CN114762085A - Sheet for manufacturing semiconductor device, method for manufacturing same, and method for manufacturing semiconductor chip with film-like adhesive - Google Patents

Abstract

The present invention provides a sheet for manufacturing a semiconductor device, comprising a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive, wherein the adhesive layer, the intermediate layer, and the film-like adhesive are sequentially laminated on the substrate, the intermediate layer contains a non-silicon resin (β 1) having a weight average molecular weight of 20000 to 100000 as a main component, the film-like adhesive contains a liquid component (α 2), or the adhesive layer contains a liquid component (γ 2), and when the haze of a first test sheet composed of the non-silicon resin (β 1) and having a thickness of 10 μm is represented by H (β), the haze of a second test sheet composed of a mixture of the non-silicon resin (β 1) and the component (α 2) and having a thickness of 10 μm is represented by H (β α), the haze of a third test sheet composed of a mixture of the non-silicon resin (β 1) and the component (γ 2) and having a thickness of 10 μm is represented by H (β γ), h (beta alpha) -H (beta) > 7% or H (beta gamma) -H (beta) > 7% is satisfied.

Description

Sheet for manufacturing semiconductor device, method for manufacturing same, and method for manufacturing semiconductor chip with film-like adhesive

Technical Field

The present invention relates to a sheet for manufacturing a semiconductor device, a method for manufacturing the 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 and 058734 filed in Japan on 27.3.2020, and the contents thereof are incorporated herein.

Background

In the manufacture of a semiconductor device, a semiconductor chip with a film-like adhesive is used, which includes a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip.

As an example of a method for manufacturing a semiconductor chip with a film-like adhesive, the following method can be mentioned.

That is, first, a dicing die bonding sheet (dicing die bonding sheet) is attached to the back surface of the semiconductor wafer.

As the dicing die, for example, there is exemplified a dicing die having 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. As the support sheet, for example, there are various support sheets having different structures, for example, a support sheet including a base material and an adhesive layer provided on one surface of the base material; a support sheet composed only of a base material, and the like. The support sheet provided with the adhesive layer has an outermost surface on the adhesive layer side as a surface on which the film-like adhesive is provided. The dicing die is attached to the back surface of the semiconductor wafer with the film-like adhesive interposed therebetween.

Subsequently, the semiconductor wafer on the supporting sheet is cut together with the film-like adhesive by dicing with a dicing blade. The "cutting" of the semiconductor wafer is also referred to as "dividing", whereby the semiconductor wafer is singulated (singulated) into target semiconductor chips. The film-like adhesive is cut along the outer periphery of the semiconductor chip. Thus, a semiconductor chip with a film-like adhesive, which includes a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip after cutting, is obtained, and a semiconductor chip group with a film-like adhesive, which is configured by holding a plurality of semiconductor chips with a film-like adhesive on a support sheet in an aligned state, is obtained at the same time.

Subsequently, the semiconductor chip with the film adhesive is pulled off from the support sheet and picked up. In the case of using a support sheet having a curable adhesive layer, in this case, the adhesive layer is cured in advance to reduce the adhesiveness, thereby facilitating pickup.

Thus, a semiconductor chip with a film-like adhesive for manufacturing a semiconductor device was obtained.

As another example of a method for manufacturing a semiconductor chip with a film-like adhesive, the following method can be mentioned.

That is, first, a back grinding tape (also referred to as a "surface protective tape") is attached to the circuit formation surface of the semiconductor wafer.

Next, a portion to be divided is set in the semiconductor wafer, and a laser beam is irradiated with a region included in the portion as a focal point so as to be focused on the focal point, thereby forming a modified layer in the semiconductor wafer. Then, the back surface of the semiconductor wafer is polished by a grinder (grinder) to adjust the thickness of the semiconductor wafer to a target value, and the semiconductor wafer is divided (singulated) at the formation portion of the modified layer by a force applied to the semiconductor wafer during polishing, thereby producing a plurality of semiconductor chips. Such a method of dividing a semiconductor wafer with formation of a modified layer is called Stealth Dicing (registered trademark), which is fundamentally completely different from laser Dicing in which a semiconductor wafer is cut at an irradiated portion by irradiating the semiconductor wafer with a laser beam and the semiconductor wafer is cut from the surface of the semiconductor wafer.

Next, a single fixed wafer is attached to the polished back surface (in other words, polished surface) of all the semiconductor chips fixed to the back grinding tape. The solid wafer may be the same sheet as the above-described diced solid wafer. As described above, the die attach film may be designed to have the same structure as the diced die, but not to be used when dicing a semiconductor wafer. The fixed wafer is also attached to the back surface of the semiconductor chip by the film-like adhesive therein.

Next, after the back grinding tape is removed from the semiconductor chip, the solid wafer is cooled while being stretched in a direction parallel to the surface of the solid wafer (for example, the surface of the film-like adhesive attached to the semiconductor chip), that is, so-called spreading (cold spreading) is performed, thereby cutting the film-like adhesive along the outer periphery of the semiconductor chip.

Thus, a semiconductor chip with a film-like adhesive is obtained, which includes the semiconductor chip and the cut film-like adhesive provided on the back surface of the semiconductor chip.

Next, the semiconductor chip with the film adhesive is pulled off from the support sheet and picked up in the same manner as in the above-described dicing with a blade, thereby obtaining a semiconductor chip with a film adhesive for use in the manufacture of a semiconductor device.

The dicing die and the die bonding die can be used for manufacturing a semiconductor chip with a film-like adhesive, and a desired semiconductor device can be finally manufactured. In the present specification, the diced solid-state wafer and the solid-state wafer are collectively referred to as a "semiconductor device manufacturing wafer".

As a sheet for manufacturing a semiconductor device, for example, a dicing die bonding tape (corresponding to the dicing die bonding sheet) having a structure in which a base material layer (corresponding to the support sheet) and a pressure-sensitive adhesive layer (corresponding to the film-like pressure-sensitive adhesive) are laminated in direct contact with each other is disclosed (see patent document 1). In the dicing die-bonding tape, it is considered that since the 90-degree peel force at-15 ℃ of the base layer and the pressure-sensitive adhesive layer is adjusted to a specific range, the pressure-sensitive adhesive layer can be divided with good precision by spreading, and since the 90-degree peel force at 23 ℃ of the base layer and the pressure-sensitive adhesive layer is adjusted to a specific range, when the dicing die-bonding tape is used, the semiconductor chip with the pressure-sensitive adhesive layer (corresponding to the semiconductor chip with the film-like pressure-sensitive adhesive) can be picked up without difficulty, and the semiconductor wafer and the semiconductor chip can be prevented from being peeled from the pressure-sensitive adhesive layer until the picking up.

Documents of the prior art

Patent literature

Patent document 1: japanese patent laid-open publication No. 2018-56289

Disclosure of Invention

Technical problem to be solved by the invention

However, when the supporting sheet in the semiconductor device production sheet includes the base material and the adhesive layer, and the adhesive layer or the film-like adhesive contains a component in a liquid state at normal temperature, the liquid component may be transferred between the adhesive layer and the film-like adhesive in the semiconductor device production sheet. If the transfer occurs as described above, either one or both of the adhesive layer and the film-like adhesive cannot normally function. The dicing die bonding tape disclosed in patent document 1 does not include an adhesive layer.

The purpose of the present invention is to provide a sheet for manufacturing a semiconductor device, which is provided with a base material, an adhesive layer, and a film-like adhesive, and which can suppress the transfer of a liquid component between the adhesive layer and the film-like adhesive even when the adhesive layer or the film-like adhesive contains the liquid component.

Means for solving the problems

The present invention provides a sheet for manufacturing a semiconductor device, comprising a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive, wherein the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the substrate, the intermediate layer contains a non-silicon resin (β 1) having a weight average molecular weight of 20000 to 100000 as a main component, further, at least the film-like adhesive contains a component (α 2) or at least the adhesive layer contains a component (γ 2), the component (α 2) is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the film-like adhesive, the component (γ 2) is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive layer, and a first test sheet in a film shape having a thickness of 10 μm and composed of the non-silicon resin (β 1) is represented by H (β), when the film-shaped adhesive contains the component (α 2), H (β α) and H (β) satisfy the following formula (X1) where H (β α) and H (β) are expressed by a haze of a film-shaped second test piece having a thickness of 10 μm and formed from a mixture of 100 parts by mass of the non-silicon resin (β 1) and 10 parts by mass of the component (α 2):

(X1)H(βα)-H(β)＞7％，

When the adhesive layer contains the component (γ 2), the haze of a film-shaped third test piece having a thickness of 10 μm, which is composed of a mixture of 100 parts by mass of the non-silicon resin (β 1) and 10 parts by mass of the component (γ 2), is represented by H (β γ), and H (β γ) and H (β) satisfy the following formula (X2):

(X2)H(βγ)-H(β)＞7％。

in the semiconductor device-manufacturing sheet of the present invention, at least the film-like adhesive may contain a component (α 1) that is solid at a temperature of 23 ℃ as a main component, or at least the adhesive layer may contain a component (γ 1) that is solid at a temperature of 23 ℃ as a main component, and the component (α 1) and the component (γ 1) may be an acrylic resin having a structural unit derived from a (meth) acrylate.

In the semiconductor device-manufacturing sheet of the present invention, the intermediate layer may contain one or more kinds selected from the group consisting of an ethylene-vinyl acetate copolymer and a polyolefin as the non-silicon resin (β 1).

In the semiconductor device-manufacturing sheet of the present invention, the intermediate layer may contain, as the non-silicone resin (β 1), an ethylene-vinyl acetate copolymer in which the proportion of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units may be 30 mass% or less.

The sheet for manufacturing a semiconductor device of the present invention can be used for cutting the film-like adhesive by cooling and spreading the film-like adhesive.

The present invention provides a method for manufacturing a sheet for manufacturing a semiconductor device, the method comprising either or both of the following steps: a film-like adhesive preparation step for preparing the film-like adhesive containing the component (. alpha.2); a step of preparing an adhesive layer, wherein the adhesive layer contains the component (. gamma.2).

The present invention provides a method for manufacturing a semiconductor chip with a film-shaped adhesive, using the sheet for manufacturing a semiconductor device, the method including the steps of: heating the semiconductor device manufacturing sheet and adhering the film-like adhesive to the back surface of the semiconductor wafer; a step of cutting the entire region of the semiconductor wafer in the thickness direction from the circuit-formation-surface side of the semiconductor wafer to which the film-like adhesive is attached, thereby dividing the semiconductor wafer, and cutting the film-like adhesive from the film-like adhesive side of the semiconductor device-manufacturing sheet to an intermediate region of the intermediate layer along the thickness direction of the semiconductor device-manufacturing sheet, thereby obtaining a plurality of semiconductor chip groups with the film-like adhesive, in which the semiconductor chips with the film-like adhesive are aligned on the intermediate layer, without cutting the film-like adhesive to the adhesive layer; and a step of pulling out the semiconductor chip with the film-like adhesive from the intermediate layer and picking up the semiconductor chip.

The present invention provides a method for manufacturing a semiconductor chip with a film-shaped adhesive, using the sheet for manufacturing a semiconductor device, the method including the steps of: irradiating a laser beam so as to focus on a focal point set in the interior of a semiconductor wafer, thereby forming a modified layer in the interior of the semiconductor wafer; a step of grinding the back surface of the semiconductor wafer after the modified layer is formed, and dividing the semiconductor wafer at a portion where the modified layer is formed by a force applied to the semiconductor wafer during grinding to obtain a semiconductor chip group in which a plurality of semiconductor chips are aligned; heating the semiconductor device manufacturing sheet and simultaneously attaching the film-like adhesive to the back surfaces of all the semiconductor chips in the semiconductor chip group; a step of cooling the semiconductor device manufacturing sheet after the semiconductor chips are attached to the sheet, and stretching the sheet in a direction parallel to the surface of the sheet, thereby cutting the film-like adhesive along the outer peripheries of the semiconductor chips to obtain a plurality of semiconductor chip groups with film-like adhesive, each of which has a plurality of semiconductor chips with film-like adhesive aligned on the intermediate layer; and a step of pulling out the semiconductor chip with the film-like adhesive from the intermediate layer and picking up the semiconductor chip.

Effects of the invention

According to the present invention, there can be provided a sheet for manufacturing a semiconductor device, which comprises a base material, an adhesive layer, and a film-like adhesive, and which can suppress transfer of a liquid component between the adhesive layer and the film-like adhesive even when the adhesive layer or the film-like adhesive contains the liquid component.

Drawings

Fig. 1 is a cross-sectional view schematically showing a semiconductor device manufacturing sheet according to an embodiment of the present invention.

Fig. 2 is a plan view of the semiconductor device manufacturing sheet shown in fig. 1.

Fig. 3A is a sectional view for schematically illustrating one example of a method for manufacturing a semiconductor chip with a film-like adhesive according to one embodiment of the present invention.

Fig. 3B is a sectional view for schematically illustrating one example of a method for manufacturing a semiconductor chip with a film-like adhesive according to one embodiment of the present invention.

Fig. 3C is a sectional view for schematically illustrating one example of a method for manufacturing a semiconductor chip with a film-like adhesive according to one embodiment of the present invention.

Fig. 4A is a sectional view for schematically illustrating one example of a manufacturing method of a semiconductor chip.

Fig. 4B is a sectional view for schematically illustrating one example of a manufacturing method of a semiconductor chip.

Fig. 4C is a sectional view for schematically illustrating one example of a manufacturing method of a semiconductor chip.

Fig. 5A is a sectional view for schematically illustrating another example of a method for manufacturing a semiconductor chip with a film-like adhesive according to an embodiment of the present invention.

Fig. 5B is a sectional view for schematically illustrating another example of the method for manufacturing a semiconductor chip with a film-like adhesive according to an embodiment of the present invention.

Fig. 5C is a sectional view for schematically illustrating another example of the method for manufacturing a semiconductor chip with a film-like adhesive according to an embodiment of the present invention.

Detailed Description

Wafer for manufacturing semiconductor device

A sheet for manufacturing a semiconductor device according to one embodiment of the present invention comprises a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive, wherein the adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order on the substrate, the intermediate layer contains a non-silicon resin (. beta.1) (in the present specification, sometimes simply referred to as "non-silicon resin (. beta.1)") having a weight average molecular weight of 20000 to 100000 as a main component, at least the film-like adhesive contains a component (. alpha.2) or at least the adhesive layer contains a component (. gamma.2), the component (. alpha.2) is a liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the film-like adhesive, the component (. gamma.2) is a liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive layer, when the haze of a first test piece having a thickness of 10 μm and made of the non-silicon resin (β 1) is H (β) and the haze of a second test piece having a thickness of 10 μm and made of a mixture of 100 parts by mass of the non-silicon resin (β 1) and 10 parts by mass of the component (α 2) is H (β α) when the film-shaped adhesive contains the component (α 2), the H (β α) and the H (β) satisfy the following formula (X1):

(X1)H(βα)-H(β)＞7％，

When the adhesive layer contains the component (γ 2), the haze of a film-shaped third test piece having a thickness of 10 μm, which is composed of a mixture of 100 parts by mass of the non-silicon resin (β 1) and 10 parts by mass of the component (γ 2), is represented by H (β γ), and H (β γ) and H (β) satisfy the following formula (X2):

(X2)H(βγ)-H(β)＞7％。

the sheet for manufacturing a semiconductor device of the present embodiment includes: a semiconductor device-manufacturing sheet comprising a non-silicon resin (. beta.1) as a main component in an intermediate layer, a film-like adhesive containing the component (. alpha.2), and an adhesive layer not containing the component (. gamma.2); a semiconductor device-manufacturing sheet comprising an intermediate layer containing the non-silicon resin (. beta.1) as a main component, an adhesive layer containing the component (. gamma.2), and a film-like adhesive not containing the component (. alpha.2); a semiconductor device-manufacturing sheet comprising a non-silicon resin (. beta.1) as the main component in the intermediate layer, a film-like adhesive containing the component (. alpha.2), and an adhesive layer containing the component (. gamma.2).

In the case where the film-like adhesive contains the component (α 2), the H (β α) and H (β) satisfy the formula (X1) regardless of whether or not the adhesive layer contains the component (γ 2). With respect to such a semiconductor device-manufacturing sheet, it can be determined that the compatibility of component (α 2) with the non-silicon resin (β 1) is low, and the transfer of component (α 2) in the film-like adhesive to the intermediate layer is suppressed, and as a result, the transfer of component (α 2) in the film-like adhesive to the adhesive layer is suppressed.

On the other hand, in the case where the adhesive layer contains the component (γ 2), the H (β γ) and H (β) satisfy the formula (X2) regardless of whether the film-like adhesive contains the component (α 2). With respect to such a semiconductor device-producing sheet, it can be determined that the compatibility of the component (γ 2) with the non-silicon resin (β 1) is low, and the transfer of the component (γ 2) in the adhesive agent layer to the intermediate layer is suppressed, and as a result, the transfer of the component (γ 2) in the adhesive agent layer to the film-like adhesive is suppressed.

That is, in the sheet for manufacturing a semiconductor device of the present embodiment, the intermediate layer functions as a layer for suppressing the transfer of the component (α 2) and the component (γ 2).

The effect of suppressing the migration of the component (α 2) in the film-like adhesive to the adhesive layer in the semiconductor device manufacturing sheet of the present embodiment can be confirmed, for example, by the following method.

That is, a semiconductor device-manufacturing sheet is left standing for a certain period of time under high temperature conditions, and a semiconductor chip set with a film-like adhesive (for example, a silicon chip set with a film-like adhesive) is produced by a method described later using the semiconductor device-manufacturing sheet after a lapse of time, in a state where a plurality of semiconductor chips with a film-like adhesive are aligned and fixed on an intermediate layer in a laminated sheet with the film-like adhesive interposed therebetween. Here, the "laminated sheet" is a laminated body 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 laminate sheet is measured, and this force is used as the pickup force of the semiconductor chip with the film-like adhesive over a period of time.

On the other hand, the force required to peel off the semiconductor chip with the film-like adhesive from the intermediate layer in the laminated sheet was measured by the same method using the sheet for semiconductor device fabrication which had not elapsed a certain period of time (before a certain period of time elapsed), and this force was used as the pickup force of the semiconductor chip with the film-like adhesive which had not elapsed a certain period of time.

In addition, when the difference between the pickup force of the semiconductor chip with the film-like adhesive when the lapse of time and the pickup force of the semiconductor chip without the lapse of time is not observed or the difference is extremely slight even if the difference is observed, it can be determined that the composition of the film-like adhesive does not change significantly even when the lapse of time is used for the semiconductor device-manufacturing sheet, and it can be determined that the semiconductor device-manufacturing sheet has an effect of suppressing the transfer of the component (α 2) in the film-like adhesive to the adhesive layer.

In the semiconductor device-manufacturing sheet of the present embodiment, for example, when the component (γ 2) is an antistatic agent, the effect of suppressing the migration of the component (γ 2) in the adhesive layer to the film-like adhesive can be confirmed by the following method.

That is, in the same manner as described above, the sheet for manufacturing a semiconductor device is stored in a standing state for a certain period of time under a high temperature condition, and a test piece of the film-like adhesive is produced by peeling the film-like adhesive from the intermediate layer with respect to the sheet for manufacturing a semiconductor device after the lapse of time. The test piece was subjected to humidity control by standing storage for a certain period of time under conditions of constant temperature and relative humidity (for example, 23 ℃ C. and 50% relative humidity), and then the surface resistivity of the exposed surface of the film-shaped adhesive after humidity control, which was the intermediate layer side, was measured and used as the surface resistivity of the film-shaped adhesive over time.

On the other hand, using a sheet for manufacturing a semiconductor device that has not elapsed a certain period of time (before a certain period of time has elapsed), the surface resistivity of the exposed surface of the film-like pressure-sensitive adhesive that has been the intermediate layer side is measured by the same method, and this value is used as the surface resistivity of the film-like pressure-sensitive adhesive that has not elapsed a certain period of time.

In addition, when the difference (more specifically, a decrease) between the surface resistivity of the film-shaped adhesive when the lapse of time is not observed and the surface resistivity of the film-shaped adhesive when the lapse of time is not observed or the degree thereof is extremely slight even if the difference is observed, it can be determined that the composition of the adhesive layer containing the antistatic agent does not change significantly even when the lapse of time is used in the semiconductor device manufacturing sheet, and it can be determined that the semiconductor device manufacturing sheet has an effect of suppressing the transfer of the component (γ 2) in the adhesive layer to the film-shaped adhesive.

When the component (γ 2) is a component other than the antistatic agent, for example, if it is not confirmed that the physical properties reflecting the adhesive layer containing the component vary depending on whether or not the adhesive layer has elapsed time or the degree of the variation is extremely slight even if the variation is confirmed, it can be determined that the semiconductor device-manufacturing sheet has the effect of suppressing the transfer of the component (γ 2) in the adhesive layer to the film-like adhesive.

In the present specification, the "main component" is not limited to the non-silicone resin (β 1) in the intermediate layer, and means a component having a maximum content (mass part) and a weight average molecular weight of 20000 or more in the layer (film) containing the component. For example, in the intermediate layer, the content (parts by mass) of the non-silicone resin (β 1) is the largest among all the components, and the weight average molecular weight of the non-silicone resin (β 1) is 20000 or more.

In the present specification, components that are liquid at a temperature of 23 ℃, such as the component (α 2) and the component (γ 2), may be collectively referred to simply as "liquid components".

The first, second, and third test pieces are each 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 first to third test pieces, and unless otherwise specified, means an average value of thicknesses measured at 5 randomly selected sites in a subject, and can be obtained by using a constant pressure thickness gauge according to JIS K7130.

The H (. beta.), H (. beta.,) and H (. beta. gamma.) can be measured according to JIS K7136: 2000.

The H (β) is not particularly limited as long as the formulas (X1) and (X2) are satisfied.

For example, H (. beta.) may be in any range of 0.1 to 20%, 1 to 18%, and 2 to 15% from the viewpoint of easier formation of the intermediate layer.

The first test strip may be manufactured by: a first test composition containing the non-silicone resin (β 1) and a solvent is prepared, and the first test composition is applied to the surface to be formed of a first test piece and dried. The surface to be formed of the first test piece may be, for example, a release-treated surface of a release film.

The first test piece was made of a non-silicone resin (. beta.1). The first test piece contained only the non-silicone resin (β 1) as a constituent component thereof, or contained impurities in addition to the non-silicone resin (β 1), but the content of the impurities was so small as not to change the physical properties of the first test piece, and it was considered that the first test piece contained substantially only the non-silicone resin (β 1). For example, in the first test piece, the proportion of the content of the non-silicone resin (β 1) to the total mass of the first test piece may be 99 mass% or more.

