WO2019182009A1

WO2019182009A1 - Die bonding film, dicing die bonding sheet, and semiconductor chip production method

Info

Publication number: WO2019182009A1
Application number: PCT/JP2019/011694
Authority: WO
Inventors: 啓示布施
Original assignee: リンテック株式会社
Priority date: 2018-03-23
Filing date: 2019-03-20
Publication date: 2019-09-26
Also published as: JP7155245B2; JPWO2019182009A1; CN111466015A; TW202004873A; KR20200135279A; CN111466015B; TWI770371B

Abstract

The invention relates to a die bonding film comprising a first layer and a second layer provided on the first layer. The first layer has a property such that the melt viscosity initial detection temperature is 75°C or lower. The second layer is tacky and energy-beam curable. With the second layer having a thickness of 10 μm and a greater width than 25 mm serving as a test piece, the following condition is provided. The test piece is pasted onto a silicon mirror wafer, the test piece is cut to a width of 25 mm, the test piece having been cut and the silicon mirror wafer are immersed together in pure water for two hours, and the test piece after the immersion is cured with an energy beam and made into a cured object so as to produce a test layered body in which the cured object is pasted onto the silicon mirror wafer. In this condition, the die bonding film has a property such that the adhesive force is 6 N/25 mm or stronger between the silicon mirror wafer and the cured object having a width of 25 mm.

Description

Die bonding film, dicing die bonding sheet, and semiconductor chip manufacturing method

The present invention relates to a die bonding film, a dicing die bonding sheet, and a method for manufacturing a semiconductor chip.
This application claims priority based on Japanese Patent Application No. 2018-057007 filed in Japan on March 23, 2018, the contents of which are incorporated herein by reference.

The semiconductor chip is usually die-bonded to the circuit forming surface of the substrate with a die-bonding film attached to the back surface thereof. Thereafter, if necessary, one or more semiconductor chips are further stacked on the semiconductor chip, wire bonding is performed, and the whole is sealed with a resin to manufacture a semiconductor package. Then, a target semiconductor device is manufactured using this semiconductor package.

A semiconductor chip having a die bonding film on the back surface is produced, for example, by dividing (cutting) a semiconductor wafer having a die bonding film on the back surface together with the die bonding film. As a method for dividing the semiconductor wafer into semiconductor chips in this manner, for example, a method of dicing the semiconductor wafer together with the die bonding film using a dicing blade is widely used. In this case, the die bonding film before division (cutting) is used as a dicing die bonding sheet that is laminated and integrated with a dicing sheet used for fixing the semiconductor wafer during dicing.
After completion of dicing, a semiconductor chip having a die bonding film on the back surface (a semiconductor chip with a die bonding film) is separated from the dicing sheet and picked up.

On the other hand, as the die bonding film, for example, a film having an elastic modulus G at 120 ° C. of 30000 Pa or less has been disclosed so far (see Patent Document 1). According to Patent Document 1, by using this die bonding film, it is said that generation of voids (voids) can be suppressed at the semiconductor chip side interface or the substrate side interface of the die bonding film.
Further, a die bonding film having a two-layer structure including a wire embedding layer and an insulating layer laminated thereon is disclosed (see Patent Document 2). According to Patent Document 2, this die bonding film is suitable for manufacturing a semiconductor package in which chips are three-dimensionally stacked.

JP 2013-77855 A JP 2007-53240 A

As described above, the semiconductor chip after dicing is picked up by being separated from the dicing sheet while being provided with the die bonding film on the back surface, and die bonded to the circuit forming surface of the substrate by the die bonding film. However, if the adhesive force (adhesive force) between the die bonding film and the semiconductor chip is insufficient, part or all of the die bonding film peels off from the semiconductor chip and remains on the dicing sheet at the time of pickup. As a result, an abnormality occurs in the transfer of the die bonding film from the dicing sheet to the semiconductor chip. In this specification, such an abnormality is referred to as “transfer defect”.

Such transfer failure of the die bonding film is particularly likely to occur when the semiconductor wafer is divided into small semiconductor chips by dicing using a dicing blade. This is because dicing is performed while water (sometimes referred to as “cutting water”) is allowed to flow through a portion where the dicing blade contacts the semiconductor wafer. The smaller the size of the semiconductor chip obtained by dicing, the greater the amount of contact with water with respect to the surface area of one semiconductor chip, which makes it much more susceptible to water. When the adhesive force (adhesive force) between the die bonding film and the semiconductor chip is insufficient, water easily enters the interface between the die bonding film and the semiconductor chip. When water permeates, the die bonding film is easily peeled from the semiconductor chip, and transfer defects are likely to occur as described above.

On the other hand, the die bonding film disclosed in Patent Document 1 is picked up when the size of the semiconductor chip is small even though the generation of voids (voids) can be suppressed at the interface on the semiconductor chip side. It is not certain whether the transfer failure of the die bonding film at the time can be suppressed.

Usually, in order to suppress the transfer failure of the die bonding film, the physical properties may be improved by increasing the adhesive force of the die bonding film. However, the die bonding film is used for die bonding a semiconductor chip to a circuit forming surface of a substrate. When the physical properties of the die bonding film are improved so as to be advantageous for suppressing transfer defects, for example, the generation of a gap between the substrate surface and the die bonding film at the time of die bonding is suppressed, and the die bonding film becomes a substrate. The so-called embedding property of the substrate covering the surface may be lowered.

On the other hand, the die bonding film disclosed in Patent Document 2 has a two-layer structure of a wire embedding layer and an insulating layer, suggesting that the embedding property of the substrate is good. However, it is not certain whether the insulating layer of this die bonding film can suppress the transfer failure of the die bonding film during pick-up when the size of the semiconductor chip is small.

The present invention provides a die bonding film capable of suppressing transfer failure to a semiconductor chip when picking up a semiconductor chip having a small size and capable of satisfactorily embedding a substrate at the time of die bonding. An object of the present invention is to provide a dicing die bonding sheet provided and a semiconductor chip manufacturing method using the dicing die bonding sheet.

In order to solve the above problems, the present invention includes a first layer, and a second layer on the first layer. The initial detection temperature of the melt viscosity of the first layer is 75 ° C. or lower. The second layer has adhesiveness and energy ray curability, has a thickness of 10 μm, and has a width larger than 25 mm as a test piece, and the test piece is affixed to a silicon mirror wafer. The test piece after cutting is immersed in pure water for 2 hours together with the silicon mirror wafer, and the test piece after immersion is cured with energy rays to obtain a cured product. As a result, the adhesive strength between the cured product having a width of 25 mm and the silicon mirror wafer when the test laminate in which the cured product was adhered to the silicon mirror wafer was 6 N / 25 mm. That's the dibondin To provide a film.
Further, the present invention includes a support sheet, the die bonding film is provided on the support sheet, and a first layer in the die bonding film is disposed on the support sheet side. Provide a sheet.

The present invention also provides a laminate (1-1) in which a semiconductor wafer is adhered to the second layer and a dicing sheet is adhered to the first layer of the die bonding film, or the dicing die bonding sheet. A step of producing a laminate (1-2) in which a semiconductor wafer is adhered to the second layer in the die bonding film, and using a dicing blade, the laminate (1-1) or laminate (1- 2) By cutting the semiconductor wafer together with the die bonding film, a laminated body (2) including the cut first layer, the cut second layer, and the semiconductor chip is manufactured. Cutting the second layer that has been cut in the laminate (2) by energy ray curing to obtain a cured product, and the first layer that has been cut, the cured product, and The step of producing the laminate (3) provided with the semiconductor chip, and the dicing sheet or the support sheet for the semiconductor chip provided with the cut first layer and the cured product in the laminate (3). And a step of picking up and picking up the semiconductor chip.

That is, the present invention includes the following aspects.
[1] including a first layer and a second layer provided on the first layer;
The first layer has an initial detection temperature of melt viscosity of 75 ° C. or less,
The second layer has adhesiveness and energy ray curability, has a thickness of 10 μm, and a width of more than 25 mm. The second layer is a test piece, and the test piece is attached to a silicon mirror wafer. Then, the test piece is cut so as to have a width of 25 mm, the cut test piece is immersed in pure water for 2 hours together with the silicon mirror wafer, and the immersed test piece is cured with energy rays. When a laminated body for test in which the cured product is adhered to the silicon mirror wafer is produced by using a cured product, the adhesive force between the cured product having a width of 25 mm and the silicon mirror wafer is reduced. , Having a characteristic of 6 N / 25 mm or more,
Die bonding film.
[2] A support sheet and the die bonding film according to [1] provided on the support sheet,
A dicing die bonding sheet, wherein the first layer in the die bonding film is disposed on the support sheet side.
[3] Of the die bonding film according to [1], a laminate (1-1) in which a semiconductor wafer is attached to the second layer and a dicing sheet is attached to the first layer, or [2] A laminated body (1-2) in which a semiconductor wafer is bonded to the second layer in the die bonding film of the dicing die bonding sheet described in the above;
By cutting the semiconductor wafer in the laminate (1-1) or the laminate (1-2) together with the die bonding film with a dicing blade, the cut first layer and the cut Producing a laminate (2) comprising a second layer and a semiconductor chip that is the cut semiconductor wafer;
A laminate (1) including the cut first layer, the cured product, and the semiconductor chip by curing the cut second layer in the laminate (2) by energy ray curing. 3) producing,
In the laminate (3), the semiconductor chip including the cut first layer and the cured product is separated from the support sheet or the dicing sheet and picked up;
A method for manufacturing a semiconductor chip, comprising:

ADVANTAGE OF THE INVENTION According to this invention, the transfer defect to a semiconductor chip can be suppressed at the time of the pick-up of a small semiconductor chip, and the die bonding film which can embed a board | substrate favorably at the time of die bonding, and this die bonding A dicing die bonding sheet provided with a film and a semiconductor chip manufacturing method using the dicing die bonding sheet are provided.

It is sectional drawing which shows typically the die-bonding film which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the dicing die-bonding sheet which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the dicing die-bonding sheet which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the dicing die-bonding sheet which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the dicing die-bonding sheet which concerns on one Embodiment of this invention. It is sectional drawing for demonstrating typically the manufacturing method of the semiconductor chip which concerns on one Embodiment of this invention. It is sectional drawing which shows typically an example of the state by which the semiconductor chip with the cured die-bonding film obtained by this invention is die-bonded to the circuit formation surface of a board | substrate.

◇ Die Bonding Film A die bonding film according to an embodiment of the present invention includes a first layer and a second layer provided on the first layer, and the first layer has an initial detection temperature of melt viscosity ( In the present specification, “T ₀ ” may be abbreviated to 75 ° C. or less, the second layer has adhesiveness and energy ray curability, and has a thickness of 10 μm. The second layer having a width greater than 25 mm is used as a test piece, the test piece is affixed to a silicon mirror wafer, the test piece is cut to a width of 25 mm, and the cut test piece is used as the test piece. The test laminate in which the silicon mirror wafer is affixed to the silicon mirror wafer by immersing the silicon mirror wafer in pure water for 2 hours, and curing the test piece after energy immersion to form a cured product. And made The adhesive strength between the cured product having a width of 25 mm and the silicon mirror wafer (in this specification, sometimes abbreviated as “adhesive strength after immersion”) is 6 N / 25 mm or more. Have
In addition, the die bonding film which has as a 2nd layer the layer formed from the same material as the formation material of the 2nd layer which has the said characteristic is included in this invention.

In the die bonding film, the first layer is used for die bonding to a substrate.
On the other hand, the second layer is affixed to a semiconductor wafer, cured by irradiation with energy rays, and then picked up together with the semiconductor chip. The bonding surface of the second layer of the semiconductor wafer is a surface opposite to the side on which the circuit of the semiconductor wafer is formed (in this specification, it may be referred to as “back surface”).

In the present specification, “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays, radiation, and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
In this specification, “energy ray curable” means a property that cures when irradiated with energy rays, and “non-energy ray curable” means a property that does not cure even when irradiated with energy rays. To do.

In the die bonding film, the first layer has adhesiveness. Further, since the initial detection temperature (T ₀ ) of the melt viscosity of the first layer is 75 ° C. or less, generation of a gap is suppressed between the substrate surface and the first layer during die bonding, One layer covers the substrate surface well, and the first layer can well embed the substrate.

On the other hand, in the die bonding film, the second layer has adhesiveness and energy ray curability. And the said adhesive force (adhesion force after immersion) measured using the test piece of a 2nd layer is 6 N / 25mm or more, Therefore When picking up a small semiconductor chip, the hardened | cured material of a 2nd layer A part or all of the film is not peeled off from the semiconductor chip, and the cured product of the second layer can suppress transfer failure to the semiconductor chip and has good transferability.

And the 1st layer and the 2nd layer can maintain these lamination structures stably irrespective of before and after energy ray hardening of the 2nd layer.
Therefore, the die bonding film has both good transferability to a small semiconductor chip and good substrate embedding property.

In the present specification, when the first layer is not in a laminated state with other layers but exists alone, such a first layer may be referred to as a “first film”.
Similarly, when the second layer is not in a laminated state with other layers but exists alone, such a second layer may be referred to as a “second film”.

◎ First layer (first film)
The first layer (first film) has adhesiveness as described above.
The first layer may further have curable properties (may be curable) or may not have curable properties (may be non-curable) and may have curable properties. In this case, for example, it may have either thermosetting property or energy ray curable property, and may have both thermosetting property and energy ray curable property.

Both the first layer having no curability and the uncured first layer having curability can be applied by lightly pressing the various adherends.
Moreover, the 1st layer may be what can be stuck to various to-be-adhered bodies by heating and softening irrespective of the presence or absence of hardening.
Both the first layer having no curability and the cured product of the first layer having curability can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

T _{0 of} the first layer is 75 ° C. or lower, preferably 73 ° C. or lower, more preferably 71 ° C. or lower, further preferably 69 ° C. or lower, such as 66 ° C. or lower and 62 Any of the following may be used. As another aspect, T _{0 of} the first layer may be 68 ° C. or lower, or 59 ° C. or lower.
When T ₀ is equal to or less than the upper limit value, the embeddability of the first layer substrate becomes higher.

The lower limit value of T ₀ of the first layer is not particularly limited.
T ₀ of the first layer is preferably 50 ° C. or higher from the viewpoint that the handleability of the die bonding film including the first layer becomes higher.

T _{0 of} the first layer can be appropriately adjusted within a range set by arbitrarily combining the above-described preferable lower limit value and upper limit value. For example, T ₀ is preferably 50 to 75 ° C., more preferably 50 to 73 ° C., further preferably 50 to 71 ° C., particularly preferably 50 to 69 ° C., for example, 50 to 66 ° C. and 50 to 62 ° C. It may be either ° C. As another aspect, T ₀ may be 50 to 68 ° C. or 50 to 59 ° C. or less.
However, these are examples of T ₀ of the first layer.

In the present embodiment, T _{0 of} the first layer can be measured by the following method, for example.
That is, using a capillary rheometer, the first film to be measured (the first layer existing alone) is set as a cylindrical test piece having a diameter of 10 mm and a height of 20 mm in the cylinder (capillary). The piston is movable in the longitudinal direction of the cylinder (in other words, in the direction of the central axis) along the inner wall while being in contact with the inner wall of the cylinder, and is constant with respect to the first film (the test piece) in the cylinder. The first film (the test piece) is heated (for example, at a heating rate of 10 ° C./min while maintaining a state where a force of a magnitude (for example, 5.10 N (50 kgf) is applied (a state where a load is applied)). The temperature is raised from 50 ° C. to 120 ° C. and is provided at the tip of the cylinder (the tip in the direction in which force is applied to the first film (the test piece)). When the extrusion of the first film (the test piece) is started from the hole (for example, a hole having a diameter of 0.5 mm and a height of 1.0 mm) to the outside of the cylinder, that is, the first film (the test piece) The temperature of the first film (the test piece) when the detection of the melt viscosity of is started is adopted as the initial detection temperature T ₀ (° C.) of the first film (in other words, the first layer). The size and shape of the first film can be appropriately adjusted in consideration of the size of the cylinder and the like.

In the present specification, “melt viscosity” means the melt viscosity measured by the above method unless otherwise specified.

The first layer may be composed of one layer (single layer), may be composed of two or more layers, and when composed of a plurality of layers, these layers may be the same as or different from each other. The combination of the multiple layers is not particularly limited.

In the present specification, not only the case of the first layer, but “a plurality of layers may be the same or different from each other” means “all layers may be the same or all layers may be the same. It may be different, 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 thicknesses of each layer is different from each other” Means that.

The thickness of the first layer is not particularly limited, but is preferably 1 to 40 μm, more preferably 3 to 30 μm, and particularly preferably 5 to 20 μm. When the thickness of the first layer is equal to or more than the lower limit value, the embedding property of the substrate of the first layer becomes higher. When the thickness of the first layer is less than or equal to the above upper limit value, the first layer (die bonding film) can be more easily cut in the semiconductor chip manufacturing process described later, and a cut piece derived from the first layer Can be further reduced.
Here, the “thickness of the first layer” means the thickness of the entire first layer. For example, the thickness of the first layer composed of a plurality of layers is the sum of all the layers constituting the first layer. Means the thickness.

