JP2022143089A - Laminate, manufacturing method of laminate, and manufacturing method of semiconductor substrate - Google Patents

Abstract

To provide a laminate or the like which can easily separate a semiconductor substrate and a support substrate without causing cutting or deformation of the semiconductor substrate and the support substrate when the semiconductor substrate and the support substrate are separated after processing the semiconductor substrate.SOLUTION: A laminate includes a semiconductor substrate 1, a support substrate 4, an adhesive layer 2 formed in contact with the semiconductor substrate, and a photoresponsive release layer 3 formed between the adhesive layer and the support substrate so as to be in contact with the adhesive layer, wherein the adhesive layer is a thermosetting adhesive layer, and the photoresponsive release layer is formed of a release agent composition containing a compound having an azobenzene skeleton.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminate, a laminate manufacturing method, and a semiconductor substrate manufacturing method.

Semiconductor wafers, which have conventionally been integrated in a two-dimensional planar direction, are required to integrate (stack) a planar surface in a three-dimensional direction for the purpose of further integration (stacking). This three-dimensional lamination is a technique of integrating in multiple layers while connecting with a through silicon via (TSV). In multi-layer integration, each wafer to be integrated is thinned by polishing the side opposite to the circuit surface (that is, the back surface), and the thinned semiconductor wafers are stacked.
A semiconductor wafer before thinning (herein simply referred to as wafer) is adhered to a support for polishing in a polishing apparatus.
The adhesion at that time is called temporary adhesion because it must be easily peeled off after polishing. This temporary adhesion must be easily removed from the support, and if a large force is applied to the removal, the thinned semiconductor wafer may be cut or deformed. easily removed. However, it is not preferable that the back surface of the semiconductor wafer is removed or displaced due to polishing stress. Therefore, the performance required for the temporary adhesion is to withstand the stress during polishing and to be easily removed after polishing.
For example, it is required to have high stress (strong adhesion) in the planar direction during polishing and low stress (weak adhesion) in the vertical direction during removal.

As such an adhesion process, a silicone oil layer and a plasma polymer layer (4 ) and a layer (5) of partially cured or curable elastomeric material such that the adhesive bond between the support layer system and the separating layer (4) after the elastomeric material has been fully cured is Wafer support structures have been proposed that are larger than adhesive bonds between the wafer (1) and the separating layer (4) (see, for example, examples in US Pat.

After thinning the semiconductor wafer, when removing the thinned semiconductor wafer from the support, if a large force is required for removal, the semiconductor wafer and the support may be cut or deformed. There is always a demand for a technology that can easily detach from the support.
In addition, the semiconductor wafer is electrically connected to the semiconductor chip through bump balls made of, for example, a metal conductive material, and the use of chips having such bump balls contributes to miniaturization of semiconductor packaging. is planned.
Bump balls made of metals such as copper and tin may be damaged or deformed by external loads such as heat and pressure applied during the process of processing semiconductor substrates. There is also a demand for a technique that can reduce or prevent deformation due to heating or pressure.

Japanese Patent No. 5335443 Japanese Patent No. 5822369

The present invention has been made in view of the above circumstances, and when separating the semiconductor substrate and the support substrate after processing the semiconductor substrate, the semiconductor substrate and the support substrate are not cut or deformed, and the semiconductor substrate can be easily manufactured. It is an object of the present invention to provide a laminate in which a substrate and a supporting substrate can be separated from each other, a method for manufacturing a semiconductor substrate using the laminate, and a method for manufacturing the laminate. In addition, the present invention provides a laminate in which a semiconductor substrate and a support substrate can be easily separated, and in which bump deformation can be suppressed, a method for manufacturing a semiconductor substrate using the laminate, and the laminate. It is also an object to provide a manufacturing method of

In order to solve the above-described problems, the inventors of the present invention have completed the present invention having the following gist as a result of intensive studies.

（式中、ｍは０～２０の整数、ｌは１～２０の整数を示す。）
［３］ 前記接着層は、ヒドロシリル化反応によって硬化する接着層である、［１］又は［２］に記載の積層体。
［４］ 前記接着層は、ヒドロシリル化反応によって硬化する成分（Ａ）を含む接着剤組成物から形成され、
前記成分（Ａ）が、
ケイ素原子に結合した炭素原子数２～４０のアルケニル基を有するポリオルガノシロキサン（ａ１）と、
Ｓｉ－Ｈ基を有するポリオルガノシロキサン（ａ２）と、
白金族金属系触媒（Ａ２）と、
を含有する、［１］から［３］のいずれかに記載の積層体。
［５］ ［１］から［４］のいずれかに記載の積層体における前記半導体基板が加工される工程と、
前記光応答性の剥離層が紫外光の照射で剥離されることにより、前記支持基板と加工された前記半導体基板とが離される工程と、
を含む、半導体基板の製造方法。
［６］ 前記加工される工程が、前記半導体基板を研磨し、前記半導体基板を薄くする処理を含む、［５］に記載の半導体基板の製造方法。
［７］ ［１］から［４］のいずれかに記載の積層体を製造する、積層体の製造方法であって、
前記半導体基板上に、熱硬化性の接着剤組成物が塗布され、接着剤塗布層が形成される工程と、
前記接着剤塗布層が加熱され、前記接着層が形成される工程と、
を含む、積層体の製造方法。
［８］ 前記半導体基板上に、熱硬化性の接着剤組成物が塗布され、接着剤塗布層が形成される工程と、
前記支持基板上に、前記剥離剤組成物が塗布され、剥離層が形成される工程と、
前記接着剤塗布層と前記剥離層とを挟み込むように、接着剤塗布層付き半導体基板と剥離層付き支持基板とを貼り合わせた後、加熱が施されることにより、前記接着剤塗布層から前記接着層が形成される工程と、
を含む、［７］に記載の積層体の製造方法。 That is, the present invention includes the following.
[1] a semiconductor substrate, a supporting substrate, an adhesive layer formed in contact with the semiconductor substrate, and a photoresponsive layer formed between the adhesive layer and the supporting substrate in contact with the adhesive layer A laminate comprising a release layer of
The adhesive layer is a thermosetting adhesive layer,
The laminate, wherein the photoresponsive release layer is formed from a release agent composition containing a compound having an azobenzene skeleton.
[2] The laminate according to [1], wherein the compound having an azobenzene skeleton is a compound containing a group represented by the following formula (1).

(Wherein, m is an integer of 0 to 20, l is an integer of 1 to 20.)
[3] The laminate according to [1] or [2], wherein the adhesive layer is an adhesive layer that is cured by a hydrosilylation reaction.
[4] The adhesive layer is formed from an adhesive composition containing a component (A) that cures by a hydrosilylation reaction,
The component (A) is
A polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom;
a polyorganosiloxane (a2) having a Si—H group;
a platinum group metal-based catalyst (A2);
The laminate according to any one of [1] to [3], containing
[5] A step of processing the semiconductor substrate in the laminate according to any one of [1] to [4];
a step of separating the support substrate and the processed semiconductor substrate by exfoliating the photoresponsive exfoliation layer by irradiation with ultraviolet light;
A method of manufacturing a semiconductor substrate, comprising:
[6] The method of manufacturing a semiconductor substrate according to [5], wherein the step of processing includes polishing the semiconductor substrate to thin the semiconductor substrate.
[7] A method for manufacturing the laminate according to any one of [1] to [4], comprising:
a step of applying a thermosetting adhesive composition onto the semiconductor substrate to form an adhesive coating layer;
a step of heating the adhesive coating layer to form the adhesive layer;
A method of manufacturing a laminate, comprising:
[8] a step of applying a thermosetting adhesive composition onto the semiconductor substrate to form an adhesive coating layer;
a step of applying the release agent composition onto the support substrate to form a release layer;
After the semiconductor substrate with the adhesive coating layer and the support substrate with the release layer are attached together so as to sandwich the adhesive coating layer and the release layer, heating is applied to remove the adhesive layer from the adhesive coating layer. forming an adhesive layer;
The method for producing a laminate according to [7], comprising:

According to the present invention, when the semiconductor substrate and the supporting substrate are separated after the semiconductor substrate is processed, the semiconductor substrate and the supporting substrate can be easily separated without cutting or deforming the semiconductor substrate or the supporting substrate. , a method for manufacturing a semiconductor substrate using the laminate, and a method for manufacturing the laminate.

It is a schematic sectional drawing of an example of a laminated body. FIG. 1 is a diagram (part 1) for explaining one aspect of manufacturing a laminated body and manufacturing a thin wafer; FIG. 10 is a diagram (part 2) for explaining one aspect of manufacturing a laminated body and manufacturing a thinned wafer; FIG. 3 is a diagram (part 3) for explaining one aspect of manufacturing a laminated body and manufacturing a thinned wafer; FIG. 4 is a diagram (part 4) for explaining one aspect of manufacturing a laminated body and manufacturing a thinned wafer; FIG. 5 is a diagram (No. 5) for explaining one aspect of manufacturing a laminated body and manufacturing a thinned wafer; FIG. 6 is a diagram (No. 6) for explaining one aspect of manufacturing a laminated body and manufacturing a thinned wafer;

(Laminate)
The laminate of the present invention has a semiconductor substrate, a support substrate, an adhesive layer, and a photoresponsive release layer.
The adhesive layer is interposed between the support substrate and the semiconductor substrate.
The adhesive layer contacts the semiconductor substrate.
A photoresponsive release layer is interposed between the supporting substrate and the adhesive layer.
A photoresponsive release layer contacts the adhesive layer.
The photoresponsive release layer preferably contacts the supporting substrate.
The laminated body is used for applications in which the supporting substrate and the semiconductor substrate are separated after processing the semiconductor substrate in the laminated body.

In the laminate of the present invention, when the supporting substrate and the semiconductor substrate are separated, the photoresponsive peeling layer is easily peeled off by irradiation with ultraviolet light. In particular, in the present invention, by using a thermosetting adhesive layer as an adhesive layer, the thermosetting adhesive layer and the photoresponsive peeling layer combine to exert excessive force on the support substrate and the semiconductor substrate during peeling. The supporting substrate and the semiconductor substrate can be easily separated without giving any stress. In other words, the support substrate and the semiconductor substrate can be separated from each other without cutting or deforming the support substrate or the semiconductor substrate.
Furthermore, in the laminate of the present invention, since the thermosetting adhesive layer is formed in contact with the semiconductor substrate, bump deformation can be suppressed when manufacturing the processed semiconductor substrate. It is believed that this is because the bumps, which are easily melted or deformed by heat and pressure during processing of the semiconductor substrate, are protected by the adhesive layer, which is difficult to melt and deform, and as a result, the shape is maintained.

<Supporting substrate>
The support substrate is not particularly limited as long as it is a member capable of supporting the semiconductor substrate when the semiconductor substrate is processed. Examples thereof include a glass support substrate and a silicon support substrate.

The shape of the support substrate is not particularly limited, but for example, a disk shape can be mentioned. It should be noted that the disc-shaped support substrate does not need to have a perfectly circular surface shape. It may have notches.
The thickness of the disc-shaped support substrate may be appropriately determined according to the size of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 μm.
The diameter of the disk-shaped support substrate may be appropriately determined according to the size of the semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.

An example of the support substrate is a glass wafer or silicon wafer having a diameter of 300 mm and a thickness of about 700 μmm.

When ultraviolet light is irradiated from the support substrate side in order to peel off the peeling layer, it is preferable to use a support substrate made of glass whose transmittance of ultraviolet light is usually 50% or more.

<Semiconductor substrate>
The main material constituting the entire semiconductor substrate is not particularly limited as long as it can be used for this type of application, and examples thereof include silicon, silicon carbide, and compound semiconductors.
The shape of the semiconductor substrate is not particularly limited, but is, for example, a disc shape. It should be noted that the disk-shaped semiconductor substrate does not need to have a perfect circular shape on its surface. It may have notches.
The thickness of the disk-shaped semiconductor substrate may be appropriately determined according to the purpose of use of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 μm.
The diameter of the disk-shaped semiconductor substrate may be appropriately determined according to the purpose of use of the semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.

The semiconductor substrate may have bumps. A bump is a projecting terminal.
In the laminate, when the semiconductor substrate has bumps, the semiconductor substrate has bumps on the support substrate side.
In a semiconductor substrate, bumps are usually formed on the surface on which circuits are formed. The circuit may be a single layer or multiple layers. The shape of the circuit is not particularly limited.
In the semiconductor substrate, the surface opposite to the surface having the bumps (back surface) is a surface to be processed.
The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited.
Examples of bumps include ball bumps, printed bumps, stud bumps, and plated bumps.
Normally, the height, diameter and pitch of the bumps are appropriately determined from the conditions that the bump height is about 1 to 200 μm, the bump diameter is 1 to 200 μm, and the bump pitch is 1 to 500 μm.
Materials for the bumps include, for example, low-melting solder, high-melting solder, tin, indium, gold, silver, and copper. The bumps may consist of only a single component, or may consist of multiple components. More specifically, Sn-based alloy plating such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps can be used.
Also, the bump may have a laminated structure including a metal layer composed of at least one of these components.

An example of a semiconductor substrate is a silicon wafer with a diameter of 300 mm and a thickness of about 770 μm.

When ultraviolet light is irradiated from the semiconductor substrate side in order to peel off the peeling layer, it is preferable to use a substrate having a transmittance of ultraviolet light of 50% or more.

