WO2020196130A1 - Film adhesive and sheet for semiconductor processing - Google Patents

Abstract

The present invention relates to a thermosetting film adhesive, wherein, by using a scanning probe microscope: when an area value x1 of a first region that corresponds to a convex section in a binarized image obtained by measuring the surface shape of the film adhesive before thermosetting, and an area value y1 of a second region outside the first region are determined, x1/y1 is 0 to 0.3; and when an area value x2 of a first region and an area value y2 of a second region outside the first region are similarly determined for the film adhesive after thermosetting, x2/y2 is greater than 0.3 and no more than 5.

Description

Film-like adhesive and semiconductor processing sheet

The present invention relates to a film-like adhesive and a sheet for semiconductor processing.
The present application claims priority based on Japanese Patent Application No. 2019-54996 filed in Japan on March 22, 2019, the contents of which are incorporated herein by reference.

The semiconductor chip is usually die-bonded to the circuit forming surface of the substrate by a film-like adhesive attached to the back surface thereof. Then, a semiconductor package is manufactured using the obtained product, and finally, a target semiconductor device is manufactured using this semiconductor package.

A semiconductor chip having a film-like adhesive on the back surface (semiconductor chip with a film-like adhesive) is, for example, a semiconductor wafer having a film-like adhesive on the back surface, and the semiconductor wafer is divided into semiconductor chips and a film. It is produced by cutting the state adhesive at the same time. As such a method, for example, a method of dividing a semiconductor wafer by using a dicing blade and cutting a film-like adhesive at the same time is known (see Patent Document 1). In this case, the film-like adhesive before cutting may be used as a dicing die bonding sheet that is laminated and integrated with a dicing sheet used for fixing a semiconductor wafer during dicing.

Japanese Unexamined Patent Publication No. 2012-222002

In the above method, if the characteristics of the film-like adhesive are insufficient, for example, so-called chip skipping occurs in which the semiconductor chip scatters from the film-like adhesive after cutting.
Further, when a semiconductor package is manufactured using a semiconductor chip with a film-like adhesive, peeling occurs between the semiconductor chip and the substrate or between the semiconductor chips in the heated semiconductor package, and the semiconductor package The reliability is reduced.

In the present invention, when a semiconductor wafer having a film-like adhesive on the back surface is used and the semiconductor wafer is divided into semiconductor chips and the film-like adhesive is cut at the same time by dying, the semiconductor chip It is an object of the present invention to provide a film-like adhesive capable of suppressing scattering from the film-like adhesive and producing a highly reliable semiconductor package, and a semiconductor processing sheet provided with the film-like adhesive.

The present invention is a thermosetting film-like adhesive, and the surface shape of the film-like adhesive before thermosetting is measured using a scanning probe microscope, and the entire distribution of the histogram of the unevenness in the surface shape is measured. Is 85% of the entire color tone bar, the image is binarized, and the area value x ₁ of the first region corresponding to the convex portion in the obtained processed image and the first When the area value y ₁ of the second region other than the region was obtained, x ₁ / y ₁ was 0 or more and 0.3 or less, and the thermosetting product of the film-like adhesive was used using a scanning probe microscope. The surface shape of the film was measured, an image was obtained in which the total distribution of the unevenness histogram in the surface shape was 85% of the entire color tone bar, and the image was binarized to obtain convexity in the obtained processed image. When the area value x ₂ of the first region corresponding to the portion and the area value y ₂ of the second region other than the first region are obtained, x ₂ / y ₂ is larger than 0.3 and 5 or less. Provide a film-like adhesive.
In the film-like adhesive of the present invention, the surface shape of the film-like adhesive after storage at 40 ° C. for 7 days and before thermosetting is measured using a scanning probe microscope, and the unevenness in the surface shape is measured. An image in which the total distribution of the histogram of the above is 85% of the entire color tone bar is acquired, and the image is binarized, and the area value x _{10 of} the first region corresponding to the convex portion in the obtained processed image. When the area value y ₁₀ of the second region other than the first region was obtained, x ₁₀ / y ₁₀ was 0 or more and 0.3 or less, and 7 at 40 ° C. using a scanning probe microscope. The surface shape of the thermosetting product obtained by thermosetting the film-like adhesive after storage for a day was measured, and an image was obtained in which the entire distribution of the histogram of the unevenness on the surface shape was 85% of the entire color tone bar. Then, the image is binarized, and the area value x ₂₀ of the first region corresponding to the convex portion in the obtained processed image and the area value y ₂₀ of the second region other than the first region are obtained. It is preferable that x ₂₀ / y ₂₀ is larger than 0.3 and 5 or less.

The present invention provides a semiconductor processing sheet provided with a support sheet and the film-like adhesive on one surface of the support sheet.
In the semiconductor processing sheet of the present invention, the support sheet includes a base material and an adhesive layer provided on one surface of the base material, and the pressure-sensitive adhesive layer is the base material. And may be arranged between the film-like adhesive.

According to the present invention, when a semiconductor wafer having a film-like adhesive on the back surface is used and the semiconductor wafer is divided into semiconductor chips and the film-like adhesive is cut at the same time by dying, the semiconductor Provided are a film-like adhesive capable of suppressing scattering of chips from the film-like adhesive and capable of producing a highly reliable semiconductor package, and a semiconductor processing sheet provided with the film-like adhesive.

It is sectional drawing which shows typically the film-like adhesive which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the semiconductor processing sheet which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the semiconductor processing sheet which concerns on other embodiment of this invention. It is sectional drawing which shows typically the semiconductor processing sheet which concerns on still another Embodiment of this invention. It is sectional drawing which shows typically the semiconductor processing sheet which concerns on still another Embodiment of this invention.

-Film Adhesive The film adhesive according to an embodiment of the present invention is a thermosetting film adhesive, which may be abbreviated as "SPM" in the scanning probe microscope (in the present specification). The surface shape of the film-like adhesive before thermosetting was measured using (A), and an image was obtained in which the total distribution of the histogram of the unevenness in the surface shape was 85% of the entire color tone bar, and the image was obtained. When the binarization process is performed to obtain the area value x ₁ of the first region corresponding to the convex portion in the obtained processed image and the area value y ₁ of the second region other than the first region, When x ₁ / y ₁ is 0 or more and 0.3 or less, the surface shape of the thermosetting product of the film-like adhesive is measured using a scanning probe microscope (SPM), and a histogram of the unevenness in the surface shape is obtained. An image in which the total distribution is 85% of the entire color tone bar is acquired, the image is binarized, and the area value x ₂ of the first region corresponding to the convex portion in the obtained processed image and the above. When the area value y ₂ of the second region other than the first region is obtained, x ₂ / y ₂ is larger than 0.3 and 5 or less.
In the present specification, the "histogram of unevenness in the surface shape" refers to the distribution of the frequency for each class, with the horizontal axis representing the color tone class and the vertical axis representing the frequency of the class. It means the represented frequency distribution map. The "color tone bar" corresponds to the horizontal axis representing the color tone class, and the "whole color tone bar" represents all the classes of the color tone class (that is, the entire color tone class). Therefore, "acquiring an image in which the entire distribution of the histogram of the unevenness in the surface shape is 85% of the entire color tone bar" means that the distribution of the histogram is distributed in 85% of all the classes of the color tone. Represents the acquisition of an image that has been tuned to.

In the film-like adhesive of the present embodiment, since x ₁ / y ₁ is 0.3 or less, a semiconductor wafer having this film-like adhesive on the back surface is used, and dicing is performed to form a semiconductor chip of the semiconductor wafer. When the division of the semiconductor chip and the cutting of the film-like adhesive are performed at the same time, it is possible to suppress the scattering of the semiconductor chip from the film-like adhesive (in the present specification, it may be referred to as “chip skipping”).

In terms of increasing the effect of suppressing chip skipping, x ₁ / y ₁ is preferably 0.29 or less, more preferably 0.25 or less, and further preferably 0.2 or less. It is preferably 0.15 or less, and particularly preferably 0.15 or less.

In the film-like adhesive of the present embodiment, x ₁ is 0 or more, y ₁ is larger than 0, and x ₁ / y ₁ is 0 or more.

In the film-like adhesive of the present embodiment, x ₁ / y ₁ can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned lower limit value and any upper limit value. For example, in one embodiment, x ₁ / y ₁ is preferably 0 or more and 0.29 or less, more preferably 0 or more and 0.25 or less, and further preferably 0 or more and 0.2 or less. It is preferably 0 or more and 0.15 or less, and may be 0.
However, these are examples of x ₁ / y ₁ .

On the other hand, in the film-like adhesive of the present embodiment, when x ₂ / y ₂ is larger than 0.3, the reliability of the semiconductor package produced by using this film-like adhesive is high.

In terms of increasing the reliability of the semiconductor package produced by using the film-like adhesive, x ₂ / y ₂ is preferably 0.4 or more, more preferably 0.5 or more. It is more preferably 0.6 or more, and particularly preferably 0.65 or more.

In the film-like adhesive of the present embodiment, x ₂ is 0 or more, y ₂ is larger than 0, and x ₂ / y ₂ is 5 or less.
x ₂ / y ₂ is preferably 3 or less, more preferably 2 or less, and particularly preferably 1 or less.

In the film-like adhesive of the present embodiment, x ₂ / y ₂ can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned lower limit value and any upper limit value. For example, in one embodiment, x ₂ / y ₂ is preferably 0.4 or more and 5 or less, more preferably 0.5 or more and 3 or less, and further preferably 0.6 or more and 2 or less. It is preferably 0.65 or more and 1 or less, and may be 1.

The method of selecting the first region for obtaining x ₂ is for obtaining x ₁ except that the object to be selected is not a film-like adhesive before thermosetting but a thermosetting product of a film-like adhesive. It is the same as the selection method of the first area.
In other words, the method of selecting the second region for obtaining y ₂ is to select y ₁ except that the object to be selected is not a film-like adhesive before thermosetting but a thermosetting product of a film-like adhesive. It is the same as the method of selecting the second region for obtaining.
A more detailed selection method of the first region and the second region will be described in Examples described later.

In the film-like adhesive of the present embodiment, the surface shape of the film-like adhesive is measured using SPM after storage at 40 ° C. for 7 days and before thermosetting, and a histogram of the unevenness in the surface shape. An image was obtained in which the total distribution of the above was 85% of the entire color tone bar, and the image was binarized to obtain an area value x ₁₀ of a first region corresponding to a convex portion in the obtained processed image. When the area value y ₁₀ of the second region other than the first region is obtained, x ₁₀ / y ₁₀ may be 0 or more and 0.3 or less. As described above, when x ₁₀ / y ₁₀ in the film-like adhesive after aging is unchanged or small as compared with x ₁ / y ₁ which is 0 or more and 0.3 or less, the film-like adhesive is formed. The storage stability of the adhesive is high, and changes in the characteristics of the film-like adhesive during storage are suppressed. For example, even when a film-like adhesive having x ₁₀ / y ₁₀ within the above range is stored and the film-like adhesive after storage is used, the effect of suppressing chip skipping is enhanced.

The method for selecting the first region for determining x ₁₀ is the method for selecting the first region for determining x ₁ , except that the film-like adhesive to be selected has been stored at 40 ° C. for 7 days. It is the same as the selection method.
In other words, the method of selecting the second region for obtaining y ₁₀ is the first method for obtaining y ₁ except that the film-like adhesive of the object to be selected has been stored at 40 ° C. for 7 days. The method for selecting two areas is the same.

In the film-like adhesive of the present embodiment, x ₁₀ / y ₁₀ may be in the same numerical range as x ₁ / y ₁ .
That is, x ₁₀ / y ₁₀ may be any one of 0.29 or less, 0.25 or less, 0.2 or less, and 0.15 or less in that the effect of suppressing chip skipping becomes higher. ..
For example, in one embodiment, x ₁₀ / y ₁₀ is any of 0 or more and 0.29 or less, 0 or more and 0.25 or less, 0 or more and 0.2 or less, 0 or more and 0.15 or less, and 0. You may.
However, these are examples of x ₁₀ / y ₁₀ .

In the film-like adhesive of the present embodiment, the surface shape of the thermosetting product obtained by thermosetting the film-like adhesive after storage at 40 ° C. for 7 days is measured using SPM, and the surface shape is measured. An image in which the entire distribution of the histogram of the unevenness in the above is 85% of the entire color tone bar is acquired, the image is binarized, and the area value of the first region corresponding to the convex portion in the obtained processed image is obtained. When x ₂₀ and the area value y ₂₀ of the second region other than the first region are obtained, x ₂₀ / y ₂₀ may be larger than 0.3 and 5 or less. As described above, when x ₂₀ / y ₂₀ in the film-like adhesive after aging is no change or small change as compared with x ₂ / y ₂ which is larger than 0.3 and 5 or less. The storage stability of the film-like adhesive is high, and changes in the characteristics of the film-like adhesive during storage are suppressed. For example, even when a film-like adhesive having x ₂₀ / y ₂₀ within the above range is stored and a semiconductor package is produced using the film-like adhesive after storage, the reliability of the obtained semiconductor package is obtained. The sex becomes high.