A 1st layer (1st film) can be formed from the 1st adhesive composition containing the constituent material. For example, a 1st layer can be formed in the target site | part by apply | coating a 1st adhesive composition to the formation object surface of a 1st layer, and making it dry as needed.
In the first adhesive composition, the content ratio of components that do not vaporize at room temperature is usually the same as the content ratio of the components of the first 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.

The first 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, Examples include a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.

Although the drying conditions of the 1st adhesive composition are not specifically limited, When the 1st adhesive composition contains the solvent mentioned later, it is preferable to heat-dry. The first adhesive composition containing the solvent is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes.
Next, the first adhesive composition will be described in detail.

<< First Adhesive Composition >>
The type of the first adhesive composition includes the presence or absence of curability of the first layer and, if the first layer is curable, whether it is thermosetting or energy ray curable. Depending on the characteristics, it can be selected.
A preferable first adhesive composition includes a thermosetting first adhesive composition.
As a thermosetting 1st adhesive composition, what contains a polymer component (a) and an epoxy-type thermosetting resin (b) is mentioned, for example. Hereinafter, each component will be described.

(Polymer component (a))
The polymer component (a) is a component that can be regarded as formed by a polymerization reaction of a polymerizable compound, and imparts film-forming properties, flexibility, etc. to the first layer and adheres to an adhesion target such as a semiconductor chip. It is a polymer compound for improving the property (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. That is, the polymer component (a) excludes components corresponding to the epoxy resin (b1) and the thermosetting agent (b2) described later.

The polymer component (a) contained in the first adhesive composition and the first layer may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrarily selected. it can.

Examples of the polymer component (a) include acrylic resins, polyesters, urethane resins, acrylic urethane resins, silicone resins, rubber resins, phenoxy resins, and thermosetting polyimides, and acrylic resins are 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 between the first layer and the adherend to a preferable range.
On the other hand, when the weight average molecular weight of the acrylic resin is not less than the lower limit, the shape stability of the first layer (time stability during storage) is improved. Moreover, the embedding property of the board | substrate of a 1st layer becomes higher because the weight average molecular weight of acrylic resin is below the said upper limit.
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., and more preferably −30 to 50 ° C. When the Tg of the acrylic resin is equal to or higher than the lower limit, the adhesive force between the first layer and a support sheet or dicing sheet described later is suppressed, and the semiconductor provided with the first layer at the time of pickup The chip can be easily separated from the support sheet or dicing sheet described later. When the Tg of the acrylic resin is equal to or less than the upper limit, the adhesive force between the first layer and the second layer is improved.

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.

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.

The acrylic resin is, for example, one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like in addition to the (meth) acrylic ester. May be obtained by copolymerization.

The monomer constituting the acrylic resin 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.
As one aspect, the acrylic resin includes an acrylic resin obtained by copolymerizing n-butyl acrylate, methyl acrylate, glycidyl methacrylate and 2-hydroxyethyl acrylate, or n-butyl acrylate, acrylic An acrylic resin obtained by copolymerizing ethyl acid, acrylonitrile and glycidyl methacrylate is preferable.

The acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a carboxy group, and an isocyanate group in addition to the above-described hydroxyl group. These functional groups including the hydroxyl group of the acrylic resin may be bonded to other compounds via the crosslinking agent (f) described later, or directly bonded to other compounds not via the crosslinking agent (f). You may do it. When the acrylic resin is bonded to another compound through the functional group, the reliability of the package obtained using the first layer 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, at the time of pickup, the semiconductor chip provided with the first layer can be more easily separated from a support sheet or a dicing sheet, which will be described later, or the embedding property of the substrate of the first layer is May be higher.

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.

The thermoplastic resin contained in the first adhesive composition and the first layer 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 first adhesive composition, the ratio of the content of the polymer component (a) to the total content (total mass) of all components other than the solvent (that is, the content of the polymer component (a) in the first layer) ) Is preferably from 5 to 20% by mass, more preferably from 6 to 16% by mass, and from 7 to 12% by mass, irrespective of the type of the polymer component (a).

In the first adhesive composition and the first layer, the ratio of the acrylic resin content to the total content (total mass) of the polymer component (a) is preferably 80 to 100% by mass, 85 It is more preferably from ˜100% by mass, even more preferably from 90 to 100% by mass, for example, from 95 to 100% by mass.

(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 first adhesive composition and the first layer may be only one type, two or more types, and when two or more types, the combination and ratio thereof are as follows. Can be arbitrarily 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.

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 first layer is improved by using an 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 viewpoint of the curability of the first layer and the strength and heat resistance of the cured product of the first layer. It is more preferably 10,000, and particularly preferably 500 to 3,000.

In the present specification, the number average molecular weight is a polystyrene conversion 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, “epoxy equivalent” means the number of grams (g / eq) of an epoxy compound containing one equivalent of an epoxy group, and can be measured according to the method of JIS K 7236: 2001.

1 type may be sufficient as the epoxy resin (b1) which a 1st adhesive composition and a 1st layer contain, and when it is 2 types or more, those combinations and ratios can be selected arbitrarily. .
As one aspect, the epoxy resin (b1) is selected from the group consisting of a bisphenol A type epoxy resin, a polyfunctional aromatic type (triphenylene type) epoxy resin, a bisphenol F type epoxy resin, and a dicyclopentadiene type epoxy resin. At least one is preferred.

・ Thermosetting agent (b2)
The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b1).
As a thermosetting agent (b2), the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. 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, and aralkyl type phenol resins. .
Among the thermosetting agents (b2), examples of the amine-based curing agent having an amino group include dicyandiamide (may be 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 the unsaturated hydrocarbon group described above.

When a phenolic curing agent is used as the thermosetting agent (b2), the thermosetting agent (b2) has a high softening point or glass transition temperature because it makes it easy to adjust the adhesive force of the die bonding film. Is preferred.

Of the thermosetting agent (b2), for example, the number average molecular weight of the resin component such as polyfunctional phenolic resin, novolac type phenolic resin, dicyclopentadiene type phenolic resin, aralkyl type phenolic resin is preferably 300 to 30000. 400 to 10,000 is more preferable, and 500 to 3000 is particularly preferable.
Among the thermosetting agents (b2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

Only 1 type may be sufficient as the thermosetting agent (b2) which a 1st adhesive composition and a 1st layer contain, and when it is 2 or more types, those combinations and ratios are selected arbitrarily. it can.

Among the thermosetting agents (b2), as a phenol resin, for example, an alkyl group or the like with respect to a carbon atom adjacent to a carbon atom to which a phenolic hydroxyl group is bonded (a carbon atom constituting a benzene ring skeleton) In the present specification, a substituent having a steric hindrance in the vicinity of the phenolic hydroxyl group (may be abbreviated as “sterically hindered phenol resin”) may be used. Examples of such sterically hindered phenol resins include o-cresol type novolac resins.

In the first adhesive composition and the first layer, the content of the thermosetting agent (b2) is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the epoxy resin (b1). It is more preferably from 160 to 160 parts by mass, further preferably from 20 to 120 parts by mass, and particularly preferably from 25 to 80 parts by mass. When the content of the thermosetting agent (b2) is equal to or greater than the lower limit, the curing of the first layer is more likely to proceed. When the content of the thermosetting agent (b2) is equal to or lower than the upper limit value, the moisture absorption rate of the first layer is reduced, and the reliability of the package obtained using the first layer is further improved.

In the first adhesive composition and the first layer, the content of the epoxy thermosetting resin (b) (the total content of the epoxy resin (b1) and the thermosetting agent (b2)) is the polymer component (a). The content is preferably 400 to 1200 parts by weight, more preferably 500 to 1100 parts by weight, still more preferably 600 to 1000 parts by weight, for example, 600 to 900 parts per 100 parts by weight. It may be any one of mass parts and 800 to 1000 mass parts. When the content of the epoxy thermosetting resin (b) is in such a range, it is easier to adjust the adhesive force between the first layer and a support sheet or a dicing sheet described later. Become.

When using the sterically hindered phenol resin, the ratio of the content of the sterically hindered phenol resin to the total content (total mass) of the thermosetting agent (b2) in the first adhesive composition and the first layer is For example, it may be any one of 80 to 100% by mass, 85 to 100% by mass, 90 to 100% by mass, and 95 to 100% by mass.
In the first adhesive composition and the first layer, the ratio of the content of the o-cresol type novolac resin to the total content (total mass) of the thermosetting agent (b2) is 80 to 100% by mass, 85 It may be any of ˜100 mass%, 90˜100 mass%, and 95˜100 mass%.

In order to improve the various physical properties, the first layer contains, in addition to the polymer component (a) and the epoxy-based thermosetting resin (b), other components not corresponding to these as necessary. May be.
Examples of other components contained in the first layer include a curing accelerator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), an energy ray curable resin (g), and light. Examples thereof include a polymerization initiator (h) and a general-purpose additive (i). Among these, preferable other components include a curing accelerator (c), a filler (d), a coupling agent (e), and a general-purpose additive (i).

(Curing accelerator (c))
The curing accelerator (c) is a component for adjusting the curing rate of the first 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; clathrate compounds to the imidazoles guest compound.

Only 1 type may be sufficient as the hardening accelerator (c) which a 1st adhesive composition and 1st layer contain, and when it is 2 or more types, those combinations and ratios are selected arbitrarily. it can.

When the curing accelerator (c) is used, in the first adhesive composition and the first layer, the content of the curing accelerator (c) is 100 parts by mass of the epoxy thermosetting resin (b). The content is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass. 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. 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) adheres to the adherend in the first layer under high temperature and high humidity conditions. The effect of suppressing movement to the interface side and segregation is increased, and the reliability of the package obtained using the first layer is further improved.

Among the above, in the inclusion compound using the imidazole as a guest compound, imidazoles which are active ingredients are included by the host compound. Therefore, it is presumed that the reaction site of imidazoles is not exposed or the degree of exposure is suppressed except during the reaction. As a result, when the inclusion compound is used as the curing accelerator (c), the progress of the reaction other than the intended purpose of the curing accelerator (c) is suppressed during storage of the first layer, whereby the first layer It is presumed that the storage stability of is higher.

Examples of the clathrate compound include those having imidazoles as a guest compound and carboxylic acid as a host compound.

The carboxylic acid that is a host compound is preferably an aromatic carboxylic acid.
The aromatic carboxylic acid may be either a monocyclic aromatic carboxylic acid or a polycyclic aromatic carboxylic acid.
The aromatic carboxylic acid includes a carboxylic acid having only an aromatic hydrocarbon ring as a ring skeleton, a carboxylic acid having only an aromatic heterocycle as a ring skeleton, and an aromatic hydrocarbon ring and an aromatic heterocycle as a ring skeleton. Any of the carboxylic acids possessed together may be used.

The aromatic carboxylic acid is preferably an aromatic hydroxycarboxylic acid.
The aromatic hydroxycarboxylic acid is not particularly limited as long as it is an aromatic carboxylic acid having both a hydroxyl group and a carboxy group in one molecule, but is a carboxyl having a structure in which both a hydroxyl group and a carboxy group are bonded to an aromatic ring skeleton. An acid is preferred.

Preferable examples of the inclusion compound include, for example, that the imidazole is 2-phenyl-4-methyl-5-hydroxymethylimidazole (in this specification, sometimes abbreviated as “2P4MHZ”), An inclusion compound in which the carboxylic acid is 5-hydroxyisophthalic acid (sometimes abbreviated as “HIPA” in this specification), and 2 molecules of 2P4MHZ and 1 molecule of HIPA More preferably, the clathrate compound is constituted.

When the inclusion compound is used, the ratio of the inclusion compound content to the total content (total mass) of the curing accelerator (c) in the first adhesive composition and the first layer is 80 to 100. Any of mass%, 85 to 100 mass%, 90 to 100 mass%, and 95 to 100 mass% may be used.
And in the first adhesive composition and the first layer, the ratio of the content of the inclusion compound composed of the above-mentioned 2P4MHZ and HIPA to the total content (total mass) of the curing accelerator (c) is: It may be any of 80 to 100% by mass, 85 to 100% by mass, 90 to 100% by mass, and 95 to 100% by mass.

(Filler (d))
Since the first layer contains the filler (d), it is easy to adjust the thermal expansion coefficient. By optimizing the thermal expansion coefficient for the first layer, the first layer The reliability of the package obtained by using is further improved. Moreover, the moisture absorption rate of the 1st layer after hardening can also be reduced or heat dissipation can be improved because a 1st layer contains 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 average particle diameter of the filler (d) is not particularly limited, but is preferably 1 to 1000 nm, more preferably 5 to 800 nm, still more preferably 10 to 600 nm, for example, 10 to 400 nm. Or any of 10 to 200 nm. As another aspect, the average particle size of the filler (d) may be 50 to 500 nm. When the average particle diameter of the filler (d) is in such a range, the adjustment of the thermal expansion coefficient, the moisture absorption rate, and the heat dissipation becomes easier.
In the present specification, “average particle size” means the value of the particle size (D ₅₀ ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified. .

The filler (d) contained in the first adhesive composition and the first layer may be only one kind, or two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected. .

In the case of using the filler (d), in the first adhesive composition, the ratio of the content of the filler (d) to the total content (total mass) of all components other than the solvent (that is, the filling of the first layer) The content of the material (d)) is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and particularly preferably 15 to 30% by mass. When the content of the filler (d) is in such a range, the adjustment of the thermal expansion coefficient, the moisture absorption rate, and the heat dissipation becomes easier.

When the filler (d) having an average particle diameter of 1 to 1000 nm is used, the average particle diameter is 1 with respect to the total content (total mass) of the filler (d) in the first adhesive composition and the first layer. The content ratio of the filler (d) that is ˜1000 nm is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, and further preferably 90 to 100% by mass. For example, it may be 95 to 100% by mass.

(Coupling agent (e))
By including the coupling agent (e), the first layer improves the adhesion and adhesion to the adherend. Moreover, when the first layer contains the coupling agent (e), the cured product has improved 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, oligomer type Or a polymer type organosiloxane etc. are mentioned.
The oligomer type or polymer type organosiloxane is an organosiloxane having an oligomer structure or a polymer structure, which can be regarded as formed by polymerization reaction of a polymerizable compound.

The coupling agent (e) contained in the first adhesive composition and the first layer may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrarily selected. it can.
In one aspect, the coupling agent (e) includes 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and an oligomeric silane cup having an epoxy group, a methyl group, and a methoxy group. At least one selected from the group consisting of ring agents is preferred.

When the coupling agent (e) is used, the content of the coupling agent (e) in the first adhesive composition and the first layer is that of the polymer component (a) and the epoxy thermosetting resin (b). The total 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 100 parts by mass. . When the content of the coupling agent (e) is not less than the lower limit, improvement in dispersibility of the filler (d) in the resin, improvement in adhesion to the adherend of the first layer, etc. The effect by using the coupling agent (e) is more remarkably obtained. Generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (e) is below the said upper limit.

When the oligomer type or polymer type organosiloxane is used, the oligomer type or polymer type organosiloxane is contained in the first adhesive composition and the first layer with respect to the total content (total mass) of the coupling agent (e). The proportion of the amount may be any of 25 to 100% by mass and 40 to 100% by mass.

(Crosslinking agent (f))
As the polymer component (a), those having functional groups such as vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxy group, isocyanate group and the like that can be bonded to other compounds such as the above-mentioned acrylic resin. When used, the first adhesive composition and the first layer may contain a cross-linking agent (f) for cross-linking the functional group with another compound. By crosslinking using the crosslinking agent (f), the initial adhesive force and cohesive force of the first layer can be adjusted.

Examples of the crosslinking agent (f) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate crosslinking agent (that is, a crosslinking agent having a metal chelate structure), and an aziridine crosslinking agent (that is, having an aziridinyl group). A crosslinking agent).

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. Examples of the adduct include a 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 easily formed in the first layer by the reaction between the cross-linking agent (f) and the polymer component (a). Can be introduced.

Only 1 type may be sufficient as the crosslinking agent (f) which a 1st adhesive composition and a 1st layer contain, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily. .

In the first adhesive composition and the first layer, the content of the crosslinking agent (f) is preferably 0 to 5 parts by mass with respect to 100 parts by mass of the polymer component (a). Is more preferably 3 parts by mass, further preferably 0-1 part by mass, and 0 parts by mass, that is, the first adhesive composition and the first layer contain the crosslinking agent (f). It is particularly preferred not to do so. When the content of the crosslinking agent (f) is equal to or less than the upper limit value, the embeddability of the substrate of the first layer becomes higher.

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

The energy beam curable resin (g) is obtained by polymerizing (curing) an energy beam curable compound.
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; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate Oligoester (meth) acrylate; urethane (meth) acrylate oligomer, epoxy-modified (meth) acrylate; the polyalkylene glycol (meth) Polyether (meth) acrylates other than the acrylates; itaconic acid oligomer, and the like.

The weight average molecular weight of the energy ray curable resin (g) is preferably 100 to 30000, and more preferably 300 to 10000.

Only 1 type may be sufficient as energy beam curable resin (g) which a 1st adhesive composition contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
As one aspect, the energy ray curable resin (g) is preferably at least one selected from the group consisting of tricyclodecane dimethylol diacrylate and ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate. .