<Adhesive layer>
The adhesive layer is interposed between the support substrate and the semiconductor substrate.
The adhesive layer contacts the semiconductor substrate.

The adhesive layer is a thermosetting adhesive layer.
A thermosetting adhesive layer means a film formed by using an adhesive composition containing a thermosetting adhesive component and curing the curable adhesive component.
Such a thermosetting adhesive component is not particularly limited as long as it is an adhesive component that cures by heat. agents, phenolic resin-based adhesives, and the like.
Among these, polysiloxane-based adhesive is used as a thermosetting adhesive component because it exhibits suitable adhesive properties during processing of semiconductor substrates, etc., can be peeled off after processing, and has excellent heat resistance. agents are preferred.
In a preferred embodiment, the adhesive composition contains polyorganosiloxane.
In addition to the thermosetting adhesive component, the adhesive composition may contain other components such as a solvent in order to adjust the viscosity of the thermosetting adhesive composition.

It is important that the adhesive layer provided in the laminate according to the present invention is a thermosetting adhesive layer. For example, when the adhesive layer is a thermoplastic adhesive layer, as shown in the following examples, even if the peeling layer is peeled off by irradiation with ultraviolet light, it cannot be peeled off. , Excessive force is applied to the substrate (wafer), causing the wafer to crack.
This is because, when manufacturing a laminate, a semiconductor substrate with an adhesive coating layer and a support substrate with a release layer are bonded together and heated. It is presumed that this is because the components of the thermoplastic adhesive layer are mixed with the release layer used in the present invention at the time of .

Also, in a preferred embodiment, the adhesive composition includes components that cure via a hydrosilylation reaction.
More specific embodiments of the thermosetting adhesive composition used in the present invention include, for example, the following <<first embodiment>> to <<third embodiment>>.

<<First Embodiment>>
As a preferred embodiment, the adhesive composition used in the present invention contains polyorganosiloxane.
For example, the adhesive composition used in the present invention contains a curable component (A) that serves as an adhesive component. The adhesive composition used in the present invention may contain a component (A) that cures as an adhesive component and a component (B) that does not cause a curing reaction. Here, examples of the component (B) that does not cause a curing reaction include polyorganosiloxane. In the present invention, "does not cause a curing reaction" does not mean that no curing reaction occurs, but rather means that the component (A) to be cured does not cause a curing reaction.
In another preferred embodiment, component (A) may be a component that cures by a hydrosilylation reaction or a polyorganosiloxane component (A') that cures by a hydrosilylation reaction.
In another preferred embodiment, component (A) comprises, for example, polyorganosiloxane (a1) having a silicon-bonded alkenyl group having 2 to 40 carbon atoms, as an example of component (A′), and Si It contains a polyorganosiloxane (a2) having —H groups and a platinum group metal-based catalyst (A2). Here, the alkenyl group having 2 to 40 carbon atoms may be substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxy groups, carboxyl groups, aryl groups, heteroaryl groups and the like.
In another preferred embodiment, the polyorganosiloxane component (A') that cures by a hydrosilylation reaction has siloxane units (Q units) represented by SiO ₂ , represented by R ¹ R ² R ³ SiO _1/2 one selected from the group consisting of siloxane units (M units), siloxane units (D units) represented by R ⁴ R ⁵ SiO _2/2 and siloxane units (T units) represented by R ⁶ SiO _3/2 Or a polysiloxane (A1) containing two or more units and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) is a siloxane unit (Q' unit) represented by SiO ₂ , R ¹ A siloxane unit represented by 'R ² 'R ³ 'SiO _1/2 (M' unit), a siloxane unit represented by R ⁴ 'R ⁵ 'SiO _2/2 (D' unit) and R ⁶ 'SiO _{3 / 2} containing one or more units selected from the group consisting of siloxane units (T' units) and at least one selected from the group consisting of M' units, D' units and T' units Polyorganosiloxane containing seeds (a1′), siloxane units represented by SiO ₂ (Q″ units), siloxane units represented by R ¹ ″R ² ″R ³ ″SiO _1/2 (M″ units) _or ^{_ _ _} _{_} A polyorganosiloxane (a2′) containing two or more types of units and containing at least one selected from the group consisting of M″ units, D″ units and T″ units.
Note that (a1') is an example of (a1), and (a2') is an example of (a2).

R ¹ to R ⁶ are groups or atoms bonded to a silicon atom and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group or a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxy groups, carboxyl groups, aryl groups, heteroaryl groups and the like.

R ¹ ' to R ⁶ ' are groups bonded to a silicon atom and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, and R ¹ ' to R ⁶ At least one of ' is an optionally substituted alkenyl group. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxy groups, carboxyl groups, aryl groups, heteroaryl groups and the like.

R ¹ ″ to R ⁶ ″ are groups or atoms bonded to a silicon atom and each independently represent an optionally substituted alkyl group or hydrogen atom, but at least one of R ¹ ″ to R ⁶ ″ One is a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxy groups, carboxyl groups, aryl groups, heteroaryl groups and the like.

The alkyl group may be linear, branched or cyclic, but is preferably a linear or branched alkyl group. Yes, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

Specific examples of optionally substituted linear or branched alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and s-butyl. group, tertiary butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n -pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl- n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl -n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2 -methyl-n-propyl group and the like, but not limited thereto, and usually have 1 to 14 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Among them, a methyl group is particularly preferred.

Specific examples of optionally substituted cyclic alkyl groups include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2- methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group , 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n -propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1 , 2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl -Cycloalkyl groups such as 2-methyl-cyclopropyl group and 2-ethyl-3-methyl-cyclopropyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, Examples include, but are not limited to, bicycloalkyl groups such as bicyclodecyl group, and the number of carbon atoms thereof is usually 3-14, preferably 4-10, more preferably 5-6.

The alkenyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and more preferably 20 or less. It is preferably 10 or less.

Specific examples of optionally substituted linear or branched alkenyl groups include, but are not limited to, vinyl groups, allyl groups, butenyl groups, pentenyl groups, and the like. 2 to 14, preferably 2 to 10, more preferably 1 to 6. Among them, an ethenyl group and a 2-propenyl group are particularly preferred.
Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl, cyclohexenyl and the like, and the number of carbon atoms thereof is usually 4 to 14, preferably 5 to 10, More preferably 5-6.

As described above, polysiloxane (A1) includes polyorganosiloxane (a1′) and polyorganosiloxane (a2′), but the alkenyl groups contained in polyorganosiloxane (a1′) and polyorganosiloxane (a2′) ) and the hydrogen atoms (Si—H groups) contained in ) form a crosslinked structure through a hydrosilylation reaction by the platinum group metal-based catalyst (A2) and are cured. As a result, a cured film is formed.

Polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units and T' units, and M' units, D' units and It contains at least one selected from the group consisting of T' units. As the polyorganosiloxane (a1'), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include (Q' unit and M' unit), (D' unit and M' unit), (T' units and M' units), (Q' units and T' units and M' units), but are not limited to these.

Further, when two or more types of polyorganosiloxanes included in the polyorganosiloxane (a1') are included, (Q' unit and M' unit) and (D' unit and M' unit) combination, (T' Units and M′ units) and (D′ units and M′ units), combinations of (Q′ units, T′ units and M′ units) and (T′ units and M′ units) are preferred, but It is not limited to these.

Polyorganosiloxane (a2′) contains one or more units selected from the group consisting of Q″ units, M″ units, D″ units and T″ units, and M″ units, D″ units and It contains at least one selected from the group consisting of T″ units. As the polyorganosiloxane (a2′), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

Preferred combinations of two or more selected from the group consisting of Q″ units, M″ units, D″ units and T″ units include (M″ units and D″ units), (Q″ units and M″ units), (Q" units and T" units and M" units).

^{Polyorganosiloxane} (a1') is composed of siloxane units in which alkyl groups and ^/ or alkenyl groups are bonded to silicon atoms thereof. The proportion of alkenyl groups is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, and the remaining R ¹ ' to R ⁶ ' can be alkyl groups. .

Polyorganosiloxane (a2') is composed of siloxane units in which alkyl groups and/or hydrogen atoms are bonded to silicon atoms thereof, and all substituents represented by R ¹ ″ to R ⁶ ″ and The ratio of hydrogen atoms in the substituted atoms is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remaining R ¹ ″ to R ⁶ ″ are alkyl groups and can do.

When component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the alkenyl group contained in polyorganosiloxane (a1) and the Si—H bond contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

The weight-average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but each is usually 500 to 1,000,000, and the effects of the present invention are realized with good reproducibility. From the viewpoint of doing, it is preferably 5,000 to 50,000.
In the present invention, the weight-average molecular weight, number-average molecular weight and degree of dispersion of the polyorganosiloxane are determined by, for example, a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N manufactured by Tosoh Corporation). , TSKgel SuperMultiporeHZ-H), the column temperature was set to 40 ° C., tetrahydrofuran was used as the eluent (elution solvent), the flow rate (flow rate) was set to 0.35 mL / min, and polystyrene (manufactured by Showdex) was used as a standard sample. can be measured.

The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are not particularly limited, but each is usually 10 to 1,000,000 (mPa s), and from the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferable. is 50 to 10000 (mPa·s). The viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are values measured at 25° C. with an E-type rotational viscometer.

Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other to form a film through a hydrosilylation reaction. Therefore, the curing mechanism differs from that via, for example, silanol groups, and therefore any siloxane need not contain silanol groups or functional groups that form silanol groups upon hydrolysis, such as alkyloxy groups. None.

In a preferred embodiment of the present invention, the adhesive composition contains a platinum group metal-based catalyst (A2) along with the polyorganosiloxane component (A').
Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl groups of the polyorganosiloxane (a1) and the Si—H groups of the polyorganosiloxane (a2).

Specific examples of platinum-based metal catalysts include platinum black, diplatinum chloride, chloroplatinic acid, reactants of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, and the like. platinum-based catalysts including, but not limited to:
Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum.
The amount of platinum group metal-based catalyst (A2) is not particularly limited, but is usually in the range of 1.0 to 50.0 ppm with respect to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2). .

The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction.
The polymerization inhibitor is not particularly limited as long as it can suppress the progress of the hydrosilylation reaction, and specific examples thereof include 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol. and alkynyl alcohols such as
Although the amount of the polymerization inhibitor is not particularly limited, it is usually 1000.0 ppm or more with respect to the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and the hydrosilylation reaction It is 10000.0 ppm or less from the viewpoint of preventing excessive suppression of.

An example of the adhesive composition used in the present invention may contain a component (B) that does not undergo a curing reaction and becomes a release agent component together with the component (A) that cures. By including the component (B) in the adhesive composition, the resulting adhesive layer can be suitably peeled off with good reproducibility.
Such component (B) typically includes polyorganosiloxanes, and specific examples thereof include epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, phenyl group-containing polyorganosiloxanes, and the like. include but are not limited to:
Moreover, a polydimethylsiloxane is mentioned as a component (B). The polydimethylsiloxane may be modified. Examples of polydimethylsiloxane that may be modified include, but are not limited to, epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, and phenyl group-containing polydimethylsiloxane.

Preferable examples of polyorganosiloxane as component (B) include, but are not limited to, epoxy group-containing polyorganosiloxane, methyl group-containing polyorganosiloxane, phenyl group-containing polyorganosiloxane, and the like.

The weight-average molecular weight of the polyorganosiloxane, which is the component (B), is not particularly limited, but is usually from 100,000 to 2,000,000. 000 to 1,200,000, more preferably 300,000 to 900,000. Further, the degree of dispersion is not particularly limited, but is usually 1.0 to 10.0, preferably 1.5 to 5.0, more preferably 2, from the viewpoint of realizing suitable peeling with good reproducibility. 0 to 3.0. The weight-average molecular weight and the degree of dispersion can be measured by the methods described above for polysiloxane.
The viscosity of the component (B) polyorganosiloxane is not particularly limited, but is usually 1,000 to 2,000,000 mm ² /s. The value of the viscosity of the polyorganosiloxane as the component (B) is represented by kinematic viscosity, centistokes (cSt) = mm ² /s. It can also be obtained by dividing the viscosity (mPa·s) by the density (g/cm ³ ). That is, the value can be obtained from the viscosity and density measured with an E-type rotational viscometer at 25° C., kinematic viscosity (mm ² /s)=viscosity (mPa·s)/density (g/cm ³ ) can be calculated from the formula:

Examples of epoxy group-containing polyorganosiloxanes include those containing siloxane units ( ^D10 units) represented by R ¹¹ R ¹² SiO _2/2 .

R ¹¹ is a group bonded to a silicon atom and represents an alkyl group, R ¹² is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group, specific examples of the alkyl group are , the above examples can be mentioned.
The epoxy group in the organic group containing an epoxy group may be an independent epoxy group without being condensed with other rings, and forms a condensed ring with other rings such as a 1,2-epoxycyclohexyl group. may be an epoxy group.
Specific examples of organic groups containing epoxy groups include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.
In the present invention, a preferable example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but the present invention is not limited thereto.

The epoxy group-containing polyorganosiloxane contains the siloxane units ( ^D10 units) described above, but may contain Q units, M units and/or T units in addition to the ^D10 units.
In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include a polyorganosiloxane consisting only of ^D10 units, a polyorganosiloxane containing ^D10 units and Q units, and a polyorganosiloxane containing ^D10 units and M units. Polyorganosiloxane containing ^D10 units and T units Polyorganosiloxane containing ^D10 units, Q units and M units Polyorganosiloxane containing ^D10 units, M units and T units , polyorganosiloxanes containing D ¹⁰ units, Q units, M units and T units.

The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1-5. Although the weight average molecular weight is not particularly limited, it is usually 1,500 to 500,000, and preferably 100,000 or less from the viewpoint of suppressing deposition in the adhesive.

Specific examples of epoxy group-containing polyorganosiloxanes include those represented by formulas (E1) to (E3), but are not limited thereto.

（ｍ_１及びｎ_１は、各繰り返し単位の数を示し、正の整数である。）

(m ₁ and n ₁ indicate the number of each repeating unit and are positive integers.)

（ｍ_２及びｎ_２は、各繰り返し単位の数を示し、正の整数であり、Ｒは、炭素数１～１０のアルキレン基である。）

(m ₂ and n ₂ indicate the number of each repeating unit and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

（ｍ_３、ｎ_３及びｏ_３は、各繰り返し単位の数を示し、正の整数であり、Ｒは、炭素数１～１０のアルキレン基である。）

(m ₃ , n ₃ and o ₃ indicate the number of each repeating unit and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

As the methyl group-containing polyorganosiloxane, for example, one containing a siloxane unit ^{( D200} unit) represented by ^R210R220SiO2 _/ ² , preferably a siloxane unit represented by ^R21R21SiO2 _/2 (D ²⁰ units).

R ²¹⁰ and R ²²⁰ are groups bonded to a silicon atom, each independently representing an alkyl group, at least one of which is a methyl group, and specific examples of the alkyl group are the above-mentioned examples. can.
R ²¹ is a group bonded to a silicon atom and represents an alkyl group, and specific examples of the alkyl group include those mentioned above. Among them, R ²¹ is preferably a methyl group.
In the present invention, a preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but the present invention is not limited thereto.

Methyl group-containing polyorganosiloxane contains the above-described siloxane units (D ²⁰⁰ units or D ²⁰ units), but in addition to D ²⁰⁰ units and D ²⁰ units, it may contain Q units, M units and / or T units. .

In one aspect of the present invention, specific examples of the methyl group-containing polyorganosiloxane include a polyorganosiloxane consisting only of D ²⁰⁰ units, a polyorganosiloxane containing D ²⁰⁰ units and Q units, and a polyorganosiloxane containing D ²⁰⁰ units and M units. polyorganosiloxane containing D ²⁰⁰ units and T units, polyorganosiloxane containing D ²⁰⁰ units, Q units and M units, polyorganosiloxane containing D ²⁰⁰ units, M units and T units , D ²⁰⁰ units, Q units, M units and T units.

In a preferred embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include polyorganosiloxane consisting only of ^D20 units, polyorganosiloxane containing ^D20 units and Q units, and polyorganosiloxane containing ^D20 units and M units. polyorganosiloxane containing ^D20 units and T units polyorganosiloxane containing ^D20 units Q units and M units polyorganosiloxane containing ^D20 units M units T units , D ²⁰ units, Q units, M units and T units.

Specific examples of the methyl group-containing polyorganosiloxane include, but are not limited to, those represented by Formula (M1).

（ｎ_４は、繰り返し単位の数を示し、正の整数である。）

₍ n4 indicates the number of repeating units and is a positive integer.)

Examples of phenyl group-containing polyorganosiloxanes include those containing siloxane units represented by R ³¹ R ³² SiO _2/2 (D ³⁰ units).

R ³¹ is a group bonded to a silicon atom and represents a phenyl group or an alkyl group; R ³² is a group bonded to a silicon atom and represents a phenyl group; can be mentioned, but a methyl group is preferred.

The phenyl group-containing polyorganosiloxane contains the siloxane units ( ^D30 units) described above, but may contain Q units, M units and/or T units in addition to the ^D30 units.

In a preferred embodiment of the present invention, specific examples of the phenyl group-containing polyorganosiloxane include a polyorganosiloxane consisting only of ^D30 units, a polyorganosiloxane containing ^D30 units and Q units, and a polyorganosiloxane containing ^D30 units and M units. polyorganosiloxane containing D ³⁰ units and T units, polyorganosiloxane containing D ³⁰ units, Q units and M units, polyorganosiloxane containing D ³⁰ units, M units and T units , D ³⁰ units, Q units, M units and T units.

Specific examples of the phenyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

（ｍ₅及びｎ₅は、各繰り返し単位の数を示し、正の整数である。）

( _m5 and _n5 indicate the number of each repeating unit and are positive integers.)

（ｍ₆及びｎ₆は、各繰り返し単位の数を示し、正の整数である。）

(m ₆ and n ₆ indicate the number of each repeating unit and are positive integers.)

In one aspect, the adhesive composition used in the present invention contains a component (A) that cures and a component (B) that does not cause a curing reaction. In a more preferred aspect, the component (B) contains polyorganosiloxane. is included.

An example of the adhesive composition used in the present invention can contain component (A) and component (B) in any ratio. The ratio with component (B) is a mass ratio [(A):(B)], preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25. is.
That is, when a polyorganosiloxane component (A') that cures by a hydrosilylation reaction is included, the ratio of component (A') and component (B) is the mass ratio [(A'):(B)], It is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

Although the viscosity of the adhesive composition used in the present invention is not particularly limited, it is usually 500 to 20,000 mPa·s, preferably 1,000 to 5,000 mPa·s at 25°C.

<<Second Embodiment>>
In a preferred embodiment, the adhesive composition used in the present invention contains, for example, the curable adhesive material described below, or the curable adhesive material and a release additive.
Curable adhesive materials are selected from, for example, polyarylene oligomers, cyclic olefin oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, and mixtures thereof.
Exfoliating additives include, for example, polyether compounds.
It is preferred that the polyether compounds contain terminal groups selected from the group consisting of hydroxy, alkoxy, aryloxy and mixtures thereof.
Preferably, the polyether compound is selected from polyethylene glycol, polypropylene glycol, poly(1,3-propanediol), polybutylene glycol, poly(tetrahydrofuran), ethylene glycol-propylene glycol copolymers, and mixtures thereof.
It is preferred that the release additive is selected from the group consisting of polyalkylene oxide homopolymers and polyalkylene oxide copolymers.
As the adhesive composition of the second embodiment, for example, a temporary bonding composition described in JP-A-2014-150239 can be used.
The adhesive composition of the second embodiment is described in greater detail below.

The adhesive composition used in the present invention comprises a curable adhesive material and a release additive, and optionally an organic solvent. Curable adhesive materials typically have a modulus >1 GPa when cured. Exemplary curable adhesive materials include, but are not limited to, polyarylene oligomers, cyclic olefin oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, and mixtures thereof. The curable adhesive material may be substituted with any suitable moieties, such as fluorine-containing groups, to provide additional hydrophobicity, although such moieties may adversely affect the mechanical properties of the cured adhesive material. Only if you don't give it. Preferably, the curable adhesive material is selected from polyarylene oligomers, cyclic olefin oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers and mixtures thereof, more preferably arylcyclobutene oligomers, vinyl aromatic oligomers or is selected from one or more of the mixtures of When mixtures of different curable adhesive materials are used in the present invention, such materials are selected to cure together during the curing process. When mixtures of different curable materials are used, such curable materials are preferably 99:1 to 1:99, preferably 95:5 to 5:95, more preferably 90:10 to 10:90, even more preferably are used in a weight ratio of 75:25 to 25:75.

A wide variety of polyarylene oligomers can be used in the present invention. As used herein, the term "polyarylene" includes polyarylene ethers. Suitable polyarylene oligomers may be synthesized from precursors such as ethynyl aromatic compounds of the formula:

式中、各Ａｒは、芳香族基又は不活性置換された芳香族基であり；各Ｒは、独立に、水素、アルキル、アリール又は不活性置換されたアルキルもしくはアリール基であり；Ｌは、共有結合、又は１つのＡｒを少なくとも１つの他のＡｒに連結する基であり；ｎ及びｍは、少なくとも２の整数であり；並びに、ｑは、少なくとも１の整数である。そういうものとして、エチニル芳香族化合物は、通常、４つ以上のエチニル基を有する（例えば、テトラエチニル芳香族化合物）。

wherein each Ar is an aromatic group or an inertly substituted aromatic group; each R is independently hydrogen, alkyl, aryl, or an inertly substituted alkyl or aryl group; n and m are integers of at least two; and q is an integer of at least one. As such, ethynyl aromatics typically have 4 or more ethynyl groups (eg, tetraethynyl aromatics).

Suitable polyarylene oligomers for use in the temporary bonding composition as the adhesive composition of the second embodiment may include polymers containing as polymerized units:

式中、Ａｒ’は、反応生成物の（Ｃ≡Ｃ）ｎ－Ａｒ又はＡｒ－（Ｃ≡Ｃ）ｍ部分の残基であり、Ｒ、Ｌ、ｎ及びｍは前記で定義された通りである。本発明に有用なポリアリーレンコポリマーとしては、重合単位として以下の式を有するモノマーを含む：

wherein Ar' is the residue of the (C≡C)n-Ar or Ar-(C≡C)m portion of the reaction product and R, L, n and m are as defined above. be. Polyarylene copolymers useful in the present invention include monomers having the following formula as polymerized units:

式中、Ａｒ’及びＲは前記で定義される通りである。

wherein Ar' and R are as defined above.

Exemplary polyarylenes include Ar-L-Ar: biphenyl; 2,2-diphenylpropane; 9,9'-diphenylfluorene;2,2-diphenylhexafluoropropane; diphenyl sulfide; bis(phenylene)diphenylsilane; bis(phenylene)phosphine oxide; bis(phenylene)benzene; bis(phenylene)naphthalene; bis(phenylene)anthracene; thiodiphenylene; -triphenylenebenzene; 1,3,5-(2-phenylene-2-propyl)benzene; 1,1,1-triphenylenemethane; 1,1,2,2-tetraphenylene-1,2-diphenylethane; bis( 1,1-diphenyleneethyl)benzene; 2,2′-diphenylene-1,1,1,3,3,3-hexafluoropropane; 1,1-diphenylene-1-phenylethane; naphthalene; (Phenylene)naphthacene; more preferably biphenylene; naphthylene; p,p'-(2,2-diphenylenepropane) (or C ₆ H ₄ —C(CH ₃ ) ₂ —C ₆ H ₄ —); '-(2,2-diphenylene-1,1,1,3,3,3 hexafluoropropene) and (-C ₆ H ₄ -C(CF ₃ ) ₂ -C ₆ H ₄ -) include but are not limited to: 9,9′-diphenylfluorene; 2,2-diphenylhexafluoropropane; diphenyl sulfide; diphenyl ether; bis(phenylene)diphenylsilane; bis(phenylene)phosphine oxide bis(phenylene)benzene; bis(phenylene)naphthalene; bis(phenylene)anthracene; or bis(phenylene)naphthacene.

Polyarylene precursor monomers can be prepared by various methods known in the art, such as (a) selectively halogenating, preferably brominating, a polyphenol (preferably a bisphenol) in a solvent, where each phenolic ring is , halogenated with one halogen in one of the two positions ortho to the phenolic hydroxyl group), (b) the phenolic hydroxyl on the resulting poly(ortho-halophenol), preferably is reactive with terminal ethynyl compounds in a solvent to leave groups such as sulfonate esters (e.g., trifluoromethanesulfonate esters prepared from trifluoromethanesulfonyl halides or trifluoromethanesulfonic anhydrides) that are displaced by them. and (c) reacting the reaction product of step (b) with an ethynyl-containing compound or ethynyl synthon in the presence of an arylethynylation catalyst, preferably a palladium catalyst, and an acid acceptor to form halogen and trifluoro It may be prepared by simultaneously replacing the methylsulfonate with an ethynyl-containing group (eg, acetylene, phenylacetylene, substituted phenylacetylene or substituted acetylene). Further description of this synthesis is provided in International Publication No. WO 97/10193 (Babb).

Ethynyl aromatic monomers of formula (I) are useful for preparing polymers of either formula (II) or (III). Polymerization of ethynyl aromatic monomers is well within the capabilities of those skilled in the art. The specific conditions for polymerization will depend on a variety of factors, including the specific ethynyl aromatic monomer(s) to be polymerized and the desired properties of the resulting polymer, but general conditions for polymerization are , International Publication No. WO 97/10193 (Babb).

Particularly suitable polyarylenes for use in the present invention include those sold as SiLK™ semiconductor dielectrics (available from Dow Electronic Materials, Marlborough, Massachusetts). Other particularly suitable polyarylenes include WO 00/31183, WO 98/11149, WO 97/10193, WO 91/09081, EP 755957, and U.S. Pat. 5,115,082; 5,155,175; 5,179,188; 5,874,516; and 6,093,636 mentioned.

Suitable cyclic olefin materials are poly(cyclic olefins), which may be thermoplastic, preferably 2000 to 200,000 daltons, more preferably 5000 to 100,000 daltons, even more preferably 2000 to 200,000 daltons. It may have a weight average molecular weight (Mw) of 50,000 Daltons. Preferred poly(cyclic olefins) have a softening temperature (melt viscosity at 3,000 PaS) of at least 100°C, more preferably at least 140°C. Suitable poly(cyclic olefins) also preferably have a glass transition temperature (Tg) of at least 60°C, more preferably 60-200°C, and most preferably 75-160°C.

Preferred poly(cyclic olefins) comprise repeating monomers of cyclic olefins and acyclic olefins, or ring-opening polymers based on cyclic olefins. Cyclic olefins suitable for use in the present invention include those derived from norbornene-based olefins, tetracyclododecene-based olefins, dicyclopentadiene-based olefins, Diels-Alder polymers such as furans and maleimides, and derivatives thereof. selected. Derivatives include alkyl (preferably C ₁ -C ₂₀ alkyl, more preferably C ₁ -C ₁₀ alkyl), alkylidene (preferably C ₁ -C ₂₀ alkylidene, more preferably C ₁ -C ₁₀ alkylidene), aralkyl ( preferably C ₆ -C ₃₀ aralkyl, more preferably C ₆ -C ₁₈ aralkyl), cycloalkyl (preferably C ₃ -C ₃₀ cycloalkyl, more preferably C ₃ -C ₁₈ cycloalkyl), ether, acetyl, aromatic family, ester, hydroxy, alkoxy, cyano, amide, imide, and silyl-substituted derivatives. Particularly preferred cyclic olefins for use in the present invention include those selected from and combinations thereof,

式中、各Ｒ^１及びＲ^２は、独立に、Ｈ及びアルキル基（好ましくはＣ_１－Ｃ_２０アルキル、より好ましくはＣ_１－Ｃ_１０アルキル）から選択され、並びに各Ｒ^３は、独立に、Ｈ、置換された及び置換されていないアリール基（好ましくはＣ_６－Ｃ_１８アリール）、アルキル基（好ましくはＣ_１－Ｃ_２０アルキル、より好ましくはＣ_１－Ｃ_１０アルキル）、シクロアルキル基（好ましくはＣ_３－Ｃ_３０シクロアルキル基、より好ましくはＣ_３－Ｃ_１８シクロアルキル基）、アラルキル基（好ましくはＣ_６－Ｃ_３０アラルキル、より好ましくはＣ_６－Ｃ_１８アラルキル基、例えばベンジル、フェネチル、フェニルプロピルなど）、エステル基、エーテル基、アセチル基、アルコール（好ましくはＣ_１－Ｃ_１０アルコール）、アルデヒド基、ケトン、ニトリル、及びこれらの組み合わせから選択される。

wherein each R ¹ and R ² is independently selected from H and an alkyl group (preferably C ₁ -C ₂₀ alkyl, more preferably C ₁ -C ₁₀ alkyl), and each R ³ is independently , H, substituted and unsubstituted aryl groups (preferably C ₆ -C ₁₈ aryl), alkyl groups (preferably C ₁ -C ₂₀ alkyl, more preferably C ₁ -C ₁₀ alkyl), cycloalkyl groups (preferably C ₃ -C ₃₀ cycloalkyl groups, more preferably C ₃ -C ₁₈ cycloalkyl groups), aralkyl groups (preferably C ₆ -C ₃₀ aralkyl groups, more preferably C ₆ -C ₁₈ aralkyl groups, such as benzyl , phenethyl, phenylpropyl, etc.), ester groups, ether groups, acetyl groups, alcohols (preferably C ₁ -C ₁₀ alcohols), aldehyde groups, ketones, nitriles, and combinations thereof.

Preferred acyclic olefins are selected from branched and unbranched C ₂ -C ₂₀ alkenes (preferably C ₂ -C ₁₀ alkenes). More preferably, the acyclic olefin has the structure (R ⁴ ) ₂ C═C(R ⁴ ) ₂ , where each R ⁴ is independently H and an alkyl group (preferably C ₁ -C ₂₀ alkyl , more preferably C ₁ -C ₁₀ alkyl). Particularly preferred acyclic olefins for use in the present invention include those selected from ethene, propene and butene, with ethene being most preferred.

Methods of making cyclic olefin copolymers are known in the art. For example, cyclic olefin copolymers can be prepared by chain polymerization of cyclic and non-cyclic monomers. When norbornene reacts with ethene under these conditions, an ethene-norbornene copolymer containing alternating norbornanediyl and ethylene units is obtained. Examples of copolymers made by this method include those available under the TOPAS™ (manufactured by Topas Advanced Polymers) and APEL™ (manufactured by Mitsui Chemicals, Inc.) brands. A suitable method for making these copolymers is disclosed in US Pat. No. 6,008,298. Cycloolefin copolymers can also be prepared by ring-opening metathesis polymerization of various cyclic monomers followed by hydrogenation. Polymers resulting from this type of polymerization can be conceptually thought of as copolymers of ethene and cyclic olefin monomers (eg, alternating units of ethylene and cyclopentane-1,3-diyl). Examples of copolymers produced by this ring-opening method include those offered under the ZEONOR™ (from Zeon Chemicals) and ARTON™ (from JSR Corporation) brands. A suitable method for making these copolymers by this ring-opening method is disclosed in US Pat. No. 5,191,026.

Arylcyclobutene oligomers useful as the curable adhesive material of the present invention are well known in the art. Suitable arylcyclobutene oligomers include, but are not limited to, those having the formula:

式中、Ｂはｎ価の連結基であり；Ａｒは多価アリール基であり、シクロブテン環の炭素原子は、Ａｒの同じ芳香族環上の隣の炭素原子に結合し；ｍは１以上の整数であり；ｎは１以上の整数であり；並びに、Ｒ^５は、一価の基である。好ましくは多価アリール基Ａｒは、１～３個の芳香族炭素環式又はヘテロ芳香族環で構成されてもよい。アリール基は単一芳香族環、より好ましくはフェニル環を含むのが好ましい。アリール基は、場合により、（Ｃ_１－Ｃ_６）アルキル、トリ（Ｃ_１－Ｃ_６）アルキルシリル、（Ｃ_１－Ｃ_６）アルコキシ及びハロから選択される１～３個の基、好ましくは（Ｃ_１－Ｃ_６）アルキル、トリ（Ｃ_１－Ｃ_３）アルキルシリル、（Ｃ_１－Ｃ_３）アルコキシ及びクロロの１つ以上、より好ましくは（Ｃ_１－Ｃ_３）アルキル、トリ（Ｃ_１－Ｃ_３）アルキルシリル及び（Ｃ_１－Ｃ_３）アルコキシの１つ以上で置換される。アリール基は置換されていないのが好ましい。ｎ＝１又は２が好ましく、より好ましくはｎ＝１である。ｍ＝１～４が好ましく、より好ましくはｍ＝２～４、さらにより好ましくはｍ＝２である。好ましくはＲ^５は、Ｈ及び（Ｃ_１－Ｃ_６）アルキル、より好ましくはＨ及び（Ｃ_１－Ｃ_３）アルキルから選択される。好ましくはＢは、１つ以上の炭素－炭素二重結合（エチレン性不飽和）を含む。好適な一価Ｂ基は、好ましくは式－［Ｃ（Ｒ^１０）＝ＣＲ^１１］ｘＺを有し、ここでＲ^１０及びＲ^１１は、独立に、水素、（Ｃ_１－Ｃ_６）アルキル、及びアリールから選択され；Ｚは、水素、（Ｃ_１－Ｃ_６）アルキル、アリール、シロキサニル、－ＣＯ_２Ｒ^１２から選択され；各Ｒ^１２は、独立に、Ｈ、（Ｃ_１－Ｃ_６）アルキル、アリール、アラルキル、及びアルカリールから選択され；並びに、ｘ＝１又は２である。好ましくは、Ｒ^１０及びＲ^１１は、独立に、Ｈ、（Ｃ_１－Ｃ_３）アルキル、及びアリールから選択され、より好ましくはＨ及び（Ｃ_１－Ｃ_３）アルキルから選択される。Ｒ^１２は、（Ｃ_１－Ｃ_３）アルキル、アリール及びアラルキルであるのが好ましい。Ｚは、好ましくはシロキシルである。好ましいシロキシル基は、式－［Ｓｉ（Ｒ^１３）_２－Ｏ］ｐ－Ｓｉ（Ｒ^１３）_２－を有し、ここで各Ｒ^１３は、独立に、Ｈ、（Ｃ_１－Ｃ_６）アルキル、アリール、アラルキル、及びアルカリールから選択され；ｐは１以上の整数である。Ｒ^１３は、（Ｃ_１－Ｃ_３）アルキル、アリール及びアラルキルから選択される。好適なアラルキル基としては、ベンジル、フェネチル及びフェニルプロピルが挙げられる。

wherein B is an n-valent linking group; Ar is a polyvalent aryl group, the carbon atom of the cyclobutene ring is bonded to the next carbon atom on the same aromatic ring of Ar; is an integer; n is an integer greater than or equal to 1; and R ⁵ is a monovalent group. Preferably, the polyvalent aryl group Ar may consist of 1 to 3 aromatic carbocyclic or heteroaromatic rings. Preferably, the aryl group contains a single aromatic ring, more preferably a phenyl ring. Aryl groups optionally have 1 to 3 groups selected from (C ₁ -C ₆ )alkyl, tri(C ₁ -C ₆ )alkylsilyl, (C ₁ -C ₆ )alkoxy and halo, preferably one or more of (C ₁ -C ₆ )alkyl, tri(C ₁ -C ₃ )alkylsilyl, (C ₁ -C ₃ )alkoxy and chloro, more preferably (C ₁ -C ₃ )alkyl, tri(C ₁ -C ₃ )alkylsilyl and (C ₁ -C ₃ )alkoxy. Aryl groups are preferably unsubstituted. Preferably n=1 or 2, more preferably n=1. Preferably m=1-4, more preferably m=2-4, even more preferably m=2. Preferably R ⁵ is selected from H and (C ₁ -C ₆ )alkyl, more preferably H and (C ₁ -C ₃ )alkyl. Preferably B contains one or more carbon-carbon double bonds (ethylenic unsaturation). Suitable monovalent B groups preferably have the formula -[C(R ¹⁰ )=CR ¹¹ ]xZ, where R ¹⁰ and R ¹¹ are independently hydrogen, (C ₁ -C ₆ )alkyl, and aryl; Z is selected from hydrogen, (C ₁ -C ₆ )alkyl, aryl, siloxanyl, —CO ₂ R ¹² ; each R ¹² is independently H, (C ₁ -C ₆ ) is selected from alkyl, aryl, aralkyl and alkaryl; and x=1 or 2. Preferably R ¹⁰ and R ¹¹ are independently selected from H, (C ₁ -C ₃ )alkyl and aryl, more preferably from H and (C ₁ -C ₃ )alkyl. R ¹² is preferably (C ₁ -C ₃ )alkyl, aryl and aralkyl. Z is preferably siloxyl. Preferred siloxyl groups have the formula -[Si(R ¹³ ) ₂ -O]p-Si(R ¹³ ) ₂ -, where each R ¹³ is independently H, (C ₁ -C ₆ )alkyl , aryl, aralkyl, and alkaryl; p is an integer of 1 or greater. R ¹³ is selected from (C ₁ -C ₃ )alkyl, aryl and aralkyl. Suitable aralkyl groups include benzyl, phenethyl and phenylpropyl.

Preferably, the arylcyclobutene oligomer comprises one or more oligomers of the formula:

式中、各Ｒ^６は、独立に、Ｈ及び（Ｃ_１－Ｃ_６）アルキルから選択され、好ましくはＨ及び（Ｃ_１－Ｃ_３）アルキルから選択され；各Ｒ^７は、独立に、（Ｃ_１－Ｃ_６）アルキル、トリ（Ｃ_１－Ｃ_６）アルキルシリル、（Ｃ_１－Ｃ_６）アルコキシ及びハロから選択され；各Ｒ^８は、独立に、二価のエチレン性不飽和有機基であり；各Ｒ^９は、独立に、Ｈ、（Ｃ_１－Ｃ_６）アルキル、アラルキル及びフェニルから選択され；ｐは１以上の整数であり；並びにｑは０～３の整数である。各Ｒ^６は、好ましくは独立に、Ｈ及び（Ｃ_１－Ｃ_３）アルキルから選択され、より好ましくは各Ｒ^６はＨである。各Ｒ７は、独立に、（Ｃ_１－Ｃ_６）アルキル、トリ（Ｃ_１－Ｃ_３）アルキルシリル、（Ｃ_１－Ｃ_３）アルコキシ及びクロロから選択されるのが好ましく、より好ましくは（Ｃ_１－Ｃ_３）アルキル、トリ（Ｃ_１－Ｃ_３）アルキルシリル及び（Ｃ_１－Ｃ_３）アルコキシから選択される。好ましくは各Ｒ^８は、独立に、（Ｃ_２－Ｃ_６）アルケニルから選択され、より好ましくは各Ｒ^８は－ＣＨ＝ＣＨ－である。各Ｒ^９は、好ましくは（Ｃ_１－Ｃ_３）アルキルから選択され、より好ましくは各Ｒ^９はメチルである。好ましくはｐ＝１～５、より好ましくはｐ＝１～３であり、さらにより好ましくはｐ＝１である。ｑ＝０であるのが好ましい。特に好ましいアリールシクロブテンオリゴマー、１，３－ビス（２－ビシクロ［４．２．０］オクタ－１，３，５－トリエン－３－イルエテニル）－１，１，３，３－テトラメチルジシロキサン（「ＤＶＳ－ｂｉｓＢＣＢ」）は、以下の式を有する。

wherein each R ⁶ is independently selected from H and (C ₁ -C ₆ )alkyl, preferably selected from H and (C ₁ -C ₃ )alkyl; each R ⁷ is independently selected from ( C ₁ -C ₆ )alkyl, tri(C ₁ -C ₆ )alkylsilyl, (C ₁ -C ₆ )alkoxy and halo; each R ⁸ is independently a divalent ethylenically unsaturated organic group; each R ⁹ is independently selected from H, (C ₁ -C ₆ )alkyl, aralkyl and phenyl; p is an integer greater than or equal to 1; and q is an integer from 0 to 3. Each R ⁶ is preferably independently selected from H and (C ₁ -C ₃ )alkyl, more preferably each R ⁶ is H. Preferably, each R7 is independently selected from (C ₁ -C ₆ )alkyl, tri(C ₁ -C ₃ )alkylsilyl, (C ₁ -C ₃ )alkoxy and chloro, more preferably (C ₁ -C ₃ )alkyl, tri(C ₁ -C ₃ )alkylsilyl and (C ₁ -C ₃ )alkoxy. Preferably each R ⁸ is independently selected from (C ₂ -C ₆ )alkenyl, more preferably each R ⁸ is -CH=CH-. Each R ⁹ is preferably selected from (C ₁ -C ₃ )alkyl, more preferably each R ⁹ is methyl. Preferably p=1-5, more preferably p=1-3, even more preferably p=1. Preferably q=0. A particularly preferred arylcyclobutene oligomer, 1,3-bis(2-bicyclo[4.2.0]octa-1,3,5-trien-3-ylethenyl)-1,1,3,3-tetramethyldisiloxane (“DVS-bisBCB”) has the formula:

Arylcyclobutene oligomers are prepared by any suitable means, such as those described in U.S. Pat. Nos. 4,812,588; 5,136,069; may be prepared by Suitable arylcyclobutene oligomers are also commercially available under the CYCLOTENE™ brand available from Dow Electronic Materials. Arylcyclobutene oligomers may be used as is or may be further purified by any suitable means.

Any curable vinyl aromatic oligomer can be used as the curable adhesive material in the present invention. Such vinyl aromatic oligomers are typically oligomers of one or more reactive ethylenically unsaturated comonomers and vinyl aromatic monomers. Preferably the vinyl aromatic monomer contains one vinyl group. Suitable vinyl aromatic monomers are unsubstituted vinyl aromatic monomers and substituted vinyl aromatic monomers wherein one or more hydrogens are (C ₁ -C ₆ )alkyl, (C ₁ -C ₆ ) substituted with a substituent selected from the group consisting of alkoxy, halo and amino; Exemplary vinyl aromatic monomers include, but are not limited to, styrene, vinyltoluene, vinylxylene, vinylanisole, vinyldimethoxybenzene, vinylaniline, halostyrenes such as fluorostyrene, α-methylstyrene, β-methoxystyrene, Ethylvinylbenzene, vinylpyridine, vinylimidazole, vinylpyrrole, and mixtures thereof. Preferred vinyl aromatic monomers are styrene, vinyltoluene, vinylxylene, vinylanisole, ethylvinylbenzene and mixtures thereof. Preferred reactive comonomers are reactive moieties in addition to the olefinic (or ethylenically unsaturated) moieties used to form the vinyl aromatic oligomer, i.e., further polymerization after formation of the vinyl aromatic oligomer ( or cross-linkable), such as allyl moieties or vinyl groups. Such reactive comonomers may suitably be any unsymmetrical diene or triene that can be further polymerized by Diels-Alder reaction after oligomerization with a vinyl aromatic monomer. More preferably, the reactive comonomer contains allyl moieties in addition to the ethylenic unsaturation used to form the vinyl aromatic oligomer, and even more preferably contains allyl ester moieties in addition to this ethylenic unsaturation. . Exemplary reactive comonomers useful for forming vinyl aromatic oligomers include vinylcyclohexenes, vinyl ethers, unsymmetrical dienes or trienes such as terpene monomers, dicyclopentadiene, diallyl maleate, allyl acrylate, allyl methacrylate, allyl thinner mate, diallyl fumarate, allyl tiglate, divinylbenzene, and mixtures thereof. Preferred reactive comonomers are diallyl maleate, allyl acrylate, allyl methacrylate, allyl cinnamate, diallyl fumarate and mixtures thereof, more preferably diallyl maleate, allyl methacrylate and mixtures thereof. Exemplary terpene monomers include, but are not limited to, limonene, dipentene, myrcene, and the like. Those skilled in the art will appreciate that one or more second comonomers may also be used to form the vinyl aromatic oligomer. Such second comonomers are ethylenically unsaturated but do not contain reactive moieties. Exemplary second comonomers include (meth)acrylic acid, (meth)acrylamide, (C1-C10)alkyl (meth)acrylates, aromatic (meth)acrylates, substituted ethylene monomers, and poly(alkylene oxide ) monomers, including but not limited to.

The molar ratio of vinyl aromatic monomer to comonomer in such vinyl aromatic oligomers is preferably from 99:1 to 1:99, more preferably from 95:5 to 5:95, even more preferably from 90:10 to It is 10:90. Such vinyl aromatic oligomers may be prepared by any suitable method, for example by any method known in the art. Vinyl aromatic oligomers are typically prepared by free radical polymerization of vinyl aromatic monomers and comonomers. Preferred vinyl aromatic oligomers contain unreacted allyl moieties that allow such oligomers to be further cured.

A wide variety of materials may be used as release additives in temporary bonding compositions, provided that such materials do not react with and cure the adhesive material under conditions of storage and use. It is non-curable under the conditions used in In addition, the release additive should be compatible with the temporary bonding composition, i.e., the release additive should include the adhesive material and any other components used in the temporary bonding composition, such as organic It must be dispersible, miscible or otherwise substantially compatible with the solvent. If organic solvents (or mixed solvent systems) are used in the temporary bonding composition, the release additive and curable adhesive material should be soluble in such solvents. The stripping additives in the present invention are sufficiently non-volatile so that they do not substantially evaporate under the conditions of use, i.e. they are substantially non-volatile during deposition processes, such as spin-coating, or to remove organic solvents or It does not evaporate during any subsequent heating steps used to cure the adhesive material. When a film or layer of temporary bonding composition is cast, for example by spin coating, much (or all) of the solvent evaporates. The release additive is soluble in any organic solvent used, but preferably not completely soluble in the curable adhesive material. The release additive is significantly more hydrophilic than the cured adhesive material. Without being bound by theory, it is believed that upon curing of the adhesive material, the release additive phase separates and preferentially migrates toward the active surface of the wafer (the surface that is more hydrophilic than the carrier surface). The use of suitable hydrophilic moieties in the exfoliation additive allows complete dispersion, or preferably dissolution, of the exfoliation additive in the temporary bonding composition, with migration of the exfoliation additive toward more hydrophilic surfaces. allows phase separation of the release additive during curing of the adhesive material. Any material that does not phase separate from the adhesive material during curing will not function as a release additive according to the present invention.

Generally, the exfoliating additive will contain one or more relatively hydrophilic moieties, such as one or more oxygen-, nitrogen-, phosphorus-, and sulfur-containing moieties. Suitable exfoliating additives include, but are not limited to: ethers, esters, carboxylates, alcohols, thioethers, thiols, amines, imines, amides, phosphate esters, sulfonate esters, and mixtures thereof. Preferably, the exfoliating additive contains one or more polar end groups, which contain one or more of oxygen, nitrogen and sulfur, preferably oxygen. Exemplary polar end groups include alkoxy, aryloxy, hydroxy, carboxylate, alkoxycarbonyl, mercapto, alkylthio, primary amines, secondary amines, and tertiary amines, with preferred end groups being (C ₁ - C ₆ )alkoxy, (C ₆ -C ₁₀ )aryloxy, hydroxy, carboxylate, (C ₁ -C ₆ )alkoxycarbonyl, mercapto, (C ₁ -C ₆ )alkylthio, amino, (C ₁ -C ₆ ) alkylamino and di(C ₁ -C ₆ )alkylamino, more preferably (C ₁ -C ₆ )alkoxy, (C ₆ -C ₁₀ )aryloxy, hydroxy, carboxylate and (C1-C6 ) alkoxycarbonyl, even more preferably selected from (C ₁ -C ₆ )alkoxy, hydroxy, carboxylate and (C ₁ -C ₆ )alkoxycarbonyl. Particularly preferred polar end groups are selected from hydroxy, methoxy, ethoxy, propoxy, butoxy, carboxyl and acetoxy. Preferably, the exfoliating additive does not contain silicon.

Suitable exfoliation additives have a number average molecular weight (Mn) of ≤10,000 Daltons, preferably ≤7500 Daltons, more preferably ≤7000 Daltons. The stripping additive is such that the stripping additive becomes substantially non-volatile during the conditions of use (i.e. <5%, preferably <3%, more preferably <1% of the stripping additive volatilizes during use) have a sufficient minimum molecular weight (Mn) to Preferably the exfoliation additive has a Mn of ≧500 Daltons. A preferred range of Mn is 500-10,000 Daltons, more preferably 500-7500 Daltons, even more preferably 500-7000 Daltons. The exfoliation additive may be a linear polymer; a branched polymer, such as a dendritic polymer, a star polymer, etc.; Linear polymers are more preferred. Without being bound by theory, it is believed that linear polymers are better able to migrate through the cured adhesive material phase towards the hydrophilic wafer surface compared to branched polymers.

Polyethers are preferred release additives. Polyether compounds include alkylene oxide homopolymers and alkylene oxide copolymers, and such copolymers may be random or block. Polyalkylene oxide release additives may have a variety of polar end groups, preferably such polar end groups are hydroxy, (C ₁ -C ₆ )alkoxy, and (C ₁ -C ₆ )alkoxycarbonyl. , more preferably hydroxy, (C ₁ -C ₃ )alkoxy, and acetoxy. Preferred polyether compounds are polyglycols (or polyalkylene oxides), such as poly(C ₁ -C ₄ ) alkylene oxide compounds, which may contain a single type of alkylene oxide repeat unit or two or more different alkylene oxide repeat units. may contain Preferred polyether compounds include polyethylene glycol, polypropylene glycol, poly(1,3-propanediol), poly(tetrahydrofuran), ethylene oxide-propylene oxide copolymers, ethylene oxide-butylene oxide copolymers, and mixtures thereof. Preferably, when the exfoliation additive contains butylene oxide as repeat units, it is a copolymer with one or more different alkylene oxide repeat units. Those skilled in the art will appreciate that mixtures of release additives may be used in the temporary bonding compositions of the present invention. Suitable exfoliating additives include PLURONIC®, TETRONIC and POLYTHF (available from BASF, Ludwigshafen, Germany), FORTEGRA (The Dow Chemical Company, Midland, Michigan), and TERATHANE ( Invista, Wichita, Kansas), all of which may be used without further purification.

One or more organic solvents are preferably used in the temporary binding composition. Any solvent or mixture of solvents that dissolves or disperses, preferably dissolves, the curable adhesive material and the release additive may be suitably used in the temporary bonding composition. Exemplary organic solvents include, but are not limited to: aromatic hydrocarbons such as toluene, xylene, and mesitylene; alcohols such as 2-methyl-1-butanol, 4-methyl-2-pentanol and methylisobutyl carbi esters such as ethyl lactate, propylene glycol methyl ether acetate, and methyl 2-hydroxyisobutyrate; lactones such as gamma-butyrolactone; lactams such as N-methylpyrrolidinone; ethers such as propylene glycol methyl ether and dipropylene glycol dimethyl ether. isomers (commercially available as PROGLYDE™ DMM from The Dow Chemical Company); ketones such as cyclohexanone and methylcyclohexanone; and mixtures thereof.

<<Third Embodiment>>
As a preferred embodiment, the adhesive composition used in the present invention contains, for example, the thermosetting polymer described below.
As the adhesive composition of the third embodiment, for example, a thermosetting polymer described in Japanese Patent No. 6528747 can be used.
The thermosetting polymer is not particularly limited, but a preferred example is a repeating unit represented by the following formula (3) and optionally a repeating unit represented by the following formula (4), with a weight-average molecular weight of 3,000 to 500,000 (hereinafter also referred to as silicone A).

［式中、Ｒ^６～Ｒ^９は、それぞれ独立に、炭素数１～８の１価炭化水素基を表す。また、ｍは１～１００の整数を表す。Ａ及びＢは、０＜Ａ＜１、０＜Ｂ＜１、かつＡ＋Ｂ＝１を満たす正数である。Ｔ^１及びＴ^２は、下記式（５）で表される２価の有機基である。

[In the formula, R ⁶ to R ⁹ each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms. In addition, m represents an integer of 1-100. A and B are positive numbers satisfying 0<A<1, 0<B<1, and A+B=1. T ¹ and T ² are divalent organic groups represented by the following formula (5).

（式中、Ａ^１は、単結合、又は下記式

(Wherein, A ¹ is a single bond, or the following formula

で表される基から選ばれる２価の有機基である。Ｒ^１０及びＲ^１１は、それぞれ独立に、炭素数１～４のアルキル基又はアルコキシ基である。ｈは、それぞれ独立に、０、１又は２である。）］

is a divalent organic group selected from groups represented by R ¹⁰ and R ¹¹ are each independently an alkyl group or an alkoxy group having 1 to 4 carbon atoms. h is each independently 0, 1 or 2; )]

Examples of monovalent hydrocarbon groups represented by R ⁶ to R ⁹ include alkyl groups such as methyl group and ethyl group, and aryl groups such as phenyl group. m is preferably an integer of 3-60, more preferably 8-40. Further, A is preferably 0.3 to 0.8, B is preferably 0.2 to 0.7, A / B is preferably 0.1 to 20, and 0.5 to 5. is more preferable.

Further, as a preferred example of the thermosetting polymer, a repeating unit represented by the following formula (6) and optionally a repeating unit represented by the following formula (7) having a weight average molecular weight of 3,000 to 500,000 siloxane bond-containing polymers (hereinafter also referred to as silicone B) may also be mentioned.

［式中、Ｒ^１２～Ｒ^１５は、それぞれ独立に、炭素数１～８の１価炭化水素基を表す。ｐは、１～１００の整数を表す。Ｃ及びＤは、０＜Ｃ≦１、０≦Ｄ＜１、かつＣ＋Ｄ＝１を満たす正数である。Ｔ^３及びＴ^４は、下記式（８）で表される２価の有機基である。

[In the formula, R ¹² to R ¹⁵ each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms. p represents an integer from 1 to 100; C and D are positive numbers satisfying 0<C≦1, 0≦D<1, and C+D=1. T3 and T4 ^{are divalent} organic groups represented by the following formula (8).

（式中、Ａ^２は、単結合、又は下記式

(Wherein, A ² is a single bond, or the following formula

で表される基から選ばれる２価の有機基である。Ｒ^１６及びＲ^１７は、それぞれ独立に、炭素数１～４のアルキル基又はアルコキシ基である。ｋは、それぞれ独立に、０、１又は２である。）］

is a divalent organic group selected from groups represented by R ¹⁶ and R ¹⁷ are each independently an alkyl group or an alkoxy group having 1 to 4 carbon atoms. k is 0, 1 or 2 each independently. )]

In this case, examples of monovalent hydrocarbon groups represented by R ¹¹ to R ¹⁴ include the same groups as those represented by R ⁵ to R ⁸ . p is preferably an integer of 3-60, more preferably 8-40. Also, C is preferably 0.3 to 1, D is preferably 0 to 0.7, and C+D=1.

The adhesive layer formed using the thermosetting polymer as the adhesive composition of the third embodiment is a layer of a cured thermosetting resin composition containing silicone A or silicone B as a main component. is preferred. Silicone A and silicone B can be used in combination. In that case, the ratio (polymerization ratio) is preferably silicone A:silicone B=0.1:99.9 to 99.9:0.1, more preferably silicone A:silicone B=20:80 to 80:20. is.

A thermosetting resin composition containing silicone A as a main component contains, for thermosetting, an amino condensate modified with formalin or formalin-alcohol, an average of 2 or more methylol groups per molecule, or an alkoxy It contains one or more cross-linking agents selected from phenolic compounds having methylol groups and epoxy compounds having an average of two or more epoxy groups per molecule.

On the other hand, a thermosetting resin composition containing silicone B as a main component is a phenolic compound having an average of 2 or more phenolic groups per molecule and an average of 2 It contains one or more cross-linking agents selected from epoxy compounds having one or more epoxy groups.

In addition, the thermosetting resin composition containing silicone A and silicone B has one or more crosslinked compounds selected from epoxy compounds having an average of two or more epoxy groups per molecule for thermosetting. containing agents.

Examples of the amino condensates include melamine resins and urea resins. For formalin or formalin-alcohol-modified melamine resins, modified melamine monomers (e.g., trimethoxymethylmonomethylolmelamine) or multimers thereof (e.g., oligomers such as dimers and trimers) are prepared by known methods. and addition condensation polymerization with formaldehyde until the desired molecular weight is obtained. In addition, these can be used individually by 1 type or in combination of 2 or more types.

Urea resins modified with formalin or formalin-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, propoxymethylated urea condensates and the like. In addition, these can be used individually by 1 type or in combination of 2 or more types. Formalin or formalin-alcohol-modified urea resins can be prepared, for example, by modifying a urea condensate of a desired molecular weight with formalin by methylolation or further by alkoxylating it with an alcohol according to known methods. can be done.

Phenolic compounds having two or more methylol groups or alkoxymethylol groups on average per molecule include, for example, (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2' ,6,6'-tetramethoxymethylbisphenol A and the like. In addition, these can be used individually by 1 type or in combination of 2 or more types.

Epoxy compounds having an average of two or more epoxy groups in one molecule are not particularly limited, but bifunctional, trifunctional, or tetrafunctional or higher polyfunctional epoxy resins, such as those manufactured by Nippon Kayaku Co., Ltd. EOCN-1020 (see the formula below), EOCN-102S, XD-1000, NC-2000-L, EPPN-201, GAN, NC6000, and those represented by the formula below.

Phenolic compounds having an average of two or more phenol groups in one molecule include m- or p-type cresol novolak resins (eg, EP-6030G manufactured by Asahi Organic Chemicals Industry Co., Ltd.), trifunctional phenol compounds ( Examples include Tris-P-PA manufactured by Honshu Chemical Industry Co., Ltd.), tetrafunctional phenol compounds (eg, TEP-TPA manufactured by Asahi Organic Chemical Industry Co., Ltd.), and the like.

The amount of the cross-linking agent in the thermosetting resin composition is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, more preferably 0.2 to 30 parts by mass, with respect to 100 parts by mass of the thermosetting polymer. 1 to 20 parts by mass. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

In addition, 10 parts by mass or less of a curing catalyst such as an acid anhydride may be added to the thermosetting resin composition with respect to 100 parts by mass of the thermosetting polymer.

<<Other Ingredients>>
The adhesive composition used in the present invention may contain a solvent for the purpose of adjusting the viscosity, etc. Specific examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but these is not limited to

More specifically, the solvent includes hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, and diisobutyl. Examples include, but are not limited to, ketones, 2-octanone, 2-nonanone, 5-nonanone, and the like. Such solvents can be used singly or in combination of two or more.

When the adhesive composition used in the present invention contains a solvent, the content thereof is appropriately set in consideration of the desired viscosity of the composition, the coating method to be employed, the thickness of the film to be produced, etc. It is in the range of about 10 to 90% by mass with respect to the entire adhesive composition.

Although the viscosity of the adhesive composition used in the present invention is not particularly limited, it is usually 500 to 20,000 mPa·s, preferably 1,000 to 5,000 mPa·s at 25°C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the types of solvents used, their ratios, the concentration of film constituents, etc., in consideration of various factors such as the coating method used and the desired film thickness. is.
In the present invention, the film-constituting component means a component other than the solvent contained in the composition.

As a method for producing the adhesive composition, for example, taking the above <<first embodiment>> as an example, the component (A) and, when used, the component (B) and/or the solvent are mixed. It can be manufactured by
The mixing order is not particularly limited, but one example of a method for easily and reproducibly producing the adhesive composition of the present invention is to dissolve component (A) and component (B) in a solvent. and a method of dissolving a part of component (A) and component (B) in a solvent, dissolving the rest in a solvent, and mixing the resulting solutions. In addition, when preparing the adhesive composition, it may be appropriately heated within a range in which the components are not decomposed or deteriorated.
In the present invention, for the purpose of removing foreign matter, the adhesive composition may be filtered using a filter or the like during the production of the adhesive composition or after all the components are mixed.

The method for forming the adhesive layer from the adhesive composition will be described in detail in the description of (Laminate production method) below.

<Photoresponsive release layer>
A photoresponsive release layer is interposed between the supporting substrate and the adhesive layer.
A photoresponsive release layer contacts the adhesive layer.
The photoresponsive release layer preferably contacts the support substrate.

The photoresponsive release layer is formed from a release agent composition containing a compound having an azobenzene skeleton,

<<Removing agent composition>>
The release agent composition contains a compound having an azobenzene skeleton.
In addition to the compound having an azobenzene skeleton, the release agent composition may contain other components such as a solvent, for example, in order to improve coatability.

<<<Compound having an azobenzene skeleton>>>
A preferred embodiment of the compound having an azobenzene skeleton includes a compound containing a group represented by the following formula (1).

（式中、ｍは０～２０の整数、ｌは１～２０の整数を示す。）

(Wherein, m is an integer of 0 to 20, l is an integer of 1 to 20.)

A more preferred embodiment of the compound containing a group represented by the following formula (1) includes a compound containing a repeating unit represented by the following formula (2).

（式中、ｍは０～２０の整数、ｌは１～２０の整数を示す。Ｒは水素原子又はメチル基を表す。）

(In the formula, m is an integer of 0 to 20, l is an integer of 1 to 20, and R represents a hydrogen atom or a methyl group.)

As the compound having an azobenzene skeleton used in the present invention, for example, if it contains a compound containing a repeating unit represented by the above formula (2), in addition to a homopolymer consisting only of such repeating units, it contains such repeating units. It may be a copolymer. That is, copolymers, which are copolymers with other comonomers, can also be used as long as the effects of the present invention are not impaired.

A more preferred embodiment of the compound containing a repeating unit represented by formula (2) above is a polymer represented by formula (3) below.

（式中、ｍは０～２０の整数、ｌは１～２０の整数、ｎは５以上の整数を示す。）

(Wherein, m is an integer of 0 to 20, l is an integer of 1 to 20, and n is an integer of 5 or more.)

A more preferred embodiment of the polymer represented by formula (3) above includes, for example, a polymer represented by formula (4) below.

（式中、ｌは１～２０の整数、ｎは５以上の整数を示す。）
本発明では、上記式（４）で表されるポリマーを含む剥離剤組成物を用いて剥離層を形成することがより好ましい。

(Wherein, l is an integer of 1 to 20, and n is an integer of 5 or more.)
In the present invention, it is more preferable to form the release layer using a release agent composition containing the polymer represented by the above formula (4).

More specific examples of the polymer represented by the formula (4) include polymers represented by the following formula (4a).

The polymer represented by formula (4a) above can be synthesized from a monomer represented by formula (m3) below. Further, the monomer represented by the formula (m3) can be, for example, 8-[4-( It can be obtained via 2-phenyldiazenyl)phenoxy]-1-octanol. The synthesis of the polymer represented by formula (4a) is described in detail in the examples below.

The release agent composition used in the present invention assumes a non-fluid state at the time of adhesion, but is softened by irradiation with ultraviolet light, resulting in a decrease in adhesive strength.
As a result, the release layer made of the release agent composition serves as an adhesive layer capable of bonding the semiconductor substrate and the support substrate during processing such as thinning of the semiconductor substrate, and after processing the semiconductor substrate, it can be easily removed by irradiation with ultraviolet light. It functions as a peelable release layer.

The release agent composition used in the present invention can control the fluidity of the release layer by irradiating it with ultraviolet light. This is thought to be due to changes. A compound having an azobenzene skeleton undergoes photoisomerization between the trans and cis isomers. As shown in the following formula, in this change in unsubstituted azobenzene, the cis isomer becomes the main component when irradiated with ultraviolet light, and the trans isomer becomes the main component when irradiated with visible light or heated.
In the present invention, it is preferable to use ultraviolet light with a wavelength of 300 to 400 nm and visible light with a wavelength of 400 to 600 nm as the ultraviolet light and visible light used for controlling the fluidity of the release layer.

Increasing the molecular weight of a compound containing a group represented by the above formula (1), for example, a polymer represented by the above formula (3) has the effect of increasing the adhesive strength, while at the same time the fluidity when photo-liquefied. performance may decrease and desorption performance may decrease.
Therefore, the compound containing the group represented by the above formula (1), for example, the weight average molecular weight of the polymer represented by the above formula (3) is preferably 1,000 or more, more preferably 3, in terms of standard polystyrene. ,000 or more, preferably 100,000 or less, more preferably 50,000 or less from the viewpoint of ensuring the solubility of the compound in a solvent. The weight average molecular weight of the polymer can be measured, for example, under the following conditions.
Apparatus: HLC-8320GPC manufactured by Tosoh Corporation
GPC column: TSKgel Super-MultiporeHZ-N (2 columns) manufactured by Tosoh Corporation
Column temperature: 40°C
Flow rate (flow rate): 0.35 mL/min Eluent (elution solvent): Tetrahydrofuran Standard sample: Polystyrene (manufactured by Showa Denko KK)

<<<Other Ingredients>>>
The stripping composition used in the present invention usually contains a solvent.
The solvent can be appropriately selected depending on the purpose, and examples thereof include organic solvents such as mesitylene, anisole, cyclohexanone, N-methyl-2-pyrrolidone, as long as the compound having an azobenzene skeleton is dissolved. , is not particularly limited.
For the purpose of adjusting liquid physical properties such as viscosity and surface tension, a solvent that does not dissolve a compound having an azobenzene skeleton may be used together with a solvent that dissolves a compound having an azobenzene skeleton.
A solvent can be used individually by 1 type or in combination of 2 or more types.

When the release agent composition used in the present invention contains a solvent, the content thereof is appropriately determined in consideration of the viscosity of the desired composition, the coating method to be employed, the thickness of the film to be produced, the molecular weight of the compound having an azobenzene skeleton, and the like. Although it is set, it is in the range of about 50 to 95% by mass with respect to the entire release agent composition.
That is, the lower limit of the film-constituting component concentration of the release agent composition is usually about 5% by mass from the viewpoint of preparing a composition that reproducibly gives a film of a desired and sufficient thickness to the composition as a whole. and its upper limit is usually about 50% by mass from the viewpoint of reproducibly preparing a highly uniform composition in which the membrane constituents are dissolved.

<Laminate characteristics>
The thickness of the adhesive layer provided in the laminate of the present invention is from the viewpoint of obtaining a good bump deformation suppression effect, and the thickness of the entire laminate is secured to improve impact resistance and handleability during semiconductor substrate processing. It is usually 20 μm or more, preferably 30 μm or more, more preferably 40 μm or more from the viewpoint of increasing the thickness of the film. It is preferably 100 μm or less. In order to obtain the effect of suppressing bump deformation, it is necessary to form the adhesive layer so that the thickness of the adhesive layer is higher than the height of the bump.
The thickness of the photoresponsive peeling layer provided in the laminate of the present invention is not particularly limited, but from the viewpoint of obtaining good peelability with good reproducibility by ultraviolet light irradiation, it is usually 0.1 μm or more, The thickness is preferably 0.5 μm or more, and is usually 5 μm or less, preferably 4 μm or less, more preferably 3 μm or less from the viewpoint of film formation easiness, avoidance of non-uniformity due to a thick film, and the like.
Therefore, the total thickness of the adhesive layer and the release layer in the laminate of the present invention is usually 20.1 μm or more.
When thinning a wafer, for example, a grindstone is rotated at high speed to grind the wafer. In this case, if the film thickness of the adhesive layer and the film thickness of the release layer are equal to or greater than the above-described lower limit values, it is possible to effectively prevent the problem of cracking of the wafer due to impact during grinding with a grindstone.
In addition, if delamination or air bubbles (voids) occur between or within layers in the laminate, the film thickness of the adhesive layer becomes uneven, or cavities occur around the structures (bumps) of the semiconductor substrate. If there is unevenness in the film thickness of the adhesive layer, when the wafer is thinned, it is directly reflected in the thickness of the thinned device, making it impossible to perform good thinning. Therefore, in order not to cause these problems, it is necessary to secure a certain amount of film thickness between the semiconductor substrate and the support substrate in the laminate. If the thickness of the adhesive layer or the total thickness of the adhesive layer and the release layer is equal to or greater than the above-described lower limit, delamination and voids can be effectively prevented from occurring.

An example of the laminate will be described below with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of an example of a laminate.
In addition, in FIG. 1, the case where a semiconductor substrate with bumps is used as the semiconductor substrate will be described as an example.
The laminate shown in FIG. 1 has a semiconductor substrate 1 having bumps 1a, an adhesive layer 2, a release layer 3 (photoresponsive release layer), and a support substrate 4 in this order.
The bumps 1a of the semiconductor substrate 1 are arranged on the support substrate 4 side.
The adhesive layer 2 is interposed between the semiconductor substrate 1 and the support substrate 4 . The adhesive layer 2 is in contact with the semiconductor substrate 1 . The adhesive layer 2 covers the bumps 1a.
A photoresponsive release layer 3 is interposed between the adhesive layer 2 and the support substrate 4 . A photoresponsive release layer 3 is in contact with the adhesive layer 2 and the support substrate 4 .

The laminate of the present invention is preferably produced by, for example, the following method for producing a laminate of the present invention.

(Laminate manufacturing method)
The method for producing a laminate of the present invention includes an adhesive coating layer forming step, an adhesive layer forming step, a release layer forming step, and, if necessary, other steps such as a bonding step.

<Adhesive coating layer forming step>
The adhesive coating layer forming step is a step of forming an adhesive coating layer by applying an adhesive composition on the semiconductor substrate.
Thus, an adhesive coating layer is formed on the semiconductor substrate.

Although the coating method is not particularly limited, it is usually a spin coating method. In addition, a method of separately forming a coating film by a spin coating method or the like and sticking the sheet-like coating film as an adhesive coating layer can be adopted.
The thickness of the adhesive coating layer is appropriately determined in consideration of the thickness of the adhesive layer in the laminate.
For the reason that the adhesive composition contains a solvent or the like, the applied adhesive composition may be heated for the purpose of drying the coating film of the applied adhesive composition.
The heating temperature of the applied adhesive composition varies depending on the type and amount of the adhesive component contained in the adhesive composition, whether or not a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, and the like. Therefore, the temperature cannot be generally specified, but the temperature is usually 80 to 150° C., and the heating time is usually 30 seconds to 5 minutes.
Heating can be performed using a hot plate, an oven, or the like.

<Adhesive Layer Forming Step>
In the adhesive layer forming step, the adhesive coating layer is heated to cure the adhesive composition to form an adhesive layer.
The heating temperature and time are not particularly limited as long as the temperature and time are such that the adhesive coating layer is converted into the adhesive layer.
The heating temperature is preferably 120° C. or higher, more preferably 150° C. or higher, from the viewpoint of achieving a sufficient curing speed, etc., and prevents deterioration of each layer (including the support substrate and the semiconductor substrate) constituting the laminate. From the viewpoint of prevention, etc., the temperature is preferably 250° C. or less. More preferably, it is 180 to 200°C.
The heating time is preferably 1 minute or more, more preferably 5 minutes or more, from the viewpoint of realizing suitable bonding of each layer (including the support substrate and the semiconductor substrate) constituting the laminate. From the viewpoint of suppressing or avoiding adverse effects on each layer due to heating, the time is preferably 180 minutes or less, more preferably 120 minutes or less. More preferably, it is 1 to 20 minutes from the viewpoint of substrate processing efficiency.
Heating can be performed using a hot plate, an oven, or the like.

<Peeling layer forming step>
The release layer forming step is a step of forming a release layer by coating a release agent composition on a support substrate to obtain a release agent coating layer and heating the release agent coating layer.
Thus, a release layer is formed on the support substrate.

The coating method is not particularly limited, and the same coating method as described in the section <Adhesive coating layer forming step> can be used.
The thickness of the release agent coating layer is appropriately determined in consideration of the thickness of the photoresponsive release layer in the laminate.
A release layer can be formed by heating the release agent coating layer to remove the solvent.
The heating temperature of the applied release agent composition is generally defined because it varies depending on the type and amount of the compound having an azobenzene skeleton, whether or not a solvent is contained, the boiling point of the solvent used, the desired thickness of the release layer, and the like. Although not possible, the temperature is usually 100 to 250° C., and the heating time is usually 30 seconds to 5 minutes. For example, the release layer can be formed by heating the release agent coating layer at 200° C. for 1 minute.
Heating can be performed using a hot plate, an oven, or the like.

<Specific embodiment of the method for manufacturing the laminate>
A preferred embodiment of the method for manufacturing the laminate includes, for example, the following manufacturing method.
1) Prepare a semiconductor substrate on which an adhesive coating layer is formed and a supporting substrate on which a release layer is formed, respectively; After disposing the substrate), heat treatment is performed.
Heating converts the adhesive coating into an adhesive layer. As a result, a laminate is obtained in which the semiconductor substrate, the adhesive layer, the release layer, and the supporting substrate are laminated in this order.

<Lamination process>
After disposing two substrates (a semiconductor substrate and a supporting substrate) so as to sandwich the release layer and the adhesive coating layer, heat treatment is performed. It is preferable to carry out a lamination step in order to obtain sufficient bonding.
The bonding process is not particularly limited as long as the substrate and the layer can be bonded together and the substrate and the layer are not damaged. can be applied, and more preferably, a load can be applied in the thickness direction of the supporting substrate and the semiconductor substrate under reduced pressure.
The load is not particularly limited as long as the substrate and layer can be bonded together and the substrate and layer are not damaged.
The degree of reduced pressure is not particularly limited as long as the substrate and layer can be bonded together and the substrate and layer are not damaged.

(Method for manufacturing semiconductor substrate)
The laminate of the present invention is used for temporary bonding for processing a semiconductor substrate, and is used for applications in which a support substrate and a semiconductor substrate are separated after processing the semiconductor substrate in the laminate.
The method for manufacturing a semiconductor substrate of the present invention includes at least a processing step of processing the semiconductor substrate and a peeling step of separating the support substrate from the processed semiconductor substrate. including the steps of

<Processing process>
The processing step is not particularly limited as long as it is a step for processing the semiconductor substrate in the laminate of the present invention, and includes, for example, polishing processing and through electrode forming processing.
For example, in various processing steps, there are cases where processing is performed under high temperature and high pressure. can be effectively prevented.

<<Polishing process>>
The polishing treatment is not particularly limited as long as it is a treatment for thinning the semiconductor substrate by polishing the surface of the semiconductor substrate opposite to the surface on which the bumps are present. polishing and the like.
The polishing process can be performed using a general polishing apparatus used for polishing semiconductor substrates.
The polishing process reduces the thickness of the semiconductor substrate to obtain a thinned semiconductor substrate to a desired thickness. The thickness of the thinned semiconductor substrate is not particularly limited, but may be, for example, 10 to 300 μm or 30 to 100 μm.

<<Through electrode forming process>>
In some cases, the polished semiconductor substrate is formed with a through electrode for achieving conduction between the thinned semiconductor substrates when a plurality of thinned semiconductor substrates are stacked.
Therefore, the method for manufacturing a semiconductor substrate may include a through electrode forming process for forming through electrodes in the polished semiconductor substrate after the polishing process and before the peeling process.
The method of forming the through electrode in the semiconductor substrate is not particularly limited, but examples include forming a through hole and filling the formed through hole with a conductive material.
Formation of the through holes is performed, for example, by photolithography.
Filling of the through-holes with a conductive material is performed by, for example, a plating technique.

<Peeling process>
The separation step is a step of separating the support substrate and the processed semiconductor substrate after the processing step.
Specifically, the laminate is irradiated with ultraviolet light (for example, ultraviolet light is irradiated from the support substrate side of the laminate) to soften the release layer and reduce the adhesive force. As a result, the release layer can be peeled off, and the release layer and the adhesive layer can be separated.
In the present invention, since the thermosetting adhesive layer is used, the thermosetting adhesive layer and the photoresponsive peeling layer combine to prevent the application of excessive force to the supporting substrate and the semiconductor substrate during peeling. , the release layer can be easily separated from the thermosetting adhesive layer.
Thereby, the support substrate and the semiconductor substrate can be separated.
Here, it is preferable to use ultraviolet light having a wavelength of 300 to 400 nm as the ultraviolet light.
The amount of exposure varies depending on the type of light source, the thickness of the laminate and release layer, etc., but is preferably 0.1 to 200 J/cm ² , more preferably 0.5 to 100 J/cm ² .
Usually, the peeling of the peeling layer is carried out after the laminate of the present invention is produced and given predetermined processing.
The ultraviolet light may be laser light or non-laser light such as an ultraviolet lamp.

<Removal process>
The removal step is not particularly limited as long as it is a step in which the adhesive layer remaining on the semiconductor substrate is removed after the peeling step. In addition, dissolution removal may be combined with removal using a removal tape or the like.
When using a cleaning composition, for example, a semiconductor substrate with an adhesive layer can be immersed in the cleaning composition, or can be sprayed with the cleaning composition.

A suitable example of the cleaning composition used in the present invention is a cleaning composition containing a quaternary ammonium salt and a solvent.
The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it can be used for this type of application.
Such quaternary ammonium cations typically include tetra(hydrocarbon)ammonium cations. On the other hand, as the anions that form a pair with it ^, there are hydroxide ions ⁽ OH ^{− ) ;} tetrafluoroborate ion (BF ₄ ⁻ ); hexafluorophosphate ion (PF ₆ ⁻ ), etc., but not limited to these.

In the present invention, the quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.
In the quaternary ammonium salt, the halogen atom may be contained in the cation or the anion, preferably the anion.

In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride.
Specific examples of the hydrocarbon group in the tetra(hydrocarbon)ammonium fluoride include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an alkynyl group having 6 to 20 carbon atoms. and the like.
In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride includes a tetraalkylammonium fluoride.
Specific examples of the tetraalkylammonium fluoride include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also referred to as tetrabutylammonium fluoride) and the like. Not limited. Among them, tetrabutylammonium fluoride is preferred.

An example of a mode in which the production of the laminate and the production of the thinned wafer are performed in series will be described with reference to FIGS. 2A to 2F.
2A to 2F are diagrams for explaining one aspect of manufacturing a laminate and manufacturing a thin wafer.
2, as in FIG. 1, a semiconductor substrate with bumps is used as an example.
First, a wafer 1 having bumps 1a is prepared (FIG. 2A).
Next, the surface of the wafer 1 on which the bumps 1a are present is coated with an adhesive composition by spin coating using a coating device 12 to form an adhesive coating layer 2a (FIG. 2B).
Next, a release layer 3 is formed by applying a release agent composition onto the support substrate 4 by spin coating using a coating device (not shown) and heating the formed release agent coating layer (not shown). do. A wafer on which an adhesive coating layer is formed and a support substrate on which a release layer is formed are prepared (FIG. 2C).
Next, the wafer 1 having the adhesive coating layer 2a formed thereon and the support substrate 4 having the peeling layer 3 formed thereon are sandwiched between the adhesive coating layer 2a and the peeling layer 3, and the wafer 1 is decompressed under reduced pressure. and the support substrate 4, a heating device (hot plate) 13 is placed on the surface of the wafer 1 opposite to the surface on which the bumps 1a are present, and the heating device 13 heats the adhesive coating layer 2a. to cure the adhesive composition and convert it into an adhesive layer 2 (FIG. 2D).
A laminate is obtained by the steps shown in FIGS. 2A to 2D.
Next, an example of manufacturing a thinned wafer will be described.
Next, a polishing apparatus (not shown) is used to polish the surface of the wafer 1 opposite to the surface on which the bumps 1a are present, thereby thinning the wafer 1 (FIG. 2E). It should be noted that through electrodes may be formed on the thinned wafer 1 .
Next, by irradiating ultraviolet light (not shown) from the support substrate 4 side, the thinned wafer 1 and the support substrate 4 are separated (FIG. 2F). At this time, the peeling layer, which had no fluidity before the ultraviolet light irradiation, is softened by the irradiation and the adhesive strength is lowered, so that the thinned wafer 1 and the support substrate 4 can be peeled off.
Next, the thinned wafer 1 is cleaned by dissolving and removing the adhesive layer 2 from the thinned wafer 1 with the cleaning composition using a cleaning device (not shown).
A thinned wafer 1 is thus obtained.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In addition, the used apparatus is as follows.

(1) Stirrer: Rotation/Revolution Mixer ARE-500 manufactured by Thinky Co., Ltd.
(2) Viscometer: Rotational viscometer TVE-22H manufactured by Toki Sangyo Co., Ltd.
(3) Vacuum bonding device: Manual bonder manufactured by Sus Microtec Co., Ltd. (4) UV irradiation device: UVI-MA manufactured by Omiya Industry Co., Ltd.
(5) Measurement of molecular weight of polymer: The molecular weight of the azobenzene-containing acrylate polymer was measured under the following conditions.
Apparatus: HLC-8320GPC manufactured by Tosoh Corporation
GPC column: TSKgel Super-MultiporeHZ-N (2 columns) manufactured by Tosoh Corporation
Column temperature: 40°C
Flow rate (flow rate): 0.35 mL/min Eluent (elution solvent): Tetrahydrofuran Standard sample: Polystyrene (manufactured by Showa Denko KK)

[1] Preparation of adhesive composition [Preparation Example 1]
In a 600 mL stirring container dedicated to the rotation/revolution mixer, 150 g of a base polymer (manufactured by Wacker Chemi Co., Ltd.) consisting of a vinyl group-containing linear polydimethylsiloxane having a viscosity of 200 mPa s and a vinyl group-containing MQ resin as the component (a1) described above, 15.81 g of SiH group-containing linear polydimethylsiloxane having a viscosity of 100 mPa·s (manufactured by Wacker Chemie) as component (a2), and 0.1 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) as component (A3). 17 g was added and stirred for 5 minutes with a rotation/revolution mixer to obtain a mixture (I).
In 50 mL of the screw tube, 0.33 g of a platinum catalyst (manufactured by Wacker Chemi Co., Ltd.) as the component (A2) described above and linear polydimethylsiloxane containing vinyl groups having a viscosity of 1000 mPa s (manufactured by Wacker Chemi Co., Ltd.) as the component (a1) described above. ) was stirred for 5 minutes with a rotation-revolution mixer to obtain a mixture (II).
0.52 g of the obtained mixture (II) was added to the mixture (I) and stirred for 5 minutes with a rotation/revolution mixer to obtain a mixture (III).
The resulting mixture (III) was filtered through a 300-mesh nylon filter to obtain an adhesive composition. The viscosity of the adhesive composition measured using a rotational viscometer was 9900 mPa·s.

[Comparative Preparation Example 1]
5.00 g of thermoplastic resin Septon 4033 (manufactured by Kuraray Co., Ltd.), which is a hydrogenated styrene/isoprene/butadiene copolymer, and 20.00 g of mesitylene were added to a 50 mL vial and stirred with a stirrer for 10 minutes to obtain The resulting mixture was used as an adhesive composition.

[2] Preparation of azobenzene-containing acrylate polymer (polymer) [Preparation Example 2-1]
Into a flask, 19.84 g of 4-(phenylazo)phenol, 13.90 g of potassium carbonate, and 100 mL of N,N-dimethylformamide as a solvent are placed and stirred at 40° C. for 30 minutes, followed by 8-chloro-1-normal octanol. 18.12 g, 3.46 g of potassium iodide, and 11 mL of N,N-dimethylformamide were added and stirred at 110° C. for 24 hours.
The reaction mixture was cooled to room temperature, quenched with 1 mol/L hydrochloric acid, and separated and extracted with dichloromethane. The extract containing dichloromethane was separated with a saturated aqueous sodium chloride solution, dehydrated by adding sodium sulfate, and sodium sulfate was filtered off. An orange solid was obtained by distilling off the solvent in the obtained solution with an evaporator. The obtained solid was dissolved in ethanol at 75° C. and cooled to room temperature to recrystallize the desired product. The solid obtained was filtered off and dried to give 20.27 g of 8-[4-(2-phenyldiazenyl)phenoxy]-1-octanol.

[Preparation Example 2-2]
A flask was charged with 16.31 g of 8-[4-(2-phenyldiazenyl)phenoxy]-1-octanol obtained in Preparation Example 2-1, 5.19 g of triethylamine, and 150 mL of dichloromethane as a solvent. It was placed in a bath and stirred. A mixed solution of 5.51 g of acryloyl chloride and 50 mL of dichloromethane was added dropwise to the flask over 30 minutes. After that, the mixture was stirred at room temperature for 24 hours. The reaction mixture was quenched with 1 mol/L hydrochloric acid and separated and extracted with ethanol and dichloromethane. The extract was liquid-separated with a saturated sodium chloride aqueous solution, then sodium sulfate was added for dehydration, and sodium sulfate was filtered off. An orange solid was obtained by distilling off the solvent in the obtained solution by evaporation. The obtained solid was dissolved in ethanol at 70° C. and cooled to room temperature to recrystallize the desired product. The resulting solid was filtered and dried to obtain 14.01 g of 8-[4-(2-phenyldiazenyl)phenoxy]-1-octyl-2-propenoate (azobenzene-containing acrylate).

[Preparation Example 2-3]
In a flask, 11.39 g of 8-[4-(2-phenyldiazenyl)phenoxy]-1-octyl-2-propenoate (azobenzene-containing acrylate) obtained in Preparation Example 2-2, 40 mL of anisole as a solvent, and radical After adding 0.05 g of 2,2'-azobisisobutyronitrile as a polymerization initiator and stirring, the resulting mixture was stirred at 80°C for 48 hours to allow the polymerization reaction to proceed. After cooling the reaction mixture to room temperature, the obtained reaction mixture was added dropwise to ethanol to reprecipitate the reaction product. The resulting solid was filtered and dried to obtain the desired azobenzene-containing acrylate polymer (Mw=6,337, Mw/Mn=1.31).

The flow of the synthesis method when synthesizing an azobenzene-containing acrylate polymer according to Preparation Examples 2-1 to 2-3 is shown in the following schematic diagram.

[3] Preparation of release agent composition [Preparation Example 3]
A release agent composition was prepared by mixing mesitylene so that the final concentration of the azobenzene-containing acrylate polymer obtained in Preparation Example 2-3 was 10% by mass.

[4] Production of laminate [Production Example 1]
The release agent composition obtained in Preparation Example 3 was spin-coated on a 100 mm glass wafer so that the film thickness in the finally obtained laminate was about 1.0 μm, and heated at 200° C. for 1 minute. , a release layer was formed on a glass wafer as a support substrate.
On the other hand, the adhesive composition obtained in Preparation Example 1 was spin-coated on a 100 mm silicon wafer so that the film thickness in the finally obtained laminate was about 65 μm, and the adhesive composition was applied onto the silicon wafer as a semiconductor substrate. to form an adhesive coating layer.
Then, using a bonding apparatus, the glass wafer and the silicon wafer were bonded together so as to sandwich the release layer and the adhesive coating layer, followed by post-heating at 200° C. for 10 minutes to prepare a laminate. The bonding was performed at a temperature of 23° C. and a reduced pressure of 1,500 Pa.

The presence or absence of voids in the obtained laminate was visually confirmed from the glass wafer (support substrate) side. As a result, voids were not confirmed.

[Comparative Production Example 1]
The release agent composition obtained in Preparation Example 3 was spin-coated on a 100 mm glass wafer so that the film thickness in the finally obtained laminate was about 1.0 μm, and heated at 200° C. for 1 minute. , a release layer was formed on a glass wafer as a support substrate.
On the other hand, the adhesive composition obtained in Comparative Preparation Example 1 was spin-coated on a 100 mm silicon wafer so that the film thickness in the finally obtained laminate was about 30 μm, and the silicon wafer as a semiconductor substrate was obtained. An adhesive coating layer was formed thereon.
Then, using a bonding apparatus, the glass wafer and the silicon wafer were bonded together so as to sandwich the release layer and the adhesive coating layer, followed by post-heating at 200° C. for 10 minutes to prepare a laminate. The bonding was performed at a temperature of 23° C. and a reduced pressure of 1,500 Pa.

[5] Confirmation of peelability by 365 nm UV light irradiation (confirmation of peeling by whole surface irradiation)
[Example 1]
The entire surface of the release layer of the laminate obtained in Production Example 1 was irradiated with UV light by irradiating the entire surface of the wafer with UV light from the glass wafer side using a UV irradiation apparatus. After that, a cutter blade was inserted between the glass wafer and the silicon wafer to confirm whether or not the glass wafer could be separated. Incidentally, the UV output was set to 36 J/cm ² .
As a result, the glass wafer (carrier side) could be easily separated manually.

[Comparative Example 1]
The entire surface of the release layer of the laminate obtained in Comparative Production Example 1 was irradiated with UV light by irradiating the entire surface of the wafer with UV light from the glass wafer side using a UV irradiation apparatus. After that, a cutter blade was inserted between the glass wafer and the silicon wafer to confirm whether or not the glass wafer could be separated. Incidentally, the UV output was set to 36 J/cm ² .
As a result, even if force was applied, it was difficult to manually separate the glass wafer (on the carrier side), and when force was applied further, the glass wafer broke.

As shown in Examples, the laminate obtained in Production Example 1 can be easily separated from the semiconductor substrate and the supporting substrate without causing cutting or deformation of the semiconductor substrate and the supporting substrate when the semiconductor substrate and the supporting substrate are separated. It is a laminate that can be peeled off. Furthermore, the laminate obtained in Production Example 1 is a laminate capable of suppressing bump deformation.

According to the present invention, when the semiconductor substrate and the supporting substrate are separated after the semiconductor substrate is processed, the semiconductor substrate and the supporting substrate can be easily separated without cutting or deforming the semiconductor substrate or the supporting substrate. In addition, since it is possible to provide a laminated body that can suppress deformation of bumps, it is useful for manufacturing processed semiconductor substrates.

Reference Signs List 1 Wafer 1a Bump 2 Adhesive Layer 2a Adhesive Coating Layer 3 Peeling Layer 4 Supporting Substrate 12 Coating Device 13 Heating Device

Claims (8)

a semiconductor substrate, a support substrate, an adhesive layer formed in contact with the semiconductor substrate, and a photoresponsive release layer formed between the adhesive layer and the support substrate so as to contact the adhesive layer. A laminate comprising
The adhesive layer is a thermosetting adhesive layer,
The laminate, wherein the photoresponsive release layer is formed from a release agent composition containing a compound having an azobenzene skeleton. The laminate according to claim 1, wherein the compound having an azobenzene skeleton is a compound containing a group represented by the following formula (1).

(Wherein, m is an integer of 0 to 20, l is an integer of 1 to 20.) 3. The laminate according to claim 1, wherein the adhesive layer is an adhesive layer that is cured by a hydrosilylation reaction. The adhesive layer is formed from an adhesive composition containing a component (A) that cures by a hydrosilylation reaction,
The component (A) is
A polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom;
a polyorganosiloxane (a2) having a Si—H group;
a platinum group metal-based catalyst (A2);
The laminate according to any one of claims 1 to 3, containing A step of processing the semiconductor substrate in the laminate according to any one of claims 1 to 4;
a step of separating the support substrate and the processed semiconductor substrate by exfoliating the photoresponsive exfoliation layer by irradiation with ultraviolet light;
A method of manufacturing a semiconductor substrate, comprising: 6. The method of manufacturing a semiconductor substrate according to claim 5, wherein said step of processing includes polishing said semiconductor substrate to thin said semiconductor substrate. A method for producing a laminate for producing the laminate according to any one of claims 1 to 4,
a step of applying a thermosetting adhesive composition onto the semiconductor substrate to form an adhesive coating layer;
a step of heating the adhesive coating layer to form the adhesive layer;
A method of manufacturing a laminate, comprising: a step of applying a thermosetting adhesive composition onto the semiconductor substrate to form an adhesive coating layer;
a step of applying the release agent composition onto the support substrate to form a release layer;
After the semiconductor substrate with the adhesive coating layer and the support substrate with the release layer are bonded together so as to sandwich the adhesive coating layer and the release layer, heating is applied to remove the adhesive layer from the adhesive coating layer. a step of forming an adhesive layer;
The method for producing a laminate according to claim 7, comprising:

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