The H (β α) is not particularly limited as long as the formula (X1) is satisfied.

For example, H (. beta.. alpha.) may be in any range of 8 to 80%, 10 to 75%, and 12 to 70% from the viewpoint of easier formation of the intermediate layer and the film-like adhesive.

The second test piece may be manufactured by: a second test composition containing the non-silicone resin (β 1), the component (α 2), and a solvent is prepared, and the second test composition is applied to a surface to be formed of a second test piece and dried. The surface to be formed of the second test piece is the same as the surface to be formed of the first test piece.

By mixing the components contained in the second test composition uniformly, it is possible to produce a second test piece in which the components contained in the second test composition are uniformly mixed, and to measure H (β α) with higher accuracy. For this reason, when the second test composition is prepared, the mixture obtained by blending all the components may be sufficiently stirred by a known method.

The second test piece was composed of a mixture of 100 parts by mass of the non-silicone resin (β 1) and 10 parts by mass of the component (α 2). The second test piece contains only the non-silicone resin (β 1) and the component (α 2) as its constituent components, or contains impurities in addition to the non-silicone resin (β 1) and the component (α 2), but the content of impurities is a trace amount to the extent that the physical properties of the second test piece are not changed, and it can be considered that the second test piece contains substantially only the non-silicone resin (β 1) and the component (α 2). For example, in the second test piece, the ratio of the total content of the non-silicon resin (β 1) and the component (α 2) to the total mass of the second test piece may be 99 mass% or more.

The H (β γ) is not particularly limited as long as the formula (X2) is satisfied.

For example, from the viewpoint of easier formation of the intermediate layer and the adhesive layer, H (β γ) may be in any range of 8 to 80%, 10 to 75%, and 12 to 70%.

The third test piece may be manufactured by: a third test composition containing the non-silicone resin (β 1), the component (γ 2), and a solvent is prepared, and the third test composition is applied to a surface to be formed of a third test piece and dried. The surface to be formed of the third test piece is the same as the surface to be formed of the first test piece.

In the third test composition, it is preferable to uniformly mix the components contained therein, whereby a third test piece in which the components contained therein are uniformly mixed can be produced, and H (β γ) can be measured with higher accuracy. For this purpose, the third test composition may be prepared by thoroughly stirring a mixture obtained by blending all the components by a known method.

The third test piece was composed of a mixture of 100 parts by mass of the non-silicone resin (β 1) and 10 parts by mass of the component (γ 2). The third test piece contains only the non-silicone resin (β 1) and the component (γ 2) as its constituent components, or contains impurities in addition to the non-silicone resin (β 1) and the component (γ 2), but the content of impurities is a trace amount to the extent that the physical properties of the third test piece are not changed, and it can be considered that the third test piece contains substantially only the non-silicone resin (β 1) and the component (γ 2). For example, in the third test piece, the ratio of the total content of the non-silicon resin (β 1) and the component (γ 2) to the total mass of the third test piece may be 99 mass% or more.

The content of H (β α) -H (β) may be more than 7%, but is preferably 7.5% or more, and may be, for example, any range of 9% or more and 11% or more, from the viewpoint of further suppressing transfer of the component (α 2) in the film-like adhesive to the adhesive agent layer.

The upper limit of H (. beta. alpha.) -H (. beta.) is not particularly limited. From the viewpoint of facilitating formation of a film-like adhesive and an intermediate layer satisfying the formula (X1), H (β α) -H (β) is preferably 90% or less.

For example, it is preferable that H (. beta.. alpha. -H (. beta.) -. beta.) is more than 7% and 90% or less (7% < H (. beta.) -. alpha. -H (. beta.) -. beta.). ltoreq.90%), and H (. beta.) -H (. beta.) may be any of 7.5 to 90%, 9 to 90%, and 11 to 90%.

The content of H (β γ) -H (β) may be more than 7%, and is preferably 7.5% or more, for example, may be in any range of 9% or more and 11% or more, from the viewpoint of further suppressing the transfer of the component (γ 2) in the adhesive layer to the film-shaped adhesive.

The upper limit of H (β γ) -H (β) is not particularly limited. From the viewpoint of easy formation of the adhesive agent layer and the intermediate layer satisfying the formula (X2), H (β γ) -H (β) is preferably 90% or less.

For example, it is preferable that H (. beta. gamma.) -H (. beta.) -90% or less is more than 7% and 90% or less (7% < H (. beta. gamma.) -H (. beta.). gamma.) -90%) and H (. beta.) -H (. beta.) -in any of the ranges of 7.5 to 90%, 9 to 90%, and 11 to 90%.

When the semiconductor device-manufacturing sheet of the present embodiment is used as a dicing solid wafer to perform dicing with a blade, since the semiconductor device-manufacturing sheet includes the intermediate layer, it is possible to easily avoid the blade from reaching the base material, and to suppress the generation of Whisker-like cutting chips (also called whiskers, hereinafter, not limited to only cutting chips generated from the base material, but also simply referred to as "cutting chips") from the base material. Further, the main component of the intermediate layer cut by the blade is a non-silicone resin (. beta.1) having a weight average molecular weight of 20000 to 100000, and particularly, the generation of the chips from the intermediate layer can be suppressed by setting the weight average molecular weight to 100000 or less.

On the other hand, when Dicing (Stealth Dicing (registered trademark)) involving formation of a modified layer in a semiconductor wafer is performed using the semiconductor device-manufacturing sheet of the present embodiment as a die, since the semiconductor device-manufacturing sheet includes the intermediate layer, the film-like adhesive can be cut at a target site with good precision and cutting defects can be suppressed by stretching, that is, spreading, the semiconductor device-manufacturing sheet in a direction parallel to the surface thereof (for example, the surface of the film-like adhesive to which the semiconductor chip is attached).

In this way, the semiconductor device manufacturing sheet of the present embodiment can be provided with the property of suppressing the occurrence of defects when dividing a semiconductor wafer, and can be made excellent in suitability for dividing a semiconductor wafer, so that the generation of chips from the base material and the intermediate layer is suppressed when dicing the blade and the cutting defect of the film-like adhesive is suppressed when spreading the blade.

In the present specification, unless otherwise specified, "weight average molecular weight" refers to a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.

Hereinafter, a method of using the sheet for manufacturing a semiconductor device according to the present embodiment will be described in detail.

Hereinafter, the semiconductor device manufacturing sheet according to the present embodiment will be described in detail with reference to the drawings. For the sake of easy understanding of the features of the present invention, important parts of the drawings used in the following description may be enlarged for convenience, and the dimensional ratios of the respective components are not necessarily the same as those in reality.

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. 1.

In the drawings subsequent to fig. 2, the same reference numerals as those in the already-described drawings are assigned to the same components as those shown in the already-described drawings, and detailed description thereof is omitted.

The sheet 101 for manufacturing a semiconductor device shown here is provided with a substrate 11, and an adhesive layer 12, an intermediate layer 13, and a film-like adhesive 14 are laminated in this order on the substrate 11. The semiconductor device manufacturing sheet 101 further includes a release film 15 on a surface 14a of the film-like adhesive 14 opposite to the side on which the intermediate layer 13 is provided (hereinafter, may be referred to as "first surface").

In the semiconductor device manufacturing sheet 101, the adhesive layer 12 is provided on one surface (in this specification, sometimes referred to as "first surface") 11a of the substrate 11, the intermediate layer 13 is provided on a surface (in this specification, sometimes referred to as "first surface") 12a of the adhesive layer 12 opposite to the side on which the substrate 11 is provided, the film-like adhesive 14 is provided on a surface (in this specification, sometimes referred to as "first surface") 13a of the intermediate layer 13 opposite to the side on which the adhesive layer 12 is provided, and the release film 15 is provided on the first surface 14a of the film-like adhesive 14. In this manner, the semiconductor device manufacturing sheet 101 is configured by sequentially laminating the base material 11, the adhesive layer 12, the intermediate layer 13, and the film-like adhesive 14 in the thickness direction thereof.

The semiconductor device manufacturing sheet 101 is used in the following manner: the first surface 14a of the film-like adhesive 14 in the semiconductor device-manufacturing sheet 101 is attached to the back surface of a semiconductor wafer, a semiconductor chip, or a semiconductor wafer (not shown) that has not been completely divided, with the release film 15 removed.

In the present specification, a surface on which a circuit is formed is referred to as a "circuit-formed surface" and a surface opposite to the circuit-formed surface is referred to as a "back surface" regardless of whether the semiconductor wafer or the semiconductor chip is used.

In the present specification, a laminate having a structure in which a base material and an adhesive layer are laminated in the thickness direction thereof and an intermediate layer is not laminated is sometimes referred to as a "support sheet". In fig. 1, reference numeral 1 denotes a support piece.

A laminate having a structure in which a base material, an adhesive layer, and an intermediate layer are sequentially laminated in the thickness direction thereof is sometimes referred to as a "laminate sheet". In fig. 1, reference numeral 10 denotes a laminate sheet. The laminate of the support sheet and the intermediate layer is contained in the laminate sheet.

When the intermediate layer 13 and the film-shaped adhesive 14 are viewed from above the intermediate layer 13 and the film-shaped adhesive 14 in plan view, the planar shapes of the intermediate layer 13 and the film-shaped adhesive 14 are both circular, and the diameter of the intermediate layer 13 is the same as the diameter of the film-shaped adhesive 14.

In the semiconductor device manufacturing sheet 101, the intermediate layer 13 and the film-like adhesive 14 are arranged so that the centers thereof coincide with each other, in other words, the outer circumferential positions of the intermediate layer 13 and the film-like adhesive 14 are arranged so that the positions thereof coincide with each other in the radial direction.

The first surface 13a of the intermediate layer 13 and the first surface 14a of the film-like adhesive 14 are smaller in area than the first surface 12a of the adhesive layer 12. And, the width W of the intermediate layer 13₁₃Of (i.e., the diameter) and the width W of the film-like adhesive 14₁₄The maximum values (i.e., diameters) of (a) and (b) are smaller than the maximum value of the width of the adhesive layer 12 and the maximum value of the width of the base material 11. Therefore, in the semiconductor device manufacturing sheet 101, a part of the first surface 12a of the adhesive layer 12 is not covered with the intermediate layer 13 and the film-like adhesive 14. The release film 15 is laminated on such a region of the first surface 12a of the adhesive agent layer 12 where the intermediate layer 13 and the film-like adhesive 14 are not laminated, in direct contact therewith, and this region is exposed in a state where the release film 15 is removed (hereinafter, this region may be referred to as a "non-laminated region" in the present specification).

In the semiconductor device manufacturing sheet 101 including the release film 15, as described herein, a region where the release film 15 is not laminated may be present or may not be present in a region of the adhesive layer 12 not covered with the intermediate layer 13 and the film-like adhesive 14.

The semiconductor device manufacturing sheet 101 in a state in which the film-like adhesive 14 is not cut and is adhered to the semiconductor wafer, the semiconductor chip, or the like by the film-like adhesive 14 can be fixed by attaching a part of the non-stacked region in the adhesive layer 12 thereof to a jig such as a ring frame for fixing the semiconductor wafer. Therefore, it is not necessary to separately provide an adhesive layer for a jig for fixing the semiconductor device manufacturing sheet 101 to the jig on the semiconductor device manufacturing sheet 101. Further, since it is not necessary to provide a jig adhesive layer, the semiconductor device-manufacturing sheet 101 can be manufactured inexpensively and efficiently.

As described above, the semiconductor device manufacturing sheet 101 exhibits excellent effects by not having a jig adhesive layer, but may have a jig adhesive layer. In this case, the adhesive layer for a jig is provided in a region near the peripheral portion of the surface of an arbitrary layer constituting the semiconductor device manufacturing sheet 101. Such a region includes the non-laminated region on the first surface 12a of the adhesive layer 12.

The pressure-sensitive adhesive layer for a jig may be a known pressure-sensitive adhesive layer for a jig, and may have, for example, a single-layer structure containing a pressure-sensitive adhesive component or a multilayer structure in which layers containing a pressure-sensitive adhesive component are laminated on both surfaces of a sheet as a core material.

In addition, when the semiconductor device manufacturing sheet 101 is stretched, i.e., spread, in a direction parallel to the surface thereof (e.g., the first surface 12a of the adhesive agent layer 12) in a manner described later, the semiconductor device manufacturing sheet 101 can be easily spread because the non-laminated region is present in the first surface 12a of the adhesive agent layer 12. In addition, the film-shaped adhesive 14 can be easily cut, and the intermediate layer 13 and the film-shaped adhesive 14 can be prevented from peeling off from the adhesive layer 12 in some cases.

In the semiconductor device-manufacturing sheet 101, the intermediate layer 13 contains a non-silicone resin (. beta.1) having a weight-average molecular weight of 20000 to 100000 as a main component.

The semiconductor device manufacturing sheet according to the present embodiment is not limited to the semiconductor device manufacturing sheet shown in fig. 1 and 2, and the configuration of the part of the semiconductor device manufacturing sheet shown in fig. 1 and 2 may be changed, deleted, or added within a range not to impair the effect of the present invention.

For example, the semiconductor device-manufacturing sheet of the present embodiment may include another layer that does not belong to any of the base material, the adhesive layer, the intermediate layer, the film-like adhesive, the release film, and the jig adhesive layer. However, as shown in fig. 1, the semiconductor device manufacturing sheet of the present embodiment preferably includes an adhesive layer in a state where the adhesive layer is in direct contact with a substrate, an intermediate layer in a state where the intermediate layer is in direct contact with the adhesive layer, and a film-like adhesive in a state where the film-like adhesive is in direct contact with the intermediate layer.

For example, in the semiconductor device manufacturing sheet of the present embodiment, the planar shapes of the intermediate layer and the film-like adhesive may be shapes other than circular, and the planar shapes of the intermediate layer and the film-like adhesive may be the same as or different from each other. Further, it is preferable that the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive are both smaller than the area of the surface of the layer closer to the substrate than the first surface of the intermediate layer (for example, the first surface of the adhesive layer), and the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive may be the same as or different from each other. The outer circumferential positions of the intermediate layer and the film-like adhesive may be uniform or nonuniform in the radial direction.

Next, the layers constituting the semiconductor device manufacturing sheet of the present embodiment will be described in more detail.

Base material

The substrate is sheet-shaped or film-shaped.

The constituent material of the base material is preferably various resins, and specific examples thereof include polyethylene (low density polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE), and the like), polypropylene (PP), polybutene, polybutadiene, polymethylpentene, styrene-ethylene-butene-styrene block copolymer, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyurethane, urethane acrylate, Polyimide (PI), ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer, ethylene copolymer other than ethylene- (meth) acrylic acid copolymer and ethylene- (meth) acrylate copolymer, polystyrene, polyethylene terephthalate, and polyethylene terephthalate, Polycarbonate, fluororesin, hydrogenated product, modified product, crosslinked product, copolymer of any of the above resins, and the like.

In the present specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". Terms similar to those of (meth) acrylic acid are also the same, and for example, "(meth) acrylate" is a concept including both "acrylate" and "methyl acrylate", and "(meth) acryl" is a concept including both "acryl" and "methacryl".

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

The substrate may be composed of one layer (single layer) or may be composed of a plurality of layers of two or more layers. When the substrate is composed of a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effect of the present invention is not impaired.

In the present specification, the phrase "a plurality of layers may be the same or different from each other" means "all the layers may be the same or different from each other, or only a part of the layers may be the same" and "a plurality of layers are different from each other" means "at least one of the constituent materials and the thicknesses of the respective layers are different from each other", not limited to the base material.

The thickness of the substrate may be appropriately selected according to the purpose, but is preferably 50 to 300. mu.m, more preferably 60 to 150 μm. By setting the thickness of the base material to be equal to or greater than the lower limit value, the structure of the base material is more stable. By setting the thickness of the base material to the upper limit or less, the film-like adhesive can be cut more easily when the dicing is performed and the expansion of the sheet for manufacturing a semiconductor device (film-like adhesive) is performed.

Here, the "thickness of the substrate" refers to the thickness of the entire substrate, and for example, the thickness of the substrate composed of a plurality of layers refers to the total thickness of all layers constituting the substrate.

In order to improve the adhesion between the substrate and another layer such as an adhesive layer provided on the substrate, the surface of the substrate may be subjected to an embossing treatment such as a sandblasting treatment, a solvent treatment, or an embossing treatment; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, and other oxidation treatments.

The surface of the substrate may also be subjected to primer treatment (primer treatment).

The substrate may also have: an antistatic coating; a layer for preventing the adhesion of the base material to other sheets or the adhesion of the base material to a suction table (suction table) when the wafers are stacked and fixed and stored.

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

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

The substrate can be manufactured by a known method. For example, a base material containing a resin (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 a sheet or film form and contains an adhesive as a main component. The weight average molecular weight of the adhesive as a main component is 20000 or more. The component having the largest content (parts by mass) in the adhesive layer is the adhesive as a main component.

The adhesive layer may contain the component (γ 2) in addition to the adhesive, but may not contain the component (γ 2). As the main component (adhesive), the adhesive layer may contain a component (γ 1) which is solid at a temperature of 23 ℃, but may not contain the component (γ 1). When the component (γ 1) is the main component (adhesive), the weight average molecular weight of the component (γ 1) is 20000 or more, and the component having the largest content (part by mass) in the adhesive agent layer is the component (γ 1).

The adhesive layer preferably contains the component (γ 1), may contain both the component (γ 1) and the component (γ 2), and may contain the component (γ 1) but not the component (γ 2).

The adhesive layer can be formed using an adhesive composition containing the adhesive and, if necessary, a component (γ 2). For example, an adhesive agent layer can be formed at a target site by applying an adhesive agent composition to a surface to be formed of the adhesive agent layer and drying the composition as necessary.

The content ratio of the components that do not vaporize at ordinary temperature in the adhesive composition is generally the same as the content ratio of the components in the adhesive layer. In the present specification, "normal temperature" refers to a temperature at which cooling or heating is not particularly performed, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ℃.

In the adhesive agent layer, the ratio of the total content of one or two or more of the following contained components in the adhesive agent layer to the total mass of the adhesive agent layer is not more than 100 mass%.

Similarly, in the adhesive composition, the ratio of the total content of one or two or more of the following-described components in the adhesive composition to the total mass of the adhesive composition is not more than 100% by mass.

The adhesive composition may be applied by a known method, and examples thereof include a method using various coaters such as a knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.

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

Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, and acrylic resins are preferred.

When the adhesive layer contains the component (γ 1) as a main component (adhesive), the component (γ 1) is preferably an acrylic resin having a structural unit derived from a (meth) acrylate.

In the present specification, the "adhesive resin" includes a resin having adhesiveness and a resin having adhesiveness. For example, the adhesive resin includes not only a resin having adhesiveness of the resin itself but also a resin exhibiting adhesiveness by being used together with other components such as an additive, a resin exhibiting adhesiveness by the presence of an inducer (trigger) such as heat or water, and the like.

The adhesive layer may be either curable or non-curable, and may be either energy ray-curable or non-energy ray-curable, for example. The curable adhesive layer can be easily adjusted in physical properties before and after curing.

In the present specification, "energy ray" refers to a ray having an energy quantum in an electromagnetic wave or a charged particle beam. Examples of the energy ray include ultraviolet rays, radiation, and electron beams. The ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp (fusion lamp), a xenon lamp, a black light lamp, an LED lamp, or the like as an ultraviolet ray source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.

In the present specification, "energy ray-curable property" refers to a property of curing by irradiation with an energy ray, and "non-energy ray-curable property" refers to a property of not curing even by irradiation with an energy ray.

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

The thickness of the 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 adhesive agent layer" refers to the thickness of the entire adhesive agent layer, and for example, the thickness of the adhesive agent layer composed of a plurality of layers refers to the total thickness of all layers constituting the adhesive agent layer.

The optical characteristics of the adhesive layer are not particularly limited as long as the effects of the present invention are not impaired. For example, the adhesive layer may be an adhesive layer that transmits energy rays.

Next, the adhesive composition will be described.

Adhesive composition

When the adhesive layer is energy ray-curable, examples of the adhesive composition containing an energy ray-curable adhesive, that is, an energy ray-curable adhesive composition, include: an adhesive composition (I-1) comprising an adhesive resin (I-1a) which is not curable with energy rays (hereinafter, may be abbreviated as "adhesive resin (I-1 a)") and an energy ray-curable compound; an adhesive composition (I-2) comprising an energy ray-curable adhesive resin (I-2a) (hereinafter, sometimes abbreviated as "adhesive resin (I-2 a)") having an unsaturated group introduced into a side chain of a non-energy ray-curable adhesive resin (I-1 a); and an adhesive composition (I-3) comprising the adhesive resin (I-2a) and an energy ray-curable compound.

The adhesive compositions (I-1), (I-2) and (I-3) may further contain the component (. gamma.2) or may not contain the component (. gamma.2). As the main component (adhesive), the adhesive compositions (I-1), (I-2) and (I-3) may contain the component (. gamma.1) or may not contain the component (. gamma.1), respectively.

The adhesive compositions (I-1), (I-2) and (I-3) preferably contain the component (. gamma.1), may contain both the component (. gamma.1) and the component (. gamma.2), or may contain the component (. gamma.1) but not the component (. gamma.2).

< adhesive composition (I-1) >)

As described above, the adhesive composition (I-1) contains the non-energy ray-curable adhesive resin (I-1a) and the energy ray-curable compound, and may further contain the component (. gamma.2) in addition to these components or may not contain the component (. gamma.2).

In the adhesive composition (I-1), the adhesive resin (I-1a) or the energy ray-curable compound may be the component (. gamma.1), and the adhesive resin (I-1a) or the energy ray-curable compound may be the main component.

[ adhesive resin (I-1a) ]

Preferably, the adhesive resin (I-1a) is an acrylic resin.

Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth) acrylate.

The acrylic resin may have only one kind of structural unit, or two or more kinds of structural units, and in the case of two or more kinds of structural units, the combination and ratio thereof may be arbitrarily selected.

The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.

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

[ energy ray-curable Compound ]

Examples of the energy ray-curable compound contained in the adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with an energy ray.

Examples of the monomer in the energy ray-curable compound include polyvalent (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylates; polyether (meth) acrylates; epoxy (meth) acrylates, and the like.

Examples of the oligomer in the energy ray-curable compound include oligomers obtained by polymerizing the monomers exemplified above.

The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer from the viewpoint that the molecular weight is large and the storage modulus of the adhesive layer is not easily lowered.

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

In the adhesive composition (I-1), the content of the energy ray-curable compound is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass, based on the total mass of the adhesive composition (I-1).

When an energy ray-curable compound which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is used, the content of the energy ray-curable compound in the adhesive composition (I-1) preferably satisfies a numerical range set separately as described below.

[ crosslinking agent ]

When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), it is preferable that the adhesive composition (I-1) further contains a crosslinking agent.