Selection of the first region for obtaining the x _20, rather than the film-like adhesive prior to selecting the object thermosetting, the film adhesive undergoing storage for 7 days at 40 ° C., a thermosetting product except for a point is the same as the method of selecting the first region for obtaining the x _1.
In other words, the method of selecting the second region for obtaining y ₂₀ is that the object to be selected is not a film-like adhesive before thermosetting, but a film-like adhesive that has been stored at 40 ° C. for 7 days. except a cured product is the same as selecting the method of the second region for obtaining the y _1.

In the film-like adhesive of the present embodiment, x ₂₀ / y ₂₀ may be in the same numerical range as x ₂ / y ₂ .
That is, in terms of increasing the reliability of the semiconductor package, x ₂₀ / y ₂₀ is 0.25 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, and 0.65. It may be any of the above.
For example, in one embodiment, x ₂₀ / y ₂₀ may be any of 3 or less, 2 or less, and 1 or less.
For example, in one embodiment, x ₂₀ / y ₂₀ is 0.25 or more and 5 or less, 0.4 or more and 5 or less, 0.5 or more and 3 or less, 0.6 or more and 2 or less, 0.65 or more and 1 or less, and It may be any one of 1.
However, these are examples of x ₂₀ / y ₂₀ .

The film-like adhesive of the present embodiment preferably satisfies both the above-mentioned conditions of x ₁₀ / y ₁₀ and x ₂₀ / y ₂₀ .
That is, in the film-like adhesive of the present embodiment, the surface shape of the film-like adhesive after storage at 40 ° C. for 7 days and before thermosetting is measured using SPM, and the unevenness in the surface shape is measured. An image in which the entire distribution of the histogram of the above is 85% of the entire color tone bar is acquired, and the image is binarized, and the area value x _{10 of} the first region corresponding to the convex portion in the obtained processed image. When the area value y ₁₀ of the second region other than the first region was obtained, x ₁₀ / y ₁₀ was 0 or more and 0.3 or less, and after storage at 40 ° C. for 7 days using SPM. The surface shape of the thermosetting product obtained by thermosetting the film-like adhesive was measured, and an image was obtained in which the entire distribution of the histogram of the unevenness in the surface shape was 85% of the entire color tone bar. The image was binarized to obtain the area value x ₂₀ of the first region corresponding to the convex portion in the obtained processed image and the area value y ₂₀ of the second region other than the first region. When, x ₂₀ / y ₂₀ is preferably greater than 0.3 and less than or equal to 5.
However, this is an example of a preferable film-like adhesive that satisfies both the above-mentioned conditions of x ₁₀ / y ₁₀ and x ₂₀ / y ₂₀ .

In the present embodiment, the film-like adhesive for which you want the x ₁ and y ₁ are immediately after its preparation, not conserved at temperatures exceeding 25 ° C., and under a temperature of Article 25 ° C. or less It is preferable that the storage time is within one year.
Further, the storage conditions of the film-like adhesive other than the temperature at this time are as follows.
That is, the film-like adhesive is preferably stored in an air atmosphere, is preferably stored in a stationary state, and is preferably stored in a dark place. Then, it is more preferable to store so as to satisfy these two or more conditions, and it is particularly preferable to store so as to satisfy all the conditions.

In the present embodiment, the film-like adhesive to be stored at 40 ° C. for 7 days in order to obtain x ₁₀ and y ₁₀ and x ₂₀ and y ₂₀ is the target for obtaining x ₁ and y ₁ described above. It is the same as the film-like adhesive.

In the present embodiment, the thermosetting product of the film-like adhesive, which is the target for obtaining x ₂ and y ₂ , and x ₂₀ and y ₂₀ , is that the film-like adhesive before heat curing is heated at 160 ° C. for 1 hour. It is preferable that the product is obtained by thermosetting.
In the cured product of the film-like adhesive obtained by heating under the above heating temperature and heating time conditions, the variation in the degree of thermosetting is suppressed, and x ₂ and y ₂ and x ₂₀ and y ₂₀ are increased. Required for accuracy.

x ₁ and y ₁ , x ₂ and y ₂ , x ₁₀ and y ₁₀ , and x ₂₀ and y ₂₀ are all, for example, the type and amount of components contained in the film-like adhesive, and the thickness of the film-like adhesive. It can be adjusted as appropriate by adjusting the size.

A silicon chip having a size of 2 mm × 2 mm (in the present specification, such a size may be referred to as “2 mm □”) and a size provided on the entire surface of one surface of the silicon chip. Using a test chip provided with a film-like adhesive having a size of 2 mm × 2 mm (that is, 2 mm □) and a thickness of 20 μm, the film-like adhesive in the test chip heated to 125 ° C. Of these, the entire surface of the surface opposite to the silicon chip side is brought into contact with the surface of a copper plate having a thickness of 0.5 mm, and the test chip is orthogonal to the contact surface with the copper plate. The test chip is pressure-bonded to the copper plate by applying a force of 2.45 N (250 gf) for 3 seconds, and then the film-like adhesive is heat-cured by heating at 160 ° C. for 1 hour. Then, a test piece was prepared, and among the silicon chips in the test piece, the surface of the copper plate in the test piece on the side on which the silicon chip was mounted was 7 μm high. A force is applied in the shearing direction at a rate of 200 μm / sec, and the force applied when the adhesive state between the heat-cured product of the film-like adhesive in the test piece and the copper plate is broken is applied. When the adhesive strength of the heat-cured product of the film-like adhesive is taken, the adhesive strength is preferably 150 N / 2 mm □ or more, more preferably 200 N / 2 mm □ or more, and 240 N / 2 mm □ or more. Is even more preferable. When the adhesive force is at least the lower limit value, the reliability of the semiconductor package obtained by using the film-like adhesive becomes higher.

The upper limit of the adhesive strength is not particularly limited. For example, the adhesive strength may be 400 N / 2 mm □ or less in that a film-like adhesive can be produced more easily.

The test chip used for measuring the adhesive strength can be produced by the same method as a known production method of a silicon chip with a film-like adhesive.
For example, a sheet for semiconductor processing, which will be described later, provided with the film-like adhesive is attached to the back surface (polished surface) of the silicon wafer by the film-like adhesive at room temperature, and the silicon wafer is used with a dicing blade. By dividing the film into a size of 2 mm × 2 mm and cutting the film-like adhesive into a size of 2 mm × 2 mm, a test chip can be produced.

In the present specification, the surface on which the circuit of the semiconductor chip is formed is referred to as a "circuit forming surface", and the surface opposite to the circuit forming surface is referred to as a "back surface". A structure including the semiconductor chip and the film-like adhesive provided on the back surface thereof is referred to as a "semiconductor chip with a film-like adhesive".
Further, in the present specification, the surface on which the circuit of the substrate is formed is also referred to as a “circuit forming surface”.
The semiconductor chip with a film-like adhesive provided with the film-like adhesive of the present embodiment can be die-bonded to the circuit-forming surface of the substrate in good condition by the film-like adhesive.

The film-like adhesive may be composed of one layer (single layer), may be composed of two or more layers, and when composed of a plurality of layers, the plurality of layers are the same as each other. However, they may be different, and the combination of these multiple layers is not particularly limited.

In addition, in this specification, not only in the case of a film-like adhesive, "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 different, or only some layers may be the same ", and" multiple layers are different from each other "means" at least one of the constituent materials and thicknesses of each layer is different from each other. It means "different".

The thickness of the film-like adhesive is not particularly limited, but is preferably 1 to 50 μm, more preferably 3 to 40 μm, and particularly preferably 5 to 30 μm. When the thickness of the film-like adhesive is at least the above lower limit value, the adhesive force of the film-like adhesive to the adherend (semiconductor wafer, semiconductor chip) becomes higher. When the thickness of the film-like adhesive is not more than the upper limit, the film-like adhesive can be cut more easily in the semiconductor chip manufacturing process described later, and cut pieces derived from the film-like adhesive are generated. The amount can be further reduced, which is advantageous for thinning the semiconductor device.
Here, the "thickness of the film-like adhesive" means the thickness of the entire film-like adhesive, and for example, the thickness of the film-like adhesive composed of a plurality of layers is all that constitute the film-like adhesive. Means the total thickness of the layers of.
As used herein, the term "thickness" refers to the average thickness of five randomly selected thicknesses measured with a contact thickness meter on a cut surface randomly cut in the thickness direction of an object. It is a value represented by.

The film-like adhesive can be formed by using an adhesive composition containing the constituent material.
For example, a film-like adhesive can be formed on a target portion by applying the adhesive composition to the surface to be formed of the film-like adhesive and drying it if necessary.
The ratio of the contents of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the contents of the components in the film-like adhesive. In addition, in this specification, "normal temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

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

The drying conditions of the adhesive composition are not particularly limited, but when the adhesive composition contains a solvent described later, it is preferable to heat-dry the adhesive composition. The solvent-containing adhesive composition is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes.
Hereinafter, the components contained in the film-like adhesive and the adhesive composition will be described in detail.

<< Adhesive composition >>
Preferred adhesive compositions include thermosetting adhesive compositions.
Examples of the thermosetting adhesive composition include those containing a polymer component (a) and a thermosetting component (b). Hereinafter, each component will be described.

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

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

Examples of the polymer component (a) include acrylic resin, urethane resin, phenoxy resin, silicone resin, saturated polyester resin, and the like, and acrylic resin is preferable.

Examples of the acrylic resin in the polymer component (a) include known acrylic polymers.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2000,000, more preferably 100,000 to 1,500,000. 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 film-like adhesive and the adherend within a preferable range.
On the other hand, when the weight average molecular weight of the acrylic resin is at least the above lower limit value, the shape stability (stability with time during storage) of the film-like adhesive is improved. Further, when the weight average molecular weight of the acrylic resin is not more than the above upper limit value, the film-like adhesive can easily follow the uneven surface of the adherend, and voids or the like can be formed between the adherend and the film-like adhesive. Occurrence is more suppressed.
In the present specification, the "weight average molecular weight" is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably −60 to 70 ° C., more preferably −30 to 50 ° C. When the Tg of the acrylic resin is at least the above lower limit value, the adhesive force between the film-like adhesive and the adherend is suppressed, and at the time of pickup, the support sheet of the semiconductor chip with the film-like adhesive, which will be described later. It will be easier to separate from. When the Tg of the acrylic resin is not more than the above upper limit value, the adhesive force between the film-like adhesive and the semiconductor chip is improved.
In the present specification, the "glass transition temperature" is represented by the temperature of the inflection point of the obtained DSC curve obtained by measuring the DSC curve of the sample using a differential scanning calorimeter.

Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (meth). N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylate Heptyl, 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 (also called lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also called myristyl (meth) acrylate), (meth) ) Pentadecyl acrylate, hexadecyl (meth) acrylate (also called palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also called stearyl (meth) acrylate), etc. The (meth) acrylic acid alkyl ester having a chain structure having 1 to 18 carbon atoms is the alkyl group constituting the above;
(Meta) Acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentanyl;
(Meta) Acrylic acid aralkyl esters such as benzyl (meth) acrylic acid;
(Meta) Acrylic acid cycloalkenyl ester such as (meth) acrylic acid dicyclopentenyl ester;
(Meta) Acrylic acid cycloalkenyloxyalkyl ester such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meta) acrylate imide;
A glycidyl group-containing (meth) acrylic acid ester such as glycidyl (meth) acrylate;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) ) Hydroxyl-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) acrylic acid. Here, the "substituted amino group" means a group having a structure in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.

In addition, in this specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth) acrylic acid.

In addition to the (meth) acrylic acid ester, the acrylic resin may contain one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like. It may be a resin obtained by copolymerization.

The monomer constituting the acrylic resin may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

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-mentioned hydroxyl group. These functional groups such as the hydroxyl group of the acrylic resin may be bonded to another compound via a cross-linking agent (f) described later, or may be directly bonded to another compound without a cross-linking agent (f). You may be. When the acrylic resin is bonded to another compound by the functional group, the reliability of the package obtained by using the film-like adhesive tends to be improved.

In the acrylic resin, the ratio (content) of the mass of the constituent unit derived from the glycidyl group-containing monomer to the total mass of the constituent units constituting the acrylic resin is preferably 25% by mass or less, for example, 15% by mass. It may be either the following and 10% by mass or less. When the ratio (content) is not more than the upper limit value, the storage stability of the film-like adhesive becomes higher. The glycidyl group-containing monomer means a monomer having a glycidyl group, such as the glycidyl group-containing (meth) acrylic acid ester.

In the acrylic resin, the lower limit of the ratio (content) of the mass of the constituent unit derived from the glycidyl group-containing monomer to the total mass of the constituent units constituting the acrylic resin is not particularly limited.
In the acrylic resin, the ratio (content) may be 0% by mass or more, and for example, if it is 2% by mass or more, the effect of using the glycidyl group-containing monomer can be more clearly obtained. ..