When the energy beam curable resin (g) is used, the content of the energy beam curable resin (g) in the first adhesive composition is 1 to 95 mass with respect to the total mass of the first adhesive composition. %, More preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.

(Photopolymerization initiator (h))
When the first adhesive composition contains the energy ray curable resin (g), the first adhesive composition contains the photopolymerization initiator (h) in order to efficiently advance the polymerization reaction of the energy ray curable resin (g). May be.

Examples of the photopolymerization initiator (h) in the first adhesive composition include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl, benzoin dimethyl ketal, and the like. 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-Trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other acyl phosphine oxide compounds; benzylphenyl sulfide, tetramethylthiuram mono Sulfide compounds such as rufide; 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; diketones such as diacetyl Compound; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 1-chloroanthraquinone, 2 -Quinone compounds such as 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 a 1st adhesive composition contains, and when it is 2 or more types and they are 2 or more types, those combinations and ratios can be selected arbitrarily.
As one aspect, the photopolymerization initiator (h) is preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1.

When the photopolymerization initiator (h) is used, the content of the photopolymerization initiator (h) in the first adhesive composition and the first layer is 100 parts by mass of the energy ray curable resin (g). On the other hand, it is preferably 0.1 to 20 parts by mass, more preferably 1 to 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, and is not particularly limited. Preferred general-purpose additives (I) include, for example, plasticizers, antistatic agents, antioxidants, colorants (dyes and pigments), gettering agents and the like.

The general-purpose additive (i) contained in the first adhesive composition and the first layer may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrarily selected. it can.
The contents of the first adhesive composition and the general-purpose additive (i) in the first layer are not particularly limited, and may be appropriately selected depending on the purpose.

(solvent)
The first adhesive composition preferably further contains a solvent. The first adhesive composition containing the 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. Alcohols; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (that is, compounds having an amide bond).
Only 1 type may be sufficient as the solvent which a 1st adhesive composition contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be selected arbitrarily.

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

Examples of the preferred first adhesive composition include those containing a polymer component (a), an epoxy thermosetting resin (b), a curing accelerator (c) and a coupling agent (e). In addition to these, those containing one or both of the filler (d) and the general-purpose additive (i) are also included.

<< Method for Producing First Adhesive Composition >>
A 1st 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.

◎ Second layer (second film)
As described above, the second layer (second film) has adhesiveness and energy ray curability.
Further, the second layer may have thermosetting properties (may be thermosetting) or may not have thermosetting properties (may be non-thermosetting).
Especially, it is preferable that a 2nd layer does not have thermosetting, but has energy-beam sclerosis | hardenability.

Any of the second layer having no curability and the uncured second layer having the curability can be applied by lightly pressing the various adherends.
Moreover, the 2nd layer may be what can be stuck on various adherends by heating and softening irrespective of the presence or absence of hardening.
Both the second layer having no curability and the cured product of the second layer having curability can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

The test laminate that defines the adhesive strength after immersion to be 6 N / 25 mm or more is prepared as follows.
That is, a second layer having a thickness of 10 μm and a width wider than 25 mm is prepared as a test piece.
A 2nd layer is prepared as a laminated body with a peeling film, for example, By using this laminated body, the laminated body for a test can be produced more easily. In this case, the release film may be removed at an appropriate timing.

The length of the test piece is not particularly limited as long as a peeling test described later can be performed stably, but is preferably 15 cm or more and 30 cm or less, for example.

Next, this test piece is attached to a silicon mirror wafer.
The test piece is preferably attached to a silicon mirror wafer while being heated to 35 to 45 ° C.
Moreover, the sticking speed and sticking pressure when sticking a test piece on a silicon mirror wafer are not particularly limited. For example, the sticking speed is preferably 5 to 20 mm / s, and the sticking pressure is preferably 0.1 to 1.0 MPa.

Next, a strip-shaped strong adhesive tape having a width of 25 mm is applied to the exposed surface (surface opposite to the silicon mirror wafer side) of the test piece after application (that is, the second layer after application of the silicon mirror wafer). .

Next, a strip-shaped cut having a width of 25 mm is formed along the outer periphery of the strong adhesive tape on the test piece (second layer) after the strong adhesive tape is applied. This notch is formed in the whole area of the test piece in the thickness direction. That is, the test piece is cut into a strip shape with a width of 25 mm.

Next, the cut test piece is immersed in pure water at 23 ° C. for 2 hours together with the silicon mirror wafer (in other words, the silicon mirror wafer provided with the cut test piece). At this time, the silicon mirror wafer provided with the cut specimen is submerged in pure water (in other words, the whole specimen after cutting and the entire silicon mirror wafer are both submerged in pure water. So that it is placed in pure water.
It is preferable that the silicon mirror wafer provided with the cut specimen is immediately immersed in pure water immediately after its production. By doing in this way, the said adhesive force of the laminated body for a test can be measured with higher precision.
The silicon mirror wafer provided with the test piece after cutting is preferably immersed in pure water in a dark place. By doing in this way, the said adhesive force of the laminated body for a test can be measured with higher precision.

The silicon mirror wafer provided with the cut test piece is dipped in pure water for 2 hours, and then pulled up from the pure water. If extra water droplets are attached to the surface, the water droplets are removed.
Next, the strip-shaped test piece is cured with energy rays by irradiating the cut test piece (second layer) with energy rays.

The irradiation conditions of energy rays are not particularly limited as long as the test piece is sufficiently cured with energy rays. For example, the energy ray illuminance during energy ray curing is preferably 4 to 280 mW / cm ² . The amount of energy rays during energy ray curing is preferably 3 to 1000 mJ / cm ² .

As described above, a test laminate in which the cured product of the test piece (second layer) is stuck on the silicon mirror wafer and immersed in pure water is obtained.

So far, the case where the second layer is used as a laminate with the release film has been described, but the second layer may be used in the form of a laminate with the first layer, that is, a die bonding film. Thus, when the die bonding film is used for the measurement of the adhesive force, the strong adhesive tape is not the exposed surface of the second layer, but the exposed surface of the first layer (on the side opposite to the second layer side). Affixed to the surface). Further, when the test piece (second layer) is cut into a strip shape, a cut is formed in the entire thickness direction of the die bonding film (the first layer and the second layer in the thickness direction). What is necessary is just to cut | disconnect the whole bonding film in strip shape. Further, as in the case of the second layer alone, the die bonding film may be used as a laminate with the release film. In this case, the release film may be removed at an appropriate timing.

The post-immersion adhesive strength of the test laminate is measured as follows.
That is, a strong adhesive tape is pulled at a peeling (tensile) speed of 300 mm / min in this test laminate at normal temperature (for example, at 23 ° C.), and a release surface is generated in the test laminate. At this time, so-called 180 ° peeling is performed by pulling the strong adhesive tape so that the newly generated peeling surfaces form an angle of 180 °. In other words, the strong adhesive tape pulls one end toward the other end. And the peeling force (load, N / 25 mm) measured when interface peeling occurs between the cured product of the second layer and the silicon mirror wafer is used as the adhesive force after immersion (into pure water). Adhesion between the second layer cured product having a width of 25 mm and the silicon mirror wafer in the test laminate after immersion is adopted.
The strong adhesive tape can be pulled by using, for example, a known tensile tester.

Up to here, the measurement method of the adhesive strength (adhesive strength after immersion) between the cured product of the second layer and the silicon mirror wafer of the test laminate that has been immersed in pure water has been described. A test laminate that has not been immersed in pure water (may be abbreviated as “non-immersion test laminate” in this specification) is a second layer having a width of 25 mm in the same manner. The adhesive force between the cured product and the silicon mirror wafer (in this specification, sometimes abbreviated as “non-immersion adhesive force”) (N / 25 mm) can be measured. The non-immersion adhesive strength can be measured by the same method as in the case of the above-mentioned post-immersion adhesive strength except that a test laminate that has not been immersed in pure water is used.

In the non-immersion test laminate, for example, instead of performing a process of immersing in pure water at 23 ° C. for 2 hours for a silicon mirror wafer provided with a test piece after cutting, in a dark place in an air atmosphere, It can be produced by the same method as in the case of the test laminate except that the step of standing still for 30 minutes under conditions of a temperature of 23 ° C. and a relative humidity of 50% is performed.

In both the measurement of the post-immersion adhesive strength and the non-immersion adhesive strength, the interface peeling between the cured product of the second layer and the silicon mirror wafer (in this specification, “ In addition to “peeling with a silicon mirror wafer”, there may be interface peeling between the strong adhesive tape and its adjacent layer (for example, a cured product of the second layer, the first layer, etc.) (this specification) In some cases, it may be referred to as “peeling with a strong adhesive tape”), cohesive failure in the cured product of the second layer, or the like.
When the adhesive force between the cured product of the second layer and the silicon mirror wafer is sufficiently large, during the peeling test, for example, peeling with a silicon mirror wafer (the cured product of the second layer and the silicon mirror wafer) In addition to the interfacial peeling between the two and the second layer, before the cohesive failure occurs in the cured product of the second layer, the peeling with the strong adhesive tape (the interfacial peeling between the strong adhesive tape and its adjacent layer). ) Is likely to occur.
In this case, if the peeling force when peeling with the strong adhesive tape occurs is 6 N / 25 mm or more, the adhesive force between the cured product of the second layer having a width of 25 mm and the silicon mirror wafer. However, it can be judged that it is 6 N / 25 mm or more.
On the other hand, when the adhesive force between the cured product of the second layer and the silicon mirror wafer is small, during the peeling test, for example, the peeling on the silicon mirror wafer is performed before peeling with the strong adhesive tape occurs. It is likely to occur.

The post-immersion adhesive strength is 6 N / 25 mm or more, preferably 7 N / 25 mm or more, more preferably 8 N / 25 mm or more, and further preferably 9 N / 25 mm or more. When the post-immersion adhesive strength is equal to or more than the lower limit value, transferability of the cured product of the second layer to the semiconductor chip becomes higher when picking up a semiconductor chip having a small size.

The upper limit value of the adhesive strength after immersion is not particularly limited.
For example, in the case of the cured product of the second layer having an adhesive strength after immersion of 20 N / 25 mm or less, it is easier to obtain the constituent materials.

The post-immersion adhesive strength can be appropriately adjusted within a range set by arbitrarily combining the above-described preferable lower limit value and upper limit value. For example, the adhesive strength after immersion is preferably 6 to 20 N / 25 mm, more preferably 7 to 20 N / 25 mm, still more preferably 8 to 20 N / 25 mm, and particularly preferably 9 to 20 N / 25 mm. Another aspect may be 10 to 20 N / 25 mm. However, these are examples of the adhesive strength after immersion.

The non-immersion adhesive strength is not particularly limited, but is preferably equal to or greater than the post-immersion adhesive strength.
For example, the non-immersion adhesive strength is any one of 6 N / 25 mm or more, 7 N / 25 mm or more, 8 N / 25 mm or more, and 9 N / 25 mm or more, and equal to or more than the adhesive strength after immersion. Also good.
Further, the non-immersion adhesive strength is 20 N / 25 mm or less, and may be equal to or greater than the post-immersion adhesive strength.
The non-immersion adhesive strength is any of 6 to 20 N / 25 mm, 7 to 20 N / 25 mm, 8 to 20 N / 25 mm, and 9 to 20 N / 25 mm, and is equivalent to the adhesive strength after immersion. It may be the above. Another aspect may be 10 to 20 N / 25 mm.

As one aspect, the die bonding film which is one embodiment of the present invention,
The second layer may have such characteristics that the post-immersion adhesive strength is 6 to 20 N / 25 mm, and the non-immersion adhesive strength is 6 to 20 N / 25 mm.

The second layer may be composed of one layer (single layer), or may be composed of two or more layers, and when composed of a plurality of layers, these layers may be the same as or different from each other. The combination of the multiple layers is not particularly limited.

The thickness of the second layer is not particularly limited, but is preferably 1 to 40 μm, more preferably 3 to 30 μm, and particularly preferably 5 to 20 μm. When the thickness of the second layer is equal to or more than the lower limit value, the adhesion to the adherend (semiconductor wafer, semiconductor chip) of the second layer becomes higher, and as a result, when picking up a semiconductor chip having a small size. The transferability of the cured product of the second layer to the semiconductor chip becomes higher. When the thickness of the second layer is less than or equal to the above upper limit value, the second layer (die bonding film) can be more easily cut in the semiconductor chip manufacturing process described later, and a cut piece derived from the second layer Can be further reduced.
Here, the “thickness of the second layer” means the thickness of the entire second layer. For example, the thickness of the second layer composed of a plurality of layers is the sum of all the layers constituting the second layer. Means the thickness.

A 2nd layer (2nd film) can be formed from the 2nd adhesive composition containing the constituent material. For example, a 2nd layer can be formed in the target site | part by applying a 2nd adhesive composition to the formation object surface of a 2nd layer, and making it dry as needed.
In the second adhesive composition, the ratio of the contents of the components that do not vaporize at room temperature is usually the same as the ratio of the contents of the components of the second layer.

The second adhesive composition can be applied in the same manner as in the case of the first adhesive composition, and the drying conditions of the second adhesive composition may be the same as the drying conditions of the first adhesive composition. it can.
Next, the second adhesive composition will be described in detail.

<< Second Adhesive Composition >>
The kind of 2nd adhesive composition can be selected according to the characteristic of a 2nd layer, such as the presence or absence of the thermosetting of a 2nd layer.
The second adhesive composition has energy ray curability and may have both energy ray curability and thermosetting properties.
As a content component of a 2nd adhesive composition and a 2nd layer, the same thing as the content component of the above-mentioned 1st adhesive composition and a 1st layer is mentioned. And the effect which the containing component show | plays is the same as the case of a 1st adhesive composition and a 1st layer.
As a 2nd adhesive composition, what contains a polymer component (a), a filler (d), energy-beam curable resin (g), and a photoinitiator (h) is mentioned, for example.

(Polymer component (a))
The polymer component (a) in the second adhesive composition and the second layer is the same as the polymer component (a) in the first adhesive composition and the first layer.

The polymer component (a) contained in the second adhesive composition and the second layer may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrarily selected. it can.

In the second adhesive composition, the ratio of the content of the polymer component (a) to the total content (total mass) of all components other than the solvent (that is, the content of the polymer component (a) in the second layer) ) Is preferably 10 to 45% by mass, more preferably 15 to 40% by mass, and particularly preferably 20 to 35% by mass, regardless of the type of the polymer component (a).

In the second adhesive composition and the second layer, the ratio of the acrylic resin content to the total content (total mass) of the polymer component (a) is preferably 80 to 100% by mass, 85 It is more preferably from ˜100% by mass, even more preferably from 90 to 100% by mass, for example, from 95 to 100% by mass.

(Filler (d))
The filler (d) in the second adhesive composition and the second layer is the same as the filler (d) in the first adhesive composition and the first layer.

As for the filler (d) which a 2nd adhesive composition and a 2nd layer contain, 1 type may be sufficient, and 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily. .

In the second adhesive composition, the ratio of the content of the filler (d) to the total content (total mass) of all components other than the solvent (that is, the content of the filler (d) in the second layer) is 25 to 70% by mass, more preferably 35 to 67% by mass, and particularly preferably 45 to 64% by mass. When the content of the filler (d) is within such a range, it becomes easier to adjust the thermal expansion coefficient, the moisture absorption rate, and the heat dissipation of the second layer.

When the filler (d) having an average particle diameter of 1 to 1000 nm is used, the average particle diameter is 1 with respect to the total content (total mass) of the filler (d) in the second adhesive composition and the second layer. The content ratio of the filler (d) that is ˜1000 nm is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, and further preferably 90 to 100% by mass. For example, it may be 95 to 100% by mass.

(Energy ray curable resin (g))
The energy ray curable resin (g) in the second adhesive composition and the second layer is the same as the energy ray curable resin (g) in the first adhesive composition and the first layer.

The energy ray curable resin (g) contained in the second adhesive composition and the second layer may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof are arbitrary. Can be selected.
In one aspect, the energy ray curable resin (g) contained in the second adhesive composition and the second layer is composed of tricyclodecane dimethylol diacrylate and ε-caprolactone modified tris- (2-acryloxyethyl) isocyanate. At least one selected from the group consisting of nurate is preferred.

In the second 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 the second adhesive composition, and 3 to 90% by mass. More preferred is 5 to 85% by mass.

(Photopolymerization initiator (h))
The photopolymerization initiator (h) in the second adhesive composition and the second layer is the same as the photopolymerization initiator (h) in the first adhesive composition and the first layer.

1 type may be sufficient as the photoinitiator (h) which a 2nd adhesive composition and a 2nd layer contain, and when it is 2 or more types, those combinations and ratios are arbitrary. You can choose.
As one aspect, the photopolymerization initiator (h) in the second adhesive composition and the second layer is preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1.

In the second adhesive composition and the second layer, the content of the photopolymerization initiator (h) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the energy beam curable resin (g). It is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass.

In order to improve the various physical properties of the second layer, in addition to the polymer component (a), the filler (d), the energy ray curable resin (g) and the photopolymerization initiator (h), if desired, Other components not corresponding to these may be contained.
Examples of other components contained in the second layer include a coupling agent (e), an epoxy thermosetting resin (b), a curing accelerator (c), a crosslinking agent (f), and a general-purpose additive (i). Etc.
Among these, preferable other components include a coupling agent (e) and a general-purpose additive (i).

