TW201936839A - Adhesive sheet and method for manufacturing semiconductor device - Google Patents

Abstract

An adhesive sheet (10) for processing an electronic component has a base material (11) and an adhesive layer (12), and the adhesive layer (12) contains a cured material formed by curing an energy ray curable component.

Description

Adhesive sheet and method of manufacturing semiconductor device

The present invention relates to an adhesive sheet and a method of manufacturing the same.

In the manufacturing step of the semiconductor device, an adhesive sheet is used for the purpose of protecting a semiconductor element (for example, a semiconductor wafer or the like). A wide variety of characteristics are required for the adhesive sheet used in the manufacturing steps of the semiconductor device.
For example, Japanese Laid-Open Patent Publication No. 2012-46763 discloses a heat-resistant adhesive tape comprising a base material layer and an adhesive layer provided on the base material layer. The heat-resistant adhesive tape described in Document 1 is composed of an ultraviolet curable adhesive containing an ultraviolet curable compound, and it is described that the adhesive layer is irradiated with ultraviolet rays and further heated at 200 ° C for one hour, according to JIS. The adhesion of the adhesive layer measured by Z0237 is 1 N/19 mm or less.
Further, JP-A-2017-82104 discloses an adhesive sheet having a base material and an adhesive layer formed on a base material, and the adhesive layer contains an energy ray-curable adhesive.
In addition, in recent years, the adhesive sheet is also required to have the following properties: when the adhesive sheet is peeled off at room temperature after being subjected to high temperature conditions, the so-called adhesive remains in the body or the like (so-called The residual glue is small and the peeling force is small.
For example, Japanese Laid-Open Patent Publication No. 2010-73853 discloses a heat-resistant adhesive tape which is adhered to a user when a semiconductor wafer mounted on a metal lead frame is resin-sealed. The heat-resistant adhesive tape described in Document 3 has at least a base material layer and an active energy ray-curable adhesive layer.
The adhesive tape and the adhesive sheet (hereinafter collectively referred to as "adhesive sheet") described in the documents 1 and 2 are formed by reducing the adhesive force of the adhesive layer by ultraviolet irradiation, so that the adhesive sheet can be relatively easily obtained. It is peeled off by the body.
According to the literature 3, it is described that the heat-resistant adhesive tape described in the document does not cause residual glue at the time of peeling, and can be easily peeled off. In Document 3, the timing at which the active energy ray-curable adhesive layer is cured is not particularly limited as long as it is after bonding and before the wire bonding step. In this regard, in Document 3, it is described that if the adhesive layer is cured before being bonded to the outer pad side of the lead frame, the effect of tracking the unevenness on the surface of the lead frame cannot be obtained. Since the adhesion is lowered, the bonding becomes difficult, and since the adhesion to the lead frame is lowered, it is difficult to prevent leakage of the sealing resin.
However, when an adhesive tape containing an active energy ray-curable adhesive in an adhesive layer as described in Document 1, Document 2, and Document 3 is used in a manufacturing process of a semiconductor device, in a high-temperature environment in a sealing step, There is a case where an adhesive tape is peeled off or swelled from the body. In addition, if the plasma treatment step is successively performed after the sealing step, the temperature rise due to heating or the step of simultaneous temperature rise and decompression may occur between the adhesive tape and the object. There are cases in which expansion (foaming) or the like is caused.

[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive sheet which can reduce the occurrence of expansion under high temperature, high temperature and reduced pressure, and inadvertently peel off from the object, and improve the adhesion during heating. Residual glue can be prevented when peeling off from the body.
Another object of the present invention is to provide a method of manufacturing a semiconductor device using the adhesive sheet to manufacture a semiconductor device.

[Means for solving the problem]
An adhesive sheet according to the present invention is an adhesive sheet having a base material and an adhesive layer, and the adhesive layer contains a cured product obtained by curing an energy ray-curable component.
Preferably, in the adhesive sheet according to the aspect of the invention, the adhesive layer further contains a polymer component containing a constituent unit derived from a monomer having a nitrogen-containing functional group, but the nitrogen-containing functional group. Does not contain the NH bond.
In the adhesive sheet according to the aspect of the invention, it is preferable that the polymer component contains a constituent unit derived from a functional group-containing monomer having a reactive functional group, and the reactive functional group is a bond of three or more. A linear methylene group is formed to bond with the main chain of the aforementioned polymer component.
In the adhesive sheet according to the aspect of the invention, it is preferable that the energy ray-curable component contains a polyfunctional energy ray-curable compound, and the polyfunctional energy ray-curable compound has two or more and five or less in one molecule. A difunctional energy ray-curable compound of a polymerizable functional group.
In the adhesive sheet according to the aspect of the invention, it is preferable that the energy ray-curable component contains a polyfunctional energy ray-curable compound, and the polyfunctional energy ray-curable compound has two or more polymerizable functionalities in one molecule. The first polymerizable functional group and the second polymerizable functional group which are arbitrarily selected from the two or more polymerizable functional groups of the polyfunctional energy ray-curable compound are bonded to each other in a linear form. The methyl group has a linear number of methylene groups bonded between the first polymerizable functional group and the second polymerizable functional group of 4 or more.
In the adhesive sheet according to the aspect of the invention, it is preferable that the number of methylene groups which are linearly bonded between the first polymerizable functional group and the second polymerizable functional group is 8 or more. 30 or less.
In the adhesive sheet according to the aspect of the invention, it is preferred that the polyfunctional energy ray-curable compound has a ring structure in a molecule.
It is preferable that the adhesive sheet of the same state of the present invention has a breaking strength per unit sectional area of the adhesive layer of 4.5 N/mm ² or more.
Among the adhesive sheets of the same state of the present invention, it is preferred that the adhesive sheet has an adhesive strength to polyimine at 100 ° C of 0.04 N/25 mm or more.
Preferably, in the adhesive sheet according to the aspect of the invention, the adhesive sheet has an adhesive strength to polyimine at 100 ° C of 0.06 N/25 mm or more, and the breaking strength per unit sectional area of the adhesive layer is 4.5N/mm ² or more.
Among the adhesive sheets of the same state of the present invention, it is preferred that the adhesive sheet after heat treatment at 190 ° C for 1.5 hours under a nitrogen atmosphere has an adhesion to polyimine at 25 ° C of 3 N / 25mm or less.
In the adhesive sheet according to the same aspect of the invention, it is preferable that the Young's modulus of the adhesive layer is 5 MPa or less.
It is preferable that the adhesive sheet of the same state of the present invention is used for fixing or protecting the aforementioned electronic component when the electronic component is processed.
In the adhesive sheet according to the aspect of the invention, it is preferable that the electronic component is a semiconductor element and used to fix the semiconductor element when the semiconductor element is sealed.
Among the adhesive sheets of the same state of the present invention, it is preferred that the electronic component is directly attached to the adhesive layer.
Among the adhesive sheets of the same state of the present invention, it is preferred that the polymer component is crosslinked by a crosslinking agent.
In the adhesive sheet according to the same aspect of the invention, it is preferred that the polymer component is a (meth)acrylic polymer.
In the adhesive sheet according to the aspect of the invention, it is preferable that the nitrogen-containing functional group is at least one selected from the group consisting of a tertiary amino group, an aminocarbonyl group, a cyano group, and a nitrogen-containing heterocyclic group. .
Preferably, among the adhesive sheets of the same state of the present invention, the monomer having a nitrogen-containing functional group is selected from the group consisting of a heterocyclic vinyl compound, a (meth) acrylamide compound, and an amine group-containing (methyl) group. At least one of the group consisting of an acrylate compound and (meth)acrylonitrile.
In the adhesive sheet according to the aspect of the invention, it is preferable that the ratio of the constituent unit derived from the monomer having a nitrogen-containing functional group to the total mass of the polymer component is 1% by mass or more and 20% by mass. The ratio below.
In the adhesive sheet according to the aspect of the invention, it is preferable that the ratio of the cured product obtained by curing the energy ray-curable component in the entire mass of the pressure-sensitive adhesive layer is 5 mass% or more and 40 mass% or less. The ratio.
A method of fabricating a semiconductor device of the same state of the present invention, comprising the steps of:
a step of fixing a semiconductor element to an adhesive sheet having an adhesive layer comprising a cured product obtained by curing an energy ray-curable component; and sealing the semiconductor element by a sealing member.

[Effects of the Invention]
According to the present invention, it is possible to provide an adhesive sheet which can reduce the occurrence of expansion under high temperature, high temperature and reduced pressure, and inadvertent peeling from the object, and improve the adhesion at the time of heating. Residual glue can be prevented from being peeled off from the body.

[Best Mode for Carrying Out the Invention]
The following is an adhesive sheet relating to the same state of the present invention, which will be described with reference to the drawings.
Further, in the present specification, the term "residual gel" refers to a component (whether in the adhesive layer or a component blended in the adhesive layer) when the adhesive sheet is peeled off from the adherend, or The component which invades into the adhesive layer after the formation of the adhesive layer) causes a residue to be formed on the object.

<First Embodiment>
[adhesive sheet]
Fig. 1 is a schematic cross-sectional view showing an adhesive sheet 10 of the present embodiment.
The state of use of the adhesive sheet 10 is not particularly limited. The state in which the adhesive sheet 10 is used is a form in which the adhesive sheet 10 is used as an adhesive sheet for processing electronic parts. Moreover, as another use aspect of the adhesive sheet 10, the aspect used for fixing or protecting an electronic component is mentioned. Further, as a more specific aspect of the use of the adhesive sheet 10, a state in which the semiconductor element on the adhesive sheet 10 is sealed can be used for fixing the semiconductor element.
A wide variety of members can be adhered to the adhesive sheet 10. In the present specification, a member that can be adhered to the adhesive sheet 10 is referred to as a subject. Examples of the object to be attached include an electronic component (a semiconductor element or the like) and a frame member. The object of the electronic component or the like is preferably attached directly to the adhesive layer 12. For example, when the semiconductor element on the adhesive sheet 10 is sealed with a sealing resin, the frame member can be used for preventing warpage of the adhesive sheet 10 with hardening shrinkage of the sealing resin. The frame member may also be in a semiconductor package obtained by sealing the semiconductor element, and may exhibit a specified function, or may be obtained by removing a portion of the frame member to obtain a semiconductor package.
The adhesive sheet 10 of the present embodiment has a substrate 11 and an adhesive layer 12. The adhesive layer 12 contains a cured product obtained by curing an energy ray curable component. In the present embodiment, the release sheet RL may be further laminated on the adhesive layer 12. When the adhesive sheet 10 is used, the release sheet RL is peeled off from the adhesive sheet 10.
The pressure-sensitive adhesive layer 12 preferably contains a polymer component (hereinafter also referred to as "polymer component (A)") and a cured product obtained by curing an energy ray-curable component (hereinafter also referred to as "hardened material (B)". ).
The adhesive layer 12 in the same state of the present embodiment includes a polymer component (hereinafter also referred to as "polymer component (AX)") and a cured product obtained by curing the energy ray-curable component (also referred to as " The cured product (B)"), the polymer component (AX) contains a constituent unit derived from a monomer having a nitrogen-containing functional group. However, the aforementioned nitrogen-containing functional group does not contain an NH bond.
The base material 11 has a first base material surface 11a and a second base material surface 11b, and the second base material surface 11b is opposite to the first base material surface 11a. In the adhesive sheet 10 of the present embodiment, the adhesive layer 12 is laminated on the first substrate surface 11a. A body of a semiconductor element or the like is adhered to the adhesive layer 12. In the manufacturing process of the semiconductor device, the adherend system is held on the adhesive sheet 10 with the adhesive layer 12.
According to the adhesive sheet 10 of the present embodiment, the occurrence of expansion under high temperature and reduced pressure conditions and the inadvertent peeling from the object can be reduced, and the adhesion at the time of heating can be improved while being self-contained. When the body is peeled off, the residual glue can be prevented (hereinafter also referred to as "the effect of the present embodiment").
The reason why the effect of the present embodiment can be obtained is presumed as follows.
The adhesive layer 12 according to the present embodiment includes a cured product (B) obtained by curing an energy ray-curable component. Therefore, even in a high temperature environment, the adhesive layer 12 can maintain a sufficient adhesion to the object. As a result, the adhesive sheet 10 can be fixed to the adhesive sheet 10 without causing the object to fall off. The high-temperature environment in the present specification is not particularly limited, and examples thereof include a sealing step of a semiconductor element, a step of sputtering a metal such as an electronic component, and a step of washing an electronic component with hot water or the like. In the present specification, the object to be adhered to the adhesive sheet is not particularly limited. However, when the adhesive sheet is used in the sealing step of the semiconductor element, the material of the object to be used may be the surface of the semiconductor element or the surface of the semiconductor element. A polyimide film of a semiconductor element or the like. When the frame member is used, the frame member can also be the object of the adhesive sheet 10, and a glass epoxy resin or the like can be used as the material. Moreover, a glass wafer or the like is exemplified as the object to be used in the application of the adhesive sheet 10 other than the sealing step of the semiconductor element.
Further, in the step of heating, heating, and decompression, the gas generated by the moisture absorbed by the adhesive sheet 10 and other members during storage or in the manufacturing step is adhered to the adherend. There will be cases of expansion (foaming). Even in a high temperature, high temperature, or reduced pressure environment, since the adhesive force is high, the adhesive sheet 10 can suppress generation of foaming or the like. Then, since the adhesive layer 12 has sufficient aggregability, the adhesive sheet 10 can be peeled off and removed without causing residue on the body after the step of heating, heating, or depressurization. In the present specification, the step of heating, heating, and depressurization is not particularly limited, and examples thereof include a sealing step or a plasma treatment step subsequent to the sealing step. The object to be exposed in the step of heating, heating, and decompression is not particularly limited, and examples thereof include a semiconductor element, a frame member, and a glass wafer.
There is a case where the following condition is referred to as a residual glue: after the adhesive sheet is peeled off from the object, the residue adheres to the surface of the object. For example, when the adhesive sheet is peeled off from the sealing body after the sealing step in the manufacturing step of the semiconductor device, the adhesive adheres to the conductive portion of the semiconductor device (semiconductor element). For example, the conductive portion may be a via portion of a semiconductor device or a frame member, and the conductive portion may be formed of, for example, copper.
According to the adhesive sheet according to the present embodiment, for example, even after the sealing step is heated, adhesion of the adhesive to the surface of the copper can be prevented. Therefore, after the semiconductor device is resin-sealed and the adhesive sheet is peeled off, it can be prevented. Residual glue for the conductive part.
The cured product (B) is different from the polymer component (A), and the hardened material (B) is uncured (unreacted) in the stage of preparing the raw material of the adhesive composition contained in the adhesive layer 12. status. The energy ray-curable component in the cured product (B) is reacted after the adhesive layer 12 is formed from the adhesive composition, and a high molecular weight body is synthesized and hardened. Therefore, the cured product (B) is continuously present in the adhesive layer 12, which is different from the discontinuity such as an organic filler.
The adhesive layer 12 is a structure in which the polymer component (A) is formed into a three-dimensional mesh structure intrusion into the cured product (B) by including the cured product (B) continuously present, and the polymer component is considered ( A) It is a state of being cross-linked by the loose restraint of the mesh structure. Thereby, the aggregability of the adhesive layer at a high temperature is improved, and it is considered that the above-described effect of improving the adhesion at a high temperature and the effect of preventing the residual glue can be obtained. In addition, the breaking strength of the adhesive layer 12 is increased.
The meaning of the polymer component (AX) will be described in the case where the adhesive component layer 12 contains the polymer component (A) as the polymer component (A).
The polymer component (AX) contains constituent units derived from a monomer having a nitrogen-containing functional group. The nitrogen atom contained in the nitrogen-containing functional group is considered to be present in the polymer component (AX) as a polar group. By the presence of the polar group (nitrogen-containing functional group), the polymer components (AX) in the adhesive layer 12 can easily interact with each other via the nitrogen-containing functional group, and it is considered that the adhesive layer 12 is thus suspected. Sexual cross-linking structure.
Thereby, even if the adhesive sheet 10 is heated, the cohesive force of the adhesive layer 12 can be easily maintained, and as a result, it is considered that the adhesive sheet 10 is less likely to be peeled off after being subjected to the sealing step. The residual glue of the body. Further, since the cohesive force of the adhesive layer 12 can be easily maintained during heating, it is considered that the adhesive force at the time of heating is also improved. In addition, the breaking strength of the adhesive layer also tends to increase.
Here, in the same manner as in the present embodiment, the nitrogen-containing functional group in the polymer component (AX) does not contain an NH bond for the following reason. In general, when a semiconductor element is sealed, an epoxy resin is often used as a sealing material. The epoxy resin and the group having an NH bond such as an amine group are likely to react. Therefore, when the adhesive sheet is peeled off from the object, the adhesive force of the adhesive layer and the adherend becomes too high, so that the adhesive sheet is difficult to be peeled off from the body, or the adhesive is suppressed in the sealing material. For the purpose, the NH bond is excluded from the nitrogen-containing functional group.
In the same manner as in the present embodiment, the adhesive layer 12 contains the polymer component (AX), and the polymer component (AX) contains a nitrogen-containing functional group. Therefore, the polarity of the entire adhesive layer becomes high, and the compatibility between the copolymer component (AX) and the energy ray-curable component becomes higher, and the intrusion of the three-dimensional mesh is facilitated. From this, it is presumed that the adhesion from the high-temperature nitrogen-containing polar group is exhibited, and the occurrence of the cured product (B) which may be a part of the residue in the adherend is suppressed. Therefore, it is considered that the adhesive force of the adhesive layer 12 at the time of heating can be more easily combined, and the residual glue can be prevented from being placed on the object.
As described above, the adhesive sheet 10 according to the present embodiment can improve the adhesion at the time of heating, and can reduce the occurrence of expansion in the step of heating, heating and decompression, and inadvertent peeling from the object. Further, for example, after the step of heating and depressurizing, the adhesive sheet 10 is peeled off, and the residual glue can be reduced in the object.
In the present embodiment, as described above, the cured product (B) is contained in the adhesive layer 12 at least at the same time as the adhesive force of the adhesive layer 12 at the time of heating and the prevention of the residual glue on the object. Therefore, as in the literature 1, document 2, and the literature 3, the component of the active energy ray-curable adhesive which is contained only for the purpose of reducing the adhesive force of the adhesive layer is a polymer component (A) or a polymer component. When (AX) is crosslinked, the polymer component (A) or the polymer component (AX) is carried out from the time when the adhesive layer is formed to the time when the active energy ray-curable adhesive is cured during use. In contrast to this, in the present embodiment, the cured product (B) is cured before the crosslinking of the polymer component (A) or the polymer component (AX). Therefore, it is easy to invade the three-dimensional network of the polymer component (A) or the polymer component (AX) and the cured product (B), and it is easier to obtain the aforementioned effect. The production of the localized hardened material (B). Further, insofar as the energy ray hardening component is hardened when the adhesive sheet is attached to the object, the problem caused by the decomposition of the polymerization initiator is not caused in the sealing step. It also has the advantage that the residual glue caused by the excessive anchoring effect of the uncured energy ray-curable component can be prevented from being generated in the object.
The configuration of the adhesive sheet 10 of the present embodiment will be described. The following is a description of the omission of the symbols.

