WO2021193913A1

WO2021193913A1 - Semiconductor device manufacturing sheet, method for manufacturing semiconductor device manufacturing sheet, and method for manufacturing semiconductor chip having film adhesive attached thereto

Info

Publication number: WO2021193913A1
Application number: PCT/JP2021/012838
Authority: WO
Inventors: 渉岩屋; 陽輔佐藤
Original assignee: リンテック株式会社
Priority date: 2020-03-27
Filing date: 2021-03-26
Publication date: 2021-09-30
Also published as: KR20220155978A; KR20220156511A; JPWO2021193910A1; WO2021193934A1; WO2021193923A1; WO2021193936A1; CN115315785A; JPWO2021193913A1; JPWO2021193942A1; KR20220159341A; TW202138510A; JPWO2021193934A1; KR20220159984A; TW202141603A; WO2021193916A1; JPWO2021193916A1; CN114467171A; KR20220156551A; CN115380363A; WO2021193942A1

Abstract

A semiconductor device manufacturing sheet comprising a substrate, a pressure sensitive adhesive layer, an intermediate layer and a film adhesive, wherein: the pressure sensitive adhesive layer, the intermediate layer and the film adhesive are laminated in said order on the substrate; the intermediate layer comprises, as the main ingredient, a non-silicon resin (β1) having a weight average molecular weight of 20,000-100,000; the film adhesive comprises a liquid ingredient (α2), or the pressure sensitive adhesive layer comprises a liquid ingredient (γ2); and H(βα)-H(β)>7% or H(βγ)-H(β)>7% is satisfied if the haze of a first test piece comprising the non-silicon resin (β1) and having a thickness of 10μm is represented by H(β), the haze of a second test piece comprising a mixture of the non-silicon resin (β1) and the ingredient (α2) and having a thickness of 10μm is represented by H(βα), and the haze of a third test piece comprising a mixture of the non-silicon resin (β1) and the ingredient (γ2) and having a thickness of 10μm is represented by H(βγ).

Description

A sheet for manufacturing a semiconductor device, a method for manufacturing a sheet for manufacturing a semiconductor device, and a method for manufacturing a semiconductor chip with a film-like adhesive.

The present invention relates to a semiconductor device manufacturing sheet, a method for manufacturing a semiconductor device manufacturing sheet, and a method for manufacturing a semiconductor chip with a film-like adhesive.
The present application claims priority based on Japanese Patent Application No. 2020-058734 filed in Japan on March 27, 2020, the contents of which are incorporated herein by reference.

At the time of manufacturing a semiconductor device, a semiconductor chip with a film-like adhesive including a semiconductor chip and a film-like adhesive provided on the back surface thereof is used.
Examples of the method for manufacturing a semiconductor chip with a film-like adhesive include those shown below.

That is, first, a dicing die bonding sheet is attached to the back surface of the semiconductor wafer.
Examples of the dicing die bonding sheet include a support sheet and a film-like adhesive provided on one surface of the support sheet, and the support sheet can be used as a dicing sheet. There is. As the support sheet, for example, there are a plurality of types having different configurations, such as one provided with a base material and an adhesive layer provided on one surface of the base material; one composed of only the base material. .. In the support sheet provided with the pressure-sensitive adhesive layer, the outermost surface on the pressure-sensitive adhesive layer side is the surface on which the film-like adhesive is provided. The dicing die bonding sheet is attached to the back surface of the semiconductor wafer by the film-like adhesive in the dicing die bonding sheet.

Next, the semiconductor wafer and the film-like adhesive on the support sheet are cut together by blade dicing. The "cutting" of a semiconductor wafer is also referred to as "splitting", whereby the semiconductor wafer is fragmented into a target semiconductor chip. The film-like adhesive is cut along the outer circumference of the semiconductor chip. As a result, a semiconductor chip with a film-like adhesive comprising a semiconductor chip and a film-like adhesive after cutting provided on the back surface thereof can be obtained, and a plurality of these film-like adhesives can be obtained on a support sheet. A group of semiconductor chips with a film-like adhesive, which are formed by holding the attached semiconductor chips in an aligned state, can be obtained.

Next, the semiconductor chip with the film-like adhesive is pulled away from the support sheet and picked up. When a support sheet provided with a curable pressure-sensitive adhesive layer is used, picking up is facilitated by curing the pressure-sensitive adhesive layer to reduce the adhesiveness at this time.
From the above, a semiconductor chip with a film-like adhesive used for manufacturing a semiconductor device can be obtained.

Other examples of the method for manufacturing a semiconductor chip with a film-like adhesive include those shown below.
That is, first, a back grind tape (sometimes referred to as "surface protection tape") is attached to the circuit forming surface of the semiconductor wafer.
Next, a region to be divided is set inside the semiconductor wafer, and a modified layer is formed inside the semiconductor wafer by irradiating a laser beam so as to focus on the region included in this focal point. Form. Next, the back surface of the semiconductor wafer is ground using a grinder to adjust the thickness of the semiconductor wafer to the desired value, and the grinding force applied to the semiconductor wafer at this time is used. At the site where the modified layer is formed, the semiconductor wafer is divided (individualized) to produce a plurality of semiconductor chips. The method of dividing a semiconductor wafer that involves the formation of a modified layer in this way is called stealth dicing (registered trademark). By irradiating the semiconductor wafer with laser light, the semiconductor wafer at the irradiation site is scraped off and the semiconductor is semiconductor. It is essentially completely different from laser dicing, which cuts a wafer from its surface.

Next, one die bonding sheet is attached to the back surface (in other words, the ground surface) of all these semiconductor chips fixed on the back grind tape after the above-mentioned grinding. Examples of the die bonding sheet include those similar to the above dicing die bonding sheet. As described above, the die bonding sheet may be designed to have the same configuration as the dicing die bonding sheet without being used when dicing the semiconductor wafer. The die bonding sheet is also attached to the back surface of the semiconductor chip by the film-like adhesive therein.

Next, after removing the back grind tape from the semiconductor chip, the die bonding sheet is stretched in a direction parallel to its surface (for example, the surface on which the film-like adhesive is attached to the semiconductor chip) while being cooled, so-called expand (so-called expand). By performing cool expansion), the film-like adhesive is cut along the outer periphery of the semiconductor chip.
As described above, a semiconductor chip with a film-like adhesive comprising a semiconductor chip and a film-like adhesive after cutting provided on the back surface thereof can be obtained.

Next, as in the case of adopting the above-mentioned blade dicing, the semiconductor chip with the film-like adhesive is separated from the support sheet and picked up to obtain the semiconductor chip with the film-like adhesive used for manufacturing the semiconductor device. Be done.

Both the dicing die bonding sheet and the die bonding sheet can be used for manufacturing a semiconductor chip with a film-like adhesive, and finally, the target semiconductor device can be manufactured. In the present specification, the dicing die bonding sheet and the die bonding sheet are collectively referred to as "semiconductor device manufacturing sheet".

The sheet for manufacturing a semiconductor device includes, for example, a dicing die bonding tape (described above) having a structure in which a base material layer (corresponding to the support sheet) and an adhesive layer (corresponding to the film-like adhesive) are directly contacted and laminated. A dicing die bonding sheet (corresponding to a dicing die bonding sheet) is disclosed (see Patent Document 1). In this dicing die bonding tape, since the 90-degree peeling force of the base material layer and the adhesive layer at -15 ° C is adjusted to a specific range, the adhesive layer can be accurately divided by expanding, and the base material can also be separated. Since the 90-degree peeling force of the layer and the adhesive layer at 23 ° C. is adjusted to a specific range, when this dicing die bonding tape is used, a semiconductor chip with an adhesive layer (the semiconductor with a film-like adhesive). It is said that (corresponding to a chip) can be picked up without difficulty, and peeling of the semiconductor wafer and the semiconductor chip from the adhesive layer can be suppressed in the process up to the pick-up.

Japanese Patent Application Laid-Open No. 2018-56289

On the other hand, the support sheet in the sheet for manufacturing a semiconductor device includes the base material and the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer or the film-like adhesive contains a liquid component at room temperature. In some cases, the liquid component may be transferred between the pressure-sensitive adhesive layer and the film-like adhesive in the sheet for manufacturing a semiconductor device. When such a transition occurs, either one or both of the pressure-sensitive adhesive layer and the film-like adhesive cannot normally exert its function. The dicing die bonding tape disclosed in Patent Document 1 does not have an adhesive layer.

The present invention comprises a base material, a pressure-sensitive adhesive layer and a film-like adhesive, and even if the pressure-sensitive adhesive layer or the film-like adhesive contains a liquid component, the liquid component is between the pressure-sensitive adhesive layer and the film-like adhesive. It is an object of the present invention to provide a sheet for manufacturing a semiconductor device in which the transition of the above is suppressed.

The present invention includes a base material, a pressure-sensitive adhesive layer, an intermediate layer, and a film-like adhesive, and the pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated on the base material in this order. The intermediate layer contains a non-silicon resin (β1) having a weight average molecular weight of 20,000 to 100,000 as a main component, and at least the film-like adhesive contains a component (α2). Alternatively, the pressure-sensitive adhesive layer contains a component (γ2), and the component (α2) is liquid at a temperature of 23 ° C. and has a functional group that reacts with the main component contained in the film-like adhesive. First, the component (γ2) is liquid at a temperature of 23 ° C., does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer, and has a thickness made of the non-silicon resin (β1). When the haze of the first test piece in the form of a film of 10 μm is H (β) and the film-like adhesive contains the component (α2), 100 parts by mass of the non-silicon resin (β1) and the non-silicon resin (β1) are used. When the haze of the film-like second test piece having a thickness of 10 μm composed of a mixture of 10 parts by mass of the component (α2) is H (βα), the H (βα) and H (β) are as follows. Equation (X1):
(X1) H (βα) -H (β)> 7%
When the pressure-sensitive adhesive layer contains the component (γ2), the thickness is composed of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (γ2). When the haze of the film-like third test piece having a mass of 10 μm is H (βγ), the H (βγ) and H (β) are expressed by the following formula (X2):
(X2) H (βγ) -H (β)> 7%
Provided is a sheet for manufacturing a semiconductor device that satisfies the above conditions.

In the sheet for manufacturing a semiconductor device of the present invention, at least the film-like adhesive contains a solid component (α1) at a temperature of 23 ° C. as a main component, or the pressure-sensitive adhesive layer has a temperature of 23 ° C. It may be an acrylic resin containing a solid component (γ1) as a main component and having the component (α1) and the component (γ1) having a structural unit derived from a (meth) acrylic acid ester.
In the semiconductor device manufacturing sheet of the present invention, the intermediate layer contains one or more selected from the group consisting of ethylene-vinyl acetate copolymer and polyolefin as the non-silicon resin (β1). May be.
In the sheet for manufacturing a semiconductor device of the present invention, the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon resin (β1), and in the ethylene-vinyl acetate copolymer, all the constituent units are contained. The ratio of the mass of the structural unit derived from vinyl acetate to the total mass may be 30% by mass or less.
The sheet for manufacturing a semiconductor device of the present invention may be for cutting the film-like adhesive by cooling and expanding the film-like adhesive.

The present invention is a method for manufacturing a sheet for manufacturing a semiconductor device, wherein the manufacturing method includes a film-like adhesive manufacturing step for manufacturing the film-like adhesive containing the component (α2) and the component (γ2). ), And a method for manufacturing a sheet for manufacturing a semiconductor device, which has one or both of the step of manufacturing the pressure-sensitive adhesive layer.

The present invention is a method for manufacturing a semiconductor chip with a film-like adhesive using the sheet for manufacturing a semiconductor device, wherein the semiconductor chip with a film-like adhesive is provided on the semiconductor chip and the back surface of the semiconductor chip. The manufacturing method includes a step of attaching the film-like adhesive to the back surface of the semiconductor wafer while heating the sheet for manufacturing the semiconductor device, and the film. The semiconductor chip is manufactured by cutting and dividing the entire area in the thickness direction of the semiconductor wafer to which the adhesive is attached from the circuit forming surface side, and the sheet for manufacturing the semiconductor device is used. By cutting from the film-like adhesive side to a region in the middle of the intermediate layer in the thickness direction, cutting the film-like adhesive, and not cutting into the pressure-sensitive adhesive layer, a plurality of pieces are formed. In the step of obtaining a group of semiconductor chips with a film-like adhesive in a state in which the semiconductor chips with a film-like adhesive are aligned on the intermediate layer, and by separating the semiconductor chips with a film-like adhesive from the intermediate layer, Provided is a method for manufacturing a semiconductor chip with a film-like adhesive, which comprises a step of picking up.

The present invention is a method for manufacturing a semiconductor chip with a film-like adhesive using the sheet for manufacturing a semiconductor device, wherein the semiconductor chip with the film-like adhesive is provided on the semiconductor chip and the back surface of the semiconductor chip. A modified layer is provided inside the semiconductor wafer by irradiating a laser beam so as to focus on a focal point set inside the semiconductor wafer. By grinding the back surface of the semiconductor wafer after forming the modified layer and using the grinding force applied to the semiconductor wafer, the semiconductor is formed at a site where the modified layer is formed. The step of dividing the wafer to obtain a semiconductor chip group in which a plurality of the semiconductor chips are aligned, and while heating the semiconductor device manufacturing sheet, the film-like adhesive therein is applied to the semiconductor chip group. The process of attaching to the back surface of all the semiconductor chips and the sheet for manufacturing the semiconductor device after being attached to the semiconductor chip are stretched in a direction parallel to the surface while being cooled to form the film. A step of cutting an adhesive along the outer periphery of the semiconductor chip to obtain a group of semiconductor chips with a film-like adhesive in a state in which a plurality of the semiconductor chips with the film-like adhesive are aligned on the intermediate layer, and the above-mentioned step. Provided is a method for manufacturing a semiconductor chip with a film-like adhesive, which comprises a step of pulling the semiconductor chip with the film-like adhesive from the intermediate layer and picking it up.

According to the present invention, the substrate, the pressure-sensitive adhesive layer and the film-like adhesive are provided, and even if the pressure-sensitive adhesive layer or the film-like adhesive contains a liquid component, between the pressure-sensitive adhesive layer and the film-like adhesive. Provided is a sheet for manufacturing a semiconductor device in which the transfer of liquid components is suppressed.

It is sectional drawing which shows typically the sheet for manufacturing the semiconductor device which concerns on one Embodiment of this invention. It is a top view of the sheet for manufacturing a semiconductor device shown in FIG. It is sectional drawing for schematically explaining an example of the manufacturing method of the semiconductor chip with a film-like adhesive which concerns on one Embodiment of this invention. It is sectional drawing for schematically explaining an example of the manufacturing method of the semiconductor chip with a film-like adhesive which concerns on one Embodiment of this invention. It is sectional drawing for schematically explaining an example of the manufacturing method of the semiconductor chip with a film-like adhesive which concerns on one Embodiment of this invention. It is sectional drawing for schematically explaining an example of the manufacturing method of a semiconductor chip. It is sectional drawing for schematically explaining an example of the manufacturing method of a semiconductor chip. It is sectional drawing for schematically explaining an example of the manufacturing method of a semiconductor chip. It is sectional drawing for schematically explaining another example of the manufacturing method of the semiconductor chip with a film-like adhesive which concerns on one Embodiment of this invention. It is sectional drawing for schematically explaining another example of the manufacturing method of the semiconductor chip with a film-like adhesive which concerns on one Embodiment of this invention. It is sectional drawing for schematically explaining another example of the manufacturing method of the semiconductor chip with a film-like adhesive which concerns on one Embodiment of this invention.

-Sheet for manufacturing semiconductor devices The sheet for manufacturing semiconductor devices according to an embodiment of the present invention includes a base material, an adhesive layer, an intermediate layer, and a film-like adhesive, and the adhesive is provided on the base material. The agent layer, the intermediate layer, and the film-like adhesive are laminated in this order, and the intermediate layer is a non-silicon resin (β1) having a weight average molecular weight of 20,000 to 100,000 (in the present specification, It contains (sometimes simply referred to as "non-silicon resin (β1)") as a main component, and at least the film-like adhesive contains a component (α2), or the pressure-sensitive adhesive layer is a component. The component (γ2) contains (γ2), is liquid at a temperature of 23 ° C., does not have a functional group that reacts with the main component contained in the film-like adhesive, and the component (γ2) is. A film-like first test piece having a thickness of 10 μm made of the non-silicon resin (β1), which is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer. When the haze is H (β) and the film-like adhesive contains the component (α2), 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (α2) are used. When the haze of the film-like second test piece having a thickness of 10 μm composed of a mixture of
(X1) H (βα) -H (β)> 7%
When the pressure-sensitive adhesive layer contains the component (γ2), the thickness is composed of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (γ2). When the haze of the film-like third test piece having a mass of 10 μm is H (βγ), the H (βγ) and H (β) are expressed by the following formula (X2):
(X2) H (βγ) -H (β)> 7%
Meet.

In the sheet for manufacturing a semiconductor device of the present embodiment, the intermediate layer contains the non-silicon resin (β1) as a main component, the film-like adhesive contains the component (α2), and the pressure-sensitive adhesive layer contains the component. A sheet for manufacturing a semiconductor device that does not contain (γ2); the intermediate layer contains the non-silicon resin (β1) as a main component, the pressure-sensitive adhesive layer contains the component (γ2), and the film-like adhesive is the component. A sheet for manufacturing a semiconductor device that does not contain (α2); the intermediate layer contains the non-silicon resin (β1) as a main component, the film-like adhesive contains the component (α2), and the pressure-sensitive adhesive layer contains the component. Examples thereof include a sheet for manufacturing a semiconductor device containing (γ2).

Then, in the sheet for manufacturing a semiconductor device of the present embodiment, when the film-like adhesive contains the component (α2), the H is regardless of the presence or absence of the component (γ2) in the pressure-sensitive adhesive layer. (Βα) and H (β) satisfy the above formula (X1). In such a sheet for manufacturing a semiconductor device, it can be determined that the compatibility between the component (α2) and the non-silicon resin (β1) is low, and the component (α2) in the film-like adhesive is transferred to the intermediate layer. It is suppressed, and as a result, the transfer of the component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer is suppressed.
On the other hand, in the semiconductor device manufacturing sheet of the present embodiment, when the pressure-sensitive adhesive layer contains the component (γ2), the H is regardless of the presence or absence of the component (α2) in the film-like adhesive. (Βγ) and H (β) satisfy the above formula (X2). In such a sheet for manufacturing a semiconductor device, it can be determined that the compatibility between the component (γ2) and the non-silicon resin (β1) is low, and the migration of the component (γ2) in the pressure-sensitive adhesive layer to the intermediate layer is suppressed. As a result, the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is suppressed.
That is, in the semiconductor device manufacturing sheet of the present embodiment, the intermediate layer functions as a layer for suppressing the migration of the component (α2) and the component (γ2).

In the semiconductor device manufacturing sheet of the present embodiment, the effect of suppressing the transfer of the component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer can be confirmed, for example, by the following method.
That is, a large number of semiconductor chips with a film-like adhesive can be obtained by aging the semiconductor device manufacturing sheet by allowing it to stand for a certain period of time under high temperature conditions, and using the semiconductor device manufacturing sheet after the aging, by a method described later. , A semiconductor chip group with a film-like adhesive (for example, a silicon chip group with a film-like adhesive) in a state of being aligned and fixed on an intermediate layer in a laminated sheet is produced by a film-like adhesive therein. .. Here, the "laminated sheet" is a laminate having a structure in which a base material, an adhesive layer, and an intermediate layer are laminated in this order in the thickness direction thereof. Then, the force required to peel the semiconductor chip with the film-like adhesive from the intermediate layer in the laminated sheet is measured, and this is adopted as the pick-up force of the semiconductor chip with the film-like adhesive over time.
On the other hand, using a sheet for manufacturing a semiconductor device that has not been aged (before aging), the force required to peel the semiconductor chip with a film-like adhesive from the intermediate layer in the laminated sheet is measured by the same method. However, this is adopted as a timeless pick-up force for a semiconductor chip with a film-like adhesive.
Then, if there is no difference between the aged pickup force and the aged pick-up force of the semiconductor chip with a film-like adhesive, or if there is a difference, but the degree is extremely slight, a semiconductor device is manufactured. It can be judged that there was no obvious change in the composition of the film-like adhesive even after the aging of the sheet for semiconductor devices, and the sheet for manufacturing semiconductor devices transferred the component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer. It can be judged that it has an suppressing effect.

In the semiconductor device manufacturing sheet of the present embodiment, the effect of suppressing the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is, for example, when the component (γ2) is an antistatic agent. , Can be confirmed by the following method.
That is, the film-like adhesive is peeled off from the intermediate layer in the semiconductor device manufacturing sheet after aging by allowing the semiconductor device manufacturing sheet to stand for a certain period of time under high temperature conditions in the same manner as described above. To prepare a test piece of a film-like adhesive. Humidity is controlled by storing the test piece in a constant temperature and relative humidity (for example, temperature 23 ° C., relative humidity 50%) for a certain period of time, and then the film-like adhesive after the humidity control is used. The surface resistance of the exposed surface that was on the intermediate layer side is measured, and this is adopted as the surface resistance of the film-like adhesive over time.
On the other hand, using a sheet for manufacturing semiconductor devices that has not been aged (before aging), the surface resistivity of the exposed surface that was on the intermediate layer side of the film-like adhesive was measured by the same method, and this was measured as a film. Adhesive is used as the surface resistivity without aging.
Then, there is no difference (more specifically, a decrease) between the surface resistivity of the film-like adhesive with time and the surface resistivity without time, or a difference is observed, but the degree is extremely slight. In some cases, it can be determined that the composition of the pressure-sensitive adhesive layer containing the antistatic agent did not change even after the semiconductor device manufacturing sheet was aged, and the semiconductor device manufacturing sheet was a component in the pressure-sensitive adhesive layer. It can be judged that it has an effect of suppressing the transfer of (γ2) to the film-like adhesive.
When the component (γ2) is a component other than the antistatic agent, for example, the physical characteristics of the pressure-sensitive adhesive layer reflecting the content of the component do not differ depending on the presence or absence of the pressure-sensitive adhesive layer over time, or Although there is a difference, if the degree is extremely slight, it can be judged that the semiconductor device manufacturing sheet has an effect of suppressing the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive. ..