(Coupling agent (e))
The coupling agent (e) in the second adhesive composition and the second layer is the same as the coupling agent (e) in the first adhesive composition and the first layer.
Among these, the coupling agent (e) is preferably an oligomer type or polymer type organosiloxane.

The coupling agent (e) contained in the second adhesive composition and the second layer may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrarily selected. it can.

When the coupling agent (e) is used, in the second adhesive composition and the second layer, the content of the coupling agent (e) is 0 with respect to 100 parts by mass of the polymer component (a). The amount is preferably 1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and particularly preferably 1 to 10 parts by mass. Since the content of the coupling agent (e) is not less than the lower limit, improvement in dispersibility of the filler (d) in the resin, improvement in adhesion with the adherend of the second layer, etc. The effect by using the coupling agent (e) is more remarkably obtained. Generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (e) is below the said upper limit.

When the oligomer type or polymer type organosiloxane is used as the coupling agent (e), the oligomer with respect to the total content (total mass) of the coupling agent (e) in the second adhesive composition and the second layer. The content ratio of the mold-type or polymer-type organosiloxane may be any of 25 to 100% by mass and 40 to 100% by mass.

(Epoxy thermosetting resin (b) (epoxy resin (b1) and thermosetting agent (b2))
The epoxy thermosetting resin (b) is composed of an epoxy resin (b1) and a thermosetting agent (b2).
The epoxy-based thermosetting resin (b) (epoxy resin (b1), thermosetting agent (b2)) in the second adhesive composition and the second layer is the epoxy-based heat in the first adhesive composition and the first layer. It is the same as curable resin (b) (epoxy resin (b1), thermosetting agent (b2)).

Each of the epoxy resin (b1) and the thermosetting agent (b2) contained in the second adhesive composition and the second layer may be only one type, two or more types, or two or more types. These combinations and ratios can be arbitrarily selected.

When using the epoxy resin (b1) and the thermosetting agent (b2), the content of the thermosetting agent (b2) in the second adhesive composition and the second layer is 100 parts by mass of the epoxy resin (b1). The amount is preferably 10 to 200 parts by mass. When the content of the thermosetting agent (b2) is equal to or greater than the lower limit, the curing of the second layer is more likely to proceed. When the content of the thermosetting agent (b2) is equal to or lower than the upper limit value, the moisture absorption rate of the second layer is reduced, and the reliability of the package obtained using the second layer is further improved.

When the epoxy resin (b1) and the thermosetting agent (b2) are used, the content of the epoxy thermosetting resin (b) in the second adhesive composition and the second layer (the epoxy resin (b1) and the thermosetting agent The total content of (b2) is preferably 400 to 1200 parts by mass with respect to 100 parts by mass of the polymer component (a). When the content of the epoxy thermosetting resin (b) is within such a range, it becomes easier to adjust the adhesive force of the second layer.

(Curing accelerator (c))
When a 2nd adhesive composition and a 2nd layer contain an epoxy-type thermosetting resin (b), it is preferable to contain a hardening accelerator (c).
The curing accelerator (c) in the second adhesive composition and the second layer is the same as the curing accelerator (c) in the first adhesive composition and the first layer.

Only one type of curing accelerator (c) contained in the second adhesive composition and the second layer may be used, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrarily selected. it can.

When the curing accelerator (c) is used, the content of the curing accelerator (c) in the second adhesive composition and the second layer is based on 100 parts by mass of the epoxy thermosetting resin (b). The content is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass. 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. 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) adheres to the adherend in the second layer under high temperature and high humidity conditions. The effect of suppressing movement to the interface side and segregation is enhanced, and the reliability of the package obtained using the second layer is further improved.

(Crosslinking agent (f))
The crosslinking agent (f) in the second adhesive composition and the second layer is the same as the crosslinking agent (f) in the first adhesive composition and the first layer.

As for the crosslinking agent (f) contained in the second adhesive composition and the second layer, only one type may be used, or two or more types may be used, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. .

In the second adhesive composition and the second layer, the content of the crosslinking agent (f) is preferably 0 to 5 parts by mass with respect to 100 parts by mass of the polymer component (a).

(General-purpose additive (i))
The general-purpose additive (i) in the second adhesive composition and the second layer is the same as the general-purpose additive (i) in the first adhesive composition and the first layer.

The general-purpose additive (i) contained in the second adhesive composition and the second layer may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrarily selected. it can.
The contents of the second adhesive composition and the general-purpose additive (i) in the second layer are not particularly limited, and may be appropriately selected depending on the purpose.

(solvent)
It is preferable that the second adhesive composition further contains a solvent. The second adhesive composition containing the solvent has good handleability.
The solvent in the second adhesive composition is the same as the solvent in the first adhesive composition.

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

As an example of a preferable second adhesive composition, a polymer component (a), a filler (d) an energy ray curable resin (g), a photopolymerization initiator (h), and a coupling agent (e) are contained. In addition to these, those containing the general-purpose additive (i) are also included.

<< Method for Producing Second Adhesive Composition >>
A 2nd adhesive composition can be manufactured by the same method as the case of the above-mentioned 1st adhesive composition.

The thickness of the die bonding film (the total thickness of the first layer and the second layer) is preferably 2 to 80 μm, more preferably 6 to 60 μm, and particularly preferably 10 to 40 μm. .

FIG. 1 is a cross-sectional view schematically showing a die bonding film according to an embodiment of the present invention. In addition, in order to make the features of the present invention easier to understand, the drawings used in the following description may show the main portions in an enlarged manner for convenience, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.

The die bonding film 13 shown here includes a first layer 131, and includes a second layer 132 on the first layer 131.
The die bonding film 13 includes a first release film 151 on one surface (sometimes referred to as a “first surface” in this specification) 13a, and the other side opposite to the first surface 13a. The second release film 152 is provided on the surface 13b (may be referred to as “second surface” in this specification).
Such a die bonding film 13 is suitable for storing as a roll, for example.

On the surface of the die bonding film 13 opposite to the first layer 131 side of the second layer 132 (which may be referred to as “first surface” in this specification) 132a, the first release film 151 is provided. The second release film 152 is laminated on the surface 131b of the first layer 131 opposite to the second layer 132 side (in this specification, sometimes referred to as “second surface”) 131b. ing.
The second surface 131 b of the first layer 131 is the same as the second surface 13 b of the die bonding film 13, and the first surface 132 a of the second layer 132 is the same as the first surface 13 a of the die bonding film 13.

In the die bonding film 13, the initial detection temperature (T ₀ ) of the first layer is 75 ° C. or lower.
Of the die bonding film 13, the second layer has adhesiveness and energy ray curability, and the post-immersion adhesive strength of the test laminate produced using the test piece of the second layer is 6 N / It is 25 mm or more.

Both the first release film 151 and the second release film 152 may be known ones.
The first release film 151 and the second release film 152 may be the same as each other, or may be different from each other, for example, different peeling forces required for peeling from the die bonding film 13 may be used. Good.

In the die bonding film 13 shown in FIG. 1, the first release film 151 is removed, and in other words, the back surface of the semiconductor wafer (not shown) is attached to the generated exposed surface, in other words, the first surface 132 a of the second layer 132. . And the 2nd peeling film 152 is removed and the exposed surface produced, in other words, the 2nd surface 131b of the 1st layer 131 turns into the sticking surface of the support sheet mentioned later.

◇ Die Bonding Film Manufacturing Method For example, the die bonding film can be manufactured by separately forming and bonding a first layer (first film) and a second layer (second film). The formation method of the layer and the second layer is as described above.

For example, the first layer is previously formed on the release film using the first adhesive composition, and similarly, the second layer is previously formed on the release film using the second adhesive composition. Form it. At this time, these compositions are preferably applied to the release-treated surface of the release film. And, the exposed surface of the formed first layer opposite to the side in contact with the release film, and the opposite side of the formed second layer in contact with the release film. A die bonding film in which the first layer and the second layer are laminated is obtained by bonding the exposed surface.
The release film that is in contact with the first layer and the release film that is in contact with the second layer may be removed at an appropriate timing when the die bonding film is used.

◇ Dicing die bonding sheet A dicing die bonding sheet according to an embodiment of the present invention includes a support sheet, and the support sheet includes the die bonding film, and the first layer in the die bonding film includes: It arrange | positions at the said support sheet side.
The dicing die bonding sheet can be used when dicing a semiconductor wafer.
Hereinafter, each layer constituting the dicing die bonding sheet will be described in detail.

Support sheet The support sheet may be composed of one layer (single layer) or may be composed of two or more layers. When the support sheet is composed of a plurality of layers, the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

Preferred support sheets include, for example, those composed only of a base material; those provided with a base material, and provided with an intermediate layer on the base material.

The support sheet made of only the base material is suitable as a carrier sheet or a dicing sheet. A dicing die bonding sheet provided with a support sheet composed only of such a base material has a surface (namely, the first surface) opposite to the side provided with the support sheet (namely, base material) of the die bonding film. Attached to the back side of the wafer and used.

On the other hand, the support sheet provided with a base material and provided with an intermediate layer on the base material is suitable as a dicing sheet. A dicing die bonding sheet provided with such a support sheet is also used by attaching a surface (first surface) opposite to the side provided with the support sheet of the die bonding film to the back surface of the semiconductor wafer. .

The method of using the dicing die bonding sheet will be described in detail later.
Hereinafter, each layer which comprises a support sheet is demonstrated.

-Base material The base material is in the form of a sheet or film, and examples of the constituent material include various resins.
Examples of the resin include polyethylene such as low density polyethylene (sometimes abbreviated as LDPE), linear low density polyethylene (sometimes abbreviated as LLDPE), and high density polyethylene (sometimes abbreviated as HDPE). Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer Ethylene copolymers such as ethylene-norbornene copolymer (copolymers obtained using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (vinyl chloride as a monomer) Resin obtained by using); polystyrene; Olefins; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalene dicarboxylate, wholly aromatic polyesters in which all structural units have aromatic cyclic groups; Polyester (poly) methacrylate; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone;
Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are mentioned, for example. The polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
Examples of the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.

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 the substrate is composed of a plurality of layers, these layers may be the same or different from each other. The combination of layers is not particularly limited.

The thickness of the substrate is preferably 50 to 300 μm, and more preferably 60 to 150 μm. When the thickness of the substrate is in such a range, the flexibility of the dicing die bonding sheet, the sticking property of the dicing die bonding sheet to the semiconductor wafer or semiconductor chip, and the semiconductor with a cured die bonding film described later The pickup property of the chip is further improved.
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.

The base material is preferably one having high thickness accuracy, that is, one in which variation in thickness is suppressed regardless of the part. Among the above-mentioned constituent materials, examples of materials that can be used to construct such a substrate with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyurethane acrylate, and ethylene. -Vinyl acetate copolymer and the like.

The base material contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent material such as the resin. May be.

The substrate may be transparent or opaque, may be colored according to the purpose, or other layers may be deposited. However, the base material is preferably one that transmits energy rays, and more preferably has high energy ray permeability.

In order to improve the adhesion with other layers such as an intermediate layer provided on the substrate, the substrate is subjected to uneven blasting treatment such as sandblasting treatment, solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment, The surface may be subjected to an oxidation treatment such as ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, or the like.
The base material may have a surface subjected to primer treatment.
In addition, the base material is an antistatic coat layer; a layer that prevents the base material from adhering to other sheets or the base material from adhering to the adsorption table when the dicing die bonding sheet is stored in an overlapping manner. It may have.

The base material can be manufactured by a known method. For example, a base material containing a resin can be produced by molding a resin composition containing the resin.

○ Intermediate layer The intermediate layer is not particularly limited as long as it is disposed between the substrate and the die bonding film and exhibits its function.
More specifically, examples of the intermediate layer include a peelability improving layer and a pressure-sensitive adhesive layer in which at least one surface is peeled.

The peelability improving layer facilitates peeling of the cured die bonding film from the support sheet at the time of picking up a semiconductor chip with a cured die bonding film, which will be described later.
The pressure-sensitive adhesive layer stabilizes the fixing of the semiconductor wafer on the support sheet during dicing, and facilitates peeling of the cured die bonding film from the support sheet when picking up a semiconductor chip with a cured die bonding film. And so on.

-Peelability improvement layer The said peelability improvement layer is a sheet form or a film form.
As the peelability improving layer, for example, a multi-layered structure including a resin layer and a release treatment layer formed on the resin layer; a single layer containing a release agent, etc. Is mentioned. In the dicing die bonding sheet, the peelability improving layer is disposed with the peeled surface facing the die bonding film side.

Among the peelable improvement layers comprising a plurality of layers, the resin layer can be produced by molding or coating a resin composition containing a resin and drying it as necessary.
And the peelability improvement layer which consists of multiple layers can be manufactured by carrying out the peeling process of one surface of the said resin layer.

The release treatment of the resin layer can be performed by various known release agents such as alkyd, silicone, fluorine, unsaturated polyester, polyolefin or wax.
In terms of heat resistance, the release agent is preferably an alkyd, silicone or fluorine release agent.

The resin that is a constituent material of the resin layer may be appropriately selected according to the purpose, and is not particularly limited.
Preferred examples of the resin include polyethylene terephthalate (sometimes abbreviated as PET), polyethylene naphthalate (sometimes abbreviated as PEN), polybutylene terephthalate (sometimes abbreviated as PBT), polyethylene ( PE (sometimes abbreviated as PE), polypropylene (sometimes abbreviated as PP), and the like.

The resin layer may be composed of one layer (single layer), may be composed of two or more layers, and when composed of a plurality of layers, these layers may be the same or different from each other, The combination of these multiple layers is not particularly limited.

The peelability improving layer comprising a single layer can be produced by molding or coating a peelable composition containing a release agent and drying it as necessary.
Examples of the release agent contained in the release composition include the same ones as the above-described various release agents used during the release treatment of the resin layer.
The peelable composition may contain a resin similar to the resin that is a constituent material of the resin layer. That is, the peelability improving layer composed of a single layer may contain a resin in addition to the release agent.

The thickness of the peelability improving layer is preferably 10 to 200 μm, more preferably 15 to 150 μm, and particularly preferably 25 to 120 μm. When the thickness of the peelability improving layer is equal to or more than the lower limit, the action of the peelability improving layer becomes more remarkable, and further, the effect of suppressing breakage such as cutting of the peelability improving layer becomes higher. When the thickness of the peelable improvement layer is not more than the above upper limit value, the pick-up force is easily transmitted to the semiconductor chip with the cured die bonding film when picking up the semiconductor chip with the cured die bonding film, which will be described later. It can be done more easily.
Here, “the thickness of the peelability improving layer” means the total of the resin layer and the release treatment layer when the peelability improvement layer is composed of a plurality of layers including the resin layer and the release treatment layer. Means the thickness. Moreover, when a peelability improvement layer consists of a single layer containing a release agent, the thickness of this single layer is meant.

-Adhesive layer The said adhesive layer is a sheet form or a film form, and contains an adhesive.
Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, ester resins, and acrylic resins are preferable. .

In the present specification, the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin. For example, the resin itself is not only adhesive. In addition, a resin exhibiting tackiness by using in combination with other components such as additives, a resin exhibiting adhesiveness due to the presence of a trigger such as heat or water, and the like are also included.

The pressure-sensitive adhesive layer may be composed of one layer (single layer), may be composed of two or more layers, and when composed of a plurality of layers, these layers may be the same or different from each other. The combination of the multiple layers is not particularly limited.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 μm.
Here, the “thickness of the pressure-sensitive adhesive layer” means the thickness of the whole pressure-sensitive adhesive layer. For example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the total of all layers constituting the pressure-sensitive adhesive layer. Means the thickness.

The pressure-sensitive adhesive layer may be transparent, opaque, or colored depending on the purpose. However, the pressure-sensitive adhesive layer preferably transmits energy rays, and more preferably has high energy ray permeability.

The pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive, or may be formed using a non-energy ray-curable pressure-sensitive adhesive. The pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.

The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, an adhesive layer can be formed in the target site | part by applying an adhesive composition to the formation object surface of an adhesive layer, and making it dry as needed.

So far, the method for forming the peelability improving layer and the pressure-sensitive adhesive layer has been described. However, the present invention is not limited thereto, and the intermediate layer can be formed by using an intermediate layer composition containing the constituent material. For example, the intermediate layer can be formed at the target site by applying the intermediate layer composition to the surface on which the intermediate layer is to be formed and drying it as necessary. Moreover, according to the kind of composition for intermediate | middle layers, an intermediate | middle layer can also be formed by shape | molding this.

Next, an example of the dicing die bonding sheet of the present invention will be described below for each type of support sheet with reference to the drawings.

FIG. 2 is a cross-sectional view schematically showing an embodiment of the dicing die bonding sheet of the present invention.
In FIG. 2 and subsequent figures, the same components as those shown in the already explained figures are given the same reference numerals as those in the already explained figures, and their detailed explanations are omitted.