(adhesive layer)
・Polymer composition (A)
In addition to the cured product (B), the adhesive layer preferably further contains a polymer component (A).
The polymer component (AX) in the same state as the polymer component (A) contains a constituent unit derived from a monomer having a nitrogen-containing functional group. However, the aforementioned nitrogen-containing functional group does not contain an NH bond.
The polymer component (A) is a component formed by polymerizing a polymerizable compound. The polymer component (AX) is a component formed by polymerizing a monomer having at least a nitrogen-containing functional group as a polymerizable compound. The polymerization reaction herein also includes a polycondensation reaction.
In the present specification, the polymer component (AX) is in the same state as the concept of the polymer component (A), so even if it is simply referred to as a polymer component (A), if the polymer component is not clearly indicated ( When AX) is excluded, it is also set to include the polymer component (AX).
The polymer component (A) is different from the energy ray-curable component, and the polymer component (A) is a component which has been polymerized in a state in which a raw material of the adhesive composition contained in the adhesive layer is prepared.
The adhesive layer is formed by further including a polymer component to form a structure in which the polymer component is in a three-dimensional network structure of a cured product that intrudes into an energy ray-curable component, and the polymer component is loosely restrained by the mesh structure. Become a cross-linked state. Thereby, it is easy to combine the adhesiveness of an adhesive layer and the aggregability of an adhesive layer.
・Type of polymer component (A)
The type of the polymer component (A) can be selected in consideration of the type of the energy ray-curable component, the use of the adhesive layer, and the type of the adherend adhered to the adhesive layer. The type of the polymer component (A) is preferably selected, for example, from a (meth)acrylic resin, a polyester resin, a polyurethane resin, an urethane resin, or a polyoxygen system. The compound of at least one of the group consisting of a resin, a rubber-based resin, a phenoxy resin, and a polystyrene resin is preferably a (meth)acrylic resin. These polymer components (A) may be used singly or in combination of two or more.
The polymer component (A) achieves a loosely restrained state by intrusion into the structure in the ternary mesh structure of the cured product (B), and does not have a direct bonding relationship with the above-described energy ray hardening component. In particular, the adhesive layer preferably contains a non-energy ray curable polymer component having no energy ray curability as the polymer component (A). The content of the non-energy-curable polymer component is preferably 60% by mass or more, more preferably 75% by mass or more, and still more preferably 90% by mass or more based on the entire polymer component (A).
In the present embodiment, the ratio of the mass of the polymer component (A) in the entire mass of the adhesive layer is from the viewpoint of the adhesion of the adhesive sheet during heating and the ease of controlling the aggregation of the adhesive layer. It is preferably 50% by mass or more and 90% by mass or less, and more preferably 65% by mass or more and 85% by mass or less.
When the type of the polymer component (A) is a (meth)acrylic resin, the polymer component (A) is preferably a (meth)acrylic polymer. When the polymer component (A) is a (meth)acrylic polymer, the compatibility with the energy ray-curable component tends to be high, and the adhesion of the adhesive layer (especially the adhesion at the time of heating) is controlled. It's easy.
However, when the polymer component (A) is a (meth)acrylic polymer, the polymer component (A) is preferably an acrylic polymer from the viewpoint of not being easily thermally decomposed and from the viewpoint that aggregation failure is unlikely to occur. .
Hereinafter, the case where the polymer component (A) is a (meth)acrylic polymer will be described.
The (meth)acrylic polymer preferably comprises an alkyl (meth)acrylate (CH) ₂ =CR ¹ COOR ² (R ¹ Is hydrogen or methyl, R ² It is a polymer unit of a linear, branched or cyclic (alicyclic) alkyl group). Alkyl acrylate (CH ₂ =CR ¹ COOR ² Part or all of the alkyl group ² The alkyl (meth)acrylate having a carbon number of 6 to 8 is preferred. As alkyl R ² The alkyl (meth)acrylate having a carbon number of 6 to 8 may, for example, be n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate or 2-ethylhexyl (meth)acrylate. , (iso)octyl (meth)acrylate, and n-octyl (meth)acrylate. Among these, R ² A linear or branched alkyl group is preferred. In addition, alkyl R ² The carbon number is preferably 8, and the adhesion of the adhesive sheet to the object immediately after the adherence is improved, and the peeling property from the object is improved even after the adhesive sheet is heated. From the viewpoint, 2-ethylhexyl (meth)acrylate is more preferable, and 2-ethylhexyl acrylate is more preferable.
As alkyl R ² Alkyl (meth) acrylate having a carbon number of 1 to 5 or 9 to 20 (the aforementioned CH ₂ =CR ¹ COOR ² Examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and n-pentyl (meth)acrylate. N-decyl methacrylate, n-dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, and stearyl (meth) acrylate Wait.
The alkyl (meth)acrylate may be used singly or in combination of two or more.
Further, "(meth)acrylic acid" in the present specification is used to indicate the case of both "acrylic acid" and "methacrylic acid", and the other similar terms are also the same.
From the viewpoint of not being easily thermally decomposed and from the viewpoint that aggregation failure is unlikely to occur, the entire polymer unit derived from the alkyl (meth)acrylate contained in the (meth)acrylic polymer is derived from Alkyl acrylate (ie, the aforementioned CH ₂ =CR ¹ COOR ² Medium R ₁ The ratio of the mass of the polymer unit which is hydrogen is preferably 80% by mass or more, and more preferably 90% by mass or more.
The total mass of the (meth)acrylic polymer is from the aforementioned CH ₂ =CR ¹ COOR ² The ratio of the mass of the polymer unit is preferably 50% by mass or more.
The (meth)acrylic polymer is derived from the alkyl (meth)acrylate (the aforementioned CH) ₂ =CR ¹ COOR ² The ratio of the mass of the polymer unit is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more. From alkyl (meth)acrylate (previous CH ₂ =CR ¹ COOR ² The ratio of the mass of the polymer unit is preferably 96% by mass or less from the viewpoint of improving the initial adhesion and the like.
Further, in the present embodiment, the adhesion of the adhesive sheet immediately after being attached to the object is improved, and the peeling property from the object is improved even after the adhesive sheet is heated. The ratio of the mass of the polymer unit derived from 2-ethylhexyl (meth)acrylate to the total mass of the (meth)acrylic polymer is preferably 50% by mass or more. The ratio of the mass of the polymer unit derived from 2-ethylhexyl (meth)acrylate to the total mass of the (meth)acrylic polymer is preferably 60% by mass or more, more preferably 80% by mass. %the above. The ratio of the mass of the polymer unit derived from 2-ethylhexyl (meth)acrylate in the total mass of the (meth)acrylic polymer is preferably 96% by mass or less.
The (meth)acrylic polymer is a copolymer, and when the first copolymer unit in the (meth)acrylic copolymer is an alkyl (meth)acrylate, the (meth) in the acrylic copolymer The type and amount of the copolymer unit other than the alkyl acrylate (hereinafter referred to as "second copolymer unit") are not particularly limited. In this case, in the polymer component (AX), the "second copolymer unit" is a constituent unit derived from a monomer having a nitrogen-containing functional group. On the other hand, in the polymer component (A) of the non-polymer component (AX), for example, as the second copolymer unit, a functional group-containing monomer having a reactive functional group is preferable. As the reactive functional group in the second copolymer unit, when a crosslinking agent to be described later is used, a functional group capable of reacting with the crosslinking agent is preferred. Examples of the reactive functional group include a carboxyl group, a hydroxyl group, an amine group, a substituted amine group, and an epoxy group.
The (meth)acrylic polymer in the polymer component (AX) is a copolymer, and the copolymer is derived from an alkyl (meth)acrylate ("first copolymer unit") derived from a nitrogen-containing functional group. When the constituent unit of the monomer ("second copolymer unit") and the copolymer unit other than the first copolymer unit and the second copolymer unit (hereinafter referred to as "third copolymer unit") are constituted, The type and amount of the tri-copolymer unit are not particularly limited. For example, as the third copolymer unit, a functional group-containing monomer having a reactive functional group is preferred. As the reactive functional group of the third copolymer unit, when a crosslinking agent to be described later is used, a functional group capable of reacting with the crosslinking agent is preferred. Examples of the reactive functional group include a carboxyl group, a hydroxyl group, and an amine group of the first or second stage. Among these, a reactive functional group is preferably a hydroxyl group. In the same manner as the above-mentioned nitrogen-containing functional group does not contain an NH bond, as the functional group-containing monomer having a reactive functional group, it is preferred not to use a functional group-containing monomer having a primary or secondary amine group. .
In the present embodiment, the (meth)acrylic copolymer preferably does not contain a monomer derived from a carboxyl group from the viewpoint of extending the pot life of the raw material composition for forming the adhesive layer. Copolymer unit. Or the (meth)acrylic copolymer is a copolymer unit containing a monomer derived from a carboxyl group, and the aforementioned monomer derived from a carboxyl group is contained in the entire mass of the (meth)acrylic copolymer. The ratio of the mass of the copolymer unit is also preferably 1% by mass or less, and more preferably 0.05% by mass or more and 1% by mass or less.
Examples of the monomer having a carboxyl group (hereinafter referred to as "carboxyl group-containing monomer") include ethylenic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Saturated carboxylic acid. When a carboxyl group-containing monomer is used, among the carboxyl group-containing monomers, (meth)acrylic acid is preferred, and acrylic acid is preferred. The carboxyl group-containing monomer may be used singly or in combination of two or more.
In the present embodiment, the (meth)acrylic copolymer preferably contains a copolymer unit derived from a monomer having a hydroxyl group.
The (meth)acrylic copolymer is a copolymer unit containing a monomer derived from a hydroxyl group, and when a crosslinking agent to be described later is used, the crosslinking density at which a hydroxyl group is used as a crosslinking point can be increased. As a result, the crosslinked structure of the (meth)acrylic copolymer can be efficiently formed. The ratio of the mass of the copolymer unit derived from the monomer having a hydroxyl group to the total mass of the (meth)acrylic copolymer is preferably 3% by mass or more from the viewpoint of the effect of the above-mentioned effect. The ratio of the mass of the copolymer unit derived from the monomer having a hydroxyl group in the total mass of the (meth)acrylic copolymer is preferably 9.9 mass% or less.
Examples of the monomer having a hydroxyl group (hereinafter referred to as a "hydroxy group-containing monomer") include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (methyl). 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3 (meth)acrylate -hydroxyl-containing phenoxypropyl ester, 2-(methyl)propenyloxyethyl-2-hydroxyethyl phthalate, and hydroxyl-containing caprolactone modified (meth) acrylate (Meth)acrylic monomer or the like. Among the hydroxyl group-containing monomers, 2-hydroxyethyl (meth)acrylate is preferred in terms of reactivity of the hydroxyl group and copolymerization. In addition, from the viewpoint of adjusting the adhesion to an appropriate degree so that the adhesive strength at normal temperature does not become excessively high, for example, 4-hydroxybutyl (meth)acrylate is preferable. The hydroxyl group-containing monomer may be used singly or in combination of two or more.
Examples of the acrylate having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
In the functional group-containing monomer having a reactive functional group, the reactive functional group is preferably bonded to the main chain of the polymer component (A) by interposing three or more methylene groups bonded in a linear form. Thereby, the association probability of the reactive functional group and the crosslinking agent increases, so that the crosslinking density increases. In addition, the possibility of remaining reactive functional groups after the formation of the adhesive layer can also be reduced. As a result, the adhesive strength at normal temperature after heating is lowered, and it is easy to peel off the adhesive sheet from the object. Further, in the present invention, the methylene does not contain a methylidyne, and one or more hydrogen atoms of the methylene group may be substituted. Further, the linear bond of the methylene group may be indirectly bonded through another base. For example, when 3-hydroxypropyl (meth)acrylate is used as a polymer component containing a functional group-containing monomer, a hydroxyl group as a reactive functional group is a methylene group bonded to a linear chain by three. Bonded to the main chain of the polymer component (A). Further, in the case where 2-propenyloxyethyl-2-hydroxyethyl-phthalic acid is used as the polymer component containing a functional group-containing monomer, the hydroxyl group as a reactive functional group is a bond of four. A linear methylene group is bonded to the main chain of the polymer component (A), and these methylene groups are indirectly bonded to each other via an ester bond with phthalic acid.
The reactive functional group containing a functional group-containing monomer is preferably bonded to the main chain of the polymer component (A) by a network of 10 or less, which is bonded to a linear chain, and is preferably separated from each other. Six or less bonds are bonded to a linear methylene group to bond with the main chain of the polymer component (A).
In the polymer component (A) of the non-polymer component (AX), the second copolymer component in the acrylic copolymer may be, for example, selected from the group consisting of alkoxy groups, in addition to the above-mentioned functional group-containing monomer. A copolymer unit of at least one of a group consisting of an alkyl (meth) acrylate, an aromatic ring-containing (meth) acrylate, vinyl acetate, and styrene.
・Monomers with nitrogen-containing functional groups
The monomer having a nitrogen-containing functional group is not particularly limited as long as it is a polymerizable compound having a nitrogen-containing functional group, but is preferably an ethylenically unsaturated monomer having a nitrogen-containing functional group.
As the nitrogen-containing functional group, for example, a tertiary amine group (-NR) ³ R ⁴ ), aminocarbonyl (-(C=O)-NR ⁵ R ⁶ ), aminocarbonyloxy (-O-(C=O)-NR) ⁷ R ⁸ ), aminocarbonylamino group (-NR) ⁹ -(C=O)-NR ¹⁰ R ^10A , a cyano group, a nitro group, a nitrogen-containing heterocyclic group or the like, preferably selected from a 3-stage amine group (-NR) ³ R ⁴ ), aminocarbonyl (-(C=O)-NR ⁵ R ⁶ At least one or more of the group consisting of a cyano group and a nitrogen-containing heterocyclic group.
R ³ ~R ¹⁰ And R ^10A The substituents are independently represented by the substituents. The substituent may, for example, be a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms (preferably having 1 to 4 carbon atoms) and a substituted or unsubstituted carbon number of 2 to 4 (preferably having a carbon number of 2) ~3) Alkenyl and the like. The alkyl group may be arbitrarily linear, branched or cyclic. The alkenyl group may be arbitrarily linear, branched or cyclic. R ³ ~R ¹⁰ And R ^10A The systems are identical or different.
In the present specification, the numerical range expressed by "~" means that the numerical value described before "~" is set to the lower limit value, and the numerical value described after "~" is set as the upper limit value. Meaning.
The nitrogen-containing heterocyclic group is a group obtained by removing one hydrogen atom from the nitrogen-containing heterocyclic compound. The nitrogen-containing heterocyclic compound may, for example, be phenylephrine, carbazole, pyrrolidone, piperidine, quinoline, pyrrolidine, aziridine, pyridine, pyrimidine, pyrazine, imidazole, and phthalic acid. Amines, etc. The nitrogen-containing heterocyclic compound having a nitrogen-containing heterocyclic group is preferably orientin from the viewpoint of improving the aggregation property of the adhesive layer.
The monomer (polymerizable compound) having a nitrogen-containing functional group may include one of the above-described nitrogen-containing functional groups in one molecule, or may contain two or more.
The monomer having a nitrogen-containing functional group is preferably selected from the group consisting of a heterocyclic vinyl compound, a (meth) acrylamide compound, an amine group-containing (meth) acrylate compound, and (meth) acrylonitrile. At least one of the groups is preferably a heterocyclic vinyl compound. However, such compounds do not contain an NH bond.
Since the heterocyclic group contained in the heterocyclic vinyl compound is derived from this structure (ring structure), it is considered that even if the adhesive sheet is heated, it is not easily decomposed.
Therefore, when the monomer having a nitrogen-containing functional group is a heterocyclic vinyl compound, it is considered that the cohesive force of the adhesive layer can be more easily maintained, and the effect of the embodiment can be further exhibited.
In the present specification, the term "(meth)acrylic acid" means both of acrylic acid and methacrylic acid. The term "(meth)acrylonitrile" means the meaning of both acrylonitrile and methacrylonitrile.
The monomer having a nitrogen-containing functional group may be used singly or in combination of two or more.
Examples of the heterocyclic vinyl compound include N-propylene hydrazinoline, N-methylpropenyl carbaryl, N-vinyl-2-pyrrolidone, and N-propenylpyrrolidone. N-methylpropenylpyrrolidone, N-propenylpyridinium, N-methylpropenylpiperidine, N-propenylpyrrolidinium, N-methylpropenylpyrrolidine, N-propylene Mercaptoaziridine, N-methylpropenyl aziridine, aziridine ethyl acrylate, aziridine ethyl methacrylate, 2-vinyl pyridine, 4-vinyl pyridine, 2-ethylene Pyrazine, 1-vinylimidazole, N-vinylcarbazole, and N-vinylphthalimide, and the like.
Among them, as the heterocyclic vinyl compound, N-propylene hydrazino, N-vinyl-2-pyrrolidone, and N-propylene fluorenyl group are preferred from the viewpoint of exhibiting the effects of the present embodiment. Pyrrolidone, N-propylene hydrazinopiperidine, N-propenylpyridyl pyrrolidine, N-propenyl aziridine, aziridine ethyl acrylate, 2-vinyl pyridine, 4-vinyl pyridine, 2 - vinylpyrazine, 1-vinylimidazole, N-vinylcarbazole, or N-vinylphthalimide, and more preferably N-propylene hydrazino.
The (meth) acrylamide compound is, for example, a compound represented by the following general formula (1).