In the present specification, the "main component" is not limited to the non-silicon resin (β1) in the above-mentioned intermediate layer, and the content (part by mass) thereof is the maximum in the layer (film) containing the component. , Means a component having a weight average molecular weight of 20,000 or more. For example, in the intermediate layer, the content (parts by mass) of the non-silicon resin (β1) is the largest among all the components, and the weight average molecular weight of the non-silicon resin (β1) is 20000 or more.

In the present specification, a liquid component such as the component (α2) and the component (γ2), which is liquid at a temperature of 23 ° C., may be collectively referred to as a “liquid component”.

The first test piece, the second test piece, and the third test piece are all in the form of a film having a thickness of 10 μm, and the overall shape thereof is not particularly limited as long as the haze can be measured. ..

In the present specification, the "thickness" is not limited to the case of the first test piece to the third test piece, and unless otherwise specified, the "thickness" is the thickness measured at five randomly selected points in the object. It means an average value and can be obtained using a constant pressure thickness measuring instrument according to JIS K7130.

The H (β), H (βα) and H (βγ) can all be measured in accordance with JIS K 7136: 2000.

The H (β) is not particularly limited as long as it satisfies the above formulas (X1) and (X2).
H (β) may be any of 0.1-20%, 1-18%, and 2-15%, for example, in that the intermediate layer is easier to form.

For the first test piece, a composition for the first test containing the non-silicon resin (β1) and a solvent is prepared, and the composition for the first test is applied to the surface to be formed of the first test piece. It can be produced by drying. Examples of the surface to be formed of the first test piece include a release-treated surface of the release film.

The first test piece is made of non-silicon resin (β1). The first test piece contains only the non-silicon resin (β1) as a constituent component, or contains impurities other than the non-silicon resin (β1), but the content of the impurities is the second. 1 It is a very small amount that does not change the physical properties of the test piece, and it can be considered that it contains substantially only the non-silicon resin (β1). For example, the ratio of the content of the non-silicon resin (β1) to the total mass of the first test piece in the first test piece may be 99% by mass or more.

The H (βα) is not particularly limited as long as the formula (X1) is satisfied.
H (βα) may be any of 8-80%, 10-75%, and 12-70%, for example, in that the intermediate layer and the film-like adhesive are easier to form.

For the second test piece, a composition for a second test containing the non-silicon resin (β1), the component (α2), and a solvent is prepared, and the second test piece is formed on the surface to be formed. It can be produced by applying the composition for the second test and drying it. The surface to be formed of the second test piece is the same as the surface to be formed of the first test piece described above.
In the composition for the second test, it is preferable that the contained components are uniformly mixed, and by doing so, a second test piece in which the contained components are uniformly mixed can be produced. , H (βα) can be measured with higher accuracy. For that purpose, at the time of preparing the composition for the second test, the one obtained by blending all the components may be sufficiently stirred by a known method.

The second test piece is composed of a mixture of 100 parts by mass of a non-silicon resin (β1) and 10 parts by mass of a component (α2). The second test piece contains only the non-silicon resin (β1) and the component (α2) as its constituent components, or contains impurities other than the non-silicon resin (β1) and the component (α2). However, the content of impurities is so small that it does not change the physical properties of the second test piece, and it can be considered that it contains substantially only non-silicon resin (β1) and component (α2). Is. For example, the ratio of the total content of the non-silicon resin (β1) and the component (α2) to the total mass of the second test piece in the second test piece may be 99% by mass or more.

The H (βγ) is not particularly limited as long as the formula (X2) is satisfied.
H (βγ) may be any of 8-80%, 10-75%, and 12-70%, for example, in that the intermediate layer and the pressure-sensitive adhesive layer are easier to form.

For the third test piece, a composition for a third test containing the non-silicon resin (β1), the component (γ2), and a solvent is prepared, and the third test piece is formed on the surface to be formed. It can be produced by applying the composition for the third test and drying it. The surface to be formed of the third test piece is the same as the surface to be formed of the first test piece described above.
In the composition for the third test, it is preferable that the contained components are uniformly mixed, and by doing so, a third test piece in which the contained components are uniformly mixed can be produced. , H (βγ) can be measured with higher accuracy. For that purpose, when preparing the composition for the third test, the one obtained by blending all the components may be sufficiently stirred by a known method.

The third test piece is composed of a mixture of 100 parts by mass of a non-silicon resin (β1) and 10 parts by mass of a component (γ2). The third test piece contains only the non-silicon resin (β1) and the component (γ2) as its constituent components, or contains impurities other than the non-silicon resin (β1) and the component (γ2). However, the content of impurities is so small that it does not change the physical properties of the third test piece, and it can be considered that it contains substantially only non-silicon resin (β1) and component (γ2). Is. For example, the ratio of the total content of the non-silicon resin (β1) and the component (γ2) to the total mass of the third test piece in the third test piece may be 99% by mass or more.

The H (βα) −H (β) may be more than 7%, but 7.5% in that the transfer of the component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer is more suppressed. The above is preferable, and for example, it may be any of 9% or more and 11% or more.
The upper limit of H (βα) −H (β) is not particularly limited. H (βα) —H (β) is preferably 90% or less in that a film-like adhesive satisfying the formula (X1) and an intermediate layer can be easily formed.
H (βα) -H (β) is preferably, for example, more than 7% and 90% or less (7% <H (βα) -H (β) ≤ 90%), 7.5 to 90%, 9 It may be any of ~ 90% and 11 ~ 90%.

The H (βγ) −H (β) may be more than 7%, but 7.5% in that the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed. The above is preferable, and for example, it may be any of 9% or more and 11% or more.
The upper limit of H (βγ) −H (β) is not particularly limited. H (βγ) −H (β) is preferably 90% or less from the viewpoint that the pressure-sensitive adhesive layer and the intermediate layer satisfying the above formula (X2) can be easily formed.
H (βγ) -H (β) is preferably, for example, more than 7% and 90% or less (7% <H (βγ) -H (β) ≤ 90%), 7.5 to 90%, 9 It may be any of ~ 90% and 11 ~ 90%.

When the semiconductor device manufacturing sheet of the present embodiment is used as a dicing die bonding sheet and blade dicing is performed, the blade reaches the base material because the semiconductor device manufacturing sheet includes the intermediate layer. This can be easily avoided, and the generation of whisker-like cutting chips (also known as Whiskers, hereinafter, not limited to those derived from the base material, but also simply referred to as "cutting chips") from the base material can be generated. Can be suppressed. Then, the main component of the intermediate layer cut by the blade is a non-silicon resin (β1) having a weight average molecular weight of 20,000 to 100,000, and particularly, the weight average molecular weight is 100,000 or less, so that the intermediate layer can be separated from the intermediate layer. It is also possible to suppress the generation of the cutting chips.

On the other hand, when the semiconductor device manufacturing sheet of the present embodiment is used as a die bonding sheet and dicing (stealth dicing (registered trademark)) accompanied by formation of a modified layer on a semiconductor wafer is performed, the semiconductor device manufacturing sheet is used. Since the sheet includes the intermediate layer, the sheet for manufacturing a semiconductor device is subsequently stretched in a direction parallel to its surface (for example, the surface on which the film-like adhesive is attached to the semiconductor chip), that is, so-called expansion is performed. As a result, the film-like adhesive can be cut accurately at the target location, and cutting defects can be suppressed.

As described above, the semiconductor device manufacturing sheet of the present embodiment suppresses the generation of cutting chips from the base material and the intermediate layer at the time of blade dicing, and suppresses the cutting failure of the film-like adhesive at the time of the expansion. It is possible to impart a characteristic of suppressing the occurrence of defects when the semiconductor wafer is divided, and it is possible to make the semiconductor wafer excellent in division suitability.

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 method of using the semiconductor device manufacturing sheet of this embodiment will be described in detail later.

Hereinafter, the semiconductor device manufacturing sheet of the present embodiment will be described in detail with reference to the drawings. 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.

FIG. 1 is a cross-sectional view schematically showing a semiconductor device manufacturing sheet according to an embodiment of the present invention, and FIG. 2 is a plan view of the semiconductor device manufacturing sheet shown in FIG.
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 device manufacturing sheet 101 shown here includes a base material 11, and the pressure-sensitive adhesive layer 12, the intermediate layer 13, and the film-like adhesive 14 are laminated in this order on the base material 11. The sheet 101 for manufacturing a semiconductor device is further peeled off on a surface (hereinafter, may be referred to as “first surface”) 14a opposite to the side on which the intermediate layer 13 of the film-like adhesive 14 is provided. The film 15 is provided.

In the sheet 101 for manufacturing a semiconductor device, the pressure-sensitive adhesive layer 12 is provided on one surface (sometimes referred to as “first surface” in the present specification) 11a of the base material 11, and the pressure-sensitive adhesive layer 12 is provided. An intermediate layer 13 is provided on a surface (sometimes referred to as a "first surface" in the present specification) 12a opposite to the side on which the base material 11 is provided, and the adhesive of the intermediate layer 13 is adhered. A film-like adhesive 14 is provided on a surface (sometimes referred to as a "first surface" in the present specification) 13a opposite to the side on which the agent layer 12 is provided, and the film-like adhesive is provided. A release film 15 is provided on the first surface 14a of 14. As described above, the semiconductor device manufacturing sheet 101 is configured by laminating the base material 11, the pressure-sensitive adhesive layer 12, the intermediate layer 13, and the film-like adhesive 14 in this order in the thickness direction.

In the semiconductor device manufacturing sheet 101, in a state where the release film 15 is removed, the first surface 14a of the film-like adhesive 14 in the sheet 101 is a semiconductor wafer, a semiconductor chip, or a semiconductor wafer in which the film-like adhesive 14 is not completely divided. It is used by being attached to the back surface of (not shown).

In the present specification, in the case of both the semiconductor wafer and the semiconductor chip, the surface on the side where the circuit 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". Refer to.

In the present specification, a laminate having a structure in which the base material and the pressure-sensitive adhesive layer are laminated in the thickness direction thereof and the intermediate layer is not laminated may be referred to as a "support sheet". In FIG. 1, a support sheet is indicated by reference numeral 1.
Further, a laminate having a structure in which a base material, an adhesive layer and an intermediate layer are laminated in this order in the thickness direction thereof may be referred to as a "laminated sheet". In FIG. 1, a laminated sheet is indicated by reference numeral 10. The support sheet and the laminate of the intermediate layer are included in the laminate sheet.

When the intermediate layer 13 and the film-like adhesive 14 are viewed in a plan view from above, they are both circular in shape, and the diameter of the intermediate layer 13 and the diameter of the film-like adhesive 14 are the same. ..
Then, in the semiconductor device manufacturing sheet 101, the intermediate layer 13 and the film-like adhesive 14 have their centers aligned with each other, in other words, the positions of the outer circumferences of the intermediate layer 13 and the film-like adhesive 14 are aligned with each other. They are arranged so that they all match in the radial direction.

Both the first surface 13a of the intermediate layer 13 and the first surface 14a of the film-like adhesive 14 have a smaller area than the first surface 12a of the pressure-sensitive adhesive layer 12. _{The maximum value (that is, diameter) of the width W 13} of the intermediate layer 13 and the maximum value (that is, diameter) of the width W ₁₄ of the film-like adhesive 14 are both the maximum value of the width of the pressure-sensitive adhesive layer 12 and the maximum value. It is smaller than the maximum width of the base material 11. Therefore, in the semiconductor device manufacturing sheet 101, a part of the first surface 12a of the pressure-sensitive adhesive layer 12 is not covered with the intermediate layer 13 and the film-like adhesive 14. In such a region of the first surface 12a of the pressure-sensitive adhesive layer 12 where the intermediate layer 13 and the film-like adhesive 14 are not laminated, the release film 15 is directly contacted and laminated, and the release film 15 is laminated. In the removed state, this region is exposed (hereinafter, this region may be referred to as a "non-stacked region" in the present specification).
In the sheet 101 for manufacturing a semiconductor device provided with the release film 15, the area of the pressure-sensitive adhesive layer 12 not covered by the intermediate layer 13 and the film-like adhesive 14 is the release film 15 as shown here. There may or may not be areas where are not laminated.

The semiconductor device manufacturing sheet 101 in which the film-like adhesive 14 is uncut and is attached to the above-mentioned semiconductor wafer, semiconductor chip, or the like by the film-like adhesive 14 is the non-cutting material in the pressure-sensitive adhesive layer 12. A part of the laminated region can be fixed by attaching it to a jig such as a ring frame for fixing a semiconductor wafer. Therefore, it is not necessary to separately provide the jig adhesive layer for fixing the semiconductor device manufacturing sheet 101 to the jig on the semiconductor device manufacturing sheet 101. Since it is not necessary to provide the adhesive layer for the jig, the sheet 101 for manufacturing the semiconductor device can be manufactured inexpensively and efficiently.

As described above, the sheet 101 for manufacturing a semiconductor device has an advantageous effect because it does not include the adhesive layer for jigs, but may include an adhesive layer for jigs. In this case, the jig adhesive layer is provided in a region near the peripheral edge of the surface of any of the layers constituting the semiconductor device manufacturing sheet 101. Examples of such a region include the non-laminated region on the first surface 12a of the pressure-sensitive adhesive layer 12.

The adhesive layer for jigs may be a known one. For example, it may have a single-layer structure containing an adhesive component, or layers containing an adhesive component are laminated on both sides of a sheet serving as a core material. It may have a multi-layer structure.

Further, as will be described later, when the so-called expanding, in which the sheet 101 for manufacturing a semiconductor device is stretched in a direction parallel to the surface thereof (for example, the first surface 12a of the pressure-sensitive adhesive layer 12), the first surface of the pressure-sensitive adhesive layer 12 is expanded. The presence of the non-laminated region on one surface 12a makes it possible to easily expand the sheet 101 for manufacturing a semiconductor device. Not only can the film-like adhesive 14 be easily cut, but the peeling of the intermediate layer 13 and the film-like adhesive 14 from the pressure-sensitive adhesive layer 12 may be suppressed.

In the semiconductor device manufacturing sheet 101, the intermediate layer 13 contains a non-silicon resin (β1) having a weight average molecular weight of 20,000 to 100,000 as a main component.

The sheet for manufacturing a semiconductor device of the present embodiment is not limited to the one shown in FIGS. 1 and 2, and a part of the configurations shown in FIGS. 1 and 2 are changed within the range not impairing the effect of the present invention. , May have been deleted or added.

For example, the sheet for manufacturing a semiconductor device of the present embodiment does not correspond to any of a base material, an adhesive layer, an intermediate layer, a film-like adhesive, a release film, and an adhesive layer for jigs. , Other layers may be provided. However, as shown in FIG. 1, the semiconductor device manufacturing sheet of the present embodiment is provided with the pressure-sensitive adhesive layer in direct contact with the base material and the intermediate layer in direct contact with the pressure-sensitive adhesive layer, and is in the form of a film. It is preferable that the adhesive is provided in direct contact with the intermediate layer.

For example, in the sheet for manufacturing a semiconductor device of the present embodiment, the planar shapes of the intermediate layer and the film-like adhesive may be shapes other than the circular shape, and the planar shapes of the intermediate layer and the film-like adhesive are the same as each other. It may be, or it may be different. Further, the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive are both the areas of the layers on the substrate side (for example, the first surface of the pressure-sensitive adhesive layer). It is preferably smaller than, and may be the same as or different from each other. The positions of the outer periphery of the intermediate layer and the film-like adhesive may or may not be the same in these radial directions.
Next, each layer constituting the semiconductor device manufacturing sheet of the present embodiment will be described in more detail.

○ Base material The base material is in the form of a sheet or a film.
The constituent material of the base material is preferably various resins, and specifically, for example, polyethylene (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE, etc.)). , Polypropylene (PP), Polybutene, Polybutadiene, Polymethylpentene, styrene / ethylenebutylene / styrene block copolymer, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyurethane, Polyurethane acrylate, polyimide (PI), ionomer resin, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, ethylene / (meth) acrylic acid copolymer and ethylene / (meth) Examples thereof include ethylene copolymers other than acrylic ester copolymers, polystyrenes, polycarbonates, fluororesins, water additives, modified products, crosslinked products or copolymers of any of these resins.

In the present specification, "(meth) acrylic acid" is a concept that includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth) acrylic acid, for example, "(meth) acrylate" is a concept that includes both "acrylate" and "methacrylate", and is a "(meth) acryloyl group". Is a concept that includes both an "acryloyl group" and a "methacryloyl group".

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) or may be composed of two or more layers. When the base material is composed of a plurality of layers, 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.
In the present specification, not only in the case of a base material, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers are different". It may mean that only a part of the layers may be the same, and further, "a plurality of layers are different from each other" means that "at least one of the constituent materials and the thickness of each layer is different from each other". means.

The thickness of the base material can be appropriately selected depending on the intended purpose, but is preferably 50 to 300 μm, more preferably 60 to 150 μm. When the thickness of the base material is at least the above lower limit value, the structure of the base material is more stabilized. When the thickness of the base material is not more than the upper limit value, the film-like adhesive can be cut more easily at the time of blade dicing and at the time of the expansion of the semiconductor device manufacturing sheet (film-like adhesive).
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 is roughened by sandblasting, solvent treatment, embossing, etc. in order to improve adhesion to other layers such as the pressure-sensitive adhesive layer provided on it; corona discharge treatment, electron beam irradiation treatment, etc. , Plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments; etc. may be applied to the surface.
The surface of the base material may be primed.
The base material has an antistatic coating layer; a layer that prevents the base material from adhering to other sheets and the base material from adhering to the adsorption table when the die bonding sheets are superposed and stored; You may be doing it.

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 optical properties of the base material are not particularly limited as long as the effects of the present invention are not impaired. The base material may be, for example, one that transmits laser light or energy rays.

The base material can be produced by a known method. For example, a base material containing a resin (using a resin as a constituent material) can be produced by molding the resin or a resin composition containing the resin.

○ Adhesive layer The adhesive layer is in the form of a sheet or a film, and contains an adhesive as a main component. The weight average molecular weight of the pressure-sensitive adhesive, which is the main component, is 20000 or more. The component having the largest content (parts by mass) in the pressure-sensitive adhesive layer is the pressure-sensitive adhesive as the main component.

The pressure-sensitive adhesive layer may or may not contain the component (γ2) in addition to the pressure-sensitive adhesive. The pressure-sensitive adhesive layer may or may not contain a solid component (γ1) at a temperature of 23 ° C. as the main component (pressure-sensitive adhesive). When the component (γ1) is the main component (adhesive), the weight average molecular weight of the component (γ1) is 20000 or more, and the content (parts by mass) in the pressure-sensitive adhesive layer is the largest. Is the component (γ1).

The pressure-sensitive adhesive layer preferably contains the component (γ1), may contain both the component (γ1) and the component (γ2), or contains the component (γ1) and contains the component (γ2). May not be contained.

The pressure-sensitive adhesive layer can be formed by using a pressure-sensitive adhesive composition containing the pressure-sensitive adhesive and, if necessary, a component (γ2). 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. In the present specification, "room temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

In the pressure-sensitive adhesive layer, the ratio of the total content of one or more of the components described below to the total mass of the pressure-sensitive adhesive layer does not exceed 100% by mass.
Similarly, in the pressure-sensitive adhesive composition, the ratio of the total content of one or more of the components described below to the total mass of the pressure-sensitive adhesive composition does not exceed 100% by mass.

The pressure-sensitive adhesive composition may be applied 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, and a screen coater. , A method using various coaters such as a Meyer bar coater and a knife coater.

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

Examples of the pressure-sensitive adhesive include adhesive resins such as acrylic resin, urethane resin, rubber-based resin, silicone resin, epoxy-based resin, polyvinyl ether, polycarbonate, and ester-based resin, and acrylic resin is preferable.

When the pressure-sensitive adhesive layer contains a component (γ1) as a main component (adhesive), the component (γ1) may be an acrylic resin having a structural unit derived from a (meth) acrylic acid ester. 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 either curable or non-curable, and may be, for example, either energy ray-curable or non-energy ray-curable. The physical properties of the curable pressure-sensitive adhesive layer before and after curing can be easily adjusted.

As used herein, the term "energy ray" means an electromagnetic wave or a charged particle beam having an energy quantum. Examples of energy rays include ultraviolet rays, radiation, electron beams and the like. 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.
Further, in the present specification, "energy ray curable" means a property of being cured by irradiating with energy rays, and "non-energy ray curable" is a property of not being cured by irradiating with energy rays. Means.

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 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 optical properties of the pressure-sensitive adhesive layer are not particularly limited as long as the effects of the present invention are not impaired. For example, the pressure-sensitive adhesive layer may be one that allows energy rays to pass through.
Next, the pressure-sensitive adhesive composition will be described.

<< Adhesive composition >>
When the pressure-sensitive adhesive layer is energy ray-curable, the pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive, that is, the energy ray-curable pressure-sensitive adhesive composition, for example, is a non-energy ray-curable pressure-sensitive adhesive. Adhesive composition (I-1) containing a resin (I-1a) (hereinafter, may be abbreviated as "adhesive resin (I-1a)") and an energy ray-curable compound; non-energy An energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the linear curable adhesive resin (I-1a) (hereinafter referred to as "adhesive resin (I-2a)"). A pressure-sensitive adhesive composition (I-2) containing (may be abbreviated); a pressure-sensitive adhesive composition (I-3) containing the pressure-sensitive resin (I-2a) and an energy ray-curable compound, etc. Can be mentioned.

The pressure-sensitive adhesive composition (I-1), (I-2) and (I-3) may or may not further contain the component (γ2), respectively. The pressure-sensitive adhesive composition (I-1), (I-2) and (I-3) may or may contain the component (γ1) as the main component (adhesive), respectively. You don't have to.
The pressure-sensitive adhesive compositions (I-1), (I-2) and (I-3) preferably contain the component (γ1), respectively, and both the component (γ1) and the component (γ2) are contained. It may be contained, or it may contain the component (γ1) and may not contain the component (γ2).

<Adhesive composition (I-1)>
As described above, the pressure-sensitive adhesive composition (I-1) contains a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) and an energy ray-curable compound. The component (γ2) may or may not be contained.
In the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive resin (I-1a) or the energy ray-curable compound may be a component (γ1), or the pressure-sensitive adhesive resin (I-1a) or energy. The linear curable compound may be the main component.

[Adhesive resin (I-1a)]
The adhesive resin (I-1a) is preferably an acrylic resin.
Examples of the acrylic resin include an acrylic polymer having a structural unit derived from at least a (meth) acrylic acid alkyl ester.
The structural unit of 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 pressure-sensitive adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when two or more types are used. The combination and ratio can be selected arbitrarily.