The dicing die bonding sheet 1 A shown here includes a support sheet 10, and a die bonding film 13 on the support sheet 10. The support sheet 10 is composed only of the base material 11, and in other words, the dicing die bonding sheet 1 A is on one surface (which may be referred to as “first surface” in this specification) 11 a of the base material 11. The die bonding film 13 has a laminated structure. The dicing die bonding sheet 1 A further includes a release film 15 on the die bonding film 13.

In the dicing die bonding sheet 1 A, the first layer 131 is laminated on the first surface 11 a of the substrate 11. In addition, the second layer 132 is laminated on a surface 131 a (which may be referred to as a “first surface” in this specification) on the opposite side to the substrate 11 side of the first layer 131. Further, the jig adhesive layer 16 is laminated on a part of the first surface 132a of the second layer 132 (in other words, the first surface 13a of the die bonding film 13), that is, in the vicinity of the peripheral portion. . Of the first surface 132 a of the second layer 132, the surface on which the jig adhesive layer 16 is not laminated and the surface 16 a of the jig adhesive layer 16 that is not in contact with the die bonding film 13. A release film 15 is laminated on the upper surface and the side surface.
Here, the first surface 11 a of the substrate 11 is also referred to as the first surface 10 a of the support sheet 10.

The release film 15 is the same as the first release film 151 or the second release film 152 shown in FIG.

The adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which layers containing an adhesive component are laminated on both surfaces of a core sheet. It may be of a structure.

In the dicing die bonding sheet 1A, the jig adhesive layer 16 is laminated on the first surface 132a of the second layer 132 (the first surface 13a of the die bonding film 13) with the release film 15 removed. The back surface of the semiconductor wafer (not shown) is attached to the unexposed region, and the upper surface of the surface 16a of the jig adhesive layer 16 is attached to a jig such as a ring frame.

FIG. 3 is a cross-sectional view schematically showing another embodiment of the dicing die bonding sheet of the present invention.
The dicing die bonding sheet 1B shown here is the same as the dicing die bonding sheet 1A shown in FIG. 2 except that the jig adhesive layer 16 is not provided. That is, in the dicing die bonding sheet 1B, the first layer 131 is laminated on the first surface 11a of the base material 11 (the first surface 10a of the support sheet 10), and the first surface 131a of the first layer 131 has the first surface 131a. Two layers 132 are laminated, and the release film 15 is laminated on the entire first surface 132 a of the second layer 132.
In other words, the dicing die bonding sheet 1B is configured by stacking the base material 11, the first layer 131, the second layer 132, and the release film 15 in this order in the thickness direction.

As in the case of the dicing die bonding sheet 1A shown in FIG. 2, the dicing die bonding sheet 1B shown in FIG. 3 is the center side of the first surface 13a of the die bonding film 13 with the release film 15 removed. The rear surface of the semiconductor wafer (not shown) is attached to a part of the region, and the region near the peripheral edge of the die bonding film 13 is attached to a jig such as a ring frame for use.

FIG. 4 is a cross-sectional view schematically showing still another embodiment of the dicing die bonding sheet of the present invention.
The dicing die bonding sheet 1C shown here is the dicing die shown in FIG. 2 except that the intermediate layer 12 is further provided between the base material 11 and the die bonding film 13 (first layer 131). It is the same as the bonding sheet 1A. The support sheet 10 is a laminate of the base material 11 and the intermediate layer 12, and the dicing die bonding sheet 1 C also has a configuration in which the die bonding film 13 is laminated on the first surface 10 a of the support sheet 10.

In the dicing die bonding sheet 1 C, the intermediate layer 12 is laminated on the first surface 11 a of the substrate 11. In addition, the first layer 131 is laminated on a surface 12 a (which may be referred to as a “first surface” in this specification) opposite to the base material 11 side of the intermediate layer 12. Further, the second layer 132 is laminated on the first surface 131 a of the first layer 131. Further, the jig adhesive layer 16 is laminated on a part of the first surface 132a of the second layer 132 (in other words, the first surface 13a of the die bonding film 13), that is, in the vicinity of the peripheral portion. . Of the first surface 132 a of the second layer 132, the surface on which the jig adhesive layer 16 is not laminated and the surface 16 a of the jig adhesive layer 16 that is not in contact with the die bonding film 13. A release film 15 is laminated on the upper surface and the side surface.

In the dicing die bonding sheet 1C, in the case where the intermediate layer 12 is the peelability improving layer composed of a plurality of layers, for example, the layer on the substrate 11 side of the intermediate layer 12 becomes the resin layer (not shown), The layer on the die bonding film 13 (first layer 131) side of the layer 12 becomes the release treatment layer (not shown). Therefore, in this case, the first surface 12a of the intermediate layer 12 is a peeling treatment surface. On the other hand, when the intermediate layer 12 is the single layer peelable improvement layer, the first surface 12a of the intermediate layer 12 is the release treatment surface as described above. Contains a release agent. Thus, when the intermediate layer 12 is a peelability improving layer, the cured die bonding film (the die bonding film 13 in FIG. 4 is cut at the time of picking up a semiconductor chip with a cured die bonding film described later, Further, the second layer 132 in the die bonding film 13 is easily peeled off by energy rays.

The dicing die bonding sheet 1C shown in FIG. 4 has a jig adhesive layer out of the first surface 132a of the second layer 132 (the first surface 13a of the die bonding film 13) with the release film 15 removed. The back surface of a semiconductor wafer (not shown) is pasted in a region where 16 is not laminated, and the top surface of the surface 16a of the jig adhesive layer 16 is stuck to a jig such as a ring frame. Is done.

FIG. 5 is a cross-sectional view schematically showing still another embodiment of the dicing die bonding sheet of the present invention.
The dicing die bonding sheet 1 D shown here is the same as the dicing die bonding sheet 1 C shown in FIG. 4 except that it does not include the jig adhesive layer 16 and the shape of the die bonding film is different. That is, the dicing die bonding sheet 1 D includes the base material 11, the intermediate layer 12 on the base material 11, and the die bonding film 23 on the intermediate layer 12. The support sheet 10 is a laminate of the base material 11 and the intermediate layer 12. The die bonding film 23 is a laminate of a first layer 231 and a second layer 232. The dicing die bonding sheet 1 D also has a configuration in which the die bonding film 23 is laminated on the first surface 10 a of the support sheet 10.

In the dicing die bonding sheet 1D, the intermediate layer 12 is laminated on the first surface 11a of the substrate 11. The first layer 231 is laminated on a part of the first surface 12 a of the intermediate layer 12, that is, in the central region. Further, the second layer 232 is laminated on the first surface 231 a of the first layer 231. And the area | region (the 1st surface 23a and side surface) which is not contacting the intermediate | middle layer 12 among the area | regions where the die bonding film 23 is not laminated | stacked among the 1st surface 12a of the intermediate | middle layer 12, and the die bonding film 23. A release film 15 is laminated on the top.

When the dicing die bonding sheet 1D is viewed from above and viewed in plan, the die bonding film 23 has a surface area smaller than that of the intermediate layer 12, and has a circular shape or the like, for example.

The dicing die bonding sheet 1D shown in FIG. 5 has a semiconductor wafer (not shown) on the first surface 232a (first surface 23a of the die bonding film 23) of the second layer 232 with the release film 15 removed. The back surface is affixed, and the region of the first surface 12a of the intermediate layer 12 where the die bonding film 23 is not laminated is affixed to a jig such as a ring frame and used.

In the dicing die bonding sheet 1D shown in FIG. 5, a jig similar to that shown in FIGS. 2 and 4 is formed on the first surface 12a of the intermediate layer 12 in the region where the die bonding film 23 is not laminated. An adhesive layer may be laminated (not shown). As in the case of the dicing die bonding sheet shown in FIGS. 2 and 4, the dicing die bonding sheet 1 D provided with such a jig adhesive layer has an upper surface on the surface of the jig adhesive layer. Used by sticking to a jig such as a frame.

Thus, the dicing die bonding sheet may be provided with an adhesive layer for jigs, regardless of the form of the support sheet and the die bonding film. However, normally, as shown in FIGS. 2 and 4, the dicing die bonding sheet provided with the jig adhesive layer is preferably provided with the jig adhesive layer on the die bonding film.

The dicing die bonding sheet of the present invention is not limited to that shown in FIGS. 2 to 5, and a part of the configuration shown in FIGS. 2 to 5 is changed or deleted within a range not impairing the effects of the present invention. In addition, another configuration may be added to what has been described so far.

For example, in the dicing die bonding sheet shown in FIGS. 2 to 5, layers other than the base material, the intermediate layer, the die bonding film, and the release film may be provided at any location.
In the dicing die bonding sheet, a gap may be partially formed between the release film and the layer that is in direct contact with the release film.
In the dicing die bonding sheet, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

◇ Manufacturing Method of Dicing Die Bonding Sheet A dicing die bonding sheet can be manufactured, for example, by bonding the die bonding film and a support sheet.

The support sheet provided with the base material and the intermediate layer can be produced by applying the above-mentioned intermediate layer composition on the base material and drying it as necessary. For example, when the intermediate layer is a releasability improving layer, the intermediate layer composition for forming the resin layer is applied on a base material to form the resin layer. A peeling process may be performed.

The support sheet provided with the base material and the intermediate layer can also be produced by the following method.
That is, the intermediate layer is formed on the release film in the same manner as in the above-described intermediate layer formation method except that a release film is used instead of the base material. At this time, the intermediate layer composition is preferably applied to the release-treated surface of the release film.
And the said support sheet can be manufactured by bonding together the exposed surface (surface on the opposite side to the peeling film side) of an intermediate | middle layer, and one surface (1st surface) of a base material.

Moreover, a dicing die bonding sheet can be manufactured, for example, without forming the die bonding film and the support sheet in advance.
For example, an intermediate layer is formed on the release film by the method described above. Furthermore, using the 1st layer (1st film) already formed on the peeling film, the 2nd layer (2nd film) already formed on the peeling film, and the base material, the base material and the intermediate formed The layer, the formed first layer, and the formed second layer are stacked in this order in the thickness direction. At this time, the release film provided in each layer is removed at an appropriate timing as necessary. By the above, a dicing die bonding sheet provided with an intermediate layer is obtained.

◇ Method for Manufacturing Semiconductor Chip The die bonding film and the dicing die bonding sheet of the present invention can be used for manufacturing a semiconductor chip, more specifically, a semiconductor chip with a cured die bonding film.

In the method for manufacturing a semiconductor chip according to an embodiment of the present invention, a laminated body in which a semiconductor wafer is stuck to the second layer and a dicing sheet is stuck to the first layer of the die bonding film (1-1) Or a step of producing a laminate (1-2) in which a semiconductor wafer is adhered to the second layer in the die bonding film of the dicing die bonding sheet (in the present specification, “laminate (1) And may have been cut by cutting the semiconductor wafer in the laminate (1-1) or laminate (1-2) together with the die bonding film with a dicing blade. A step of producing a laminated body (2) including the first layer, the cut second layer, and the semiconductor chip (cut semiconductor wafer) (this specification) In this case, it may be referred to as “laminated body (2) production process”) and the second layer that has been cut in the laminated body (2) is cured by energy ray to obtain a cured product. A step of producing a laminated body (3) provided with the finished first layer, the cured product, and the semiconductor chip (in this specification, sometimes referred to as “laminated body (3) producing step”); In the laminate (3), the semiconductor chip including the cut first layer and the cured product is separated from the dicing sheet or the support sheet and picked up (in this specification, “pickup And may be referred to as a “process”).
In this specification, the laminated body (1-1) and the laminated body (1-2) may be collectively referred to as “laminated body (1)”.

In the manufacturing method, by using the die bonding film or the dicing die bonding sheet, even if the size of the semiconductor chip is small, the cured product of the second layer that has been cut (cut and cured) in the pickup process. The second layer) is partly or entirely peeled off from the semiconductor chip, and the transferability of the cured product of the second layer to the semiconductor chip is high.

Hereinafter, the manufacturing method will be described in detail with reference to the drawings.
FIG. 6 is a cross-sectional view for schematically explaining a method for manufacturing a semiconductor chip according to an embodiment of the present invention. Here, a method for manufacturing a semiconductor chip when the dicing die bonding sheet 1A shown in FIG. 2 is used will be described.

<< Laminated body (1) production process >>
In the laminated body (1) manufacturing process, as shown in FIG. 6A, in the dicing die bonding sheet 1A, the semiconductor wafer 9 is stuck to the second layer 132 in the die bonding film 13. The body (1-2) 101 is produced.
The laminated body (1-2) 101 includes the base material 11, the first layer 131, the second layer 132, and the semiconductor wafer 9 (in other words, the base material 11, the die bonding film 13 and the semiconductor wafer 9) in this order. Laminated in the thickness direction.

In the laminated body (1-2) 101, the back surface 9b of the semiconductor wafer 9 is attached to the first surface 132a of the second layer 132.
The dicing die bonding sheet 1A is used with the release film 15 removed.

Here, although the case where the dicing die bonding sheet 1A is used is described, in this step, the die bonding film 13 is used instead of the dicing die bonding sheet 1A, and the second layer 132 includes a semiconductor. A laminated body (1-1) in which the wafer 9 is affixed and the substrate 11 (support sheet 10) as a dicing sheet is affixed to the first layer 131 may be produced.
In the laminate (1-1), the base material 11, the first layer 131, the second layer 132, and the semiconductor wafer 9 (in other words, the base material 11, the die bonding film 13, and the semiconductor wafer 9) are arranged in this order. They are stacked in the vertical direction.
Thus, the obtained laminate (1-2) and laminate (1-1) are apparently the same, and both can be described as laminate (1) 101.

The affixing of the semiconductor wafer 9 to the second layer 132 may be performed by softening the second layer 132 by heating. In this case, the heating temperature of the second layer 132 is preferably 35 to 45 ° C.
Moreover, the sticking speed and the sticking pressure when the semiconductor wafer 9 is stuck to the second layer 132 are not particularly limited. For example, the sticking speed is preferably 5 to 20 mm / s, and the sticking pressure is preferably 0.1 to 1.0 MPa.

When the die bonding film 13 is used instead of the dicing die bonding sheet 1A, the dicing sheet (the base material 11 and the support sheet 10) is attached to the first layer 131, and then the semiconductor wafer 9 is attached to the second layer 132. It is preferable to affix. The dicing sheet may be attached to the first layer 131 by a known method. For example, the same conditions as when the semiconductor wafer 9 is attached may be adopted.

<< Laminated body (2) production process >>
In the laminate (2) manufacturing step, the semiconductor wafer 9 in the laminate (1) 101 is cut together with the die bonding film 13 (that is, the first layer 131 and the second layer 132) using a dicing blade. Thereby, as shown in FIG. 6B, the stacked body (2) 102 including the cut first layer 131 ′, the cut second layer 132 ′, and the semiconductor chip 9 ′ is manufactured.
In the laminated body (2) 102, the cut first layer 131 ′, the cut second layer 132 ′, and the semiconductor chip 9 ′ (in other words, the cut die bonding film 13 ′ and the semiconductor chip 9 ′) are provided. In this order, a plurality of laminates laminated in the thickness direction are fixed in an aligned state on the substrate 11 by the first layer 131 ′.
In FIG. 6 (b), the dicing die bonding sheet 1A from which the die bonding film 13 has been cut is newly indicated by reference numeral 1A ′.

In this step, usually, dicing is performed while water (cutting water) is allowed to flow through the portion where the dicing blade contacts the semiconductor wafer 9. At this time, the first surface 132a of the second layer 132 and the back surface 9b of the semiconductor wafer 9 have high adhesive strength and adhesion, and the first surface 132a ′ of the cut second layer 132 ′ and the semiconductor chip 9 Since the adhesive strength and adhesiveness with the “back surface 9 b” are high, the penetration of water between these contact surfaces is suppressed.

The size of the semiconductor chip 9 'produced in this step is not particularly limited, but the length of one side of the semiconductor chip 9' is preferably 0.1 to 2.5 mm. The effect of the present invention can be obtained more remarkably when the semiconductor chip 9 'having such a small size is manufactured.

The dicing conditions are not particularly limited, and may be adjusted as appropriate according to the purpose.
Usually, the rotational speed of the dicing blade is preferably 15000 to 50000 rpm, and the moving speed of the dicing blade is preferably 5 to 75 mm / sec.

During dicing, the substrate 11 may be cut with a dicing blade from the first surface 11a to a depth of, for example, about 30 μm or less.

<< Laminated body (3) production process >>
In the laminate (3) manufacturing step, the cut second layer 132 ′ in the laminate (2) 102 is cured with energy rays to obtain a cured product 1320 ′, as shown in FIG. 6C. Then, a laminated body (3) 103 including the cut first layer 131 ′, the cured product 1320 ′, and the semiconductor chip 9 ′ is prepared.
In the stacked body (3) 103, a plurality of first layers 131 ′ that have been cut, second layers 1320 ′ that have been cut and hardened, and semiconductor chips 9 ′ are stacked in this order in the thickness direction. The laminate is fixed in an aligned state on the substrate 11 by the first layer 131 ′. The layered product (3) 103 is the same as the layered product (2) 102 except that the cut second layer 132 ′ is cured.