In the acrylic resin, the ratio (content) of the mass of the constituent unit derived from the glycidyl group-containing monomer to the total mass of the constituent units constituting the acrylic resin is arbitrarily set to any of the above lower limit value and upper limit value. It can be adjusted as appropriate within the range set in combination with. For example, in one embodiment, the proportion is preferably 0 to 25% by mass, and may be, for example, 0 to 15% by mass, or 0 to 10% by mass. Further, in one embodiment, the ratio is preferably 2 to 25% by mass, and may be, for example, 2 to 15% by mass, or 2 to 10% by mass. However, these are examples of the above ratio.

In the present invention, as the polymer component (a), a thermoplastic resin other than the acrylic resin (hereinafter, may be simply abbreviated as “thermoplastic resin”) may be used alone without using the acrylic resin. However, it may be used in combination with an acrylic resin. By using the thermoplastic resin, it becomes easier to separate the semiconductor chip with the film-like adhesive from the support sheet described later at the time of pickup, and the film-like adhesive follows the uneven surface of the adherend. This facilitates the process, and the generation of voids and the like between the adherend and the film-like adhesive may be further suppressed.

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

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

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

The thermoplastic resin contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

In the adhesive composition, the ratio of the content of the polymer component (a) to the total content of all the components other than the solvent (that is, the polymer component (that is, the polymer component to the total mass of the film-like adhesive in the film-like adhesive). The content ratio) of a) is preferably 5 to 40% by mass, more preferably 6 to 30% by mass, and for example, 7 to 20%, regardless of the type of the polymer component (a). It may be mass% or the like. When the ratio is equal to or higher than the lower limit, the structure of the film-like adhesive is more stabilized. When the ratio is equal to or less than the upper limit value, x ₁ and y ₁ , x ₂ and y ₂ , x ₁₀ and y ₁₀ , and x ₂₀ and y ₂₀ can be adjusted more easily.

In the adhesive composition and the film-like adhesive, the ratio of the content of the acrylic resin to the total content of the polymer component (a) is preferably 25 to 100% by mass, for example, 50 to 100% by mass. , 70 to 100% by mass, and 90 to 100% by mass. When the ratio of the content is at least the lower limit value, the storage stability of the film-like adhesive becomes higher.

<Thermosetting component (b)>
The thermosetting component (b) is composed of an epoxy resin (b1) and a thermosetting agent (b2).
The thermosetting component (b) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof may be arbitrarily selected. it can.
Examples of the thermosetting component (b) include epoxy-based thermosetting resins, polyimide resins, unsaturated polyester resins, and the like.
Among these, the thermosetting component (b) is preferably an epoxy-based thermosetting resin.
[Epoxy thermosetting resin]
The epoxy-based thermosetting resin is composed of an epoxy resin (b1) and a thermosetting agent (b2).
The epoxy-based thermosetting resin contained in the adhesive composition and the film-like adhesive may be only one type, two or more types, or a combination thereof and two or more types. The ratio can be selected arbitrarily.

[Epoxy resin (b1)]
Examples of the epoxy resin (b1) include known ones, such as polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, and dicyclopentadiene type epoxy resin. Biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and other bifunctional or higher functional epoxy compounds can be mentioned.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group may be used. An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin described later than an epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the film-like adhesive is improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound having a structure in which a part of the epoxy group of the polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting an epoxy group to an addition reaction of (meth) acrylic acid or a derivative thereof. In the present specification, the term "derivative" means a compound having a structure in which one or more groups of the original compound are substituted with other groups (substituents) unless otherwise specified. Here, the "group" includes not only an atomic group composed of a plurality of atoms bonded together, but also one atom.

Further, examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
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. , (Meta) acrylamide group and the like, and an acryloyl group is preferable.

The number average molecular weight of the epoxy resin (b1) is not particularly limited, but is preferably 300 to 30,000 from the viewpoint of the curability of the film-like adhesive and the strength and heat resistance of the cured product of the film-like adhesive. It is more preferably 400 to 10000, and particularly preferably 500 to 3000.
As used herein, "number average molecular weight" means a number average molecular weight represented by a standard polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method, unless otherwise specified.
The epoxy equivalent of the epoxy resin (b1) is preferably 100 to 1000 g / eq, more preferably 150 to 800 g / eq.
As used herein, the term "epoxy equivalent" means the number of grams (g / eq) of an epoxy compound containing an epoxy group equivalent to 1 gram, and can be measured according to the method of JIS K 7236: 2001.

The epoxy resin (b1) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

Commercially available products of the epoxy resin (b1) include those containing acrylic resin fine particles (fine particle acrylic resin). In the present embodiment, by using the epoxy resin (b1) that does not contain the acrylic resin fine particles, for example, as the polymer component (a), one that easily aggregates the acrylic resin fine particles by interaction with the acrylic resin fine particles is used. Even when used, such agglomeration of acrylic resin fine particles may be suppressed, which may increase the storage stability of the film-like adhesive.
In that such an effect can be obtained more clearly, for example, in the adhesive composition, the ratio of the content of the acrylic resin fine particles to the total content of all the components other than the solvent (that is, in the film-like adhesive). The ratio of the content of the acrylic resin fine particles to the total mass of the film-like adhesive) is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, regardless of the origin of the acrylic resin fine particles. preferable.

[Thermosetting agent (b2)]
The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b1).
As the thermosetting agent (b2), for example, the following general formula (1):

　（一般式（１）中、ｎは１以上の整数である。）
で表される樹脂（本明細書においては、「樹脂（１）」と称することがある）と、それ以外の熱硬化剤と、が挙げられる。

(In the general formula (1), n is an integer of 1 or more.)
(In the present specification, it may be referred to as "resin (1)") and other thermosetting agents.

The thermosetting agent (b2) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. .. For example, the adhesive composition and the film-like adhesive may contain only the resin (1) as the thermosetting agent (b2), or may contain only the thermosetting agent other than the resin (1). Alternatively, the resin (1) and other thermosetting agents may be contained together.

・ Resin (1)
More specifically, the resin (1) is an o-cresol type novolak resin.
In the general formula (1), n is an integer of 1 or more, and may be, for example, any of 2 or more, 4 or more, and 6 or more.
The upper limit of n is not particularly limited as long as the effect of the present invention is not impaired. For example, the resin (1) having n of 10 or less is easier to manufacture or obtain.

In the general formula (1), these o-cresols of the methylene group (-CH _2- ) connecting the o-cresol-diyl groups (-C ₆ H ₄ (-OH) (-CH ₃ )-) are connected to each other. -The bond position with respect to the diyl group is not particularly limited.

Further, the softening point of the resin (1) is 60 to 130 ° C. When the softening point of the resin (1) is 60 ° C. or higher, the force with which the film-like adhesive adheres to the adherends to be adhered to each other, that is, the so-called adhesive force becomes high. When the softening point of the resin (1) is 130 ° C. or lower, the die bonding temperature of the film-like adhesive can be lowered, and the warpage of the substrate after die bonding can be highly suppressed.
In the present specification, the "softening point" can be measured by a method conforming to JIS K7234.

The resin (1) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

-The thermosetting agent other than the resin (1) The thermosetting agent other than the resin (1) is not particularly limited as long as it does not correspond to the resin (1).
Examples of the thermosetting agent other than the resin (1) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group is anhydrated, and the like.

Among the thermosetting agents other than the resin (1), the phenolic curing agent having a phenolic hydroxyl group includes, for example, polyfunctional phenol resin, biphenol, novolak type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin and the like. Can be mentioned.
Among the thermosetting agents other than the resin (1), examples of the amine-based curing agent having an amino group include dicyandiamide (DICY) and the like.

Thermosetting agents other than the resin (1) may have unsaturated hydrocarbon groups.
Examples of the thermosetting agent other than the resin (1) having an unsaturated hydrocarbon group include a compound having a structure in which some of the hydroxyl groups of the phenol resin are substituted with a group having an unsaturated hydrocarbon group, a phenol resin. Examples thereof include compounds having a structure in which a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of.
The unsaturated hydrocarbon group in the thermosetting agent other than the resin (1) 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 other than the resin (1), the adhesive strength of the film-like adhesive can be easily adjusted. Therefore, the thermosetting agent other than the resin (1) has a softening point. Alternatively, one having a high glass transition temperature is preferable.

Among the thermosetting agents other than the resin (1), the number average molecular weight of the resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin is 300 to 30,000. It is preferable, it is more preferably 400 to 10000, and particularly preferably 500 to 3000.
Among the thermosetting agents other than the resin (1), for example, the molecular weight of the non-resin component such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

The thermosetting agent other than the resin (1) contained in the adhesive composition and the film-like adhesive 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 It can be selected arbitrarily.

In the adhesive composition and the film-like adhesive, the content of the thermosetting agent (b2) is 0 with respect to 100 parts by mass of the content of the epoxy resin (b1) regardless of the type of the thermosetting agent (b2). It is preferably 1 to 500 parts by mass, more preferably 1 to 200 parts by mass, and may be, for example, 5 to 100 parts by mass or 10 to 75 parts by mass. When the content of the thermosetting agent (b2) is at least the lower limit value, the curing of the film-like adhesive becomes easier to proceed. When the content of the thermosetting agent (b2) is not more than the upper limit value, the hygroscopicity of the film-like adhesive is reduced, and the reliability of the package obtained by using the film-like adhesive is further improved. ..

In the adhesive composition and the film-like adhesive, the content of the thermosetting component (b) (total content of the epoxy resin (b1) and the thermosetting agent (b2)) is the content of the polymer component (a). With respect to 100 parts by mass, it is preferably 100 to 900 parts by mass, more preferably 130 to 850 parts by mass, further preferably 160 to 800 parts by mass, for example, 400 to 800 parts by mass. It may be any of 500 to 800 parts by mass and 600 to 800 parts by mass. When the content of the thermosetting component (b) is in such a range, it becomes easier to adjust the adhesive force between the film-like adhesive and the support sheet described later.

When the adhesive composition and the film-like adhesive contain the resin (1), [amount (part by mass) of the resin (1) in the film-like adhesive] / [epoxy resin (b1) in the film-like adhesive) Amount (parts by mass)] (in the present specification, it may be abbreviated as "(1) / (b1) value") is preferably greater than 0 and less than or equal to 1. When the (1) / (b1) value is 1 or less, the thermosetting of the film-like adhesive progresses to a high degree, and as a result, the film-like adhesive is stored regardless of whether or not the semiconductor processing sheet described later is stored. The reliability of the semiconductor package obtained by using the above is increased. On the other hand, the amount (parts by mass) of the resin (1) in the film-like adhesive and the adhesive composition and the amount (parts by mass) of the epoxy resin (b1) in the film-like adhesive and the adhesive composition are Since both of them are positive values, the (1) / (b1) values do not become 0 (zero) and do not become negative values.
The values of [amount of resin (1) in film-like adhesive (parts by mass)] / [amount of epoxy resin (b1) in film-like adhesive (parts by mass)] are [in the adhesive composition. [Amount of resin (1) (parts by mass)] / [Amount of epoxy resin (b1) in the adhesive composition (parts by mass)] is synonymous with the value of.

The value (1) / (b1) may be, for example, 0.1 to 1, 0.2 to 1, 0.3 to 1, or 0.4 to 1 from the viewpoint of increasing the above-mentioned effect. It may be greater than 0, 0.9 or less, greater than 0, 0.8 or less, greater than 0, 0.7 or less, and greater than 0, 0.6 or less. It may be any of 0.1 to 0.9, 0.2 to 0.8, 0.3 to 0.7, and 0.4 to 0.6.

The values (1) / (b1) are, for example, [ratio of the content of the resin (1) to the total mass of the film-like adhesive in the film-like adhesive (mass%)] / [film-like adhesive. Is synonymous with [ratio of the content of the epoxy resin (b1) to the total mass of the film-like adhesive (% by mass)], and [with respect to the total content of all components other than the solvent in the adhesive composition. Ratio of content of resin (1) (% by mass)] / [Ratio of content of epoxy resin (b1) to total content of all components other than solvent in the adhesive composition (% by mass)] It is synonymous.

When the resin (1) is used as the thermosetting agent (b2), the storage stability of the film-like adhesive and the adhesive composition is higher than when a thermosetting agent other than the resin (1) is used. These tend to be advantageous for storage at room temperature.

The film-like adhesive of the present embodiment has thermosetting property and is preferably pressure-sensitive adhesive property. The film-like adhesive having both thermosetting property and pressure-sensitive adhesive property can be attached by lightly pressing against various adherends in an uncured state. Further, the film-like adhesive may be one that can be attached to various adherends by heating and softening. The film-like adhesive eventually becomes a cured product having high impact resistance by curing, and this cured product can retain sufficient adhesive properties even under severe high temperature and high humidity conditions.