The crosslinking agent reacts with the functional groups, for example, to crosslink the adhesive resins (I-1a) with each other.

Examples of the crosslinking agent include isocyanate crosslinking agents (crosslinking agents having an isocyanate group), such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; epoxy crosslinking agents (crosslinking agents having a glycidyl group) such as ethylene glycol glycidyl ether; aziridine crosslinking agents (crosslinking agents having an aziridinyl group) such as hexa [1- (2-methyl) -azidinyl ] triphosphazine (hexa [1- (2-methyl) -azidinyl ] triphosphatriazine); metal chelate crosslinking agents (crosslinking agents having a metal chelate structure) such as aluminum chelate; an isocyanurate-based crosslinking agent (a crosslinking agent having an isocyanurate skeleton), and the like.

From the viewpoint of improving the cohesive force of the adhesive, improving the adhesive force of the adhesive layer, and easy availability, the crosslinking agent is preferably an isocyanate-based crosslinking agent.

The crosslinking agent contained in the adhesive composition (I-1) may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When a crosslinking agent is used, the content of the crosslinking agent in the adhesive composition (I-1) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-1 a).

When a crosslinking agent which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is used, the content of the crosslinking agent in the adhesive composition (I-1) preferably satisfies a numerical range set separately as described later.

[ photopolymerization initiator ]

The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator can sufficiently undergo a curing reaction even when irradiated with relatively low-energy radiation 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, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2, 2-dimethoxy-1, 2-diphenylethan-1-one; acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; sulfur compounds such as benzylphenylsulfide, tetramethylthiuram monosulfide and the like; α -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; a peroxide compound; diketone compounds such as diacetyl; benzil; dibenzoyl; benzophenone; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; 2-chloroanthraquinone, and the like.

Further, as the photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like.

The photopolymerization initiator contained in the adhesive composition (I-1) may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.

When a photopolymerization initiator is used, the content of the photopolymerization initiator in the adhesive composition (I-1) 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, relative to 100 parts by mass of the content of the energy ray-curable compound.

When a photopolymerization initiator that is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is used, the content of the photopolymerization initiator in the adhesive composition (I-1) preferably satisfies a numerical range set separately as described later.

[ other additives ]

The adhesive composition (I-1) may contain other additives not belonging to any of the above components within a range not impairing the effects of the present invention.

Examples of the other additives include known additives such as antistatic agents, antioxidants, softening agents (plasticizers), fillers, rust inhibitors, coloring agents (pigments and dyes), sensitizers, tackifiers, reaction retarders, and crosslinking accelerators (catalysts).

The reaction retarder is, for example, a component for suppressing an unintended crosslinking reaction in the adhesive composition (I-1) during storage due to the action of a catalyst mixed in the adhesive composition (I-1). Examples of the reaction retarder include a reaction retarder which forms a chelate complex (chelate complex) by a chelate corresponding to a catalyst, and more specifically, a reaction retarder having two or more carbonyl groups (-C (═ O) -) in one molecule.

The other additives contained in the adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.

The content of the other additives in the adhesive composition (I-1) is not particularly limited, and may be appropriately selected depending on the type thereof.

When another additive which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is used, the content of the other additive in the adhesive composition (I-1) preferably satisfies a numerical range set separately as described later.

[ solvent ]

The adhesive composition (I-1) may contain a solvent. By containing the solvent, the applicability of the adhesive composition (I-1) to 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 (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.

[ component (. gamma.2) ]

The component (. gamma.2) in the adhesive composition (I-1) is in a liquid state at a temperature of 23 ℃. Further, the component (γ 2) does not have a functional group that reacts with the main component contained in the adhesive agent layer (i.e., does not react with the main component). A component which has a functional group that reacts with the main component contained in the adhesive agent layer and is liquid at a temperature of 23 ℃ reacts with the main component in the adhesive agent layer, and therefore, the component does not migrate from the adhesive agent layer to the intermediate layer and, as a result, does not migrate to the film-like adhesive. In the present embodiment, the transfer of the component (γ 2) which has no functional group and is liquid at a temperature of 23 ℃ from the adhesive agent layer to the film-like adhesive is suppressed, instead of the transfer of the component having the functional group and which is liquid at a temperature of 23 ℃ from the adhesive agent layer to the film-like adhesive being 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 which reacts with the main component.

As long as such conditions are satisfied, the component (γ 2) is not particularly limited and may be arbitrarily selected according to the purpose. Among the components contained in the adhesive composition (I-1) which are not included in any of the adhesive resin (I-1a) and the solvent, that is, among the energy ray-curable compound, the crosslinking agent, the photopolymerization initiator and the other additives, a component which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive layer is a component (. gamma.2). The adhesive layer is generally free of solvent.

Examples of the preferable component (. gamma.2) include an antistatic agent and a tackifier resin (tackifier).

(antistatic agent which is liquid at a temperature of 23 ℃ C.)

The antistatic agent which is liquid at a temperature of 23 ℃ may be a known antistatic agent 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 ionic liquids such as a pyrimidinium salt, a pyridinium salt, a piperidinium salt, a pyrrolidinium salt, an imidazolium salt, a morpholinium salt, a sulfonium salt, a phosphonium salt, and an ammonium salt.

The component (. gamma.2) contained in the adhesive composition (I-1) may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the component (γ 2) is used, the content of the component (γ 2) in the adhesive composition (I-1) and the adhesive agent layer can be appropriately adjusted depending on the kind of the component (γ 2).

In the adhesive composition (I-1) and the adhesive layer, the content of the component (. gamma.2) is preferably 0.1 to 40 parts by mass per 100 parts by mass of the content of the adhesive resin (I-1 a). When the content is not more than the upper limit, the migration of the component (γ 2) in the adhesive layer to the film-like adhesive is further suppressed. By making the content equal to or more than the lower limit value, the effect obtained by using the component (γ 2) becomes higher.

Particularly when the component (γ 2) is an antistatic agent, the content of the component (γ 2) (antistatic agent) is preferably 1 to 7 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the content of the adhesive resin (I-1a) in the adhesive composition (I-1) and the adhesive agent layer. When the content is not more than the upper limit, the migration of the component (γ 2) in the adhesive agent layer to the film-like adhesive agent is further suppressed, and the excessive use of the component (γ 2) is suppressed. By making the content equal to or more than the lower limit value, the effect obtained by using the component (γ 2) becomes higher.

< adhesive composition (I-2) >)

As described above, the adhesive composition (I-2) contains the energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1 a).

In addition, the adhesive composition (I-2) may further contain the component (γ 2) or may not contain the component (γ 2).

In the adhesive composition (I-2), the adhesive resin (I-2a) may be the component (. gamma.1) and the adhesive resin (I-2a) may be the main component.

[ adhesive resin (I-2a) ]

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

The unsaturated group-containing compound is a compound having a group capable of bonding to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a), in addition to the energy ray-polymerizable unsaturated group.

Examples of the energy ray-polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group (ethylene group), and an allyl group (2-propenyl group), and a (meth) acryloyl group is preferable.

Examples of the group capable of bonding to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group capable of bonding to a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of bonding to a carboxyl group or an epoxy group.

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

The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.

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

[ crosslinking agent ]

For example, when the same acrylic polymer having a structural unit derived from a functional group-containing monomer as in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), the adhesive composition (I-2) may further contain a crosslinking agent.

The crosslinking agent in the adhesive composition (I-2) may be the same crosslinking agent as that in the adhesive composition (I-1).

The crosslinking agent contained in the adhesive composition (I-2) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When a crosslinking agent is used, the content of the crosslinking agent in the adhesive composition (I-2) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-2 a).

When a crosslinking agent which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is used, the content of the crosslinking agent in the adhesive composition (I-2) preferably satisfies a numerical range set in addition to the range described later.

[ photopolymerization initiator ]

The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator can sufficiently undergo a curing reaction even when irradiated with a relatively low energy ray such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-2) may be the same photopolymerization initiator as that in the adhesive composition (I-1).

The photopolymerization initiator contained in the adhesive composition (I-2) may be one type only, or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.

When a photopolymerization initiator is used, the content of the photopolymerization initiator in the adhesive composition (I-2) 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, per 100 parts by mass of the content of the adhesive resin (I-2 a).

When a photopolymerization initiator that is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is used, the content of the photopolymerization initiator in the adhesive composition (I-2) preferably satisfies a numerical range set separately as described later.

[ other additives, solvents ]

The adhesive composition (I-2) may contain other additives not belonging to any of the above components within a range not impairing the effects of the present invention.

Further, the adhesive composition (I-2) may contain a solvent for the same purpose as the adhesive composition (I-1).

Examples of the other additives and solvents in the adhesive composition (I-2) include the same additives and solvents as those in the adhesive composition (I-1).

The other additives and solvents contained in the adhesive composition (I-2) may be each one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

The content of each of the other additives and the solvent in the adhesive composition (I-2) is not particularly limited, and may be appropriately selected depending on the type thereof.

When another additive which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is used, the content of the other additive in the adhesive composition (I-2) preferably satisfies a numerical range set separately as described later.

[ component (. gamma.2) ]

The component (. gamma.2) in the adhesive composition (I-2) is in a liquid state at a temperature of 23 ℃. Further, the component (γ 2) does not have a functional group that reacts with the main component contained in the adhesive agent layer (i.e., does not react with the main component). In the case of using the adhesive composition (I-2), the transfer of the component (. gamma.2) from the adhesive layer to the film-like adhesive is suppressed, similarly to the adhesive composition (I-1).

As long as such conditions are satisfied, the component (γ 2) is not particularly limited and may be arbitrarily selected according to the purpose. Among the components contained in the adhesive composition (I-2) which are not included in any of the adhesive resin (I-2a) and the solvent, that is, among the crosslinking agent, the photopolymerization initiator and the other additives, a component which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is a component (. gamma.2).

Examples of the preferable component (. gamma.2) in the adhesive composition (I-2) include the same components (antistatic agent, tackifier resin (tackifier), etc.) as those of the preferable component (. gamma.2) in the adhesive composition (I-1).

The component (. gamma.2) contained in the adhesive composition (I-2) may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the component (. gamma.2) is used, the content of the component (. gamma.2) in the adhesive composition (I-2) can be appropriately adjusted depending on the kind of the component (. gamma.2).

In the adhesive composition (I-2) and the adhesive layer, the content of the component (. gamma.2) is preferably 0.1 to 10 parts by mass per 100 parts by mass of the content of the adhesive resin (I-2 a). When the content is not more than the upper limit, the migration of the component (γ 2) in the adhesive layer to the film-like adhesive is further suppressed. By making the content equal to or more than the lower limit value, the effect obtained by using the component (γ 2) becomes higher.

Particularly when the component (γ 2) is an antistatic agent, the content of the component (γ 2) (antistatic agent) is preferably 1 to 7 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the content of the adhesive resin (I-2a) in the adhesive composition (I-2) and the adhesive agent layer. When the content is not more than the upper limit, the migration of the component (γ 2) in the adhesive agent layer to the film-like adhesive agent is further suppressed, and the excessive use of the component (γ 2) is suppressed. By making the content equal to or more than the lower limit value, the effect obtained by using the component (γ 2) becomes higher.

< adhesive composition (I-3) >)

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

In addition, the adhesive composition (I-3) may further contain the above-mentioned component (. gamma.2) or may not contain the component (. gamma.2).

In the adhesive composition (I-3), the adhesive resin (I-2a) or the energy ray-curable compound may be the component (. gamma.1), and the adhesive resin (I-2a) or the energy ray-curable compound may be the main component.

[ adhesive resin (I-2a) ]

The adhesive resin (I-2a) in the adhesive composition (I-3) may be the same adhesive resin as the adhesive resin (I-2a) in the adhesive composition (I-2).

The adhesive resin (I-2a) contained in the adhesive composition (I-3) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.

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

[ energy ray-curable Compound ]

Examples of the energy ray-curable compound contained in the adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with an energy ray, and examples include the same energy ray-curable compounds as those contained in the adhesive composition (I-1).

The energy ray-curable compound contained in the adhesive composition (I-3) may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

The content of the energy ray-curable compound in the adhesive composition (I-3) and the adhesive layer is preferably 0.01 to 300 parts by mass, more preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2 a).

When an energy ray-curable compound which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is used, the content of the energy ray-curable compound in the adhesive composition (I-3) preferably satisfies a numerical range set separately as described below.

[ photopolymerization initiator ]

The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator can sufficiently undergo a curing reaction even when irradiated with relatively low-energy radiation such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-3) may be the same photopolymerization initiator as that in the adhesive composition (I-1).

The photopolymerization initiator contained in the adhesive composition (I-3) may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When a photopolymerization initiator is used, the content of the photopolymerization initiator in the adhesive composition (I-3) 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, based on 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound.

When a photopolymerization initiator which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is used, the content of the photopolymerization initiator in the adhesive composition (I-3) preferably satisfies a numerical range set separately as described later.

[ other additives, solvents ]

The adhesive composition (I-3) may contain other additives not belonging to any of the above components within a range not impairing the effects of the present invention.

Further, the adhesive composition (I-3) may contain a solvent for the same purpose as the adhesive composition (I-1).

Examples of the other additive and the solvent in the adhesive composition (I-3) include the same additives and solvents as those in the adhesive composition (I-1).

The adhesive composition (I-3) may contain only one type of other additive and one or more types of solvent, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.

The contents of other additives and solvents in the adhesive composition (I-3) are not particularly limited, and may be appropriately selected depending on the type thereof.

When another additive which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is used, the content of the other additive in the adhesive composition (I-3) preferably satisfies a numerical range set separately as described later.

[ component (. gamma.2) ]

The component (. gamma.2) in the adhesive composition (I-3) is in a liquid state at a temperature of 23 ℃. Further, the component (γ 2) does not have a functional group that reacts with the main component contained in the adhesive agent layer (i.e., does not react with the main component). In the case of using the adhesive composition (I-3), the transfer of the component (. gamma.2) from the adhesive layer to the film-like adhesive is suppressed, similarly to the adhesive composition (I-1).

As long as such conditions are satisfied, the component (γ 2) is not particularly limited and may be arbitrarily selected according to the purpose. Among the components contained in the adhesive composition (I-3) which are not included in any of the adhesive resin (I-2a) and the solvent, that is, among the energy ray-curable compound, the photopolymerization initiator and the other additives, a component which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is the component (. gamma.2).

Examples of the preferable component (. gamma.2) in the adhesive composition (I-3) include the same components (antistatic agent, tackifier resin (tackifier), etc.) as those of the preferable component (. gamma.2) in the adhesive composition (I-1).

The component (. gamma.2) contained in the adhesive composition (I-3) may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the component (. gamma.2) is used, the content of the component (. gamma.2) in the adhesive composition (I-3) can be appropriately adjusted depending on the kind of the component (. gamma.2).

In the adhesive composition (I-3) and the adhesive layer, the content of the component (. gamma.2) is preferably 0.1 to 10 parts by mass per 100 parts by mass of the content of the adhesive resin (I-2 a). When the content is not more than the upper limit, the migration of the component (γ 2) in the adhesive layer to the film-like adhesive is further suppressed. By making the content equal to or more than the lower limit value, the effect obtained by using the component (γ 2) becomes higher.

In particular, when the component (γ 2) is an antistatic agent, the content of the component (γ 2) (antistatic agent) in the adhesive composition (I-3) and the adhesive agent layer is preferably 1 to 7 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the content of the adhesive resin (I-2 a). When the content is not more than the upper limit, the transfer of the component (γ 2) in the adhesive layer to the film-like adhesive is further suppressed, and the excessive use of the component (γ 2) is suppressed. By making the content the lower limit or more, the effect obtained by using the component (γ 2) becomes higher.

< adhesive compositions other than the adhesive compositions (I-1) to (I-3) >

Although the adhesive composition (I-1), the adhesive composition (I-2) and the adhesive composition (I-3) have been mainly described so far, the components described as the components contained therein can be similarly used in all adhesive compositions other than the three adhesive compositions (in the present specification, referred to as "adhesive compositions other than the adhesive compositions (I-1) to (I-3)").

Examples of the adhesive compositions other than the adhesive compositions (I-1) to (I-3) include energy ray-curable adhesive compositions and non-energy ray-curable adhesive compositions.

Examples of the non-energy ray-curable adhesive composition include an adhesive composition (I-4) containing a non-energy ray-curable adhesive resin (I-1a) such as an acrylic resin, a urethane resin, a rubber resin, a silicone resin, an epoxy resin, a polyvinyl ether, a polycarbonate, or an ester resin, and a non-energy ray-curable adhesive composition containing an acrylic resin is preferable.

The adhesive compositions other than the adhesive compositions (I-1) to (I-3) preferably contain one or more kinds of crosslinking agents, and the content thereof may be set to the same level as that of the adhesive composition (I-1).

< adhesive composition (I-4) >)

As a preferred adhesive composition (I-4), for example, an adhesive composition comprising the adhesive resin (I-1a) and a crosslinking agent may be mentioned, and in addition thereto, the component (. gamma.2) may be further contained or the component (. gamma.2) may not be contained.

In the adhesive composition (I-4), the adhesive resin (I-1a) may be the component (. gamma.1), and the adhesive resin (I-1a) may be the main component.

[ adhesive resin (I-1a) ]

The adhesive resin (I-1a) in the adhesive composition (I-4) may be the same adhesive resin as the adhesive resin (I-1a) in the adhesive composition (I-1).

The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.

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

[ crosslinking agent ]

When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), it is preferable that the adhesive composition (I-4) further contains a crosslinking agent.

The crosslinking agent in the adhesive composition (I-4) may be the same crosslinking agent as that in the adhesive composition (I-1).

The crosslinking agent contained in the adhesive composition (I-4) may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

In the adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 25 parts by mass, and particularly preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-1 a).

When a crosslinking agent which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is used, the content of the crosslinking agent in the adhesive composition (I-4) preferably satisfies a numerical range set separately as described later.

[ other additives, solvents ]

The adhesive composition (I-4) may contain other additives not belonging to any of the above components within a range not impairing the effects of the present invention.

Further, the adhesive composition (I-4) may contain a solvent for the same purpose as the adhesive composition (I-1).

Examples of the other additive and the solvent in the adhesive composition (I-4) include the same additives and solvents as those in the adhesive composition (I-1).

The adhesive composition (I-4) may contain only one type of other additive and one or more types of solvent, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.

The contents of other additives and solvents in the adhesive composition (I-4) are not particularly limited, and may be appropriately selected depending on the type thereof.

When another additive which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is used, the content of the other additive in the adhesive composition (I-4) preferably satisfies a numerical range set separately as described later.

[ component (. gamma.2) ]

The component (. gamma.2) in the adhesive composition (I-4) is in a liquid state at a temperature of 23 ℃. Further, the component (γ 2) does not have a functional group that reacts with the main component contained in the adhesive agent layer (i.e., does not react with the main component). In the case of using the adhesive composition (I-4), the transfer of the component (. gamma.2) from the adhesive layer to the film-like adhesive is suppressed, similarly to the adhesive composition (I-1).

As long as such conditions are satisfied, the component (γ 2) is not particularly limited and may be arbitrarily selected according to the purpose. Among the components contained in the adhesive composition (I-4) which are not contained in any of the adhesive resin (I-1a) and the solvent, that is, the crosslinking agent and the other additives, the component which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive agent layer is the component (. gamma.2).

Examples of the preferable component (. gamma.2) in the adhesive composition (I-4) include the same components (antistatic agent, tackifier resin (tackifier), etc.) as those of the preferable component (. gamma.2) in the adhesive composition (I-1).

The component (. gamma.2) contained in the adhesive composition (I-4) may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the component (. gamma.2) is used, the content of the component (. gamma.2) in the adhesive composition (I-4) can be appropriately adjusted depending on the type of the component (. gamma.2).

In the adhesive composition (I-4) and the adhesive layer, the content of the component (. gamma.2) is preferably 0.1 to 10 parts by mass per 100 parts by mass of the content of the adhesive resin (I-1 a). When the content is not more than the upper limit, the migration of the component (γ 2) in the adhesive layer to the film-like adhesive is further suppressed. By making the content equal to or more than the lower limit value, the effect obtained by using the component (γ 2) becomes higher.

Particularly when the component (γ 2) is an antistatic agent, the content of the component (γ 2) (antistatic agent) is preferably 1 to 7 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the content of the adhesive resin (I-1a) in the adhesive composition (I-4) and the adhesive agent layer. When the content is not more than the upper limit, the migration of the component (γ 2) in the adhesive agent layer to the film-like adhesive agent is further suppressed, and the excessive use of the component (γ 2) is suppressed. By making the content equal to or more than the lower limit value, the effect obtained by using the component (γ 2) becomes higher.

When the component (γ 2) is used, the content of the component (γ 2) in the adhesive agent layer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the content of the adhesive agent, regardless of whether the adhesive agent composition is any of the adhesive agent compositions (I-1) to (I-4).

Particularly when the component (γ 2) is an antistatic agent, the content of the component (γ 2) (antistatic agent) in the adhesive agent layer is preferably 1 to 7 parts by mass, more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the content of the adhesive agent.

Method for preparing adhesive composition

The adhesive compositions other than the adhesive compositions (I-1) to (I-3), such as the adhesive compositions (I-1) to (I-3) and the adhesive composition (I-4), can be obtained by blending the components constituting the adhesive compositions, that is, by blending the adhesive and, if necessary, components other than the adhesive.

The order of addition of the components in blending is not particularly limited, and two or more components may be added simultaneously.

When a solvent is used, the solvent may be mixed with any of the components other than the solvent to dilute the components in advance, or the solvent may be mixed with the components without diluting any of the components other than the solvent to use.

When blending, the method for mixing the components is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a stirring blade, or the like; a method of mixing using a mixer (mixer); a method of mixing by applying ultrasonic waves, and the like.

The temperature and time for adding and mixing the components are not particularly limited and may be appropriately adjusted as long as the components are not deteriorated, but the temperature is preferably 15 to 30 ℃.

Intermediate layer and intermediate layer-forming composition

The intermediate layer is in the form of a sheet or a film and contains the non-silicon resin (. beta.1) as a main component.

The intermediate layer may contain only the non-silicone resin (β 1) (composed of the non-silicone resin (β 1)), or may contain the non-silicone resin (β 1) and components other than the non-silicone resin (β 1).

The intermediate layer can be formed using, for example, an intermediate layer-forming composition containing the non-silicon resin (. beta.1). For example, the intermediate layer can be formed on a target site by applying the intermediate layer-forming composition to a surface to be formed of the intermediate layer and drying the composition as necessary.

In the intermediate layer, the ratio of the total content of one or two or more of the below-described components contained in the intermediate layer to the total mass of the intermediate layer is not more than 100 mass%.