Here, a reference numeral 130 ′ is attached to a laminate of the cut first layer 131 ′ and the cut and hardened second layer 1320 ′. In the present specification, such a laminate derived from the die bonding film 13 may be referred to as a “cured die bonding film”.

As described above, the cut second layer 132 ′ and the semiconductor chip 9 ′ have high adhesive force and adhesiveness, but the cut second layer 132 ′ becomes a cured product 1320 ′. The cured product 1320 ′ and the semiconductor chip 9 ′ are further improved in adhesive force and adhesion.

When the second layer 132 ′ that has been cut is irradiated with energy rays and the second layer 132 ′ is cured with energy rays, the irradiation conditions of the energy rays are as long as the second layer 132 ′ is sufficiently cured with energy rays. There is no particular limitation. For example, the energy ray illuminance during energy ray curing is preferably 4 to 280 mW / cm ² . The amount of energy rays during energy ray curing is preferably 3 to 1000 mJ / cm ² .
It is preferable to irradiate the cut second layer 132 ′ from the base material 11 side through the base material 11 and the cut first layer 131 ′.

<< Pickup process >>
In the pick-up step, as shown in FIG. 6 (d), in the laminate (3) 103, the semiconductor chip 9 ′ having the cut first layer 131 ′ and the cured product 1320 ′ is attached to the support sheet 10. Pull away from (base material 11). In this specification, such a semiconductor chip may be referred to as a “semiconductor chip with a cured die bonding film”.

As described above, even if the size of the semiconductor chip 9 ′ is small, the adhesiveness and adhesion between the cut second layer 132 ′ and the semiconductor chip 9 ′ are high. Intrusion of water between the surfaces is suppressed. In addition, the adhesive strength and adhesion between the cured product 1320 'and the semiconductor chip 9' are further increased. Therefore, in this step, part or all of the cured product 1320 'is prevented from peeling from the semiconductor chip 9', and the transfer property of the cured product 1320 'to the semiconductor chip 9' is high.

Here, the direction of pickup is indicated by an arrow I.
Examples of the separating means 8 for separating the semiconductor chip 9 ′ from the support sheet 10 together with the cut first layer 131 ′ and the cured product 1320 ′ include a vacuum collet. In FIG. 6, the separating means 8, which is different from the cured semiconductor chip with a die bonding film, is not shown in cross section.

So far, the manufacturing method of the semiconductor chip when the dicing die bonding sheet 1A is used has been described. However, other dicing die bondings of the present invention other than the dicing die bonding sheet 1A, such as the dicing die

bonding sheet

1B, 1C or 1D. Even when a sheet is used or when a die bonding film is used instead of a dicing die bonding sheet in the initial stage, a semiconductor chip can be manufactured by the same method as described above. And the effect which shows in that case is the same as the case where dicing die bonding sheet 1A is used. In the case of using another dicing die bonding sheet, a semiconductor chip can be manufactured by appropriately adding an arbitrary process according to the structure.

<< Semiconductor Device and Method for Manufacturing the Same >>
A semiconductor chip with a cured die-bonding film (a semiconductor chip having a cut first layer and a cut and hardened second layer) obtained by applying the manufacturing method is a semiconductor device. Particularly suitable for use in manufacturing.
For example, the semiconductor chip with a cured die bonding film is die bonded to the circuit forming surface of the substrate by the cut first layer.
FIG. 7 is a cross-sectional view schematically showing an example of a state in which a semiconductor chip with a cured die bonding film is die-bonded on the circuit forming surface of the substrate. Here, the semiconductor chip 9 provided with the cut first layer 131 ′ and the cured product 1320 ′, which is a target in the manufacturing method described with reference to FIG. The case where 'is used is shown.

As shown in FIG. 7, the semiconductor chip 9 ′ having the cured die bonding film 130 ′ is die-bonded to the circuit forming surface 7a of the substrate 7 by the cut first layer 131 ′ of the film 130 ′. Has been.
More specifically, the surface of the cut first layer 131 ′ opposite to the cured product 1320 ′ (referred to as “second surface” in this specification) 131b ′. The circuit formation surface 7a of the substrate 7 is in direct contact, and the semiconductor chip 9 ′ is fixed on the substrate 7. In the substrate 7, the description of the circuit is omitted.

The first layer 131 of the die bonding film 13 described above has a good substrate embedding property. Therefore, as shown here, the generation of a gap (void) is suppressed between the circuit forming surface 7a of the substrate 7 and the cut first layer 131 ′, and the cut first layer 131 is cut off. 'Satisfactorily embeds and covers the circuit forming surface 7a of the substrate 7.

Here, the die bonding of the semiconductor chip in the case of using the dicing die bonding sheet 1A has been described. Even when a sheet is used or when a die bonding film is used instead of a dicing die bonding sheet in the initial stage, the substrate can be embedded satisfactorily by the first layer as described above.

As described above, after the semiconductor chip is die-bonded using the cured semiconductor chip with a die-bonding film, the semiconductor package and the semiconductor device are manufactured by the same method as the conventional method. For example, if necessary, at least one semiconductor chip is further laminated on this die-bonded semiconductor chip, wire bonding is performed, and then the entire product is sealed with a resin, whereby a semiconductor package is obtained. Is produced. Then, a target semiconductor device is manufactured using this semiconductor package.
By using the die bonding film or dicing die bonding sheet of the present invention, the embedding property of the substrate by the first layer is good, and as a result, the obtained semiconductor package has high reliability.

As one aspect, the die bonding film which is one embodiment of the present invention,
A first layer and a second layer provided on the first layer;
The first layer has a characteristic that an initial detection temperature of melt viscosity is 50 to 75 ° C. (or may be 50 to 68 ° C. or 50 to 59 ° C.);
The second layer has adhesiveness and energy ray curability;
A laminate of the first layer and the second layer having a thickness of 10 μm and a width greater than 25 mm is used as a test piece, and the test piece is affixed to a silicon mirror wafer so that the width is 25 mm. The silicon mirror is obtained by cutting a piece, immersing the cut test piece together with the silicon mirror wafer in pure water for 2 hours, and curing the test piece after the immersion to energy rays. When a test laminate in which the cured product is affixed to a wafer is produced, the adhesive force between the cured product having a width of 25 mm and the silicon mirror wafer is 6 to 20 N / 25 mm, or 10 to 10 A laminate of the first layer and the second layer having a thickness of 10 μm and a width greater than 25 mm is used as a test piece, and the test piece is applied to a silicon mirror wafer. Affixed, width The test piece was cut to 5 mm, and the cut test piece was allowed to stand for 30 minutes under the conditions of a temperature of 23 ° C. and a relative humidity of 50% together with the silicon mirror wafer in a dark place under an air atmosphere. When the laminated body for non-immersion test in which the cured product is pasted on the silicon mirror wafer is prepared by curing the test piece after storage and standing to be cured by energy ray curing. The adhesive strength between the cured product of 25 mm and the silicon mirror wafer is 6 to 20 N / 25 mm, or 10 to 20 N / 25 mm;
Die bonding film.

Furthermore, the die bonding film is
The first layer is formed from a first adhesive composition;
The second layer is formed from a second adhesive composition;
The first adhesive composition comprises a polymer component (a), an epoxy thermosetting resin (b) composed of an epoxy resin (b1) and a thermosetting agent (b2), an effect accelerator (c), a filler ( d) and a coupling agent (e),
The polymer component (a) is an acrylic resin obtained by copolymerizing n-butyl acrylate, methyl acrylate, glycidyl methacrylate and 2-hydroxyethyl acrylate, or n-butyl acrylate, ethyl acrylate, An acrylic resin obtained by copolymerizing acrylonitrile and glycidyl methacrylate (the content of the polymer component (a) is 5 to 20% by mass with respect to the total mass of the first adhesive composition (other than the solvent), Preferably 7-12%);
The epoxy resin (b1) is a bisphenol A type epoxy resin and a polyfunctional aromatic type (triphenylene type) epoxy resin, or a bisphenol F type epoxy resin and a dicyclopentadiene type epoxy resin;
The thermosetting agent (b2) is an o-cresol type novolak resin (the content of the epoxy thermosetting resin (b) is 100 parts by mass of the polymer component (a)). 800 to 1000 parts by mass, and the content of the thermosetting agent (b2) is preferably 25 to 80 parts by mass with respect to 100 parts by mass of the epoxy resin (b1));
The curing accelerator (c) is an inclusion compound of 1 molecule of 5-hydroxyisophthalic acid (HIPA) and 2 molecules of 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ), or 2-phenyl-4 , 5-dihydroxymethylimidazole (the content of the curing accelerator (c) is preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the epoxy thermosetting resin (b). );
The filler (d) is spherical silica modified with an epoxy group (the content of the filler (d) is preferably relative to the total mass (other than the solvent) of the first adhesive composition). 15 to 30% by mass);
The coupling agent (e) is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and an oligomeric silane coupling agent having an epoxy group, a methyl group and a methoxy group. (The content of the coupling agent (e) is preferably based on 100 parts by mass of the total content of the polymer component (a) and the epoxy thermosetting resin (b)). Is 0.1 to 5 parts by mass);
The second adhesive composition includes a polymer component (a), a filler (d), a coupling agent (e), an energy ray curable resin (g), and a photopolymerization initiator (h).
The polymer component (a) is an acrylic resin obtained by copolymerizing n-butyl acrylate, methyl acrylate, glycidyl methacrylate and 2-hydroxyethyl acrylate, or n-butyl acrylate, ethyl acrylate, It is an acrylic resin obtained by copolymerizing acrylonitrile and glycidyl methacrylate (the content of the polymer component (a) is preferably 20 with respect to the total mass (other than the solvent) of the second adhesive composition). ~ 35% by weight);
The filler (d) is spherical silica or silica filler modified with an epoxy group (the content of the filler (d) is based on the total mass (other than the solvent) of the second adhesive composition). , Preferably 45 to 64% by weight);
The coupling agent (e) is an oligomer type silane coupling agent having an epoxy group, a methyl group and a methoxy group (preferably 0.1 parts per 100 parts by mass of the polymer component (a)). ~ 5 parts by mass);
The energy ray curable resin (g) is tricyclodecane dimethylol diacrylate or ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate (the content of the energy ray curable resin (g) is , Preferably 5 to 85% by mass relative to the total mass of the second adhesive composition (other than the solvent));
The photopolymerization initiator (h) is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (the photopolymerization initiator (h) 1 to 10 parts by mass with respect to 100 parts by mass of the resin (g)),
It may be a die bonding film.

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.

<Monomer>
In the examples and comparative examples, the formal names of the monomers abbreviated are shown below.
BA: n-butyl acrylate MA: methyl acrylate HEA: 2-hydroxyethyl acrylate GMA: glycidyl methacrylate EA: ethyl acrylate AN: acrylonitrile

<Production raw material of adhesive composition>
In the examples and comparative examples, the raw materials used for the production of the adhesive composition are shown below.

[Polymer component (a)]
(A) -1: Acrylic resin (weight average molecular weight 500000, glass transition) obtained by copolymerizing BA (10 parts by mass), MA (70 parts by mass), GMA (5 parts by mass) and HEA (15 parts by mass) Temperature-1 ° C).
(A) -2: Acrylic resin (weight average molecular weight 700,000, glass transition) obtained by copolymerizing BA (40 parts by mass), EA (25 parts by mass), AN (30 parts by mass) and GMA (5 parts by mass) Temperature 10 ° C.).
(A) -3: Acrylic resin obtained by copolymerizing BA (55 parts by mass), MA (10 parts by mass), GMA (20 parts by mass) and HEA (15 parts by mass) (weight average molecular weight 800000, glass transition Temperature-30 ° C).
(A) -4: Thermoplastic resin, polyester (Toyobo “Byron 220”, weight average molecular weight 35000, glass transition temperature 53 ° C.)
[Epoxy resin (b1)]
(B1) -1: Bisphenol A type epoxy resin (“JER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 184 to 194 g / eq)
(B1) -2: 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) -3: Bisphenol F type epoxy resin (“YL983U” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 170 g / eq)
(B1) -4: Dicyclopentadiene type epoxy resin (“XD-1000-L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 248 g / eq)
(B1) -5: Mixture of liquid bisphenol A type epoxy resin and acrylic rubber fine particles (“BPA328” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 235 g / eq)
(B1) -6: Dicyclopentadiene type epoxy resin (“Epiclon HP-7200HH” manufactured by DIC, epoxy equivalent of 255 to 260 g / eq)
[Thermosetting agent (b2)]
(B2) -1: o-cresol type novolak resin (“Phenolite KA-1160” manufactured by DIC)
(B2) -2: Novolac type phenolic resin (novolak resin other than o-cresol type, “BRG-556” manufactured by Showa Denko KK)
(B2) -3: Dicyandiamide (“ADEKA HARDNER EH-3636AS” manufactured by ADEKA, solid dispersion type latent curing agent, active hydrogen amount 21 g / eq)
[Curing accelerator (c)]
(C) -1: an inclusion compound of one molecule of 5-hydroxyisophthalic acid (HIPA) and two molecules of 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ) (“HIPA-2P4MHZ” manufactured by Nippon Soda Co., Ltd.) )
(C) -2: 2-phenyl-4,5-dihydroxymethylimidazole (“Cureazole 2PHZ-PW” manufactured by Shikoku Chemicals)
[Filler (d)]
(D) -1: Spherical silica modified with an epoxy group (“Admanano YA050C-MKK” manufactured by Admatechs, average particle size 50 nm)
(D) -2: Silica filler (“SC2050MA” manufactured by Admatechs, silica filler surface-modified with an epoxy compound, average particle diameter of 500 nm)
[Coupling agent (e)]
(E) -1: 3-Glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Silicone Co., Ltd., silane coupling agent, methoxy equivalent 12.7 mmol / g, molecular weight 236.3)
(E) -2: 3-Glycidoxypropyltriethoxysilane (“KBE-403” manufactured by Shin-Etsu Silicone Co., Ltd., silane coupling agent, methoxy equivalent 8.1 mmol / g, molecular weight 278.4)
(E) -3: Oligomer type silane coupling agent having an epoxy group, a methyl group and a methoxy group (“X-41-1056” manufactured by Shin-Etsu Silicone Co., Ltd., epoxy equivalent: 280 g / eq)
(E) -4: Trimethoxy [3- (phenylamino) propyl] silane (“SZ6083” manufactured by Toray Dow Co., silane coupling agent)
(E) -5: A silicate compound to which 3-glycidoxypropyltrimethoxysilane is added (“MKC silicate MSEP2” manufactured by Mitsubishi Chemical Corporation)
[Crosslinking agent (f)]
(F) -1: Tolylene diisocyanate trimer adduct of trimethylolpropane (“BHS8515” manufactured by Toyochem)
[Energy ray curable resin (g)]
(G) -1: Tricyclodecane dimethylol diacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd., UV curable resin, molecular weight 304)
(G) -2: ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (“A-9300-1CL”, trifunctional ultraviolet curable compound manufactured by Shin-Nakamura Chemical Co., Ltd.)
[Photoinitiator (h)]
(H) -1: 1-hydroxycyclohexyl phenyl ketone (“IRGACURE (registered trademark) 184” manufactured by BASF)
(H) -2: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (“IRGACURE® 369” manufactured by BASF)

[Example 1]
<< Manufacture of die bonding film >>
<Manufacture of 1st adhesive composition>
Polymer component (a) -1 (10 parts by mass), epoxy resin (b1) -1 (20 parts by mass), epoxy resin (b1) -2 (25 parts by mass), thermosetting agent (b2) -1 (25 Parts by weight), curing accelerator (c) -1 (0.3 parts by weight), filler (d) -1 (20 parts by weight), coupling agent (e) -1 (0.3 parts by weight), cup The solid component concentration is obtained by dissolving or dispersing the ring agent (e) -2 (0.4 parts by mass) and the coupling agent (e) -3 (0.5 parts by mass) in methyl ethyl ketone and stirring at 23 ° C. The 1st adhesive composition which is 55 mass% was obtained. In addition, all the compounding quantities of components other than the methyl ethyl ketone shown here are solid content conversion values.

<Production of second adhesive composition>
Polymer component (a) -1 (22 parts by mass), filler (d) -2 (50 parts by mass), coupling agent (e) -3 (0.5 parts by mass), energy ray curable resin (g ) -1 (20 parts by mass) and photopolymerization initiator (h) -2 (0.3 parts by mass) are dissolved or dispersed in methyl ethyl ketone and stirred at 23 ° C., so that the solid content concentration is 55% by mass. A second adhesive composition was obtained. In addition, all the compounding quantities of components other than the methyl ethyl ketone shown here are solid content conversion values.

<Formation of the first layer>
Using a release film (“SP-PET381031H” manufactured by Lintec Co., Ltd., thickness: 38 μm) in which one side of a polyethylene terephthalate (PET) film is subjected to release treatment by silicone treatment, the release-treated surface obtained above is used. 1 adhesive composition was applied, and dried at 100 ° C. for 2 minutes to form a first layer having a thickness of 10 μm.

<Formation of second layer>
Using a release film (“SP-PET381031H” manufactured by Lintec Co., Ltd., thickness: 38 μm) in which one side of a polyethylene terephthalate (PET) film is subjected to release treatment by silicone treatment, the release-treated surface obtained above is used. 2 Adhesive composition was applied and dried at 100 ° C. for 2 minutes to form a second layer having a thickness of 10 μm.