In order to improve various physical properties of the adhesive composition and the film-like adhesive, in addition to the polymer component (a) and the thermosetting component (b), if necessary, other components that do not correspond to these are added. May be contained.
Other components contained in the adhesive composition and the film-like adhesive include, for example, a curing accelerator (c), a filler (d), a coupling agent (e), a cross-linking agent (f), and an energy ray curable property. Examples thereof include a resin (g), a photopolymerization initiator (h), and a general-purpose additive (i). Among these, preferable other components include a curing accelerator (c), a filler (d), and a coupling agent (e).

In the present specification, the "energy beam" means an electromagnetic wave or a charged particle beam having an energy quantum, 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 source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present specification, "energy ray curable" means a property of being cured by irradiating with energy rays, and "non-energy ray curable" means a property of not being cured by irradiating with energy rays. To do.

<Curing accelerator (c)>
The curing accelerator (c) is a component for adjusting the curing rate of the adhesive composition and the film-like adhesive.
Preferred curing accelerators (c) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole. , 2-Phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and other imidazoles (one or more hydrogen atoms other than hydrogen atoms) (Imidazole substituted with an organic group); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphine in which one or more hydrogen atoms are substituted with an organic group); tetraphenylphosphonium tetraphenylborate, triphenylphosphine Tetraphenylborone salts such as tetraphenylborate; inclusion compounds having the above imidazoles as guest compounds can be mentioned.

The curing accelerator (c) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

When the curing accelerator (c) is used, the content of the curing accelerator (c) in the adhesive composition and the film-like adhesive is the content of the thermosetting component (b) (that is, the epoxy resin (b1)). And the total content of the thermosetting agent (b2)) is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass. When the content of the curing accelerator (c) is at least the lower limit value, the effect of using the curing accelerator (c) is more remarkable. 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) can be combined with the adherend in the film-like adhesive under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the bonding interface side is enhanced, and the reliability of the package obtained by using the film-like adhesive is further improved.

<Filler (d)>
By containing the filler (d), the film-like adhesive makes it easy to adjust its coefficient of thermal expansion, and by optimizing this coefficient of thermal expansion for the object to which the film-like adhesive is attached, the film The reliability of the package obtained by using the state adhesive is further improved. Further, when the film-like adhesive contains the filler (d), it is possible to reduce the hygroscopicity of the cured product of the film-like adhesive and improve the heat dissipation.

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, red iron oxide, silicon carbide, boron nitride and the like; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Goods; Single crystal fibers of these inorganic fillers; Glass fibers and the like.
Among these, the inorganic filler is preferably silica, alumina or a surface-modified product thereof.

The average particle size of the filler (d) is not particularly limited, but is preferably 10 nm to 5 μm, and may be any of, for example, 10 to 800 nm, 10 to 600 nm, 20 to 300 nm, and 30 to 150 nm. Good. When the average particle size of the filler (d) is in such a range, the effect of using the filler (d) can be sufficiently obtained, and the storage stability of the film-like adhesive becomes higher.
In the present specification, the "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 adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When the filler (d) is used, the ratio of the content of the filler (d) to the total content of all the components other than the solvent in the adhesive composition (that is, the film-like adhesive in the film-like adhesive). The ratio of the content of the filler (d) to the total mass) is preferably 5 to 30% by mass, more preferably 7 to 25% by mass, and particularly preferably 9 to 20% by mass. preferable. When the content of the filler (d) is in such a range, the above-mentioned coefficient of thermal expansion can be easily adjusted.

<Coupling agent (e)>
By containing the coupling agent (e) in the film-like adhesive, the adhesiveness and adhesion to the adherend are improved. Further, when the film-like adhesive 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 groups of the polymer component (a), the thermosetting component (b) and the like, and is preferably a silane coupling agent. More preferred.
Preferred silane coupling agents include, for example, 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-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfan, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, oligomer-type or polymer-type organosiloxane. ..

The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

When the coupling agent (e) is used, the content of the coupling agent (e) in the adhesive composition and the film-like adhesive is the total content of the polymer component (a) and the thermosetting component (b). It 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 at least the lower limit value, the dispersibility of the filler (d) in the resin is improved, and the adhesiveness of the film-like adhesive to the adherend is improved. , The effect of using the coupling agent (e) is more remarkable. When the content of the coupling agent (e) is not more than the upper limit value, the generation of outgas is further suppressed.

<Crosslinking agent (f)>
As the polymer component (a), one having a functional group such as a vinyl group capable of binding to another compound, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group, such as the above-mentioned acrylic resin, is used. In the case, the adhesive composition and the film-like adhesive may contain a cross-linking agent (f) for bonding the functional group with another compound to cross-link. By cross-linking with the cross-linking agent (f), the initial adhesive force and the cohesive force of the film-like adhesive can be adjusted.

Examples of the cross-linking agent (f) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (that is, a cross-linking agent having a metal chelate structure), and an aziridine-based cross-linking agent (that is, an aziridine-based group). Cross-linking agent) and the like.

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”. (May be abbreviated); trimerics such as the aromatic polyvalent isocyanate compound, isocyanurates and adducts; terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the like with a polyol compound. And so on. The "adduct" is a low content of the aromatic polyhydric isocyanate compound, the aliphatic polyhydric isocyanate compound or the alicyclic polyvalent isocyanate compound, and 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 body include a xylylene diisocyanate adduct of trimethylolpropane, which will be described later. Further, the "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion 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-xylylene diisocyanate; diphenylmethane- 4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; tri Compounds in which any one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or some hydroxyl groups of a polyol such as methylolpropane; lysine diisocyanate and the like can be mentioned.

Examples of the organic polyvalent imine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylpropan-tri-β-aziridinyl propionate, and tetramethylolmethane. Examples thereof include -tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylene melamine and the like.

When an organic multivalent isocyanate compound is used as the cross-linking 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 is simplified to a film-like adhesive by the reaction between the cross-linking agent (f) and the polymer component (a). Can be introduced in.

The cross-linking agent (f) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The content of the cross-linking agent (f) is preferably 0 to 5 parts by mass, more preferably 0 to 3 parts by mass, and 0, based on 100 parts by mass of the polymer component (a). It is more preferably to 1 part by mass, and particularly preferably 0 part by mass, that is, the adhesive composition and the film-like adhesive do not contain the cross-linking agent (f). When the content of the cross-linking agent (f) is at least the lower limit value, the effect of using the cross-linking agent (f) is more remarkable. When the content of the cross-linking agent (f) is not more than the upper limit value, the storage stability of the film-like adhesive becomes higher.

<Energy ray curable resin (g)>
The adhesive composition and the film-like adhesive may contain an energy ray-curable resin (g). Since the film-like adhesive contains an energy ray-curable resin (g), its characteristics can be changed by irradiation with energy rays.

The energy ray-curable resin (g) is obtained by polymerizing (curing) an energy ray-curable compound.
Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate-based compounds having a (meth) acryloyl group are preferable.

Examples of the acrylate-based compound include trimethyl propantri (meth) acrylate, tetramethylol methanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol monohydroxypenta ( Chain aliphatic skeleton-containing (meth) acrylates such as meta) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate; Cyclic aliphatic skeleton-containing (meth) acrylate such as cyclopentanyldi (meth) acrylate; Polyalkylene glycol (meth) acrylate such as polyethylene glycol di (meth) acrylate; Oligoester (meth) acrylate; Urethane (meth) acrylate oligomer Examples thereof include epoxy-modified (meth) acrylates; polyether (meth) acrylates other than the polyalkylene glycol (meth) acrylates; itaconic acid oligomers and the like.

The weight average molecular weight of the energy ray-curable resin (g) is preferably 100 to 30,000, and more preferably 300 to 10,000.

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

When the energy ray-curable resin (g) is used, the ratio of the content of the energy ray-curable resin (g) to the total mass of the adhesive composition in the adhesive composition is 1 to 95% by mass. Is preferable, and for example, it may be any one of 1 to 50% by mass, 1 to 25% by mass, and 1 to 10% by mass.

<Photopolymerization initiator (h)>
When the adhesive composition and the film-like adhesive contain the energy ray-curable resin (g), the photopolymerization initiator (h) is used in order to efficiently proceed with the polymerization reaction of the energy ray-curable resin (g). It may be contained.

Examples of the photopolymerization initiator (h) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone, Acetphenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) Acylphosphine oxide compounds such as phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide; α-ketol such as 1-hydroxycyclohexylphenylketone Compounds; azo compounds such as azobisisobutyronitrile; titanosen compounds such as titanosen; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1, 2-Diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone can be mentioned.
Further, examples of the photopolymerization initiator (h) include a photosensitizer such as amine.

The photopolymerization initiator (h) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof may be arbitrarily selected. it can.

When the photopolymerization initiator (h) is used, the content of the photopolymerization initiator (h) in the adhesive composition is 0.1 with respect to 100 parts by mass of the content of the energy ray-curable resin (g). The amount is preferably from 20 parts by mass, more preferably from 1 to 10 parts by mass, and particularly preferably from 2 to 5 parts by mass.

<General-purpose additive (i)>
The general-purpose additive (i) may be a known one, and may be arbitrarily selected depending on the intended purpose, and is not particularly limited. Preferred general-purpose additives (i) include, for example, plasticizers, antistatic agents, antioxidants, colorants (dye, pigment), gettering agents and the like.

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

<Solvent>
The adhesive composition preferably further contains a solvent. The adhesive composition containing a solvent has good handleability.
The solvent is not particularly limited, but preferred ones include, for example, 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) and the like.
The solvent contained in the adhesive composition may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

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

As one aspect, the film-like adhesive of the present embodiment includes a polymer component (a), an epoxy resin (b1), a thermosetting agent (b2), a curing accelerator (c), a filler (d), and a coupling. It is composed of the agent (e) and has the property of showing the specified values for x _1, y ₁ , x _2, and y ₂ described above.
As used herein, the term "property" means the chemical or physicochemical properties of a film-like adhesive.
As another aspect, the film-like adhesive of the present embodiment includes a polymer component (a), an epoxy resin (b1), a thermosetting agent (b2), a curing accelerator (c), a filler (d), and a coupling. It is composed of the agent (e), and in addition to the values specified for x _1, y ₁ , x ₂ and y ₂ described above, the above-mentioned x _10, y ₁₀ , x ₂₀ and y ₂₀ are specified. It has the property of showing the value obtained.
As another aspect, the film-like adhesive of the present embodiment may be further contained with an energy ray-curable resin (g) and a photopolymerization initiator (h).

The present invention has, for example, the following aspects.
(1) The adhesive composition or the film-like adhesive is a structural unit derived from n-butyl acrylate (38 to 42% by mass, more preferably 40 with respect to the mass of the acrylic resin) as the polymer component (a). (% by mass), structural unit derived from ethyl acrylate (23 to 27% by mass, more preferably 25% by mass with respect to the mass of acrylic resin), structural unit derived from acrylonitrile (28 to 28 to mass with respect to the mass of acrylic resin). Acrylic resin (content: adhesive) consisting of 32% by mass, more preferably 30% by mass) and a structural unit derived from glycidyl methacrylate (3 to 7% by mass, more preferably 5% by mass with respect to the mass of the acrylic resin). 7 to 13% by mass, more preferably 8 to 12% by mass, particularly preferably 10% by mass, based on the total solid content of the agent composition or the film-like adhesive;
As the epoxy resin (b1), a bisphenol A type epoxy resin (content: 20 to 30% by mass, more preferably 23.5 to 28% by mass, based on the total solid content of the adhesive composition or film-like adhesive). , Particularly preferably 25.8% by mass) and cresol novolac type epoxy resin (content: 18 to 28% by mass, more preferably 21 to 25% by mass with respect to the total solid content of the adhesive composition or film-like adhesive. Mass%, especially preferably 23%);
As the thermosetting agent (b2), an o-cresol type novolak resin, more specifically, an o-cresol type novolak resin in which n in the general formula (1) is 6 or 7 (softening point: 77 to 83 ° C., More preferably 80 ° C.) (Content: 20 to 30% by mass, more preferably 23 to 27% by mass, particularly preferably 25% by mass with respect to the total solid content of the adhesive composition or film-like adhesive) ；
As the curing accelerator (c), 2-phenyl-4,5-dihydroxymethylimidazole (content: 0.1 to 0.3% by mass with respect to the total mass of the solid content of the adhesive composition or the film-like adhesive). , More preferably 0.2% by mass);
As the filler (d), a silica filler (surface modifying group: epoxy group) (content: 13 to 17% by mass, more preferably 15% by mass, based on the total solid content of the adhesive composition or the film-like adhesive. %);
As the coupling agent (e), an oligomer-type silane coupling agent having an epoxy group, a methyl group and a methoxy group (content: 0.1 to 0.1 to the total solid content of the adhesive composition or the film-like adhesive). 5% by mass, more preferably 0.8 to 1.2% by mass, particularly preferably 1% by mass) (however, the sum of the contents of each component is the solid of the adhesive composition or the film-like adhesive. Does not exceed 100% by mass with respect to the total mass of the minute).
(2) The adhesive composition or the film-like adhesive is a structural unit derived from n-butyl acrylate (53 to 57% by mass, more preferably 55 with respect to the mass of the acrylic resin) as the polymer component (a). (% by mass), structural unit derived from methyl acrylate (8 to 12% by mass, more preferably 10% by mass with respect to the mass of acrylic resin), structural unit derived from glycidyl methacrylate (based on mass of acrylic resin). Acrylic resin consisting of 18 to 22% by mass, more preferably 20% by mass) and a structural unit derived from 2-hydroxyethyl acrylate (13 to 17% by mass, more preferably 15% by mass with respect to the mass of the acrylic resin). (Content: 7 to 13% by mass, more preferably 8 to 12% by mass, particularly preferably 9.4% by mass, based on the total solid content of the adhesive composition or film-like adhesive), and polyester resin. (Content: 16 to 23% by mass, more preferably 18 to 20% by mass, particularly preferably 18.8% by mass, based on the total solid content of the adhesive composition or film-like adhesive).
As the epoxy resin (b1), a mixture of a liquid bisphenol A type epoxy resin and acrylic rubber fine particles (content: 16 to 23% by mass, more preferably 16 to 23% by mass, based on the total mass of the solid content of the adhesive composition or the film-like adhesive. 18 to 20% by mass, particularly preferably 18.8% by mass) and polyfunctional aromatic type (particularly triphenylene type) epoxy resin (content: relative to the total mass of solid content of the adhesive composition or film-like adhesive 16-23% by mass, more preferably 18-20% by mass, particularly preferably 18.8% by mass);
As the thermosetting agent (b2), a novolak type phenol resin (content: 16 to 23% by mass, more preferably 18 to 20% by mass, particularly 18 to 20% by mass, based on the total solid content of the adhesive composition or the film-like adhesive. Preferably 18.8% by mass);
As the curing accelerator (c), 2-phenyl-4,5-dihydroxymethylimidazole (content: 0.1 to 0.4% by mass with respect to the total mass of the solid content of the adhesive composition or the film-like adhesive). , More preferably 0.28% by mass);
As the filler (d), a silica filler surface-modified with an epoxy-based compound (content: 7 to 13% by mass, more preferably 8 to 13% by mass, based on the total solid content of the adhesive composition or the film-like adhesive). 12% by weight, especially preferably 9.4% by weight);
As the coupling agent (e), a silicate compound to which 3-glycidoxypropyltrimethoxysilane is added (content: 0.2 to 1 with respect to the total mass of the solid content of the adhesive composition or the film-like adhesive). Mass%, more preferably 0.3-0.6% by mass, particularly preferably 0.47% by mass) and trimethoxy [3- (phenylamino) propyl] silane (content: adhesive composition or film-like adhesive) 0.05 to 0.6% by mass, more preferably 0.1 to 0.5% by mass, particularly preferably 0.28% by mass) based on the total mass of the solid content of
As the energy ray-curable resin (g), tricyclodecanedimethylol diacrylate (content: 2 to 7% by mass, more preferably 3 to 7% by mass, based on the total mass of the solid content of the adhesive composition or the film-like adhesive. 6% by weight, particularly preferably 4.7% by weight);
As the photopolymerization initiator (h), 1-hydroxycyclohexylphenylketone (content: 0.05 to 0.5% by mass, more preferably 0.05 to 0.5% by mass with respect to the total solid content of the adhesive composition or the film-like adhesive). Includes (0.1 to 0.2% by mass, particularly preferably 0.14% by mass) (however, the sum of the contents of each component is the total mass of the solid content of the adhesive composition or film-like adhesive. On the other hand, it does not exceed 100% by mass).
(3) In (1), x ₁ / y ₁ of the film-like adhesive is 0 or more and 0.15 or less, more preferably 0 or more and 0.015 or less, particularly preferably 0.01, and x ₂ /. y ₂ is 0.65 or more and 1 or less, more preferably 0.7 or more and 0.9 or less, and particularly preferably 0.8.
(4) In (1) or (3), the x ₁₀ / y ₁₀ of the film-like adhesive is 0 or more and 0.15 or less, more preferably 0 or more and 0.015 or less, and particularly preferably 0.01. And x ₂₀ / y ₂₀ is 0.65 or more and 1 or less, more preferably 0.7 or more and 0.9 or less, and particularly preferably 0.8.
(5) In (2), x ₁ / y ₁ of the film-like adhesive is 0 or more and 0.25 or less, more preferably 0 or more and 0.2 or less, particularly preferably 0.1, and x ₂ /. y ₂ is 0.65 or more and 1 or less, more preferably 0.65 or more and 0.9 or less, and particularly preferably 0.7.
(6) In (2) or (5), the x ₁₀ / y ₁₀ of the film-like adhesive is 0 or more and 0.3 or less, more preferably 0.15 or more and 0.3 or less, and particularly preferably 0.3. Yes, and x ₂₀ / y ₂₀ is 0.25 or more and 1 or less, more preferably 0.25 or more and 0.5 or less, and particularly preferably 0.3.
(7) In any one of (1) to (6), the adhesive strength of the thermosetting product of the film-like adhesive measured by the measuring method described in the present specification is 210 to 300 N / 2 mm □. , More preferably 230 to 270 N / 2 mm □, and particularly preferably 245 to 255 N / 2 mm □.

<Manufacturing method of adhesive composition>
The adhesive composition is obtained by blending each component for constituting the adhesive composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and diluted in advance, or any compounding component other than the solvent may be diluted in advance. You may use it by mixing the solvent with these compounding components without leaving.

The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

FIG. 1 is a cross-sectional view schematically showing a film-like adhesive according to an embodiment of the present invention. In addition, in the figure used in the following description, in order to make it easy to understand the features of the present invention, the main part may be enlarged for convenience, and the dimensional ratio and the like of each component are the same as the actual ones. Is not always the case.

The film-like adhesive 13 shown here has a first release film 151 on one surface (sometimes referred to as a “first surface” in the present specification) 13a, and is referred to as the first surface 13a. A second release film 152 is provided on the other surface (sometimes referred to as the "second surface" in the present specification) 13b on the opposite side.
Such a film-like adhesive 13 is suitable for storage as, for example, a roll.

In the film-like adhesive 13, the first surface 13a and second surface 13b, both, can be targeted to determine the _{x 1} and _{y 1,} and _{x 10} and _{y 10.} Then, after the film-like adhesive 13 is thermally cured, both the surface corresponding to the first surface 13a, a surface corresponding to the second surface 13b, and, _{x 2} and _{y 2,} and _{x 20} and _{y 20} Can be the target for which.
The film-like adhesive 13 has the above-mentioned properties. That is, both the first surface 13a and the second surface 13b of the film-like adhesive 13 satisfy the above-mentioned conditions of x ₁ / y ₁ and x ₂ / y ₂ . Further, both the first surface 13a and the second surface 13b of the film-like adhesive 13 may satisfy the above-mentioned x ₁₀ / y ₁₀ condition, or may satisfy the above-mentioned x ₂₀ / y ₂₀ condition. Good.

The film-like adhesive 13 can be formed by using the above-mentioned adhesive composition.

Both the first release film 151 and the second release film 152 may be known.
The first release film 151 and the second release film 152 may be the same as each other, or are different from each other, for example, the peeling force required for peeling from the film-like adhesive 13 is different from each other. May be good.

In the film-like adhesive 13 shown in FIG. 1, either the first release film 151 or the second release film 152 is removed, and the resulting exposed surface becomes the back surface of the semiconductor wafer (not shown). Then, the other remaining of the first release film 151 and the second release film 152 is removed, and the generated exposed surface becomes a sticking surface of a support sheet or a dicing sheet described later.

-Semiconductor processing sheet The semiconductor processing sheet according to the embodiment of the present invention includes a support sheet, and the film-like adhesive is provided on one surface of the support sheet.
The semiconductor processing sheet is suitable as, for example, a dicing die bonding sheet.

Since the semiconductor processing sheet of the present embodiment is configured by using the film-like adhesive, when the semiconductor wafer is divided into semiconductor chips and the film-like adhesive is cut at the same time by dicing. In addition, chip skipping can be suppressed. Further, the semiconductor package formed by incorporating the film-like adhesive using the semiconductor processing sheet has high reliability.

<< 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 the 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 comprising only a base material; a base material and a pressure-sensitive adhesive layer provided on one surface of the base material.
When the support sheet includes the base material and the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is arranged between the base material and the film-like adhesive in the semiconductor processing sheet.

The support sheet made of only a base material is suitable as a carrier sheet or a dicing sheet. A semiconductor processing sheet provided with a support sheet composed of only such a base material is a surface of the film-like adhesive opposite to the side provided with the support sheet (that is, the base material) (in the present specification, The "first surface") is attached to the back surface of the semiconductor wafer and used.

On the other hand, the support sheet provided with the base material and the pressure-sensitive adhesive layer is suitable as a dicing sheet. A semiconductor processing sheet provided with such a support sheet can also be used by attaching the surface (first surface) of the film-like adhesive opposite to the side provided with the support sheet to the back surface of the semiconductor wafer. Will be done.

The method of using the semiconductor processing sheet will be described in detail later.
Hereinafter, each layer constituting the support sheet will be described.

<Base material>
The base material is in the form of a sheet or a film, and examples of the constituent material thereof include various resins.
Examples of the resin include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin. Polyethylene; polyethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, and ethylene-norbornene copolymer (ethylene as monomer) (Copolymer obtained using); Vinyl chloride resin such as polyvinyl chloride, vinyl chloride copolymer (resin obtained using vinyl chloride as a monomer); Polystyrene; Polycycloolefin; Polyethylene terephthalate, polyethylene Polyester resins such as naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, all aromatic polyesters in which all constituent units have an aromatic cyclic group; two or more of the polyesters. Copolymers; poly (meth) acrylic acid esters; polyurethane resins; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluororesins; polyacetals; modified polyphenylene oxides; polyphenylene sulfides; polysulfones; polyether ketones and the like.
Further, examples of the resin include polymer alloys such as a mixture of the polyester resin and other resins. The polymer alloy of the polyester resin and the resin other than the polyester resin preferably has a relatively small amount of the resin other than the polyester resin.
Further, as the resin, for example, a crosslinked resin obtained by cross-linking one or more of the resins exemplified above; modification of an ionomer or the like using one or more of the resins exemplified so far. Resin is also mentioned.

The resin constituting the base material may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The base material 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 multiple layers are the same or different from each other. The combination of these plurality of layers may be not particularly limited.

The thickness of the base material is preferably 50 to 300 μm, more preferably 60 to 150 μm. When the thickness of the base material is within such a range, the flexibility of the semiconductor processing sheet and the stickability to the semiconductor wafer or the semiconductor chip are further improved.
Here, the "thickness of the base material" means the thickness of the entire base material, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material. means.

The base material preferably has a high thickness accuracy, that is, a material in which variation in thickness is suppressed regardless of the site. Among the above-mentioned constituent materials, materials that can be used to compose such a highly accurate base material in thickness include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like. Can be mentioned.

In addition to the main constituent materials such as the resin, the base material contains various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers). You may.

The base material may be transparent, opaque, colored depending on the purpose, or another layer may be vapor-deposited.

In order to improve the adhesion of the base material to other layers such as the pressure-sensitive adhesive layer provided on the base material, the base material is subjected to unevenness treatment by sandblasting treatment, solvent treatment, etc., corona discharge treatment, electron beam irradiation treatment, plasma treatment. , Ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments may be applied to the surface.
Further, the base material may have a surface surface treated with a primer.
Further, the base material is an antistatic coat layer; a layer that prevents the base material from adhering to other sheets or adhering to the adsorption table when the semiconductor processing sheets are superposed and stored. It may have.

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

<Adhesive layer>
The pressure-sensitive adhesive layer is in the form of a sheet or a film and contains a pressure-sensitive adhesive.
Examples of the pressure-sensitive adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin, and those containing acrylic resin are preferable. ..

In the present specification, the "adhesive resin" includes both a resin having adhesiveness and a resin having adhesiveness. For example, the adhesive resin includes not only the resin itself having adhesiveness, but also a resin showing adhesiveness when used in combination with other components such as additives, and adhesiveness due to the presence of a trigger such as heat or water. Also included are resins and the like.

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

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.
Here, the "thickness of the pressure-sensitive adhesive layer" means the thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the sum of all the layers constituting the pressure-sensitive adhesive layer. Means the thickness of.

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

The pressure-sensitive adhesive layer can be formed by using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive layer can be formed on a target portion by applying the pressure-sensitive adhesive composition to the surface to be formed of the pressure-sensitive adhesive layer and drying it if necessary. The ratio of the contents of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the pressure-sensitive adhesive layer.

The pressure-sensitive adhesive composition can be applied in the same manner as in the case of the above-mentioned adhesive composition.

When the pressure-sensitive adhesive layer is energy ray-curable, examples of the energy ray-curable pressure-sensitive adhesive composition include non-energy ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter, "sticky resin (I-)". 1a) ”) and an energy ray-curable compound (adhesive composition (I-1); an unsaturated group is introduced into the side chain of the adhesive resin (I-1a). A pressure-sensitive adhesive composition (I-2) containing the energy ray-curable pressure-sensitive adhesive resin (I-2a) (hereinafter, may be abbreviated as "sticky resin (I-2a)"); Examples thereof include a pressure-sensitive adhesive composition (I-3) containing a sex resin (I-2a) and an energy ray-curable compound.

When the pressure-sensitive adhesive layer is non-energy ray-curable, examples of the non-energy ray-curable pressure-sensitive adhesive composition include the pressure-sensitive adhesive composition (I-4) containing the pressure-sensitive adhesive resin (I-1a). Can be mentioned.

The pressure-sensitive adhesive compositions such as the pressure-sensitive adhesive compositions (I-1) to (I-4) can be produced by the same method as in the case of the above-mentioned adhesive composition, except that the compounding components are different.

Next, an example of the semiconductor processing sheet of the present embodiment will be described for each type of support sheet with reference to the drawings below.

FIG. 2 is a cross-sectional view schematically showing a semiconductor processing sheet according to an embodiment of the present invention.
In the drawings after FIG. 2, the same components as those shown in the already explained figures are designated by the same reference numerals as in the case of the already explained figures, and detailed description thereof will be omitted.

The semiconductor processing sheet 101 shown here includes a support sheet 10, and a film-like adhesive 13 on the support sheet 10. The support sheet 10 is composed of only the base material 11, and the semiconductor processing sheet 101 is, in other words, on one surface of the base material 11 (sometimes referred to as a “first surface” in the present specification) 11a. It has a structure in which the film-like adhesive 13 is laminated.
Further, the semiconductor processing sheet 101 further includes a release film 15 on the film-like adhesive 13.

In the semiconductor processing sheet 101, the film-like adhesive 13 is laminated on the first surface 11a of the base material 11, and the surface of the film-like adhesive 13 opposite to the side on which the base material 11 is provided (this specification). In the document, the adhesive layer 16 for jigs is laminated on a part of 13a (sometimes referred to as the "first surface"), that is, in the region near the peripheral edge portion, and the first surface 13a of the film-like adhesive 13 Among them, the release film 15 is formed on the surface on which the adhesive layer 16 for jigs is not laminated and the surface 16a (upper surface and side surface) of the adhesive layer 16 for jigs which is not in contact with the film-like adhesive 13. It is laminated.
Here, the first surface 11a of the base material 11 is also referred to as the first surface 10a 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 multi-layer structure in which layers containing an adhesive component are laminated on both sides of a sheet serving as a core material. There may be.

Film adhesive 13 in the semiconductor processing sheet 101 after removing the release film 15, the first surface 13a, it can be targeted to determine the _{x 1} and _{y 1,} and _{x 10} and _{y 10.}

In the semiconductor processing sheet 101, with the release film 15 removed, the back surface of the semiconductor wafer (not shown) is attached to the first surface 13a of the film-like adhesive 13, and further, the adhesive layer 16 for jigs is attached. The upper surface of the surface 16a is attached to a jig such as a ring frame and used.

FIG. 3 is a cross-sectional view schematically showing a semiconductor processing sheet according to another embodiment of the present invention.
The semiconductor processing sheet 102 shown here is the same as the semiconductor processing sheet 101 shown in FIG. 2, except that the jig adhesive layer 16 is not provided. That is, in the semiconductor processing sheet 102, the film-like adhesive 13 is laminated on the first surface 11a of the base material 11 (the first surface 10a of the support sheet 10), and the entire surface of the first surface 13a of the film-like adhesive 13 is laminated. The release film 15 is laminated on the surface.
In other words, the semiconductor processing sheet 102 is configured by laminating the base material 11, the film-like adhesive 13, and the release film 15 in this order in the thickness direction.

Similar to the case of the semiconductor processing sheet 101 shown in FIG. 2, the semiconductor processing sheet 102 shown in FIG. 3 is in the center of the first surface 13a of the film-like adhesive 13 with the release film 15 removed. The back surface of the semiconductor wafer (not shown) is attached to a part of the region on the side, and the region near the peripheral edge of the film-like adhesive 13 is attached to a jig such as a ring frame for use.

FIG. 4 is a cross-sectional view schematically showing a semiconductor processing sheet according to still another embodiment of the present invention.
The semiconductor processing sheet 103 shown here is the same as the semiconductor processing sheet 101 shown in FIG. 2, except that the pressure-sensitive adhesive layer 12 is further provided between the base material 11 and the film-like adhesive 13. It is the same. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and the semiconductor processing sheet 103 also has a structure in which the film-like adhesive 13 is laminated on the first surface 10a of the support sheet 10.

In the semiconductor processing sheet 103, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the surface of the pressure-sensitive adhesive layer 12 opposite to the base material 11 side (in the present specification, the "first surface" The film-like adhesive 13 is laminated on the entire surface of the 12a (sometimes referred to as "one surface"), and is bonded to a part of the first surface 13a of the film-like adhesive 13, that is, a region near the peripheral edge. Of the first surface 13a of the film-like adhesive 13 on which the agent layer 16 is laminated and the surface on which the jig adhesive layer 16 is not laminated and the jig adhesive layer 16, the film-like adhesive 13 The release film 15 is laminated on the surfaces 16a (upper surface and side surfaces) that are not in contact with the surface 16a.

In the semiconductor processing sheet 103 shown in FIG. 4, the back surface of the semiconductor wafer (not shown) is attached to the first surface 13a of the film-like adhesive 13 in a state where the release film 15 is removed, and further, for a jig. The upper surface of the surface 16a of the adhesive layer 16 is attached to a jig such as a ring frame and used.

FIG. 5 is a cross-sectional view schematically showing a semiconductor processing sheet according to still another embodiment of the present invention.
The semiconductor processing sheet 104 shown here is the same as the semiconductor processing sheet 103 shown in FIG. 4, except that the jig adhesive layer 16 is not provided and the shape of the film-like adhesive is different. That is, the semiconductor processing sheet 104 includes the base material 11, the pressure-sensitive adhesive layer 12 on the base material 11, and the film-like adhesive 23 on the pressure-sensitive adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and the semiconductor processing sheet 104 also has a structure in which the film-like adhesive 23 is laminated on the first surface 10a of the support sheet 10.

In the semiconductor processing sheet 104, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and a film-like adhesive is formed on a part of the first side surface 12a of the pressure-sensitive adhesive layer 12, that is, on the central region. 23 are laminated. Then, the area of the first surface 12a of the pressure-sensitive adhesive layer 12 on which the film-like adhesive 23 is not laminated and the surface of the film-like adhesive 23 opposite to the pressure-sensitive adhesive layer 12 side (the present specification). The release film 15 is laminated on the 23a (sometimes referred to as the "first surface"). In FIG. 5, reference numeral 23b indicates the other surface of the film-like adhesive 23 opposite to the first surface 23a (in the present specification, it may be referred to as “second surface”). ..

When the semiconductor processing sheet 104 is viewed in a plan view from above on the release film 15 side, the film-like adhesive 23 has a smaller surface area than the pressure-sensitive adhesive layer 12, and has a shape such as a circular shape.

Film adhesive 23 in the semiconductor processing sheet 104 after removing the release film 15, the first surface 23a, it can be targeted to determine the _{x 1} and _{y 1,} and _{x 10} and _{y 10.}

In the semiconductor processing sheet 104 shown in FIG. 5, the back surface of the semiconductor wafer (not shown) is attached to the first surface 23a of the film-like adhesive 23 in a state where the release film 15 is removed, and further, the pressure-sensitive adhesive layer is attached. A region of the first surface 12a of 12 on which the film-like adhesive 23 is not laminated is attached to a jig such as a ring frame and used.

In the semiconductor processing sheet 104 shown in FIG. 5, similarly to those shown in FIGS. 2 and 4, in the region of the first surface 12a of the pressure-sensitive adhesive layer 12 where the film-like adhesive 23 is not laminated. The jig adhesive layer may be laminated (not shown). In the semiconductor processing sheet 104 provided with such a jig adhesive layer, the upper surface of the surface of the jig adhesive layer is a ring, as in the case of the semiconductor processing sheet shown in FIGS. 2 and 4. It is used by being attached to a jig such as a frame.

As described above, the semiconductor processing sheet may be provided with an adhesive layer for jigs regardless of the form of the support sheet and the film-like adhesive. However, as shown in FIGS. 2 and 4, the semiconductor processing sheet provided with the jig adhesive layer is usually preferably a sheet having a jig adhesive layer on a film-like adhesive.

The semiconductor processing sheet of the present embodiment is not limited to those shown in FIGS. 2 to 5, and a part of the configurations shown in FIGS. 2 to 5 are changed or deleted within a range that does not impair the effects of the present invention. It may be the one described above or the one described above with other configurations added.

For example, in the semiconductor processing sheets shown in FIGS. 2 to 5, layers other than the base material, the pressure-sensitive adhesive layer, the film-like adhesive, and the release film may be provided at arbitrary positions.
Further, in the semiconductor processing sheet, a partial gap may be formed between the release film and the layer in direct contact with the release film.
Further, in the semiconductor processing sheet, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

◇ How to use the film-like adhesive and the semiconductor processing sheet The film-like adhesive and the semiconductor processing sheet of the present embodiment are used for manufacturing a semiconductor package and a semiconductor device after manufacturing a semiconductor chip with a film-like adhesive. , Can be used.

After the film-like adhesive without the support sheet is attached to the back surface of the semiconductor wafer, for example, the release film is removed as needed, and the exposed surface (in other words, the side attached to the semiconductor wafer) is used. A dicing sheet is attached to the opposite surface (sometimes referred to as the "second surface" in the present specification). The laminated structure in which the dicing sheet, the film-like adhesive, and the semiconductor wafer thus obtained are laminated in this order in the thickness direction thereof is subsequently subjected to a known dicing step. .. The laminated structure of the dicing sheet and the film-like adhesive can be regarded as a dicing die bonding sheet.

In the present specification, the laminated structure in which the dicing die bonding sheet or the semiconductor processing sheet and the semiconductor wafer are laminated in this way may be referred to as a "first laminated structure". ..

By performing the dicing step, the semiconductor wafer is divided into a plurality of semiconductor chips, and the film-like adhesive is also cut along the outer periphery of the semiconductor chip, and the cut film-like adhesive is provided on the back surface. A plurality of semiconductor chips (that is, semiconductor chips with a film-like adhesive) can be obtained. These plurality of semiconductor chips with a film-like adhesive are fixed in an aligned state on a dicing sheet.

In the present specification, as described above, a laminated structure in which a plurality of semiconductor chips with a film-like adhesive are fixed in an aligned state on a dicing sheet or the support sheet is referred to as a “second laminated structure”. May be called.

On the other hand, the semiconductor processing sheet already has a structure as a dicing die bonding sheet. Therefore, at the stage when the semiconductor processing sheet is attached to the back surface of the semiconductor wafer, the semiconductor processing sheet (dicing sheet, film-like adhesive) and the semiconductor wafer are laminated in this order in these thickness directions. A laminated structure (that is, the first laminated structure) is obtained. After that, as described above, the dicing step is performed in the same manner as when the film-like adhesive without the support sheet is used, so that the second lamination including the plurality of semiconductor chips with the film-like adhesive is included. The structure is obtained.

Examples of the method for dicing a semiconductor wafer include, but are not limited to, a method using a blade (that is, blade dicing), and a general known method for individualizing a semiconductor wafer can be applied.

Regardless of whether the film-like adhesive or the semiconductor processing sheet is used, in the dicing step, since the film-like adhesive of the present embodiment is provided on the back surface of the semiconductor wafer, chip skipping is suppressed. To.

Regardless of whether a film-like adhesive or a semiconductor processing sheet is used, the obtained semiconductor chip with the film-like adhesive is then separated from the dicing sheet or the support sheet, picked up, and adhered to the film. The agent is diced to the circuit forming surface of the substrate. Then, after die bonding, the semiconductor package and the semiconductor device are manufactured by the same method as the conventional method. For example, if necessary, one or more semiconductor chips are further laminated on the die-bonded semiconductor chip, and then wire bonding is performed. Next, the film-like adhesive is heat-cured, and the entire obtained product is sealed with a resin. By going through these steps, a semiconductor package is manufactured. Then, the target semiconductor device is manufactured using this semiconductor package.

The semiconductor package thus obtained has high reliability by using the film-like adhesive of the present embodiment. For example, in the semiconductor package before and after mounting, peeling is suppressed at the joint portion between the substrate and the semiconductor chip, the joint portion between the semiconductor chips, and the like where the film-like adhesive is involved.

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

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

<Raw materials for manufacturing adhesive compositions>
In this example and comparative example, the raw materials used for producing the adhesive composition are shown below.

[Polymer component (a)]
(A) -1: Acrylic resin (weight average molecular weight 700,000, glass) obtained by copolymerizing BA (40 parts by mass), EA (25 parts by mass), AN (30 parts by mass) and GMA (5 parts by mass). Transition temperature 14 ° C.).
(A) -2: Acrylic resin (weight average molecular weight 800,000, glass) obtained by copolymerizing BA (55 parts by mass), MA (10 parts by mass), GMA (20 parts by mass) and HEA (15 parts by mass). Transition temperature -28 ° C).
(A) -3: Acrylic resin (weight average molecular weight 400,000, glass) obtained by copolymerizing BA (10 parts by mass), MA (70 parts by mass), GMA (5 parts by mass) and HEA (15 parts by mass). Transition temperature -1 ° C).
(A) -4: Thermoplastic resin, polyester resin ("Byron 220" manufactured by Toyobo Co., Ltd., number average molecular weight 3000, glass transition temperature 53 ° C.)
[Epoxy resin (b1)]
(B1) -1: Bisphenol A type epoxy resin ("JER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184-194 g / eq)
(B1) -2: Cresol novolac type epoxy resin ("EOCN-103S, epoxy equivalent 209 to 219 g / eq" manufactured by Nippon Kayaku Co., Ltd.)
(B1) -3: Mixture of liquid bisphenol A type epoxy resin and acrylic rubber fine particles (“BPA328” manufactured by Nippon Catalyst Co., Ltd., epoxy equivalent 235 g / eq)
(B1) -4: 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)
[Thermosetting agent (b2)]
(B2) -1: o-cresol type novolak resin ("Phenolite KA-1160" manufactured by DIC, hydroxyl group equivalent 117 g / eq, softening point 80 ° C., represented by the general formula (1), n is 6 to 7 A resin)
(B2) -2: Novolac type phenolic resin ("BRG556" manufactured by Showa Denko KK) [Curing accelerator (c)]
(C) -1: 2-Phenyl-4,5-dihydroxymethylimidazole ("Curesol 2PHZ-PW" manufactured by Shikoku Chemicals Corporation)
[Filler (d)]
(D) -1: Spherical silica modified with an epoxy group (“Admanano YA050C-MKK” manufactured by Admatex, average particle diameter 50 nm)
(D) -2: Silica filler ("SC2050MA" manufactured by Admatex, silica filler surface-modified with an epoxy compound, average particle size 500 nm)
[Coupling agent (e)]
(E) -1: Oligomer-type silane coupling agent having an epoxy group, a methyl group and a methoxy group ("X-41-1056" manufactured by Shinetsu Silicone Co., Ltd., epoxy equivalent 280 g / eq)
(E) -2: 3-Sylicate compound to which glycidoxypropyltrimethoxysilane is added ("MKC silicate MSEP2" manufactured by Mitsubishi Chemical Corporation)
(E) -3: Trimethoxy [3- (phenylamino) propyl] silane ("SZ6083" manufactured by Toray Dow, silane coupling agent)
(E) -4: 3-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shinetsu Silicone Co., Ltd., silane coupling agent, methoxy equivalent 12.7 mmol / g, molecular weight 236.3)
(E) -5: 3-glycidoxypropyltriethoxysilane ("KBE-403" manufactured by Shinetsu Silicone Co., Ltd., silane coupling agent, methoxy equivalent 8.1 mmol / g, molecular weight 278.4)
[Energy ray curable resin (g)]
(G) -1: Tricyclodecanedimethyloldiacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd., ultraviolet curable resin, molecular weight 304)
[Photopolymerization Initiator (h)]
(H) -1: 1-Hydroxycyclohexylphenyl ketone (BASF's "IRGACURE® 184")

[Example 1]
<< Manufacturing of film-like adhesive >>
<Manufacturing of adhesive composition>
Polymer component (a) -1 (10 parts by mass), epoxy resin (b1) -1 (25.8 parts by mass), epoxy resin (b1) -2 (23 parts by mass), thermosetting agent (b2) -1 (25 parts by mass), curing accelerator (c) -1 (0.2 parts by mass), filler (d) -1 (15 parts by mass), and coupling agent (e) -1 (1 part by mass). By dissolving or dispersing in methyl ethyl ketone and stirring at 23 ° C., an adhesive composition having a total concentration of all the above-mentioned components of 50% by mass was obtained. The blending amounts of the components other than the methyl ethyl ketone shown here are all the amounts of the target product containing no solvent component.

<Manufacturing of film-like adhesive>
A release film (“SP-PET38131” manufactured by Lintec Corporation, thickness 38 μm) in which one side of a polyethylene terephthalate (PET) film is peeled by a silicone treatment is used, and the adhesion obtained above is applied to the peeled surface. The agent composition was applied and dried by heating at 100 ° C. for 1 minute to form a film-like adhesive having a thickness of 20 μm.

<< Manufacturing of semiconductor processing sheets >>
A polyethylene film (manufactured by Gunze Co., Ltd., thickness 80 μm) is attached as a base material to the surface (in other words, the exposed surface) of the film-like adhesive obtained above on the side opposite to the side provided with the release film. As a result, a sheet for semiconductor processing was obtained in which the base material, the film-like adhesive and the release film were laminated in this order in the thickness direction thereof.

<< Evaluation of film-like adhesive >>
<Calculation of x ₁ / y ₁ and x ₂ / y ₂ >
[Measurement of surface shape of film adhesive]
Immediately after production, a film-like adhesive (thickness 20 μm) with a release film obtained by the same method as described above was attached to a silicon wafer.
Next, immediately at room temperature, the release film was removed from the film-like adhesive before thermosetting, and the surface opposite to the surface to be attached to the silicon wafer exposed by this was SPM (Shimadzu Corporation "SPM-9700"). ”) Was used to measure the surface shape. The surface shape was measured by using SPM as a phase observation mode. Further, as the cantilever, "Micro cantilever OMCL-AC240TS-C3" manufactured by OLYMPUS was used. Then, among the Z control parameters, the P gain was set to 0.001, the I gain was set to 1000, and the surface shape was measured under the following conditions.
(Image acquisition conditions)
Scanning range: 2 μm x 2 μm
Scanning speed: 1.0Hz
Number of pixels: 256 x 256

[Binarization of the film-like adhesive of the surface shape of the image, and calculation of x _{1 /} y _1]
Further, in the surface shape, an image was acquired in which the entire distribution of the histogram of the unevenness was 85% of the entire color tone bar.
Next, using image analysis software (“ImagePro” manufactured by Nippon Roper Co., Ltd.), the image obtained above was binarized by the following method. That is, the image is automatically calculated on the software in a 256-pixel histogram, and processing is performed with an intermediate value of the histogram to acquire a shape image, of which the convex portion is classified as black and classified into the first region, and the rest The image was modified by classifying the portion as white into the second region. In the obtained modified image, a pseudo color profile was assigned and the relative area and ratio were calculated.
As described above, the binarized image was acquired, the area value x ₁ of the first region and the area value y ₁ of the second region were obtained, and x ₁ / y ₁ was calculated. The results are shown in Table 1.

[Measurement of surface shape of the heat cured product of the adhesive film, the binarized image of the surface shape, and the calculation of x _{2 /} y _2]
The film-like adhesive after calculating x ₁ / y ₁ above was thermoset by heating at 160 ° C. for 1 hour. The surface shape of the surface of the thermosetting film-like adhesive opposite to the surface to which it is attached to the silicon wafer is measured by the same method as above, and the acquired image is binarized to obtain a first area. The area value x _{2 of the above} and the area value y ₂ of the second region were obtained, and x ₂ / y ₂ was calculated. The results are shown in Table 1.

<Calculation of x ₁₀ / y ₁₀ and x ₂₀ / y ₂₀ >
[Measurement of surface shape of the film-like adhesive, the calculation of the surface binarization shape of the image, and x _{10 /} y ₁₀ film adhesive]
Immediately after production, a film-like adhesive (thickness 20 μm) with a release film obtained by the same method as described above was left to stand for 7 days in an air atmosphere at 40 ° C.
Next, the same method as in the case of calculating x ₁ and y ₁ described above, except that the film adhesive immediately after production was replaced with the film adhesive after static storage, that is, after aging. Then, the surface shape of this film-like adhesive was measured, and the acquired image was binarized to obtain the area value x ₁₀ of the first region and the area value y ₁₀ of the second region, and x ₁₀ / Y ₁₀ was calculated.
The results are shown in Table 1.

[Measurement of surface shape of the heat cured product of the adhesive film, the calculation of the surface binarization shape of the image, and x _{20 /} y _20]
The film-like adhesive after calculating x ₁₀ / y ₁₀ above was thermoset by heating at 160 ° C. for 1 hour. The surface shape of the surface of the thermosetting film-like adhesive opposite to the surface to which it is attached to the silicon wafer is measured by the same method as above, and the acquired image is binarized to obtain a first area. The area value x _{20 of the above} and the area value y ₂₀ of the second region were obtained, and x ₂₀ / y ₂₀ was calculated. The results are shown in Table 1.

<Evaluation of semiconductor package reliability>
[Manufacturing of semiconductor chips with film-like adhesive]
The release film was removed from the semiconductor processing sheet obtained above immediately after production.
A silicon wafer (diameter 200 mm, thickness 75 μm) whose back surface is polished with a dry polish finish is used, and a tape bonding device (Lintec's “Adwill RAD2500”) is immediately used on the back surface (polished surface) at room temperature. , The above-mentioned semiconductor processing sheet was attached by the film-like adhesive. As described above, the first laminated structure (the present specification) is formed by laminating a base material, a film-like adhesive, and a silicon wafer in this order in the thickness direction of a semiconductor processing sheet having no time history. (Sometimes referred to as "first laminated structure (1)") was obtained.

Next, among the film-like adhesives in the first laminated structure (1), the exposed surface in the vicinity of the peripheral edge portion not attached to the silicon wafer was fixed to the ring frame for wafer dicing.
Next, by dicing using a dicing device (“DFD6361” manufactured by Disco Corporation), the silicon wafer was divided and the film-like adhesive was also cut to obtain a silicon chip having a size of 8 mm × 8 mm. For dicing at this time, the moving speed of the dicing blade is 30 mm / sec, the rotation speed of the dicing blade is 30,000 rpm, and the depth of the film-like adhesive is 40 μm from the surface to which the silicon wafer is attached to the semiconductor processing sheet. This was done by cutting with a dicing blade up to the region (that is, the entire region in the thickness direction of the film-like adhesive and the region at a depth of 20 μm from the surface of the substrate on the film-like adhesive side). As the dicing blade, "Z05-SD2000-D1-90 CC" manufactured by DISCO Co., Ltd. was used.
As described above, using a sheet for semiconductor processing having no history of aging, a plurality of silicon chips (in other words, a plurality of silicon chips with a film-like adhesive) having a film-like adhesive after cutting on the back surface are formed into a film. A second laminated structure (sometimes referred to as "second laminated structure (1)" in the present specification) is obtained, which is fixed in an aligned state on the base material by the state adhesive.

[Die bonding of semiconductor chips with film-like adhesive to substrates]
As a substrate, a circuit pattern is formed on a copper foil (thickness 15 μm) of a copper foil-clad laminate (“CCL-HL830” manufactured by Mitsubishi Gas Chemical Company), and a solder resist (“PSR-” manufactured by Taiyo Ink Co., Ltd.) is formed on this circuit pattern. A substrate (“SM15-031-10A” manufactured by Cima Electronics Co., Ltd., size: 157.0 mm × 70.0 mm × 0.2 mm) on which a layer of (4000 AUS308”) was formed was prepared.

Using a pickup die bonding device (“BESTEM D-02” manufactured by Canon Machinery Co., Ltd.), the silicon chip with a film-like adhesive in the second laminated structure (1) obtained above was picked up from the base material. Next, the picked-up silicon chip with a film-like adhesive was die-bonded to the substrate by pressure-bonding the film-like adhesive in the silicon chip with the film-like adhesive onto the substrate. In the die bonding at this time, a force of 2.45 N (250 gf) is applied to the silicon chip with a film-like adhesive heated to 120 ° C. in a direction orthogonal to the contact surface with the substrate by 0.5. I did it by adding seconds.
From the above, a substrate on which a semiconductor chip with a film-like adhesive was die-bonded was obtained.

[Manufacturing of semiconductor package (1)]
The substrate after die bonding obtained above was heated at 160 ° C. for 1 hour to thermoset the film-like adhesive on the substrate.
Next, using a sealing device (“MPC-06M TriAl Press” manufactured by Apic Yamada Corporation), a sealing resin (“KE-1100AS3” manufactured by Kyocera Chemical Co., Ltd.) is placed on the substrate after die bonding and heat curing. This sealing resin was heated to 175 ° C., and a pressure of 7 MPa was further applied to the sealing resin in this state for 2 minutes to form a layer (sealing layer) made of a sealing resin having a thickness of 400 μm. Next, the sealing resin forming the sealing layer was thermoset by heating at 175 ° C. for 5 hours to obtain a sealing substrate.