Similarly, in the intermediate layer-forming composition, the ratio of the total content of one or two or more of the later-described components in the intermediate layer-forming composition to the total mass of the intermediate layer-forming composition is not more than 100% by mass.

The intermediate layer-forming composition can be applied by the same method as the application of the adhesive composition described above.

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

The weight-average molecular weight of the non-silicone resin (. beta.1) is 20000 to 100000.

From the viewpoint of further improving the suitability for dividing the semiconductor wafer of the semiconductor device manufacturing sheet, the weight average molecular weight of the non-silicon resin (β 1) may be, for example, 20000 to 80000, 20000 to 60000, or 20000 to 40000.

The component having the largest content (mass part) in the intermediate layer is the non-silicone resin (. beta.1).

From the viewpoint of the intermediate layer exerting a higher effect of containing the non-silicon resin (β 1), the proportion of the content of the non-silicon resin (β 1) in the intermediate layer with respect to the total mass of the intermediate layer (in other words, the proportion of the content of the non-silicon resin (β 1) in the intermediate layer-forming composition with respect to the total content of all the components excluding the solvent) is preferably 75 mass% or more, more preferably 85 mass% or more, and may be, for example, any one of 95 mass% or more, 97 mass% or more, and 99 mass% or more.

On the other hand, the proportion is 100 mass% or less.

The non-silicon resin (. beta.1) is not particularly limited as long as it is a resin component having a weight average molecular weight of 20000 to 100000 and no silicon atom as a constituent atom.

The non-silicone resin (. beta.1) 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-silicone resin (β 1) is preferably a polar resin from the viewpoint of high solubility in the intermediate layer-forming composition and higher coatability of the intermediate layer-forming composition.

The non-silicone resin (β 1) may be, for example, a homopolymer of a polymer (in other words, having only one kind of structural unit) as one kind of monomer, or a copolymer of polymers (in other words, having two or more kinds of structural units) as two or more kinds of monomers.

Examples of the polar group include a carbonyloxy group (-C (═ O) -O-), an oxycarbonyl group (-O-C (═ 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 structural units derived from vinyl acetate.

Examples of the structural unit having no polar group include structural units derived from ethylene.

In the polar resin, the proportion of the mass of the structural unit having a polar group to the total mass of all the structural units is preferably 45 mass% or less, and more preferably 30 mass% or less. The lower the ratio, the higher the effect of suppressing migration of the component (α 2) in the film-shaped adhesive to the adhesive agent layer and suppressing migration of the component (γ 2) in the adhesive agent layer to the film-shaped adhesive becomes.

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 remarkably the polar resin has the characteristic 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 may be appropriately adjusted within a range set by arbitrarily combining any upper limit value and any lower limit value. For example, in one embodiment, the ratio may be in a range of 5 to 45 mass%, 7.5 to 45 mass%, 10 to 45 mass%, 5 to 30 mass%, 7.5 to 30 mass%, and 10 to 30 mass%.

Examples of the polar resin include an ethylene-vinyl acetate copolymer.

Among these, preferable examples of the polar resin include those 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 present specification, it may be referred to as "content of the structural unit derived from vinyl acetate") in the ethylene-vinyl acetate copolymer is within any numerical range of the above-mentioned "ratio of the mass of the structural unit having a polar group", and particularly preferable examples thereof are those in which the ratio is 30% by mass or less. Specifically, a particularly preferred example of the polar resin is a polar resin in which the ratio of the mass of a structural unit derived from vinyl acetate to the total mass of all the structural units in an ethylene-vinyl acetate copolymer is 30% by mass or less. In other words, a particularly preferable example of the polar resin is a polar resin in which the ratio of the mass of the structural unit derived from ethylene to the total mass of all the structural units in the ethylene-vinyl acetate copolymer is 70 mass% or more.

Examples of the nonpolar resin include Polyethylene (PE) such as Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), metallocene catalyst linear low density polyethylene (metallocene LLDPE), Medium Density Polyethylene (MDPE), and High Density Polyethylene (HDPE); polyolefins such as polypropylene (PP).

The non-silicone resin (. beta.1) contained in the composition for forming an intermediate layer and the intermediate layer may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.

For example, the composition for forming an intermediate layer and the intermediate layer may contain one or more non-silicone resins (β 1) as polar resins and not contain the non-silicone resin (β 1) as a non-polar resin, may contain one or more non-silicone resins (β 1) as non-polar resins and not contain the non-silicone resin (β 1) as a polar resin, and may contain one or more non-silicone resins (β 1) as polar resins and the non-silicone resin (β 1) as a non-polar resin at the same time.

Preferably, the composition for forming an intermediate layer and the intermediate layer contain at least a non-silicone resin (. beta.1) as a polar resin.

The intermediate layer-forming composition and the intermediate layer preferably contain one or more selected from the group consisting of an ethylene-vinyl acetate copolymer and a polyolefin as the non-silicone resin (β 1). In the semiconductor device manufacturing sheet provided with such an intermediate layer, when the film-like adhesive contains the component (α 2), the transfer of the component (α 2) in the film-like adhesive to the adhesive layer is further suppressed, and when the adhesive layer contains the component (γ 2), the transfer of the component (γ 2) in the adhesive layer to the film-like adhesive is further suppressed.

In the composition for forming an intermediate layer and the intermediate layer, the proportion of the content of the non-silicone resin (β 1) as a polar resin to the total content of the non-silicone resins (β 1) is preferably 80% by mass or more, more preferably 90% by mass or more, and may be, for example, any one of the ranges of 95% by mass or more, 97% by mass or more, and 99% by mass or more. By setting the ratio to be equal to or higher than the lower limit, the effect of using the polar resin can be more remarkably obtained.

On the other hand, the proportion is 100 mass% or less.

That is, in the composition for forming an intermediate layer and the intermediate layer, the proportion of the content of the non-silicone resin (β 1) as a non-polar resin to the total content of the non-silicone resins (β 1) is preferably 20% by mass or less, more preferably 10% by mass or less, and may be, for example, any range of 5% by mass or less, 3% by mass or less, and 1% by mass or less.

On the other hand, the ratio is 0 mass% or more.

From the viewpoint of good workability of the composition for forming an intermediate layer, the composition for forming an intermediate layer preferably contains a solvent in addition to the non-silicone resin (β 1), and may contain a component not belonging to either the non-silicone resin (β 1) or the solvent (in the present specification, it may be referred to as a component that is sometimes referred to as a component that is not included in the non-silicone resin (β 1) or the solvent (in this specification)

An "additive").

The intermediate layer may contain only the non-silicone resin (. beta.1), or may contain both the non-silicone resin (. beta.1) and the additive.

The additive may be any of a resin component (sometimes referred to as "other resin component" in the present specification) and a non-resin component.

Examples of the other resin component include a non-silicone resin and a silicone resin having a weight average molecular weight (Mw) of more than 100000(Mw > 100000).

The non-silicone resin having a weight average molecular weight of more than 100000 is not particularly limited as long as such a condition is satisfied.

As described later, the intermediate layer containing the silicone resin makes the pickup of the semiconductor chip with the film adhesive easier.

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 silicone resin is not particularly limited.

Examples of the preferred silicone resin include a resin component that exhibits a releasing action on the adhesive component, and more preferably a silicone resin (also referred to as a resin component having a siloxane bond (-Si-O-Si-) or a silicone compound).

Examples of the silicone resin include polydialkylsiloxane.

The number of carbon atoms of the alkyl group of the polydialkylsiloxane is preferably 1 to 20.

Examples of the polydialkylsiloxane include polydimethylsiloxane.

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

The composition for forming an intermediate layer and the additive contained in the intermediate layer may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

For example, the composition for forming an intermediate layer and the intermediate layer may contain one or two or more resin components and not contain a non-resin component, may contain one or two or more non-resin components and not contain a resin component, and may contain one or two or more resin components and non-resin components at the same time as the additive.

When the intermediate layer-forming composition and the intermediate layer contain the additive, the ratio of the content of the non-silicon resin (β 1) to the total mass of the intermediate layer in the intermediate layer (in other words, the ratio of the content of the non-silicon resin (β 1) to the total content of all components excluding the solvent in the intermediate layer-forming composition) is preferably 90 to 99.99 mass%, and may be, for example, any one of 90 to 97.5 mass%, 90 to 95 mass%, and 90 to 92.5 mass%, or may be any one of 92.5 to 99.99 mass%, 95 to 99.99 mass%, and 97.5 to 99.99 mass%, or may be 92.5 to 97.5 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, the ratio of the content of the additive to the total content of all components except the solvent in the intermediate layer-forming composition) is preferably 0.01 to 10% by mass, and may be, for example, any one of 2.5 to 10% by mass, 5 to 10% by mass, and 7.5 to 10% by mass, or may be any one of 0.01 to 7.5% by mass, 0.01 to 5% by mass, and 0.01 to 2.5% by mass, and may be 2.5 to 7.5% by mass.

The solvent contained in the composition for forming the intermediate layer is not particularly limited, but preferable examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.

The intermediate layer-forming composition may contain only one kind of solvent, or may contain two or more kinds of solvents, and in the case of two or more kinds of solvents, the combination and ratio thereof may be arbitrarily selected.

The solvent contained in the intermediate layer-forming composition is preferably tetrahydrofuran or the like, from the viewpoint of enabling more uniform mixing of the components contained in the intermediate layer-forming composition.

The content of the solvent in the intermediate layer-forming composition is not particularly limited, and may be appropriately selected depending on the kind of components other than the solvent.

As described later, from the viewpoint of enabling easier pickup of the semiconductor chip with the film-like adhesive, preferable examples of the intermediate layer include the following intermediate layers: and an intermediate layer containing an ethylene-vinyl acetate copolymer as the non-silicone resin (β 1) and a siloxane compound as the additive, wherein the ratio of the content of the ethylene-vinyl acetate copolymer (the non-silicone resin (β 1)) in the intermediate layer to the total mass of the intermediate layer is within any one of the numerical value ranges described above, and the ratio of the content of the siloxane compound (the additive) in the intermediate layer to the total mass of the intermediate layer is within any one of the numerical value ranges described above.

Examples of such an intermediate layer include the following intermediate layers: and an intermediate layer containing an ethylene-vinyl acetate copolymer as the non-silicone resin (. beta.1) and a siloxane compound as the additive, wherein the ratio of the content of the ethylene-vinyl acetate copolymer in the intermediate layer to the total mass of the intermediate layer is 90 to 99.99 mass%, and the ratio of the content of the siloxane compound in the intermediate layer to the total mass of the intermediate layer is 0.01 to 10 mass%. However, this is only one example of a preferred intermediate layer.

More preferred examples of the intermediate layer include the following intermediate layers: the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicone resin (. beta.1) and a siloxane compound as the additive, wherein the ratio of the mass of a structural unit derived from vinyl acetate to the total mass of all the structural units (in other words, the content of a structural unit derived from vinyl acetate) in the ethylene-vinyl acetate copolymer is 30% by mass or less, the ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the intermediate layer in the intermediate layer 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. However, this is only one example of a more preferred intermediate layer.

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

XPS analysis can be performed in the following manner: the surface of the film-like adhesive side of the intermediate layer to be analyzed was subjected to an X-ray photoelectron spectroscopy analysis using an X-ray photoelectron spectroscopy analyzer, the irradiation angle of the X-ray was set to 45 °, and the beam diameter of the X-ray was set to 45 °

The output was set to 4.5W.

The ratio of the silicon concentration can be calculated using the following formula:

[ measured value of silicon concentration (atomic%) by XPS analysis ]/{ [ measured value of carbon concentration (atomic%) by XPS analysis ] + [ measured value of oxygen concentration (atomic%) by XPS analysis ] + [ measured value of nitrogen concentration (atomic%) by XPS analysis ] + [ measured value of silicon concentration (atomic%) by XPS analysis ] + ] }. times.100

From the viewpoint of making the above-mentioned effects more remarkable, for example, the proportion of the silicon concentration may be in any range of 4 to 20%, 8 to 20%, and 12 to 20%, may be in any range of 1 to 16%, 1 to 12%, and 1 to 8%, and may be in any range of 4 to 16%, and 8 to 12%, on a molar basis of the element.

When the XPS analysis is performed in the above manner, another element which does not belong to any of carbon, oxygen, nitrogen, and silicon may be detected in the surface of the intermediate layer (the surface to be analyzed by XPS). However, since the concentration of the other element is usually trace even if it is detected, the ratio of the silicon concentration can be calculated with high accuracy by using the measured values of the concentrations of carbon, oxygen, nitrogen, and silicon when calculating the ratio of the silicon concentration.

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

As described above, the first test piece composed of the non-silicone resin (β 1) contained in the intermediate layer satisfies the relationship between the formula (X1) and the formula (X2).

As described above, the maximum value of the width of the intermediate layer is preferably smaller than the maximum value of the width of the adhesive layer and the maximum value of the width of the substrate.

The maximum value of the width of the intermediate layer may be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum value of the width of the intermediate layer may be 150 to 160mm, 200 to 210mm, or 300 to 310 mm. These three numerical ranges correspond to semiconductor wafers having a maximum value of width in a direction parallel to a surface to which the semiconductor device manufacturing sheet is attached of 150mm, 200mm, or 300 mm. However, when the film-like adhesive is cut by expanding the semiconductor device manufacturing sheet (film-like adhesive) after the dicing accompanied by the formation of the modified layer in the semiconductor wafer as described above, the semiconductor device manufacturing sheet is attached to a plurality of semiconductor chips (semiconductor chip groups) after the dicing as a whole as described later.

In the present specification, unless otherwise specified, "the width of the intermediate layer" means, for example

"width of the intermediate layer in a direction parallel to the first face". For example, in the case of an intermediate layer having a circular planar shape, the maximum value of the width of the intermediate layer is the diameter of the circle having the planar shape.

This is also the case with semiconductor wafers. That is, "the width of the semiconductor wafer" means "the width of the semiconductor wafer in the direction parallel to the surface of the semiconductor wafer to be bonded to the semiconductor device manufacturing sheet". For example, in the case of a semiconductor wafer having a circular planar shape, the maximum value of the width of the semiconductor wafer is the diameter of the circle having the planar shape.

The maximum value of the width of the intermediate layer of 150 to 160mm is equal to or greater than the maximum value of the width of the semiconductor wafer of 150mm in a range of not more than 10 mm.

Similarly, the maximum value of the width of the intermediate layer of 200 to 210mm is equal to or greater than the maximum value of the width of the semiconductor wafer of 200mm in a range of not more than 10 mm.

Similarly, the maximum value of the width of the intermediate layer of 300 to 310mm is equal to or greater than the maximum value of the width of the semiconductor wafer of 300mm in a range of not more than 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 may be, for example, 0 to 10mm, regardless of which value of 150mm, 200mm and 300mm the maximum value of the width of the semiconductor wafer is.

The thickness of the intermediate layer may be appropriately selected according to the purpose, but is preferably 5 to 150 μm, more preferably 5 to 120 μm, and may be, for example, any one of 10 to 90 μm and 10 to 60 μm, or may be any one of 30 to 120 μm and 60 to 120 μm. By making the thickness of the intermediate layer more than the lower limit value, the structure of the intermediate layer is more stable. By setting the thickness of the intermediate layer to the upper limit or less, the film-like adhesive can be cut more easily during the dicing and the spreading of the sheet for manufacturing a semiconductor device (film-like adhesive).

Here, the "thickness of the intermediate layer" refers to the thickness of the entire intermediate layer, and for example, the thickness of the intermediate layer composed of a plurality of layers refers to the total thickness of all layers constituting the intermediate layer.

When the intermediate layer contains the silicon-based resin, particularly when the compatibility of the silicon-based resin with the non-silicon-based resin (β 1) as a main component is low, the silicon-based resin in the intermediate layer tends to unevenly exist on both surfaces (the first surface and the surface opposite to the first surface) of the intermediate layer and the vicinity thereof in the semiconductor device-manufacturing sheet. Further, the stronger this tendency, the more easily the film-like adhesive adjacent to (in direct contact with) the intermediate layer is peeled off from the intermediate layer, and the more easily the semiconductor chip with the film-like adhesive can be picked up as described later.

For example, when comparing intermediate layers that differ from each other only in thickness but are identical to each other in composition, area of both sides, and the like except for thickness, in these intermediate layers, the proportions (mass%) of the content of the silicone-based resin with respect to the total mass of the intermediate layers are identical to each other. However, the content (parts by mass) of the silicone resin in the intermediate layer having a relatively large thickness is larger than the content (parts by mass) of the silicone resin in the intermediate layer having a relatively small thickness. Therefore, when the silicon-based resin is likely to be unevenly present in the intermediate layer as described above, the amount of the silicon-based resin unevenly present on both surfaces (the first surface and the surface opposite to the first surface) and the vicinity thereof of the intermediate layer having a large thickness is larger than that of the intermediate layer having a small thickness. Therefore, the pick-up suitability of the semiconductor chip with the film-like adhesive can be adjusted 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 the film-like adhesive can be picked up more easily.

The composition for forming the intermediate layer can be obtained by blending the components for constituting the composition.

The intermediate layer-forming composition can be produced, for example, by the same method as the above-described method for producing the adhesive composition, except that the kind of the blending component is different.

Film-like adhesive

The film-like adhesive has curability, preferably thermosetting, and preferably pressure-sensitive adhesiveness. A film-like adhesive having both thermosetting and pressure-sensitive adhesive properties can be attached to various adherends by light pressing in an uncured state. The film-like adhesive may be attached to various adherends by softening the adhesive by heating. The film-like adhesive is cured to finally form a cured product having high impact resistance, which can maintain sufficient adhesive properties even under severe conditions of high temperature and high humidity.

As a preferable film-like adhesive, for example, a film-like adhesive containing a polymer component (a) and a thermosetting component (b) can be mentioned.

The film-like adhesive may contain the component (. alpha.2) or may not contain the component (. alpha.2). The component (. alpha.2) may be a thermosetting component (b) or a component other than the thermosetting component (b), other than the polymer component (a).

The film-shaped adhesive may contain, as the polymer component (a), the component (α 1) which is solid at a temperature of 23 ℃, or may not contain the component (α 1).

The film-shaped adhesive may contain the polymer component (a) as the main component, or may not contain the component (a).

The film-shaped adhesive may contain the component (. alpha.1) as the main component, or may not contain the component (. alpha.1). When the component (α 1) is the main component, the component (α 1) has a weight average molecular weight of 20000 or more, and the component having the largest content (parts by mass) in the film-like adhesive is the component (α 1).

The film-like adhesive preferably contains the component (. alpha.1), may contain both the component (. alpha.1) and the component (. alpha.2), and may contain the component (. alpha.1) but not the component (. alpha.2).

When the film-like adhesive contains component (α 1) as a main component, component (α 1) is preferably an acrylic resin having a structural unit derived from a (meth) acrylate ester.

The film-shaped adhesive can be formed using an adhesive composition containing the constituent materials thereof. For example, a film-shaped adhesive can be formed on a target site by applying an adhesive composition to a surface to be formed with the film-shaped adhesive and drying the adhesive composition as needed.

The content ratio of the components that do not vaporize at ordinary temperature in the adhesive composition to each other is generally the same as the content ratio of the components to each other in the film-shaped adhesive.

In the film-shaped adhesive, the ratio of the total content of one or two or more of the following-described components in the film-shaped adhesive to the total mass of the film-shaped adhesive is not more than 100% by mass.

Similarly, in the binder composition, the ratio of the total content of one or two or more of the following-described components in the binder composition to the total mass of the binder composition is not more than 100% by mass.

The adhesive composition can be applied by the same method as the application of the adhesive composition described above.

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

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

When the semiconductor device manufacturing sheet is viewed from above in a downward direction, the area of the film-like adhesive (i.e., the area of the first surface) is preferably set to be smaller than the area of the base material (i.e., the area of the first surface) and the area of the adhesive layer (i.e., the area of the first surface) so as to be close to the area of the semiconductor wafer before dicing. In such a semiconductor device manufacturing sheet, a region not in contact with the intermediate layer and the film-like adhesive (i.e., the non-laminated region) is present in a part of the first surface of the adhesive layer. This makes it easier to spread the sheet (film-like adhesive) for manufacturing a semiconductor device, and also makes it easier to cut the film-like adhesive because the force applied to the film-like adhesive does not disperse during spreading.

As described above, the maximum value of the width of the film-like adhesive is preferably smaller than the maximum value of the width of the adhesive layer and the maximum value of the width of the base material.

The maximum value of the width of the film-like adhesive may be the same as the maximum value of the width of the intermediate layer explained above with respect to the size of the semiconductor wafer.

That is, the maximum value of the width of the film-like adhesive can be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum value of the width of the film-like adhesive may be 150 to 160mm, 200 to 210mm, or 300 to 310 mm. These three numerical ranges correspond to semiconductor wafers having a maximum value of width in a direction parallel to a surface to which the semiconductor device manufacturing sheet is attached of 150mm, 200mm, or 300 mm.

In the present specification, unless otherwise specified, "width of the film-like adhesive" means, for example, "width of the film-like adhesive in a direction parallel to the first surface of the film-like adhesive". For example, in the case of a film-like adhesive having a circular planar shape, the maximum value of the width of the film-like adhesive is the diameter of a circle having the planar shape.

Unless otherwise specified, the "width of the film-like adhesive" refers to "the width of the film-like adhesive before cutting (without cutting)" and 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.

The maximum value of the width of the film-like adhesive of 150 to 160mm is equal to or larger than the maximum value of the width of a semiconductor wafer of 150mm in a range of not more than 10 mm.

Similarly, the maximum value of the width of the film-like adhesive of 200 to 210mm means the maximum value of the width of a semiconductor wafer which is equal to or larger than 200mm within a range of not more than 10 mm.

Similarly, the maximum value of the width of the film-like adhesive of 300 to 310mm is equal to or larger than the maximum value of the width of a semiconductor wafer of 300mm in a range of not more than 10 mm.

That is, in the present embodiment, the difference between the maximum value of the width of the film-shaped adhesive and the maximum value of the width of the semiconductor wafer may be, for example, 0 to 10mm, regardless of which value of 150mm, 200mm, and 300mm the maximum value of the width of the semiconductor wafer is.

In the present embodiment, the maximum value of the width of the intermediate layer and the maximum value of the width of the film-shaped adhesive may be any one of the above numerical value ranges.

That is, as an example of the sheet for manufacturing a semiconductor device of the present embodiment, there can be mentioned a sheet for manufacturing a semiconductor device in which the maximum value of the width of the intermediate layer and the maximum value of the width of the film-like adhesive are 150 to 160mm, 200 to 210mm, or 300 to 310 mm.