In general formula (1), R ¹¹ Represents a hydrogen atom or a methyl group. R ¹² And R ¹³ The substituted or unsubstituted alkyl group having 1 to 6 carbon atoms (preferably having 1 to 4 carbon atoms) or substituted or unsubstituted carbon having 2 to 4 carbon atoms (preferably having 2 to 3 carbon atoms) is independently represented. base. The alkyl group may be arbitrarily linear, branched or cyclic. The alkenyl group may be arbitrarily linear, branched or cyclic.
If R ¹² And R ¹³ When having a substituent, the substituent is independently a dialkylamine group (-NR) ¹⁴ R ¹⁵ Or, a hydroxyl group is preferred.
R ¹⁴ And R ¹⁵ The unsubstituted alkyl group having 1 to 4 carbon atoms (preferably having 1 to 3 carbon atoms) is independently represented.
Examples of the (meth) acrylamide compound include N,N-dimethyl decylamine, N,N-dimethylmethacrylamide, N,N-diethyl acrylamide, and N. N-Diethylmethacrylamide, N,N-di-n-propylpropenylamine, N,N-di-n-propylmethacrylamide, N,N-di-isopropyl Acrylamide, N,N-di-isopropylmethacrylamide, N,N-diallylpropenylamine, N,N-diallylmethacrylamide, N,N-di -n-butyl acrylamide, N,N-di-n-butyl methacrylamide, N,N-ethyl methacrylamide, and N,N-ethylmethyl methacrylamide .
In view of the effect of the present embodiment, the (meth) acrylamide compound is preferably N,N-dimethyl acrylamide or N,N-diethyl acrylamide. N,N-di-n-propyl acrylamide, N,N-di-isopropyl acrylamide, N,N-diallyl acrylamide, N,N-di-n-butyl propylene Indoleamine, or N,N-ethylmethacrylamide, is further preferably N,N-dimethylpropenamide.
The amine group-containing (meth) acrylate compound may, for example, be a compound represented by the following general formula (2).

In general formula (2), R ¹⁶ Represents a hydrogen atom or a methyl group. R ¹⁷ And R ¹⁸ The substituted or unsubstituted alkyl group having 1 to 3 carbon atoms (preferably having 1 to 2 carbon atoms) is independently represented. The alkyl group may be a straight chain, a branched chain, or a cyclic (alicyclic). k is 1 or more and 4 or less, preferably 1 or more and 3 or less.
Examples of the amino group-containing (meth) acrylate compound include N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, and N,N-. Diethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminopropyl acrylate, and N,N-dimethylamino Propyl methacrylate and the like.
Among them, as the amino group-containing (meth) acrylate compound, from the viewpoint of exhibiting the effects of the embodiment, N,N-dimethylaminoethyl acrylate and N,N-di are preferable. Ethylaminoethyl acrylate, and N,N-dimethylaminopropyl acrylate.
The ratio of the constituent units derived from the monomer having a nitrogen-containing functional group in the overall mass of the polymer component (A) is preferably 1% by mass or more from the viewpoint of exhibiting the effects of the present embodiment. The ratio of the mass% or less is preferably 4.5% by mass or more and 18% by mass or less, more preferably 9% by mass or more and 15% by mass or less.
When the ratio of the constituent unit derived from the monomer having a nitrogen-containing functional group is in such a range, the adhesion at the time of heating the adhesive sheet and the aggregation property of the adhesive layer are more easily adjusted.
When the acrylic copolymer contains the polymer component (AX), the third copolymer component as the polymer component (AX) may be, for example, selected from the group consisting of alkane-containing monomers, in addition to the above-described functional group-containing monomer. A copolymer unit of at least one of a group consisting of a (meth) acrylate having an oxyalkyl group, a (meth) acrylate having an aromatic ring, a vinyl acetate, and a styrene group.
Examples of the (meth) acrylate containing an alkoxyalkyl group include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxymethyl (meth)acrylate. And ethoxyethyl (meth)acrylate.
The (meth) acrylate having an aromatic ring may, for example, be phenyl (meth)acrylate.
These monomers may be used singly or in combination of two or more.
The weight average molecular weight (Mw) of the (meth)acrylic copolymer is preferably 50,000 or more and 2,000,000 or less, more preferably 80,000 or more and 1,000,000 or less, and still more preferably 100,000 or more and 400,000 or less. When the weight average molecular weight Mw of the (meth)acrylic copolymer is 50,000 or more, the adhesive is not allowed to adhere to the object, and the adhesive sheet can be easily peeled off. When the weight average molecular weight Mw of the (meth)acrylic copolymer is smaller, the adhesive sheet after heat treatment at 190 ° C for 1.5 hours is applied under a nitrogen atmosphere, and the polyimide is adsorbed at 25 ° C (normal temperature). Adhesion will tend to decrease.
The weight average molecular weight (Mw) of the (meth)acrylic copolymer is a standard polystyrene equivalent value measured by Gel Permeation Chromatography (GPC), specifically, the following conditions Measured.
(measurement conditions)
・GPC device: manufactured by Tosoh Co., Ltd., product name "HLC-8320"
・Measurement sample: a sample concentration of 1% by mass of tetrahydrofuran solution
・Pipe column: Two "TSK gel Super HM-H" and one "TSK gel Super H2000" (both manufactured by Tosoh Co., Ltd.) are connected in sequence.
・column temperature: 40 °C
・Expanding solvent: tetrahydrofuran
・Flow rate: 0.60mL/min
The weight average molecular weight (Mw) of the polymer component (A) can also be measured in the same manner as the weight average molecular weight (Mw) of the (meth)acrylic copolymer.
The (meth)acrylic copolymer can be produced by using various raw material monomers as described above and according to a conventionally known method.
The copolymerization form of the (meth)acrylic copolymer is not particularly limited, and may be any block copolymer, random copolymer, or graft copolymer.
In the present embodiment, the ratio of the mass of the polymer component in the entire mass of the adhesive layer 12 is preferably 50% by mass or more and 90% by mass or less, and more preferably 65% by mass or more and 85% by mass or less.
In the present embodiment, the ratio of the mass of the acrylic copolymer in the entire mass of the adhesive layer 12 is preferably 50% by mass or more and 90% by mass or less, and more preferably 65% by mass or more and 85% by mass or less.
In the present embodiment, the polymer component (A) is preferably crosslinked by a crosslinking agent.
The polymer component (A) is further crosslinked by a crosslinking agent, and it is considered that the cohesive force of the adhesive layer can be further maintained. This reason is considered to be because the three-dimensional mesh structure formed by the polymer component (A) and the three-dimensional mesh structure of the cured product (B) form a mutual intrusion into the mesh structure.
In the present embodiment, the crosslinking agent of the (meth)acrylic copolymer may, for example, be an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent or a metal chelate crosslinking agent. An amine crosslinking agent, an amine resin crosslinking agent, and the like. These crosslinking agents may be used singly or in combination of two or more.
In the present embodiment, among the crosslinking agents, a crosslinking agent (isocyanate) as a compound having an isocyanate group is used for the heat resistance and adhesion of the (meth)acrylic adhesive composition. A crosslinking agent is preferred. Examples of the isocyanate crosslinking agent include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, and diphenylmethane-4. , 4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4 A polyvalent isocyanate compound such as 4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and isocyanuric acid isocyanate.
Further, the polyvalent isocyanate compound may be a modified form of a trimethylolpropane addition type of the compound, a biuret type modified body obtained by reacting with water, or a different having an isocyanurate ring. A cyanurate type modified body.
In the case where the adhesive layer contains the polymer component (A) crosslinked by a crosslinking agent in the present embodiment, the ratio of the polymer component (A) to the crosslinking agent before crosslinking is compared with that of the crosslinking agent. 100 parts by mass, preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less.
When the (meth)acrylic copolymer is used as the polymer component (A), the ratio of the crosslinking before the crosslinking of the (meth)acrylic copolymer and the crosslinking agent is also as follows. 100 parts by mass, preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less.
The blending ratio of the polymer component (A) and the cross-linking agent before crosslinking is preferably within the above range, so that the adhesion of the adhesive sheet during heating can be easily improved.
In the present embodiment, when the polymer component (A) is crosslinked by a crosslinking agent, the polymer component (A), the crosslinking agent, and the crosslinking accelerator may be blended in the adhesive layer. It is preferred to appropriately select a crosslinking accelerator in accordance with the type of the crosslinking agent or the like. For example, when the (meth)acrylic copolymer is crosslinked by a polyisocyanate compound as a crosslinking agent, an organometallic compound-based crosslinking accelerator such as an organotin compound can be used.
The adhesive layer 12 also preferably contains the above-mentioned (meth)acrylic copolymer as a crosslinked product obtained by crosslinking by a crosslinking agent.
・Cured (B)
The adhesive layer according to the embodiment includes a cured product (cured material (B)) of an energy ray-curable component.
The energy ray-curable component contains an energy ray-curable compound. The energy ray-curable compound is a compound which is hardened by irradiation with an energy ray. The energy line for curing the energy ray-curable component is preferably at least one of an ultraviolet ray (UV) and an electron beam (EB), and is preferably ultraviolet ray.
The energy ray-curable compound according to the present embodiment is not particularly limited, and can be selected from among conventionally known energy ray-curable compounds. Examples of the energy ray-curable compound include an energy ray-curable monomer, a low molecular compound, an oligomer, and a resin. The energy ray-curable component may be a composition comprising at least one selected from the group consisting of an energy ray-curable monomer, a low molecular compound, an oligomer, and a resin.
In the energy ray-curable component, at least one of a low molecular compound having a polymerizable functional group and an oligomer having a polymerizable functional group is preferably used as the energy ray-curable compound. When the energy ray-curable component is a low molecular compound or oligomer having a polymerizable functional group, the crosslinking density of the ternary mesh structure in the cured product (B) becomes high. The adhesive layer is a cured product (B) containing an energy ray-curable component (which contains at least one of a low molecular compound having a polymerizable functional group and an oligomer having a polymerizable functional group), and The polymer component (A) allows the polymer component (A) to easily intrude into the three-dimensional mesh structure of the cured product, and the effect of further enhancing the cohesive force of the adhesive layer can be obtained.
The formula of the low molecular weight compound having a polymerizable functional group is usually 3,000 or less, preferably 2,000 or less.
The theoretical molecular weight of the oligomer having a polymerizable functional group is usually 10,000 or less, preferably 8,000 or less.
The polymerizable functional group includes a functional group having a polymerizable carbon-carbon double bond. The polymerizable functional group is preferably, for example, any one selected from the group consisting of a (meth) acrylonitrile group, a vinyl group, and an allyl group.
The number of polymerizable functional groups of the energy ray-curable compound contained in the energy ray-curable component is higher in one molecule from the viewpoint of enhancing the adhesion of the adhesive sheet to the polyimide at 100 ° C. It is preferably two or more and six or less, more preferably two or more and five or less, more preferably two or more and three or less, and particularly preferably two.
When the energy ray-curable component is a compound having two polymerizable functional groups (difunctional energy ray-curable compound) in one molecule, the cohesive force of the adhesive layer can be improved, and the hardening of three or more functional groups can be achieved. The substance (B) can suppress the crosslinking density to be low, and the followability of the adhesive layer to the minute irregularities on the surface of the body can be improved.
In addition, it is also easy to improve the adhesion in the heating environment of the sealing step, and to maintain the softness of the adhesive, and it is easier to suppress the generation of the residual glue. The heating environment in the present embodiment is not particularly limited, but a sealing step is exemplified as an example.
If the adhesion in a high temperature environment is improved, it is easy to prevent the adhesive sheet from being placed in a high temperature and a vacuum environment: the gas generated from the adhesive sheet itself or the member may be in the adhesive sheet and the object to be adhered. The interface creates foaming or peeling off from the adhesive sheet by the body. The high-temperature environment in the present embodiment is not particularly limited. However, as an example, a sealing step of a semiconductor element can be exemplified, and a process may be exemplified as follows: in the state in which the adhesive sheet is adhered after the sealing step, the sealing material is attached The surface is subjected to a process such as plasma treatment for pre-treatment of wiring.
Further, by setting the number of the polymerizable functional groups in one molecule to 2 or more, a three-dimensional network structure can be easily formed.
In the same manner as in the present embodiment, the adhesion to the object such as polyimide or the like is improved (in the same state as in the embodiment, the so-called high temperature, high temperature, and reduced pressure environment) The energy ray-curable compound is preferably a compound having a polymerizable functional group and a cyclic structure from the viewpoint of improving the adhesion of the polyimide. Regarding the polymerizable functional group, as described above. The ring structure is preferably a ring structure selected from at least one of a group consisting of an aromatic ring, a hetero ring, and an aliphatic ring. The energy ray-curable compound is also preferably a compound having a cyclic structure of at least one of an aromatic ring and an aliphatic ring.
The breaking strength per unit sectional area of the adhesive layer of the cured product (B) containing the energy ray-curable compound is preferably 4.5 N/mm. ² Above, it is preferably 5.0 N/mm ² the above. The method of measuring the breaking strength per unit sectional area of the adhesive layer is as described in the examples described later.
When the energy ray-curable compound is a compound having two or more (preferably two) polymerizable functional groups in one molecule and having a cyclic structure, an adhesive layer containing a cured product of the energy ray-curable compound The breaking strength per unit sectional area is preferably 4.5 N/mm. ² Above, it is preferably 5.0 N/mm ² the above. By thus increasing the breaking strength, the effect of preventing the residual glue can be further enhanced. For example, when the adhesive layer contains the polymer component (AX) and the cured product (B), the energy ray-curable compound is derived from a compound having a cyclic structure, and the adhesion at 100 ° C is improved. However, by increasing the breaking strength, the effect of preventing the residual glue can be further enhanced.
Further, in the same manner as in the present embodiment, the energy ray-curable compound is preferably a compound having a polymerizable functional group and a chain structure without a ring structure, and in this case, it is preferably not a ring type. A polyfunctional energy ray-curable compound having a chain structure.
In the same manner as in the present embodiment, the first polymerizable functional group and the second polymerizable functional group which are arbitrarily selected from the two or more polymerizable functional groups of the polyfunctional energy ray-curable compound are bonded to each other. The linear methylene group is a number of methylene groups which are linearly bonded between the first polymerizable functional group and the second polymerizable functional group (hereinafter also referred to as "inter-functional chain length") It is preferably 4 or more, and more preferably 6 or more. When the number of methylene groups which are linearly bonded between the first polymerizable functional group and the second polymerizable functional group is 4 or more, the Young's modulus of the pressure-sensitive adhesive layer can be lowered. As a result, even when the adhesive strength at normal temperature after heating is low, the initial adhesion after attaching the adhesive sheet to the subject can be maintained. The method for determining the amount of the methylene group bonded to the linear relationship between the first polymerizable functional group and the second polymerizable functional group is exemplified by dipentaerythritol hexaacrylate.

In the case of dipentaerythritol hexaacrylate, two polymerizable functional groups are selected, and a bond existing between the first polymerizable functional group (propylene fluorenyl group) and the second polymerizable functional group (propylene fluorenyl group) is linearly bonded. The number of methylene groups in the form of a maximum number is 6. When three or more polymerizable functional groups are contained in the molecule such as dipentaerythritol hexaacrylate, the maximum number of chain lengths between the functional groups may be four or more. In the case of all the functional groups in the molecule, the chain length between the functional groups is preferably 4 or more. In the case of dipentaerythritol hexaacrylate, two hydrogen atoms are substituted by other groups among the linear methylene groups bonded to the above-mentioned structural formulas 2 and 5. Further, for example, in the tripropylene glycol diacrylate, a part of the methylene group bonded to the linear chain is substituted with a methyl group, and the methylene group is indirectly attached to the oxygen atom. Bonding.
In the same manner as in the present embodiment, the first polymerizable functional group and the second polymerizable functional group which are arbitrarily selected from the two or more polymerizable functional groups of the polyfunctional energy ray-curable compound are present in the same state. The number of the methylene groups which are linearly bonded between the first polymerizable functional group and the second polymerizable functional group is preferably 8 or more and 30 or less, and more preferably 8 or more and 12 or less. When the number of the methylene groups which are linearly bonded between the first polymerizable functional group and the second polymerizable functional group is 8 or more and 30 or less, the effect of preventing the residual glue can be further enhanced, and It is also possible to obtain an effect of lowering the adhesion at room temperature after heating. In this case, when the polyfunctional energy ray-curable compound has three or more polymerizable functional groups in the molecule, the maximum number of chain lengths between the functional groups may be within the above range, and all in the molecule. Among the functional groups, the chain length between the functional groups is preferably in the above range.
The energy ray-curable low molecular compound may, for example, be a polyfunctional (meth) acrylate. Examples of the energy ray-curable oligomer include polyfunctional urethane (meth) acrylate, polyfunctional polyester (meth) acrylate, polyfunctional polyether (meth) acrylate, and the like. Functionalized polyoxy(oxy) (meth) acrylate, and the like. These may be used alone or in combination of two or more. The term "multifunctional" means that two or more polymerizable functional groups are contained in one molecule.
Among the polyfunctional (meth) acrylates, as the (meth) acrylate having two (meth) acrylonitrile groups in one molecule, 1,4-butanediol di(meth) acrylate is exemplified. 1,6-hexanediol di(meth)acrylate, tripropylene glycol diacrylate, 1,9-nonanediol diacrylate, 1,10-nonanediol diacrylate, neopentyl glycol di Methyl) acrylate, ethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate, polypropylene glycol #400 diacrylate (product name: APG-400), polypropylene glycol #700 diacrylate ( Product name: APG-700), hexanediol di(meth) acrylate, tricyclodecane dimethanol di(meth) acrylate, 9,9-bis[4-(2-acryloxy ethoxy ethoxylate) Phenyl] fluorene, and propoxylated bisphenol A diacrylate.
Among the polyfunctional (meth) acrylates, trimethylol ethane tri(meth) acrylate is exemplified as the (meth) acrylate having three (meth) acrylonitrile groups in one molecule. Trimethylolpropane tri(meth)acrylate, ε-caprolactone modified ginseng-(2-propenyloxyethyl)isocyanurate, and glycerol tri(meth)acrylate .
Among the polyfunctional (meth) acrylates, a (meth) acrylate having four (meth) acrylonitrile groups in one molecule may, for example, be pentaerythritol tetra(meth)acrylate.
Among the polyfunctional (meth) acrylates, as the (meth) acrylate having six (meth) acrylonitrile groups in one molecule, dipentaerythritol hexa(meth) acrylate or the like is exemplified.
As the propoxylated bisphenol A diacrylate, for example, A-BPP (trade name) manufactured by Shin-Nakamura Chemical Co., Ltd. can be used. As the ε-caprolactone-modified ginseng-(2-propenyl methoxyethyl) isocyanurate, for example, A-9300-1CL (trade name) manufactured by Shin-Nakamura Chemical Co., Ltd. can be used.
The polyfunctional (meth) acrylate may be used singly or in combination of two or more.
Among the polyfunctional (meth) acrylates, the number of (meth) acrylonitrile groups in one molecule is preferably two or more and five or less (meth) acrylates, and two or three. Further, (meth) acrylate is preferable, and two (meth) acrylates are more preferable.
In addition, as the energy ray-curable low molecular compound, a (meth) acrylate having a cyclic structure is preferable, and a ring structure having at least one of an aromatic ring and an aliphatic ring (methyl) is preferable. Acrylate is also preferred.
Further, as the energy ray-curable low molecular compound, a polyfunctional (meth) acrylate having a cyclic structure is preferable. Among the polyfunctional (meth) acrylates having a cyclic structure, the (meth) acrylonitrile group is preferably 2 or more and 5 or less, more preferably 2 or 3, and more preferably 2 or more. good. In the polyfunctional (meth) acrylate having a cyclic structure, the ring structure is preferably at least one of an aromatic ring and an aliphatic ring.
When the energy ray which is irradiated to the energy ray-curable component is ultraviolet ray, the energy ray-curable component preferably contains a photopolymerization initiator. By containing a photopolymerization initiator, the energy ray-curable component can be efficiently cured, and the polymerization hardening time and the irradiation amount of the active energy ray can be reduced.
The photopolymerization initiator may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone or dimethylamine. Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 4-( 2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)one, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone , Dichlorobenzophenone, 2-methylhydrazine, 2-ethylhydrazine, 2-tert-butylhydrazine, 2-aminopurine, 2-methylthioxanthone, 2-B Thiophenone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethyl Ketal, p-dimethylamino benzoate, oligomeric [2-hydroxy-2-methyl-1[4-(1-methylvinyl)phenyl]propanone], 2,4,6- Trimethyl benzhydryl-diphenyl-phosphine oxide, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl ] -2-methyl-phenyl} - propan-1-one. These may be used alone or in combination of two or more.
The photopolymerization initiator is preferably used in an amount of from 2 parts by mass to 15 parts by mass, more preferably from 5 parts by mass to 12 parts by mass, per 100 parts by mass of the energy ray-curable component. .
The adhesive layer may also contain other components within the range not impairing the effects of the present invention. Other components which can be contained as an adhesive layer are, for example, selected from the group consisting of an adhesion aid, an organic solvent, a flame retardant, an adhesion-imparting agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a preservative, and an anti-mildew. At least one of the components of the group consisting of a agent, a plasticizer, an antifoaming agent, a colorant, a filler, and a wettability adjuster.
In the present embodiment, the ratio of the cured product (B) to the total mass of the adhesive layer is preferably 5% by mass or more and 40% by mass or less, and more preferably 10% by mass or more and 30% by mass or less. proportion.
The thickness of the adhesive layer can be appropriately determined depending on the use of the adhesive sheet. In the present embodiment, the thickness of the adhesive layer is preferably 5 μm or more and 60 μm or less, and more preferably 10 μm or more and 50 μm or less. When the thickness of the adhesive layer is 5 μm or more, it is easy to follow the irregularities of the adherend layer, and it is possible to prevent the occurrence of a gap. The object having the unevenness is not particularly limited, and a wafer circuit surface is exemplified as an example. Therefore, for example, an interlayer insulating material and a sealing resin do not enter the gap of the unevenness of the circuit surface of the semiconductor wafer, and the electrode pad for wiring connection on the wafer circuit surface may be blocked. If the thickness of the adhesive layer is 60 μm or less, the semiconductor wafer will not easily sink into the adhesive layer, and the height difference between the semiconductor wafer portion and the resin portion of the sealed semiconductor wafer will not easily occur. Therefore, there is no possibility that the wiring is broken due to the height difference when rewiring.
・Adhesion to polyimine at 100 ° C
The adhesion of the adhesive sheet to the polyimide at 100 ° C is preferably 0.04 N / 25 mm or more, more preferably 0.05 N / 25 mm or more, still more preferably 0.08 N / 25 mm or more.
The adhesive sheet having an adhesive force of 0.04 [N/25 mm] or more is a sheet which can secure adhesion at the time of heating and exhibits good process suitability.
Therefore, by using an adhesive sheet of 0.04 [N/25 mm] or more, peeling of the adhesive sheet from the object of the semiconductor element or the like can be suppressed. Further, it is possible to suppress the offset (displacement) of the adhering position of the adherend to the adhesive sheet. In addition, in the state where the adhesive sheet is attached to the semiconductor element (sealing body) sealed by the sealing resin, it is difficult to perform processing such as plasma treatment in a high temperature or high temperature and a reduced pressure environment. The expansion (foaming) between the adhesive sheet and the sealing body or the peeling from the self-sealing body occurs.
The adhesion of the adhesive sheet to the polyimide at 100 ° C is preferably 1 N / 25 mm or less, and more preferably 0.5 N / 25 mm or less.
The adhesive sheet after heat treatment at 190 ° C for 1.5 hours in a nitrogen atmosphere is preferably 3 N / 25 mm or less, and preferably 2.5 N / 25 mm at 25 ° C (normal temperature). the following. When the adhesive force is 3 N/25 mm or less, peeling and removal of the adhesive sheet after processing of the electronic component becomes easy.
The Young's modulus of the adhesive layer is preferably 5 MPa or less, and more preferably 4 MPa or less. By having such a Young's modulus, the adhesive layer can improve the adhesion when the adhesive sheet is attached to the electronic component, and can prevent peeling of the adhesive sheet until the start of the subsequent processing.
The adhesive strength of the adhesive sheet to the polyimine at 100 ° C is 0.06 N / 25 mm or more, and the breaking strength per unit sectional area of the adhesive layer is 4.5 N / mm. ² The above is preferred. By satisfying such adhesion and breaking strength, the effect of preventing residual glue can be enhanced.

(substrate)
The substrate is a member that supports the adhesive layer.
As the substrate, for example, a sheet material such as a synthetic resin film can be used. Examples of the synthetic resin film include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, and a poly(terephthalic acid). Ethylene glycol film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate film, polyionic polymer resin film, ethylene - (meth)acrylic copolymer film, ethylene-(meth)acrylate copolymer film, polystyrene film, polycarbonate film, and polyimide film. Examples of the other base material include the crosslinked film and the laminated film.
The base material preferably contains a polyester resin, and is preferably made of a material mainly composed of a polyester resin. In the present specification, the term "polyester-based resin as a main component" means that the ratio of the mass of the polyester-based resin to the total mass of the material constituting the substrate is 50% by mass or more. As the polyester resin, for example, it is preferably selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, and polybutylene naphthalate resin. Any one of the groups of the copolymerized resins of the resins is preferably a polyethylene terephthalate resin.
As the substrate, a polyethylene terephthalate film or a polyethylene naphthalate film is preferable, and a polyethylene terephthalate film is preferable.
When the energy ray is irradiated from the substrate side to cure the energy ray-curable component, it is preferred to form the substrate with a material that allows the energy ray to pass through. When ultraviolet rays are used as the energy ray, it is preferred to form the substrate by a material having an ultraviolet ray permeability.
The lower limit of the storage modulus of the substrate at 100 ° C is preferably 1 × 10 from the viewpoint of dimensional stability during processing. ⁷ Above Pa, preferably 1×10 ⁸ Pa above. The upper limit of the storage modulus of the substrate at 100 ° C is preferably 1 × 10 from the viewpoint of process suitability. ¹² Pa below.
Further, in the present specification, the storage modulus at 100 ° C of the substrate is a value of a tensile modulus measured at a frequency of 1 Hz using a viscoelasticity measuring machine. The measurement substrate was cut into a width of 5 mm and a length of 20 mm, and a storage viscoelasticity of 100 ° C was measured by a tensile mode using a viscoelasticity measuring apparatus (manufactured by TA Instruments, DMAQ800) at a frequency of 1 Hz.
In order to improve the adhesion between the substrate and the adhesive layer, at least one of the surface treatments such as primer treatment, corona treatment, and plasma treatment may be applied to the first substrate surface.
The thickness of the substrate is preferably 10 μm or more and 500 μm or less, more preferably 15 μm or more and 300 μm or less, and still more preferably 20 μm or more and 250 μm or less.

(stripping sheet)
The release sheet is not particularly limited. For example, from the viewpoint of easy handling, the release sheet preferably has a release substrate and a release agent layer formed by applying a release agent to the release substrate. Further, the release sheet may have a release agent layer on only one side of the release substrate, or may have a release agent layer on both sides of the release substrate.
When the energy ray is irradiated from the side of the release sheet and the energy ray-curable component is cured by laminating the release sheet, it is preferable to form the release sheet with a material that can transmit the energy ray. When ultraviolet rays are used as the energy ray, it is preferable to form a release sheet with a material having an ultraviolet ray permeability.
The release substrate may, for example, be a paper substrate, a laminate paper obtained by laminating a thermoplastic resin such as polyethylene to the paper substrate, or a plastic film. Examples of the paper substrate include cellophane, coated paper, and cast coated paper. Examples of the plastic film include polyester films (for example, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate), and polyolefin films (for example, polypropylene, And polyethylene, etc.).
Examples of the release agent include an olefin resin, a rubber-based elastomer (for example, a butadiene-based resin and an isoprene-based resin), a long-chain alkyl resin, an alkyd resin, a fluorine-based resin, and Polyoxymethylene resin or the like. When the adhesive layer is composed of a polyoxynitride-based adhesive composition, the release agent is preferably a non-polyoxyl-based release agent.
The thickness of the release sheet is not particularly limited. The thickness of the release sheet is usually 20 μm or more and 200 μm or less, preferably 25 μm or more and 150 μm or less.
The thickness of the release agent layer is not particularly limited. When the release agent layer is formed by applying a solution containing a release agent, the thickness of the release agent layer is preferably 0.01 μm or more and 2.0 μm or less, and more preferably 0.03 μm or more and 1.0 μm or less.
When a plastic film is used as the release substrate, the thickness of the plastic film is preferably 3 μm or more and 50 μm or less, and more preferably 5 μm or more and 40 μm or less.

(Method of manufacturing adhesive sheet)
The method of producing the adhesive sheet is not particularly limited.
In the case where the adhesive layer is formed by a coating method, it is preferred to prepare a coating liquid (adhesive liquid for coating) by diluting the adhesive composition with an organic solvent.
The adhesive composition contains at least an energy ray hardening component and a polymer component (A). The adhesive composition may further contain at least one component selected from the group consisting of a crosslinking agent, a crosslinking accelerator, and other components.
Examples of the organic solvent include an aromatic solvent, an aliphatic solvent, an ester solvent, a ketone solvent, and an alcohol solvent. Examples of the aromatic solvent include benzene, toluene, and xylene. Examples of the aliphatic solvent include n-hexane and n-heptane. The ester-based solvent may, for example, be ethyl acetate or butyl acetate. Examples of the ketone-based solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone. Examples of the alcohol-based solvent include isopropyl alcohol and methanol.
For example, the adhesive sheet can be manufactured by the steps as described below.
First, an adhesive composition is applied over the first substrate surface of the substrate to form a coating film. Next, the coating film is dried, and the energy ray is further irradiated to harden the energy ray hardening component to form a cured product, thereby forming an adhesive layer. Thereafter, the release sheet is pasted to cover the adhesive layer.
As another manufacturing method of the adhesive sheet, it can be manufactured by the following steps. First, an adhesive composition is applied over the release sheet to form a coating film. Next, the coating film is dried to bond the first substrate surface of the substrate to the coating film. Next, the energy ray is passed through the release sheet to irradiate the coating film to cure the energy ray-curable component to form a cured product, thereby forming an adhesive layer.
As another method for producing the adhesive sheet, a method of applying an adhesive composition to the upper surface of the first substrate of the substrate to form a coating film is exemplified. Next, the coating film is dried, and the release sheet is adhered to the coating film to coat the coating film. After that, the energy line is irradiated from at least one side of the substrate side and the release sheet side to cure the energy ray-curable component in the coating film to form a cured product, thereby forming a pressure-sensitive adhesive layer.
The method of applying the coating liquid is not particularly limited. Examples of the coating method include a spin coating method, a spray coating method, a rod coating method, a blade coating method, a roll coating method, a roll coating method, a knife coating method, a die coating method, and a gravure method. Coating method, etc.
In order to prevent the organic solvent and the low boiling point component from remaining in the adhesive layer, after applying the coating liquid to the substrate or peeling off the sheet, it is preferred to heat and dry the coating film.
When a crosslinking agent is blended in the adhesive composition, it is preferred to heat the coating film in order to carry out the crosslinking reaction and enhance the cohesive force. The energy ray may be irradiated before or after the heating for carrying out the crosslinking reaction, but it is preferred to use the irradiation energy ray after heating. When the adhesive composition is heated to dry the coating film and promote the crosslinking reaction of the adhesive composition, it is considered that all the reaction of the functional groups involved in crosslinking by heating does not end, but is followed by The functional groups remaining in the storage of the adhesive sheet are still slowly reacted, and the crosslinking of the adhesive composition proceeds. Therefore, after heating the coating film, irradiation with an energy ray forms a structure in which the polymer component (A) is restrained in the ternary mesh structure of the cured product (B), and further crosslinking of the polymer component (A) is performed. Therefore, it is considered that the crosslinked structure of the cured product (B) and the polymer component (A) is in a state of intrusion into each other.

(Use of adhesive sheets)
The adhesive sheet is used as an adhesive sheet for processing electronic parts. Further, as another use form of the adhesive sheet, a form for fixing or protecting an electronic component can be cited. As an example of fixing or protecting an electronic component, an adhesive sheet is used to seal a semiconductor element. The adhesive sheet of the present embodiment is used after the energy ray-curable component in the adhesive composition is cured to form a cured product.
It is preferable that the adhesive sheet is used for sealing a semiconductor element in a state of being adhered to the adhesive sheet, instead of being mounted on a metal lead frame. Specifically, the adhesive sheet is not used for sealing a semiconductor element mounted on a metal lead frame, but is preferably used for sealing a semiconductor element in a state of being adhered to an adhesive layer. That is, it is preferable to use the semiconductor element in a state of being directly attached to the adhesive sheet. The adhesive sheet of the present invention is less likely to cause swelling (foaming) between the adhesive sheet and the sealing body or peeling off from the sealing body even when the steps are carried out under high temperature or high temperature and reduced pressure. . As a form in which the semiconductor element is packaged without using a metal lead frame, a panel level package (PLP), a WLP, or the like can be given.
The adhesive sheet is preferably used in a process of the steps of: adhering an adhesive sheet to a frame member having a plurality of openings; and adhering the semiconductor wafer to the adhesive layer exposed at the opening of the frame member. a step of coating the semiconductor wafer with a sealing resin; and a step of thermally hardening the sealing resin.
In addition, the material of the sealing resin is not particularly limited, and may be a thermosetting resin or an energy ray-curable resin which is cured by an energy ray such as ultraviolet rays.
In the adhesive sheet of the present embodiment, when the polymer component (AX) is contained in the adhesive layer, the polymer component (AX) has a "nitrogen-containing functional group not containing an NH bond", so that it can be suitably used as a material of the sealing resin. An epoxy resin is used.
When the material of the sealing resin is an epoxy resin, when the adhesive sheet is peeled off from the object, the reaction between the epoxy resin and the group having the NH bond does not occur, so that it can be relatively easily The adhesive sheet is peeled off from the body, and the residual glue can be more easily reduced in the subject.
After the step of thermally curing the sealing resin, a step of performing a plasma treatment or the like may be performed as a step of performing at a high temperature or a high temperature and a reduced pressure environment.
In addition to the step of thermally curing the sealing resin and the plasma treatment step, the steps performed in a high temperature, high temperature, and reduced pressure environment include a step of sputtering a metal such as an electronic component, and a hot water. The step of washing the electronic parts.
An intermediate layer may also be provided between the substrate and the adhesive layer. The intermediate layer is preferably functional in response to the desired purpose. The intermediate layer may, for example, be an oligomer sealing layer, a primer layer, an antistatic layer or the like which will be described later. For example, by providing the intermediate layer, at least one of the adhesion between the substrate and the adhesive layer, the precipitation of the oligomer on the surface of the substrate, and the antistatic property can be improved.
Further, a functional layer may be provided on the surface of the substrate on the side where the adhesive layer is not provided. Examples of the functional layer include an oligomer sealing layer to be described later, an antistatic layer, and the like. For example, by providing the intermediate layer, at least one of the precipitation of the oligomer on the surface of the substrate and the antistatic property can be improved.

<Second embodiment>
The adhesive sheet according to the second embodiment differs from the adhesive sheet according to the first embodiment in that an oligomer sealing layer is provided between the substrate and the adhesive layer. Since the other aspects are the same as those of the first embodiment, the description is omitted or simplified. Hereinafter, the description of the symbols will be omitted.

(oligomer sealing layer)
The oligomer sealing layer is disposed between the substrate and the adhesive layer. The oligomer sealing layer is a layer used to encapsulate an oligomer resulting from a substrate into a substrate. It is preferable that the oligomer sealing layer prevents the immersion of the oligomer into the adhesive layer even under a high temperature condition of, for example, 180 ° C or more and 200 ° C or less.
Fig. 2 is a cross-sectional view showing an adhesive sheet 10A according to a second embodiment. The adhesive sheet 10A has an oligomer sealing layer 13.
The adhesive sheet 10A has, in order, a base material 11, an oligomer sealing layer 13, and an adhesive layer 12. In the adhesive sheet 10A, the oligomer sealing layer 13 is laminated on the first substrate surface 11a.
The adhesive layer 12 contains a polymer component (A) and a cured product (B).
In the adhesive sheet 10A of the second embodiment, since the oligomer sealing layer 13 is provided between the substrate 11 and the adhesive layer 12, even if the adhesive sheet 10A is heated, the oligomer can be prevented from moving to the adhesive layer 12 and The interface of the body.
Therefore, with the adhesive sheet 10A of the second embodiment, the adhesive force at the time of heating can be further enhanced, and the occurrence of residual glue at the time of peeling from the object can be further prevented.
・Thickness of the oligomer sealing layer
The thickness of the oligomer sealing layer is preferably 50 nm or more and 500 nm or less, and more preferably 80 nm or more and 300 nm or less.
When the thickness of the oligomer sealing layer is 50 nm or more, the immersion of the oligomer contained in the substrate into the adhesive layer can be effectively prevented.
When the thickness of the oligomer sealing layer is 500 nm or less, for example, when the adhesive sheet is wound into a roll shape with a core material, winding up can be facilitated. Examples of the material of the core material include paper, plastic, and metal.
The material of the oligomer sealing layer is not particularly limited as long as it can prevent the oligomer in the substrate from entering the adhesive layer 12 .
For example, the oligomer sealing layer is preferably a hardened film obtained by hardening a composition for an oligomer sealing layer. The composition for an oligomer sealing layer, for example, preferably contains at least one selected from the group consisting of (A) an epoxy compound, (B) a polyester compound, and (C) a polyfunctional amine-based compound. Further preferably, it comprises (A) an epoxy compound, and (C) a polyfunctional amine-based compound, more preferably an (A) epoxy compound, (B) a polyester compound, and (C) a polyfunctional amine compound. .
In order to promote the hardening reaction, the composition for the oligomer sealing layer may further contain (D) an acidic catalyst.
・(A) epoxy compound
The (A) epoxy compound is preferably a bisphenol A type epoxy compound. Examples of the bisphenol A type epoxy compound include bisphenol A diglycidyl ether.
・(B) Polyester compound
The (B) polyester compound is not particularly limited, and can be appropriately selected from known polyester compounds. Specific examples of the polyester compound include a condensate of a dibasic acid and a divalent alcohol of a resin obtained by a condensation reaction between a polyhydric alcohol and a polybasic acid, or a modification of a fatty acid such as a non-drying oil. A non-transformable polyester compound of the obtained compound, and a converted polyester compound which is a condensate of a dibasic acid and a trivalent or higher alcohol.
The polyhydric alcohol and the polybasic acid can be used as a raw material of the (B) polyester compound, and can be suitably selected from well-known polyols and polybasic acids.
・(C) Polyfunctional Amine Compounds
As the (C) polyfunctional amine-based compound, for example, a melamine compound, a urea compound, a benzoguanamine compound, and a diamine can be used.
Examples of the melamine compound include hexamethoxymethyl melamine, a methylated melamine compound, and a butylated melamine compound.
Examples of the urea compound include a methylated urea compound and a butylated urea compound.
The benzoguanamine compound may, for example, be a methylated benzoguanamine compound or a butylated benzoguanamine compound.
Examples of the diamines include ethylenediamine, tetramethylenediamine, hexamethylenediamine, N,N'-diphenylethylenediamine, and p-xylenediamine.
From the viewpoint of hardenability, as the (C) polyfunctional amine-based compound, hexamethoxymethylmelamine is preferred.
・(D) Acid Catalyst
Examples of the acidic catalyst (D) include hydrochloric acid and p-toluenesulfonic acid.
・Sclerosing film
In the present embodiment, the oligomer sealing layer is preferably a cured film obtained by curing a composition for an oligomer sealing layer, and the composition for the oligomer sealing layer is (A) 50% by mass or more. 80% by mass or less, (B) 5% by mass or more and 30% by mass or less, and (C) 10% by mass or more and 40% by mass or less of the compounding ratio (A) bisphenol A type epoxy compound, (B) polyester a compound, and (C) a polyfunctional amine based compound. When the (D) acidic catalyst is blended in the composition for the oligomer sealing layer, the content of the component (D) is preferably 1% by mass or more and 5% by mass or less.
By the hardening film obtained by hardening the composition of the oligomer sealing layer of the above-mentioned range, the effect of preventing the oligomer from entering the adhesive layer 12 by the oligomer sealing layer can be enhanced.

(Method of Manufacturing Adhesive Sheet of Second Embodiment)
For example, the adhesive sheet of the second embodiment can be manufactured by the following steps.
First, the oligomer sealing layer forming composition is applied over the first substrate surface of the substrate to form a coating film. Next, the coating film is heated and hardened to form a cured film as an oligomer sealing layer. The conditions for heat curing are, for example, 120 ° C or more and 170 ° C or less, and 5 seconds or longer and 5 minutes or less.
Next, an adhesive layer is formed on the upper side of the oligomer sealing layer formed above the first substrate surface of the substrate in the same manner as described in the first embodiment.

<Third embodiment>
The adhesive sheet according to the third embodiment differs from the adhesive sheet according to the second embodiment in that an epoxy resin sealing layer is provided on both surfaces of the substrate. Since the other aspects are the same as those of the second embodiment, the description is omitted or simplified.
Fig. 3 is a cross-sectional view showing an adhesive sheet 10B according to an example of the third embodiment.
The adhesive sheet 10B has, in order, an oligomer sealing layer 13B formed on the second substrate surface 11b of the substrate 11, a substrate 11, and an oligomer sealing layer formed on the first substrate surface 11a of the substrate 11. 13A, and adhesive layer 12.
In the adhesive sheet 10B of the third embodiment, since the oligomer sealing layers 13A and 13B are provided on both surfaces of the substrate 11, the oligomer deposited from the second substrate surface 11b can be suppressed in addition to the effects of the second embodiment. Contamination of components and devices other than the object being attached. For example, at the time of manufacturing a semiconductor device, contamination of a plate-like member in contact with an adhesive sheet in the heat pressing step can be suppressed.

(Method for Producing Adhesive Sheet According to Third Embodiment)
In the adhesive sheet of the second embodiment, the coating film comprising the oligomer sealing layer forming composition is formed on the first substrate surface and the second substrate of the substrate. It is manufactured by the upper side of the base material surface.

[Modification of Embodiment]
The present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the scope of the object of the invention are also included in the present invention. In the following description, the same components as those in the above-described embodiments are denoted by the same reference numerals, and their description is omitted or simplified.
The adhesive sheet may be a sheet-like sheet, or may be provided in a state in which a plurality of sheets of adhesive sheets are laminated. In this case, for example, the adhesive layer can be covered with a substrate of another adhesive sheet to be laminated.
Further, the adhesive sheet may be a strip-shaped sheet or may be provided in a state of being wound into a roll. The adhesive sheet wound into a roll shape can be used by being wound up from a roll and cut into a desired size or the like. Further, the adhesive sheet can be previously cut into a desired size and supplied in a state of being carried on the strip-shaped release sheet.
Further, the oligomer sealing layer may be provided only on the second substrate surface of the substrate. On the second substrate surface of the substrate, an adhesive layer may be provided directly or via an oligomer sealing layer or the like. The adhesive layer is attached to a support substrate or the like by an adhesive layer, and is used to fix the electronic component to the adhesive layer of the adhesive sheet. The adhesive used for the adhesive layer may be of the same type as the adhesive of the adhesive layer, or may be of a different type.

[Examples]
Hereinafter, the present invention will be described in further detail by way of examples. The invention is not limited by the examples.

[evaluation method]
The evaluation of the adhesive sheet was carried out according to the method shown below. The results are shown in Table 1, Table 2, and Table 3.

(Evaluation of foaming during high temperature vacuum)
A glass epoxy substrate (manufactured by Hitachi Chemical Co., Ltd., "MCL-E-679FG" (trade name), 100 mm × 100 mm × 0.4 mm) was polished using a #800 abrasive. After the polishing, the adhesive sheets produced in the examples and the comparative examples were attached to the entire polished surface of the glass epoxy substrate. The adhesive sheet is attached using a roll laminator.
After attaching the adhesive sheet to the glass epoxy substrate, a vacuum lamination machine ("V130" (trade name), manufactured by Nikko-Materials Co., Ltd.) was used, and vacuum lamination was performed at 100 ° C to prepare a measurement sample.
After vacuum lamination, the measurement sample was immersed in warm water of 85 ° C for 30 minutes. After the immersion, the measurement sample was taken out from the warm water, and the water droplets on the surface of the measurement sample were wiped. After wiping, the measurement sample was placed in a heating vacuum dryer at 25 °C.
Thereafter, the inside of the vacuum dryer was depressurized (less than 0.005 MPa), and the set temperature was set to 130 ° C to heat the measurement sample. The temperature increase rate was set to 5 ° C / min. In the heating vacuum dryer, from 25 ° C to 130 ° C, it was visually confirmed whether or not expansion (foaming) occurred.
Judgment A: No expansion (foaming) occurred.
Judgment B: 10cm in the area of the body ² Less than 50% of the area produced expansion (foaming).
J: C: 10cm in the area of the body ² More than 50% of the area produced expansion (foaming).

(initial adhesion test)
The surface of a glass epoxy substrate (manufactured by Hitachi Chemical Co., Ltd., "MCL-E-679FG" (trade name), 100 mm × 100 mm × 0.4 mm) was polished using a #800 abrasive. After the polishing, the adhesive sheets produced in the examples and the comparative examples were attached to the entire polished surface of the glass epoxy substrate. The attachment of the adhesive sheet was carried out by taking a 2 kg roll back and forth. After standing for 30 minutes in a standard environment (23 ° C 50% RH), the adhesion was measured in the same standard environment.
The measurement conditions are as follows.
・Installation: Tensile testing machine AG-X plus 10kN manufactured by Shimadzu Corporation
・Peeling angle: 180°
・Peeling speed: 300mm/min
The adhesion is evaluated as A if it is 0.08 N/25 mm or more, and B if it is less than 0.08 N/25 mm.

(Adhesion to polyimine at 100 ° C)
A polyimide film (manufactured by Toray Dupont Co., Ltd., Kempton 200H (trade name)) was attached to an aluminum plate using a double-sided tape (manufactured by Lintec Co., Ltd., TL-450S-16 (trade name)). 150mm × 70mm, thickness 1mm). The adhesion of the adhesive sheet was measured by changing the measurement temperature with respect to the polyimide film by JIS Z 0237 (2000). The adhesive sheets prepared in the examples and the comparative examples were attached to the above-mentioned polyimide film to prepare a measurement sample, and the measurement sample was placed in an environment of 23° C. and 50% relative humidity for 30 minutes, and then, After standing for 3 minutes in an environment of 100 ° C, a tensile test was carried out in an environment of 100 ° C.
In addition, the adhesive sheet having an adhesive force of 0.04 [N/25 mm] or more was judged to be a sheet which can secure adhesion and exhibit good process suitability.
The measurement conditions were set as follows.
・Device: Tensile testing machine with thermostatic bath ("TENSILON" (trade name) made by ORIENTEC)
・Peeling angle: 180°
・Peeling speed: 300mm/min
However, in this specification, the polyimine is sometimes coded as PI.

(Adhesion to polyimine at room temperature after heating)
The adhesive sheets prepared in the examples and the comparative examples were attached to the above-mentioned polyimide film to prepare a measurement sample in the same manner as the adhesion to the polyimide at 100 ° C. Thereafter, the measurement sample was heated under a nitrogen atmosphere.
The heating conditions are as follows.
・Device: MOTOYAMA MS-3642
・N ₂ Flow rate: 1.5L/min (N ₂ Purity: 99.995% by volume)
・Real temperature: 190 °C
・Time: 1.5hr
Thereafter, after standing for 6 hours or more in a standard environment (23° C., 50% RH), the adhesive sheet was peeled off from the measurement sample at a peeling angle of 180° and a peeling speed of 300 mm/min in the same standard environment.

(Young's modulus of the adhesive layer)
In the examples and the comparative examples, the coating film of the coating adhesive liquid after drying was bonded to the substrate with the oligomer sealing layer instead of the peeling film "SP-PET381031" manufactured by Lintec (trade name). The surface of the release agent layer is bonded to each other to produce a single layer of the adhesive layer without the substrate. The layer of the adhesive layer 4 was laminated so that the sample became 200 μm thick. The laminate of only the pressure-sensitive adhesive layer was used as a sample, and a tensile test was performed under the following conditions, and the change in stress was plotted against the change in strain from the measurement results of strain and stress. The Young's modulus of the adhesive is determined from the initial slope of the change in strain for the change in strain.
・Installation: Tensile testing machine AG-X plus 10kN manufactured by Shimadzu Corporation
・Test sample size: Measurement area length 50mm × 15mm width
・Tensile test speed: 200mm/min

(breaking strength per unit sectional area of the adhesive layer)
The tensile test is performed by the same method as the Young's modulus of the adhesive layer, and the maximum value (breaking strength) of the force at the time of the fracture is divided by the sectional area of the initial sample to calculate the breaking strength per unit area. .

(1st residue evaluation (1st residue evaluation))
The copper foil was previously polished using the #800 abrasive material, and a scratch (a mathematical average roughness Ra after polishing was 0.2 ± 0.1 μm) was formed along one direction of the surface of the copper foil. The adhesive sheets produced in the examples and the comparative examples were attached to the surface of the copper foil on which the scratches were formed. Here, only the adhesive sheet of Comparative Example 1-3 was used, and a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd. as an ultraviolet irradiation device was used, and the illuminance was 200 mW/cm. ² , cumulative light quantity 200mJ / cm ² Under the conditions, to irradiate ultraviolet rays. Thereafter, the adhesive sheet attached to the copper foil was heated at 100 ° C for 30 minutes, then heated at 180 ° C for 30 minutes, and then heated at 190 ° C for 60 minutes. After heating, the adhesive sheet was peeled off at a rate of 3 mm/min at room temperature. The direction in which the adhesive sheet is peeled off is set to be a vertical direction with respect to the abrasion. The surface of the copper foil after peeling off the adhesive sheet was observed using a digital microscope, and the residual glue was evaluated. The criterion for the evaluation of the residual glue is as follows.
A judgment: no residue.
B judgment: Partially existing residual glue.
C judgment: Residual glue exists comprehensively.

(the second residue evaluation (the second residual rubber evaluation))
A polyimide film (manufactured by Toray Dupont Co., Ltd., Kempton 200H (trade name)) was attached to a 矽 mirror surface crystal using a double-sided tape (manufactured by Lintec Co., Ltd., TL-450S-16 (trade name)). A mirror surface with a diameter of 6 inches and a thickness of 0.68 mm.
Thereafter, a laser mark (CSM300M manufactured by EO TECHNICS Co., Ltd.) was used to mark a circular mark of 200 μmø on the surface of the polyimide film at a distance of 3 mm (laser wavelength: 512 nm, output: 1.0 W, scanning speed: 300 mm/s).
Further, in the evaluation, in order to evaluate the condition in which the residual glue is easily generated, the above-mentioned mark is imprinted on the surface of the polyimide film by laser ablation to form the unevenness as described above. .
Referring to JIS Z0237 (2000), an adhesive sheet produced in the examples and the comparative examples was laminated on the processed surface of the polyimide film by applying a force by the weight of the 2 kg roll, and further, heating lamination was performed from above. After that, a measurement sample was prepared.
The conditions for heating the lamination are as follows.
・Device: Nikko-Materials, vacuum laminator V-130
・Heating temperature: 100°C
・Vacuum standby: 60sec
・Separator pressure: 0.3MPa
Thereafter, the sample was measured by heating under a nitrogen atmosphere.
The heating conditions are as follows.
・Device: MOTOYAMA MS-3642
・N ₂ Flow rate: 1.5L/min (N ₂ Purity: 99.995% by volume)
・Real temperature: 190 °C
・Time: 1.5hr
Thereafter, after standing for 6 hours or more in a standard environment (23° C., 50% RH), the adhesive sheet was peeled off from the measurement sample at a peeling angle of 180° and a peeling speed of 300 mm/min. The surface of the polyimide film after peeling off the adhesive sheet was observed by SEM (scanning electron microscope, observation magnification: 3000 times), and the residual gel was evaluated based on the state of generation of the residue. The criterion for the evaluation of the residual glue is as follows.
-Judgement benchmark -
A judgment: no residue.
B. It is judged that there is a residue and the size of the residue is less than 5 μm.
C: There is a residue and the size of the residue is 5 μm or more and less than 10 μm.
D judged that there is a residue and the size of the residue is 10 μm or more.

[Production of adhesive sheets]
[Example 1-1]
(1-1) Modulation of coating oligomer solvent sealant
The following (A) bisphenol A type epoxy compound, (B) polyester compound, (C) polyfunctional amine group compound, and (D) acidic catalyst were prepared and stirred sufficiently to prepare Example 1-1. A related coating oligomer sealant liquid (a composition for an oligomer sealing layer).
(A) bisphenol A epoxy compound
DIC company "EPICLON H-360" (trade name), solid content concentration: 40% by mass, mass average molecular weight: 25000
(B) Polyester compound
"Vylon GK680" (trade name) manufactured by Toyobo Co., Ltd., number average molecular weight: 6000, glass transfer temperature: 10 °C
(C) polyfunctional amine compounds
Hexamethoxymethyl melamine, "CYMEL303" (trade name) manufactured by Cytec Industries Japan
(D) Acid catalyst
Methanol solution of p-toluenesulfonic acid (solid content concentration: 50% by mass)
Specifically, the toluene diluted solution (solid content concentration: 30% by mass) of the (B) polyester compound is added to 1 part by mass of the above-mentioned (B) bisphenol A type epoxy compound, and the above (C) 11.4 parts by mass of hexamethoxymethylmelamine, and further diluted with a mixed solvent of toluene/methyl ethyl ketone=50% by mass/50% by mass to prepare a solution having a solid content concentration of 3% by mass. The prepared solution was stirred, and 2.9 parts by mass of a (D) p-toluenesulfonic acid methanol solution (solid content concentration: 50% by mass) was added to the stirred solution to obtain a coating oligomer sealant liquid. Still, the mass fractions are all converted into solid fractions.

(1-2) Production of oligomer sealing layer (production of substrate with oligomer sealing layer)
The prepared coating oligomer sealant solution was uniformly applied to the annealed biaxially-oriented polyethylene terephthalate film by a Mayer bar coating method (Teijin Film Solutions shares) The company's "Teijin Tetoron G2A" (trade name), thickness 25μm) on one side. The coated film was passed through the inside of the oven, and the coating film was heat-hardened to form an oligomer sealing layer having a thickness of 150 nm, thereby obtaining a substrate with an oligomer sealing layer. The blowing conditions of the hot air in the oven were set to 150 ° C and the wind speed was set to 8 m / min. The processing speed in the oven was adjusted to the film after coating, and the speed inside the oven was passed for 20 seconds.

(1-3) Preparation of adhesive composition
The following materials (polymer (polymer component), crosslinking agent, low molecular compound having a polymerizable functional group, photopolymerization initiator, and diluent solvent) were blended and sufficiently stirred to prepare Example 1-1. Related coating adhesive fluids.
・Polymer: acrylate copolymer, 100 parts by mass (solids)
The acrylate copolymer was prepared by copolymerizing 92.8% by mass of 2-ethylhexyl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid.
・Crosslinking agent: an aliphatic isocyanate having hexamethylene diisocyanate [Polyate HZ, manufactured by Polyurethane Industry Japan Co., Ltd.; 7.4 parts by mass (solid content)
・Low-molecular compound having a polymerizable functional group: tricyclodecane dimethanol diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.; A-DCP] 23.3 parts by mass (solid content)
・Photopolymerization initiator: 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propane-1- Ketone [manufactured by IGM Resin; Omnirad 127] 4.1 parts by mass (solids)
- Dilution solvent: Ethyl acetate was used, and the solid content concentration of the coating adhesive liquid was adjusted to 30% by mass.

(1-4) Production of adhesive layer
The prepared coating adhesive liquid was applied to a release film made of a transparent polyethylene terephthalate film having a thickness of 38 μm having a polyoxynitride-based release layer using a blade coater [Lintec (shared) ) company system; SP-PET382150] peeling layer side. Next, the coating film of the coating adhesive liquid on the release film was heated at 90 ° C for 90 seconds, and then heated at 115 ° C for 90 seconds to dry the coating film. Thereafter, the coating film was bonded to the surface of the base material with the oligomer sealing layer obtained by the above-described process, in which the oligomer sealing layer was provided. Further, as a UV irradiation device, a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd. was used, and the illuminance was 200 mW/cm. ² , cumulative light quantity 200mJ/cm ² Under the conditions, the coating film was irradiated with ultraviolet rays from the side of the release film to prepare an adhesive layer having a thickness of 50 μm. The adhesive sheet relating to Example 1-1 was obtained in such a manner.

[Example 1-2]
In addition to the use of 9,9-bis[4-(2-propenyloxyethoxy)phenyl]indole [Xinzhongcun Chemical Co., Ltd.; A-BPEF] 23.3 parts by mass (solids) instead of the tricyclic ring The adhesive sheet of Example 1-2 was obtained in the same manner as in Example 1-1 except that 23.3 parts by mass of the decane dimethanol diacrylate (solid content) was used.

[Example 1-3]
In addition to propoxylated bisphenol A diacrylate [Xinzhongcun Chemical Co., Ltd.; A-BPP] 23.3 parts by mass (solids), instead of tricyclodecane dimethanol diacrylate 23.3 parts by mass (solids) The adhesive sheets of Examples 1-3 were obtained in the same manner as in Example 1-1 except for the above.

[Example 1-4]
In place of tricyclodecane dimethanol diacrylate 23.3, except that dipentaerythritol hexaacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.; A-DPH] (inter-chain length: 6) 23.3 parts by mass (solids) was used. The adhesive sheets of Examples 1 to 4 were obtained in the same manner as in Example 1-1 except for the parts by mass (solid content).

[Example 1-5]
In addition to using ε-caprolactone to modify gin-(2-propenyloxyethyl) isocyanurate [manufactured by Shin-Nakamura Chemical Co., Ltd.; A-9300-1CL] 23.3 parts by mass (solids), An adhesive sheet of Example 1-5 was obtained in the same manner as in Example 1-1, except that 23.3 parts by mass (solid content) of tricyclodecane dimethanol diacrylate was used.

[Comparative Example 1-1]
In addition to the preparation of the adhesive composition, the following materials (polymer, adhesion aid, crosslinking agent, and diluent solvent) are formulated, and in the preparation of the adhesive layer, the steps of irradiating ultraviolet rays are omitted, and other examples and examples are employed. 1-1 was the same manner, whereby the adhesive sheet of Comparative Example 1-1 was obtained.
・Polymer: acrylate copolymer, 100 parts by mass (solids)
The acrylate copolymer was prepared by copolymerizing 92.8% by mass of 2-ethylhexyl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid.
・Adhesive adjuvant: Hydroxylated polybutadiene at both ends [Japan Soda Co., Ltd.; GI-1000], 12.5 parts by mass (solids)
- Crosslinking agent: an aliphatic isocyanate having hexamethylene diisocyanate [Polyurethane Industry Japan; Coronate HX], 8.75 parts by mass (solid content)
- Dilution solvent: Methyl ethyl ketone was used, and the solid content concentration of the coating adhesive liquid was adjusted to 30% by mass.

[Comparative Example 1-2]
The adhesive sheet of Comparative Example 1-2 was obtained in the same manner as in Comparative Example 1-1 except that the adhesive composition was not prepared in the preparation of the adhesive composition.

[Comparative Example 1-3]
The adhesive sheet of Comparative Example 1-3 was obtained in the same manner as in Example 1-1, except that the step of irradiating ultraviolet rays was omitted. Further, in the evaluation of the first residue, the ultraviolet rays are irradiated under the above conditions and then evaluated.









[Test and evaluation results]
As a result of the foaming test, regarding Examples 1-1, 1-2, and 1-3, expansion (foaming) was not generated, but A was determined; and Examples 1-4 and 1-5 were judged by B; Examples 1-1 and 1-2 were judged by C, and Comparative Example 1-3 was judged by B. Before the adhesion to the object to be placed, the ultraviolet curable component is hardened in advance and becomes a cured product, and the adhesive strength of the adhesive layer containing the cured product is improved, and the effect of suppressing generation of foaming is confirmed. In Examples 1-1, 1-2, and 1-3 using an ultraviolet curable component having two polymerizable functional groups in one molecule, the effect of suppressing expansion (foaming) was higher.
As a result of the evaluation of the first residue, Examples 1-1, 1-2, 1-3, 1-4, and 1-5 were judged as A-free. Comparative Example 1-1 is a B determination in which a residual glue is partially present; and Comparative Example 1-2 and Comparative Example 1-3 are C determinations in which a residual adhesive is present in its entirety.
From this result, it was confirmed that even in the case where the adhesive sheets relating to Examples 1-1, 1-2, 1-3, 1-4 and 1-5 were used in the sealing step, no residual glue was generated. Further, the adhesive sheets according to Examples 1-1, 1-2, and 1-3 are less likely to be peeled off even if the foaming step is easy to occur as in the plasma step.

[Example 2-1]
(2-1) Modulation of coating oligomer solvent sealant
The coating oligomer sealant liquid according to Example 2-1 was prepared in the same manner as in the preparation of the coating oligomer sealant liquid according to Example 1-1.

(2-2) Production of oligomer sealing layer (production of substrate with oligomer sealing layer)
As the substrate, an annealed biaxially-oriented polyethylene terephthalate film ("Teijin Tetoron G2A" (trade name) manufactured by Teijin Film Solutions Co., Ltd., thickness: 25 μm) was prepared. Hereinafter, the annealed biaxially-oriented polyethylene terephthalate film is also simply referred to as "PET film".
The prepared coating oligomer sealant liquid was uniformly applied to one side of the "PET film" by a Mayer rod coating method. The "PET film" coated with the coating oligomer sealant liquid was passed through the inside of the oven, and the coating film was heat-cured to form an oligomer sealing layer having a thickness of 150 nm on one surface of the PET film. Next, an oligomer sealing layer having a thickness of 150 nm was formed in the same manner on the other surface of the "PET film" to obtain a substrate with a double-sided oligomer sealing layer. The blowing conditions of the hot air in the oven were set to 150 ° C and the wind speed was set to 8 m / min. The processing speed in the oven was adjusted to the "PET film" after coating, and the speed inside the oven was passed for 20 seconds.

(2-3) Preparation of adhesive composition
The following materials (polymer (polymer component (A)), a crosslinking agent, a low molecular compound having a polymerizable functional group, a photopolymerization initiator, and a diluent solvent) were mixed and sufficiently stirred to prepare an example. 2-1 related adhesive solution for coating.
・Polymer: acrylate copolymer (polymer component (A)), 100 parts by mass (solid content)
The acrylate copolymer is 8-0.8% by mass of 2-ethylhexyl acrylate, 12.0% by mass of acrylofyl-based carbaryl (monomer having a nitrogen-containing functional group), 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2 of acrylic acid. The mass % was copolymerized to prepare a polymer having a weight average molecular weight of 440,000.
・Crosslinking agent: an aliphatic isocyanate having hexamethylene diisocyanate [Polyate HZ, manufactured by Polyurethane Industry Japan Co., Ltd.; 7.4 parts by mass (solid content)
・Low-molecular compound having a polymerizable functional group: propoxylated bisphenol A diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.; A-BPP-3] 23.3 parts by mass (solid content)
・Photopolymerization initiator: 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propane-1- Ketone [manufactured by IGM Resin; Omnirad 127] 4.1 parts by mass (solids)
- Dilution solvent: Ethyl acetate was used, and the solid content concentration of the coating adhesive liquid was adjusted to 30% by mass.

(2-4) Production of adhesive layer
The prepared coating adhesive liquid was applied to a release film made of a transparent polyethylene terephthalate film having a thickness of 38 μm having a polyoxynitride-based release layer using a blade coater [Lintec (shared) ) company system; SP-PET382150] peeling layer side. Next, the coating film of the coating adhesive liquid on the release film was heated at 90 ° C for 90 seconds, and then heated at 115 ° C for 90 seconds to dry the coating film. Thereafter, the coating film was bonded to one side of the substrate with the oligomer sealing layer obtained by the above-described process, and the one surface of the oligomer sealing layer was provided. Further, as a UV irradiation device, a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd. was used, and the illuminance was 200 mW/cm. ² , cumulative light quantity 200mJ/cm ² Under the conditions, the coating film was irradiated with ultraviolet rays from the side of the release film to prepare an adhesive layer having a thickness of 50 μm. In this manner, the adhesive sheet of Example 2-1 was obtained.

[Example 2-2]
In addition to the acrylate copolymer as the polymer component (A), 8-6.8% by mass of 2-ethylhexyl acrylate, 6.0% by mass of acrylofyl-valproate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2 of acrylic acid. The adhesive sheet of Example 2-2 was obtained in the same manner as in Example 2-1 except that the mass % was copolymerized to prepare a polymer having a weight average molecular weight of 510,000.

[Example 2-3]
In addition to the acrylate copolymer as the polymer component (A), 8-9.8% by mass of 2-ethylhexyl acrylate, 3.0% by mass of propylene mercapent, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2 of acrylic acid. The adhesive sheet of Example 2-3 was obtained in the same manner as in Example 2-1 except that the mass % was copolymerized to prepare a polymer having a weight average molecular weight of 520,000.

[Example 2-4]
In addition to the acrylate copolymer as the polymer component (A), 80.8 mass% of 2-ethylhexyl acrylate, N,N-dimethyl decylamine as a monomer having a nitrogen-containing functional group (having The catalyst of the nitrogen functional group), 12.0% by mass, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid were copolymerized to prepare a polymer having a weight average molecular weight of 500,000, and the same as in Example 2-1. In the same manner, the adhesive sheets of Examples 2-4 were obtained.

[Example 2-5]
The acrylate copolymer was copolymerized with 92.8% by mass of 2-ethylhexyl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid to prepare a polymer having a weight average molecular weight of 1,050,000. The adhesive sheet of Example 2-5 was obtained in the same manner as in Example 2-1. Further, the acrylate copolymer itself was the same as the acrylate copolymers related to Examples 1-3.

[Comparative Example 2-2]
In addition to the preparation of the adhesive composition, the following materials (polymer, adhesion aid, crosslinking agent, and diluent solvent) are formulated, and in the preparation of the adhesive layer, the steps of irradiating ultraviolet rays are omitted, and other examples and examples are employed. 2-1 was the same manner, thereby obtaining an adhesive sheet of Comparative Example 2-2.
・Polymer: acrylate copolymer, 100 parts by mass (solids)
The acrylate copolymer was obtained by copolymerizing 92.8% by mass of 2-ethylhexyl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid to prepare a polymer having a weight average molecular weight of 1,050,000.
・Adhesive adjuvant: Hydroxylated polybutadiene at both ends [Japan Soda Co., Ltd.; GI-1000], 12.5 parts by mass (solids)
- Crosslinking agent: an aliphatic isocyanate having hexamethylene diisocyanate [Polyurethane Industry Japan; Coronate HX], 8.75 parts by mass (solid content)
- Dilution solvent: Methyl ethyl ketone was used, and the solid content concentration of the coating adhesive liquid was adjusted to 30% by mass.
Further, the acrylate copolymer itself was the same as the acrylate copolymer of Comparative Example 1-1.





(Description of Table 2)
・"ACMO" means the meaning of acrylonitrile-based phenylephrine.
・ "DMAA" means N,N-dimethyl propylene amide.
・ "PI" means the meaning of polyimine.

[evaluation result]
The second residue of the adhesive sheets of Examples 2-1, 2-2, 2-3, and 2-4 was evaluated to be good as compared with the adhesive sheet of Comparative Example 2-2.
Further, in the adhesive sheet of Example 2-5, the structure of the adhesive layer itself was the same as that of Example 1-3, and therefore, compared with Comparative Example 2-2 (Structure of the adhesive layer itself and Comparative Example 1-1) In the same manner, the evaluation of the first residue as shown in Table 1 was good, but both of them were judged as D in terms of the evaluation of the second residue.
The adhesive sheets of Examples 2-1, 2-2, 2-3 and 2-4 had an adhesion to polyimine at 100 ° C of 0.04 [N/25 mm] or more. That is, the adhesive sheets of Examples 2-1, 2-2, 2-3, and 2-4 were sheets which ensured adhesion and exhibited good processability of the steps.
According to the adhesive sheet of the present embodiment, the adhesive layer is formed by including the polymer component (A) and the cured product (B), thereby improving the adhesion at the time of heating and preventing peeling from the object. Residue.

[Production of adhesive sheets]
[Example 3-1]
(3-1) Modulation of coating oligomer solvent sealant
The coating oligomer-containing sealant liquid according to Example 3-1 was prepared in the same manner as in the preparation of the coating oligomer sealant liquid according to Example 1-1.
(3-2) Preparation of oligomer sealing layer (production of substrate with oligomer sealing layer)
The substrate with the oligomer sealing layer according to Example 2-1 was prepared in the same manner to prepare the substrate with the oligomer sealing layer according to Example 3-1.
(3-3) Preparation of adhesive composition
The following materials (polymer (polymer component), crosslinking agent, low molecular compound having a polymerizable functional group, a photopolymerization initiator, and a diluent solvent) were blended, and sufficiently stirred to prepare Example 3-1. Related coating adhesive fluids.
The acrylate copolymer is 80.8% by mass of 2-ethylhexyl acrylate, 12.0% by mass of acrylonitrile-based phenanthrene (monomer having a nitrogen-containing functional group), 7.0% by mass of 4-hydroxybutyl acrylate, and 0.2 of acrylic acid. The mass % was copolymerized to prepare a polymer having a weight average molecular weight of 120,000.
・Crosslinking agent: an aliphatic isocyanate having hexamethylene diisocyanate [Polyate HZ, manufactured by Polyurethane Industry Japan Co., Ltd.; 7.4 parts by mass (solid content)
・Low-molecular compound having a polymerizable functional group: propoxylated bisphenol A diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.; A-BPP-3] 23.3 parts by mass (solid content)
・Photopolymerization initiator: 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propane-1- Ketone [manufactured by IGM Resin; Omnirad 127] 4.1 parts by mass (solids)
- Dilution solvent: Ethyl acetate was used, and the solid content concentration of the coating adhesive liquid was adjusted to 30% by mass.
(3-4) Production of adhesive layer
In the adhesive layer according to Example 3-1, the coating adhesive liquid in "(2-4) Preparation of Adhesive Layer" of Example 2-1 was changed to the coating material of Example 3-1. The same procedure as in Example 2-1 was carried out except that the adhesive liquid for the cloth was used.

[Example 3-2]
In addition to the propoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.; A-BPP-3) in Example 3-1, it was changed to 1,6-hexanediol diacrylate [new The adhesive sheet of Example 3-2 was obtained in the same manner as in Example 3-1 except that Nakamura Chemical Co., Ltd.; A-HD-N] (inter-linkage chain length: 4) was used.

[Example 3-3]
In addition to the propoxylated bisphenol A diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.; A-BPP-3] in Example 3-1, it was changed to tripropylene glycol diacrylate [Xinzhongcun Chemical Co., Ltd.] The adhesive sheet of Example 3-3 was obtained in the same manner as in Example 3-1 except that APG-200] (linkage between functional groups: 6) was used.

[Example 3-4]
In addition to the propoxylated bisphenol A diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.; A-BPP-3] in Example 3-1, it was changed to 1,9-nonanediol diacrylate [new The adhesive sheet of Example 3-4 was obtained in the same manner as in Example 3-1 except that Amura (manufactured by Nakamura Chemical Co., Ltd.; A-NOD-N) (chain length between functional groups: 9).

[Example 3-5]
In addition to the propoxylated bisphenol A diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.; A-BPP-3] in Example 3-1, it was changed to 1,10-nonanediol diacrylate [new The adhesive sheet of Example 3-5 was obtained in the same manner as in Example 3-1 except that Amura Chemical Co., Ltd.; A-DOD-N] (chain length between functional groups: 10) was used.

[Examples 3-6]
In addition to the acrylate copolymer of Example 3-1, it was changed to Example 2-5, and further, propoxylated bisphenol A diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.; A-BPP- 3] Changed to 1,10-nonanediol diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.; A-DOD-N] (chain length between functional groups: 10), and the same applies to Example 3-1. In the same manner, the adhesive sheets of Examples 3 to 6 were obtained.

[Examples 3-7]
The acrylate copolymer in Example 3-1 was changed to the one in Example 2-5, and the propoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.; A-BPP-) was further changed. 3] changed to polypropylene glycol #400 diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.; APG-400] (inter-functional chain length: 14), and the same manner as in Example 3-1 was employed. Adhesive sheets of Examples 3-7 were obtained.

[Examples 3-8]
In addition to the acrylate copolymer of Example 3-1, it was changed to Example 2-5, and further, propoxylated bisphenol A diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.; A-BPP- 3] and further into polypropylene glycol (#700) diacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd.; APG-700] (carbon number of chain between functional groups: 24), and the other examples are as in Example 3-1. In the same manner, the adhesive sheets of Examples 3 to 8 were obtained.
The evaluation results of the adhesive sheets relating to Examples 3-1 to 3-8 are shown in Table 3.
In addition, in order to evaluate the adhesive sheets related to Examples 3-1 to 3-8, the evaluation results of the adhesive sheets relating to Examples 1-3, 2-1 and Comparative Example 1-1 which were comparative objects were evaluated. Also included in Table 3.

[evaluation result]
The second residual rubber evaluation results of the adhesive sheets according to Examples 3-1 to 3-8 were good as compared with Comparative Example 1-1.
According to the adhesive sheets of Examples 3-1 to 3-5, the peeling property can be improved. As Example 2-1 using HEA as a functional group-containing monomer, the adhesion to polyimine at room temperature after heating was slightly higher, and as a functional group-containing monomer, it was used. The adhesive sheets of Examples 3-1 to 3-5 of HBA exhibited an appropriate adhesion to polyimine at normal temperature and improved peelability.
When the adhesive sheets relating to Example 3-1 and Examples 3-2 to 3-6 were compared, the adhesive sheets according to Examples 3-2 to 3-6 were excellent in initial adhesion.
In Example 3-1, as the energy ray-curable compound, an energy ray-curable compound having a ring structure was used. In Examples 3-2 to 3-6, as a result of using an energy ray-curable compound having a predetermined chain structure, the initial adhesion was improved. This is considered to be because the Young's modulus is lowered and the initial adhesion is improved by using an energy ray-curable compound having a specified chain structure, rather than the ring structure.
The adhesive sheet according to Examples 3-6 to 3-8 does not contain ACMO as a constituent unit of the polymer component, but the effect of preventing the residual glue is improved by using an energy ray-curable compound having a specified chain structure. .
When comparing Examples 1-3, 2-1, and 3-1, the results of the first residue evaluation were all A, but as a result of the second residue evaluation of the more stringent conditions, Examples 1-3 were D determined that Examples 2-1 and 3-1 of ACMO using a monomer having a nitrogen-containing functional group as a polymer component were judged by A.

10‧‧‧Adhesive sheets

11‧‧‧Substrate

11a‧‧‧First substrate surface

11b‧‧‧Second substrate surface

12‧‧‧Adhesive layer

RL‧‧‧ peeling sheet

10A‧‧‧Adhesive sheets

13‧‧‧ oligomer sealing layer

10B‧‧‧Adhesive sheets

13A‧‧‧ oligomer sealing layer

13B‧‧‧ oligomer sealing layer

Fig. 1 is a schematic cross-sectional view showing an adhesive sheet according to a first embodiment.

Fig. 2 is a schematic cross-sectional view showing an adhesive sheet according to a second embodiment.

Fig. 3 is a schematic cross-sectional view showing an adhesive sheet according to a third embodiment.

Claims (22)

An adhesive sheet for processing electronic parts, which has a substrate and an adhesive layer, The pressure-sensitive adhesive layer contains a cured product obtained by curing an energy ray-curable component. The adhesive sheet of claim 1, wherein the adhesive layer further comprises a polymer component, The polymer component contains a constituent unit derived from a monomer having a nitrogen-containing functional group, but the aforementioned nitrogen-containing functional group does not include an N-H bond. The adhesive sheet of claim 2, wherein the polymer component comprises a constituent unit derived from a functional group-containing monomer having a reactive functional group, The reactive functional group is a main chain which is bonded to the polymer component by interposing three or more methylene groups bonded in a linear form. The adhesive sheet of claim 1, wherein the energy ray-curable component comprises a polyfunctional energy ray-curable compound, The polyfunctional energy ray-curable compound is a difunctional energy ray-curable compound having two or more and five or less polymerizable functional groups in one molecule. The adhesive sheet of claim 1, wherein the energy ray-curable component comprises a polyfunctional energy ray-curable compound, The polyfunctional energy ray-curable compound has two or more polymerizable functional groups in one molecule. The methylene group bonded to the linear chain is present between the first polymerizable functional group and the second polymerizable functional group which are arbitrarily selected from the two or more polymerizable functional groups of the polyfunctional energy ray-curable compound. , The number of methylene groups which are linearly bonded between the first polymerizable functional group and the second polymerizable functional group is 4 or more. The adhesive sheet according to claim 5, wherein the number of methylene groups bonded to the linear relationship between the first polymerizable functional group and the second polymerizable functional group is 8 or more and 30 or less. The adhesive sheet of claim 4, wherein the polyfunctional energy ray-curable compound has a cyclic structure in the molecule. The adhesive sheet according to claim 7, wherein the adhesive layer has a breaking strength per unit sectional area of 4.5 N/mm ² or more. The adhesive sheet of claim 1, wherein the adhesive sheet has an adhesive strength to polyimine at 100 ° C of 0.04 N/25 mm or more. The adhesive sheet according to claim 9, wherein the adhesive sheet has an adhesive strength to polyimine at 100 ° C of 0.06 N/25 mm or more, and the breaking strength per unit sectional area of the adhesive layer is 4.5 N/mm ² the above. The adhesive sheet according to claim 1, wherein the adhesive sheet after heat treatment at 190 ° C for 1.5 hours in a nitrogen atmosphere has an adhesion to polyimine at 25 ° C of 3 N/25 mm or less. The adhesive sheet of claim 1, wherein the adhesive layer has a Young's modulus of 5 MPa or less. The adhesive sheet of claim 1, which is used to fix or protect the aforementioned electronic component when processing the electronic component. The adhesive sheet of claim 13, wherein the electronic component is a semiconductor component, When the semiconductor element is sealed, it is used to fix the semiconductor element. The adhesive sheet of claim 1, wherein the electronic component is directly attached to the adhesive layer. The adhesive sheet of claim 2, wherein the polymer component is crosslinked by a crosslinking agent. The adhesive sheet of claim 2, wherein the polymer component is a (meth)acrylic polymer. The adhesive sheet according to claim 2, wherein the nitrogen-containing functional group is at least one selected from the group consisting of a tertiary amino group, an aminocarbonyl group, a cyano group, and a nitrogen-containing heterocyclic group. The adhesive sheet of claim 2, wherein the monomer having a nitrogen-containing functional group is selected from the group consisting of a heterocyclic vinyl compound, a (meth) acrylamide compound, an amine group-containing (meth) acrylate compound, and At least one of the group consisting of methyl)acrylonitrile. The adhesive sheet according to claim 2, wherein a ratio of the constituent unit derived from the monomer having a nitrogen-containing functional group to the total mass of the polymer component is 1% by mass or more and 20% by mass or less. The adhesive sheet according to any one of Claims 1 to 20, wherein the ratio of the cured product obtained by curing the energy ray-curable component in the entire mass of the pressure-sensitive adhesive layer is 5% by mass or more and 40% The ratio of the mass% or less. A method of fabricating a semiconductor device, comprising the steps of: a step of fixing a semiconductor element to an adhesive sheet having an adhesive layer comprising a cured product obtained by hardening an energy ray hardening component; The step of sealing the aforementioned semiconductor element by a sealing material.