<Manufacture of die bonding film>
The exposed surface of the first layer obtained on the opposite side to the release film side and the exposed surface of the second layer obtained on the opposite side to the release film side are adjusted to a temperature of these two layers of 40. By sticking together as ° C., a release film, a first layer, a second layer, and a release film were laminated in this order in the thickness direction to obtain a die bonding film with a release film.

<< Manufacture of dicing die bonding sheet >>
By removing the release film on the first layer side from the die bonding film obtained above and bonding the newly-exposed exposed surface of the first layer to the substrate, the substrate, the first layer, the first layer A dicing die bonding sheet in which two layers and a release film (in other words, a substrate, a die bonding film, and a release film) were laminated in this thickness direction in this order was obtained. The base material used here is a polyethylene film (thickness: 100 μm).

<< Evaluation of die bonding film >>
<Calculation of initial detection temperature T ₀ of the melt viscosity>
The first layer of the die bonding film obtained above was laminated, and a cylindrical test piece having a diameter of 10 mm and a height of 20 mm was immediately produced.
Place the test piece immediately after the preparation at the measurement point of the capillary rheometer (“CFT-100D” manufactured by Shimadzu Corporation), and apply the force of 5.10 N (50 kgf) to the test piece. The temperature was raised from 50 ° C. to 120 ° C. at 10 ° C./min. Then, when the extrusion of the test piece from the hole of 0.5 mm in diameter and 1.0 mm in height provided in the die is started, that is, the temperature at which the detection of the melt viscosity of the test piece is started (initial detection temperature). T ₀ ) (° C.) was determined. The results are shown in Table 1.

<Evaluation of embeddability of substrate>
(Manufacture of semiconductor chip with cured die-bonding film)
The peeling film is removed from the dicing die bonding sheet obtained above, and the exposed surface of the second layer (die bonding film) newly generated thereby is used as the mirror surface (back surface) of an 8-inch silicon mirror wafer (thickness 350 μm). Affixed to. At this time, the dicing die bonding sheet was heated to 40 ° C. and pasted under conditions of a pasting speed of 20 mm / s and a pasting pressure of 0.5 MPa.
By the above, the base material, the first layer, the second layer, and the silicon mirror wafer (in other words, the base material, the die bonding film, and the silicon mirror wafer) are laminated in this order in the thickness direction. Body (1) was obtained.

Next, by dicing using a dicing apparatus (“DFD6361” manufactured by Disco), the silicon mirror wafer in the laminate (1) is divided, and the first layer and the second layer (die bonding film) are also cut. A silicon chip having a size of 2 mm × 2 mm was obtained. Dicing at this time is performed by cutting the dicing blade to a depth of 20 μm from the first layer application surface with a dicing blade moving speed of 30 mm / sec and a dicing blade rotation speed of 40000 rpm. It was. In addition, dicing was performed while flowing water (cutting water) through the portion of the dicing blade in contact with the silicon mirror wafer.
Thus, the cut first layer, the cut second layer, and the silicon chip (cut silicon mirror wafer) (in other words, the cut die bonding film and silicon chip) are arranged in this order in the thickness direction. A laminate (2) was obtained, in which a plurality of laminates laminated in step 1 were fixed in an aligned state on the substrate by the first layer.

Next, using an ultraviolet irradiation device (“RAD-2000 m / 12” manufactured by Lintec Corporation) under the conditions of an illuminance of 220 mW / cm ² and a light amount of 120 mJ / cm ² from the outside on the base material side of the laminate (2), The cut second layer in the laminate (2) was irradiated with ultraviolet rays to cure the second layer.
As described above, a plurality of laminates in which the cut first layer, the cut second layer cured product, and the silicon chip are laminated in this order in the thickness direction are formed by the first layer. A laminate (3) was obtained which was fixed in an aligned state on the material. The laminate (3) is the same as the laminate (2) except that the cut second layer is cured.

Next, using a pickup and die bonding apparatus ("BESTEM D02" manufactured by Canon Machinery Co., Ltd.), the first layer and the cured second layer (cured) are formed on the back surface from the base material in the laminate (3) obtained above. A silicon chip provided with a die bonding film) (ie, a silicon chip with a cured die bonding film) was pulled away and picked up.
Thus, a silicon chip with a cured die bonding film was obtained.

Table 1 shows the order of steps of dicing (cutting of the die bonding film), curing of the die bonding film (second layer), and pick-up so far. Note that the order in which these three steps are performed is not limited to the time of evaluation of this item (embedding property of the substrate), but is the same when other items described later are evaluated.
The abbreviations described in Table 1 have the following meanings.
DF: Die bonding film DC: Dicing PU: Pickup

(Evaluation of embedding property of die bonding film substrate)
A disc-shaped transparent glass substrate (manufactured by NSG Precision Co., Ltd., diameter 8 inches, thickness 100 μm) was divided into 8 mm × 8 mm and separated into individual pieces.
Next, using the pickup die bonding apparatus ("BESTEM D02" manufactured by Canon Machinery Co., Ltd.), the above-obtained silicon chip with a cured die bonding film obtained above was separated into individual transparent glass substrates obtained above. Die bonded. At this time, the cured die bonding film is placed on this substrate by bringing the cured die bonding film into contact with the transparent glass substrate after separation under a temperature condition of 20 ° C. Die bonding was performed by applying a force of 5N to the cured silicon chip with a die-bonding film and pressing it for 0.5 seconds.

Subsequently, the transparent glass substrate after the die bonding was observed from the side opposite to the cured die bonding film side using an optical microscope (“VHX-1000” manufactured by Keyence Corporation). And the presence or absence of a void (gap part) is confirmed between the cured die bonding film and the glass substrate, and the cured die bonding film is in close contact with the entire surface of the glass substrate on the cured die bonding film side. The ratio of the surface (contact ratio, area%) was determined.

The above operation was performed on nine silicon chips with a cured die bonding film, and the embedding property of the substrate of the die bonding film was evaluated according to the following criteria. The results are shown in Table 1.
A: The adhesion ratio was 90 area% or more in all nine silicon chips with a cured die bonding film.
B: There was at least one silicon chip with a cured die bonding film in which the adhesion ratio was less than 90 area%.

<Evaluation of transferability to semiconductor chip>
(Manufacture of laminate (3))
A laminate (3) was manufactured by the same method as that for manufacturing a semiconductor chip with a cured die bonding film as described above.

(Evaluation of transferability to semiconductor chip)
Next, the laminate (3) obtained above was immersed in pure water at 23 ° C. for 2 hours. At this time, the laminate (3) was arranged so that the entire laminate (3) was submerged in pure water.
Next, the laminate (3) was pulled up from pure water, and water droplets adhering to the surface were removed.
And using the pick-up die bonding apparatus ("BESTEM D02" by Canon Machinery Co., Ltd.), the back surface was provided with the 1st layer and the hardened 2nd layer from the base material in the laminated body (3). An attempt was made to pick up a silicon chip (in other words, a silicon chip with a cured die-bonding film).
The steps of dicing, curing of the die bonding film (second layer), and picking up so far are the same as those in the evaluation of the embedding property of the substrate of the die bonding film.

Next, the surface (in other words, the first surface) on which the first layer (die bonding film) of the base material was laminated was observed using an optical microscope (“VHX-1000” manufactured by Keyence Corporation). The transferability of the cured die bonding film to the semiconductor chip was evaluated. The results are shown in Table 1.
A: The cured die bonding film does not remain on the substrate.
B: The cured die bonding film (at least the first layer) remains on the substrate.

<Measurement of non-immersion adhesive strength and post-immersion adhesive strength>
(Manufacture of test laminates)
The release film on the second layer side is removed from the die bonding film obtained above, and the exposed surface of the second layer newly generated thereby is used as a mirror surface (back surface) of a 6-inch silicon mirror wafer (thickness 350 μm). Affixed to. At this time, the die bonding film was heated to 40 ° C. and pasted under the conditions of a pasting speed of 20 mm / s and a pasting pressure of 0.5 MPa.
Next, the peel-off film on the first layer side is removed from the die-bonding film after the application, and a strong adhesive tape having a width of 25 mm ("PET50PL Thin" manufactured by Lintec Co., Ltd.) is newly formed on the exposed surface of the first layer. ") Was affixed.

Next, for the die bonding film affixed to the 6-inch silicon mirror wafer, along the outer periphery of the strong adhesive tape, the entire area in the thickness direction of the die bonding film (the thicknesses of the first layer and the second layer). Cuts were formed in the entire area in the vertical direction, and the die bonding film was cut into a strip having a width of 25 mm.
Next, immediately after the cutting, in the dark place, the cut die bonding film was immersed in pure water at 23 ° C. for 2 hours together with the silicon mirror wafer. At this time, the silicon mirror wafer with the die bonding film after cutting was placed in pure water so that the entire silicon mirror wafer was submerged in pure water.
Next, the silicon mirror wafer with the die bonding film after cutting was pulled up from pure water, and water droplets adhering to the surface were removed.
Next, using a UV irradiation device (“RAD-2000 m / 12” manufactured by Lintec Corporation), the die bonding film after cutting was irradiated with UV light under the conditions of an illuminance of 220 mW / cm ² and a light amount of 120 mJ / cm ^2. The second layer was cured.
As described above, the strong adhesive tape, the first layer in which the cut is formed, the cured product of the second layer in which the cut is formed, and the silicon mirror wafer are laminated in this order in the thickness direction. A test laminate was obtained.

(Measurement of adhesive strength after immersion of test laminate)
Under the condition of 23 ° C., using the universal tensile tester (“Autograph AG-IS” manufactured by Shimadzu Corporation), the strong adhesive tape was pulled in the test laminate obtained above. At this time, the strong adhesive tape is pulled at a peeling (tensile) speed of 300 mm / min so that the peeled surfaces generated in the test laminate form an angle of 180 ° by pulling the strong adhesive tape, so-called 180 °. Peeling was performed. And while peeling force (load, N / 25mm) at this time was measured, the peeling location which arose in the laminated body for a test, and the peeling form were confirmed. And the said peeling force was made into the adhesive force (N / 25mm) between the hardened | cured material of the 2nd layer whose width | variety is 25 mm in a laminated body for a test, and a silicon mirror wafer. The results are shown in the column “Adhesive strength after immersion” in Table 1.

(Manufacture of non-immersion laminates)
Instead of immersing the cut silicon bonding wafer with the die bonding film in pure water at 23 ° C. for 2 hours in a dark place, the temperature is 23 ° C. and the relative humidity is 50 ° in a dark place under an air atmosphere. A laminate for non-immersion test was produced in the same manner as in the case of the test laminate described above, except that the sample was allowed to stand for 30 minutes.

(Measurement of non-immersion adhesive strength of laminate for non-immersion test)
For the non-immersion test laminate obtained above, the peel force (load, N / 25 mm) was measured in the same manner as in the case of the test laminate, and the peel occurred in the non-immersion test laminate. The location and the peeling form were confirmed, and the peeling force was defined as the adhesive strength (N / 25 mm) between the cured product of the second layer having a width of 25 mm and the silicon mirror wafer. The results are shown in the column of “Non-immersion adhesive strength” in Table 1.

<< Manufacture of die bonding film, manufacture of dicing die bonding sheet, and evaluation of die bonding film >>
[Example 2]
About the 1st adhesive composition and the 2nd adhesive composition, the kind and combination of a compounding ingredient at the time of manufacture of these compositions so that the kind and content of these ingredients may become as shown in Table 1. A die bonding film and a dicing die bonding sheet were produced by the same method as in Example 1 except that the amount was changed, and the die bonding film was evaluated. The results are shown in Table 1.

[Comparative Example 1]
<< Manufacture of die bonding film, manufacture of dicing die bonding sheet >>
A die bonding film and a dicing die bonding sheet were produced in the same manner as in Example 1.

<< Evaluation of die bonding film >>
<Calculation of initial detection temperature T ₀ of the melt viscosity>
The initial detection temperature T ₀ (° C.) was determined by the same method as in Example 1. The results are shown in Table 2.

<Evaluation of embeddability of substrate>
(Manufacture of semiconductor chip with cured die bonding film for comparison)
A laminate (1) was produced in the same manner as in Example 1.

Next, using an ultraviolet irradiation device (“RAD-2000 m / 12” manufactured by Lintec Corporation) under the conditions of an illuminance of 220 mW / cm ² and a light amount of 120 mJ / cm ² , from the outside on the substrate side of the laminate (1), The second layer in the laminate (1) was irradiated with ultraviolet rays to cure the second layer.
As described above, a laminated body (4) constituted by laminating the first layer, the second layer cured product, and the silicon mirror wafer in this order in the thickness direction was obtained. The laminate (4) is the same as the laminate (1) except that the second layer is cured.

Next, the silicon mirror wafer in the laminate (4) is divided by dicing using a dicing apparatus ("DFD6361" manufactured by Disco), and the first layer and the cured second layer (cured die bonding film) ) Was also cut to obtain a silicon chip having a size of 2 mm × 2 mm. Dicing at this time is performed by cutting the dicing blade to a depth of 20 μm from the first layer application surface with a dicing blade moving speed of 30 mm / sec and a dicing blade rotation speed of 40000 rpm. It was.
As described above, a plurality of laminates in which the cut first layer, the cut second layer cured product, and the silicon chip are laminated in this order in the thickness direction are formed by the first layer. A comparative laminate (3 ′) was obtained which was fixed in alignment on the material. In the comparative laminate (3 ′), the apparent type of each layer and the order of lamination are the same as in the above-described laminate (3), but the order of dicing and second layer curing is the same. This is different from the case of the laminate (3) described above.

Next, using the pickup / die bonding apparatus (“BESTEM D02” manufactured by Canon Machinery Co., Ltd.), the first layer and the cured material are formed on the back surface from the base material in the comparative laminate (3 ′) obtained above. A silicon chip provided with the second layer (cured die bonding film) (that is, a silicon chip with a cured die bonding film for comparison) was pulled away and picked up.
As a result, a comparative silicon chip with a cured die bonding film was obtained.

(Evaluation of embedding property of die bonding film substrate)
Except for the use of the comparative silicon chip with a cured die bonding film obtained above, the embedding property of the cured die bonding film on the substrate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Evaluation of transferability to semiconductor chip>
(Manufacture of comparative laminate (3 '))
A comparative laminate (3 ′) was produced in the same manner as in the case of producing a comparative semiconductor chip with a cured die bonding film as described above.

(Evaluation of transferability to semiconductor chip)
Next, the comparative laminate (3 ′) obtained above was immersed in pure water at 23 ° C. for 2 hours.
At this time, the comparative laminate (3 ′) was arranged so that the entire comparative laminate (3 ′) was submerged in pure water.
Next, the comparative laminate (3 ′) was pulled up from the pure water to remove water droplets adhering to the surface. Then, using a pickup die bonding apparatus ("BESTEM D02" manufactured by Canon Machinery Co., Ltd.), the first layer and the cured second layer are formed on the back surface from the base material in the comparative laminate (3 ') after the immersion. Attempts were made to pull apart and pick up a silicon chip with a layer (in other words, a silicon chip with a cured die bonding film for comparison).
Next, the transferability of the cured die bonding film to the semiconductor chip was evaluated in the same manner as in Example 1 except that the comparative silicon chip with a cured die bonding film obtained above was used. did. The results are shown in Table 2.

<Measurement of non-immersion adhesive strength and post-immersion adhesive strength>
(Manufacture of test laminates)
In the same manner as in Example 1, a silicon mirror wafer to which a die bonding film after cutting was attached was obtained.
Next, using a UV irradiation device (“RAD-2000 m / 12” manufactured by Lintec Corporation), the die bonding film after cutting was irradiated with UV light under the conditions of an illuminance of 220 mW / cm ² and a light amount of 120 mJ / cm ^2. The second layer was cured.
Next, in a dark place, the die bonding film after curing the second layer was immersed in pure water at 23 ° C. for 2 hours together with the silicon mirror wafer immediately after curing the second layer. At this time, the silicon mirror wafer to which the cured die bonding film was attached was placed in pure water so that the entire silicon mirror wafer was submerged in pure water.
Next, the silicon mirror wafer on which the cured die bonding film was adhered was pulled up from pure water, and water droplets adhering to the surface were removed.
As described above, the strong adhesive tape, the first layer in which the cut is formed, the cured product of the second layer in which the cut is formed, and the silicon mirror wafer are laminated in this order in the thickness direction. In addition, a comparative test laminate was obtained.

(Manufacture of non-immersion laminates)
Instead of immersing the silicon mirror wafer with the die-bonding film after curing the second layer in pure water at 23 ° C. for 2 hours in the dark, the temperature is 23 ° C. in the dark under an air atmosphere. A comparative non-immersion test laminate was produced in the same manner as in the comparative test laminate described above, except that the sample was stored at a relative humidity of 50% for 30 minutes.

(Measurement of non-immersion adhesive strength and post-immersion adhesive strength of test laminate)
Using the comparative test laminate obtained above, the post-immersion adhesive strength was measured in the same manner as in Example 1. Moreover, the non-immersion adhesive force was measured by the same method as in Example 1 using the comparative non-immersion test laminate obtained above. The results are shown in Table 2.