In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the pressure-sensitive adhesive resin (I-1a) to the total mass of the pressure-sensitive adhesive composition (I-1) is preferably 5 to 99% by mass. It is more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
Among the energy ray-curable compounds, examples of the monomer include trimethylpropantri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4. Multivalent (meth) acrylates such as -butylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( Meta) Acrylate and the like can be mentioned.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer obtained by polymerizing the monomers exemplified above.
The energy ray-curable compound has a relatively large molecular weight, and urethane (meth) acrylate and urethane (meth) acrylate oligomer are preferable in that the storage elastic modulus of the pressure-sensitive adhesive layer is unlikely to be lowered.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be only one kind, two or more kinds, and when two or more kinds, a combination thereof and The ratio can be selected arbitrarily.

In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the energy ray-curable compound to the total mass of the pressure-sensitive adhesive composition (I-1) is preferably 1 to 95% by mass, and 5 It is more preferably to 90% by mass, and particularly preferably 10 to 85% by mass.
When an energy ray-curable compound that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer is used, its content in the pressure-sensitive adhesive composition (I-1). Preferably satisfies the numerical range specified separately as described later.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), the pressure-sensitive adhesive composition (I) -1) preferably further contains a cross-linking agent.

The cross-linking agent reacts with the functional group, for example, to cross-link the adhesive resins (I-1a) with each other.
Examples of the cross-linking agent include isocyanate-based cross-linking agents such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates (cross-linking agents having an isocyanate group); and epoxy-based cross-linking agents such as ethylene glycol glycidyl ether (cross-linking agents). Cross-linking agent having a glycidyl group); Isocyanate-based cross-linking agent such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (cross-linking agent having an aziridinyl group); Metal chelate-based cross-linking agent such as aluminum chelate (metal) A cross-linking agent having a chelate structure); an isocyanurate-based cross-linking agent (a cross-linking agent having an isocyanurate skeleton) and the like can be mentioned.
The cross-linking agent is preferably an isocyanate-based cross-linking agent from the viewpoints of improving the cohesive force of the pressure-sensitive adhesive to improve the adhesive force of the pressure-sensitive adhesive layer and being easily available.

The cross-linking agent contained in the pressure-sensitive adhesive composition (I-1) 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 arbitrary. You can choose.

When a cross-linking agent is used, the content of the cross-linking agent in the pressure-sensitive adhesive composition (I-1) is 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-1a). It is preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
When a cross-linking agent that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer is used, the content in the pressure-sensitive adhesive composition (I-1) will be described later. It is preferable to satisfy the numerical range specified separately.

[Photopolymerization initiator]
The pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator 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 and 2-hydroxy. Acetphenone compounds such as -2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenylketone; azo Azo compounds such as bisisobutyronitrile; titanocene 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; 2-chloroanthraquinone and the like can be mentioned.
Further, as the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can also be used.

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are It can be selected arbitrarily.

When a photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1) is 0.01 to 20 mass by mass with respect to 100 parts by mass of the content of the energy ray-curable compound. The amount is preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
When a photopolymerization initiator that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer is used, the content in the pressure-sensitive adhesive composition (I-1) is , It is preferable to satisfy the numerical range specified separately as described later.

[Other additives]
The pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust preventives, colorants (pigments, dyes), sensitizers, and tackifiers. , Known additives such as reaction retarders and cross-linking accelerators (catalysts).

The reaction retarder means that, for example, an unintended cross-linking reaction proceeds in the pressure-sensitive adhesive composition (I-1) being stored by the action of a catalyst mixed in the pressure-sensitive adhesive composition (I-1). It is a component for suppressing. Examples of the reaction retarder include those that form a chelate complex by chelating to a catalyst, and more specifically, those having two or more carbonyl groups (-C (= O)-) in one molecule. Can be mentioned.

The other additives contained in the pressure-sensitive adhesive composition (I-1) may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof are It can be selected arbitrarily.

The content of the other additives in the pressure-sensitive adhesive composition (I-1) is not particularly limited, and may be appropriately selected depending on the type thereof.
When other additives that are liquid at a temperature of 23 ° C. and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer are used, the content in the pressure-sensitive adhesive composition (I-1) is , It is preferable to satisfy the numerical range specified separately as described later.

[solvent]
The pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the pressure-sensitive adhesive composition (I-1) contains a solvent, the suitability for coating on the surface to be coated is improved.

The solvent is preferably an organic solvent.
Examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; toluene, xylene and the like. Aromatic hydrocarbons; alcohols such as 1-propanol and 2-propanol can be mentioned.

[Component (γ2)]
The component (γ2) in the pressure-sensitive adhesive composition (I-1) is liquid at a temperature of 23 ° C. Further, the component (γ2) does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer (that is, does not react with the main component). A component having a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer and that is liquid at a temperature of 23 ° C. reacts with the main component in the pressure-sensitive adhesive layer to move from the pressure-sensitive adhesive layer to the intermediate layer. It does not migrate, and as a result, it does not migrate to film-like adhesives. In the present embodiment, it is not such a component having the functional group and liquid at a temperature of 23 ° C., and originally has the functional group which cannot suppress the transition from the pressure-sensitive adhesive layer to the film-like adhesive. For the component (γ2) that is liquid at a temperature of 23 ° C., the transition from the pressure-sensitive adhesive layer to the film-like adhesive is suppressed.
For example, when the main component has a hydroxyl group or an amino group, an isocyanate group can be mentioned as a functional group that reacts with the main component.

The component (γ2) is not particularly limited as long as such conditions are satisfied, and can be arbitrarily selected depending on the intended purpose. A component of the pressure-sensitive adhesive composition (I-1) that does not correspond to any of the pressure-sensitive resin (I-1a) and the solvent, that is, the energy ray-curable compound, a cross-linking agent, and a photopolymerization initiator. And other additives that are liquid at a temperature of 23 ° C. and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer are components (γ2). The solvent is usually not contained in the pressure-sensitive adhesive layer.
Preferred components (γ2) include, for example, an antistatic agent, a tackifier resin, and the like.

(Liquid antistatic agent at a temperature of 23 ° C)
The antistatic agent liquid at a temperature of 23 ° C. may be a known one such as a conductive compound, and is not particularly limited.
Examples of the antistatic agent include various ionic liquids.
Examples of the ionic liquid include known ones such as pyridinium salt, pyridinium salt, piperidinium salt, pyrrolidinium salt, imidazolium salt, morpholinium salt, sulfonium salt, phosphonium salt, and ammonium salt.

The component (γ2) contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are It can be selected arbitrarily.

When the component (γ2) is used, the content of the pressure-sensitive adhesive composition (I-1) and the component (γ2) of the pressure-sensitive adhesive layer can be appropriately adjusted according to the type of the component (γ2).
In the pressure-sensitive adhesive composition (I-1) and the pressure-sensitive adhesive layer, the content of the component (γ2) is 0.1 to 40 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-1a). It is preferable to have. When the content is not more than the upper limit value, the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed. When the content is at least the lower limit value, the effect obtained by using the component (γ2) becomes higher.

In particular, when the component (γ2) is an antistatic agent, the content of the component (γ2) (antistatic agent) in the pressure-sensitive adhesive composition (I-1) and the pressure-sensitive adhesive layer is determined by the pressure-sensitive adhesive resin (I-1a). ) Is preferably 1 to 7 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass. When the content is not more than the upper limit value, the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed, and the excessive use of the component (γ2) is suppressed. When the content is at least the lower limit value, the effect obtained by using the component (γ2) becomes higher.

<Adhesive composition (I-2)>
As described above, the pressure-sensitive adhesive composition (I-2) is an energy ray-curable pressure-sensitive adhesive resin in which an unsaturated group is introduced into the side chain of the non-energy ray-curable pressure-sensitive adhesive resin (I-1a). (I-2a) is contained.
In addition to these, the pressure-sensitive adhesive composition (I-2) may or may not further contain the above-mentioned component (γ2).
In the pressure-sensitive adhesive composition (I-2), the pressure-sensitive adhesive resin (I-2a) may be a component (γ1), or the pressure-sensitive adhesive resin (I-2a) may be a main component. ..

[Adhesive resin (I-2a)]
The adhesive resin (I-2a) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group.

The unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by further reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray-polymerizable unsaturated group. It is a compound having a group.
Examples of the energy ray-polymerizable unsaturated group include (meth) acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, and (meth) acryloyl group is preferable.
Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxy group or an epoxy group. And so on.

Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, and glycidyl (meth) acrylate.

The pressure-sensitive adhesive resin (I-2a) contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when two or more types are used. The combination and ratio can be selected arbitrarily.

In the pressure-sensitive adhesive composition (I-2), the ratio of the content of the pressure-sensitive adhesive resin (I-2a) to the total mass of the pressure-sensitive adhesive composition (I-2) is preferably 5 to 99% by mass. It is more preferably 10 to 95% by mass, and particularly preferably 10 to 90% by mass.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer similar to that in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), for example, the pressure-sensitive adhesive composition (I) -2) may further contain a cross-linking agent.

Examples of the cross-linking agent in the pressure-sensitive adhesive composition (I-2) include the same cross-linking agents as those in the pressure-sensitive adhesive composition (I-1).
The cross-linking agent contained in the pressure-sensitive adhesive composition (I-2) 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 arbitrary. You can choose.

When a cross-linking agent is used, the content of the cross-linking agent in the pressure-sensitive adhesive composition (I-2) is 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). It is preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
When a cross-linking agent that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer is used, the content in the pressure-sensitive adhesive composition (I-2) will be described later. It is preferable to satisfy the numerical range specified separately.

[Photopolymerization initiator]
The pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-2) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiators in the pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are It can be selected arbitrarily.

When a photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) is 0.01 to 100 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). It is preferably 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
When a photopolymerization initiator that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer is used, the content in the pressure-sensitive adhesive composition (I-2) is , It is preferable to satisfy the numerical range specified separately as described later.

[Other additives and solvents]
The pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Further, the pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).
Examples of the other additives and solvents in the pressure-sensitive adhesive composition (I-2) include the same as the other additives and solvents in the pressure-sensitive adhesive composition (I-1), respectively.
The other additives and solvents contained in the pressure-sensitive adhesive composition (I-2) may be only one type, two or more types, or two or more types, if they are two or more types. The combination and ratio of are arbitrarily selectable.
The contents of the other additives and the solvent in the pressure-sensitive adhesive composition (I-2) are not particularly limited, and may be appropriately selected depending on the type thereof.
When other additives that are liquid at a temperature of 23 ° C. and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer are used, the content in the pressure-sensitive adhesive composition (I-2) is , It is preferable to satisfy the numerical range specified separately as described later.

[Component (γ2)]
The component (γ2) in the pressure-sensitive adhesive composition (I-2) is liquid at a temperature of 23 ° C. Further, the component (γ2) does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer (that is, does not react with the main component). Similar to the case of the pressure-sensitive adhesive composition (I-1), when the pressure-sensitive adhesive composition (I-2) is used, such a component (γ2) is subjected to a film-like adhesive from the pressure-sensitive adhesive layer. The transition to is suppressed.

The component (γ2) is not particularly limited as long as such conditions are satisfied, and can be arbitrarily selected depending on the intended purpose. The components of the pressure-sensitive adhesive composition (I-2) that do not fall under any of the pressure-sensitive resin (I-2a) and the solvent, that is, the cross-linking agent, photopolymerization initiator and other additives. Among them, the component (γ2) is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer.
The preferred component (γ2) in the pressure-sensitive adhesive composition (I-2) is, for example, the same as the preferred component (γ2) in the pressure-sensitive adhesive composition (I-1) (antistatic agent, tackifier resin (tack fire)). Etc.).

The component (γ2) contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are It can be selected arbitrarily.

When the component (γ2) is used, the content of the component (γ2) in the pressure-sensitive adhesive composition (I-2) can be appropriately adjusted according to the type of the component (γ2).
In the pressure-sensitive adhesive composition (I-2) and the pressure-sensitive adhesive layer, the content of the component (γ2) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). It is preferable to have. When the content is not more than the upper limit value, the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed. When the content is at least the lower limit value, the effect obtained by using the component (γ2) becomes higher.

In particular, when the component (γ2) is an antistatic agent, the content of the component (γ2) (antistatic agent) in the pressure-sensitive adhesive composition (I-2) and the pressure-sensitive adhesive layer is determined by the pressure-sensitive adhesive resin (I-2a). ) Is preferably 1 to 7 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass. When the content is not more than the upper limit value, the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed, and the excessive use of the component (γ2) is suppressed. When the content is at least the lower limit value, the effect obtained by using the component (γ2) becomes higher.

<Adhesive composition (I-3)>
As described above, the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable compound.

In addition to these, the pressure-sensitive adhesive composition (I-3) may or may not further contain the above-mentioned component (γ2).
In the pressure-sensitive adhesive composition (I-3), the pressure-sensitive adhesive resin (I-2a) or the energy ray-curable compound may be a component (γ1), or the pressure-sensitive adhesive resin (I-2a) or energy. The linear curable compound may be the main component.

[Adhesive resin (I-2a)]
Examples of the adhesive resin (I-2a) in the pressure-sensitive adhesive composition (I-3) include the same adhesive resin (I-2a) as in the pressure-sensitive adhesive composition (I-2).
The pressure-sensitive adhesive resin (I-2a) contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when two or more types are used. The combination and ratio can be selected arbitrarily.

In the pressure-sensitive adhesive composition (I-3), the ratio of the content of the pressure-sensitive adhesive resin (I-2a) to the total mass of the pressure-sensitive adhesive composition (I-3) is preferably 5 to 99% by mass. It is more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays, and the pressure-sensitive adhesive composition. Examples thereof include the same energy ray-curable compounds contained in the substance (I-1).
The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one kind, two or more kinds, and when two or more kinds, a combination thereof and The ratio can be selected arbitrarily.

In the pressure-sensitive adhesive composition (I-3) and the pressure-sensitive adhesive layer, the content of the energy ray-curable compound is 0.01 to 300 with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). It is preferably parts by mass, more preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass.
When an energy ray-curable compound that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer is used, its content in the pressure-sensitive adhesive composition (I-3). Preferably satisfies the numerical range specified separately as described later.

[Photopolymerization initiator]
The pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiators in the pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are It can be selected arbitrarily.

When a photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) is 100 parts by mass of the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray-curable compound. On the other hand, it is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
When a photopolymerization initiator that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer is used, the content in the pressure-sensitive adhesive composition (I-3) is , It is preferable to satisfy the numerical range specified separately as described later.

[Other additives and solvents]
The pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Further, the pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).
Examples of the other additives and solvents in the pressure-sensitive adhesive composition (I-3) include the same as the other additives and solvents in the pressure-sensitive adhesive composition (I-1), respectively.
The other additives and solvents contained in the pressure-sensitive adhesive composition (I-3) may be only one type, two or more types, or two or more types, if they are two or more types. The combination and ratio of are arbitrarily selectable.
The contents of the other additives and the solvent in the pressure-sensitive adhesive composition (I-3) are not particularly limited, and may be appropriately selected depending on the type thereof.
When other additives that are liquid at a temperature of 23 ° C. and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer are used, the content in the pressure-sensitive adhesive composition (I-3) is , It is preferable to satisfy the numerical range specified separately as described later.

[Component (γ2)]
The component (γ2) in the pressure-sensitive adhesive composition (I-3) is liquid at a temperature of 23 ° C. Further, the component (γ2) does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer (that is, does not react with the main component). Similar to the case of the pressure-sensitive adhesive composition (I-1), when the pressure-sensitive adhesive composition (I-3) is used, such a component (γ2) is subjected to a film-like adhesive from the pressure-sensitive adhesive layer. The transition to is suppressed.

The component (γ2) is not particularly limited as long as such conditions are satisfied, and can be arbitrarily selected depending on the intended purpose. Ingredients of the pressure-sensitive adhesive composition (I-3) that do not fall under any of the pressure-sensitive resin (I-2a) and the solvent, that is, the energy ray-curable compound, photopolymerization initiator and other components. Among the additives, those that are liquid at a temperature of 23 ° C. and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer are components (γ2).
The preferred component (γ2) in the pressure-sensitive adhesive composition (I-3) is, for example, the same as the preferred component (γ2) in the pressure-sensitive adhesive composition (I-1) (antistatic agent, tackifier resin (tack fire)). Etc.).

The component (γ2) contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are It can be selected arbitrarily.

When the component (γ2) is used, the content of the component (γ2) in the pressure-sensitive adhesive composition (I-3) can be appropriately adjusted according to the type of the component (γ2).
In the pressure-sensitive adhesive composition (I-3) and the pressure-sensitive adhesive layer, the content of the component (γ2) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). It is preferable to have. When the content is not more than the upper limit value, the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed. When the content is at least the lower limit value, the effect obtained by using the component (γ2) becomes higher.

In particular, when the component (γ2) is an antistatic agent, the content of the component (γ2) (antistatic agent) in the pressure-sensitive adhesive composition (I-3) and the pressure-sensitive adhesive layer is determined by the pressure-sensitive adhesive resin (I-2a). ) Is preferably 1 to 7 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass. When the content is not more than the upper limit value, the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed, and the excessive use of the component (γ2) is suppressed. When the content is at least the lower limit value, the effect obtained by using the component (γ2) becomes higher.

<Adhesive compositions other than adhesive compositions (I-1) to (I-3)>
Up to this point, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), and the pressure-sensitive adhesive composition (I-3) have been mainly described. General pressure-sensitive adhesive compositions other than these three types of pressure-sensitive adhesive compositions (referred to in the present specification as "pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3)"). However, it can be used in the same way.

Examples of the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions in addition to the energy-ray-curable pressure-sensitive adhesive composition.
Examples of the non-energy ray-curable pressure-sensitive adhesive composition include non-energy ray-curable pressure-sensitive adhesives such as acrylic resin, urethane resin, rubber-based resin, silicone resin, epoxy-based resin, polyvinyl ether, polycarbonate, and ester-based resin. Examples thereof include a pressure-sensitive adhesive composition (I-4) containing a sex resin (I-1a), and those containing an acrylic resin are preferable.

The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contain one or more cross-linking agents, and the content thereof is the above-mentioned pressure-sensitive adhesive composition. The same can be applied to the case of (I-1) and the like.

<Adhesive composition (I-4)>
Preferred examples of the pressure-sensitive adhesive composition (I-4) include those containing the pressure-sensitive adhesive resin (I-1a) and a cross-linking agent, and in addition to these, the component (γ2). May or may not be contained.
In the pressure-sensitive adhesive composition (I-4), the pressure-sensitive adhesive resin (I-1a) may be a component (γ1), or the pressure-sensitive adhesive resin (I-1a) may be a main component. ..

[Adhesive resin (I-1a)]
Examples of the adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-4) include the same adhesive resin (I-1a) as in the pressure-sensitive adhesive composition (I-1).
The pressure-sensitive adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-4) may be only one type, may be two or more types, and when two or more types are used. The combination and ratio can be selected arbitrarily.

In the pressure-sensitive adhesive composition (I-4), the ratio of the content of the pressure-sensitive adhesive resin (I-1a) to the total mass of the pressure-sensitive adhesive composition (I-4) is preferably 5 to 99% by mass. It is more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), the pressure-sensitive adhesive composition (I) -4) preferably further contains a cross-linking agent.

Examples of the cross-linking agent in the pressure-sensitive adhesive composition (I-4) include the same cross-linking agents as those in the pressure-sensitive adhesive composition (I-1).
The cross-linking agent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

In the pressure-sensitive adhesive composition (I-4), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-1a). It is more preferably 0.1 to 25 parts by mass, and particularly preferably 0.1 to 10 parts by mass.
When a cross-linking agent that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer is used, the content in the pressure-sensitive adhesive composition (I-4) will be described later. It is preferable to satisfy the numerical range specified separately.

[Other additives and solvents]
The pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Further, the pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).
Examples of the other additives and solvents in the pressure-sensitive adhesive composition (I-4) include the same as the other additives and solvents in the pressure-sensitive adhesive composition (I-1), respectively.
The other additives and solvents contained in the pressure-sensitive adhesive composition (I-4) may be only one type, two or more types, or two or more types, if they are two or more types. The combination and ratio of are arbitrarily selectable.
The contents of the other additives and the solvent in the pressure-sensitive adhesive composition (I-4) are not particularly limited, and may be appropriately selected depending on the type thereof.
When other additives that are liquid at a temperature of 23 ° C. and do not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer are used, the content in the pressure-sensitive adhesive composition (I-4) is , It is preferable to satisfy the numerical range specified separately as described later.

[Component (γ2)]
The component (γ2) in the pressure-sensitive adhesive composition (I-4) is liquid at a temperature of 23 ° C. Further, the component (γ2) does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer (that is, does not react with the main component). Similar to the case of the pressure-sensitive adhesive composition (I-1), when the pressure-sensitive adhesive composition (I-4) is used, such a component (γ2) is subjected to a film-like adhesive from the pressure-sensitive adhesive layer. The transition to is suppressed.

The component (γ2) is not particularly limited as long as such conditions are satisfied, and can be arbitrarily selected depending on the intended purpose. Among the components of the pressure-sensitive adhesive composition (I-4) that do not correspond to any of the pressure-sensitive resin (I-1a) and the solvent, that is, the cross-linking agent and other additives, the temperature is 23 ° C. The component (γ2) is liquid and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer.
The preferred component (γ2) in the pressure-sensitive adhesive composition (I-4) is, for example, the same as the preferred component (γ2) in the pressure-sensitive adhesive composition (I-1) (antistatic agent, tackifier resin (tack fire)). Etc.).

The component (γ2) contained in the pressure-sensitive adhesive composition (I-4) may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof are It can be selected arbitrarily.

When the component (γ2) is used, the content of the component (γ2) in the pressure-sensitive adhesive composition (I-4) can be appropriately adjusted according to the type of the component (γ2).
In the pressure-sensitive adhesive composition (I-4) and the pressure-sensitive adhesive layer, the content of the component (γ2) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-1a). It is preferable to have. When the content is not more than the upper limit value, the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed. When the content is at least the lower limit value, the effect obtained by using the component (γ2) becomes higher.

In particular, when the component (γ2) is an antistatic agent, the content of the component (γ2) (antistatic agent) in the pressure-sensitive adhesive composition (I-4) and the pressure-sensitive adhesive layer is determined by the pressure-sensitive adhesive resin (I-1a). ) Is preferably 1 to 7 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass. When the content is not more than the upper limit value, the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed, and the excessive use of the component (γ2) is suppressed. When the content is at least the lower limit value, the effect obtained by using the component (γ2) becomes higher.

When the component (γ2) is used, the content of the component (γ2) in the pressure-sensitive adhesive layer regardless of whether the pressure-sensitive adhesive composition is any of the pressure-sensitive adhesive compositions (I-1) to (I-4). Is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive.
In particular, when the component (γ2) is an antistatic agent, the content of the component (γ2) (antistatic agent) in the pressure-sensitive adhesive layer is 1 to 7 mass by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive. It is preferably parts, and more preferably 1 to 5 parts by mass.

<< Manufacturing method of adhesive composition >>
The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) and the pressure-sensitive adhesive compositions (I-1) to (I-3) such as the pressure-sensitive adhesive composition (I-4) , The pressure-sensitive adhesive and, if necessary, components other than the pressure-sensitive adhesive, and the like, are obtained by blending each component for forming a pressure-sensitive 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, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or diluting any of the compounding components other than the solvent 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.

-Composition for forming an intermediate layer and an intermediate layer The intermediate layer is in the form of a sheet or a film, and contains the non-silicon resin (β1) as a main component.
The intermediate layer may be one containing only a non-silicon resin (β1) (consisting of a non-silicon resin (β1)), or may contain a non-silicon resin (β1) and other components. It may be a thing.

The intermediate layer can be formed, for example, by using an intermediate layer forming composition containing the non-silicon resin (β1). For example, the intermediate layer can be formed at a target portion by applying the intermediate layer forming composition to the surface to be formed of the intermediate layer and drying it if necessary.

In the intermediate layer, the ratio of the total content of one or more of the components described below to the total mass of the intermediate layer does not exceed 100% by mass.
Similarly, in the intermediate layer forming composition, the ratio of the total content of one or more of the components described below to the total mass of the intermediate layer forming composition is 100 mass. Does not exceed%.

The coating of the intermediate layer forming composition can be carried out in the same manner as in the case of the above-mentioned coating of the pressure-sensitive adhesive composition.

The drying conditions of the composition for forming the intermediate layer are not particularly limited. When the composition for forming an intermediate layer contains a solvent described later, it is preferably dried by heating. In this case, for example, it is preferably dried at 60 to 130 ° C. for 1 to 6 minutes.

The weight average molecular weight of the non-silicon resin (β1) is 20000 to 100,000.
The weight average molecular weight of the non-silicon resin (β1) is, for example, 20,000 to 80,000, 20,000 to 60,000, and 20,000 to 40,000 in that the division suitability of the above-mentioned semiconductor wafer of the semiconductor device manufacturing sheet is further improved. It may be any of.

The component having the largest content (parts by mass) in the intermediate layer is the non-silicon resin (β1).
The content of the non-silicon resin (β1) in the intermediate layer with respect to the total mass of the intermediate layer is that the intermediate layer has a higher effect due to the inclusion of the non-silicon resin (β1). (In other words, in the composition for forming an intermediate layer, the ratio of the content of the non-silicon resin (β1) to the total content of all the components other than the solvent) is 75% by mass or more. It is more preferably 85% by mass or more, and for example, it may be any of 95% by mass or more, 97% by mass or more, and 99% by mass or more.
On the other hand, the ratio is 100% by mass or less.

The non-silicon resin (β1) is not particularly limited as long as it is a resin component having no silicon atom as a constituent atom and having a weight average molecular weight of 20,000 to 100,000.
The non-silicon resin (β1) may be, for example, either a polar resin having a polar group or a non-polar resin having no polar group.
For example, the non-silicon resin (β1) is preferably a polar resin in that it has high solubility in the intermediate layer forming composition and higher coating suitability of the intermediate layer forming composition. ..

The non-silicon resin (β1) may be, for example, a copolymer of one kind of monomer (in other words, having only one kind of constituent unit), or a weight of two or more kinds of monomers. It may be a copolymer that is a coalescence (in other words, has two or more constituent units).

Examples of the polar group include a carbonyloxy group (-C (= O) -O-), an oxycarbonyl group (-OC (= O)-) and the like.

The polar resin may have only a structural unit having a polar group, or may have both a structural unit having a polar group and a structural unit having no polar group.

Examples of the structural unit having a polar group include a structural unit derived from vinyl acetate.
Examples of the structural unit having no polar group include a structural unit derived from ethylene.

In the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all the structural units is preferably 45% by mass or less, and more preferably 30% by mass or less. The lower the ratio, the more effective it is to suppress the transfer of the component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer and the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive. It gets higher.
On the other hand, the ratio is preferably 5% by mass or more, more preferably 7.5% by mass or more, and further preferably 10% by mass or more. The higher the ratio, the more prominently the polar resin has the property of having a polar group.

In the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all the structural units is set by arbitrarily combining any of the above-mentioned upper limit values and any of the lower limit values. It can be adjusted appropriately within the range. For example, in one embodiment, the proportions are 5 to 45% by weight, 7.5 to 45% by weight, 10 to 45% by weight, 5 to 30% by weight, 7.5 to 30% by weight, and 10 to 30% by weight. It may be any of%.

Examples of the polar resin include ethylene-vinyl acetate copolymer and the like.
Among them, as the preferred polar resin, for example, in an ethylene-vinyl acetate copolymer, the ratio of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units (in the present specification, "acetic acid". The content of the structural unit derived from vinyl is sometimes referred to as "content of the structural unit derived from vinyl"), which is in the numerical range of any one of the above-mentioned "ratio of the mass of the structural unit having a polar group", and is 30% by mass or less. Is particularly preferable. That is, as the particularly preferable polar resin, for example, in an ethylene-vinyl acetate copolymer, the ratio of the mass of the structural units derived from vinyl acetate to the total mass of all the structural units is 30% by mass or less. Can be mentioned. In other words, as the particularly preferable polar resin, for example, in an ethylene-vinyl acetate copolymer, the ratio of the mass of the constituent units derived from ethylene to the total mass of all the constituent units is 70% by mass or more. Can be mentioned.

Examples of the non-polar resin include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), metallocene-catalyzed linear low-density polyethylene (metallocene LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene ( Examples thereof include polyethylene (PE) such as HDPE) and polyolefins such as polypropylene (PP).

The composition for forming an intermediate layer and the non-silicon resin (β1) contained in the intermediate layer may be only one type, may be two or more types, and when two or more types, they may be used. The combination and ratio can be selected arbitrarily.
For example, the composition for forming an intermediate layer and the intermediate layer contain one or more types of non-silicon resin (β1) which is a polar resin, and also contain a non-silicon resin (β1) which is a non-polar resin. It does not have to be, and it does not have to contain one or more kinds of non-silicon resin (β1) which is a non-polar resin and does not contain non-silicon resin (β1) which is a polar resin. Alternatively, one or more of the non-silicon-based resin (β1) which is a polar resin and the non-silicon-based resin (β1) which is a non-polar resin may be contained.
The composition for forming the intermediate layer and the intermediate layer preferably contain at least a non-silicon resin (β1) which is a polar resin.

The composition for forming an intermediate layer and the intermediate layer preferably contain one or more selected from the group consisting of ethylene vinyl acetate copolymer and polyolefin as the non-silicon resin (β1). .. In the sheet for manufacturing a semiconductor device provided with such an intermediate layer, when the film-like adhesive contains the component (α2), the component (α2) in the film-like adhesive is applied to the pressure-sensitive adhesive layer. The migration is further suppressed, and when the pressure-sensitive adhesive layer contains the component (γ2), the transfer of the component (γ2) in the pressure-sensitive adhesive layer to the film-like adhesive is further suppressed.

The ratio of the content of the non-silicon resin (β1), which is a polar resin, to the total content of the non-silicon resin (β1) in the composition for forming the intermediate layer and the intermediate layer is 80% by mass or more. It is preferably 90% by mass or more, and for example, it may be any one of 95% by mass or more, 97% by mass or more, and 99% by mass or more. When the ratio is at least the lower limit value, the effect of using the polar resin can be obtained more remarkably.
On the other hand, the ratio is 100% by mass or less.

That is, the ratio of the content of the non-silicon resin (β1), which is a non-polar resin, to the total content of the non-silicon resin (β1) in the composition for forming the intermediate layer and the intermediate layer is 20% by mass. It is preferably less than or equal to, more preferably 10% by mass or less, and may be, for example, 5% by mass or less, 3% by mass or less, and 1% by mass or less.
On the other hand, the ratio is 0% by mass or more.

The composition for forming an intermediate layer preferably contains a solvent in addition to the non-silicon resin (β1) from the viewpoint of good handleability, and the non-silicon resin (β1) and the solvent And, a component that does not correspond to any of the above (in this specification, it may be referred to as an "additive") may be contained.
The intermediate layer may contain only the non-silicon resin (β1), or may contain both the non-silicon resin (β1) and the additive.

The additive may be either a resin component (in the present specification, it may be referred to as "another resin component") or a non-resin component.

Examples of the other resin component include a non-silicon resin having a weight average molecular weight (Mw) of more than 100,000 (Mw> 100,000) and a silicon resin.

The non-silicon resin having a weight average molecular weight of more than 100,000 is not particularly limited as long as these conditions are satisfied.

The intermediate layer containing the silicon-based resin makes it easier to pick up a semiconductor chip with a film-like adhesive, as will be described later.

The silicon-based resin is not particularly limited as long as it is a resin component having a silicon atom as a constituent atom. For example, the weight average molecular weight of the silicon-based resin is not particularly limited.

Preferred silicon-based resins include, for example, a resin component having a mold-releasing action on a pressure-sensitive adhesive component, and both a siloxane-based resin (a resin component having a siloxane bond (-Si-O-Si-) and a siloxane-based compound). ) Is more preferable.

Examples of the siloxane-based resin include polydialkylsiloxane and the like.
The alkyl group of the polydialkylsiloxane preferably has 1 to 20 carbon atoms.
Examples of the polydialkylsiloxane include polydimethylsiloxane.

The non-resin component may be, for example, an organic compound or an inorganic compound, and is not particularly limited.

The composition for forming an intermediate layer and the additive contained in the intermediate layer may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
For example, the composition for forming an intermediate layer and the intermediate layer may contain one or more resin components as the additive and may not contain a non-resin component, or may contain one non-resin component. It may contain seeds or two or more kinds and may not contain a resin component, or may contain one kind or two or more kinds of both a resin component and a non-resin component.

When the composition for forming an intermediate layer and the intermediate layer contain the additive, the ratio of the content of the non-silicon resin (β1) to the total mass of the intermediate layer in the intermediate layer (in other words, for forming the intermediate layer). In the composition, the ratio of the content of the non-silicon resin (β1) to the total content of all the components other than the solvent) is preferably 90 to 99.99% by mass, for example, 90 to 97. It may be any of 5.5% by mass, 90 to 95% by mass, and 90 to 92.5% by mass, 92.5 to 99.99% by mass, 95 to 99.99% by mass, and 97. It may be any of 5 to 99.99% by mass, and may be 92.5 to 97.5% by mass.
When the intermediate layer forming composition and the intermediate layer contain the additive, the ratio of the content of the additive to the total mass of the intermediate layer in the intermediate layer (in other words, in the intermediate layer forming composition, the solvent. The ratio of the content of the additive to the total content of all the components other than the above) is preferably 0.01 to 10% by mass, for example, 2.5 to 10% by mass, 5 to 10% by mass. , And any of 7.5 to 10% by mass, 0.01 to 7.5% by mass, 0.01 to 5% by mass, and 0.01 to 2.5% by mass. It may be 2.5 to 7.5% by mass.

The solvent contained in the composition for forming an intermediate layer is not particularly limited, but preferred ones are, for example, hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol and isobutyl alcohol (2-methylpropan-1). -All), alcohols such as 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond) and the like. ..
The solvent contained in the intermediate layer forming composition may be only one kind, two or more kinds, and when two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

The solvent contained in the intermediate layer forming composition is preferably tetrahydrofuran or the like from the viewpoint that the components contained in the intermediate layer forming composition can be mixed more uniformly.

The content of the solvent in the composition for forming the intermediate layer is not particularly limited, and may be appropriately selected depending on the type of the component other than the solvent, for example.

As will be described later, in terms of making it easier to pick up the semiconductor chip with a film-like adhesive, preferred intermediate layers include, for example, the ethylene-vinyl acetate copolymer which is the non-silicon resin (β1) and the addition thereof. The ratio of the content of the ethylene-vinyl acetate copolymer (the non-silicon resin (β1)) to the total mass of the intermediate layer in the intermediate layer, which contains the siloxane-based compound as an agent, is any of the above. The ratio of the content of the siloxane-based compound (the additive) to the total mass of the intermediate layer in the intermediate layer is in any of the above numerical ranges.
For example, such an intermediate layer contains the ethylene-vinyl acetate copolymer which is the non-silicon resin (β1) and the siloxane compound which is the additive, and is the total of the intermediate layers in the intermediate layer. The ratio of the content of the ethylene-vinyl acetate copolymer to the mass is 90 to 99.99 mass%, and the ratio of the content of the siloxane compound to the total mass of the intermediate layer in the intermediate layer is 0. Examples thereof are those having a content of 0.01 to 10% by mass. However, this is an example of a preferred intermediate layer.

As a more preferable intermediate layer, for example, the intermediate layer contains the ethylene-vinyl acetate copolymer which is the non-silicon resin (β1) and the siloxane-based compound which is the additive, and the ethylene vinyl acetate is used. In the copolymer, the ratio of the mass of the structural unit derived from vinyl acetate (in other words, the content of the structural unit derived from vinyl acetate) to the total mass of all the structural units is 30% by mass or less. In the intermediate layer, the ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the intermediate layer is 90 to 99.99 mass%, and in the intermediate layer, the ratio of the content to the total mass of the intermediate layer is 90 to 99.99 mass%. , The content ratio of the siloxane-based compound is 0.01 to 10% by mass. However, this is an example of a more preferred intermediate layer.

In the sheet for manufacturing a semiconductor device, X-ray Photoelectron Spectroscopy (X-ray Photoelectron Spectroscopy, the present specification) is used for the surface of the intermediate layer on the film-like adhesive side (for example, the first surface 13a of the intermediate layer 13 in FIG. 1). When analyzed by "XPS" in the book), the ratio of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen and silicon (in this specification, abbreviated as "ratio of silicon concentration"). (May be) is preferably 1 to 20% on a molar basis of the element. By using a semiconductor device manufacturing sheet provided with such an intermediate layer, a semiconductor chip with a film-like adhesive can be more easily picked up, as will be described later.

In XPS analysis, the analysis target is the surface of the intermediate layer on the film-like adhesive side, an X-ray photoelectron spectroscopy analyzer is used, the X-ray irradiation angle is 45 °, the X-ray beam diameter is 20 μmφ, and the output is 4. It can be done by setting it to .5W.

The ratio of the silicon concentration is calculated by the following formula:
[Measured value of silicon concentration in XPS analysis (atomic%)] / {[Measured value of carbon concentration in XPS analysis (atomic%)] + [Measured value of oxygen concentration in XPS analysis (atomic%)) ] + [Measured value of nitrogen concentration in XPS analysis (atomic%)] + [Measured value of silicon concentration in XPS analysis (atomic%)]} x 100
Can be calculated by

In that such an effect becomes more remarkable, the ratio of the silicon concentration may be, for example, any of 4 to 20%, 8 to 20%, and 12 to 20% on a molar basis of the element. However, it may be any one of 1 to 16%, 1 to 12%, and 1 to 8%, and may be any of 4 to 16% and 8 to 12%.

When XPS analysis is performed as described above, other elements that do not correspond to any of carbon, oxygen, nitrogen, and silicon can be detected in the plane (analytical plane of XPS) of the intermediate layer. There is sex. However, usually, even if the other element is detected, its concentration is very small. Therefore, when calculating the ratio of the silicon concentration, the measured values of the concentrations of carbon, oxygen, nitrogen and silicon can be used. The ratio of the silicon concentration can be calculated with high accuracy.

The intermediate 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.

As described above, the first test piece made of the non-silicon resin (β1) contained in the intermediate layer satisfies the relationship of the formula (X1) and the formula (X2).

As described above, the maximum width of the intermediate layer is preferably smaller than the maximum width of the pressure-sensitive adhesive layer and the maximum width of the base material.
The maximum value of the width of the intermediate layer can be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum width of the intermediate layer may be 150 to 160 mm, 200 to 210 mm, or 300 to 310 mm. These three numerical ranges correspond to a semiconductor wafer having a maximum width of 150 mm, a semiconductor wafer of 200 mm, or a semiconductor wafer having a width of 300 mm in a direction parallel to the attachment surface with a sheet for manufacturing a semiconductor device. doing. However, as described above, the film-like adhesive is cut by expanding the semiconductor device manufacturing sheet (film-like adhesive) after dicing with the formation of the modified layer on the semiconductor wafer. In this case, as will be described later, a large number of semiconductor chips (semiconductor chip group) after dicing are put together, and a sheet for manufacturing a semiconductor device is attached to these semiconductor chips.

In the present specification, unless otherwise specified, the "width of the intermediate layer" means, for example, "the width of the intermediate layer in a direction parallel to the first surface of the intermediate layer". For example, in the case of an intermediate layer having a circular shape, the maximum width of the intermediate layer is the diameter of the circular shape.
This also applies to semiconductor wafers. That is, the "semiconductor wafer width" means "the width of the semiconductor wafer in a direction parallel to the attachment surface of the semiconductor wafer to the semiconductor device manufacturing sheet". For example, in the case of a semiconductor wafer having a circular shape, the maximum width of the above-mentioned semiconductor wafer is the diameter of the circular shape.

The maximum value of the width of the intermediate layer of 150 to 160 mm means that it is equal to or larger than the maximum value of the width of the semiconductor wafer of 150 mm within a range not exceeding 10 mm.
Similarly, the maximum width of the intermediate layer of 200 to 210 mm means that it is equal to or larger than the maximum width of the semiconductor wafer of 200 mm within a range not exceeding 10 mm.
Similarly, the maximum width of the intermediate layer of 300 to 310 mm means that it is equal to or larger than the maximum width of the semiconductor wafer of 300 mm within a range not exceeding 10 mm.
That is, in the present embodiment, the difference between the maximum value of the width of the intermediate layer and the maximum value of the width of the semiconductor wafer is, for example, whether the maximum value of the width of the semiconductor wafer is 150 mm, 200 mm, or 300 mm. Also, it may be 0 to 10 mm.

The thickness of the intermediate layer can be appropriately selected depending on the intended purpose, but is preferably 5 to 150 μm, more preferably 5 to 120 μm, and is, for example, 10 to 90 μm or 10 to 60 μm. It may be either 30 to 120 μm and 60 to 120 μm. When the thickness of the intermediate layer is equal to or greater than the lower limit, the structure of the intermediate layer is more stabilized. When the thickness of the intermediate layer is not more than the upper limit value, the film-like adhesive can be cut more easily at the time of blade dicing and at the time of the expansion of the semiconductor device manufacturing sheet (film-like adhesive).
Here, the "thickness of the intermediate layer" means the thickness of the entire intermediate layer, and for example, the thickness of the intermediate layer composed of a plurality of layers is the total thickness of all the layers constituting the intermediate layer. means.

When the intermediate layer contains the silicon-based resin, particularly when the compatibility between the silicon-based resin and the non-silicon-based resin (β1) which is the main component is low, the intermediate layer is used in the semiconductor device manufacturing sheet. The silicon-based resin in the layer tends to be unevenly distributed on both surfaces (the first surface and the surface opposite to the first surface) of the intermediate layer and the region in the vicinity thereof. The stronger this tendency, the easier it is for the film-like adhesive adjacent to (directly in contact with) the intermediate layer to peel off from the intermediate layer, and as will be described later, the semiconductor chip with the film-like adhesive is used. It can be picked up more easily.
For example, when comparing intermediate layers in which only the thickness is different from each other and the points other than the thickness such as the composition and the areas of both sides are the same, these intermediate layers are silicon-based with respect to the total mass of the intermediate layers. The proportions (mass%) of the resin content are the same as each other. However, the content (parts by mass) of the silicon-based resin in the intermediate layer is higher in the thick intermediate layer than in the thin intermediate layer. Therefore, when the silicon-based resin is likely to be unevenly distributed in the intermediate layer as described above, the thick intermediate layer is more double-sided (the first surface and the opposite side) than the thin intermediate layer. The amount of silicon-based resin unevenly distributed in the surface) and the region in the vicinity thereof increases. Therefore, it is possible to adjust the pickup suitability of the semiconductor chip with a film-like adhesive by adjusting the thickness of the intermediate layer in the semiconductor device manufacturing sheet without changing the ratio. For example, by increasing the thickness of the intermediate layer in the semiconductor device manufacturing sheet, the semiconductor chip with a film-like adhesive can be picked up more easily.

The composition for forming an intermediate layer is obtained by blending each component for constituting the composition.
The intermediate layer forming composition can be produced, for example, by the same method as in the case of the pressure-sensitive adhesive composition described above, except that the types of compounding components are different.

○ Film-like adhesive The film-like adhesive preferably has curability and thermosetting property, and preferably has 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.

Preferred film-like adhesives include, for example, those containing a polymer component (a) and a thermosetting component (b).

The film-like adhesive may or may not contain the component (α2). The component (α2) is a component other than the polymer component (a), and may be a thermosetting component (b) or a component other than the thermosetting component (b).

The film-like adhesive may or may not contain a solid component (α1) at a temperature of 23 ° C. as the polymer component (a).
The film-like adhesive may or may not contain the polymer component (a) as the main component.
The film-like adhesive may or may not contain the component (α1) as the main component. When the component (α1) is the main component, the component (α1) has a weight average molecular weight of 20000 or more, and the component (α1) having the maximum content (parts by mass) in the film-like adhesive is the component (α1). ).

The film-like adhesive preferably contains the component (α1), may contain both the component (α1) and the component (α2), or contains the component (α1) and contains the component (α2). ) May not be contained.

When the film-like adhesive contains a component (α1) as a main component, the component (α1) is preferably an acrylic resin having a structural unit derived from a (meth) acrylic acid ester.

The film-like adhesive can be formed by using an adhesive composition containing the constituent material. For example, the 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 the film-like adhesive, the ratio of the total content of one or more of the components described below to the total mass of the film-like adhesive does not exceed 100% by mass.
Similarly, in the adhesive composition, the ratio of the total content of one or more of the components described below to the total mass of the adhesive composition does not exceed 100% by mass.

The coating of the adhesive composition can be performed by the same method as in the case of coating the adhesive composition described above.

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

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.

When the sheet for manufacturing a semiconductor device is viewed from above in a plan view, the area of the base material (that is, the area of the first surface) is close to the area of the semiconductor wafer before division (that is, the area of the first surface). That is, it is preferable that the area is set smaller than the area of the first surface) and the area of the pressure-sensitive adhesive layer (that is, the area of the first surface). In such a sheet for manufacturing a semiconductor device, a region (that is, the non-laminated region) that is not in contact with the intermediate layer and the film-like adhesive is present on a part of the first surface of the pressure-sensitive adhesive layer. As a result, the sheet for manufacturing a semiconductor device (film-like adhesive) can be expanded more easily, and the force applied to the film-like adhesive at the time of expansion is not dispersed, so that the film-like adhesive can be cut more easily.

As described above, the maximum width of the film-like adhesive is preferably smaller than the maximum width of the pressure-sensitive adhesive layer and the maximum width of the base material.
The maximum width of the film-like adhesive may be the same as the maximum width of the intermediate layer described above with respect to the size of the semiconductor wafer.
That is, the maximum width of the film-like adhesive can be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum width of the film-like adhesive may be 150 to 160 mm, 200 to 210 mm, or 300 to 310 mm. These three numerical ranges correspond to a semiconductor wafer having a maximum width of 150 mm, a semiconductor wafer of 200 mm, or a semiconductor wafer having a width of 300 mm in a direction parallel to the attachment surface with a sheet for manufacturing a semiconductor device. doing.

In the present specification, unless otherwise specified, the "width of the film-like adhesive" means, for example, "the width of the film-like adhesive in a direction parallel to the first surface of the film-like adhesive". means. For example, in the case of a film-like adhesive having a circular plane shape, the maximum width of the film-like adhesive described above is the diameter of the circle having a planar shape.
Unless otherwise specified, the "width of the film-like adhesive" is not the width of the film-like adhesive after cutting in the process of manufacturing a semiconductor chip with a film-like adhesive, which will be described later, but "before cutting (not yet). Width of film-like adhesive (cut) "means.

The maximum width of the film-like adhesive of 150 to 160 mm means that it is equal to or larger than the maximum width of the semiconductor wafer of 150 mm within a range not exceeding 10 mm.
Similarly, the maximum width of the film-like adhesive of 200 to 210 mm means that it is equal to or larger than the maximum width of the semiconductor wafer of 200 mm within a range not exceeding 10 mm.
Similarly, the maximum width of the film-like adhesive of 300 to 310 mm means that it is equal to or large in the range not exceeding 10 mm with respect to the maximum width of the semiconductor wafer of 300 mm.
That is, in the present embodiment, the difference between the maximum width of the film-like adhesive and the maximum width of the semiconductor wafer is, for example, when the maximum width of the semiconductor wafer is 150 mm, 200 mm, or 300 mm. Even if there is, it may be 0 to 10 mm.

In the present embodiment, the maximum value of the width of the intermediate layer and the maximum value of the width of the film-like adhesive may both be in any of the above-mentioned numerical ranges.
That is, as an example of the semiconductor device manufacturing sheet of the present embodiment, the maximum value of the width of the intermediate layer and the maximum value of the width of the film-like adhesive are both 150 to 160 mm, 200 to 210 mm, or 300 to 300. The one which is 310 mm is mentioned.

The thickness of the film-like adhesive is not particularly limited, but is preferably 1 to 30 μm, more preferably 2 to 20 μm, and particularly preferably 3 to 10 μm. When the thickness of the film-like adhesive is at least the above lower limit value, a higher adhesive force to the adherend (semiconductor chip) can be obtained. When the thickness of the film-like adhesive is not more than the upper limit value, the film-like adhesive can be cut more easily at the time of blade dicing and at the time of expanding the sheet (film-like adhesive) for manufacturing a 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.
Next, the adhesive composition will be described.

<< Adhesive composition >>
Preferred adhesive compositions include, for example, those containing a polymer component (a) and a thermosetting component (b).
In addition to these, the adhesive composition may or may not contain the component (α2).
In the adhesive composition, the polymer component (a) may be the component (α1), or the polymer component (a) may be the main component.

Hereinafter, each component in the adhesive composition and the film-like adhesive will be described.
The adhesive composition shown below is an example of a preferable one, and the adhesive composition in the present embodiment is not limited to the one shown below.

[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 adhered to a semiconductor chip or the like. It is a polymer compound for improving adhesiveness (in other words, adhesiveness). The polymer component (a) has thermoplasticity and does not have thermosetting property. In the present specification, the polymer compound also includes a product of a polycondensation reaction.

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

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

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 with respect to the total mass of the film-like adhesive in the film-like adhesive). The content ratio of (a)) is preferably 20 to 75% by mass, more preferably 30 to 65% by mass.

[Thermosetting component (b)]
The thermosetting component (b) has thermosetting property and is a component for thermosetting the film-like adhesive.
The thermosetting component (b) contained in the adhesive composition and the film-like adhesive may be only one type, two or more types, or a combination thereof when two or more types are used. And the ratio can be selected arbitrarily.

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.

〇 Epoxy-based 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, dicyclopentadiene type epoxy resin, and the like. 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. Epoxy resins having unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins having no unsaturated hydrocarbon groups. 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.

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, a combination and ratio thereof. Can be selected arbitrarily.

・ Thermosetting agent (b2)
The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b1).
Examples of the thermosetting agent (b2) include compounds having 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 annealed, and the like, and the phenolic hydroxyl group, an amino group, or an acid group is annealed. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among the heat-curing agents (b2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins. ..
Among the thermosetting agents (b2), examples of the amine-based curing agent having an amino group include dicyandiamide (DICY) and the like.

The thermosetting agent (b2) may have an unsaturated hydrocarbon group.

The thermosetting agent (b2) 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.

In the adhesive composition and the film-like adhesive, the content of the heat-curing agent (b2) is preferably 0.1 to 500 parts by mass with respect to 100 parts by mass of the content of the epoxy resin (b1). It is more preferably 1 to 200 parts by mass, and may be, for example, 1 to 100 parts by mass, 1 to 50 parts by mass, or 1 to 25 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) (for example, the total content of the epoxy resin (b1) and the thermosetting agent (b2)) is the content of the polymer component (a). The content is preferably 5 to 100 parts by mass, more preferably 5 to 75 parts by mass, particularly preferably 5 to 50 parts by mass, and for example, 5 to 35 parts by mass with respect to 100 parts by mass. It may be any of parts and 5 to 20 parts by mass. When the content of the thermosetting component (b) is in such a range, the peeling force between the intermediate layer and the film-like adhesive becomes more stable.

A thermosetting component (b) (for example, an epoxy resin (b1) and a thermosetting agent (b2)) that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive. When either one or both) is used, it is preferable that the content in the adhesive composition and the film-like adhesive satisfies a numerical range separately determined as described later.

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

[Curing accelerator (c)]
The curing accelerator (c) is a component for adjusting the curing rate of the adhesive composition.
Preferred curing accelerators (c) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole. , 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 (phosphenyl in which one or more hydrogen atoms are substituted with an organic group); tetraphenylphosphonium tetraphenylborate, triphenylphosphine Examples thereof include tetraphenylborone salts such as tetraphenylborate.

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

When the curing accelerator (c) is used, the content of the curing accelerator (c) in the adhesive composition and the film-like adhesive is 0 with respect to 100 parts by mass of the content of the thermosetting component (b). It is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 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) can be obtained more remarkably. When the content of the curing accelerator (c) is not more than the above upper limit value, for example, the highly polar curing accelerator (c) is attached to 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.
When a curing accelerator (c) that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive is used, in the adhesive composition and the film-like adhesive. The content preferably satisfies a numerical range specified separately as described later.

[Filler (d)]
By containing the filler (d), the film-like adhesive further improves its cutting property by expanding. Further, since the film-like adhesive contains the filler (d), it becomes easy to adjust the thermal expansion coefficient, and by optimizing this thermal expansion coefficient with respect to the object to which the film-like adhesive is attached. , The reliability of the package obtained by using the film-like adhesive is further improved. Further, when the film-like adhesive contains the filler (d), it is possible to reduce the hygroscopicity of the film-like adhesive after curing 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 or alumina.

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, a combination and ratio thereof. Can be selected arbitrarily.

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 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 60% by mass. preferable. When the ratio is in such a range, the effect of using the filler (d) can be obtained more remarkably.

[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.

The coupling agent (e) 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.

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, the adhesiveness of the film-like adhesive to the adherend is improved, and the like. , 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.
When a coupling agent (e) that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive is used, in the adhesive composition and the film-like adhesive. The content preferably satisfies a numerical range specified separately as described later.

[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, an isocyanate group, etc., such as the above-mentioned acrylic resin, is used. In this case, the adhesive composition and the film-like adhesive may contain a cross-linking agent (f). The cross-linking agent (f) is a component for bonding the functional group in the polymer component (a) with another compound to cross-link, and by cross-linking in this way, the initial adhesive force of the film-like adhesive is obtained. And the cohesive force 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 (a cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (a cross-linking agent having an aziridinyl group), and the like. Can be mentioned.

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 into 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, a combination and ratio thereof. Can be selected arbitrarily.

When the cross-linking agent (f) is used, the content of the cross-linking agent (f) in the adhesive composition is 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the polymer component (a). It is preferably 0.1 to 10 parts by mass, and particularly preferably 0.3 to 5 parts by mass. 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) can be obtained more remarkably. When the content of the cross-linking agent (f) is not more than the upper limit value, the excessive use of the cross-linking agent (f) is suppressed.
When a cross-linking agent (f) that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive is used, it is contained in the adhesive composition and the film-like adhesive. The amount preferably satisfies a numerical range specified separately as described later.

[Energy ray curable resin (g)]
Since the adhesive composition and the film-like adhesive contain the energy ray-curable resin (g), the properties of the film-like adhesive can be changed by irradiation with energy rays.

The energy ray-curable resin (g) may be a component (α1), but is preferably not a component (α1).

The energy ray-curable resin (g) is obtained from 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.

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 are arbitrary. Can be 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 more preferable, 5 to 90% by mass is more preferable, and 10 to 85% by mass is particularly preferable.

[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) in the adhesive composition include benzoins 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. Compounds; Acetphenone compounds such as acetophenone, 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; 1-hydroxycyclohexylphenylketone and the like. Α-Ketol 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-diethyl Thioxanthone; 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 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 arbitrary. You can choose.

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). It is preferably about 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass.
When a photopolymerization initiator (h) that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive is used, the adhesive composition and the film-like adhesive are used. It is preferable that the content in the above satisfies a numerical range specified separately as described later.

[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, but preferred ones are, for example, a plasticizer, an antistatic agent, an antioxidant, and a colorant (dye). , Pigments), gettering agents and the like.

The general-purpose additive (i) contained in the adhesive composition and the film-like adhesive may be only one kind, two or more kinds, and when two or more kinds, a combination thereof and The ratio can be selected arbitrarily.

The contents of the adhesive composition and the film-like adhesive are not particularly limited and may be appropriately selected depending on the intended purpose.
When a general-purpose additive (i) that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive is used, in the adhesive composition and the film-like adhesive. The content preferably satisfies a numerical range specified separately as described later.

[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 are, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol. Examples thereof include esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond).
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.

The content of the solvent in the adhesive composition is not particularly limited, and may be appropriately selected depending on the type of component other than the solvent, for example.

[Component (α2)]
The component (α2) in the adhesive composition and the film-like adhesive is liquid at a temperature of 23 ° C. Further, the component (α2) does not have a functional group that reacts with the main component contained in the film-like adhesive (that is, does not react with the main component). The component that has a functional group that reacts with the main component contained in the film-like adhesive and is liquid at a temperature of 23 ° C. is intermediate from the film-like adhesive by reacting with the main component in the film-like adhesive. It does not migrate to the layer and, as a result, does not migrate to the pressure-sensitive adhesive layer. In the present embodiment, it is not such a component having the functional group and liquid at a temperature of 23 ° C., and originally has the functional group which cannot suppress the transition from the film-like adhesive to the pressure-sensitive adhesive layer. No, the component (α2) that is liquid at a temperature of 23 ° C. is suppressed from being transferred from the film-like adhesive to the pressure-sensitive adhesive layer.
For example, when the main component has a hydroxyl group or an amino group, an isocyanate group can be mentioned as a functional group that reacts with the main component.

The component (α2) is not particularly limited as long as such conditions are satisfied, and can be arbitrarily selected depending on the intended purpose. A component that does not correspond to any of the polymer component (a), the filler (d), the energy ray-curable resin (g), and the solvent of the adhesive composition, that is, the thermosetting component ( b) (For example, epoxy resin (b1) and thermosetting agent (b2)), curing accelerator (c), coupling agent (e), cross-linking agent (f), photopolymerization initiator (h), and general-purpose additive. Of (i), the component (α2) is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive. The solvent is usually not contained in the film adhesive.
Preferred components (α2) include, for example, epoxy resin (b1) and the like.

The component (α2) 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 component (α2) is used, the content of the component (α2) in the adhesive composition can be appropriately adjusted according to the type of the component (α2).
In the adhesive composition and the film-like adhesive, the content of the component (α2) is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the content of the polymer component (a). When the content is not more than the upper limit value, the transfer of the component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer is further suppressed. When the content is at least the lower limit value, the effect obtained by using the component (α2) becomes higher.

In particular, when the component (α2) is the epoxy resin (b1), the content of the component (α2) (epoxy resin (b1)) in the adhesive composition and the film-like adhesive is the content of the polymer component (a). The content is preferably 3 to 17 parts by mass and more preferably 6 to 14 parts by mass with respect to 100 parts by mass. When the content is not more than the upper limit value, the transfer of the component (α2) in the film-like adhesive to the pressure-sensitive adhesive layer is further suppressed, and the excessive use of the component (α2) is suppressed. When the content is at least the lower limit value, the effect obtained by using the component (α2) becomes higher.

The film-like adhesive can be cut satisfactorily by cooling and expanding it, as will be described later. That is, the sheet for manufacturing a semiconductor device of the present embodiment is suitable for cutting the film-like adhesive by cooling and expanding the film-like adhesive.

<< Manufacturing method of adhesive composition >>
The adhesive composition is obtained by blending each component for constituting the adhesive composition.
The adhesive composition can be produced, for example, by the same method as in the case of the pressure-sensitive adhesive composition described above, except that the types of compounding components are different.

In the semiconductor device manufacturing sheet of the present embodiment, at least the film-like adhesive contains the component (α1) as a main component, or the pressure-sensitive adhesive layer contains the component (γ1) as a main component. It is preferable to do so.
That is, as an example of a preferred sheet for manufacturing a semiconductor device of the present embodiment, a semiconductor in which the film-like adhesive contains the component (α1) as a main component and the pressure-sensitive adhesive layer does not contain the component (γ1) as a main component. Device manufacturing sheet; A semiconductor device manufacturing sheet in which the pressure-sensitive adhesive layer contains the component (γ1) as a main component and the film-like adhesive does not contain the component (α1) as a main component; the film-like adhesive is the component. Examples thereof include a sheet for manufacturing a semiconductor device containing (α1) as a main component and the pressure-sensitive adhesive layer containing the component (γ1) as a main component.
In the sheet for manufacturing a semiconductor device, it is more preferable that the film-like adhesive contains the component (α1) as a main component and the pressure-sensitive adhesive layer contains the component (γ1) as a main component.

In the semiconductor device manufacturing sheet of the present embodiment, at least the film-like adhesive contains the component (α1) as a main component, or the pressure-sensitive adhesive layer contains the component (γ1) as a main component. However, it is more preferable that the component (α1) and the component (γ1) are an acrylic resin having a structural unit derived from a (meth) acrylic acid ester.
That is, as an example of a more preferable sheet for manufacturing a semiconductor device of the present embodiment, the film-like adhesive contains the component (α1) as a main component, and the pressure-sensitive adhesive layer contains the component (γ1) as a main component. A sheet for manufacturing a semiconductor device in which the component (α1) is an acrylic resin having a structural unit derived from a (meth) acrylic acid ester; the pressure-sensitive adhesive layer contains the component (γ1) as a main component, and a film. A sheet for manufacturing a semiconductor device, which is an acrylic resin in which the adhesive does not contain the component (α1) as a main component and the component (γ1) has a structural unit derived from a (meth) acrylic acid ester; film-like. The adhesive contains the component (α1) as a main component, the pressure-sensitive adhesive layer contains the component (γ1) as a main component, and the component (α1) and the component (γ1) are derived from the (meth) acrylic acid ester. Examples thereof include a sheet for manufacturing a semiconductor device, which is an acrylic resin having an derived structural unit.
Then, in the sheet for manufacturing a semiconductor device, the film-like adhesive contains the component (α1) as a main component, and the pressure-sensitive adhesive layer contains the component (γ1) as a main component, and the component (α1) and the component. It is more preferable that (γ1) is an acrylic resin having a structural unit derived from a (meth) acrylic acid ester.

As an example of a preferred semiconductor device manufacturing sheet of the present embodiment, a base material, an adhesive layer, an intermediate layer, and a film-like adhesive are provided.
The pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material.
The intermediate layer contains a non-silicon resin (β1) having a weight average molecular weight of 20,000 to 100,000 as a main component.
Further, the film-like adhesive contains the component (α2), and the pressure-sensitive adhesive layer contains the component (γ2).
The component (α2) is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive.
The component (γ2) is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer.
The haze of the film-shaped first test piece made of the non-silicon resin (β1) and having a thickness of 10 μm was defined as H (β).
When the haze of the film-like second test piece having a thickness of 10 μm composed of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (α2) is H (βα). , The H (βα) and H (β) are expressed by the following formula (X1):
(X1) H (βα) -H (β)> 7%
The filling,
When the haze of the film-like third test piece having a thickness of 10 μm composed of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (γ2) is H (βγ). , The H (βγ) and H (β) are expressed by the following formula (X2):
(X2) H (βγ) -H (β)> 7%
The filling,
Further, the film-like adhesive contains a solid component (α1) as a main component at a temperature of 23 ° C., the component (α1) is a polymer component (a), and the pressure-sensitive adhesive layer is at a temperature of 23 ° C. It contains a solid component (γ1) as a main component, and the component (γ1) is an adhesive.
Examples thereof include a sheet for manufacturing a semiconductor device in which the intermediate layer contains one or more selected from the group consisting of ethylene vinyl acetate copolymer and polyolefin as the non-silicon resin (β1).
In this semiconductor device manufacturing sheet, the intermediate layer may further contain a silicon-based resin.

As another example of the preferred semiconductor device manufacturing sheet of the present embodiment, the base material, the pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are provided.
The pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material.
The intermediate layer contains a non-silicon resin (β1) having a weight average molecular weight of 20,000 to 100,000 as a main component.
Further, the film-like adhesive contains the component (α2), and the pressure-sensitive adhesive layer contains the component (γ2).
The component (α2) is an epoxy resin (b1) that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive.
The component (γ2) is an antistatic agent that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer.
The haze of the film-shaped first test piece made of the non-silicon resin (β1) and having a thickness of 10 μm was defined as H (β).
When the haze of the film-like second test piece having a thickness of 10 μm composed of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (α2) is H (βα). , The H (βα) and H (β) are expressed by the following formula (X1):
(X1) H (βα) -H (β)> 7%
The filling,
When the haze of the film-like third test piece having a thickness of 10 μm composed of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (γ2) is H (βγ). , The H (βγ) and H (β) are expressed by the following formula (X2):
(X2) H (βγ) -H (β)> 7%
The filling,
Further, the film-like adhesive contains a solid component (α1) as a main component at a temperature of 23 ° C., the component (α1) is a polymer component (a), and the pressure-sensitive adhesive layer is at a temperature of 23 ° C. It contains a solid component (γ1) as a main component, and the component (γ1) is an adhesive.
The intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon resin (β1).
In the film-like adhesive, the content of the epoxy resin (b1) is 1 to 20 parts by mass with respect to 100 parts by mass of the content of the polymer component (a).
In the pressure-sensitive adhesive layer, the content of the antistatic agent is 0.1 to 10 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive.
Examples thereof include a sheet for manufacturing a semiconductor device in which the ratio of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units in the ethylene-vinyl acetate copolymer is 45% by mass or less.
In this semiconductor device manufacturing sheet, the ratio of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units in the ethylene-vinyl acetate copolymer may be 30% by mass or less. ..
In this semiconductor device manufacturing sheet, the intermediate layer may further contain a silicon-based resin, and in that case, the content of the silicon-based resin in the intermediate layer with respect to the total mass of the intermediate layer. The ratio of may be 0.01 to 10% by mass.

Still another example of the preferred semiconductor device manufacturing sheet of the present embodiment includes a base material, an adhesive layer, an intermediate layer, and a film-like adhesive.
The pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material.
The intermediate layer contains a non-silicon resin (β1) having a weight average molecular weight of 20,000 to 100,000 as a main component.
Further, the film-like adhesive contains the component (α2), and the pressure-sensitive adhesive layer contains the component (γ2).
The component (α2) is an epoxy resin (b1) that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive.
The component (γ2) is an antistatic agent that is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer.
The haze of the film-shaped first test piece made of the non-silicon resin (β1) and having a thickness of 10 μm was defined as H (β).
When the haze of the film-like second test piece having a thickness of 10 μm composed of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (α2) is H (βα). , The H (βα) and H (β) are expressed by the following formula (X1):
(X1) H (βα) -H (β)> 7%
The filling,
When the haze of the film-like third test piece having a thickness of 10 μm composed of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (γ2) is H (βγ). , The H (βγ) and H (β) are expressed by the following formula (X2):
(X2) H (βγ) -H (β)> 7%
The filling,
Further, the film-like adhesive contains a solid component (α1) as a main component at a temperature of 23 ° C., the component (α1) is a polymer component (a), and the pressure-sensitive adhesive layer is at a temperature of 23 ° C. A structural unit containing a solid component (γ1) as a main component, the component (γ1) being a pressure-sensitive adhesive, and the polymer component (a) and the pressure-sensitive adhesive derived from a (meth) acrylic acid ester. It is an acrylic resin that has
The intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon resin (β1).
In the film-like adhesive, the content of the epoxy resin (b1) is 1 to 20 parts by mass with respect to 100 parts by mass of the content of the polymer component (a).
In the pressure-sensitive adhesive layer, the content of the antistatic agent is 0.1 to 10 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive.
Examples thereof include a sheet for manufacturing a semiconductor device in which the ratio of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units in the ethylene-vinyl acetate copolymer is 45% by mass or less.
In this semiconductor device manufacturing sheet, the ratio of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units in the ethylene-vinyl acetate copolymer may be 30% by mass or less. ..
In this semiconductor device manufacturing sheet, the intermediate layer may further contain polydimethylsiloxane, in which case the content of the polydimethylsiloxane in the intermediate layer with respect to the total mass of the intermediate layer. The ratio of may be 0.01 to 10% by mass.

-Method of manufacturing a sheet for manufacturing a semiconductor device The sheet for manufacturing a semiconductor device can be manufactured by laminating the above-mentioned layers so as to have a corresponding positional relationship. The method of forming each layer is as described above.

For example, in the sheet for manufacturing a semiconductor device, a base material, an adhesive layer, an intermediate layer and a film-like adhesive are prepared in advance, and these are used as a base material, an adhesive layer, an intermediate layer and a film-like adhesive. It can be manufactured by laminating and laminating in the order of.
However, this is an example of a method for manufacturing a sheet for manufacturing a semiconductor device.

For the semiconductor device manufacturing sheet, for example, two or more types of intermediate laminates, which are formed by laminating a plurality of layers to form the sheet, are prepared in advance, and the intermediate laminates are bonded to each other. It can also be manufactured. The configuration of the intermediate laminate can be arbitrarily selected as appropriate. For example, a first intermediate laminate having a structure in which a base material and an adhesive layer are laminated (corresponding to the support sheet), and a second intermediate laminate having a structure in which an intermediate layer and a film-like adhesive are laminated. Can be manufactured in advance, and the adhesive layer in the first intermediate laminate and the intermediate layer in the second intermediate laminate are bonded to each other to produce a sheet for manufacturing a semiconductor device.
However, this is also an example of a method for manufacturing a sheet for manufacturing a semiconductor device.

As the sheet for manufacturing a semiconductor device, for example, as shown in FIG. 1, the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive are both the first surface of the pressure-sensitive adhesive layer. In the case of manufacturing a material smaller than the area of the first surface of the base material, a step of processing the intermediate layer and the film-like adhesive into a desired size is performed at any stage of the above-mentioned manufacturing method. , May be added. For example, in the manufacturing method using the second intermediate laminate, a semiconductor device is manufactured by additionally performing a step of processing the intermediate layer and the film-like adhesive in the second intermediate laminate to a desired size. Sheets may be manufactured.

When manufacturing a sheet for manufacturing a semiconductor device in which a release film is provided on a film-like adhesive, for example, a film-like adhesive is produced on the release film, and the remaining layers are formed while maintaining this state. A sheet for manufacturing a semiconductor device may be laminated, or a base material, an adhesive layer, an intermediate layer and a film-like adhesive may all be laminated, and then a release film may be laminated on the film-like adhesive. A sheet for manufacturing a semiconductor device may be manufactured. The release film may be removed at a necessary stage by the time the semiconductor device manufacturing sheet is used.

A sheet for manufacturing a semiconductor device including a base material, an adhesive layer, an intermediate layer, a film-like adhesive, and another layer that does not correspond to a release film is suitable in the above-mentioned manufacturing method. It can be manufactured by additionally performing a step of forming and laminating this other layer at various timings.

However, in order to manufacture the sheet for manufacturing the semiconductor device, the above formula (X1) is used as a combination of the non-silicon resin (β1) in the film-like adhesive and the component (α2) in the intermediate layer. Select a combination that satisfies the above formula (X2), or select a combination that satisfies the above formula (X2) as a combination of the non-silicon resin (β1) in the film-like adhesive and the component (γ2) in the pressure-sensitive adhesive layer. There is a need.

That is, the present embodiment is a method for manufacturing a sheet for manufacturing a semiconductor device.
The sheet for manufacturing a semiconductor device includes a base material, an adhesive layer, an intermediate layer, and a film-like adhesive.
The pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material.
The intermediate layer contains a non-silicon resin (β1) having a weight average molecular weight of 20,000 to 100,000 as a main component.
Further, at least, the film-like adhesive contains the component (α2), or the pressure-sensitive adhesive layer contains the component (γ2).
The component (α2) is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive.
The component (γ2) is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer.
The haze of the film-shaped first test piece made of the non-silicon resin (β1) and having a thickness of 10 μm was defined as H (β).
When the film-like adhesive contains the component (α2), the thickness is 10 μm composed of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (α2). When the haze of the film-like second test piece is H (βα), the H (βα) and H (β) are expressed by the following formula (X1):
(X1) H (βα) -H (β)> 7%
The filling,
When the pressure-sensitive adhesive layer contains the component (γ2), the thickness is 10 μm, which is a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (γ2). When the haze of the film-like third test piece is H (βγ), the H (βγ) and H (β) are expressed by the following formula (X2):
(X2) H (βγ) -H (β)> 7%
The filling,
The production method includes a film-like adhesive manufacturing step of producing the film-like adhesive containing the component (α2) and a pressure-sensitive adhesive layer manufacturing step of producing the pressure-sensitive adhesive layer containing the component (γ2). , Either one or both.

As described above, the method for manufacturing a sheet for manufacturing a semiconductor device of the present embodiment includes the film-like adhesive manufacturing step according to the configuration of the target sheet for manufacturing a semiconductor device, and the pressure-sensitive adhesive layer manufacturing step is performed. It may be a manufacturing method that does not have, or a manufacturing method that has the pressure-sensitive adhesive layer manufacturing step and does not have the film-shaped adhesive manufacturing step, or the film-shaped adhesive manufacturing step and the pressure-sensitive adhesive. It may be a manufacturing method having both layer forming steps.
In the film-like adhesive production step, a film-like adhesive is produced using the adhesive composition containing the component (α2).
In the pressure-sensitive adhesive layer preparation step, a pressure-sensitive adhesive layer is prepared using the pressure-sensitive adhesive composition containing the component (γ2).

◇ Manufacturing method of semiconductor chips with film-like adhesive (How to use sheets for manufacturing semiconductor devices)
The sheet for manufacturing a semiconductor device can be used in the manufacturing process of a semiconductor device when manufacturing a semiconductor chip with a film-like adhesive.
Hereinafter, a method for manufacturing the semiconductor chip with a film-like adhesive (a method for using a sheet for manufacturing a semiconductor device) will be described in detail with reference to the drawings.

3A, 3B, and 3C are cross-sectional views for schematically explaining an example of a method for manufacturing a semiconductor chip with a film-like adhesive, and are used after a sheet for manufacturing a semiconductor device is attached to a semiconductor wafer. The manufacturing method in the case of In this method, a semiconductor device manufacturing sheet is used as a dicing die bonding sheet. Here, a case where the semiconductor device manufacturing sheet 101 shown in FIG. 1 is used will be described as an example.

First, as shown in FIG. 3A, while heating the semiconductor device manufacturing sheet 101 with the release film 15 removed, the film-like adhesive 14 therein is attached to the back surface 9b'of the semiconductor wafer 9'. ..
Reference numeral 9a'indicates a circuit forming surface of the semiconductor wafer 9'.

The heating temperature at the time of sticking the semiconductor device manufacturing sheet 101 is not particularly limited, but is preferably 40 to 70 ° C. from the viewpoint of further improving the heating sticking stability of the semiconductor device manufacturing sheet 101.

The maximum value of the width W ₁₃ of the intermediate layer 13 of the semiconductor device in manufacturing sheet 101, the maximum value of the width W ₁₄ of the film-like adhesive 14, the maximum value of both, 'width W _{9 of'} the semiconductor wafer 9 It is preferable that the errors are exactly the same or not the same, but the errors are slight and almost the same.

For example, when the maximum value of the 'width W _{9 of'} the semiconductor wafer 9 is 150mm, the maximum value of the width _{W 13} of the intermediate layer 13, the maximum value of the width _{W 14} of the film-like adhesive 14, 150 preferably from ~ 160 mm, the maximum value of the 'width W _{9 of'} the semiconductor wafer 9 in the case of 200mm has a maximum width _{W 13} of the intermediate layer 13, the width _{W 14} of the film-like adhesive 14 maximum value is preferably 200 ~ 210 mm, when the maximum value of the 'width W _{9 of'} the semiconductor wafer 9 is 300mm, the maximum value of the width _{W 13} of the intermediate layer 13 and the film-like adhesive The maximum value of the width W ₁₄ of 14 is preferably 300 to 310 mm.
Thus, in the present embodiment, the maximum value of the width W ₁₃ of the intermediate layer 13, the maximum value and the difference in the 'width W _{9 of'} the semiconductor wafer 9, and the width of the film-like adhesive 14 W ₁₄ and maximum, the maximum value and the difference of the 'Haba W _9' of the semiconductor wafer 9 may be Izure Mo in 0 ~ 10 mm.
Here, the 'width W _{9 of'} the semiconductor wafer 9 is, for example, 'of its back surface 9b' semiconductor wafer 9 means the width in the direction parallel to.

Next, the laminate of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9'obtained above is cut with a blade from the circuit forming surface 9a'side of the semiconductor wafer 9'(blade dicing is performed) to form a semiconductor. The wafer 9'is divided and the film-like adhesive 14 is cut.

Blade dicing can be performed by a known method. For example, in the first surface 12a of the pressure-sensitive adhesive layer 12 in the semiconductor device manufacturing sheet 101, a region (the non-laminated region) near the peripheral edge portion where the intermediate layer 13 and the film-like adhesive 14 are not laminated is set as a ring. After fixing to a jig (not shown) such as a frame, the semiconductor wafer 9'can be divided and the film-like adhesive 14 can be cut by using a blade.

By this step, as shown in FIG. 3B, a plurality of semiconductor chips 914 with a film-like adhesive provided with the semiconductor chip 9 and the film-like adhesive 140 after cutting provided on the back surface 9b thereof are obtained. Be done. The semiconductor chips 914 with a film-like adhesive are aligned and fixed on the intermediate layer 13 in the laminated sheet 10, and constitute the semiconductor chip group 910 with a film-like adhesive.
The back surface 9b of the semiconductor chip 9 corresponds to the back surface 9b'of the semiconductor wafer 9'. Further, in FIG. 3B, reference numeral 9a indicates a circuit forming surface of the semiconductor chip 9, and corresponds to the circuit forming surface 9a'of the semiconductor wafer 9'.

At the time of blade dicing, the semiconductor wafer 9'is divided by cutting the entire area in the thickness direction by the blade, and the semiconductor device manufacturing sheet 101 is divided into an intermediate layer from the first surface 14a of the film-like adhesive 14. It is preferable that the film-like adhesive 14 is cut over the entire area in the thickness direction by cutting up to the region in the middle of 13, and the pressure-sensitive adhesive layer 12 is not cut.
That is, at the time of blade dicing, a laminate of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9'is formed by the blade from the circuit forming surface 9a'of the semiconductor wafer 9'in at least the intermediate layer 13th. It is preferable that the cut is made to the first surface 13a and not to the surface of the intermediate layer 13 opposite to the first surface 13a (that is, the contact surface with the pressure-sensitive adhesive layer 12).

In this step, it is possible to easily prevent the blade from reaching the base material 11 in this way, and thereby it is possible to suppress the generation of cutting chips from the base material 11. The main component of the intermediate layer 13 cut by the blade is a non-silicon resin (β1) having a weight average molecular weight of 20,000 to 100,000, and in particular, the intermediate layer 13 has a weight average molecular weight of 100,000 or less. It is also possible to suppress the generation of cutting chips from silicon.

The conditions for blade dicing may be appropriately adjusted according to the intended purpose, and are not particularly limited.
Generally, the rotation speed of the blade is preferably 15,000 to 50,000 rpm, and the moving speed of the blade is preferably 5 to 85 mm / sec, and may be 5 to 75 mm / sec.

After the blade dicing, as shown in FIG. 3C, the semiconductor chip 914 with the film-like adhesive is separated from the intermediate layer 13 in the laminated sheet 10 and picked up. Here, a case is shown in which the semiconductor chip 914 with a film-like adhesive is pulled away in the direction of arrow P by using a pulling means 7 such as a vacuum collet. Here, the pulling means 7 is not displayed in cross section.
The semiconductor chip 914 with a film-like adhesive can be picked up by a known method.

When the ratio of the silicon concentration on the first surface 13a of the intermediate layer 13 is 1 to 20%, the semiconductor chip 914 with a film-like adhesive can be picked up more easily.
The intermediate layer 13 contains, for example, an ethylene-vinyl acetate copolymer which is the non-silicon resin (β1) and a siloxane compound which is the additive, and is based on the total mass of the intermediate layer in the intermediate layer. The ratio of the content of the ethylene-vinyl acetate copolymer is 90 to 99.99% by mass, and the ratio of the content of the siloxane compound to the total mass of the intermediate layer in the intermediate layer is 0.01 to 10. When the mass is%, the semiconductor chip 914 with a film-like adhesive can be picked up more easily.

In the method for manufacturing a semiconductor chip with a film-like adhesive described so far, a preferred embodiment is, for example, a method for manufacturing a semiconductor chip with a film-like adhesive using a sheet for manufacturing a semiconductor device.
The semiconductor chip with a film-like adhesive includes a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip.
The sheet for manufacturing a semiconductor device includes a base material, an adhesive layer, an intermediate layer, and a film-like adhesive.
The pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material.
The intermediate layer contains a non-silicon resin (β1) having a weight average molecular weight of 20,000 to 100,000 as a main component.
Further, at least, the film-like adhesive contains the component (α2), or the pressure-sensitive adhesive layer contains the component (γ2).
The component (α2) is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive.
The component (γ2) is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer.
Let H (β) be the haze of the film-like test piece having a thickness of 10 μm made of the non-silicon resin (β1).
When the film-like adhesive contains the component (α2), the thickness is 10 μm composed of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (α2). When the haze of the film-like second test piece is H (βα), the H (βα) and H (β) are expressed by the following formula (X1):
(X1) H (βα) -H (β)> 7%
The filling,
When the pressure-sensitive adhesive layer contains the component (γ2), the thickness is 10 μm, which is a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (γ2). When the haze of the film-like third test piece is H (βγ), the H (βγ) and H (β) are expressed by the following formula (X2):
(X2) H (βγ) -H (β)> 7%
The filling,
The manufacturing method includes a step of attaching the film-like adhesive in the sheet for manufacturing a semiconductor device to the back surface of the semiconductor wafer while heating the sheet.
The semiconductor chip to which the film-like adhesive is attached is divided by cutting the entire area in the thickness direction from the circuit forming surface side thereof to produce the semiconductor chip and the semiconductor device manufacturing sheet. By cutting from the film-like adhesive side to the middle region of the intermediate layer in the thickness direction, cutting the film-like adhesive, and not cutting to the pressure-sensitive adhesive layer. A step of obtaining a group of semiconductor chips with a film-like adhesive in a state where a plurality of the semiconductor chips with a film-like adhesive are aligned on the intermediate layer.
Examples thereof include a step of pulling the semiconductor chip with a film-like adhesive away from the intermediate layer and picking it up (in the present specification, it may be referred to as "manufacturing method 1").

4A, 4B, and 4C are cross-sectional views for schematically explaining an example of a method for manufacturing a semiconductor chip, which is a target for using a sheet for manufacturing a semiconductor device, and is a cross-sectional view for forming a modified layer on a semiconductor wafer. The case where a semiconductor chip is manufactured by performing dicing with the above is shown.
5A, 5B, and 5C are cross-sectional views for schematically explaining another example of a method for manufacturing a semiconductor chip with a film-like adhesive, in which a semiconductor device manufacturing sheet is attached to the semiconductor chip. It shows the manufacturing method when it is used from. In this method, a semiconductor device manufacturing sheet is used as a die bonding sheet. Here, the semiconductor device manufacturing sheet 101 shown in FIG. 1 will be taken as an example, and a method of using the sheet 101 will be described.

First, prior to the use of the semiconductor device manufacturing sheet 101, as shown in FIG. 4A, a semiconductor wafer 9'is prepared, and a back grind tape (sometimes referred to as "surface protection tape") is provided on the circuit forming surface 9a'. ) Attach 8.
In Figure 4A, reference numeral W _{9 ',} the semiconductor wafer 9' indicates the width of the.

Next, by irradiating a laser beam (not shown) so as to focus on the focal point set inside the semiconductor wafer 9', the modified layer 90' is inside the semiconductor wafer 9'as shown in FIG. 4B. To form.
It is preferable that the laser beam irradiates the semiconductor wafer 9'from the back surface 9b' side of the semiconductor wafer 9'.

The focal position at this time is the planned division (dicing) position of the semiconductor wafer 9', and is set so that the desired size, shape, and number of semiconductor chips can be obtained from the semiconductor wafer 9'.

Next, the back surface 9b'of the semiconductor wafer 9'is ground using a grinder (not shown). As a result, the thickness of the semiconductor wafer 9'is adjusted to the desired value, and by utilizing the grinding force applied to the semiconductor wafer 9'at this time, the thickness of the modified layer 90'is formed at the site where the modified layer 90'is formed. The semiconductor wafer 9'is divided to produce a plurality of semiconductor chips 9 as shown in FIG. 4C.

Unlike other parts of the semiconductor wafer 9', the modified layer 90'of the semiconductor wafer 9'has been altered by irradiation with laser light, and its strength is weakened. Therefore, by applying a force to the semiconductor wafer 9'on which the modified layer 90'is formed, the force is applied to the modified layer 90', and the semiconductor wafer 9'is cracked at the portion of the modified layer 90', and the semiconductor wafer 9'is cracked. A plurality of semiconductor chips 9 can be obtained.

From the above, the semiconductor chip 9 to be used for the semiconductor device manufacturing sheet 101 can be obtained. More specifically, by this step, a semiconductor chip group 901 in a state in which a plurality of semiconductor chips 9 are aligned and fixed on the back grind tape 8 is obtained.

When the semiconductor chip group 901 is viewed in a plan view from above, a planar shape formed by connecting the outermost parts of the semiconductor chip group 901 (in the present specification, such a planar shape is simply referred to as "semiconductor". The planar shape of the chip group) is exactly the same as the planar shape when the semiconductor wafer 9'is similarly viewed in a planar view, or the differences between these planar shapes are negligible. It can be said that the planar shape of the semiconductor chip group 901 is substantially the same as the planar shape of the semiconductor wafer 9'.
Therefore, the width of the planar shape of the semiconductor chip group 901, as shown in FIG. 4C,做cause appears to be the same as 'the width W _{9 of'} the semiconductor wafer 9. Then, the maximum value of the width of the planar shape of the semiconductor chip group 901,做causes appear to be the same as the maximum value of the 'width W _{9 of'} the semiconductor wafer 9.

Here, the case where the semiconductor chip 9 can be manufactured from the semiconductor wafer 9'as intended is shown, but depending on the conditions at the time of grinding the back surface 9b'of the semiconductor wafer 9', a part of the semiconductor wafer 9'. In this region, the semiconductor chip 9 may not be divided.

Next, the semiconductor chip 9 (semiconductor chip group 901) obtained above is used to manufacture a semiconductor chip with a film-like adhesive.
First, as shown in FIG. 5A, while heating one sheet 101 for manufacturing a semiconductor device in a state where the release film 15 is removed, the film-like adhesive 14 in the sheet is applied to all the sheets in the semiconductor chip group 901. It is attached to the back surface 9b of the semiconductor chip 9. The target of the film-like adhesive 14 at this time may be a semiconductor wafer that is not completely divided.

_{The maximum value of the width W 13} of the intermediate layer 13 and the maximum value of the width W ₁₄ of the film-like adhesive 14 in the semiconductor device manufacturing sheet 101 are both the width W 9'of the semiconductor wafer _9' (in other words, the width W 9'(in other words,). It is preferable that it is exactly the same as or not the same as the maximum value of the semiconductor chip group 901), but the error is slight and almost the same.

In other words, the maximum value of the width W ₁₃ of the intermediate layer 13, and the maximum width of the semiconductor chip group 901, the relationship between the maximum value of the width W ₁₃ of the intermediate layer 13 described above, the semiconductor wafer 9 ' It may be the same as the relationship with the maximum value of the width W _9'. The relationship between the maximum value of the width W 14 of the film-like adhesive _{14 and} the maximum value of the width of the semiconductor chip group 901 is the maximum value of the width W ₁₄ of the film-like adhesive 14 described above and the semiconductor. and the maximum value of the 'width W _{9 of'} wafer 9 may be the same as the relationship.

At this time, the film-like adhesive 14 (semiconductor device manufacturing sheet 101) is attached to the semiconductor chip group 901 according to the manufacturing method 1 except that the semiconductor chip group 901 is used instead of the semiconductor wafer 9'. It can be carried out in the same manner as in the case of attaching the film-like adhesive 14 (semiconductor device manufacturing sheet 101) to the semiconductor wafer 9'.

Next, the back grind tape 8 is removed from the semiconductor chip group 901 in the fixed state. Then, as shown in FIG. 5B, while cooling the semiconductor device manufacturing sheet 101 (film-like adhesive 14), in a direction parallel to the surface (for example, the first surface 12a of the pressure-sensitive adhesive layer 12). Expand by stretching. Here, an expanding direction of the semiconductor device producing sheet 101 in the arrow E _1. By expanding in this way, the film-like adhesive 14 is cut along the outer circumference of the semiconductor chip 9.

By this step, a plurality of semiconductor chips 914 with a film-like adhesive including the semiconductor chip 9 and the film-like adhesive 140 after cutting provided on the back surface 9b thereof are obtained. The semiconductor chips 914 with a film-like adhesive are aligned and fixed on the intermediate layer 13 in the laminated sheet 10, and constitute the semiconductor chip group 910 with a film-like adhesive.
The semiconductor chip 914 with a film-like adhesive and the semiconductor chip group 910 with a film-like adhesive obtained here are both the semiconductor chip 914 with a film-like adhesive and the film-like adhesive obtained by the manufacturing method 1 described above. It is substantially the same as the agent-containing semiconductor chip group 910.

As described above, when the semiconductor wafer 9'is divided, if the semiconductor wafer 9'is not divided into the semiconductor chip 9 in a part of the region, this region can be obtained by performing this step. It is divided into semiconductor chips.

The semiconductor device manufacturing sheet 101 (film-like adhesive 14) is preferably expanded at a temperature of −5 to 5 ° C. By cooling and expanding the semiconductor device manufacturing sheet 101 in this way (performing cool expansion), the film-like adhesive 14 can be cut more easily and with high accuracy.

The expansion of the semiconductor device manufacturing sheet 101 (film-like adhesive) can be performed by a known method. For example, in the first surface 12a of the pressure-sensitive adhesive layer 12 in the semiconductor device manufacturing sheet 101, a region (the non-laminated region) near the peripheral edge portion where the intermediate layer 13 and the film-like adhesive 14 are not laminated is set as a ring. After fixing to a jig (not shown) such as a frame, the entire region where the intermediate layer 13 and the film-like adhesive 14 of the semiconductor device manufacturing sheet 101 are laminated is directed from the base material 11 to the pressure-sensitive adhesive layer 12. By pushing up from the base material 11 side, the semiconductor device manufacturing sheet 101 can be expanded.

In FIG. 5B, of the first surface 12a of the pressure-sensitive adhesive layer 12, the non-laminated region in which the intermediate layer 13 and the film-like adhesive 14 are not laminated is substantially parallel to the first surface 13a of the intermediate layer 13. However, as described above, in the state of being expanded by pushing up the semiconductor device manufacturing sheet 101, the non-laminated region is different from the above-mentioned pushing direction as it approaches the outer periphery of the pressure-sensitive adhesive layer 12. Includes an inclined surface whose height descends in the opposite direction.

In this step, the semiconductor device manufacturing sheet 101 is provided with the intermediate layer 13 (in other words, the film-like adhesive 14 before cutting is provided on the intermediate layer 13), so that the film-like adhesive 14 is formed. It can be accurately cut at a target location (in other words, along the outer periphery of the semiconductor chip 9), and cutting defects can be suppressed.

After the expansion, as shown in FIG. 5C, the semiconductor chip 914 with the film-like adhesive is separated from the intermediate layer 13 in the laminated sheet 10 and picked up.
The pickup at this time can be performed by the same method as the pickup in the manufacturing method 1 described above, and the pickup suitability is also the same as the pickup suitability in the manufacturing method 1.

For example, also in this step, when the ratio of the silicon concentration on the first surface 13a of the intermediate layer 13 is 1 to 20%, the semiconductor chip 914 with a film-like adhesive can be picked up more easily.
Further, the intermediate layer 13 contains, for example, the ethylene-vinyl acetate copolymer which is the non-silicon resin and the siloxane compound which is the additive, and is ethylene with respect to the total mass of the intermediate layer in the intermediate layer. The ratio of the content of the vinyl acetate copolymer is 90 to 99.99% by mass, and the ratio of the content of the siloxane compound to the total mass of the intermediate layer in the intermediate layer is 0.01 to 10% by mass. When it is%, the semiconductor chip 914 with a film-like adhesive can be picked up more easily.

In the method for manufacturing a semiconductor chip with a film-like adhesive described so far, a preferred embodiment is, for example, a method for manufacturing a semiconductor chip with a film-like adhesive using a sheet for manufacturing a semiconductor device.
The semiconductor chip with a film-like adhesive includes a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip.
The sheet for manufacturing a semiconductor device includes a base material, an adhesive layer, an intermediate layer, and a film-like adhesive.
The pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material.
The intermediate layer contains a non-silicon resin (β1) having a weight average molecular weight of 20,000 to 100,000 as a main component.
Further, at least, the film-like adhesive contains the component (α2), or the pressure-sensitive adhesive layer contains the component (γ2).
The component (α2) is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive.
The component (γ2) is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer.
Let H (β) be the haze of the film-like test piece having a thickness of 10 μm made of the non-silicon resin (β1).
When the film-like adhesive contains the component (α2), the thickness is 10 μm composed of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (α2). When the haze of the film-like second test piece is H (βα), the H (βα) and H (β) are expressed by the following formula (X1):
(X1) H (βα) -H (β)> 7%
The filling,
When the pressure-sensitive adhesive layer contains the component (γ2), the thickness is 10 μm, which is a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (γ2). When the haze of the film-like third test piece is H (βγ), the H (βγ) and H (β) are expressed by the following formula (X2):
(X2) H (βγ) -H (β)> 7%
The filling,
The manufacturing method includes a step of forming a modified layer inside the semiconductor wafer by irradiating a laser beam so as to focus on a focal point set inside the semiconductor wafer.
By grinding the back surface of the semiconductor wafer after forming the modified layer and utilizing the grinding force applied to the semiconductor wafer, the semiconductor wafer is divided at the formation site of the modified layer. A step of obtaining a semiconductor chip group in which a plurality of the semiconductor chips are aligned, and
A step of attaching the film-like adhesive in the sheet for manufacturing a semiconductor device to the back surface of all the semiconductor chips in the semiconductor chip group while heating the sheet.
The film-like adhesive is cut along the outer periphery of the semiconductor chip by stretching the sheet for manufacturing the semiconductor device after being attached to the semiconductor chip in a direction parallel to the surface thereof while cooling. A step of obtaining a group of semiconductor chips with a film-like adhesive in a state where a plurality of the semiconductor chips with a film-like adhesive are aligned on the intermediate layer.
Examples thereof include a step of pulling the semiconductor chip with a film-like adhesive away from the intermediate layer and picking it up (in the present specification, it may be referred to as "manufacturing method 2").

Up to this point, in both the manufacturing method 1 and the manufacturing method 2, the manufacturing method of the semiconductor chip with a film-like adhesive has been described by taking as an example the case where the semiconductor device manufacturing sheet 101 shown in FIG. 1 is used. However, when the other semiconductor device manufacturing sheet according to the present embodiment is used, the semiconductor chip with a film-like adhesive can be similarly manufactured. In that case, if necessary, other steps are appropriately added based on the difference in configuration between the semiconductor device manufacturing sheet and the semiconductor device manufacturing sheet 101 to obtain a semiconductor chip with a film-like adhesive. It may be manufactured.

Not limited to the cases of the manufacturing method 1 and the manufacturing method 2, after obtaining the film-shaped adhesive-attached semiconductor chip group, before picking up the film-shaped adhesive-attached semiconductor chip, the laminated sheet is subjected to the pressure-sensitive adhesive. The semiconductor chip with a film-like adhesive (film-like adhesive) among the laminated sheets is expanded in a direction parallel to the surface (first surface) of the layer on the intermediate layer side, and while maintaining this state. The peripheral portion on which the attached semiconductor chip group) is not mounted may be heated.
By doing so, the distance between adjacent semiconductor chips, that is, the calf width can be maintained with sufficiently wide and high uniformity on the laminated sheet while shrinking the peripheral edge portion. Then, the semiconductor chip with the film-like adhesive can be picked up more easily.

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.

<< Raw materials for manufacturing adhesive compositions >>
The raw materials used in the production of the adhesive composition are shown below.
[Polymer component (a)]
(A) -1: An acrylic resin obtained by copolymerizing methyl acrylate (95 parts by mass) and -2-hydroxyethyl acrylate (5 parts by mass) (weight average molecular weight 800,000, glass transition temperature 9 ° C.).
[Epoxy resin (b1)]
(B1) -1: Bisphenol A type epoxy resin liquid at 23 ° C (“jER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 to 194 g / eq, number average molecular weight 370, viscosity 120 to 150 P (12 to 15 Pa. s)))
[Thermosetting agent (b2)]
(B2) -1: Aralkyl type phenol resin (“Millex XLC-4L” manufactured by Mitsui Chemicals, Inc., number average molecular weight 1100, softening point 63 ° C.)
[Filler (d)]
(D) -1: Spherical silica ("YA050C-MJE" manufactured by Admatex, average particle size 50 nm, methacrylic silane treated product)
[Coupling agent (e)]
(E) -1: Silane coupling agent, 3-glycidoxypropylmethyldiethoxysilane ("KBE-402" manufactured by Shinetsu Silicone Co., Ltd.)
[Crosslinking agent (f)]
(F) -1: Tolylene diisocyanate cross-linking agent ("Coronate L" manufactured by Tosoh Corporation)

[Example 1]
<< Manufacturing of Sheets for Manufacturing Semiconductor Devices >>
<Manufacturing of base material>
By melting low-density polyethylene (LDPE, "Sumikasen L705" manufactured by Sumitomo Chemical Co., Ltd.) using an extruder, extruding the melt by the T-die method, and stretching the extruded product in two shafts using a cooling roll. A substrate made of LDPE (thickness 110 μm) was obtained.

<Preparation of adhesive layer>
Acrylic resin (“Olivine BPS 6637X” manufactured by Toyochem Co., Ltd.) (100 parts by mass) is contained as the adhesive resin (I-1a), and a cross-linking agent (“BXX 5640” manufactured by Toyo-Chem Co., Ltd., xylylene diisocyanate-based cross-linking agent) (1). A non-energy ray-curable pressure-sensitive adhesive composition containing (3 parts by mass) of an amine-based ionic liquid (“IL-A2” manufactured by Koei Chemical Industry Co., Ltd.) (3 parts by mass) that is liquid at 23 ° C. as an antioxidant. Manufactured a thing.

Next, a release film in which one side of the polyethylene terephthalate film was peeled by a silicone treatment was used, and the pressure-sensitive adhesive composition obtained above was applied to the peeled surface and dried by heating at 100 ° C. for 2 minutes. A non-energy ray-curable pressure-sensitive adhesive layer (thickness 10 μm) was prepared by allowing the adhesive layer to be formed.

<Preparation of intermediate layer>
At room temperature, an ethylene-vinyl acetate copolymer (EVA, weight average molecular weight of 30,000, content of a structural unit derived from vinyl acetate of 25% by mass) (15 g) was dissolved in 85 g of tetrahydrofuran, and siloxane was added to the obtained solution. System compounds (polydimethylsiloxane, "BYK-333" manufactured by Big Chemie Japan Co., Ltd., and the number of structural units represented by _{the formula "-Si (-CH 3} ) _{2-O-" in one molecule is 45 to 230) (} 1.5 g) was added and stirred to prepare a composition for forming an intermediate layer.

Using a release film in which one side of a polyethylene terephthalate film has been peeled off by a silicone treatment, the peeling-treated surface is coated with the composition for forming an intermediate layer obtained above, and dried by heating at 70 ° C. for 5 minutes. An intermediate layer (thickness 20 μm) was prepared by allowing the mixture to be formed.

<Making a film-like adhesive>
Polymer component (a) -1 (100 parts by mass), epoxy resin (b1) -1 (10 parts by mass), thermosetting agent (b2) -1 (1.5 parts by mass), filler (d) -1 A thermosetting adhesive composition containing (75 parts by mass), a coupling agent (e) -1 (0.5 parts by mass), and a cross-linking agent (f) -1 (0.5 parts by mass) is produced. bottom. The contents shown here are all the contents of the target product containing no solvent.

Next, a release film in which one side of the polyethylene terephthalate film was peeled by a silicone treatment was used, and the adhesive composition obtained above was applied to the peeled surface and dried by heating at 80 ° C. for 2 minutes. A thermosetting film-like adhesive (thickness 7 μm) was produced by allowing the adhesive to be formed.

<Manufacturing of sheets for manufacturing semiconductor devices>
By bonding the exposed surface of the pressure-sensitive adhesive layer obtained above on the side opposite to the side provided with the release film to one surface of the base material obtained above, the first intermediate with the release film is attached. A laminate (in other words, a support sheet with a release film) was produced.
The exposed surface of the film-like adhesive obtained above on the side opposite to the side with the release film, and the exposed surface of the intermediate layer obtained above on the side opposite to the side with the release film. A second intermediate laminate with a release film (a release film, an intermediate layer, a film-like adhesive, and a laminate of release films) was produced.

Next, the second intermediate laminate with the release film is punched from the release film on the intermediate layer side to the film-like adhesive using a cutting blade to remove unnecessary parts, thereby forming a film-like bond. On the release film on the agent side, a film-like adhesive (thickness 7 μm) having a circular planar shape (diameter 305 mm), an intermediate layer (thickness 20 μm), and a release film are laminated in this order in these thickness directions. A second intermediate laminated body processed product with a release film was prepared.

Next, the release film was removed from the first intermediate laminate with the release film obtained above to expose one surface of the pressure-sensitive adhesive layer.
Further, the circular release film was removed from the second intermediate laminate work piece with the release film obtained above to expose one surface of the intermediate layer.
Next, the newly generated exposed surface of the pressure-sensitive adhesive layer in the first intermediate laminate and the newly generated exposed surface of the intermediate layer in the second intermediate laminate processed product were bonded together. With respect to the base material and the pressure-sensitive adhesive layer (that is, the support sheet) in the laminate thus obtained, the planar shape of these (support sheets) is circular (diameter 370 mm), and the circular film-like adhesive and the intermediate. An unnecessary portion was removed by punching from the base material side using a cutting blade (diameter 370 mm) so as to be concentric with the layer (diameter 305 mm).
As described above, the base material (thickness 110 μm), the pressure-sensitive adhesive layer (thickness 10 μm), the intermediate layer (thickness 20 μm), the film-like adhesive (thickness 7 μm), and the release film are formed in this order in these thickness directions. A sheet for manufacturing a semiconductor device with a release film, which was formed by laminating, was obtained.

<< Evaluation of semiconductor device manufacturing sheets >>
<Measurement of H (β)>
Ethylene-vinyl acetate is coated on the peel-treated surface of the release film (Lintec's "SP-PET381031") with a liquid material containing the ethylene-vinyl acetate copolymer (composition for the first test) and dried to obtain ethylene-acetic acid. A film-like first test piece having a thickness of 10 μm made of a vinyl copolymer was prepared.
Using a haze meter (“NDH7000” manufactured by Nippon Denshoku Kogyo Co., Ltd.), the haze (H (β)) (%) of the first test piece from the exposed surface side in accordance with JIS K 7136: 2000. Was measured. The results are shown in Table 1.

<Measurement of H (βα), calculation of H (βα) -H (β)>
A liquid material (composition for the second test) containing the ethylene-vinyl acetate copolymer and the epoxy resin (b1) -1 and uniformly mixed with the epoxy resin (b1) -1 is used as a release film (Lintec Corporation "SP-PET38131"". ) Is coated on the peeled surface and dried to form a film having a thickness of 10 μm composed of a mixture of an ethylene-vinyl acetate copolymer (100 parts by mass) and an epoxy resin (b1) -1 (10 parts by mass). The second test piece of was prepared.
For this second test piece, haze (H (βα)) (%) was measured by the same method as in the case of the first test piece described above. Then, H (βα) −H (β) (%) was calculated from the obtained measured values. The results are shown in Table 1.

<Measurement of H (βγ), calculation of H (βγ) -H (β)>
A liquid material (composition for a third test) containing the ethylene-vinyl acetate copolymer and the amine-based ionic liquid (IL-A2) and in which these are uniformly mixed is formed into a release film ("SP" manufactured by Lintec Corporation. -PET381031 ") is coated on the peeled surface and dried to form a 10 μm-thick film composed of a mixture of an ethylene-vinyl acetate copolymer (100 parts by mass) and the amine-based ionic liquid (10 parts by mass). A third test piece in the shape of a shape was prepared.
For this third test piece, haze (H (βγ)) (%) was measured by the same method as in the case of the first test piece described above. Then, H (βγ) −H (β) (%) was calculated from the obtained measured values. The results are shown in Table 1.

<Measurement of pick-up force of silicon chip with film adhesive without aging>
[Manufacturing of silicon chips with film-like adhesive]
Using a dicing device (Disco "DFD6361") and a dicing blade (Disco "ZH05-SD2000-NI-90-BB"), the blade rotation speed is 50,000 rpm and the blade movement speed is 25 mm / sec. , So-called half-cutting was performed to form a notch from one surface of a silicon wafer (diameter 150 mm, thickness 350 μm) to a depth of 75 μm. This half-cut was performed so that a silicon chip having a size of 5 mm × 5 mm was finally obtained.
Next, a back grind tape (“AdwillE-3100TN” manufactured by Lintec Corporation) was attached to the half-cut surface of the silicon wafer. Then, using a back grind device (“DGP8761” manufactured by DISCO Corporation), the exposed surface of the silicon wafer to which the back grind tape is not attached is ground until the thickness of the silicon wafer reaches 30 μm. To prepare a large number of silicon chips (thickness 30 μm) having a size of 5 mm × 5 mm (in the present specification, such a size may be referred to as “5 mm □”). As a result, a group of silicon chips in a state in which a large number of silicon chips were aligned and fixed on the back grind tape was obtained.

Next, the release film was removed from the above-mentioned sheet for manufacturing a semiconductor device that had not been aged. Then, using a tape mounter (“Adwill RAD2700” manufactured by Lintec Corporation), while heating this semiconductor device manufacturing sheet to 60 ° C., all of the above silicon chips in the above silicon chip group are subjected to the film-like adhesive in the sheet. It was attached to the exposed surface of the silicon chip. In addition, the back grind tape was then removed from all silicon chips. As a result, a laminate (the laminated sheet and the film-like adhesive) formed by laminating the base material, the pressure-sensitive adhesive layer, the intermediate layer, the film-like adhesive, and the silicon chip group in this order in the thickness direction thereof. , The silicon chip group and the silicon chip group were laminated in this order in these thickness directions to obtain a laminated product).

Then, using an expander (“DDS2300” manufactured by Disco Corporation), the film-like adhesive was cut by expanding in the following procedure. That is, first, the laminate was placed on the table. At this time, the base material in the laminate was brought into contact with the table. Next, the laminate was adsorbed on the table and fixed, and the table was pushed up under the conditions of an expansion speed of 100 mm / s and an expansion amount of 10 mm under the condition of 0 ° C. to bring the laminate to the surface thereof. Expanded in parallel directions. As a result, the film-like adhesive was cut.
Next, the adsorption and expansion of the laminate were released, and the region near the outer peripheral portion of the film-like adhesive in the laminate was heated to eliminate the slack of the film-like adhesive in the region.
As described above, a large number of silicon chips with a film-like adhesive comprising a silicon chip and a film-like adhesive after cutting provided on the back surface thereof are formed in the laminated sheet by the film-like adhesive in the silicon chip. A group of silicon chips with a film-like adhesive was obtained in a state of being aligned and fixed on the intermediate layer.

[Measurement of pick-up force of silicon chip with film adhesive without aging]
Next, using a pickup device (“PU100” manufactured by Fasford Technology Co., Ltd., number of pins 5), in the silicon chip group with the film-like adhesive obtained above under the conditions of a push-up height of 250 μm and an expansion amount of 4 mm, the silicon chip group with the film-like adhesive obtained above was used. A silicon chip with a film-like adhesive was picked up, and the pick-up force at that time was measured. The pick-up force was measured at 30 points, and the average value of those measured values was adopted as the timeless pick-up force (mN / 5 mm □) of the silicon chip with a film-like adhesive. The results are shown in Table 1.

<Measurement of pickup force of silicon chips with film-like adhesive over time>
The semiconductor device manufacturing sheet obtained above was allowed to stand in an environment of 40 ° C. for 1 week and allowed to age.
Then, the film-like adhesion is performed by the same method as in the above-mentioned measurement of the non-aged pickup force, except that the semiconductor device manufacturing sheet with aged time is used instead of the above-mentioned semiconductor device manufacturing sheet that has not been aged. The pick-up force of the silicone chip with the agent over time was measured. The results are shown in Table 1.

<Measurement of surface resistivity of film-like adhesive without aging>
In the semiconductor device manufacturing sheet obtained above, the release film is removed, and the entire exposed surface of the film-like adhesive produced thereby is covered with an adhesive tape having a polyethylene terephthalate layer (Lintec Corporation "PET50 (A) PL Thin". It was attached to the adhesive surface of "8LK"). Then, the obtained product was cut into a size of 100 mm × 100 mm, and the laminate of the adhesive tape and the film-like adhesive was peeled from the intermediate layer to obtain a test piece. After adjusting the humidity of this test piece by allowing it to stand for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, the surface resistivity of the exposed surface (the surface on the intermediate layer side) of the film-like adhesive was determined. It was measured. The surface resistivity was measured using DIGITAL ELECTROMETER (manufactured by ADVANTEST) with the applied voltage as 100V. The results are shown in Table 1.

<Measurement of surface resistivity of film adhesive over time>
The semiconductor device manufacturing sheet obtained above was allowed to stand in an environment of 40 ° C. for 1 week and allowed to age.
Then, in place of the above-mentioned semiconductor device manufacturing sheet that has not been aged, the film-like sheet is used in the same manner as in the above-mentioned measurement of the non-aging surface resistivity, except that this aged semiconductor device manufacturing sheet is used. The surface resistivity of the adhesive over time was measured. The results are shown in Table 1.

<Calculation of the ratio of silicon concentration on the surface of the intermediate layer on the film-like adhesive side>
In the manufacturing process of the above-mentioned semiconductor device manufacturing sheet, the exposed surface of the intermediate layer in the stage before bonding with the pressure-sensitive adhesive layer is analyzed by XPS, and carbon (C), oxygen (O), nitrogen (N) and The concentration of silicon (Si) (atomic%) was measured, and the ratio (%) of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen and silicon was determined from the measured value.
The XPS analysis was performed using an X-ray photoelectron spectroscopy analyzer (“Quantra SXM” manufactured by ULVAC, Inc.) under the conditions of an irradiation angle of 45 °, an X-ray beam diameter of 20 μmφ, and an output of 4.5 W. The results are shown in the column of "Percentage of element concentration in the intermediate layer (%)" in Table 1 together with the ratio (%) of the concentration of other elements.

<Evaluation of the effect of suppressing the generation of cutting chips during blade dicing>
[Manufacturing of silicon chips with film-like adhesive]
In the semiconductor device manufacturing sheet obtained above, the release film was removed.
A silicon wafer (diameter 300 mm, thickness 75 μm) whose back surface is ground with a dry polish finish is used, and a tape mounter (“Adwill RAD2500” manufactured by Lintec Corporation) is used on the back surface (ground surface) for manufacturing the above-mentioned semiconductor device. The sheet was attached with the film-like adhesive while heating at 60 ° C. As a result, a laminate formed by laminating a base material, an adhesive layer, an intermediate layer, a film-like adhesive, and a silicon wafer in this order in the thickness direction thereof (the laminated sheet, the film-like adhesive, and the like). A laminate composed of silicon wafers and silicon wafers laminated in this order in these thickness directions) was obtained.

Next, of the first surface of the pressure-sensitive adhesive layer in the laminate, a region near the peripheral edge portion where the intermediate layer was not provided (the non-laminated region) was fixed to the wafer dicing ring frame.
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. In the dicing at this time, the rotation speed of the blade is set to 30,000 rpm, the moving speed of the blade is set to 30 mm / sec, and the film-like adhesive is applied to the sheet for manufacturing the semiconductor device from the surface to which the silicon wafer is attached, in the middle of the intermediate layer. This was done by cutting with a blade to the region (that is, the entire region of the film adhesive in the thickness direction and the region of the intermediate layer from the surface of the film adhesive side to the middle region). As the blade, "Z05-SD2000-D1-90 CC" manufactured by DISCO was used.
As described above, a large number of silicon chips with a film-like adhesive comprising a silicon chip and a film-like adhesive after cutting provided on the back surface thereof are formed in the laminated sheet by the film-like adhesive in the silicon chip. A group of silicon chips with a film-like adhesive was obtained in a state of being aligned and fixed on the intermediate layer.

[Evaluation of the effect of suppressing the generation of cutting chips]
Using a digital microscope (“VH-Z100” manufactured by KEYENCE CORPORATION), the group of silicon chips with a film-like adhesive obtained above was observed from above on the silicon chip side to confirm the presence or absence of cutting chips. .. Then, when no cutting chips were generated, it was determined as "A", and when even a small amount of cutting chips were generated, it was determined as "B". The results are shown in Table 1.

<Evaluation of the cutability of the film-like adhesive during expansion>
[Manufacturing of silicon chips with film-like adhesive]
A silicon wafer having a circular planar shape, a diameter of 300 mm, and a thickness of 775 μm was used, and a back grind tape (“Adwill E-3100TN” manufactured by Lintec Corporation) was attached to one surface of the silicon wafer.
Next, a modified layer is formed inside the silicon wafer by irradiating the silicon wafer with laser light so as to focus on the focal point set inside the silicon wafer by using a laser light irradiation device (“DFL73161” manufactured by DISCO Corporation). Formed. At this time, the focal point was set so that a large number of silicon chips having a size of 8 mm × 8 mm could be obtained from the silicon wafer. Further, the laser beam was applied to the silicon wafer from the other side (the side to which the back grind tape was not attached).
Next, the other surface of the silicon wafer is ground using a grinder to reduce the thickness of the silicon wafer to 30 μm, and the force applied to the silicon wafer at this time during grinding is used to improve the thickness of the silicon wafer. A silicon wafer was divided at a site where a layer was formed to prepare a plurality of silicon chips. As a result, a group of silicon chips in a state in which a plurality of silicon chips were aligned and fixed on the back grind tape was obtained.

Next, using a tape mounter (“Adwill RAD2500” manufactured by Lintec Corporation), while heating the one sheet for manufacturing a semiconductor device obtained above to 60 ° C., the film-like adhesive in the sheet was applied to all the above. It was attached to the other surface (in other words, the ground surface) of the silicon chip (silicon chip group).
Next, of the first surface of the pressure-sensitive adhesive layer in the semiconductor device manufacturing sheet after being attached to the silicon chip group, a region near the peripheral edge portion where the intermediate layer is not provided (the non-laminated region) is used for wafer dicing. Fixed to the ring frame.

Then, the back grind tape was removed from this group of fixed silicon chips. Then, using a fully automatic die separator ("DDS2300" manufactured by DISCO), the sheet (film-like adhesive) for manufacturing a semiconductor device is cooled in an environment of 0 ° C. in a direction parallel to the surface thereof. By expanding, the film-like adhesive was cut along the outer circumference of the silicon chip. At this time, by fixing the peripheral edge of the semiconductor device manufacturing sheet and pushing up the entire region where the intermediate layer of the semiconductor device manufacturing sheet and the film-like adhesive are laminated by a height of 15 mm from the base material side. , Expanded.
As a result, a plurality of silicon chips with a film-like adhesive provided with the silicon chip and the film-like adhesive after cutting provided on the other surface (ground surface) thereof are aligned on the intermediate layer. A group of silicon chips with a film-like adhesive was obtained in a fixed state.

Next, after the expansion of the above-mentioned semiconductor device manufacturing sheet is once released, a laminate (that is, the laminated sheet) formed by laminating a base material, an adhesive layer, and an intermediate layer at room temperature is subjected to an adhesive. Expanded in a direction parallel to the first surface of the layer. Further, while maintaining this expanded state, the peripheral portion of the laminated sheet on which the silicon chip with a film-like adhesive was not placed was heated. As a result, the calf width between the adjacent silicon chips was maintained at a certain value or more on the laminated sheet while contracting the peripheral portion.

[Evaluation of cutability of film adhesive]
At the time of manufacturing the above-mentioned film-like adhesive-attached silicon chip group, a digital microscope (“VH-Z100” manufactured by KEYENCE CORPORATION) was used to obtain the above-mentioned film-like adhesive-attached silicon chip group on the silicon chip side. Observed from above. Then, by expanding the sheet (film-like adhesive) for manufacturing a semiconductor device, a plurality of film-like adhesives extending in one direction, which should have been formed on the assumption that the film-like adhesive was cut normally, Of the cutting lines and the cutting lines of a plurality of film-like adhesives extending in a direction orthogonal to this direction, the number of cutting lines that are not actually formed and the cutting lines that are incompletely formed. Was confirmed, and the cutability of the film-like adhesive was evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
A: The total number of cutting lines of the film-like adhesive that is not actually formed and the cutting lines of the film-like adhesive that is incompletely formed is 5 or less.
B: The total number of cutting lines of the film-like adhesive that is not actually formed and the cutting lines of the film-like adhesive that is incompletely formed is 6 or more.

<Evaluation of pick-up property of silicon chip with film adhesive after expansion>
After the evaluation of the cutability of the film-like adhesive described above, the silicon chips with the film-like adhesive and the die bonding device (“PU100” manufactured by Fasford Technology Co., Ltd.) were subsequently used to make a rise height of 250 μm and a rise. A silicon chip with a film-like adhesive was picked up from the intermediate layer in the laminated sheet under the condition of a speed of 5 mm / s. Then, if all the silicon chips with film-like adhesive can be picked up normally under the condition of the rise time of 500 ms, it is evaluated as "A", and under the condition of the rise time of 500 ms, one or more film-like adhesives are adhered. Although the silicon chip with the agent cannot be picked up normally, if all the silicon chips with the film-like adhesive can be picked up normally under the condition of the rise time of 10 s, it is evaluated as "B", and even under the condition of the rise time of 10 s. When one or more silicon chips with a film-like adhesive could not be picked up normally, it was evaluated as "C". The results are shown in Table 1.

<Measurement of T-shaped peel strength between the intermediate layer and the film-like adhesive>
In the semiconductor device manufacturing sheet obtained above, the release film was removed.
The entire exposed surface of the film-like adhesive in the semiconductor device manufacturing sheet, which is generated by this, is bonded to the adhesive surface of an adhesive tape having a polyethylene terephthalate layer (Lintec Corporation "PET50 (A) PL Thin 8LK"). , The obtained laminate was cut into a size of 50 mm × 100 mm to prepare a test piece.
In this test piece, the laminate of the base material, the adhesive layer and the intermediate layer (that is, the laminated sheet) and the laminate of the film-like adhesive and the adhesive tape are peeled off in accordance with JIS K6854-3. The test piece was peeled into a T shape, and the maximum value of the peeling force (mN / 50 mm) measured at this time was adopted as the T-shaped peeling strength. At this time, the peeling speed was set to 50 mm / min. The results are shown in Table 1.

<< Manufacturing and evaluation of sheets for manufacturing semiconductor devices >>
[Example 2]
When the composition for forming the intermediate layer was prepared, the siloxane compound was not added, and the amount of the ethylene-vinyl acetate copolymer used was 16.5 g instead of 15 g (in other words, the siloxane compound was used as the siloxane compound. A sheet for manufacturing a semiconductor device was produced by the same method as in Example 1 except that the ethylene-vinyl acetate copolymer having the same mass was replaced with the ethylene-vinyl acetate copolymer and only the ethylene-vinyl acetate copolymer was dissolved in tetrahydrofuran). ,evaluated. The results are shown in Table 1. The description of "-" in the additive column in Table 1 means that this additive is unused.

[Example 3]
At the time of preparing the composition for forming the intermediate layer, instead of the ethylene-vinyl acetate copolymer, the ethylene-vinyl acetate copolymer having the same mass (EVA, weight average molecular weight 30,000, content of the structural unit derived from vinyl acetate 40) A sheet for manufacturing a semiconductor device was manufactured and evaluated by the same method as in Example 2 except that (% by mass) was used. The results are shown in Table 1.

[Comparative Example 1]
At room temperature, an acrylic resin (acrylic copolymer) dispersion (Nippon Polyurethane Industry Co., Ltd. "Corponil N2359-6, solid content concentration 34%" (100 parts by mass) and a polyvalent isocyanate compound (Nippon Polyurethane Industry Co., Ltd.) A composition for forming an intermediate layer for comparison was prepared by blending "Coronate L" (made in Japan) with a solid content concentration of 75% (10 parts by mass) and stirring.
Then, a sheet for manufacturing a semiconductor device for comparison is prepared in the same manner as in Example 1 except that the composition for forming an intermediate layer for comparison is used instead of the composition for forming an intermediate layer described above. Manufactured and evaluated. The results are shown in Table 1.

[Comparative Example 2]
A sheet for manufacturing a semiconductor device for comparison was manufactured by the same method as in Example 1 except that the intermediate layer was not manufactured. More specifically, in the manufacturing process of the above-mentioned sheet for manufacturing a semiconductor device in Example 1, the exposed surface of the film-like adhesive provided with the release film is the exposed surface of the intermediate layer provided with the release film. Instead of the second intermediate laminate with the release film, a laminate of the release film, the film-like adhesive, and the release film is produced by laminating with the release-treated surface of the release film. A sheet for manufacturing a semiconductor device for comparison was manufactured by the same method as in the case of Example 1 except that the above was used.
Then, the semiconductor device manufacturing sheet for comparison was evaluated by the same method as in the case of Example 1. The results are shown in Table 1.

As is clear from the above results, in Examples 1 to 3, no change was observed in the pick-up force of the silicon chip with the film-like adhesive depending on the presence or absence of the semiconductor device manufacturing sheet over time, and the semiconductor device manufacturing sheet was used over time. However, no change was observed in the physical properties of the film-like adhesive. This indicated that there was no obvious change in the composition of the film-like adhesive even when the semiconductor device manufacturing sheet was aged. That is, the film-like adhesive contains the epoxy resin (b1) -1 as the component (α2) (the cross-linking agent (f) -1 is not the component (α2)), but is transferred to the pressure-sensitive adhesive layer side. Was suppressed even after the semiconductor device manufacturing sheet was aged.

Further, in Examples 1 to 3, the surface resistivity of the film-like adhesive is more than 1.0 × 10 ¹⁴ Ω / □ regardless of the presence or absence of the semiconductor device manufacturing sheet, and the semiconductor device manufacturing sheet is used. Even with the passage of time, it was not recognized that there was a change in the antistatic property on the surface of the film-like adhesive on the intermediate layer side. This indicates that the composition of the pressure-sensitive adhesive layer, which is the only layer containing the antistatic agent, did not change significantly even after the semiconductor device manufacturing sheet was aged. Here, the antistatic property of the film-like adhesive was confirmed, but it was presumed that even if the antistatic property of the pressure-sensitive adhesive layer was confirmed, the influence of the sheet for manufacturing the semiconductor device over time was not observed. That is, the pressure-sensitive adhesive layer contains the amine-based ionic liquid, which is an antistatic agent, as a component (γ2), but the transfer to the film-like adhesive side is caused by aging the semiconductor device manufacturing sheet. Was also suppressed.

As described above, in the sheets for manufacturing semiconductor devices of Examples 1 to 3, the intermediate layer suppresses the migration of the liquid component in the film-like adhesive to the pressure-sensitive adhesive layer side, and the liquid component in the pressure-sensitive adhesive layer It was confirmed that the transfer to the film-like adhesive side was suppressed.
In Examples 1 to 3, both H (βα) -H (β) and H (βγ) -H (β) were 8% or more.

Further, from the values of H (βα) -H (β) and H (βγ) -H (β), the semiconductor device manufacturing sheet of Examples 1 and 2 is higher than the semiconductor device manufacturing sheet of Example 3. It was suggested that the transfer of liquid components between the pressure-sensitive adhesive layer and the film-like adhesive was more strongly suppressed.
In the ethylene-vinyl acetate copolymer which is the main component of the intermediate layer (non-silicon resin (β1)), the ratio of the mass of the constituent units derived from vinyl acetate to the total mass of all the constituent units is determined in Example 1. In ~ 2, it was 25% by mass, and in Example 3, it was 40% by mass.

Further, in Examples 1 to 3, the generation of cutting chips was suppressed at the time of blade dicing, and the cutting failure of the film-like adhesive was suppressed at the time of expanding, and the division suitability of the semiconductor wafer was excellent.
In Examples 1 to 3, the weight average molecular weight of the ethylene-vinyl acetate copolymer containing the intermediate layer in the semiconductor device manufacturing sheet as the main component (non-silicon resin (β1)) was 30,000 or less.

In Examples 1 to 3, in the intermediate layer, the ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the intermediate layer is 90.9% by mass or more, and the total mass of the intermediate layer is 90.9% by mass or more. The ratio of the content of the siloxane compound to the mass was 9.1% by mass or less.

Further, in Example 1, the pick-up property of the silicon chip with a film-like adhesive after expansion was further excellent.
In Example 1, the T-shaped peel strength between the intermediate layer and the film-like adhesive was 100 mN / 50 mm, which was moderately low, and the ratio of the silicon concentration in the intermediate layer was 9%, which was appropriate. It was getting higher. These evaluation results were consistent with the above-mentioned evaluation results of the pick-up property of the silicon chip with a film-like adhesive.
In Examples 2 and 3, the intermediate layer in the semiconductor device manufacturing sheet did not contain the siloxane compound.

In Examples 1 to 3, nitrogen was not detected during the XPS analysis of the exposed surface of the intermediate layer.

On the other hand, in Comparative Example 1, the pick-up force of the silicon chip with the film-like adhesive decreased with the aging of the semiconductor device manufacturing sheet, and the physical properties of the film-like adhesive were changed. This indicated that the composition of the film-like adhesive changed significantly with the aging of the semiconductor device manufacturing sheet. That is, although the film-like adhesive contains epoxy resin (b1) -1 as a component (α2), it is presumed that the migration to the pressure-sensitive adhesive layer side was not suppressed by the aging of the semiconductor device manufacturing sheet. Was done.

Further, in Comparative Example 1, the surface resistivity of the film-like adhesive decreases with time of the semiconductor device manufacturing sheet, and the film-like adhesive is on the intermediate layer side with time of the semiconductor device manufacturing sheet. On the other hand, a change in antistatic property was observed. This indicates that the composition of the pressure-sensitive adhesive layer, which is the only layer containing the antistatic agent, changed over time in the semiconductor device manufacturing sheet. Here, the antistatic property of the film-like adhesive was confirmed, but it was presumed that even if the antistatic property of the pressure-sensitive adhesive layer was confirmed, the influence of time on the sheet for manufacturing the semiconductor device was recognized. That is, the pressure-sensitive adhesive layer contains the amine-based ionic liquid, which is an antistatic agent, as a component (γ2), but the migration to the film-like adhesive side is caused by the aging of the semiconductor device manufacturing sheet. It was speculated that it was not suppressed.

As described above, in the comparative semiconductor device manufacturing sheet of Comparative Example 1, the intermediate layer does not suppress the migration of the liquid component in the film-like adhesive to the pressure-sensitive adhesive layer side, and is contained in the pressure-sensitive adhesive layer. Also did not suppress the transfer of the liquid component to the film-like adhesive side.
In Comparative Example 1, both H (βα) -H (β) and H (βγ) -H (β) were 1%.

In Comparative Example 2, the silicon chip with a film-like adhesive could not be picked up regardless of the presence or absence of the semiconductor device manufacturing sheet over time, and the pick-up force could not be measured. This indicated that the composition of the film-like adhesive had already changed significantly before the aging of the semiconductor device manufacturing sheet. That is, the film-like adhesive contains the epoxy resin (b1) -1 as the component (α2), but the migration to the pressure-sensitive adhesive layer side has already occurred at the stage before the aging of the semiconductor device manufacturing sheet. It was presumed that it was. This was because the comparative semiconductor device manufacturing sheet of Comparative Example 2 did not have an intermediate layer.
In Comparative Example 2, the pick-up property of the silicon chip with a film-like adhesive after expansion was also inferior.

In Comparative Example 2, not only the silicon chip with the film-like adhesive could not be picked up by pulling it away from the intermediate layer, but also the test piece for measuring the surface resistivity of the film-like adhesive could be produced. The surface resistivity could not be measured because it was not present.

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

101 ... Semiconductor device manufacturing sheet, 11 ... Base material, 12 ... Adhesive layer, 13 ... Intermediate layer, 13a ... First surface of intermediate layer, 14 ... Film-like adhesion Agent

Claims

A base material, an adhesive layer, an intermediate layer, and a film-like adhesive are provided.
The pressure-sensitive adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the base material.
The intermediate layer contains a non-silicon resin (β1) having a weight average molecular weight of 20,000 to 100,000 as a main component.
Further, at least, the film-like adhesive contains the component (α2), or the pressure-sensitive adhesive layer contains the component (γ2).
The component (α2) is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the film-like adhesive.
The component (γ2) is liquid at a temperature of 23 ° C. and does not have a functional group that reacts with the main component contained in the pressure-sensitive adhesive layer.
The haze of the film-shaped first test piece made of the non-silicon resin (β1) and having a thickness of 10 μm was defined as H (β).
When the film-like adhesive contains the component (α2), the thickness is 10 μm composed of a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (α2). When the haze of the film-like second test piece is H (βα), the H (βα) and H (β) are expressed by the following formula (X1):
(X1) H (βα) -H (β)> 7%
The filling,
When the pressure-sensitive adhesive layer contains the component (γ2), the thickness is 10 μm, which is a mixture of 100 parts by mass of the non-silicon resin (β1) and 10 parts by mass of the component (γ2). When the haze of the film-like third test piece is H (βγ), the H (βγ) and H (β) are expressed by the following formula (X2):
(X2) H (βγ) -H (β)> 7%
A sheet for manufacturing semiconductor devices that meets the requirements.
Further, at least, the film-like adhesive contains a solid component (α1) at a temperature of 23 ° C. as a main component, or the pressure-sensitive adhesive layer contains a solid component (γ1) at a temperature of 23 ° C. as a main component. Contains as
The sheet for manufacturing a semiconductor device according to claim 1, wherein the component (α1) and the component (γ1) are an acrylic resin having a structural unit derived from a (meth) acrylic acid ester.
The semiconductor device according to claim 1 or 2, wherein the intermediate layer contains one or more selected from the group consisting of ethylene vinyl acetate copolymer and polyolefin as the non-silicon resin (β1). Manufacturing sheet.
The intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicon resin (β1).
In any one of claims 1 to 3, the ratio of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units in the ethylene-vinyl acetate copolymer is 30% by mass or less. The sheet for manufacturing a semiconductor device according to the description.
The semiconductor according to any one of claims 1 to 4, wherein the semiconductor device manufacturing sheet is for cutting the film-like adhesive by cooling and expanding the film-like adhesive. Sheet for manufacturing equipment.
The method for manufacturing a sheet for manufacturing a semiconductor device according to any one of claims 1 to 5.
The manufacturing method includes a film-like adhesive manufacturing step of producing the film-like adhesive containing the component (α2) and a pressure-sensitive adhesive layer manufacturing step of producing the pressure-sensitive adhesive layer containing the component (γ2). A method for manufacturing a sheet for manufacturing a semiconductor device, which has either one or both of the above.
A method for manufacturing a semiconductor chip with a film-like adhesive using the sheet for manufacturing a semiconductor device according to any one of claims 1 to 5.
The semiconductor chip with a film-like adhesive includes a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip.
The manufacturing method includes a step of heating the semiconductor device manufacturing sheet and attaching the film-like adhesive in the sheet to the back surface of the semiconductor wafer.
The semiconductor chip to which the film-like adhesive is attached is divided by cutting the entire area in the thickness direction from the circuit forming surface side thereof to produce the semiconductor chip and the semiconductor device manufacturing sheet. By cutting from the film-like adhesive side to the middle region of the intermediate layer in the thickness direction, cutting the film-like adhesive, and not cutting to the pressure-sensitive adhesive layer. A step of obtaining a group of semiconductor chips with a film-like adhesive in a state where a plurality of the semiconductor chips with a film-like adhesive are aligned on the intermediate layer.
A method for manufacturing a semiconductor chip with a film-like adhesive, which comprises a step of pulling the semiconductor chip with the film-like adhesive from the intermediate layer and picking it up.
A method for manufacturing a semiconductor chip with a film-like adhesive using the sheet for manufacturing a semiconductor device according to any one of claims 1 to 5.
The semiconductor chip with a film-like adhesive includes a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip.
The manufacturing method includes a step of forming a modified layer inside the semiconductor wafer by irradiating a laser beam so as to focus on a focal point set inside the semiconductor wafer.
By grinding the back surface of the semiconductor wafer after forming the modified layer and utilizing the grinding force applied to the semiconductor wafer, the semiconductor wafer is divided at the formation site of the modified layer. A step of obtaining a semiconductor chip group in which a plurality of the semiconductor chips are aligned, and
A step of attaching the film-like adhesive in the sheet for manufacturing a semiconductor device to the back surface of all the semiconductor chips in the semiconductor chip group while heating the sheet.
The film-like adhesive is cut along the outer periphery of the semiconductor chip by stretching the sheet for manufacturing the semiconductor device after being attached to the semiconductor chip in a direction parallel to the surface thereof while cooling. A step of obtaining a group of semiconductor chips with a film-like adhesive in a state where a plurality of the semiconductor chips with a film-like adhesive are aligned on the intermediate layer.
A method for manufacturing a semiconductor chip with a film-like adhesive, which comprises a step of pulling the semiconductor chip with the film-like adhesive from the intermediate layer and picking it up.