Next, a dicing tape (“Adwill D-510T” manufactured by Lintec Corporation) is attached to this sealing substrate, and the sealing substrate is diced using a dicing device (“DFD6361” manufactured by Disco Corporation) to obtain a size. Obtained a semiconductor package of 15 mm × 15 mm. For dicing at this time, the moving speed of the dicing blade is 50 mm / sec, the rotation speed of the dicing blade is 30,000 rpm, and the dicing tape is cut into the dicing tape from the sticking surface of the sealing substrate to a depth of 40 μm. I went by. As the dicing blade, “ZHDG-SD400-D1-60 56 × 0.17 A3 × 40-LS3” manufactured by DISCO was used.
As described above, a target semiconductor package (sometimes referred to as "semiconductor package (1)" in the present specification) was obtained by using a semiconductor processing sheet having no history of time.
Here, 25 semiconductor packages (1) were obtained by the above method.

[Manufacturing of semiconductor package (2)]
The semiconductor processing sheet immediately after production obtained above was stored standing for 7 days in an air atmosphere of 40 ° C.
Next, in the same manner as in the case of the semiconductor package (1) described above, except that the semiconductor processing sheet immediately after production was replaced with the semiconductor processing sheet after static storage, that is, after aging. Obtained a semiconductor package.
As described above, a target semiconductor package (sometimes referred to as "semiconductor package (2)" in the present specification) was obtained by using a semiconductor processing sheet having a time history.
Here, 25 semiconductor packages (2) were obtained by the above method.

[Evaluation of semiconductor package reliability]
The 25 semiconductor packages (1) obtained above were allowed to absorb moisture by being left to stand for 168 hours in an environment of a temperature of 85 ° C. and a relative humidity of 60%.
Immediately after that, the semiconductor package (1) after absorbing moisture was preheated at a temperature of 160 ° C., and then IR reflow was performed three times for 1 minute with a maximum temperature of 260 ° C. The IR reflow at this time was performed using a tabletop reflow furnace (“STR-2010N2M” manufactured by Senju Metal Industry Co., Ltd.).

Next, the semiconductor package after IR reflow was analyzed using a scanning ultrasonic flaw detector (“D-9600” manufactured by Sonoscan). In addition, a cross-section polishing machine (“Refine Polisher HV” manufactured by Refine Tech) is used to cut the semiconductor package after IR reflow to form a cross-section, and a digital microscope (“VHX-1000” manufactured by KEYENCE). This cross section was observed using. Then, when peeling with a width of 0.5 mm or more is observed at at least one of the joint portion between the substrate and the silicon chip and the joint portion between the silicon chips, it is determined that there is peeling, and it is not recognized. In this case, it was determined that there was no peeling. Further, based on this determination result, the reliability of the semiconductor package (1) was evaluated according to the following criteria.
(Evaluation criteria)
A: The number of semiconductor packages determined to be "peeled" is 3 or less.
B: The number of semiconductor packages determined to be "peeled" is 4 or more.

Further, the reliability of the semiconductor package (2) was evaluated by the same method as in the case of the semiconductor package (1) described above.
The evaluation results of these semiconductor packages (1) and (2) are shown in Table 1 together with the number of semiconductor packages determined to be "peeled" (indicated in parentheses in the corresponding column of Table 1).

<Evaluation of chip skipping suppression>
[Manufacturing of semiconductor chips with film-like adhesive]
As the silicon wafer whose back surface is polished with a dry polish finish, a silicon wafer having a diameter of 200 mm and a thickness of 350 μm is used instead of a silicon wafer having a diameter of 200 mm and a thickness of 75 μm. In the same manner as at the time, a first laminated structure (1) was obtained in which a base material, a film-like adhesive, and a silicon wafer were laminated in this order in these thickness directions.

Next, except that the first laminated structure (1) was used and the cutting position of the dicing blade was changed so that a silicon chip having a size of 2 mm × 2 mm could be obtained, the above-mentioned “semiconductor package” was described. Dicing was performed in the same manner as in "Evaluation of reliability" to obtain a silicon chip having a size of 2 mm x 2 mm.
As described above, using a semiconductor processing sheet having no time history, a plurality of silicon chips (in other words, a plurality of silicon chips with a film-like adhesive) having a film-like adhesive after cutting on the back surface are formed into a film. A second laminated structure (1) was obtained, which was fixed on the substrate in an aligned state by using a silicone-like adhesive.

Further, the same method as above is used except that the semiconductor processing sheet immediately after production is replaced with the semiconductor processing sheet after standing and storing for 7 days in an air atmosphere of 40 ° C., that is, after aging. Dicing was performed to obtain a silicon chip having a size of 2 mm × 2 mm.
As described above, using a semiconductor processing sheet having a time history, a plurality of silicon chips (in other words, a plurality of silicon chips with a film-like adhesive) having a film-like adhesive after cutting on the back surface are formed into a film. A second laminated structure (2) was obtained, which was fixed on the substrate in an aligned state by using a silicone-like adhesive.

[Evaluation of chip skipping inhibition]
The second laminated structure (1) obtained above was observed, and the number of silicon chips scattered from the film-like adhesive after cutting was confirmed during dicing. Then, when the number of scattered silicon chips is 0 (that is, the silicon chips are not scattered at all from the film-like adhesive after cutting during dicing), it is determined as "A", and the number of scattered silicon chips is 1. When the number was more than one, it was determined as "B".
Further, the second laminated structure (2) was evaluated in the same manner as in the case of the second laminated structure (1) described above.
The results are shown in Table 1.

<Measurement of adhesive strength of thermosetting film-like adhesive>
[Manufacturing of semiconductor chips with film-like adhesive]
The above-mentioned except that a silicon wafer (diameter 200 mm, thickness 75 μm) having a # 2000 polished surface on the back surface was used instead of a silicon wafer (diameter 200 mm, thickness 75 μm) whose back surface was polished with a dry polish finish. A first laminated structure (1) in which a base material, a film-like adhesive, and a silicon wafer are laminated in this order in the same manner as in "Evaluation of reliability of semiconductor package" in the above. Got

Next, except that the first laminated structure (1) was used and the cutting position of the dicing blade was changed so that a silicon chip having a size of 2 mm × 2 mm could be obtained, the above-mentioned “semiconductor package” was described. Dicing was performed in the same manner as in "Evaluation of reliability" to obtain a silicon chip having a size of 2 mm x 2 mm.
As described above, using a semiconductor processing sheet having no time history, a plurality of silicon chips (in other words, a plurality of silicon chips with a film-like adhesive) having a film-like adhesive after cutting on the back surface are formed into a film. A second laminated structure (1) was obtained, which was fixed on the substrate in an aligned state by using a silicone-like adhesive.

[Die bonding of semiconductor chips with film-like adhesive to substrates]
The silicon chip with a film-like adhesive in the second laminated structure (1) obtained above is picked up from the base material, and a manual die bonder (“EDB65” manufactured by CAMMAX Precima) is used to obtain this film-like adhesive. By crimping the silicon chip with a film to the surface of a copper plate (thickness 0.5 mm), the silicon chip with a film-like adhesive was die-bonded onto the copper plate. In the die bonding at this time, a force of 2.45 N (250 gf) is applied to the silicon chip with a film-like adhesive heated to 125 ° C. in a direction orthogonal to the contact surface with the copper plate for 3 seconds. I went there. Further, among the film-like adhesives in the silicon chip with the film-like adhesive, the entire surface of the surface opposite to the silicon chip side was brought into contact with the surface of the copper plate.

[Measurement of adhesive strength of thermosetting film-like adhesive]
Next, the copper plate after die bonding was heated at 160 ° C. for 1 hour to thermoset the film-like adhesive on the copper plate.
Next, this thermosetting test piece was used as a test piece, and the test piece was placed on the stage using a bond tester (“Series 4000” manufactured by Dage). Then, a force was applied to the silicon chip in the test piece at a speed of 200 μm / sec in the shearing direction.
At this time, the position of the head of the tester for applying the force was adjusted so as to be 7 μm above the surface of the copper plate in the test piece on the side on which the silicon chip is mounted. A force is applied to the silicon chip under these conditions, and the force (N) applied when the adhesive state between the thermosetting product of the film-like adhesive and the copper plate is broken is applied to the thermosetting of the film-like adhesive. It was adopted as the adhesive strength of the object (N / 2 mm □). The results are shown in Table 1.

<< Manufacture and evaluation of film-like adhesives >>
[Example 2, Comparative Example 1]
The point that either one or both of the types and amounts of the compounding components were changed at the time of manufacturing the adhesive composition so that the types and contents of the components contained in the adhesive composition were as shown in Table 1. A film-like adhesive and a sheet for semiconductor processing were produced by the same method as in Example 1 except for the above, and the film-like adhesive was evaluated. The results are shown in Table 1.

In addition, the description of "-" in the column of the contained component in Table 1 means that the adhesive composition does not contain the component.

As is clear from the above results, in Examples 1 and 2, the reliability of the semiconductor package (1) is high, and in the second laminated structure (1), the silicon chips are not scattered and the chips are scattered. It was suppressed. Further, the adhesive strength of the thermosetting product of the film-like adhesive was 250 N / 2 mm □ or more (250 to 258 N / 2 mm □), which was sufficiently high.

Further, in the first embodiment, the reliability of the semiconductor package (2) is high, and even in the second laminated structure (2), the silicon chip with the film-like adhesive is not scattered, and the chip flying is suppressed. It was. As described above, after storage at 40 ° C., the film-like adhesive of Example 1 had better characteristics than the film-like adhesive of Example 2, and the storage stability was remarkably high. In Example 2, it was considered that the total area of the scattered silicon chips corresponded to 10% or more of the area of the initial silicon wafer, and the number of scattered silicon chips was 700 or more. However, the film-like adhesive of Example 2 had sufficient properties when stored under normal conditions.

In Examples 1 and 2, x ₁ / y ₁ was 0.01 or more and 0.1 or less, and x ₂ / y ₂ was 0.7 or more and 0.8 or less. Then, x ₁₀ / y ₁₀ was 0.01 or more and 0.3 or less, and x ₂₀ / y ₂₀ was 0.3 or more and 0.8 or less. In the case of Example 2, x ₂₀ / y ₂₀ was smaller than that in Example 1.

On the other hand, in Comparative Example 1, the reliability of the semiconductor package (1) was low, and naturally, the reliability of the semiconductor package (2) was also low. In Comparative Example 1, x ₂ / y ₂ and x ₂₀ / y ₂₀ were both 0.2, which were small.

The present invention can be used in the manufacture of semiconductor devices.

101, 102, 103, 104 ... Semiconductor processing sheet,
10 ... Support sheet,
10a ... The first surface of the support sheet,
11 ... Base material,
11a ... The first surface of the base material,
12 ... Adhesive layer,
13, 23 ... Film-like adhesive,
13a, 23a ... First surface of film-like adhesive,
13b, 23b ... Second surface of film-like adhesive

Claims (4)

A thermosetting film-like adhesive
Using a scanning probe microscope, the surface shape of the film-like adhesive before thermosetting was measured, and an image was obtained in which the entire distribution of the histogram of the unevenness in the surface shape was 85% of the entire color tone bar. The image was binarized to obtain the area value x ₁ of the first region corresponding to the convex portion in the obtained processed image and the area value y ₁ of the second region other than the first region. When x ₁ / y ₁ is 0 or more and 0.3 or less,
Using a scanning probe microscope, the surface shape of the thermosetting film-like adhesive was measured, and an image was obtained in which the total distribution of the histogram of the unevenness in the surface shape was 85% of the entire color tone bar. The image was binarized, and the area value x ₂ of the first region corresponding to the convex portion in the obtained processed image and the area value y ₂ of the second region other than the first region were obtained. When x ₂ / y ₂ is greater than 0.3 and less than or equal to 5, a film-like adhesive. Using a scanning probe microscope, the surface shape of the film-like adhesive after storage at 40 ° C. for 7 days and before thermosetting was measured, and the entire distribution of the histogram of the unevenness in the surface shape was measured over the entire color tone bar. An image of 85% of the above was acquired, the image was binarized, and the area value x ₁₀ of the first region corresponding to the convex portion in the obtained processed image and the second region other than the first region were obtained. When the area value y _{10 of the} region was obtained, x ₁₀ / y ₁₀ was 0 or more and 0.3 or less.
Using a scanning probe microscope, the surface shape of the thermosetting product obtained by thermosetting the film-like adhesive after storage at 40 ° C. for 7 days was measured, and the entire distribution of the histogram of the unevenness in the surface shape was measured. , An image of 85% of the entire color tone bar was acquired, and the image was binarized to obtain an area value x ₂₀ of a first region corresponding to a convex portion in the obtained processed image and the first region. The film-like adhesive according to claim 1, wherein x ₂₀ / y ₂₀ is greater than 0.3 and greater than or equal to 5 when the area value y ₂₀ of the second region other than the above is obtained. A semiconductor processing sheet provided with a support sheet and having the film-like adhesive according to claim 1 or 2 on one surface of the support sheet. The support sheet includes a base material and an adhesive layer provided on one surface of the base material.
The semiconductor processing sheet according to claim 3, wherein the pressure-sensitive adhesive layer is arranged between the base material and the film-like adhesive.

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