<< Manufacture of die bonding film, manufacture of dicing die bonding sheet, and evaluation of die bonding film >>
[Comparative Example 2]
<< Manufacture of die bonding film, manufacture of dicing die bonding sheet, evaluation of die bonding film >>
Except for using a die bonding film and a dicing die bonding sheet manufactured by the same method as in Example 2 in place of the die bonding film and the dicing die bonding sheet manufactured by the same method as in Example 1, a comparison was made. The die bonding film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 3]
<< Manufacture of die bonding film >>
<Manufacture of adhesive composition>
Polymer component (a) -3 (10 parts by mass), Polymer component (a) -4 (20 parts by mass), Epoxy resin (b1) -2 (20 parts by mass), Epoxy resin (b1) -5 (20 Parts by mass), thermosetting agent (b2) -2 (20 parts by mass), curing accelerator (c) -2 (0.3 parts by mass), filler (d) -2 (10 parts by mass), coupling agent (E) -4 (0.3 parts by mass), coupling agent (e) -5 (0.5 parts by mass), energy beam curable resin (g) -1 (5 parts by mass) and photopolymerization initiator ( h) -1 (0.15 parts by mass) was dissolved or dispersed in methyl ethyl ketone and stirred at 23 ° C. to obtain an adhesive composition having a solid content concentration of 55% by mass. In addition, all the compounding quantities of components other than the methyl ethyl ketone shown here are solid content conversion values.

<Manufacture of die bonding film>
Using a release film (“SP-PET381031H” manufactured by Lintec Co., Ltd., thickness 38 μm) on which one side of a polyethylene terephthalate (PET) film has been subjected to a release treatment by silicone treatment, the adhesion obtained above is applied to the release treatment surface. The agent composition was applied and dried by heating at 100 ° C. for 2 minutes to form a die bonding film having a thickness of 20 μm.

<< Manufacture of dicing die bonding sheet >>
Dicing die bonding in which the base material, the die bonding film and the release film are laminated in this order in the thickness direction by bonding the exposed surface of the die bonding film obtained above to the base material. A sheet was obtained. The base material used here is the same as that used in Example 1.

<< Evaluation of die bonding film >>
<Calculation of initial detection temperature T ₀ of the melt viscosity>
About the die bonding film obtained above, the initial detection temperature T ₀ (° C.) was determined by the same method as in Example 1. The results are shown in Table 2.

<Evaluation of embeddability of substrate>
(Manufacture of semiconductor chip with cured die bonding film for comparison)
The release film was removed from the dicing die bonding sheet obtained above, and the newly-exposed surface of the die bonding film thus formed was affixed to the mirror surface (back surface) of an 8-inch silicon mirror wafer (thickness 350 μm). At this time, the dicing die bonding sheet was heated to 40 ° C. and pasted under conditions of a pasting speed of 20 mm / s and a pasting pressure of 0.5 MPa.
As described above, a laminate (5) was obtained in which the substrate, the die bonding film, and the silicon mirror wafer were laminated in this order in the thickness direction.

Next, by dicing using a dicing apparatus (“DFD6361” manufactured by Disco), the silicon mirror wafer in the laminated body (5) is divided and the die bonding film is also cut to obtain a silicon having a size of 2 mm × 2 mm. I got a chip. Dicing at this time is performed by cutting the dicing blade to a depth of 20 μm from the surface of the die bonding film to the substrate with a moving speed of the dicing blade of 30 mm / sec and a rotating speed of the dicing blade of 40000 rpm. It was.
As described above, a laminated structure in which a plurality of laminates in which a cut die bonding film and a silicon chip are laminated in the thickness direction are fixed in an aligned state on the substrate by the die bonding film. Body (6) was obtained.

Next, using an ultraviolet irradiation device (“RAD-2000 m / 12” manufactured by Lintec Corporation) under the conditions of an illuminance of 220 mW / cm ² and a light amount of 120 mJ / cm ² , from the outside on the substrate side of the laminate (6), The die bonding film in the laminate (6) was irradiated with ultraviolet rays to cure the die bonding film.
As described above, a cured product of the cut die bonding film and a plurality of laminates in which the silicon chip is laminated in the thickness direction are fixed in an aligned state on the substrate by the cured product. A laminate (7) was obtained. The laminate (7) is the same as the laminate (6) except that the cut die bonding film is cured.

Next, using a pick-up die bonding apparatus ("BESTEM D02" manufactured by Canon Machinery Co., Ltd.), a silicon chip having a cured die bonding film on the back surface from the base material in the laminate (7) obtained above ( That is, the comparative cured silicon chip with a die bonding film was pulled apart and picked up.
As a result, a comparative silicon chip with a cured die bonding film was obtained.

<Evaluation of transferability to semiconductor chip>
(Manufacture of laminate (7))
A laminate (7) was produced by the same method as in the case of producing a comparative semiconductor chip with a cured die bonding film as described above.

(Evaluation of transferability to semiconductor chip)
Next, the laminate (7) obtained above was immersed in pure water at 23 ° C. for 2 hours. At this time, the laminate (7) was arranged so that the entire laminate (7) was submerged in pure water.
Next, the laminate (7) was pulled up from the pure water to remove water droplets adhering to the surface.
Then, using a pick-up die bonding apparatus (“BESTEM D02” manufactured by Canon Machinery Co., Ltd.), a silicon chip (in other words, a cured die bonding film on the back surface from the base material in the laminated body (7) after the immersion) Then, an attempt was made to separate and pick up a comparatively hardened die bonding film-attached silicon chip.
Next, the transferability of the cured die bonding film to the semiconductor chip was evaluated in the same manner as in Example 1 except that the comparative silicon chip with a cured die bonding film obtained above was used. did. The results are shown in Table 2.

<Measurement of non-immersion adhesive strength and post-immersion adhesive strength>
(Manufacture of test laminates)
The exposed surface of the die bonding film obtained above was attached to the mirror surface (back surface) of a 6 inch silicon mirror wafer (thickness 350 μm). At this time, the die bonding film was heated to 40 ° C. and pasted under the conditions of a pasting speed of 20 mm / s and a pasting pressure of 0.5 MPa.
Next, the release film was removed from the die bonding film after the application, and a strong adhesive tape (“PET50PL Thin” manufactured by Lintec Co., Ltd.) having a width of 25 mm was applied to the exposed surface of the die bonding film newly generated thereby.

Next, on the die bonding film to which the 6-inch silicon mirror wafer is attached, a cut is formed in the entire thickness direction of the die bonding film along the outer periphery of the strong adhesive tape. It was cut into a band shape having a width of 25 mm.
Next, in the dark place, the die bonding film after cutting was immersed in pure water at 23 ° C. for 2 hours together with the silicon mirror wafer immediately after the cutting. At this time, the silicon mirror wafer with the die bonding film after cutting was placed in pure water so that the entire silicon mirror wafer was submerged in pure water.
Next, the silicon mirror wafer with the die bonding film after cutting was pulled up from pure water, and water droplets adhering to the surface were removed.
Next, using a UV irradiation device (“RAD-2000 m / 12” manufactured by Lintec Corporation), the die bonding film after cutting was irradiated with UV light under the conditions of an illuminance of 220 mW / cm ² and a light amount of 120 mJ / cm ^2. The die bonding film was cured.
As described above, the comparative test laminate, in which the strong adhesive tape, the cured die bonding film on which the cuts are formed, and the silicon mirror wafer are laminated in this order in the thickness direction, is configured. Obtained.

(Measurement of adhesive strength after immersion of test laminate)
Under the condition of 23 ° C., the strong adhesive tape was pulled in the test laminate using a universal tensile tester (“Autograph AG-IS” manufactured by Shimadzu Corporation). At this time, the adhesive tape is pulled at a peeling (tensile) speed of 300 mm / min so that the peeled surfaces generated in the test laminate make an angle of 180 ° by pulling the strong adhesive tape, so-called 180 °. Peeling was performed. And while peeling force (load, N / 25mm) at this time was measured, the peeling location which arose in the said test laminated body, and the peeling form were confirmed. And the said peeling force was made into the adhesive force (N / 25mm) between the hardened | cured material of the die bonding film whose width | variety is 25 mm in the said test laminated body, and a silicon mirror wafer. The results are shown in the column of “Adhesive strength after immersion” in Table 2.

(Manufacture of non-immersion laminates)
Instead of immersing the cut silicon bonding wafer with the die bonding film in pure water at 23 ° C. for 2 hours in a dark place, the temperature is 23 ° C. and the relative humidity is 50 ° in a dark place under an air atmosphere. A comparative non-immersed test laminate was produced in the same manner as in the comparative test laminate described above except that the sample was stored at 30% for 30 minutes.

(Measurement of non-immersion adhesive strength of laminate for non-immersion test)
For the non-immersion test laminate obtained above, the peel force (load, N / 25 mm) was measured in the same manner as in the case of the test laminate, and the peel occurred in the non-immersion test laminate. The location and the peeling form were confirmed, and the peeling force was defined as the adhesive strength (N / 25 mm) between the cured product of the second layer having a width of 25 mm and the silicon mirror wafer. The results are shown in the column of “Non-immersion adhesive strength” in Table 2.

[Comparative Example 4]
<< Manufacture of die bonding film >>
<Manufacture of adhesive composition>
Polymer component (a) -3 (10 parts by mass), epoxy resin (b1) -4 (10 parts by mass), epoxy resin (b1) -5 (10 parts by mass), epoxy resin (b1) -6 (20 parts by mass) Part), thermosetting agent (b2) -3 (1 part by mass), curing accelerator (c) -2 (1 part by mass), filler (d) -2 (50 parts by mass), coupling agent (e) -5 (0.5 part by mass), crosslinking agent (f) -1 (0.3 part by mass), energy beam curable resin (g) -1 (5 parts by mass), and photopolymerization initiator (h) -1 (0.15 parts by mass) was dissolved or dispersed in methyl ethyl ketone and stirred at 23 ° C. to obtain an adhesive composition having a solid content concentration of (55)% by mass. In addition, all the compounding quantities of components other than the methyl ethyl ketone shown here are solid content conversion values.

<Manufacture of die bonding film>
A die bonding film was produced in the same manner as in Comparative Example 3 except that the adhesive composition obtained above was used.

<< Manufacture of dicing die bonding sheet and evaluation of die bonding film >>
A dicing die bonding sheet was produced by the same method as in Comparative Example 3 except that the die bonding film obtained above was used, and the die bonding film was evaluated. The results are shown in Table 2.

As is clear from the above results, in Examples 1 and 2, the initial detection temperature T ₀ of the first layer of the die bonding film is 68 ° C. or lower (59 to 68 ° C.), and the first layer is a substrate. The embeddability was excellent.

In Examples 1 and 2, the adhesive strength after immersion between the cured product of the second layer and the silicon mirror wafer was 10 N / 25 mm or more (10 N / 25 mm ≦). At the time of measuring the adhesive strength after immersion, in the test laminate, peeling (interfacial peeling) occurred first between the first layer and the strong adhesive tape, and the peeling force at this time was 10 N / 25 mm. No peeling occurred between the cured product of the second layer and the silicon mirror wafer. The non-immersion adhesive strength between the cured product of the second layer and the silicon mirror wafer is also 10 N / 25 mm or more and the test laminate not immersed (non-immersion), similarly to the post-immersion adhesive strength. Also in the test laminate, no peeling occurred between the cured product of the second layer and the silicon mirror wafer.
The die bonding film in which the second layer has been cured was excellent in transferability to the semiconductor chip.

As described above, the die bonding films of Examples 1 and 2 have a two-layer structure, so that transfer failure to a semiconductor chip can be suppressed when picking up a semiconductor chip having a small size, and At the time of die bonding, the substrate could be satisfactorily embedded.

On the other hand, in Comparative Examples 1 and 2, the adhesive strength after immersion between the cured product of the second layer and the silicon mirror wafer is 3.0 N / 25 mm or less (2.3 to 3.0 N / 25 mm). At this time, in the comparative test laminate, peeling (interfacial peeling) occurred between the cured product of the second layer and the silicon mirror wafer. Note that the non-immersion adhesive force between the cured product of the second layer and the silicon mirror wafer was 10 N / 25 mm or more, as in Examples 1 and 2.
And the die-bonding film with which the 2nd layer was hardened was inferior to the transferability to a semiconductor chip.

Comparative Example 1 is the same as Example 1, and Comparative Example 2 is the same as Example 2. The die bonding film and the dicing die bonding sheet are the same. Nevertheless, the reason for such a result is that, at the time of evaluation, the die bonding film after cutting, which is affixed to the silicon mirror wafer, is immersed in pure water and cured (the second layer). This is because the order of (hardening) is reverse in Examples 1-2 and Comparative Examples 1-2. In the case of Examples 1 and 2, the die bonding film after cutting is cured after being immersed in pure water. Considering that dicing using a dicing blade is performed while flowing water (cutting water), it can be said that the evaluation in Examples 1 and 2 reflects the order of steps in which the die bonding film is cured after dicing. . On the other hand, in Comparative Examples 1 and 2, the die bonding film after cutting is immersed in pure water after curing. That is, it can be said that the evaluation of Comparative Examples 1 and 2 reflects the order of processes in which dicing is performed after the die bonding film is cured. Therefore, the evaluation results of these Examples and Comparative Examples are the above-described laminate (1) production process, laminate (2) production process, laminate (3) production process and pickup using the die bonding film of the present invention. By performing the steps in this order, it is shown that the semiconductor chip can be manufactured while suppressing transfer failure of the die bonding film to the semiconductor chip when picking up the semiconductor chip having a small size.

In Comparative Example 3, the die bonding film had a single-layer structure, and the post-immersion adhesive force between the cured product of the die bonding film and the silicon mirror wafer was as small as 3.1 N / 25 mm. At this time, in the test laminate, peeling (interfacial peeling) occurred between the cured product of the die bonding film and the silicon mirror wafer. The non-immersion adhesive force between the cured die bonding film and the silicon mirror wafer was 10 N / 25 mm or more, as in Examples 1-2.
And the hardened | cured material of the die bonding film was inferior to the transferability to a semiconductor chip.

On the other hand, in Comparative Example 4, the initial detection temperature T ₀ of the die bonding film having a single layer configuration was as high as 83 ° C., and the die bonding film was inferior in the embedding property of the substrate. On the other hand, the post-immersion adhesive strength and the non-immersion adhesive strength between the cured product of the die bonding film and the silicon mirror wafer are both 10 N / 25 mm or more, as in Examples 1 and 2. there were.

The present invention provides a die bonding film capable of suppressing transfer failure to a semiconductor chip when picking up a semiconductor chip having a small size and capable of satisfactorily embedding a substrate at the time of die bonding. Since the dicing die bonding sheet provided and the semiconductor chip manufacturing method using the dicing die bonding sheet can be provided, it is extremely useful in the industry.

1A, 1B, 1C, 1D ... dicing die bonding sheet,
10 ... Support sheet (dicing sheet),
12 ... intermediate layer,
13, 23 ... Die bonding film,
131, 231 ... the first layer,
131 ′ ・・・ cut first layer,
132,232 ... the second layer,
132 '... the cut second layer,
1320 '... a cut and hardened second layer,
9: Semiconductor wafer,
9 '... semiconductor chip,
101 ... Laminated body (1-2) (laminated body (1), laminated body (1-1)),
102 ... Laminated body (2),
103 ... Laminated body (3)

Claims

Including a first layer and a second layer provided on the first layer;
The first layer has an initial detection temperature of melt viscosity of 75 ° C. or less,
The second layer has adhesiveness and energy ray curability, has a thickness of 10 μm, and a width of more than 25 mm. The second layer is a test piece, and the test piece is affixed to a silicon mirror wafer. Then, the test piece is cut so as to have a width of 25 mm, the cut test piece is immersed in pure water for 2 hours together with the silicon mirror wafer, and the immersed test piece is cured with energy rays. Adhesive force between the cured product having a width of 25 mm and the silicon mirror wafer when a laminated body for test in which the cured product is affixed to the silicon mirror wafer is prepared by using a cured product. Has a characteristic of 6N / 25mm or more,
Die bonding film.
Comprising a support sheet and the die bonding film according to claim 1 provided on the support sheet;
A dicing die bonding sheet, wherein the first layer in the die bonding film is disposed on the support sheet side.
The laminated body (1-1) in which a semiconductor wafer is stuck to the second layer and a dicing sheet is stuck to the first layer of the die bonding film according to claim 1, or the die bonding film according to claim 2. Producing a laminated body (1-2) in which a semiconductor wafer is bonded to the second layer in the die bonding film of the dicing die bonding sheet;
By cutting the semiconductor wafer in the laminated body (1-1) or the laminated body (1-2) together with the die bonding film with a dicing blade, the cut first layer and the cut first layer Producing a laminate (2) comprising two layers and a semiconductor chip which is the cut semiconductor wafer;
A laminate (1) including the cut first layer, the cured product, and the semiconductor chip by curing the cut second layer in the laminate (2) by energy ray curing. 3) producing,
In the laminate (3), the semiconductor chip including the cut first layer and the cured product is pulled away from the dicing sheet or the support sheet and picked up;
A method for manufacturing a semiconductor chip, comprising: