treated surface of the release film and drying it may be bonded to the surface of the substrate, and the release film may be removed as necessary. An adhesive layer can be formed on the material.

Application of the adhesive composition to the surface of the base material or the surface of the release layer of the release material may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife. Examples include a method using various coaters such as a coater, a curtain coater, a die coater, a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.

<Film adhesive>
The film adhesive has curability. The film adhesive preferably has thermosetting properties, and preferably has pressure sensitive adhesive properties. A film adhesive having both thermosetting and pressure-sensitive adhesive properties can be applied by lightly pressing on various adherends in an uncured state. The film adhesive may be one that can be applied to various adherends by heating and softening. The film adhesive finally becomes a cured product having high impact resistance by curing, and this cured product can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

The thickness of the film adhesive is 1 to 50 μm, preferably 3 to 25 μm, and more preferably 5 to 15 μm. When the thickness of the film adhesive is equal to or more than the lower limit, a high adhesive force can be obtained for the adherend (semiconductor chip). In addition, when the thickness of the film adhesive is equal to or less than the above upper limit value, it is generated in this operation by performing an operation to apply a force to the film adhesive through a support sheet, which is usually performed when manufacturing a semiconductor device. The film-like adhesive can be easily cut using the shearing force, and there is no need to provide a separate process mainly for cutting the film-like adhesive.

In the present invention, the “adhesive strength A (N / 24 mm)” of the film adhesive before curing with respect to the semiconductor wafer means a value measured by the following method. That is, a laminated sheet of a film adhesive and an adhesive tape having a width of 24 mm and an arbitrary length is produced. In this laminated sheet, a film adhesive is laminated on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive tape. As the pressure-sensitive adhesive tape, for example, “Cello Tape (registered trademark) No. 405” manufactured by Nichiban Co., Ltd. has a width of 24 mm. Can be used. Next, the laminated sheet is attached to a semiconductor wafer with a film adhesive heated to 60 ° C. to produce a laminate in which the adhesive tape, the film adhesive and the semiconductor wafer are laminated in this order. After the production, the laminated body is immediately left for 30 minutes in a standard environment defined in JIS Z0237 2009, and then the laminated sheet of film adhesive and adhesive tape is attached to the film adhesive and semiconductor wafer from each other. The so-called 180 ° peeling is performed by peeling off at a peeling speed of 150 mm / min so that the surfaces that are in contact with each other form an angle of 180 °. The peeling force at this time is measured, and the measured value is defined as adhesive strength A (N / 24 mm). The length of the laminated sheet used for the measurement is not particularly limited as long as the peel force can be stably measured.

The adhesive force A is not particularly limited as long as the relationship of the formula (1) is satisfied, but is preferably 0.3 N / 24 mm or more, and more preferably 0.4 N / 24 mm or more. The upper limit value of the adhesive force A can be, for example, any one of 15 N / 24 mm, 11 N / 24 mm, and 7 N / 24 mm, but these are examples.
For example, the adhesive strength A is preferably 0.3 N / 24 mm to 15 N / 24 mm, more preferably 0.3 N / 24 mm to 11 N / 24 mm, and still more preferably 0.4 N / 24 mm to 7 N / 24 mm.
As another aspect, the adhesive force A may be 0.45 N / 24 mm or more and less than 10 N / 24 mm, or 0.45 N / 24 mm or more and 5.8 N / 24 mm or less.

In the present invention, “breaking elongation B (%)” means the breaking elongation of a laminate obtained by laminating the film adhesive before curing so that the total thickness becomes 200 μm. To do. In the present invention, the elongation at break of the film-like adhesive or the laminate obtained by laminating the same, including the elongation at break B, is JIS K7161-1994 (ISO 527-1) or JIS K7127: 1999 ( It is obtained in accordance with ISO 527-3). If the object to be measured (test specimen) does not have a yield point, the tensile fracture strain is measured, and if it has a yield point, the nominal strain at the time of tensile fracture is measured. Ask for.

The laminate for which the elongation at break B is to be determined is a film adhesive before curing having a thickness of less than 200 μm, preferably a thickness of 1 to 50 μm for constituting the film adhesive composite sheet of the present invention. Is obtained by laminating at least two sheets of the uncured film adhesive so that the total thickness becomes 200 μm.

The elongation at break B is 15 mm in width, 100 mm in length, and the laminate (test piece) of the film adhesive having a thickness of 200 μm so that the distance between the fixing points is 75 mm. It is obtained by fixing at two places, pulling the laminated body between the fixed places at a tensile speed of 200 mm / min, and measuring the elongation of the test piece when the laminated body breaks.
In the present specification, “the breaking elongation B is X% (wherein X is a positive number)” means that the test piece (laminate) is pulled in the measurement method described above. Is stretched by X% of the original length (length when not being pulled) in the tensile direction, that is, the total length in the tensile direction of the test piece is [1 + X of the length before pulling / 100] means that the test piece breaks when it is doubled.

The elongation at break B is not particularly limited as long as the relationship of the formula (1) is satisfied. For example, it is preferably 1200% or less, more preferably 30 to 1200%, and 40 to 1100%. Is more preferable, and 45 to 1050% is particularly preferable. When the breaking elongation B is equal to or less than the upper limit, the film adhesive can be more easily cut before picking up the semiconductor chip to which the film adhesive is attached.

Further, as another aspect, the breaking elongation B is preferably 900% or less, more preferably 700% or less, and particularly preferably 500% or less, for example, 30 to 500%, 40 It can be any of ˜500%, 45˜500%, and the like.
As yet another aspect, the breaking elongation B may be 50 to 440%.
When the breaking elongation B is equal to or less than the upper limit, the film adhesive can be more easily cut by various methods before picking up the semiconductor chip to which the film adhesive is attached. That is, as the film adhesive cutting method, not only the most general pin push-up method but also other methods such as a slider push-up method can be suitably applied, and the versatility of the film adhesive composite sheet is enhanced.

In the present invention, “breaking strength C (MPa)” means the breaking strength of a laminate obtained by laminating the film adhesive before curing so that the total thickness becomes 200 μm. The laminated body here means the same laminated body as the laminated body which is a measurement target of the above-described breaking elongation B (%).
The breaking strength C is a tensile stress when the test piece is broken (broken) at the time of breaking elongation B measurement, that is, tensile breaking stress, and can be measured simultaneously with the breaking elongation B.

The breaking strength C is not particularly limited as long as the relationship of the above formula (1) is satisfied, but is preferably 0.4 to 17 MPa, more preferably 0.5 to 15 MPa, and 0.6 to 13 MPa. It is particularly preferred.
As another aspect, the breaking strength C may be 0.8 to 11 MPa or 2.5 to 11 MPa.

In the present invention, the adhesive force A, breaking elongation B, and breaking strength C satisfy the relationship of the formula (1), that is, the value of A / (B × C) may be 0.0005 or more. The value of A / (B × C) is preferably 0.0006 or more, and more preferably 0.0007 or more. The upper limit value of A / (B × C) is not particularly limited, and can be any one of 0.0170, 0.0140, and 0.0115, but these are examples.
That is, the value of A / (B × C) may be, for example, 0.0005 or more and 0.0170 or less, preferably 0.0006 or more and 0.0140 or less, and is 0.00067 or more and 0.0115. More preferably as another aspect below, the value of A / (B × C) may be 0.0008 or more and less than 0.0125, or 0.0008 or more and 0.0105 or less.

The adhesive strength A of the film adhesive is the type and amount of the components contained in the film adhesive, the thickness of the film adhesive, the material constituting the surface of the support sheet on which the film adhesive is provided, It can adjust suitably by adjusting a state (surface state) etc.
For example, if it is a content component of a film adhesive, the adhesive force A of a film adhesive can be easily adjusted by adjusting the kind or quantity of coupling agents (e), such as a silane coupling agent mentioned later. .
Further, for example, the surface state of the support sheet is, for example, the surface treatment mentioned above as improving the adhesion to the other layers of the base material, that is, the unevenness treatment by sandblasting, solvent treatment, etc .; corona It can be adjusted by performing oxidation treatment such as discharge treatment, electron beam irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc .; primer treatment.
However, these adjustment methods are only examples.

The breaking elongation B and breaking strength C of the film adhesive can be adjusted as appropriate by adjusting the type and amount of the components contained in the film adhesive. For example, the molecular weight and content of the polymer component (a) described later, the structure of the component constituting the epoxy thermosetting resin (b), the softening point and the content, and the content of the filler (c) are adjusted. By doing this, the breaking elongation B and breaking strength C of the film adhesive can be easily adjusted.
However, these adjustment methods are only examples.

[Adhesive composition]
The film adhesive can be formed from an adhesive composition containing the constituent materials. For example, a film adhesive can be formed in the target site | part by applying an adhesive composition to the formation object surface of a film adhesive, and making it dry as needed. In the adhesive composition, the content ratio of components that do not vaporize at normal temperature is usually the same as the content ratio of the components of the film adhesive. Here, “normal temperature” is as described above.

The adhesive composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. And a method using various coaters such as a Meyer bar coater and a kiss coater.

The drying conditions of the adhesive composition are not particularly limited, but the adhesive composition is preferably dried by heating when it contains a solvent described later. In this case, for example, at 70 to 130 ° C. for 10 seconds to It is preferable to dry under conditions of 5 minutes.

Preferred adhesive compositions include, for example, those containing a polymer component (a) and an epoxy thermosetting resin (b). Hereinafter, each component will be described.

(Polymer component (a))
The polymer component (a) is a component that can be regarded as formed by polymerization reaction of a polymerizable compound, and imparts film-forming properties, flexibility, etc. to the film adhesive, and is attached to an object to be bonded such as a semiconductor chip. It is a polymer compound for improving adhesiveness (sticking property). Moreover, a polymer component (a) is also a component which does not correspond to the epoxy resin (b1) and thermosetting agent (b2) which are mentioned later.

As the polymer component (a), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.

Examples of the polymer component (a) include acrylic resins (for example, resins having a (meth) acryloyl group), polyesters, urethane resins (for example, resins having a urethane bond), acrylic urethane resins, silicone resins ( Examples thereof include a resin having a siloxane bond), a rubber-based resin (for example, a resin having a rubber structure), a phenoxy resin, a thermosetting polyimide, and the like, and an acrylic resin is preferable.

As said acrylic resin in a polymer component (a), a well-known acrylic polymer is mentioned.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1500,000. When the weight average molecular weight of the acrylic resin is within such a range, it becomes easy to adjust the adhesive force A of the film adhesive within the above-described range.
On the other hand, when the weight average molecular weight of the acrylic resin is equal to or more than the lower limit, the shape stability of the film adhesive (time stability during storage) is improved. Moreover, since the weight average molecular weight of the acrylic resin is not more than the above upper limit value, the film adhesive can easily follow the uneven surface of the adherend, and voids or the like between the adherend and the film adhesive. Occurrence is further suppressed.
In the present specification, “weight average molecular weight” is a polystyrene equivalent value measured by gel permeation chromatography (GPC) method unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably −60 to 70 ° C., more preferably −30 to 50 ° C. When the Tg of the acrylic resin is equal to or greater than the lower limit, the adhesive force between the film adhesive and the support sheet is suppressed, and the semiconductor chip provided with the film adhesive is separated from the support sheet at the time of pickup. Becomes easier. Moreover, the adhesive force of a film adhesive and a semiconductor chip improves because Tg of acrylic resin is below the said upper limit.
In the present specification, the “glass transition temperature” is represented by the temperature of the inflection point of the DSC curve obtained by measuring the DSC curve of the sample using a differential scanning calorimeter.

Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , Undecyl (meth) acrylate, dodecyl (meth) acrylate ((meth) acrylic acid (Also known as uril), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also referred to as myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (also known as palmityl (meth) acrylate) The alkyl group constituting the alkyl ester such as heptadecyl (meth) acrylate and octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate) has a chain structure having 1 to 18 carbon atoms. (Meth) acrylic acid alkyl ester;
(Meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentanyl;
(Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
(Meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meth) acrylic imide;
Glycidyl group-containing (meth) acrylic acid ester such as (meth) acrylic acid glycidyl;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meta ) Hydroxyl group-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate;
Examples thereof include substituted amino group-containing (meth) acrylic acid esters such as N-methylaminoethyl (meth) acrylate. Here, the “substituted amino group” means a group formed by replacing one or two hydrogen atoms of an amino group with a group other than a hydrogen atom.
Among the above, butyl acrylate, methyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate and the like are preferable.

The acrylic resin is, for example, one or more selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like in addition to the (meth) acrylic acid ester. A monomer may be copolymerized.

Only one type of monomer constituting the acrylic resin may be used, or two or more types may be used, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The acrylic resin may have a functional group that can be bonded to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a cross-linking agent (f) described later, or may be directly bonded to another compound not via the cross-linking agent (f). . When the acrylic resin is bonded to another compound through the functional group, the reliability of the package obtained using the film-like adhesive composite sheet tends to be improved.

In the present invention, as the polymer component (a), a thermoplastic resin other than an acrylic resin (hereinafter sometimes simply referred to as “thermoplastic resin”) is used alone without using an acrylic resin. Alternatively, it may be used in combination with an acrylic resin. By using the thermoplastic resin, it becomes easier to separate the semiconductor chip provided with the film adhesive from the support sheet at the time of pickup, or the film adhesive can easily follow the uneven surface of the adherend. Therefore, the occurrence of voids or the like may be further suppressed between the adherend and the film adhesive.

The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100,000, more preferably 3000 to 80,000.

The glass transition temperature (Tg) of the thermoplastic resin is preferably −30 to 150 ° C., and more preferably −20 to 120 ° C.

Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.

1 type may be sufficient as the said thermoplastic resin which an adhesive composition and a film adhesive contain, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

The content of the acrylic resin as the polymer component (a) is based on the total mass of all components other than the solvent constituting the adhesive composition (that is, based on the total mass of the film adhesive). The content is preferably 5 to 40% by mass, more preferably 7 to 25% by mass.

The proportion of the content of the polymer component (a) is based on the total mass of all components other than the solvent constituting the adhesive composition regardless of the type of the polymer component (a) (that is, film-like adhesion) It is preferably 5 to 85% by mass, and more preferably 7 to 80% by mass (relative to the total mass of the agent).

By using the thermoplastic resin, the above-described effects can be obtained. On the other hand, when the uncured film-like adhesive is exposed to a high temperature (for example, 120 ° C. to 200 ° C.), its hardness decreases, There is a concern that the wire-bonding suitability of the film adhesive in a cured or semi-cured state is lowered. Therefore, the content of the polymer component (a) in the adhesive composition is preferably set in consideration of such influence.

(Epoxy thermosetting resin (b))
The epoxy thermosetting resin (b) is composed of an epoxy resin (b1) and a thermosetting agent (b2).
The epoxy-based thermosetting resin (b) contained in the adhesive composition and the film adhesive may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

・ Epoxy resin (b1)
Examples of the epoxy resin (b1) include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like, and bifunctional or higher functional epoxy compounds are listed.
Among these, bisphenol A type epoxy resins, phenylene skeleton type epoxy resins (for example, triphenylene type epoxy resins), dicyclopentadiene type epoxy resins, and the like are preferable.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group may be used. An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the film-like adhesive composite sheet is improved by using the epoxy resin having an unsaturated hydrocarbon group.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group. In the present specification, the “derivative” means a compound obtained by substituting at least one group of the original compound with another group (substituent) unless otherwise specified. Here, the “group” includes not only an atomic group formed by bonding a plurality of atoms but also one atom.

Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), and a (meth) acryloyl group. , (Meth) acrylamide groups and the like, and an acryloyl group is preferred.

The number average molecular weight of the epoxy resin (b1) is not particularly limited, but is preferably 300 to 30000 from the viewpoints of curability of the film adhesive and strength and heat resistance of the cured film adhesive.
In the present specification, the “number average molecular weight” means a number average molecular weight represented by a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
The epoxy equivalent of the epoxy resin (b1) is preferably 100 to 1000 g / eq, and more preferably 150 to 800 g / eq.
In the present specification, the “epoxy equivalent” means the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236: 2001.

As the epoxy resin (b1), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.

・ Thermosetting agent (b2)
The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b1).
Examples of the thermosetting agent (b2) include compounds having at least two functional groups that can react with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (b2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, biphenyl type phenol resins, and aralkyl type phenols. Examples thereof include resins. Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).

The thermosetting agent (b2) may have an unsaturated hydrocarbon group.
As the thermosetting agent (b2) having an unsaturated hydrocarbon group, for example, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, an aromatic ring of the phenol resin, Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (b2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.

When a phenolic curing agent is used as the thermosetting agent (b2), the thermosetting agent (b2) is softened because it becomes easy to adjust the adhesive force A of the film adhesive within the above-described range. Those having a high point or glass transition temperature are preferred.

The molecular weight of the thermosetting agent (b2) is preferably 60 to 30000, for example.

A thermosetting agent (b2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

In the adhesive composition and the film adhesive, the content of the thermosetting agent (b2) is preferably 0.1 to 500 parts by mass with respect to 100 parts by mass of the epoxy resin (b1). It is more preferably 1 to 200 parts by mass. When the content of the thermosetting agent (b2) is greater than or equal to the lower limit value, the curing of the film adhesive is more likely to proceed. Moreover, the moisture absorption rate of a film adhesive is reduced because the said content of a thermosetting agent (b2) is below the said upper limit, and the reliability of the package obtained using the film adhesive composite sheet Will be improved.

In the adhesive composition and the film adhesive, the content of the epoxy thermosetting resin (b) (total content of the epoxy resin (b1) and the thermosetting agent (b2)) is the same as that of the polymer component (a). The content is preferably 50 to 1000 parts by mass, more preferably 100 to 900 parts by mass, and particularly preferably 150 to 870 parts by mass with respect to the content of 100 parts by mass. When the content of the epoxy thermosetting resin (b) is within such a range, the semiconductor chip provided with the film-like adhesive can be easily detached from the support sheet at the time of pickup.

In order to improve the various physical properties, the film adhesive contains, in addition to the polymer component (a) and the epoxy-based thermosetting resin (b), other components not corresponding to these, if necessary. You may do it.
Preferred examples of other components contained in the film adhesive include a curing accelerator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), and an energy ray curable resin. (G), photoinitiator (h), general-purpose additive (i), etc. are mentioned.

(Curing accelerator (c))
The curing accelerator (c) is a component for adjusting the curing rate of the adhesive composition.
Preferred curing accelerators (c) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (at least one hydrogen atom is other than a hydrogen atom) An imidazole substituted with a group of; an organic phosphine such as tributylphosphine, diphenylphosphine, triphenylphosphine (a phosphine having at least one hydrogen atom substituted with an organic group); tetraphenylphosphonium tetraphenyl Ruboreto, tetraphenyl boron salts such as triphenyl phosphine tetraphenyl borate and the like.
Among the above, 2-phenyl-4,5-dihydroxymethylimidazole is preferable.

The curing accelerator (c) contained in the adhesive composition and the film adhesive may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily selected. .

When the curing accelerator (c) is used, the content of the curing accelerator (c) in the adhesive composition and the film adhesive is based on 100 parts by mass of the epoxy thermosetting resin (b). 0.01 to 10 parts by mass is preferable, and 0.1 to 5 parts by mass is more preferable. The effect by using a hardening accelerator (c) is acquired more notably because the said content of a hardening accelerator (c) is more than the said lower limit. In addition, when the content of the curing accelerator (c) is not more than the above upper limit value, for example, the highly polar curing accelerator (c) is adhered in the film adhesive under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the adhesive interface side becomes higher, and the reliability of the package obtained using the film-like adhesive composite sheet is further improved.

(Filler (d))
By including the filler (d), the film-like adhesive can easily adjust its thermal expansion coefficient, and the film-like adhesive is optimized by optimizing the thermal expansion coefficient for the object to be adhered to the film-like adhesive. The reliability of the package obtained using the adhesive composite sheet is further improved. Moreover, a film adhesive can also reduce the moisture absorption rate of the film adhesive after hardening, or can improve heat dissipation by containing a filler (d).

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina.

The filler (d) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

When the filler (d) is used, the content of the filler (d) is based on the total mass of all components other than the solvent constituting the adhesive composition (that is, the total mass of the film adhesive). The content is preferably 5 to 80% by mass, and more preferably 7 to 60% by mass. When the content of the filler (d) is in such a range, the adjustment of the thermal expansion coefficient becomes easier.

(Coupling agent (e))
When the film adhesive contains the coupling agent (e), the adhesion and adhesion to the adherend are improved. Moreover, when a film adhesive contains a coupling agent (e), the hardened | cured material improves water resistance, without impairing heat resistance. The coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (a), the epoxy thermosetting resin (b), etc., and is a silane coupling agent. It is more preferable.
Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropi Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, epoxy group Containing oligomers and the like.

As for the coupling agent (e) which an adhesive composition and a film adhesive contain, only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily. .
In one aspect, the coupling agent (e) comprises an epoxy group-containing oligomeric silane coupling agent, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 2- (3,4-epoxy It may be at least one selected from the group consisting of (cyclohexyl) ethyltrimethoxysilane.

When the coupling agent (e) is used, the content of the coupling agent (e) in the adhesive composition and the film-like adhesive is the sum of the polymer component (a) and the epoxy thermosetting resin (b). The content is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass with respect to the content of 100 parts by mass.
When the content of the coupling agent (e) is equal to or higher than the lower limit, the dispersibility of the filler (d) in the resin is improved, the adhesiveness of the film adhesive to the adherend is improved, and the like. The effect obtained by using the coupling agent (e) is more remarkably obtained. Moreover, generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (e) is below the said upper limit.

(Crosslinking agent (f))
Polymer having functional group such as vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxy group, isocyanate group and the like that can be combined with other compounds such as the above-mentioned acrylic resin as polymer component (a) When using a component, the adhesive composition and the film adhesive may contain a crosslinking agent (f) for bonding the functional group with another compound to crosslink. By crosslinking using the crosslinking agent (f), the initial adhesive force and cohesive force of the film adhesive can be adjusted.

Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), and the like. Is mentioned.

Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”). A trimer such as the aromatic polyisocyanate compound, isocyanurate and adduct; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the polyol compound. Etc. The “adduct body” includes the aromatic polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound, and a low amount such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include an xylylene diisocyanate adduct of trimethylolpropane as described later. The “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Dimethylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate is added to all or some hydroxyl groups of a polyol such as propane. Or two or more compounds are added; lysine diisocyanate.

Examples of the organic polyvalent imine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, and tetramethylolmethane. -Tri-β-aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the polymer component (a). When the cross-linking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, the cross-linking structure can be simplified in the film adhesive by the reaction between the cross-linking agent (f) and the polymer component (a). Can be introduced.

The cross-linking agent (f) contained in the adhesive composition and the film adhesive may be only one kind, two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily selected.

When the crosslinking agent (f) is used, the content of the crosslinking agent (f) in the adhesive composition is 0.01 to 20 parts by mass with respect to 100 parts by mass of the polymer component (a). It is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass. When the content of the cross-linking agent (f) is equal to or higher than the lower limit value, the effect of using the cross-linking agent (f) is more remarkably obtained. Moreover, the excessive use of a crosslinking agent (f) is suppressed because the said content of a crosslinking agent (f) is below the said upper limit.

(Energy ray curable resin (g))
Since the film adhesive contains the energy beam curable resin (g), the characteristics can be changed by irradiation with the energy beam.

The energy ray curable resin (g) has a property of being cured (polymerized) when irradiated with energy rays.
Examples of the energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth) acryloyl group are preferable.

Examples of the acrylate compound include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta ( Chain aliphatic skeleton-containing (meth) acrylates such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Cyclic aliphatic skeleton-containing (meth) acrylates such as cyclopentanyl di (meth) acrylate and tricyclodecane dimethylol diacrylate; polyethylene glycol di (meth) acrylate and the like Realkylene glycol (meth) acrylate; oligoester (meth) acrylate; urethane (meth) acrylate oligomer; epoxy-modified (meth) acrylate; polyether (meth) acrylate other than the above polyalkylene glycol (meth) acrylate; itaconic acid oligomer, etc. Is mentioned.

The weight average molecular weight of the energy ray curable resin (g) is preferably 100 to 30000.

The energy ray curable resin (g) contained in the adhesive composition may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the adhesive composition, the content of the energy ray curable resin (g) is preferably 1 to 95% by mass with respect to the total mass of components other than the solvent constituting the adhesive composition. It is more preferably 90% by mass, and particularly preferably 5 to 85% by mass.

(Photopolymerization initiator (h))
When the adhesive composition contains the energy beam curable resin (g), the adhesive composition may contain the photopolymerization initiator (h) in order to efficiently advance the polymerization reaction of the energy beam curable resin (g). Good.

Examples of the photopolymerization initiator (h) in the adhesive composition include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Compounds; Acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6 Acylphosphine oxide compounds such as -trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzylphenyl sulfide, tetramethylthiuram monosulfate Sulfide compounds such as amides; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; Diketone compound; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 1-chloroanthraquinone; And quinone compounds such as 2-chloroanthraquinone.
Moreover, as a photoinitiator (h), photosensitizers, such as an amine, etc. are mentioned, for example.

1 type may be sufficient as the photoinitiator (h) which an adhesive composition contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

In the adhesive composition, the content of the photopolymerization initiator (h) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the energy ray curable resin (g). More preferably, it is ˜10 parts by mass, and particularly preferably 2 to 5 parts by mass.

(General-purpose additive (i))
The general-purpose additive (I) may be a known one, and can be arbitrarily selected according to the purpose. The general-purpose additive (I) is not particularly limited, but preferred examples thereof include a plasticizer, an antistatic agent, an antioxidant, and a colorant (dye Pigments), gettering agents and the like.

The general-purpose additive (i) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. .
Content of an adhesive composition and a film adhesive is not specifically limited, What is necessary is just to select suitably according to the objective.

(solvent)
It is preferable that the adhesive composition further contains a solvent. The adhesive composition containing a solvent has good handleability.
The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (also referred to as 2-methylpropan-1-ol), 1-butanol and the like. And alcohols; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
As for the solvent which an adhesive composition contains, only 1 type may be sufficient, and it may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

The solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the adhesive composition can be mixed more uniformly.

[Method for producing adhesive composition]
An adhesive composition is obtained by mix | blending each component for comprising this.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.

The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

The film-like adhesive composite sheet of the present invention is preferably one in which the support sheet is made of a base material and the film-like adhesive is provided in direct contact with the base material. Thus, when the support sheet does not have a pressure-sensitive adhesive layer or the like and the film-like adhesive is provided directly on the substrate, the components in the film-like adhesive are on the substrate such as the pressure-sensitive adhesive layer. Transition to other layers, or conversely, components in such other layers migrate to a film adhesive, etc. Occurrence of process abnormality and a decrease in reliability of the semiconductor package are remarkably suppressed.
Normally, when a film-like adhesive composite sheet that does not have an adhesive layer is used, a double die is generated when the semiconductor chip is pulled away from the support sheet with the film-like adhesive attached. easy. However, if the film-like adhesive composite sheet of the present invention is used, even if this composite sheet does not have a pressure-sensitive adhesive layer, generation of a double die is suppressed.

<< Method for producing film-like adhesive composite sheet >>
The film-like adhesive composite sheet of the present invention can be produced by sequentially laminating the above-described layers so as to have a corresponding positional relationship. The method for forming each layer is as described above.
For example, when laminating a pressure-sensitive adhesive layer on a base material when producing a support sheet, the above-mentioned pressure-sensitive adhesive composition is applied on the base material, and dried as necessary. Layers can be stacked.

On the other hand, for example, in the case of further laminating a film-like adhesive on a pressure-sensitive adhesive layer that has been laminated on a base material, an adhesive composition is applied on the pressure-sensitive adhesive layer, It can be formed directly. As described above, when a continuous two-layer laminated structure is formed using any of the compositions, the composition is further applied onto the layer formed from the composition to newly form a layer. Can be formed. However, the layer laminated after these two layers is formed in advance using the composition on another release film, and the side of the formed layer that is in contact with the release film is It is preferable to form a continuous two-layer laminated structure by bonding the opposite exposed surface to the exposed surfaces of the remaining layers already formed. At this time, the composition is preferably applied to the release-treated surface of the release film. The release film may be removed as necessary after forming the laminated structure.

For example, a film-like adhesive composite sheet in which a pressure-sensitive adhesive layer is laminated on a base material and a film-like adhesive is laminated on the pressure-sensitive adhesive layer (that is, the support sheet is a laminate of the base material and the pressure-sensitive adhesive layer). In the case of producing a certain film-like adhesive composite sheet), a pressure-sensitive adhesive composition is coated on a base material, and dried as necessary, thereby laminating a pressure-sensitive adhesive layer on the base material, Separately, an adhesive composition is applied on the release film, and dried as necessary to form a film adhesive on the release film, and the exposed surface of the film adhesive is used as a base material. A film-like adhesive composite sheet is obtained by laminating the exposed surface of the pressure-sensitive adhesive layer laminated thereon and laminating the film-like adhesive on the pressure-sensitive adhesive layer.

In addition, when laminating the pressure-sensitive adhesive layer on the substrate, as described above, instead of the method of coating the pressure-sensitive adhesive composition on the substrate, the pressure-sensitive adhesive composition is applied on the release film. The adhesive layer is formed on the release film by drying as necessary, and the exposed surface of the adhesive layer is bonded to one surface of the substrate, so that the adhesive layer is placed on the substrate. May be laminated.
In any method, the release film may be removed at an arbitrary timing after the target laminated structure is formed.

In this way, all the layers other than the base material constituting the film-like adhesive composite sheet can be formed in advance on a release film and laminated on the surface of the target layer, so that it can be used as needed. A film-like adhesive composite sheet may be produced by appropriately selecting a layer employing such a process.

The film-like adhesive composite sheet is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a film-like adhesive) on the side opposite to the support sheet. Therefore, on this release film (preferably its release-treated surface), a composition for forming a layer constituting the outermost layer, such as an adhesive composition, is applied and dried as necessary. A layer constituting the outermost layer is formed on the release film, and the remaining layers are laminated on the exposed surface opposite to the side in contact with the release film of this layer by any of the methods described above. A film-like adhesive composite sheet can also be obtained by keeping the peeled film without removing the release film.

<< Semiconductor Device Manufacturing Method >>
The method for manufacturing a semiconductor device of the present invention is a method for manufacturing a semiconductor device using the film-like adhesive composite sheet, wherein the film-like adhesive composite sheet is divided into a plurality of pieces that are already divided through the film-like adhesive. A film adhesive is provided on the support sheet of the film adhesive composite sheet affixed to the semiconductor chip (hereinafter sometimes abbreviated as “applying process”). A step of applying a force from the opposite side to the side to apply a force to the film-like adhesive through the support sheet to cut the film-like adhesive (hereinafter sometimes abbreviated as “cutting step”) And a step of separating the semiconductor chip and the film adhesive after cutting attached to the semiconductor chip from the support sheet (hereinafter, sometimes abbreviated as “detaching step”). No.

According to the manufacturing method, by using the film-like adhesive composite sheet, a semiconductor chip to which the film-like adhesive is attached is produced in a simplified manner at the time of manufacturing a semiconductor device. It is possible to suppress the separation from the support sheet.

<Paste process>
In the attaching step, the film adhesive composite sheet is attached to a plurality of divided semiconductor chips via the film adhesive. In this step, the film-like adhesive of one film-like adhesive composite sheet is attached to the back surfaces of a plurality of semiconductor chips.

The plurality of divided semiconductor chips, for example, form a groove from the surface of the semiconductor wafer opposite to the attachment surface of the film-like adhesive composite sheet (the back surface of the semiconductor wafer), and until the groove reaches the groove It can be produced by grinding the back surface. As a method of forming the groove, for example, a method of forming a groove by cutting a semiconductor wafer using a blade (that is, blade dicing), a method of forming a groove by cutting a semiconductor wafer by laser irradiation (that is, a method of forming a groove) Laser dicing), a method of forming a groove by cutting a semiconductor wafer by spraying water containing an abrasive (namely, water dicing), and the like.

In addition, after the plurality of divided semiconductor chips are irradiated with infrared laser light so as to be focused on the focal point set inside the semiconductor wafer, a modified layer is formed inside the semiconductor wafer. By grinding the back surface of the semiconductor wafer and further applying a force to the semiconductor wafer after grinding the back surface or by applying a grinding force to the semiconductor wafer being ground on the back surface The semiconductor wafer can also be manufactured by dividing the modified layer at the site where the modified layer is formed.

<Cutting process>
In the cutting step, after the attaching step, a force is applied to the support sheet in the film-like adhesive composite sheet attached to the semiconductor chip from the side opposite to the side on which the film-like adhesive is provided. Then, a force is applied to the film adhesive through the support sheet to cut the film adhesive. Hereinafter, the manufacturing method of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing an embodiment from cutting of a film adhesive to separation of a semiconductor chip from a support sheet in the production method of the present invention. In FIG. 1, only the configuration related to the film-like adhesive composite sheet is shown in cross section.

As shown in FIG. 1A, the film adhesive 12 of the film adhesive composite sheet 1 is adhered to the back surfaces 9b of the plurality of semiconductor chips 9 by the pasting step. In this step, the support sheet 11 of the film-like adhesive composite sheet 1 has a surface (also referred to as the back surface) 11b opposite to the surface (also referred to as the front surface) 11a on which the film-like adhesive 12 is provided. In the semiconductor device manufacturing apparatus (illustration of the whole figure is omitted), a push-up portion 81 that pushes up the semiconductor chip is in contact.

When the support sheet 11 is a sheet made of a base material, the film-like adhesive composite sheet 1 is a side where the base material and the film-like adhesive 12 are laminated and in contact with the base material in the film-like adhesive 12. The surface on the opposite side is attached to the back surface 9 b of the semiconductor chip 9.
When the support sheet 11 is a sheet in which a base material and a pressure-sensitive adhesive layer are laminated, the film-like adhesive composite sheet 1 has a base material, a pressure-sensitive adhesive layer, and a film-like adhesive 12 laminated in this order, and a film The surface of the adhesive 12 opposite to the side in contact with the pressure-sensitive adhesive layer is affixed to the back surface 9 b of the semiconductor chip 9.

Next, in this step, as shown in FIG. 1 (b), a film-like adhesion is made through the support sheet 11 by applying a force from the back surface 11b to the support sheet 11 of the film-like adhesive composite sheet 1. Apply force to agent 12. Here, a protrusion (pin) 811 protrudes from the push-up portion 81, and the tip portion of the protrusion 811 pushes up the support sheet 11 from the back surface 11 b, so that the protrusion 811 against the film adhesive 12 through the support sheet 11. The example which applies force to the protrusion direction of is shown. At this time, push-up conditions such as a protrusion amount (push-up amount), a protrusion speed (push-up speed), and a protruding state holding time (lifting waiting time) of the protrusion 811 can be appropriately adjusted.
Here, although the case where the number of the protrusions 811 that push up the support sheet 11 is one is shown, it may be two or more, and the number of the protrusions 811 may be appropriately selected.

According to the film-like adhesive composite sheet 1, when a force is applied to the film-like adhesive 12 as described above, the film-like shape is suppressed while suppressing the occurrence of process abnormality due to the shearing force generated when the protrusions 811 are pushed up. The adhesive 12 can be cut. More specifically, the film-like adhesive 12 can be cut at room temperature at a target location, that is, a location surrounding only the semiconductor chip 9 that is to be separated from the support sheet 11. And, for example, a process mainly for cutting the film adhesive 12 such as a process of irradiating the film adhesive 12 with a laser and a process of cutting the film adhesive 12 by expanding, etc. It can cut without providing.

<Separation process>
In the separating step, after the cutting step, as shown in FIG. 1C, the semiconductor chip 9 and the film adhesive 12 after cutting attached to the semiconductor chip 9 are separated from the support sheet 11 (pick up). . This step is usually performed continuously immediately after the cutting step. Here, an example is shown in which the cut film adhesive 12 attached to the semiconductor chip 9 is peeled off from the support sheet 11 by pulling up the semiconductor chip 9 by the pulling portion 82 of the semiconductor device manufacturing apparatus. . Thus, the method of pulling up the semiconductor chip 9 may be a known method, for example, a method of sucking and pulling up the surface of the semiconductor chip 9 with a vacuum collet.

According to the film-like adhesive composite sheet 1, when the semiconductor chip 9 is pulled up in this way, the film-like adhesive 12 can be peeled off from the support sheet 11 while suppressing the occurrence of process abnormality. More specifically, the part corresponding to the target semiconductor chip 9 of the film adhesive 12 is peeled off from the support sheet 11 and the part corresponding to the non-target semiconductor chip 9 in the film adhesive 12 is The phenomenon of peeling from the support sheet 11 is suppressed. And since the film adhesive 12 is cut | disconnected in the predetermined location, the pulled-up semiconductor chip 9 is pulled away from the support sheet 11 with the film adhesive 12. FIG.

In the manufacturing method of the present invention, a semiconductor device is manufactured by a method similar to the conventional method using a semiconductor chip separated (picked up) together with a film adhesive. For example, the semiconductor chip is die-bonded to the circuit surface of the substrate with a film adhesive, and if necessary, at least one semiconductor chip is further laminated on the semiconductor chip and wire bonding is performed, and then the whole is resin By sealing with, it is set as a semiconductor package. Then, a target semiconductor device may be manufactured using this semiconductor package.

The manufacturing method of the semiconductor device of the present invention is not limited to the above-described method described with reference to FIG. 1, and a part of the configuration is changed, deleted, or deleted in the above-described method within a range not impairing the effect of the present invention. It may be added.
For example, as a method of applying force to the film adhesive 12 through the support sheet 11, the method of applying force to the film adhesive 12 by pushing up the support sheet 11 with the protrusions 811 has been described so far. As a method other than this, for example, a method of applying force to the film adhesive 12 by pushing up the support sheet 11 with a slider instead of the protrusion 811 can be mentioned.

FIG. 2 is a cross-sectional view for schematically explaining another embodiment in which a force is applied to the above-described film-like adhesive to cut it. 2, the same components as those shown in FIG. 1 are denoted by the same reference numerals as those in FIG. 1, and detailed description thereof is omitted. The same applies to the drawings after FIG.
What is shown here is an alternative to the film adhesive cutting method described with reference to FIG.

Also in the case of applying this embodiment, first, the pasting process is performed by the same method as described with reference to FIG.
Next, a force is applied to the film adhesive 12 through the support sheet 11 by applying a force from the back surface 11 b to the support sheet 11 of the film adhesive composite sheet 1. However, in this embodiment, the protrusion 81 does not protrude from the protrusion 811 as shown in FIG. 1B, but moves by the slider 812 as shown in FIGS. 2A and 2B. The support sheet 11 is pushed up from the back surface 11b.

In this embodiment, as shown in FIG. 2A, the surface 812a of the slider 812 protruding from the push-up portion 81 is in contact with the back surface 11b of the support sheet 11. At this time, the front surface 812a of the slider 812 is not parallel to the back surface 11b of the support sheet 11 before the cutting step as shown in FIG. Therefore, by applying a force from the back surface 11b to the support sheet 11 in a direction orthogonal to the front surface 812a of the slider 812, that is, in an oblique direction rather than a vertical direction, a difference in the push-up height of the film adhesive 12 is obtained. Occurs. However, the force applied to the film adhesive 12 through the support sheet 11 is the same as in the case of FIG. Thereby, in the region where the semiconductor chip 9 is not affixed in the region where the push-up height of the film adhesive 12 is high (the first region 121 in FIG. 2A), the shear force generated along with the push-up is generated. Thus, the film adhesive 12 can be cut while suppressing the occurrence of process abnormality.

When the slider 812 is pushed up, the pushing conditions such as the protruding amount (push-up amount), inclination angle (push-up speed), moving speed (lifting waiting time) of the slider 812 can be adjusted as appropriate.

In this embodiment, the slider 812 is then moved in a direction parallel to the back surface 11b of the support sheet 11 that has not been pushed up, as shown in FIG. Thereby, the push-up site | part of the support sheet 11 moves. Then, after the movement of the push-up portion, the push-up is performed in the region where the semiconductor chip 9 is not affixed (the second region 122 in FIG. 2B) in the region where the push-up height of the film adhesive 12 is high. The film-like adhesive 12 can be cut while suppressing the occurrence of process abnormality by the shearing force generated along with the above.

Due to the shearing force generated along with the movement of the slider 812, the film adhesive 12 is cut while suppressing the occurrence of process abnormality as in the case described with reference to FIG.
Thereafter, the separation step can be performed by the same method as described with reference to FIG.

However, the cutting effect of the film adhesive is usually higher in the pin push-up method as described with reference to FIG. 1 than in the slider push-up method as described with reference to FIG. Therefore, it is preferable to select which method is adopted in consideration of characteristics relating to strength such as breaking elongation B of the film adhesive.

As described above, according to the method for manufacturing a semiconductor device of the present invention, in the cutting step, since the film adhesive can be cut at a target location, the film adhesive is not cut. Pulling (lifting) defects are suppressed.
In addition, according to the method for manufacturing a semiconductor device of the present invention, in the separation step, the target portion of the film adhesive is peeled off from the support sheet, so that occurrence of a separation (lifting) defect of the semiconductor chip is suppressed. . In addition, since the non-target portion of the film adhesive is prevented from peeling off from the support sheet, not only the target semiconductor chip but also the semiconductor chip adjacent thereto is simultaneously separated from the support sheet together with the film adhesive. Generation of so-called double die is suppressed.
Thus, according to the present invention, it is possible to manufacture a semiconductor device by suppressing the occurrence of process abnormality by a simplified method.

When the film-like adhesive composite sheet of the present invention is not used, there is a possibility that the occurrence of process abnormalities as shown below cannot be suppressed during the manufacture of the semiconductor device.

FIG. 3 is a cross-sectional view schematically showing one embodiment of the film adhesive composite sheet and the semiconductor chip in the manufacturing process of the semiconductor device when the conventional film adhesive composite sheet is used.
When the film-like adhesive composite sheet 7 shown in FIG. 3 is used, as shown in FIG. 3 (a), even if a force is applied to the film-like adhesive 72, the film-like adhesive 72 is not cut. When the semiconductor chip 9 is pulled up, the film adhesive 72 is peeled off from the semiconductor chip 9 and remains laminated on the support sheet 71. As a result, as shown in FIG. 3B, the lifting failure of the semiconductor chip 9 occurs.
Such a process abnormality is, for example, in the film-like adhesive composite sheet 7, the values of the breaking elongation B and the breaking strength C are large, and the adhesion when compared with the values of the breaking elongation B and the breaking strength C is as follows. This is likely to occur when the value of the force A is small to an undesirable level and does not satisfy the relationship of the expression (1).

FIG. 4 is a cross-sectional view schematically showing another embodiment of the film adhesive composite sheet and the semiconductor chip in the process of manufacturing the semiconductor device when the conventional film adhesive composite sheet is used.
When the film adhesive composite sheet 7 shown in FIG. 4 is used, as shown in FIG. 4A, only a cut is formed in the film adhesive 72, and the film adhesive 72 is cut. In addition, when the semiconductor chip 9 is further pulled up, the film adhesive 72 is peeled off from the semiconductor chip 9 and remains laminated on the support sheet 71. As a result, as shown in FIG. 4B, the lifting failure of the semiconductor chip 9 occurs.
Such a process abnormality also occurs when, for example, in the film-like adhesive composite sheet 7, the values of the breaking elongation B and the breaking strength C are large, and the adhesion when compared with the values of the breaking elongation B and the breaking strength C is as described above. This is likely to occur when the value of the force A is small to an undesirable level and does not satisfy the relationship of the expression (1).

Note that the process abnormality described with reference to FIGS. 3 to 4 is an example, and other process abnormality may occur depending on circumstances.
On the other hand, when the film-like adhesive composite sheet of the present invention is used, the occurrence of such a process abnormality is suppressed, and as a result, a semiconductor device is manufactured at a lower cost by a simplified method than before. it can.

As one aspect of the film-like adhesive composite sheet that is one embodiment of the present invention,
A film-like adhesive composite sheet,
The film adhesive composite sheet is on a support sheet having a substrate,
A curable film adhesive having a thickness of 1 to 50 μm, preferably 3 to 25 μm, more preferably 5 to 15 μm is provided;
The adhesive strength of the film adhesive before curing to a semiconductor wafer is defined as adhesive strength A (N / 24 mm), and the film adhesive before curing is laminated so that the total thickness becomes 200 μm. When the breaking elongation is the breaking elongation B (%) and the breaking strength of the laminate is the breaking strength C (MPa),
The adhesive force A is 0.3 to 15 N / 24 mm, preferably 0.3 to 11 N / 24 mm, more preferably 0.4 to 7 N / 24 mm, still more preferably 0.45 N / 24 mm or more and less than 10 N / 24 mm, Particularly preferably, it is 0.45 N / 24 mm or more and 5.8 N / 24 mm or less;
The elongation at break B is 1200% or less, preferably 30 to 1200%, more preferably 40 to 1100%, even more preferably 45 to 1050%, or 30 to 500%, 40 to 500%, 45 to 500. % Or 50-440%;
The breaking strength C is 0.4 to 17 MPa, preferably 0.5 to 15 MPa, more preferably 0.6 to 13 MPa, still more preferably 0.8 to 11 MPa, particularly preferably 2.5 to 11 MPa; and A / (B × C) is 0.0005 or more and 0.0170 or less, preferably 0.0006 or more and 0.0140 or less, more preferably 0.00067 or more and 0.0115 or less, and further preferably 0.0008 or more and 0 or less. Less than .0125, 0.0008 or more and 0.0105 or less,
A film-like adhesive composite sheet.

As another side surface of the film-like adhesive composite sheet which is one embodiment of the present invention,
The film-like adhesive composite sheet,
Furthermore, the film adhesive is
Formed from an adhesive composition comprising a polymer component (a), an epoxy-based thermosetting resin (b), a filler (d), and a coupling agent (e);
The polymer component (a) is an acrylic resin having a weight average molecular weight (Mw) of 10,000 to 2,000,000, preferably from the group consisting of butyl acrylate, methyl acrylate, glycidyl methacrylate, and 2-hydroxyethyl acrylate. The selected monomer is a copolymerized resin;
The epoxy thermosetting resin (b) is composed of an epoxy resin (b1) and a thermosetting agent (b2),
The epoxy resin (b1) is preferably at least one selected from the group consisting of a bisphenol A type epoxy resin, a phenylene skeleton type epoxy resin, and a dicyclopentadiene type epoxy resin product;
The filler (d) is silica or alumina;
The coupling agent (e) includes an epoxy group-containing oligomer type silane coupling agent, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltri At least one selected from the group consisting of methoxysilane;
The content of the acrylic resin in the polymer component (a) is 5 to 40% by mass, preferably 7 to 25% by mass, or 9 to 28% by mass, based on the total mass of the film adhesive. May be;
The content of the epoxy thermosetting resin (b) is 50 to 1000 parts by weight, preferably 100 to 900 parts by weight, more preferably 150 parts per 100 parts by weight of the polymer component (a). 870 parts by weight; or 47 to 81% by weight or 47 to 80% by weight;
The content of the filler (d) is 5 to 80% by mass, preferably 7 to 60% by mass, or 8 to 12% by mass or 9 to 12% by mass with respect to the total mass of the film adhesive. May be%;
The content of the coupling agent (e) is 0.03 to 20 parts by mass, preferably 100 parts by mass of the total content of the polymer component (a) and the epoxy thermosetting resin (b). Is 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, or 0.28 to 1% by weight.
A film-like adhesive composite sheet.

Furthermore, the film adhesive composite sheet is
The base material is a base material in which a layer made of low density polyethylene, a layer containing polypropylene, a styrene / ethylene butylene / styrene block copolymer, and a layer made of low density polyethylene are laminated in this order. May be.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

The component used for manufacture of an adhesive composition is shown below.
Polymer component (a) -1: butyl acrylate (hereinafter abbreviated as “BA”) (55 parts by mass), methyl acrylate (hereinafter abbreviated as “MA”) (10 parts by mass), methacrylic acid Acrylic resin (weight) obtained by copolymerizing glycidyl (hereinafter abbreviated as “GMA”) (20 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as “HEA”) (15 parts by mass) (Average molecular weight 800,000, glass transition temperature -28 ° C.).
(A) -2: an acrylic resin (weight average molecular weight 370000, glass transition temperature 6 ° C.) obtained by copolymerizing MA (85 parts by mass) and HEA (15 parts by mass).
(A) -3: an acrylic resin obtained by copolymerizing MA (95 parts by mass) and HEA (5 parts by mass) (weight average molecular weight 760000, glass transition temperature 9 ° C.).
(A) -4: Thermoplastic resin, polyester (“Byron 220” manufactured by Toyobo Co., Ltd., weight average molecular weight 35000, glass transition temperature 53 ° C.))
Epoxy resin (b1) -1: Bisphenol A type epoxy resin (“JER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 184 to 194 g / eq)
(B1) -2: Liquid bisphenol A type epoxy resin (“JER834” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 250 g / eq, weight average molecular weight 470)
(B1) -3: Polyfunctional aromatic type (triphenylene type) epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 167 g / eq, softening point 54 ° C., weight average molecular weight 1200)
(B1) -4: Cresol novolak type epoxy resin to which an acryloyl group is added (“CNA147” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 518 g / eq, number average molecular weight 2100, unsaturated group content is equivalent to epoxy group)
(B1) -5: Dicyclopentadiene type epoxy resin (“ADEKA RESIN EP-4088L” manufactured by ADEKA, epoxy equivalent 165 g / eq)
Thermosetting agent (b2) -1: Novolac type phenolic resin (“BRG-556” manufactured by Showa Denko KK, softening point 80 ° C., weight average molecular weight 950)
(B2) -2: Biphenyl type phenolic resin (“MEH-7851-SS” manufactured by Meiwa Kasei Co., Ltd., softening point: 67 ° C.)
(B2) -3: Aralkyl-type phenol resin (“Mirex XLC-4L” manufactured by Mitsui Chemicals, softening point 63 ° C.)
Curing accelerator (c) -1: 2-phenyl-4,5-dihydroxymethylimidazole (“Curesol 2PHZ” manufactured by Shikoku Chemicals)
Filler (d) -1: Spherical silica ("Advertex" SC2050MA ")
(D) -2: Spherical silica (“SC2050” manufactured by Admatechs)
(D) -3: Spherical silica (“YA050C-MJE” manufactured by Admatechs)
Coupling agent (e) -1: Silane coupling agent, epoxy group-containing oligomer type (“MKC silicate MSEP-2” manufactured by Mitsubishi Chemical, epoxy equivalent 222 g / eq)
(E) -2: Silane coupling agent, epoxy group-containing oligomer type (“X-41-1056” manufactured by Shin-Etsu Silicone, epoxy equivalent: 280 g / eq)
(E) -3: Silane coupling agent, 3-glycidyloxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Silicone)
(E) -4: Silane coupling agent, 3-glycidyloxypropyltriethoxysilane (“KBE-403” manufactured by Shin-Etsu Silicone)
(E) -5: Silane coupling agent, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (“KBM-303” manufactured by Shin-Etsu Silicone)
(E) -6: Silane coupling agent, 3-glycidyloxypropylmethyldiethoxysilane (“KBE-402” manufactured by Shin-Etsu Silicone)
Crosslinking agent (f) -1: Tolylene diisocyanate crosslinking agent (“Coronate L” manufactured by Tosoh Corporation)
Energy ray curable resin Energy ray curable resin (g) -1: Tricyclodecane dimethylol diacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd., UV curable resin, molecular weight 304)
Photopolymerization initiator Photopolymerization initiator (h) -1: 1-hydroxycyclohexyl phenyl ketone (“IRGACURE 184” manufactured by BASF)
Other components (z) -1: Silicone oil (“XF42-334” manufactured by Momentive Performance Materials Japan)

The base material used for manufacture of a film adhesive composite sheet is shown below.
Substrate (1): a layer made of low-density polyethylene (“Novatec LC520” manufactured by Nippon Polyethylene Co., Ltd., density 0.923 g / cm ³ , MFR 3.6 g / 10 min, thickness 8 μm) and a layer containing polypropylene (homopolypropylene) Resin (“Prime Polypro F-300SP” manufactured by Prime Polymer Co., Ltd., density 0.90 g / cm ³ , MFR 3.0 g / 10 min) and styrene / ethylene butylene / styrene block copolymer (“Dynalon 8601P” manufactured by JSR, density) 0.89 g / cm ³ , MFR 3.5 g / 10 min) layer, thickness 60 μm) and low density polyethylene layer (same as above except that thickness is 12 μm instead of 8 μm) And a substrate formed by laminating in this order. The above MFR (melt flow rate) is measured in accordance with JIS K7210: 1999. The measurement temperature is 190 ° C. for low density polyethylene, 230 ° C. for homopolypropylene resin, and styrene / ethylene butylene / styrene block copolymer. Is a value measured at 230 ° C. and a load of 21.18 N.
Base material (2): A base material having a two-layer structure in which a layer made of polyethylene-methacrylic acid copolymer and a layer made of polyethylene are laminated (“HUSL1301” manufactured by Achilles).

<Manufacture of film adhesive composite sheet>
[Example 1]
(Manufacture of adhesive composition)
Polymer component (a) -1, Polymer component (a) -4, Epoxy resin (b1) -1, Epoxy resin (b1) -3, Thermosetting agent (b2) -1, Curing accelerator (c)- 1. Filler (d) -1, coupling agent (e) -1, energy ray curable resin (g) -1, and photopolymerization initiator (h) -1, and their contents (parts by mass) Was dissolved or dispersed in methyl ethyl ketone so as to have the value shown in Table 1, and stirred at 23 ° C. to obtain an adhesive composition having a solid content concentration of 50 mass% as an adhesive composition. In addition, the description of “-” in the column of the contained component in Table 1 means that the adhesive composition does not contain the component.

(Manufacture of film adhesive composite sheet)
The adhesive composition obtained above was applied to the release-treated surface of a release film (“SP-PET3811” manufactured by Lintec Co., Ltd., thickness 38 μm) from which one side of a polyethylene terephthalate film was release-treated. By drying for a minute, a film adhesive having a thickness of 7 μm was formed. Next, a film-like adhesive composite sheet was obtained by laminating a layer made of low-density polyethylene having a thickness of 8 μm of the base material (1) on the exposed surface of this film-like adhesive.

[Examples 2-5, Comparative Examples 1-2]
A film-like adhesive composite sheet was produced in the same manner as in Example 1 except that the components contained in the substrate or the adhesive composition were as shown in Table 1.
In addition, when the base material (2) was used, the layer made of polyethylene was bonded to the exposed surface of the film adhesive.

<Evaluation of film adhesive composite sheet>
The following items were evaluated for the film-like adhesive composite sheets of Examples and Comparative Examples obtained above.

(Measurement of adhesive strength A)
The film-like adhesive composite sheet is cut into a size of 24 mm × 300 mm, and the film-like adhesive is heated to 60 ° C., and cellophane tape (“Cellotape (registered trademark) No. .405 ", width 24 mm). Next, the base material is peeled off from the film-like adhesive, and the exposed film-like adhesive is heated to 60 ° C. and attached to the dry polished surface of a 6-inch silicon wafer (thickness: 350 μm). A cellophane tape, a film adhesive, and a silicon wafer were laminated to obtain a laminate.
The obtained laminate was immediately left for 30 minutes in an environment of 23 ° C. and a relative humidity of 50% (standard environment defined in JIS Z0237 2009), and then the film adhesive and cellophane tape were removed from the silicon wafer. The laminated sheet is peeled off at a peeling speed of 150 mm / min so that the surfaces of the film adhesive and silicon wafer that are in contact with each other form an angle of 180 °, so-called 180 ° peeling is performed. The peel force was measured, and the measured value was defined as adhesive strength A (N / 24 mm). The results are shown in Table 1.

(Measurement of elongation at break B)
Using a laminator, two film adhesives (thickness 20 μm) were heated to 60 ° C. and bonded together, and then the same film adhesive was bonded in the same manner until the total thickness was 200 μm. A laminated body in which a film adhesive was laminated was prepared.
Next, the obtained laminate was heated for 30 seconds using a hot plate heated to 80 ° C. Next, this heated laminate was cut within 10 seconds using a super cutter (“PH1-600” manufactured by Sugano Seiki Seisakusho) to prepare a test piece having a width of 15 mm, a length of 100 mm, and a thickness of 200 μm. . When the cutting time exceeds 10 seconds, the cutting is stopped once, and the laminate being cut is heated again using a hot plate heated to 80 ° C., and then cut within 10 seconds. A piece was made. The reason why the laminate is cut after heating is to prevent the end of the test piece from having a defective portion that causes breakage.

Subsequently, the elongation at break of the obtained test piece was measured according to JIS K7161-1994. More specifically, it is as follows.
That is, a universal testing machine (“Autograph AG-IS 500N” manufactured by Shimadzu Corporation) was used, and the test piece was fixed at two locations with the fixing gripping device. At this time, the distance between the tips of the fixed gripping tool (the length of the exposed portion of the test piece, the distance between the fixed portions) was set to 75 mm.
Then, the tensile speed was set to 200 mm / min, the test piece was pulled between the fixed portions, and the elongation at break of the test piece was obtained to obtain the breaking elongation B (%). The results are shown in Table 1.

(Measurement of breaking strength C)
At the time of measuring the breaking elongation B, the tensile stress when the test piece was broken (broken), that is, the tensile breaking stress was measured, and the measured value was defined as the breaking strength C (MPa). The results are shown in Table 1.

(Calculation of A / (B × C) value)
The value of A / (B × C) was calculated from the measured values of adhesive strength A, breaking elongation B, and breaking strength C obtained above. The results are shown in Table 1.

(Evaluation of pick-up suitability by pushing up with a pin)
An 8-inch silicon wafer was divided into chips of 2 mm × 2 mm and a thickness of 50 μm. Then, using a laminator, the film adhesive of the film adhesive composite sheet was heated to 60 ° C., and the heated film adhesive was bonded to the dry polished surface of the chip. By the above operation, a test sheet in which one film-like adhesive composite sheet was affixed to a number of silicon chips was obtained.
Next, for this test sheet, using a pickup device (“BESTEM-D02” manufactured by Canon Machinery Co., Ltd.), using a 1-pin push-up method with a push-up amount of 150 μm, a push-up speed of 20 mm / min, and a lift waiting time of 1 sec. The pickup was performed 54 times. When the pickup was successful 40 times or more, the pickup suitability was determined to be good (X), and otherwise, the pickup suitability was determined to be poor (Y). The results are shown in Table 1.

(Evaluation of pick-up suitability by pushing up with a slider)
The above-mentioned 1 except that the slider kit is mounted on the pickup device used in the above-described pickup aptitude evaluation and the pickup device having the same structure as that shown in FIG. The pick-up suitability was evaluated by the same method as the pin push-up method. At this time, the pickup was performed under the conditions of a stroke distance of 1.5 mm, a stroke speed of 90 mm / sec, and a waiting time of 1 sec. The results are shown in Table 1.

As is clear from the above results, the film-like adhesive composite sheets of Examples 1 to 5 have a value of A / (B × C) in the range of 0.0008 or more and satisfy the relationship of the above formula (1). It was. And in the silicon chip to which the film-like adhesive of these sheets is stuck, the occurrence of process abnormality is suppressed by the 1-pin push-up method, without providing a separate process mainly for cutting the film-like adhesive. However, the film adhesive could be cut. Furthermore, the silicon chip to which the film adhesive after cutting was attached could be separated from the support sheet while suppressing the occurrence of process abnormality. As described above, the film-like adhesive composite sheets of Examples 1 to 5 exhibited good pickup suitability in the 1-pin push-up method.

Further, when the film-like adhesive composite sheets of Examples 1 to 2 and 4 to 5 in which the breaking elongation B of the film-like adhesive is in the range of 440% or less are used, the slider push-up method also uses 1 pin. As in the case of the push-up method, good pickability was shown.

In contrast, the film-like adhesive composite sheets of Comparative Examples 1 and 2 had a value of A / (B × C) in the range of 0.0004 or less, and did not satisfy the relationship of the formula (1). . And in the silicon chip to which the film-like adhesive of these sheets is attached, in both cases of the 1-pin push-up method and the slider push-up method, from the cutting of the film adhesive, the support sheet for the silicon chip with the film adhesive Until the separation from the process, the number of occurrences of process abnormalities was large, and the pickup suitability was poor.

Since the present invention can be used for manufacturing semiconductor devices, it is extremely useful industrially.

DESCRIPTION OF SYMBOLS 1 ... Film adhesive composite sheet, 11 ... Support sheet, 11a ... Front surface of support sheet, 11b ... Back surface of support sheet, 12 ... Film adhesive, 9 ... Semiconductor Chip, 9b ... back side of semiconductor chip

Claims (4)

A film-like adhesive composite sheet,
The film-like adhesive composite sheet is provided with a curable film-like adhesive having a thickness of 1 to 50 μm on a support sheet having a substrate;
The adhesive strength of the film adhesive before curing to a semiconductor wafer is defined as adhesive strength A (N / 24 mm), and the film adhesive before curing is laminated so that the total thickness becomes 200 μm. A film-like adhesive composite sheet satisfying the relationship of the following formula (1) when the breaking elongation is B (%) and the breaking strength of the laminate is C (MPa).
A / (B × C) ≧ 0.0005 (1) The film-like adhesive composite sheet according to claim 1, wherein the breaking elongation B is 500% or less. The film adhesive composite sheet according to claim 1 or 2, wherein the support sheet is made of the substrate, and the film adhesive is provided in direct contact with the substrate. A method for manufacturing a semiconductor device, comprising:
A step of affixing the film adhesive composite sheet according to any one of claims 1 to 3 to a plurality of divided semiconductor chips via the film adhesive;
By applying a force from the side opposite to the side on which the film-like adhesive is provided to the support sheet in the film-like adhesive composite sheet attached to the semiconductor chip, the film-like shape is passed through the support sheet. Applying a force to the adhesive to cut the film adhesive;
A step of separating the semiconductor adhesive and the film adhesive after cutting attached to the semiconductor chip from the support sheet;
A method for manufacturing a semiconductor device, comprising:

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