The thickness of the film-like binder is not particularly limited, but is preferably 1 to 30 μm, more preferably 2 to 20 μm, and particularly preferably 3 to 10 μm. By setting the thickness of the film-like pressure-sensitive adhesive to the lower limit or more, a higher adhesive force to an adherend (semiconductor chip) can be obtained. By setting the thickness of the film-like adhesive to the upper limit or less, the film-like adhesive can be cut more easily when the dicing is performed and when the sheet for manufacturing a semiconductor device (film-like adhesive) is expanded.

Here, the "thickness of the film-shaped adhesive" refers to the thickness of the entire film-shaped adhesive, and for example, the thickness of the film-shaped adhesive composed of a plurality of layers refers to the total thickness of all the layers constituting the film-shaped adhesive.

Next, the adhesive composition will be described.

Adhesive composition

Examples of a preferable pressure-sensitive adhesive composition include a pressure-sensitive adhesive composition containing a polymer component (a) and a thermosetting component (b).

The adhesive composition may further contain the component (α 2) or may not contain the component (α 2) in addition to the polymer component (a) and the thermosetting component (b).

In the adhesive composition, the polymer component (a) may be the component (α 1), and the polymer component (a) may be a main component.

The respective components in the adhesive composition and the film-like adhesive are explained below.

In addition, the adhesive composition shown below is only one example of a preferable adhesive composition, and the adhesive composition in the present embodiment is not limited to the adhesive composition shown below.

[ Polymer component (a) ]

The polymer component (a) is a component formed by polymerizing a polymerizable compound, and is a polymer compound for imparting film-forming properties, flexibility, and the like to a film-like adhesive and simultaneously improving the adhesiveness (in other words, adhesiveness) to an object to be bonded such as a semiconductor chip. The polymer component (a) has thermoplasticity and does not have thermosetting properties. In the present specification, the polymer compound also includes a product of polycondensation reaction.

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

Examples of the polymer component (a) include acrylic resins, urethane resins, phenoxy resins, silicone resins, and saturated polyester resins.

Among them, the polymer component (a) is preferably an acrylic resin.

In the adhesive composition, the proportion of the content of the polymer component (a) to the total content of all components except the solvent (i.e., the proportion of the content of the polymer component (a) in the film-shaped adhesive to the total mass of the film-shaped adhesive) is preferably 20 to 75 mass%, more preferably 30 to 65 mass%.

[ thermosetting component (b) ]

The thermosetting component (b) is a component having thermosetting properties for thermosetting the film-like adhesive.

The thermosetting component (b) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

Examples of the thermosetting component (b) include epoxy thermosetting resins, polyimide resins, and unsaturated polyester resins.

Among them, the thermosetting component (b) is preferably an epoxy thermosetting resin.

Good epoxy thermosetting resin

The epoxy thermosetting resin is composed of an epoxy resin (b1) and a thermosetting agent (b 2).

The epoxy thermosetting resin contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.

Epoxy resin (b1)

Examples of the epoxy resin (b1) include known epoxy resins, and examples thereof include epoxy compounds having two or more functionalities such as polyfunctional epoxy resins, biphenyl compounds, bisphenol a diglycidyl ether and hydrogenated products thereof, o-cresol novolac (novolak) epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol a epoxy resins, bisphenol F epoxy resins, and phenylene skeleton epoxy resins.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The compatibility of the epoxy resin having an unsaturated hydrocarbon group with the acrylic resin is higher than that of the epoxy resin having no unsaturated hydrocarbon group with the acrylic resin. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, the reliability of the semiconductor package obtained using the film-like adhesive is increased.

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

Thermosetting agent (b2)

The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b 1).

Examples of the thermosetting agent (b2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group obtained by anhydrizing an acid group, and the like, and a phenolic hydroxyl group, an amino group, or a group obtained by anhydrizing an acid group are preferable, and a phenolic hydroxyl group or an amino group is more preferable.

Examples of the phenolic curing agent having a phenolic hydroxyl group in the heat curing agent (b2) include polyfunctional phenol resins, biphenol, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins.

Examples of the amine-based curing agent having an amino group in the heat-curing agent (b2) include Dicyandiamide (DICY).

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

The heat-curing agent (b2) contained in the adhesive composition and the film-like adhesive may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.

In the adhesive composition and the film-like adhesive, the content of the thermosetting agent (b2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, and may be any one of 1 to 100 parts by mass, 1 to 50 parts by mass, and 1 to 25 parts by mass, for example, relative to 100 parts by mass of the content of the epoxy resin (b 1). When the content of the thermosetting agent (b2) is not less than the lower limit, the film-shaped adhesive can be more easily cured. When the content of the thermosetting agent (b2) is not more than the upper limit, the moisture absorption rate of the film-like adhesive decreases, and the reliability of the package obtained using the film-like adhesive further increases.

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 (b 2)) 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 may be, for example, any one of 5 to 35 parts by mass and 5 to 20 parts by mass, relative to 100 parts by mass of the content of the polymer component (a). By setting the content of the thermosetting component (b) to the above range, the peeling force between the intermediate layer and the film-like adhesive is more stabilized.

When a thermosetting component (b) (for example, either or both of the epoxy resin (b1) and the thermosetting agent (b 2)) which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the film-like adhesive is used, the content of the thermosetting component (b) in the adhesive composition and the film-like adhesive preferably satisfies a numerical range set separately as described later.

In order to improve various physical properties of the film-shaped adhesive, the adhesive composition and the film-shaped adhesive may further contain other components not belonging to the polymer component (a) and the thermosetting component (b) as necessary, in addition to the polymer component (a) and the thermosetting component (b).

Preferred examples of the other components contained in the adhesive composition and the film-like adhesive include a curing accelerator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), an energy ray-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 speed of the adhesive composition.

Examples of the preferable curing accelerator (c) include tertiary amines such as triethylene diamine, benzyl dimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles (imidazole in which one or more hydrogen atoms are substituted with a group other than a hydrogen atom), such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines (phosphines in which one or more hydrogen atoms are substituted with an organic group), such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylboron salts such as tetraphenylphosphonium (tetraphenylphosphonium tetraphenylborate) and triphenylphosphine tetraphenylboron (triphenylphosphonium tetraphenylborate).

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

When the curing accelerator (c) is used, the content of the curing accelerator (c) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the content of the thermosetting component (b) in the adhesive composition and the film-like adhesive. By setting the content of the curing accelerator (c) to the lower limit or more, the effect of using the curing accelerator (c) can be more remarkably obtained. When the content of the curing accelerator (c) is not more than the upper limit, for example, the effect of suppressing the occurrence of segregation due to the highly polar curing accelerator (c) moving to the side of the adhesive surface with the adherend in the film-shaped adhesive under high-temperature and high-humidity conditions is increased, and the reliability of the package obtained using the film-shaped adhesive is further improved.

When the curing accelerator (c) which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the film-like adhesive is used, the content of the curing accelerator (c) in the adhesive composition and the film-like adhesive preferably satisfies a numerical range set separately as described later.

[ Filler (d) ]

By containing the filler (d) in the film-like adhesive, the cuttability by the spread film-like adhesive is further improved. Further, by containing the filler (d) in the film-like adhesive, the thermal expansion coefficient of the film-like adhesive can be easily adjusted, and by optimizing the thermal expansion coefficient for the object to which the film-like adhesive is attached, the reliability of the package obtained using the film-like adhesive can be further improved. Further, by containing the filler (d) in the film-shaped adhesive, the moisture absorption rate of the cured film-shaped adhesive can be reduced or the heat dissipation property can be improved.

The filler (d) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.

Examples of the preferable inorganic filler include powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, and the like; beads (beads) obtained by spheroidizing these inorganic fillers; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fibers, and the like.

Among them, the inorganic filler is preferably silica or alumina.

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

When the filler (d) is used, the content of the filler (d) in the adhesive composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 60% by mass, based on the total content of all the components except the solvent (i.e., the content of the filler (d) in the film-shaped adhesive based on the total mass of the film-shaped adhesive). By making the ratio the above range. The effects of using the filler (d) can be more remarkably obtained.

[ coupling agent (e) ]

When the film-shaped adhesive contains the coupling agent (e), the adhesiveness and adherence of the film-shaped adhesive to an adherend are improved. Further, by containing the coupling agent (e) in the film-shaped adhesive, the water resistance of the cured product of the film-shaped adhesive is increased without impairing the heat resistance. The coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (a), the thermosetting component (b), or the like, and more preferably a silane coupling agent.

The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the coupling agent (e) is used, the content of the coupling agent (e) 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, based on 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (b) in the adhesive composition and the film-like adhesive. By setting the content of the coupling agent (e) to the lower limit or more, the effects of using the coupling agent (e), that is, improvement in dispersibility of the filler (d) in the resin, improvement in adhesiveness between the film-shaped adhesive and the adherend, and the like can be more remarkably obtained. By making the content of the coupling agent (e) the upper limit value or less, the generation of outgas (outgas) can be further suppressed.

When the coupling agent (e) which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the film-shaped adhesive is used, the content of the coupling agent (e) in the adhesive composition and the film-shaped adhesive preferably satisfies a numerical range set separately as described later.

[ crosslinking agent (f) ]

When a substance having a functional group such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, or isocyanate group, which is capable of bonding to another compound, is used as the polymer component (a), the adhesive composition and the film-like adhesive may contain a crosslinking agent (f). The crosslinking agent (f) is a component for bonding and crosslinking the functional group in the polymer component (a) with another compound, and by crosslinking in this way, the initial adhesive force and cohesive force of the film-shaped adhesive can be adjusted.

Examples of the crosslinking agent (f) include an organic polyisocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine crosslinking agent (a crosslinking agent having an aziridine group), and the like.

When an organic polyisocyanate compound is used as the crosslinking agent (f), a hydroxyl group-containing polymer is preferably used as the polymer component (a). When the crosslinking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, a crosslinked structure can be easily introduced into the film-shaped adhesive by the reaction of the crosslinking agent (f) with the polymer component (a).

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

When the crosslinking agent (f) is used, the content of the crosslinking agent (f) in the adhesive composition is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the content of the polymer component (a). By setting the content of the crosslinking agent (f) to the lower limit or more, the effect of using the crosslinking agent (f) can be more remarkably obtained. By making the content of the crosslinking agent (f) the upper limit value or less, the excessive use of the crosslinking agent (f) can be suppressed.

When the crosslinking agent (f) which is liquid at a temperature of 23 ℃ and does not have a functional group which reacts with the main component contained in the film-like adhesive is used, the content of the crosslinking agent (f) in the adhesive composition and the film-like adhesive preferably satisfies a numerical range which is set separately as described later.

Energy ray-curable resin (g)

When 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 an energy ray.

The energy ray-curable resin (g) may be the component (α 1), but is preferably not the component (α 1).

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 compounds having a (meth) acryloyl group are preferable.

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

When the energy ray-curable resin (g) is used, the content of the energy ray-curable resin (g) in the adhesive composition is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass, based on the total mass of the adhesive composition.

[ photopolymerization initiator (h) ]

When the adhesive composition and the film-like adhesive contain the energy ray-curable resin (g), the photopolymerization initiator (h) may be contained in order to efficiently advance the polymerization reaction of the energy ray-curable resin (g).

Examples of the photopolymerization initiator (h) in the adhesive composition include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2, 2-dimethoxy-1, 2-diphenylethan-1-one; acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; sulfur compounds such as benzylphenylsulfide, tetramethylthiuram monosulfide and the like; α -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; a peroxide compound; diketone compounds such as diacetyl; benzil; dibenzoyl; benzophenone; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.

Examples of the photopolymerization initiator (h) include photosensitizers such as amines.

The photopolymerization initiator (h) contained in the adhesive composition may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

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

When the photopolymerization initiator (h) which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the film-like adhesive is used, the content of the photopolymerization initiator (h) in the adhesive composition and the film-like adhesive preferably satisfies a numerical range set separately as described later.

[ general additive (i) ]

The general-purpose additive (i) may be a known additive, may be arbitrarily selected according to the purpose, and is not particularly limited, but preferable additives include, for example, a plasticizer, an antistatic agent, an antioxidant, a colorant (dye, pigment), a gettering agent (gettering agent), and the like.

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

The content of the adhesive composition and the film-like adhesive is not particularly limited, and may be appropriately selected according to the purpose.

When the general-purpose additive (i) which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the film-shaped adhesive is used, the content of the general-purpose additive (i) in the adhesive composition and the film-shaped adhesive preferably satisfies a numerical range set separately as described later.

[ solvent ]

The adhesive composition preferably further contains a solvent. The workability of the adhesive composition containing a solvent becomes good.

The solvent is not particularly limited, but preferable examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.

The binder composition may contain only one kind of solvent, or two or more kinds of solvents, and in the case of two or more kinds of solvents, the combination and ratio thereof may be arbitrarily selected.

The solvent contained in the pressure-sensitive adhesive composition is preferably methyl ethyl ketone or the like, from the viewpoint of enabling more uniform mixing of the components contained in the pressure-sensitive adhesive composition.

The content of the solvent in the adhesive composition is not particularly limited, and may be appropriately selected according to the kind of the component other than the solvent.

[ component (. alpha.2) ]

The component (. alpha.2) in the adhesive composition and the film adhesive is in a liquid state at a temperature of 23 ℃. Further, the component (α 2) does not have a functional group that reacts with the main component contained in the film-shaped adhesive (i.e., does not react with the main component). A component which has a functional group that reacts with the main component contained in the film-shaped adhesive and is liquid at a temperature of 23 ℃ reacts with the main component in the film-shaped adhesive, and therefore, the component does not migrate from the film-shaped adhesive to the intermediate layer and, as a result, does not migrate to the adhesive layer. In the present embodiment, the transfer of the component (α 2) which has no functional group and is liquid at a temperature of 23 ℃ from the film-shaped adhesive to the adhesive agent layer, which cannot be originally inhibited, is inhibited, instead of the transfer of the component which has the functional group and is liquid at a temperature of 23 ℃ from the film-shaped adhesive to the adhesive agent 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 which reacts with the main component.

As long as such conditions are satisfied, the component (α 2) is not particularly limited and may be arbitrarily selected according to the purpose. Among the components contained in the adhesive composition which are not included in any of the polymer component (a), the filler (d), the energy ray-curable resin (g) and the solvent, that is, among the thermosetting component (b) (for example, the epoxy resin (b1) and the thermosetting agent (b2)), the curing accelerator (c), the coupling agent (e), the crosslinking agent (f), the photopolymerization initiator (h) and the general-purpose additive (i), a component which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the film-shaped adhesive is a component (α 2). The film adhesive is generally free of solvent.

As a preferable component (α 2), for example, an epoxy resin (b1) and the like can be mentioned.

The component (α 2) contained in the adhesive composition may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.

When the component (. alpha.2) is used, the content of the component (. alpha.2) in the adhesive composition may be appropriately adjusted depending on the kind of the component (. alpha.2).

In the adhesive composition and the film-shaped adhesive, the content of the component (α 2) 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, the migration of the component (α 2) in the film-like adhesive to the adhesive layer is further suppressed. By making the content the lower limit or more, the effect obtained by using the component (α 2) becomes higher.

In particular, when the component (α 2) is the epoxy resin (b1), the content of the component (α 2) (epoxy resin (b1)) is preferably 3 to 17 parts by mass, and more preferably 6 to 14 parts by mass, based on 100 parts by mass of the content of the polymer component (a) in the adhesive composition and the film adhesive. When the content is not more than the upper limit, the migration of the component (α 2) in the film-like adhesive to the adhesive layer is further suppressed, and the excessive use of the component (α 2) is suppressed. By making the content the lower limit or more, the effect obtained by using the component (α 2) becomes higher.

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

Production method of adhesive composition

The adhesive composition can be obtained by blending the respective ingredients for constituting the adhesive composition.

For example, the adhesive composition can be prepared by the same method as the adhesive composition described above, except that the kinds of the blending components are different.

In the semiconductor device manufacturing sheet of the present embodiment, it is preferable that at least the film-like adhesive contains the component (α 1) as a main component or at least the adhesive layer contains the component (γ 1) as a main component.

That is, as an example of a preferable semiconductor device manufacturing sheet of the present embodiment, there can be mentioned: a sheet for manufacturing a semiconductor device, wherein the film-like adhesive contains the component (. alpha.1) as a main component and the adhesive layer does not contain the component (. gamma.1) as a main component; a semiconductor device-manufacturing sheet in which the adhesive layer contains the component (. gamma.1) as a main component and the film-like adhesive does not contain the component (. alpha.1) as a main component; a sheet for manufacturing a semiconductor device, wherein the film-like adhesive contains the component (. alpha.1) as a main component and the adhesive layer contains the component (. gamma.1) as a main component.

In the sheet for manufacturing a semiconductor device, it is more preferable that the film-like adhesive contains the component (α 1) as a main component, and the adhesive layer contains the component (γ 1) as a main component.

In the semiconductor device-manufacturing sheet of the present embodiment, it is more preferable that at least the film-like adhesive contains the component (α 1) as a main component or at least the adhesive layer contains the component (γ 1) as a main component, and the component (α 1) and the component (γ 1) are acrylic resins having a structural unit derived from a (meth) acrylate.

That is, as an example of a more preferable semiconductor device manufacturing sheet of the present embodiment, there can be mentioned: a semiconductor device-manufacturing sheet in which the film-shaped adhesive contains the component (α 1) as a main component, the adhesive layer does not contain the component (γ 1) as a main component, and the component (α 1) is an acrylic resin having a structural unit derived from a (meth) acrylate; a semiconductor device-manufacturing sheet in which the adhesive layer contains the component (γ 1) as a main component, the film-like adhesive does not contain the component (α 1) as a main component, and the component (γ 1) is an acrylic resin having a structural unit derived from a (meth) acrylate; the film-like adhesive contains the component (alpha 1) as a main component, the adhesive layer contains the component (gamma 1) as a main component, and the component (alpha 1) and the component (gamma 1) are acrylic resins having a structural unit derived from (meth) acrylate.

In the semiconductor device-producing sheet, it is further preferable that the film-like adhesive contains the component (α 1) as a main component, the adhesive layer contains the component (γ 1) as a main component, and the component (α 1) and the component (γ 1) are acrylic resins having a structural unit derived from a (meth) acrylate.

As an example of a preferable semiconductor device-manufacturing sheet of this embodiment, there is mentioned a semiconductor device-manufacturing sheet comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,

the sheet for manufacturing a semiconductor device is formed by sequentially laminating the adhesive layer, the intermediate layer, and the film-like adhesive on the base material,

the intermediate layer contains a non-silicone resin (beta 1) having a weight-average molecular weight of 20000 to 100000 as a main component,

further, the film-shaped adhesive contains a component (α 2), the adhesive layer contains a component (γ 2), the component (α 2) is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with a main component contained in the film-shaped adhesive,

the component (. gamma.2) is liquid at a temperature of 23 ℃ and has no functional group that reacts with the main component contained in the adhesive agent layer,

H (beta) is the haze of a film-shaped first test piece having a thickness of 10 [ mu ] m and made of the non-silicon resin (. beta.1),

when the haze of a film-shaped second test piece having a thickness of 10 μm and comprising 100 parts by mass of a mixture of the non-silicone resin (β 1) and 10 parts by mass of the component (α 2) is represented by H (β α), the H (β α) and H (β) satisfy the following formula (X1):

(X1)H(βα)-H(β)＞7％，

when the haze of a film-shaped third test piece having a thickness of 10 μm and comprising 100 parts by mass of a mixture of the non-silicone resin (β 1) and 10 parts by mass of the component (γ 2) is H (β γ), the H (β γ) and H (β) satisfy the following formula (X2):

(X2)H(βγ)-H(β)＞7％，

further, the film-shaped adhesive contains a component (α 1) that is solid at a temperature of 23 ℃ as a main component, the component (α 1) is a polymer component (a), the adhesive layer contains a component (γ 1) that is solid at a temperature of 23 ℃ as a main component, the component (γ 1) is an adhesive, and the intermediate layer contains one or more selected from the group consisting of an ethylene-vinyl acetate copolymer and a polyolefin as the non-silicon resin (β 1).

In the semiconductor device manufacturing sheet, the intermediate layer may further contain a silicone resin.

As another example of a preferable semiconductor device-producing sheet of the present embodiment, there is mentioned a semiconductor device-producing sheet comprising a substrate, an adhesive layer, an intermediate layer and a film-like adhesive,

the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the substrate,

the intermediate layer contains a non-silicone resin (beta 1) having a weight-average molecular weight of 20000 to 100000 as a main component,

further, the film-like adhesive contains a component (. alpha.2), the adhesive layer contains a component (. gamma.2),

the component (α 2) is an epoxy resin (b1) which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the film-like adhesive,

the component (. gamma.2) is an antistatic agent which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive layer,

h (beta) represents the haze of a film-shaped first test piece composed of the non-silicon resin (. beta.1) and having a thickness of 10 μm,

when the haze of a film-shaped second test piece having a thickness of 10 μm and comprising a mixture of 100 parts by mass of the non-silicone resin (β 1) and 10 parts by mass of the component (α 2) is H (β α), the H (β α) and H (β) satisfy the following formula (X1):

(X1)H(βα)-H(β)＞7％，

When the haze of a film-shaped third test piece having a thickness of 10 μm and comprising 100 parts by mass of a mixture of the non-silicone resin (β 1) and 10 parts by mass of the component (γ 2) is represented by H (β γ), the H (β γ) and H (β) satisfy the following formula (X2):

(X2)H(βγ)-H(β)＞7％，

further, the film-shaped adhesive contains a component (α 1) which is solid at a temperature of 23 ℃ as a main component, the component (α 1) is a polymer component (a), the adhesive layer contains a component (γ 1) which is solid at a temperature of 23 ℃ as a main component, the component (γ 1) is an adhesive,

the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicone resin (. beta.1),

the film-shaped adhesive contains 1 to 20 parts by mass of the epoxy resin (b1) per 100 parts by mass of the polymer component (a),

the adhesive layer contains 0.1 to 10 parts by mass of the antistatic agent per 100 parts by mass of the adhesive,

in the ethylene-vinyl acetate copolymer, the proportion of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units is 45 mass% or less.

In the 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 the semiconductor device manufacturing sheet, the intermediate layer may further contain a silicone resin, and in this case, the intermediate layer may contain the silicone resin in an amount of 0.01 to 10 mass% with respect to the total mass of the intermediate layer.

As another example of a preferable semiconductor device-manufacturing sheet according to this embodiment, there is mentioned a semiconductor device-manufacturing sheet comprising a substrate, an adhesive layer, an intermediate layer and a film-like adhesive,

the sheet for manufacturing a semiconductor device is formed by sequentially laminating the adhesive layer, the intermediate layer, and the film-like adhesive on the base material,

the intermediate layer contains a non-silicone resin (beta 1) having a weight-average molecular weight of 20000 to 100000 as a main component,

further, the film-shaped adhesive contains a component (α 2), the adhesive layer contains a component (γ 2), the component (α 2) is an epoxy resin (b1) which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with a main component contained in the film-shaped adhesive,

the component (. gamma.2) is an antistatic agent which is liquid at a temperature of 23 ℃ and does not have a functional group that reacts with the main component contained in the adhesive layer,

H (beta) is the haze of a film-shaped first test piece having a thickness of 10 [ mu ] m and made of the non-silicon resin (. beta.1),

when the haze of a film-shaped second test piece having a thickness of 10 μm and comprising 100 parts by mass of a mixture of the non-silicone resin (β 1) and 10 parts by mass of the component (α 2) is represented by H (β α), the H (β α) and H (β) satisfy the following formula (X1):

(X1)H(βα)-H(β)＞7％，

when the haze of a film-shaped third test piece having a thickness of 10 μm and comprising 100 parts by mass of a mixture of the non-silicone resin (β 1) and 10 parts by mass of the component (γ 2) is represented by H (β γ), the H (β γ) and H (β) satisfy the following formula (X2):

(X2)H(βγ)-H(β)＞7％，

further, the film-shaped adhesive contains a component (α 1) that is solid at a temperature of 23 ℃ as a main component, the component (α 1) is a polymer component (a), the adhesive layer contains a component (γ 1) that is solid at a temperature of 23 ℃ as a main component, the component (γ 1) is an adhesive, the polymer component (a) and the adhesive are acrylic resins having a structural unit derived from (meth) acrylate,

the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicone resin (. beta.1),

the film-shaped adhesive contains 1 to 20 parts by mass of the epoxy resin (b1) per 100 parts by mass of the polymer component (a),

In the adhesive agent layer, the content of the antistatic agent is 0.1-10 parts by mass relative to 100 parts by mass of the content of the adhesive agent,

in the ethylene-vinyl acetate copolymer, the proportion of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units is 45 mass% or less.

In the 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 the semiconductor device-manufacturing sheet, the intermediate layer may further contain polydimethylsiloxane, and in this case, the ratio of the polydimethylsiloxane content in the intermediate layer to the total mass of the intermediate layer may be 0.01 to 10 mass%.

Manufacturing method of semiconductor device manufacturing wafer

The semiconductor device manufacturing sheet can be manufactured by stacking the layers so that the layers are in a corresponding positional relationship. The formation method of each layer is as described above.

For example, the semiconductor device manufacturing sheet can be manufactured by: the base material, the adhesive layer, the intermediate layer, and the film-like adhesive are prepared in advance, and the base material, the adhesive layer, the intermediate layer, and the film-like adhesive are laminated in this order.

However, this is just one example of a method for manufacturing a sheet for manufacturing a semiconductor device.

The semiconductor device manufacturing sheet can be manufactured, for example, by: two or more kinds of intermediate laminated bodies, each of which is formed by laminating a plurality of layers, are prepared in advance to form a sheet for manufacturing a semiconductor device, and these intermediate laminated bodies are bonded to each other. The structure of the intermediate laminated body can be arbitrarily selected as appropriate. For example, a semiconductor device manufacturing sheet can be manufactured by preparing in advance a first intermediate laminate (corresponding to the support sheet) having a structure in which a base material and an adhesive layer are laminated, and a second intermediate laminate having a structure in which an intermediate layer and a film-like adhesive are laminated, and bonding the adhesive layer in the first intermediate laminate and the intermediate layer in the second intermediate laminate.

However, this is also only one example of a method for manufacturing a sheet for manufacturing a semiconductor device.

In the case of manufacturing a semiconductor device-manufacturing sheet in which both the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive are smaller than the area of the first surface of the adhesive layer and the area of the first surface of the substrate, as shown in fig. 1, for example, a step of processing the intermediate layer and the film-like adhesive into a desired size may be additionally performed at any stage of the above-described manufacturing method. For example, in the manufacturing method using the second intermediate laminate, a step of processing the intermediate layer and the film-like adhesive in the second intermediate laminate into a desired size may be additionally performed, thereby manufacturing the sheet for manufacturing a semiconductor device.

When a semiconductor device-manufacturing sheet having a release film on a film-like adhesive is manufactured, for example, the film-like adhesive may be manufactured on the release film, and the remaining layers may be stacked while maintaining this state to manufacture the semiconductor device-manufacturing sheet; the sheet for manufacturing a semiconductor device may be produced by laminating all of the substrate, the adhesive layer, the intermediate layer, and the film-like adhesive and then laminating a release film on the film-like adhesive. The release film may be removed at a necessary stage before the use of the sheet for manufacturing a semiconductor device.

The sheet for manufacturing a semiconductor device, which is provided with another layer not belonging to any of the base material, the adhesive layer, the intermediate layer, the film-like adhesive and the release film, can be manufactured by additionally forming the other layer at an appropriate timing and laminating the other layer in the above-described manufacturing method.

However, in order to produce the semiconductor device-producing sheet, as a combination of the non-silicon resin (β 1) in the film-like binder and the component (α 2) in the intermediate layer, a combination satisfying the formula (X1) needs to be selected; or as a combination of the non-silicon resin (. beta.1) in the film-like adhesive and the component (. gamma.2) in the adhesive layer, a combination satisfying the above formula (X2) needs to be selected.

That is, the present embodiment is a method for producing a sheet for semiconductor device production, in which,

the sheet for manufacturing a semiconductor device comprises a base material, an adhesive layer, an intermediate layer, and a film-like adhesive,

the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the substrate,

the intermediate layer contains a non-silicone resin (beta 1) having a weight-average molecular weight of 20000 to 100000 as a main component,

further, at least the film-like adhesive contains a component (α 2) or at least the adhesive layer contains a component (γ 2),

the component (. alpha.2) is liquid at a temperature of 23 ℃ and has no functional group that reacts with the main component contained in the film-like adhesive,

the component (. gamma.2) is liquid at a temperature of 23 ℃ and has no functional group that reacts with the main component contained in the adhesive agent layer,

h (beta) represents the haze of a film-shaped first test piece composed of the non-silicon resin (. beta.1) and having a thickness of 10 μm,

when the film-shaped adhesive contains the component (α 2), the haze of a film-shaped second test piece having a thickness of 10 μm and composed of a mixture of 100 parts by mass of the non-silicon resin (β 1) and 10 parts by mass of the component (α 2) is represented by H (β α), and when H (β α) and H (β) satisfy the following formula (X1):

(X1)H(βα)-H(β)＞7％，

When the adhesive layer contains the component (γ 2), the haze of a third test piece in the form of a film having a thickness of 10 μm and formed from a mixture of 100 parts by mass of the non-silicon resin (β 1) and 10 parts by mass of the component (γ 2) is H (β γ), and when H (β γ) and H (β) satisfy the following formula (X2):

(X2)H(βγ)-H(β)＞7％，

the manufacturing method comprises any one or two of the following steps: a film-like adhesive preparation step for preparing the film-like adhesive containing the component (. alpha.2); and an adhesive layer production step of producing the adhesive layer containing the component (. gamma.2).

As described above, according to the structure of the target sheet for manufacturing a semiconductor device, the method for manufacturing a sheet for manufacturing a semiconductor device according to the present embodiment may have the film-like adhesive layer manufacturing step without the adhesive layer manufacturing step, may have the adhesive layer manufacturing step without the film-like adhesive layer manufacturing step, and may have both the film-like adhesive layer manufacturing step and the adhesive layer manufacturing step.

In the film-like adhesive preparation step, a film-like adhesive is prepared using the adhesive composition containing the component (α 2).

In the adhesive layer production step, an adhesive layer is produced using the adhesive composition containing component (γ 2).

O-film adhesive manufacturing method of semiconductor chip (method of Using semiconductor device manufacturing sheet)

In the manufacturing process of a semiconductor device, the semiconductor device manufacturing sheet can be used in manufacturing a semiconductor chip with a film-like adhesive.

A method for manufacturing the semiconductor chip with the film-like adhesive (a method for using a sheet for manufacturing a semiconductor device) will be described in detail below with reference to the drawings.

Fig. 3A, 3B, and 3C are sectional views schematically illustrating an example of a method for manufacturing a semiconductor chip with a film-like adhesive, and show the manufacturing method when used after attaching a semiconductor device manufacturing sheet on a semiconductor wafer. In this method, a semiconductor device manufacturing sheet is used as a dicing die. 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, the semiconductor device manufacturing sheet 101 with the release film 15 removed is heated, and the film-like adhesive 14 is applied to the back surface 9b 'of the semiconductor wafer 9'.

Reference numeral 9a 'denotes a circuit forming surface of the semiconductor wafer 9'.

The heating temperature when the semiconductor device manufacturing sheet 101 is attached is not particularly limited, but is preferably 40 to 70 ℃ from the viewpoint of further improving the heat attachment stability of the semiconductor device manufacturing sheet 101.

The width W of the intermediate layer 13 in the semiconductor device-manufacturing sheet 101 is preferably set₁₃And the width W of the film-like adhesive 14₁₄Is equal to the width W of the semiconductor wafer 9_9’Are exactly the same or, although different, have slight to almost the same error.

For example, when the width W of the semiconductor wafer 9_9’Has a maximum value of 150mm, the width W of the intermediate layer 13₁₃Maximum value of (d) and width W of film-like adhesive 14₁₄The maximum value of (a) is preferably 150 to 160mm when the width W of the semiconductor wafer 9_9’Has a maximum value of 200mm, the width W of the intermediate layer 13₁₃Maximum value of (d) and width W of film-like adhesive 14₁₄The maximum value of (a) is preferably 200 to 210mm when the width W of the semiconductor wafer 9_9’At a maximum value of 300mm, the width W of the intermediate layer 13₁₃Maximum value of (d) and width W of film-like adhesive 14₁₄The maximum value of (A) is preferably 300 to 310 mm.

Thus, in the present embodiment, the width W of the intermediate layer 13 ₁₃And the width W of the semiconductor wafer 9_9’Maximum value of (2)The difference between the film thickness and the width W of the film-like adhesive 14₁₄And the width W of the semiconductor wafer 9_9’The difference between the maximum values of (a) and (b) may be 0 to 10 mm.

Here, the width W of the semiconductor wafer 9_9’For example, the width of the semiconductor wafer 9 'in a direction parallel to the rear surface 9 b'.

Next, the laminated body of the semiconductor device-manufacturing sheet 101 and the semiconductor wafer 9 'obtained above is cut by a blade from the circuit-forming surface 9 a' side of the semiconductor wafer 9 '(dicing is performed), thereby dividing the semiconductor wafer 9' and cutting the film-like adhesive 14.

The blade cutting may be performed by a known method. For example, the semiconductor wafer 9' can be divided and the film-like adhesive 14 can be cut by a dicing blade after fixing a region (the non-lamination region) in the vicinity of the peripheral portion where the intermediate layer 13 and the film-like adhesive 14 are not laminated in the first surface 12a of the adhesive layer 12 in the semiconductor device manufacturing sheet 101 to a jig (not shown) such as a ring frame.

As shown in fig. 3B, in this step, a plurality of semiconductor chips 914 with a film adhesive are obtained, and the semiconductor chips 914 with a film adhesive include the semiconductor chip 9 and the cut film adhesive 140 provided on the back surface 9B of the semiconductor chip 9. These semiconductor chips 914 with a film adhesive are aligned and fixed on the interlayer 13 in the laminate sheet 10, and constitute a semiconductor chip group 910 with a film adhesive.

The rear side 9b of the semiconductor chip 9 corresponds to the rear side 9b 'of the semiconductor wafer 9'. In addition, in fig. 3B, reference numeral 9a denotes a circuit forming surface of the semiconductor chip 9, which corresponds to the circuit forming surface 9a 'of the semiconductor wafer 9'.

In the dicing, it is preferable that the entire region in the thickness direction of the semiconductor wafer 9' is diced by a dicing blade to be divided, and the film-shaped adhesive 14 is cut from the first surface 14a of the film-shaped adhesive 14 to the intermediate region of the intermediate layer 13 of the semiconductor device manufacturing sheet 101, thereby cutting the entire region in the thickness direction thereof and not cutting the adhesive layer 12.

That is, when dicing is performed, it is preferable to use a dicing blade to dice the stacked body of the semiconductor device manufacturing sheet 101 and the semiconductor wafer 9 ' from the circuit forming surface 9a ' of the semiconductor wafer 9 ' at least to the first surface 13a of the intermediate layer 13 and not to the surface of the intermediate layer 13 opposite to the first surface 13a (i.e., the contact surface with the adhesive layer 12) in the stacking direction thereof.

In this step, the blade can be easily prevented from reaching the base material 11, and thus the generation of chips from the base material 11 can be suppressed. Further, by using a non-silicone resin (β 1) having a weight average molecular weight of 20000 to 100000 as a main component of the intermediate layer 13 cut by the blade, particularly by setting the weight average molecular weight to 100000 or less, it is possible to suppress the generation of chips by the intermediate layer 13.

The cutting conditions of the blade are not particularly limited and may be appropriately adjusted according to the purpose.

Usually, the rotation speed of the blade is preferably 15000-50000 rpm, and the moving speed of the blade is preferably 5-85 mm/s, and can be 5-75 mm/s.

As shown in fig. 3C, after the blade dicing is performed, the semiconductor chip 914 with the film adhesive is pulled away from the intermediate layer 13 in the laminated sheet 10 and picked up. Here, a case where the semiconductor chip 914 with a film-like adhesive is pulled off in the direction of the arrow P by using a pulling-off tool 7 such as a vacuum nozzle (vacuum collet) is shown. Here, the pull-off tool 7 is not shown in cross section.

The semiconductor chip 914 with the film adhesive can be picked up by a known method.

When the ratio of the silicon concentration in the first face 13a of the intermediate layer 13 is 1 to 20%, the semiconductor chip 914 with a film adhesive can be picked up more easily.

For example, when the intermediate layer 13 contains an ethylene-vinyl acetate copolymer as the non-silicone resin (β 1) and a siloxane compound as the additive, the ratio of the content of the ethylene-vinyl acetate copolymer in the intermediate layer to the total mass of the intermediate layer is 90 to 99.99 mass%, and the ratio of the content of the siloxane compound in the intermediate layer to the total mass of the intermediate layer is 0.01 to 10 mass%, the semiconductor chip 914 with a film adhesive can be picked up more easily.

Preferred embodiments of the method for manufacturing a semiconductor chip with a film-like adhesive described above include, for example:

a method for manufacturing a semiconductor chip with a film-like adhesive, which uses a sheet for manufacturing a semiconductor device,

the semiconductor chip with the film-shaped adhesive comprises a semiconductor chip and a film-shaped adhesive provided on the back surface of the semiconductor chip,

the sheet for manufacturing a semiconductor device comprises a base material, an adhesive layer, an intermediate layer and a film-like adhesive,

the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the substrate,

the intermediate layer contains a non-silicone resin (beta 1) having a weight-average molecular weight of 20000 to 100000 as a main component,

further, at least the film-like adhesive contains a component (α 2) or at least the adhesive layer contains a component (γ 2),

the component (. alpha.2) is liquid at a temperature of 23 ℃ and has no functional group which reacts with the main component contained in the film-shaped adhesive,

the component (. gamma.2) is liquid at a temperature of 23 ℃ and has no functional group which reacts with the main component contained in the adhesive layer,

H (. beta.) represents the haze of a film-shaped test piece having a thickness of 10 μm and comprising the non-silicone resin (. beta.1),

when the film-shaped adhesive contains the component (α 2), the haze of a film-shaped second test piece having a thickness of 10 μm and composed of a mixture of 100 parts by mass of the non-silicon resin (β 1) and 10 parts by mass of the component (α 2) is represented by H (β α), and when H (β α) and H (β) satisfy the following formula (X1):

(X1)H(βα)-H(β)＞7％，

when the adhesive layer contains the component (γ 2), the haze of a film-shaped third test piece having a thickness of 10 μm, which is composed of a mixture of 100 parts by mass of the non-silicon resin (β 1) and 10 parts by mass of the component (γ 2), is represented by H (β γ), and H (β γ) and H (β) satisfy the following formula (X2):

(X2)H(βγ)-H(β)＞7％，

the manufacturing method comprises the following steps:

heating the semiconductor device manufacturing sheet and adhering the film-like adhesive to the back surface of the semiconductor wafer;

a step of cutting the entire region of the semiconductor wafer in the thickness direction from the circuit-formation-surface side of the semiconductor wafer to which the film-like adhesive is attached, thereby dividing the semiconductor wafer, and cutting the film-like adhesive from the film-like adhesive side of the semiconductor device-manufacturing sheet to an intermediate region of the intermediate layer along the thickness direction of the semiconductor device-manufacturing sheet, thereby obtaining a plurality of semiconductor chip groups with the film-like adhesive, in which the semiconductor chips with the film-like adhesive are aligned on the intermediate layer, without cutting the film-like adhesive to the adhesive layer; and

And a step of separating the semiconductor chip with the film-like pressure-sensitive adhesive from the intermediate layer and picking up the semiconductor chip (in this specification, this step may be referred to as "production method 1").

Fig. 4A, 4B, and 4C are cross-sectional views schematically illustrating an example of a method for manufacturing semiconductor chips to be used as a sheet for manufacturing a semiconductor device, and show a case where semiconductor chips are manufactured by dicing accompanied by formation of a modified layer in a semiconductor wafer.

Fig. 5A, 5B, and 5C are sectional views schematically illustrating another example of a method for manufacturing a semiconductor chip with a film-like adhesive, showing the manufacturing method when used after attaching a semiconductor device manufacturing sheet on the semiconductor chip. In this method, the semiconductor device manufacturing sheet is used as a solid wafer. Here, a method of using the sheet 101 for manufacturing a semiconductor device shown in fig. 1 will be described as an example.

First, before using the semiconductor device manufacturing sheet 101, as shown in fig. 4A, a semiconductor wafer 9 'is prepared, and a back-grinding tape (also referred to as a "surface protection tape") 8 is attached to the circuit forming surface 9 a'.

In FIG. 4A, reference numeral W _9’Indicating the width of the semiconductor wafer 9'.

Next, as shown in fig. 4B, laser light (not shown) is irradiated so as to be focused on a focal point set in the semiconductor wafer 9 ', thereby forming a modified layer 90 ' in the semiconductor wafer 9 '.

The semiconductor wafer 9 ' is preferably irradiated with the laser light from the back surface 9b ' side of the semiconductor wafer 9 '.

The position of the focal point at this time is a position of the semiconductor wafer 9 'to be divided (diced), and is set so that a 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 polished by a polishing machine (not shown). Thus, the thickness of the semiconductor wafer 9 'is adjusted to a target value, and the semiconductor wafer 9' is divided at the portion where the modified layer 90 'is formed by using the force applied to the semiconductor wafer 9' at the time of polishing, thereby producing a plurality of semiconductor chips 9 as shown in fig. 4C.

Unlike other portions of the semiconductor wafer 9 ', the modified layer 90 ' of the semiconductor wafer 9 ' is modified by laser irradiation and is weakened in strength. Therefore, by applying a force to the semiconductor wafer 9 ' on which the modified layer 90 ' is formed, a force is applied to the modified layer 90 ', and the semiconductor wafer 9 ' is cracked at the modified layer 90 ', thereby obtaining a plurality of semiconductor chips 9.

In this way, the semiconductor chip 9 to be used as the semiconductor device manufacturing sheet 101 is obtained. More specifically, in this step, the semiconductor chip group 901 is obtained in which the plurality of semiconductor chips 9 are fixed to the back-grinding tape 8 in an aligned state.

When the semiconductor chip group 901 is viewed in plan from above the semiconductor chip group 901, a planar shape formed by connecting outermost portions of the semiconductor chip group 901 (in this specification, such a planar shape may be abbreviated as "planar shape of the semiconductor chip group") is completely the same as a planar shape of the semiconductor wafer 9 ' when the semiconductor wafer 9 ' is viewed in plan in the same manner, or a difference between planar shapes of the two is slight to the extent of negligible, and 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, as shown in fig. 4C, the width of the planar shape of the semiconductor chip group 901 can be regarded as the width W of the semiconductor wafer 9_9’The same is true. Also, the maximum value of the width of the planar shape of the semiconductor chip group 901 can be regarded as the width W of the semiconductor wafer 9_9’The maximum values of (a) are the same.

Although the semiconductor chips 9 can be produced from the semiconductor wafer 9 'as intended, a partial region of the semiconductor wafer 9' may not be divided into the semiconductor chips 9 depending on conditions for polishing the back surface 9b 'of the semiconductor wafer 9'.

Next, using the semiconductor chip 9 (semiconductor chip group 901) obtained above, a semiconductor chip with a film-like adhesive is manufactured.

First, as shown in fig. 5A, a piece of the semiconductor device-manufacturing sheet 101 in a state where the release film 15 is removed is heated while the film-like adhesive 14 therein is attached to the back surfaces 9b of all the semiconductor chips 9 in the semiconductor chip group 901. The film-like adhesive 14 may be applied to a semiconductor wafer that is not completely divided.

The width W of the intermediate layer 13 in the semiconductor device-manufacturing sheet 101 is preferably set₁₃And the width W of the film-like adhesive 14₁₄Is equal to the width W of the semiconductor wafer 9_9’(in other words, the width of the semiconductor chip group 901) is the same or the error is slight to almost the same although different.

Namely, the width W of the intermediate layer 13₁₃The relationship between the maximum value of (a) and the maximum value of the width of the semiconductor chip group 901 may be related to the width W of the intermediate layer 13 explained above ₁₃Maximum value of (d) and width W of semiconductor wafer 9_9’The same relationship is applied to the maximum values of (a). The width W of the film-like adhesive 14₁₄The relationship between the maximum value of (a) and the maximum value of the width of the semiconductor chip group 901 may be related to the width W of the film-like adhesive 14 explained above₁₄Maximum value of (d) and width W of semiconductor wafer 9_9’The same relationship is applied to the maximum values of (a).

The film-like adhesive 14 (semiconductor device manufacturing sheet 101) can be attached to the semiconductor chip group 901 in the same manner as the film-like adhesive 14 (semiconductor device manufacturing sheet 101) is attached to the semiconductor wafer 9 'in the above-described manufacturing method 1, except that the semiconductor chip group 901 is used instead of the semiconductor wafer 9'.

Next, the back-grinding tape 8 is removed from the semiconductor chip group 901 in a fixed state. Then, as shown in fig. 5B, the sheet 101 for manufacturing a semiconductor device (film-like adhesive 14) is cooled and stretched in a direction parallel to the surface thereof (for example, the first surface 12a of the adhesive layer 12), thereby spreading. Here, with arrow E₁The direction of expansion of the semiconductor device manufacturing sheet 101 is shown. By spreading in this manner, the film-like adhesive 14 is cut along the outer periphery of the semiconductor chip 9.

Through this step, a plurality of semiconductor chips 914 with a film-like adhesive are obtained, which include the semiconductor chip 9 and the cut film-like adhesive 140 provided on the back surface 9b of the semiconductor chip 9. The semiconductor chips 914 with the film adhesive are aligned and fixed to the intermediate layer 13 in the laminate sheet 10, and constitute a semiconductor chip group 910 with a film adhesive.

The semiconductor chip 914 with a film adhesive and the semiconductor chip group 910 with a film adhesive obtained here are basically the same as the semiconductor chip 914 with a film adhesive and the semiconductor chip group 910 with a film adhesive obtained in the above-described manufacturing method 1.

When the partial region of the semiconductor wafer 9 'is not divided into the semiconductor chips 9 when the semiconductor wafer 9' is divided as described above, the partial region is divided into the semiconductor chips by performing the present step.

The temperature of the semiconductor device manufacturing sheet 101 (film-like adhesive 14) is preferably set to-5 to 5 ℃. By cooling and expanding (cold expanding) the semiconductor device manufacturing sheet 101 in this manner, the film-like adhesive 14 can be cut more easily and with high accuracy.

The sheet 101 for manufacturing a semiconductor device (film-like adhesive) can be spread by a known method. For example, the first surface 12a of the adhesive layer 12 in the semiconductor device-manufacturing sheet 101 may be treated

Of the layers (the non-lamination region) in the semiconductor device manufacturing sheet 101, the region in the vicinity of the peripheral portion where the intermediate layer 13 and the film-like adhesive 14 are not laminated (the non-lamination region) is fixed to a jig such as a ring frame (not shown), and then the entire region of the semiconductor device manufacturing sheet 101 where the intermediate layer 13 and the film-like adhesive 14 are laminated is pushed up from the substrate 11 side in the direction from the substrate 11 toward the adhesive layer 12, thereby spreading the semiconductor device manufacturing sheet 101.

In fig. 5B, the non-laminated region where the intermediate layer 13 and the film-like adhesive 14 are not laminated in the first surface 12a of the adhesive layer 12 is almost parallel to the first surface 13a of the intermediate layer 13, but as described above, in a state of being spread by the push-up of the semiconductor device manufacturing sheet 101, the non-laminated region includes an inclined surface whose height gradually decreases as it approaches the outer periphery of the adhesive layer 12 in a direction opposite to the push-up direction.

In this step, by providing the sheet 101 for manufacturing a semiconductor device with the intermediate layer 13 (in other words, by providing the film-like adhesive 14 before cutting on the intermediate layer 13), the film-like adhesive 14 can be cut at a target portion (in other words, along the outer periphery of the semiconductor chip 9) with good accuracy, and a cutting failure can be suppressed.

As shown in fig. 5C, after the spreading, the semiconductor chip 914 with the film adhesive is pulled away from the intermediate layer 13 in the laminate sheet 10 and picked up.

The pickup in this case can be performed by the same method as the pickup in the above-described manufacturing method 1, and the pickup suitability is also the same as the pickup suitability in the manufacturing method 1.

For example, in this step, when the ratio of the silicon concentration in the first surface 13a of the intermediate layer 13 is 1 to 20%, the semiconductor chip 914 with the film adhesive can be picked up more easily.

Further, for example, when the intermediate layer 13 contains the ethylene-vinyl acetate copolymer as the non-silicone resin and the siloxane compound as the additive, the ratio of the content of the ethylene-vinyl acetate copolymer in the intermediate layer to the total mass of the intermediate layer is 90 to 99.99 mass%, and the ratio of the content of the siloxane compound in the intermediate layer to the total mass of the intermediate layer is 0.01 to 10 mass%, the semiconductor chip 914 with a film adhesive can be picked up more easily.

Preferred embodiments of the method for manufacturing a semiconductor chip with a film-like adhesive described above include, for example:

A method for manufacturing a semiconductor chip with a film-like adhesive, which uses a sheet for manufacturing a semiconductor device,

the semiconductor chip with the film-shaped adhesive comprises a semiconductor chip and a film-shaped adhesive provided on the back surface of the semiconductor chip,

the sheet for manufacturing a semiconductor device comprises a base material, an adhesive layer, an intermediate layer, and a film-like adhesive,

the sheet for manufacturing a semiconductor device is formed by sequentially laminating the adhesive layer, the intermediate layer, and the film-like adhesive on the base material,

the intermediate layer contains a non-silicone resin (beta 1) having a weight-average molecular weight of 20000 to 100000 as a main component,

further, at least the film-like adhesive contains a component (α 2) or at least the adhesive layer contains a component (γ 2),

the component (. alpha.2) is liquid at a temperature of 23 ℃ and has no functional group that reacts with the main component contained in the film-like adhesive,

the component (. gamma.2) is liquid at a temperature of 23 ℃ and has no functional group that reacts with the main component contained in the adhesive agent layer,

h (β) represents the haze of a film-shaped test piece having a thickness of 10 μm and made of the non-silicon resin (. beta.1),

When the film-shaped adhesive contains the component (α 2), the haze of a film-shaped second test piece having a thickness of 10 μm and composed of a mixture of 100 parts by mass of the non-silicone resin (β 1) and 10 parts by mass of the component (α 2) is represented by H (β α), and H (β α) and H (β) satisfy the following formula (X1):

(X1)H(βα)-H(β)＞7％，

when the adhesive layer contains the component (γ 2), the haze of a film-shaped third test piece having a thickness of 10 μm, which is composed of a mixture of 100 parts by mass of the non-silicon resin (β 1) and 10 parts by mass of the component (γ 2), is represented by H (β γ), and H (β γ) and H (β) satisfy the following formula (X2):

(X2)H(βγ)-H(β)＞7％，

the manufacturing method comprises the following steps:

irradiating a laser beam so as to focus on a focal point set in the interior of a semiconductor wafer, thereby forming a modified layer in the interior of the semiconductor wafer;

a step of grinding the back surface of the semiconductor wafer after the modified layer is formed, and dividing the semiconductor wafer at a portion where the modified layer is formed by a force applied to the semiconductor wafer during grinding to obtain a semiconductor chip group in which a plurality of semiconductor chips are aligned;

Heating the semiconductor device manufacturing sheet and simultaneously attaching the film-like adhesive to the back surfaces of all the semiconductor chips in the semiconductor chip group;

a step of cooling the semiconductor device manufacturing sheet after the semiconductor chips are attached to the sheet, and stretching the sheet in a direction parallel to the surface of the sheet, thereby cutting the film-like adhesive along the outer peripheries of the semiconductor chips to obtain a plurality of semiconductor chip groups with film-like adhesive, each of which has a plurality of semiconductor chips with film-like adhesive aligned on the intermediate layer; and

and a step of separating the semiconductor chip with the film-like pressure-sensitive adhesive from the intermediate layer and picking up the semiconductor chip (in this specification, this step may be referred to as "production method 2").

Although the manufacturing method 1 and the manufacturing method 2 have been described using the semiconductor device manufacturing sheet 101 shown in fig. 1 as an example of the manufacturing method of the semiconductor chip with the film-like adhesive, the semiconductor chip with the film-like adhesive can be manufactured similarly using the semiconductor device manufacturing sheet of the present embodiment other than the above. In this case, if necessary, a different step may be added as appropriate based on the difference in structure between the semiconductor device manufacturing sheet and the semiconductor device manufacturing sheet 101 to manufacture a semiconductor chip with a film-like adhesive.

After the semiconductor chip group with the film-like adhesive is obtained, the laminated sheet may be stretched in a direction parallel to the surface (first surface) of the adhesive layer on the intermediate layer side, and the peripheral portion of the semiconductor chip without the film-like adhesive (the semiconductor chip group with the film-like adhesive) placed thereon may be further heated while maintaining this state, before the semiconductor chip with the film-like adhesive is picked up, without being limited to the production method 1 and the production method 2.

This makes it possible to sufficiently widen a notch width (kerf width), which is a distance between adjacent semiconductor chips on the laminated sheet, while contracting the peripheral portion, and to maintain the notch width with high uniformity. Also, the semiconductor chip with the film adhesive can be picked up more easily.

Examples

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

Raw material for preparing adhesive composition

The raw materials used to prepare the adhesive composition are shown below.

[ Polymer component (a) ]

(a) -1: an acrylic resin (weight average molecular weight 800000, glass transition temperature 9 ℃) obtained by copolymerizing methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 parts by mass).

[ epoxy resin (b1) ]

(b1) -1: bisphenol A epoxy resin (jER 828 manufactured by Mitsubishi Chemical Corporation) which is liquid at 23 ℃, has an epoxy equivalent of 184 to 194g/eq, a number average molecular weight of 370, and a viscosity of 120 to 150P (12 to 15 Pa.s) at 25 ℃

[ Heat-curing agent (b2) ]

(b2) -1: aralkyl type phenol resin ("Milex XLC-4L" manufactured by Mitsui Chemicals, Inc., number average molecular weight 1100, softening point 63 ℃ C.)

[ Filler (d) ]

(d) -1: spherical silica (YA 050C-MJE manufactured by Admatech corporation, average particle diameter 50nm, methacryl silane-treated product)

[ coupling agent (e) ]

(e) -1: silane coupling agent, 3-glycidyloxypropylmethyldiethoxysilane ("KBE-402" manufactured by shin-Ethersilicon Co., Ltd.)

[ crosslinking agent (f) ]

(f) -1: toluene diisocyanate crosslinking agent ("CORONATE L" manufactured by TOSOH CORPORATION)

[ example 1]

Production of wafer for semiconductor device fabrication

< production of substrate >

Low density polyethylene ("SUMIKATHENE L705" manufactured by Sumitomo Chemical co., ltd.) was melted using an extruder, the melt was extruded by a T-die method, and the extrudate was biaxially stretched using a chill roll, thereby obtaining a base material (thickness of 110 μm) made of LDPE.

< preparation of adhesive layer >

A non-energy ray-curable adhesive composition was prepared which contained 100 parts by mass of an acrylic resin (TOYOCHEM co., ltd. "ORIBAIN BPS 6367X" manufactured by ltd.) (I-1a) as an adhesive resin, 1 part by mass of an amine-based ionic liquid (Koei Chemical industry co., ltd. "IL-a 2" manufactured by ltd.) (BXX 5640 "manufactured by TOYOCHEM co., ltd.," xylylene diisocyanate-based crosslinking agent) as an antistatic agent, and 3 parts by mass of an amine-based ionic liquid (Koei Chemical industry co., ltd.) (ii-a 2 ").

Next, a release film obtained by subjecting one surface of the polyethylene terephthalate film to a release treatment by a silicone treatment was used, and the obtained adhesive composition was applied to the release-treated surface of the release film, and dried by heating at 100 ℃ for 2 minutes, thereby producing a non-energy ray-curable adhesive layer (thickness: 10 μm).

< production of intermediate layer >

An ethylene-vinyl acetate copolymer (EVA, weight average molecular weight of 30000, content of structural units derived from vinyl acetate 25 mass%) (15g) was dissolved in 85g of tetrahydrofuran at ordinary temperature, and a siloxane compound (polydimethylsiloxane, "BYK-333" manufactured by BYK Japan KK., formula "-Si (-CH) in one molecule was added to the solution thus obtained ₃)₂The number of the structural units represented by-O- "is 45 to 230) (1.5g), and stirring is carried out, thereby preparing the composition for forming an intermediate layer.

The intermediate layer (thickness: 20 μm) was prepared by applying the composition for forming an intermediate layer obtained above to the release-treated surface of a release film obtained by subjecting one surface of a polyethylene terephthalate film to a release treatment by a silicone treatment, and drying the composition for forming an intermediate layer at 70 ℃ for 5 minutes.

Production of film-shaped adhesive

A thermosetting adhesive composition containing 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(75 parts by mass), coupling agent (e) -1(0.5 part by mass), and crosslinking agent (f) -1(0.5 part by mass) was prepared. The contents shown here are all contents of the target product without a solvent.

Next, using a release film obtained by subjecting one surface of a polyethylene terephthalate film to a release treatment by a silicone treatment, the obtained adhesive composition was applied to the release-treated surface of the release film, and dried by heating at 80 ℃ for 2 minutes, thereby producing a thermosetting film-like adhesive (thickness: 7 μm).

< manufacture of sheet for manufacturing semiconductor device >

The exposed surface of the obtained adhesive layer on the side opposite to the side having the release film was bonded to one surface of the obtained base material, thereby producing a first intermediate laminate with a release film (in other words, a support sheet with a release film).

The exposed surface of the obtained film-like adhesive on the side opposite to the side provided with the release film and the exposed surface of the obtained intermediate layer on the side opposite to the side provided with the release film were bonded to each other, thereby producing a second intermediate laminate with a release film (laminate of release film, intermediate layer, film-like adhesive and release film).

Next, a second intermediate laminate with a release film was produced by punching out the part of the second intermediate laminate with a release film from the release film on the intermediate layer side to the film-shaped adhesive with a cutter blade to remove unnecessary parts, and this second intermediate laminate with a release film was formed by laminating a film-shaped adhesive (thickness of 7 μm) having a circular planar shape (diameter of 305mm), an intermediate layer (thickness of 20 μm), and a release film in this order in the thickness direction on the release film on the film-shaped adhesive side.

Next, the release film was removed from the first intermediate laminate with the release film obtained above, and one surface of the adhesive layer was exposed.

Further, the circular release film was removed from the second release-film-attached intermediate laminate processed product obtained above, and one surface of the intermediate layer was exposed.

Next, the newly generated exposed surface of the adhesive layer in the first intermediate laminate and the newly generated exposed surface of the intermediate layer in the second intermediate laminate processed product are bonded. The base material and the adhesive layer (i.e., the supporting sheet) in the laminate thus obtained were punched out from the base material side using a cutting blade (diameter of 370mm) so that the planar shape of the base material and the adhesive layer (supporting sheet) was circular (diameter of 370mm) and the planar shape thereof was concentric with the circular film-shaped adhesive and the intermediate layer (diameter of 305mm), and unnecessary portions were removed.

Thus, a sheet with a release film for manufacturing a semiconductor device was obtained, which was formed by sequentially laminating a base material (having a thickness of 110 μm), an adhesive layer (having a thickness of 10 μm), an intermediate layer (having a thickness of 20 μm), a film-like adhesive (having a thickness of 7 μm), and a release film in the thickness direction thereof.

[ evaluation of wafer for manufacturing semiconductor device ]

< determination of H (β) >

A liquid material (first test composition) containing the ethylene-vinyl acetate copolymer was applied to the release-treated surface of a release film ("SP-PET 381031" manufactured by linetec Corporation) and dried, thereby producing a film-shaped first test piece having a thickness of 10 μm and made of the ethylene-vinyl acetate copolymer.

The haze (H (β)) (%) was measured from the exposed surface side of the first test piece according to JIS K7136: 2000 using a haze meter ("NDH 7000" manufactured by NIPPON DENSHOKU INDUSTRIES co. The results are shown in Table 1.

< measurement of H (. beta.), calculation of H (. beta.) -H (. beta.)

A liquid material (second test composition) containing the ethylene-vinyl acetate copolymer and the epoxy resin (b1) -1 and uniformly mixed therewith was applied to a release-treated surface of a release film ("SP-PET 381031" manufactured by linec Corporation) and dried, thereby producing a film-shaped second test piece having a thickness of 10 μm and made of a mixture of the ethylene-vinyl acetate copolymer (100 parts by mass) and the epoxy resin (b1) -1(10 parts by mass).

The haze (H (β α)) (%) of this second test piece was measured in the same manner as in the first test piece. Then, H (β α) -H (β) (%) was calculated from the obtained measurement values. The results are shown in Table 1.

< measurement of H (. beta. gamma.), calculation of H (. beta. gamma) -H (. beta.) >)

A liquid material (third test composition) containing the ethylene-vinyl acetate copolymer and the amine-based ionic liquid (IL-a2) and uniformly mixed therewith was applied to a release-treated surface of a release film ("SP-PET 381031" manufactured by linec Corporation) and dried, thereby producing a film-shaped third test piece having a thickness of 10 μm, which was composed of a mixture of the ethylene-vinyl acetate copolymer (100 parts by mass) and the amine-based ionic liquid (10 parts by mass).

The third test piece was measured for haze (H (β γ)) (%) in the same manner as the first test piece. Then, H (β γ) -H (β) (%) was calculated from the obtained measurement value. The results are shown in Table 1.

< measurement of pickup force without lapse of time for silicon chip with film adhesive >

[ production of silicon chip set with film adhesive ]

So-called half-cutting in which a notch having a depth of 75 μm was formed from one surface of a silicon wafer (having a diameter of 150mm and a thickness of 350 μm) was performed using a cutting device ("DFD 6361" manufactured by DISCO Corporation) and a cutting blade ("ZH 05-SD 2000-NI-90-BB" manufactured by DISCO Corporation) with the rotational speed of the blade set to 50000rpm and the moving speed of the blade set to 25 mm/sec. The half-cutting was performed so as to obtain a silicon chip having a size of 5mm × 5 mm.

Next, a back grinding tape ("Adwill E-3100 TN" manufactured by LINTEC Corporation) was attached to the half-cut surface of the silicon wafer. Then, the exposed surface of the silicon wafer to which the back grinding tape was not attached was polished by a back grinding apparatus ("DGP 8761" manufactured by DISCO Corporation) until the thickness of the silicon wafer became 30 μm, thereby dividing the silicon wafer and producing a plurality of silicon chips (having a thickness of 30 μm) having a size of 5mm × 5mm (in the present specification, this size is sometimes referred to as "5 mm □"). Thus, a silicon chip set in which a plurality of silicon chips are aligned and fixed to a back-grinding tape was obtained.

Then, the release film was removed from the thus obtained sheet for manufacturing a semiconductor device without lapse of time. Then, the semiconductor device manufacturing sheet was heated to 60 ℃ using a chip mounter ("Adwill RAD 2700" manufactured by LINTEC Corporation), and simultaneously attached to the exposed surfaces of all the silicon chips in the above silicon chip group by a film-like adhesive therein. Further, the back grinding tape was removed from all the silicon chips. In this way, a laminate (a laminate in which the laminate sheet, the film-like adhesive, and the silicon chip group are laminated in this order in the thickness direction) is obtained, the laminate being formed by laminating the substrate, the adhesive layer, the intermediate layer, the film-like adhesive, and the silicon chip group in this order in the thickness direction.

Then, using a die expander (expander) ("DDS 2300" manufactured by DISCO Corporation), the film-shaped adhesive was expanded by the following steps, thereby cutting the film-shaped adhesive. That is, first, the laminate is disposed on a table. At this time, the base material in the laminate is brought into contact with the table. Next, the laminate was adsorbed and fixed on a stage, and the stage was pushed up at a spreading rate of 100mm/s and a spreading amount of 10mm under a condition of 0 ℃, thereby spreading the laminate in a direction parallel to the surface of the laminate. Thereby, the film-shaped adhesive is cut.

Next, the adsorption and expansion of the laminate are released, and a region in the laminate near the outer periphery of the film-shaped adhesive is heated, thereby eliminating the relaxation of the film-shaped adhesive in the region.

Thus, a silicon chip set with a film-like adhesive is obtained in a state where a plurality of silicon chips with a film-like adhesive, each including a silicon chip and a cut film-like adhesive provided on the back surface of the silicon chip, are aligned and fixed to the intermediate layer in the laminate by the film-like adhesive.

[ measurement of pickup force without elapse of time for silicon chip with film-like adhesive ]

Next, a silicon chip with a film-like adhesive was picked up from the silicon chip set with a film-like adhesive obtained above under the conditions of an upward push height of 250 μm and an expansion of 4mm using a pickup device ("PU 100" manufactured by ltd., and the number of pins was 5), and the pickup force at this time was measured. The pick-up force was measured at 30 positions, and the average of these measured values was used as the pick-up force (mN/5mm □) of the silicon chip with the film-like adhesive when no time had elapsed. The results are shown in Table 1.

< measurement of pickup force of silicon chip with film adhesive over time >

The semiconductor device-manufacturing sheet obtained as described above was left to stand at 40 ℃ for one week for a while.

Next, the pickup force of the silicon chip with the film-like adhesive was measured with the lapse of time in the same manner as the measurement of the pickup force without the lapse of time, except that the semiconductor device-manufacturing sheet with the lapse of time was used instead of the semiconductor device-manufacturing sheet without the lapse of time. The results are shown in Table 1.

< measurement of surface resistivity of film-shaped adhesive without lapse of time >

The release film was removed from the semiconductor device-manufacturing sheet obtained above, and the entire exposed surface of the film-like adhesive agent thus produced was attached to the adhesive surface of an adhesive tape having a polyethylene terephthalate layer ("PET 50(a) PL thin 8 LK" manufactured by linetec Corporation). Then, the obtained laminate was cut into a size of 100mm × 100mm, and the laminate of the adhesive tape and the film-like adhesive was peeled from the intermediate layer to prepare a test piece. The test piece was left to stand at 23 ℃ under an environment with a relative humidity of 50% for 24 hours to adjust the humidity, and then the surface resistivity of the exposed surface (surface on the intermediate layer side) of the film-like adhesive was measured. The surface resistivity was measured using a digital electrometer (manufactured by ADVANTEST CORPORATION) with the applied voltage set at 100V. The results are shown in Table 1.

< measurement of surface resistivity of film-shaped adhesive over time >

The semiconductor device-manufacturing sheet obtained as described above was left to stand at 40 ℃ for one week for a while.

Then, the surface resistivity of the film-like adhesive with lapse of time was measured in the same manner as in the case of measuring the surface resistivity with lapse of time, except that the sheet for manufacturing a semiconductor device with lapse of time was used instead of the sheet for manufacturing a semiconductor device with lapse of time. The results are shown in Table 1.

< calculation of the proportion of silicon concentration in the film-shaped adhesive-side surface of intermediate layer >

In the process of manufacturing the semiconductor device manufacturing wafer, the exposed surface of the intermediate layer at the stage before the bonding to the adhesive layer is analyzed by XPS, the concentrations (atomic%) of carbon (C), oxygen (O), nitrogen (N), and silicon (Si) are measured, and the ratio (%) of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen, and silicon is determined from the measured values.

XPS analysis Using an X-ray photoelectron spectroscopy apparatus ("Quantra SXM" manufactured by ULVAC, Inc.) with an irradiation angle of 45 ° and an X-ray beam diameter of

The output was 4.5W. The results are shown in the column "the proportion (%) of the concentration of the element in the intermediate layer" in table 1 together with the proportion (%) of the concentration of the other element.

< evaluation of the Effect of suppressing the Generation of chips when cutting with a blade >

[ production of silicon chip group with film adhesive ]

The release film was removed from the semiconductor device manufacturing sheet obtained above.

The above-mentioned semiconductor device-manufacturing sheet was heated to 60 ℃ using a silicon wafer (diameter 300mm, thickness 75 μm) whose back surface was polished by dry polishing processing, using a chip mounter ("Adwill RAD 2500" manufactured by LINTEC Corporation), and was simultaneously attached to the back surface (polished surface) of the above-mentioned silicon wafer via a film-like adhesive therein. In this way, a laminate (a laminate in which the laminate sheet, the film-like adhesive, and the silicon wafer are laminated in this order in the thickness direction) is obtained, the laminate being formed by laminating a substrate, an adhesive layer, an intermediate layer, a film-like adhesive, and a silicon wafer in this order in the thickness direction.

Next, a region (the non-lamination region) in the vicinity of the peripheral portion of the first surface of the adhesive layer in the laminate where the intermediate layer is not provided is fixed to the ring frame for dicing.

Subsequently, a dicing apparatus ("DFD 6361" manufactured by DISCO Corporation) was used to perform dicing, thereby dividing the silicon wafer and simultaneously cutting the film-like adhesive to obtain silicon chips having a size of 8mm × 8 mm. The cutting at this time was performed by: the silicon wafer was cut from the bonding surface of the film-like adhesive of the semiconductor device manufacturing wafer to the middle region of the intermediate layer (i.e., the entire region of the film-like adhesive in the thickness direction and the region of the intermediate layer from the surface on the film-like adhesive side to the middle) using a blade with the rotation speed of the blade set to 30000rpm and the moving speed of the blade set to 30 mm/sec. As the blade, "Z05-SD 2000-D1-90 CC" manufactured by DISCO Corporation was used.

Thus, a silicon chip set with a film-like adhesive is obtained in a state where a plurality of silicon chips with a film-like adhesive, each including a silicon chip and a cut film-like adhesive provided on the back surface of the silicon chip, are aligned and fixed to the intermediate layer in the laminate sheet by the film-like adhesive.

[ evaluation of the Effect of suppressing the production of chips ]

The obtained silicon chip group with a film-like pressure-sensitive adhesive was observed from above on the silicon chip side thereof using a digital microscope ("VH-Z100" manufactured by KEYENCE CORPORATION) to confirm whether or not cutting chips were generated. Further, a case where no chips are generated is determined as "a", and a case where chips are generated even in a small amount is determined as "B". The results are shown in Table 1.

< evaluation of cuttability of film-shaped adhesive during expansion >

[ production of silicon chip set with film adhesive ]

A silicon wafer having a circular planar shape with a diameter of 300mm and a thickness of 775 μm was used, and a back grinding tape ("Adwill E-3100 TN" manufactured by LINTEC Corporation) was attached to one surface of the silicon wafer.

Next, a laser irradiation apparatus ("DFL 73161" manufactured by DISCO Corporation) was used to irradiate a laser beam so as to be focused on a focal point set inside the silicon wafer, thereby forming a modified layer inside the silicon wafer. In this case, the focal point is set so that a plurality of silicon chips having a size of 8mm × 8mm can be obtained from the silicon wafer. The silicon wafer is irradiated with laser light from the other surface (surface to which the back grinding tape is not attached) side of the silicon wafer.

Next, the other surface of the silicon wafer was polished with a grinder to a thickness of 30 μm, and the silicon wafer was divided at the formation site of the modified layer by a force applied to the silicon wafer during polishing at this time to produce a plurality of silicon chips. Thus, a silicon chip set in which a plurality of silicon chips are aligned and fixed to a back-grinding tape was obtained.

Next, one piece of the semiconductor device manufacturing sheet obtained above was heated to 60 ℃ using a chip mounter ("adwil RAD 2500" manufactured by LINTEC Corporation), and the film-like adhesive therein was attached to the other face (in other words, a ground face) of all the silicon chips (silicon chip groups) at the same time.

Next, a region (the non-lamination region) in the vicinity of the peripheral portion where the intermediate layer is not provided in the first surface of the adhesive layer in the semiconductor device manufacturing sheet after the silicon chip group is attached is fixed to the ring frame for dicing.

Then, the back grinding tape was removed from the silicon chip set in the fixed state. Then, using a full-automatic die cutter ("DDS 2300" manufactured by DISCO Corporation), a sheet for semiconductor device fabrication (film-like adhesive) was cooled in an environment of 0 ℃ while being spread in a direction parallel to the surface thereof, thereby cutting the film-like adhesive along the outer periphery of the silicon chip. At this time, the peripheral portion of the semiconductor device manufacturing sheet was fixed, and the entire region of the semiconductor device manufacturing sheet on which the intermediate layer and the film-like adhesive were laminated was pushed up to a height of 15mm from the base material side of the semiconductor device manufacturing sheet, thereby spreading the sheet.

Thus, a silicon chip set with a film-like adhesive, which is a silicon chip set with a film-like adhesive comprising a silicon chip and a film-like adhesive after cutting provided on the other surface (polished surface) of the silicon chip, was obtained in a state where a plurality of silicon chips with a film-like adhesive were aligned and fixed to an intermediate layer.

Next, after the spread of the semiconductor device manufacturing sheet is once released, a laminated body (that is, the laminated sheet) formed by laminating the base material, the adhesive agent layer, and the intermediate layer is spread in a direction parallel to the first surface of the adhesive agent layer at normal temperature. Further, the peripheral portion of the silicon chip on which the film-like pressure-sensitive adhesive is not mounted in the laminated sheet is heated while maintaining the spread state.

Thereby, the peripheral portion is contracted, and the width of the notch between the adjacent silicon chips on the laminated sheet is kept at a certain value or more.

[ evaluation of cuttability of film-shaped adhesive ]

In the production of the silicon chip set with the film-like pressure-sensitive adhesive, the silicon chip set was observed from above on the silicon chip side of the obtained silicon chip set with the film-like pressure-sensitive adhesive using a digital microscope ("VH-Z100" manufactured by KEYENCE CORPORATION). Then, when the film-like adhesive is supposed to be normally cut by spreading of the semiconductor device manufacturing sheet (film-like adhesive), among a plurality of cutting lines of the film-like adhesive extending in one direction to be formed and a plurality of cutting lines of the film-like adhesive extending in a direction orthogonal to the one direction, the number of cutting lines that are not actually formed and the number of cutting lines that are incomplete are confirmed, and the cuttability of the film-like adhesive is evaluated according to the following evaluation criteria. The results are shown in Table 1.

(evaluation criteria)

A: the total number of the cutting lines of the film-shaped adhesive which is not actually formed and the cutting lines of the incomplete film-shaped adhesive is 5 or less.

B: the total number of the cutting lines of the film-shaped adhesive which is not actually formed and the cutting lines of the incomplete film-shaped adhesive is more than 6.

< evaluation of pickup Property of silicon chip with film-shaped adhesive after expansion >

After the evaluation of the cuttability of the film-like adhesive, the silicon chip with the film-like adhesive was picked up from the intermediate layer in the laminate sheet under the conditions of a push-up height of 250 μm and a push-up speed of 5mm/s using a silicon chip set with the film-like adhesive and a die bonder ("PU 100" manufactured by ltd.). Then, the case where all the silicon chips with the film-like adhesive could be picked up normally under the condition that the push-up time was 500ms was evaluated as "a", the case where one or more silicon chips with the film-like adhesive could not be picked up normally under the condition that the push-up time was 500ms but all the silicon chips with the film-like adhesive could be picked up normally under the condition that the push-up time was 10s was evaluated as "B", and the case where one or more silicon chips with the film-like adhesive could not be picked up normally even under the condition that the push-up time was 10s was evaluated as "C". The results are shown in Table 1.

< measurement of T-shaped peeling Strength between intermediate layer and film adhesive >

The release film was removed from the semiconductor device manufacturing sheet obtained above.

The entire exposed surface of the film-like adhesive in the thus produced sheet for manufacturing a semiconductor device was bonded to the adhesive surface of an adhesive tape having a polyethylene terephthalate layer ("PET 50(a) PL thin 8 LK" manufactured by LINTEC Corporation), and the resulting laminate was cut into a size of 50mm × 100mm, thereby producing a test sheet.

In this test piece, a laminate of the substrate, the adhesive agent layer and the intermediate layer (i.e., the laminate) and a laminate of the film-shaped adhesive agent and the adhesive tape were pulled apart in accordance with JIS K6854-3, and the test piece was peeled in a T-shape, and the maximum value of the peel force (mN/50mm) measured at this time was used as the T-type peel strength. At this time, the peeling speed was set to 50 mm/min. The results are shown in Table 1.

Production and evaluation of wafer for producing semiconductor device

[ example 2]

A semiconductor device-manufacturing sheet was manufactured and evaluated in the same manner as in example 1, except that the silicone compound was not added when the intermediate layer-forming composition was prepared, and the amount of the ethylene-vinyl acetate copolymer used was set to 16.5g instead of 15g (in other words, only the ethylene-vinyl acetate copolymer was dissolved in tetrahydrofuran by using the same mass of the ethylene-vinyl acetate copolymer instead of the silicone compound). The results are shown in Table 1. The "-" in the column of additives in Table 1 indicates that the additives were not used.

[ example 3]

A semiconductor device-manufacturing sheet was manufactured and evaluated in the same manner as in example 2, except that, in the preparation of the intermediate layer-forming composition, the same mass of an ethylene-vinyl acetate copolymer (EVA, weight average molecular weight 30000, content of structural units derived from vinyl acetate 40 mass%) was used instead of the ethylene-vinyl acetate copolymer. The results are shown in Table 1.

Comparative example 1

An acrylic resin (acrylic copolymer) dispersion ("copony N2359-6, having a solid content concentration of 34%" (100 parts by mass) and a polyisocyanate compound ("CORONATE L", having a solid content concentration of 75%, manufactured by Nippon Polyurethane Industry co., ltd.) (10 parts by mass) were blended and stirred at room temperature to prepare a composition for forming an intermediate layer for comparison.

A comparative semiconductor device-manufacturing sheet was manufactured in the same manner as in example 1, except that the comparative intermediate layer-forming composition was used instead of the intermediate layer-forming composition. The results are shown in Table 1.

Comparative example 2

A comparative semiconductor device-manufacturing sheet was manufactured in the same manner as in example 1, except that the intermediate layer was not formed. More specifically, in the production process of the above-described sheet for manufacturing a semiconductor device in example 1, a laminate of a release film, a film-like adhesive, and a release film was produced instead of the second intermediate laminate with a release film by bonding the release-treated surface of the release film to the exposed surface of the film-like adhesive with a release film, instead of the exposed surface of the intermediate layer with a release film, and the laminate of the release film, the film-like adhesive, and the release film was used in the subsequent step, and a sheet for manufacturing a semiconductor device for comparison was produced in the same manner as in example 1, except that the above-described sheet for manufacturing a semiconductor device was used.

Then, the comparative semiconductor device-manufacturing sheet was evaluated in the same manner as in example 1. The results are shown in Table 1.

[ Table 1]

From the above results, in examples 1 to 3, it was not confirmed that the picking force of the silicon wafer with the film-like adhesive was changed depending on whether or not the semiconductor device manufacturing sheet was used for a while, and even if the semiconductor device manufacturing sheet was used for a while, the physical properties of the film-like adhesive were changed. This indicates that the composition of the film-like adhesive did not change significantly even after a lapse of time in the sheet for manufacturing a semiconductor device. That is, although the film-like adhesive contains the epoxy resin (b1) -1 (the crosslinking agent (f) -1 is not the component (α 2)) as the component (α 2), the component (α 2) is inhibited from transferring to the adhesive layer side even after a lapse of time from the sheet for manufacturing a semiconductor device.

Further, in examples 1 to 3, the surface resistivity of the film-like adhesive was more than 1.0X 10 regardless of whether the sheet for producing a semiconductor device was left for a while¹⁴Omega/□, no change in antistatic properties was observed on the surface of the film-like pressure-sensitive adhesive that was on the middle layer side even after a lapse of time. This indicates that the composition of the adhesive layer, which is the only layer containing the antistatic agent, did not change significantly even after a period of time for the semiconductor device-manufacturing sheet. The antistatic property of the film-like adhesive was confirmed here, but it is presumed that even if the antistatic property of the adhesive agent layer was confirmed, the influence of the semiconductor device production sheet over time could not be confirmed. That is, although the adhesive layer contains the amine-based ionic liquid as an antistatic agent as the component (γ 2), even when a semiconductor device is manufacturedThe transfer of the component (γ 2) to the film-like adhesive side is also suppressed over time of the construction sheet.

In this manner, it was confirmed that in the semiconductor device manufacturing sheets of examples 1 to 3, the intermediate layer suppressed the transfer of the liquid component in the film-like adhesive to the adhesive layer side, and the transfer of the liquid component in the adhesive layer to the film-like adhesive side.

In examples 1 to 3, H (. beta.) -B) were each 8% or more.

Further, the values of H (β α) -H (β) and H (β γ) -H (β) suggest that the semiconductor device-manufacturing sheets of examples 1 to 2 more strongly inhibit the transfer of liquid components between the adhesive layer and the film-like adhesive than the semiconductor device-manufacturing sheet of example 3.

In the ethylene-vinyl acetate copolymer as the main component (non-silicone resin (β 1)) of the intermediate layer, the ratio of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units was 25 mass% in examples 1 to 2 and 40 mass% in example 3.

Further, in examples 1 to 3, the generation of chips was suppressed when dicing was performed, the cutting failure of the film-like adhesive was suppressed when spreading was performed, and the suitability for dividing the semiconductor wafer was excellent.

In examples 1 to 3, the weight average molecular weight of the ethylene-vinyl acetate copolymer contained as the main component (non-silicone resin (. beta.1)) in the intermediate layer in the sheet for producing a semiconductor device was 30000 or less.

In examples 1 to 3, the content of the ethylene-vinyl acetate copolymer in the intermediate layer was 90.9 mass% or more with respect to the total mass of the intermediate layer, and the content of the siloxane compound was 9.1 mass% or less with respect to the total mass of the intermediate layer.

In example 1, the silicon chip with the film-like adhesive after spreading was further excellent in pickup properties.

In example 1, the T-peel strength between the intermediate layer and the film-like adhesive was 100mN/50mm and was moderately low, and the ratio of the silicon concentration of the intermediate layer was 9% and was moderately high. These evaluation results were in agreement with the evaluation results of the pickup property of the silicon chip with the film-like pressure-sensitive adhesive.

In examples 2 to 3, the intermediate layer in the sheet for producing a semiconductor device did not contain the siloxane compound.

In examples 1 to 3, no nitrogen was detected when the exposed surface of the intermediate layer was analyzed by XPS.

In contrast, in comparative example 1, the pickup force of the silicon wafer with the film-like adhesive was reduced over time by the semiconductor device-manufacturing sheet, and it was confirmed that the physical properties of the film-like adhesive were changed. This indicates that the composition of the film-like adhesive significantly changed over time due to the sheet for manufacturing a semiconductor device. That is, it is presumed that although the film-like adhesive contains the epoxy resin (b1) -1 as the component (α 2), the transfer of the component to the adhesive layer side is not suppressed by the passage of time of the semiconductor device-manufacturing sheet.

Further, in comparative example 1, it was confirmed that the surface resistivity of the film-like adhesive was lowered with the lapse of time due to the semiconductor device-producing sheet, and the antistatic property of the surface of the film-like adhesive which was on the intermediate layer side was changed with the lapse of time due to the semiconductor device-producing sheet. This indicates that the composition of the adhesive layer, which is the only layer containing the antistatic agent, significantly changed over time due to the semiconductor device-manufacturing sheet. Although the antistatic property of the film-like adhesive was confirmed here, it is presumed that even if the antistatic property of the adhesive agent layer was confirmed, the influence of the semiconductor device production sheet over time was confirmed. That is, it is presumed that although the adhesive layer contains the amine-based ionic liquid as an antistatic agent as the component (γ 2), the transfer of the component to the film-like adhesive side is not suppressed by the passage of time of the semiconductor device-manufacturing sheet.

As described above, in the comparative semiconductor device manufacturing sheet of comparative example 1, the intermediate layer did not inhibit the transfer of the liquid component in the film-like adhesive to the adhesive layer side, nor did it inhibit the transfer of the liquid component in the adhesive layer to the film-like adhesive side.

In comparative example 1, H (β α) -H (β) and H (β γ) -H (β) were both 1%.

In comparative example 2, the silicon wafer with the film-like adhesive could not be picked up and the picking force could not be measured regardless of whether the sheet for manufacturing a semiconductor device had elapsed time. This means that the composition of the film-like adhesive has significantly changed at a stage before the sheet for manufacturing a semiconductor device has elapsed some time. That is, it is presumed that although the film-like adhesive contains the epoxy resin (b1) -1 as the component (α 2), the transfer of the component (α 2) to the adhesive layer side occurs at a stage before the semiconductor device manufacturing sheet has passed for a while. This is because the comparative semiconductor device-manufacturing sheet of comparative example 2 does not have an intermediate layer.

In comparative example 2, the pickup property of the silicon chip with the film-like adhesive after spreading was also poor.

In comparative example 2, as described above, not only the silicon chip with the film-like adhesive was not pulled off from the intermediate layer and picked up, but also the test piece for measuring the surface resistivity of the film-like adhesive was not produced, and therefore the surface resistivity was not measured.

Industrial applicability

The invention can be used for manufacturing semiconductor devices.

Description of the reference numerals

101: a semiconductor device manufacturing sheet; 11: a substrate; 12: an adhesive layer; 13: an intermediate layer; 13 a: a first side of the intermediate layer; 14: a film-like adhesive.

Claims (8)

1. A sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,

the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the substrate,

the intermediate layer contains a non-silicone resin (beta 1) having a weight-average molecular weight of 20000 to 100000 as a main component,

further, at least the film-like adhesive contains a component (α 2) or at least the adhesive layer contains a component (γ 2),

the component (. alpha.2) is liquid at a temperature of 23 ℃ and has no functional group which reacts with the main component contained in the film-like adhesive,

the component (. gamma.2) is in a liquid state at a temperature of 23 ℃ and has no functional group which reacts with the main component contained in the adhesive agent layer,

h (beta) represents the haze of a film-shaped first test piece composed of the non-silicon resin (. beta.1) and having a thickness of 10 μm,

when the film-shaped adhesive contains the component (α 2), the haze of a film-shaped second test piece having a thickness of 10 μm and composed of a mixture of 100 parts by mass of the non-silicon resin (β 1) and 10 parts by mass of the component (α 2) is represented by H (β α), and when H (β α) and H (β) satisfy the following formula (X1):

(X1)H(βα)-H(β)＞7％，

When the adhesive layer contains the component (γ 2), the haze of a film-shaped third test piece having a thickness of 10 μm, which is composed of a mixture of 100 parts by mass of the non-silicon resin (β 1) and 10 parts by mass of the component (γ 2), is represented by H (β γ), and H (β γ) and H (β) satisfy the following formula (X2):

(X2)H(βγ)-H(β)＞7％。

2. the semiconductor device-manufacturing sheet according to claim 1,

further, at least the film-shaped adhesive contains a component (α 1) which is solid at a temperature of 23 ℃ as a main component, or at least the adhesive layer contains a component (γ 1) which is solid at a temperature of 23 ℃ as a main component,

the component (. alpha.1) and the component (. gamma.1) are acrylic resins having a structural unit derived from a (meth) acrylate ester.

3. The semiconductor device-manufacturing sheet according to claim 1 or 2,

the intermediate layer contains one or more selected from the group consisting of ethylene-vinyl acetate copolymers and polyolefins as the non-silicone resin (. beta.1).

4. The sheet for manufacturing a semiconductor device according to any one of claims 1 to 3,

the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicone resin (. beta.1),

In the ethylene-vinyl acetate copolymer, the proportion of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units is 30% by mass or less.

5. The sheet for manufacturing a semiconductor device according to any one of claims 1 to 4, which is used for cutting the film-like adhesive by cooling and spreading the film-like adhesive.

6. A method for producing a sheet for manufacturing a semiconductor device according to any one of claims 1 to 5,

the manufacturing method comprises one or two of the following steps:

a film-like adhesive preparation step of preparing the film-like adhesive containing the component (α 2);

and an adhesive layer production step of producing the adhesive layer containing the component (. gamma.2).

7. A method for producing a semiconductor chip with a film-like adhesive, which comprises using the sheet for producing a semiconductor device according to any one of claims 1 to 5,

the semiconductor chip with the film-like adhesive includes a semiconductor chip and a film-like adhesive provided on a back surface of the semiconductor chip,

The manufacturing method comprises the following steps:

heating the semiconductor device manufacturing sheet and adhering the film-like adhesive to the back surface of the semiconductor wafer;

a step of dicing the semiconductor wafer by dicing the entire region in the thickness direction of the semiconductor wafer from the circuit forming surface side of the semiconductor wafer to which the film-shaped adhesive is attached, thereby producing the semiconductor chips, and dicing the semiconductor device-producing sheet along the thickness direction thereof from the film-shaped adhesive side thereof to an intermediate region of the intermediate layer, thereby obtaining a plurality of semiconductor chip groups with the film-shaped adhesive, in which the semiconductor chips with the film-shaped adhesive are aligned on the intermediate layer, by cutting the film-shaped adhesive without cutting the adhesive layer; and

and a step of pulling out the semiconductor chip with the film-like adhesive from the intermediate layer and picking up the semiconductor chip.

8. A method for producing a semiconductor chip with a film-like adhesive, using the sheet for producing a semiconductor device according to any one of claims 1 to 5,

The semiconductor chip with the film-shaped adhesive comprises a semiconductor chip and a film-shaped adhesive provided on the back surface of the semiconductor chip,

the manufacturing method comprises the following steps:

irradiating a laser beam so as to focus on a focal point set in a semiconductor wafer, thereby forming a modified layer in the semiconductor wafer;

a step of grinding the back surface of the semiconductor wafer after the modified layer is formed, and dividing the semiconductor wafer at a portion where the modified layer is formed by a force applied to the semiconductor wafer during grinding to obtain a semiconductor chip group in which a plurality of semiconductor chips are aligned;

a step of heating the semiconductor device manufacturing sheet while attaching the film-like adhesive to the back surfaces of all the semiconductor chips in the semiconductor chip group;

a step of cooling the semiconductor device manufacturing sheet after the semiconductor chips are attached to the sheet, and stretching the sheet in a direction parallel to the surface of the sheet, thereby cutting the film-like adhesive along the outer peripheries of the semiconductor chips to obtain a plurality of semiconductor chip groups with film-like adhesive, each of which has a plurality of semiconductor chips with film-like adhesive aligned on the intermediate layer; and

And a step of pulling out the semiconductor chip with the film-like adhesive from the intermediate layer and picking up the semiconductor chip.

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