JP2022141031A - Adhesive composition and laminate - Google Patents

Abstract

To provide an adhesive composition which gives an adhesive layer capable of suitably temporarily bonding a semiconductor substrate and a support substrate together and is excellent in storage stability.SOLUTION: The adhesive composition to be used to form an adhesive layer for temporary bonding for processing a semiconductor substrate contains a thermosetting adhesive component and thermally expandable particles. The thermosetting adhesive component contains a polyorganosiloxane. The thermally expandable particles are contained in an amount of 3.5 mass% or less based on the thermosetting adhesive component.SELECTED DRAWING: None

Description

The present invention relates to adhesive compositions and laminates.

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.

Under the above circumstances, the inventors have reported an adhesive composition containing a component such as polydimethylsiloxane together with a component that cures by a hydrosilylation reaction, as an adhesive composition capable of realizing such temporary adhesion. (See Patent Documents 1 and 2, for example).

On the other hand, Patent Document 3 discloses a silicone composition containing a thermally expandable powder in order to provide an adhesive that can be separated in a relatively simple manner and/or without any residue in a silicone composition for temporary bonding. However, as a result of confirmation by the present inventors, when the adhesive composition contains the thermally expandable particles in the amount described in the examples of Patent Document 3, good storage stability is obtained. It was found that no adhesive composition was obtained.

WO2017/221772 WO2018/216732 Special table 2020-529488 publication

The present invention has been made in view of the above circumstances, and provides an adhesive composition that provides an adhesive layer that can suitably temporarily bond a semiconductor substrate and a support substrate, and that has excellent storage stability. With the goal.

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

That is, the present invention includes the following.
[1] An adhesive composition used for forming an adhesive layer for temporary bonding for processing a semiconductor substrate,
including a thermosetting adhesive component and thermally expandable particles,
The thermosetting adhesive component contains polyorganosiloxane,
An adhesive composition in which the thermally expandable particles are contained in an amount of 3.5% by mass or less with respect to the thermosetting adhesive component.
[2] The adhesive composition according to [1], wherein the thermosetting adhesive component is a component that cures through a hydrosilylation reaction.
[3] A laminate comprising an adhesive layer interposed between a semiconductor substrate and a supporting substrate and in contact with the semiconductor substrate,
A laminate, wherein the adhesive layer is a layer formed from the adhesive composition according to [1] or [2].
[4] An adhesive composition used for forming an adhesive layer for temporary bonding for processing a semiconductor substrate, containing a thermosetting adhesive component containing polyorganosiloxane and thermally expandable particles. A method for improving storage stability of an object,
A method for improving the storage stability of an adhesive composition, characterized in that the content of the thermally expandable particles is 3.5% by mass or less with respect to the thermosetting adhesive component.

ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition which gives the adhesive layer which can temporarily bond a semiconductor substrate and a support substrate suitably, and is excellent in storage stability can be provided.

It is a schematic sectional drawing of an example of a laminated body. FIG. 4 is a schematic cross-sectional view of another example of a laminate; 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; FIG. 11 is a diagram (No. 7) for explaining one aspect of manufacturing a laminated body and manufacturing a thinned wafer; FIG. 10 is a diagram (No. 8) for explaining one aspect of manufacturing a laminated body and manufacturing a thinned wafer; FIG. 10 is a diagram (No. 9) for explaining one aspect of manufacturing a laminated body and manufacturing a thinned wafer; FIG. 10 is a diagram (No. 10) for explaining one aspect of manufacturing a laminated body and manufacturing a thinned wafer; FIG. 11 is a diagram (No. 11) for explaining one aspect of manufacturing a laminated body and manufacturing a thin wafer; FIG. 12 is a diagram (No. 12) for explaining one aspect of manufacturing a laminated body and manufacturing a thinned wafer; FIG. 13 is a diagram (No. 13) for explaining one aspect of manufacturing a laminated body and manufacturing a thinned wafer; FIG. 14 is a diagram (No. 14) for explaining one aspect of manufacturing a laminated body and manufacturing a thinned wafer;

(Adhesive composition)
The adhesive composition of the present invention is a composition used for forming an adhesive layer for temporary adhesion for processing semiconductor substrates.
The adhesive composition of the present invention comprises a thermosetting adhesive component and thermally expandable particles.
The thermosetting adhesive component contains polyorganosiloxane.
The adhesive composition of the present invention contains thermally expandable particles in an amount of 3.5 mass % or less based on the thermosetting adhesive component.
In addition to the thermosetting adhesive component and the thermally expandable particles, the adhesive composition of the present invention may contain other components such as a solvent, for example, in order to adjust the viscosity of the adhesive composition.
As shown in the examples below, the adhesive composition of the present invention is capable of forming an adhesive layer that can be easily peeled off, and exhibits good storage stability without precipitation even after long-term storage.

<Thermosetting adhesive component>
The thermosetting adhesive component contains polyorganosiloxane. By containing polyorganosiloxane, the obtained adhesive layer can achieve excellent heat resistance.
Moreover, from the viewpoint of realizing excellent heat resistance of the resulting adhesive layer with good reproducibility, etc., as a preferred embodiment, the thermosetting adhesive component contains a component that cures by a hydrosilylation reaction.
A preferred embodiment of the thermosetting adhesive component used in the present invention contains, for example, a curable component (A) that serves as an adhesive component. The thermosetting adhesive component 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 represent 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 cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 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- Cycloalkyl groups such as ethyl-2-methyl-cyclopropyl group and 2-ethyl-3-methyl-cyclopropyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group , and bicycloalkyl groups such as a bicyclodecyl group, etc., but are not limited thereto, and usually have 3 to 14 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 5 to 6 carbon atoms.

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 Sigma-Aldrich) was used as a standard sample. can be measured using

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 thermosetting adhesive component 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, platinum 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 thermosetting adhesive component used in the present invention may contain a component (B) that does not cause a curing reaction and becomes a release agent component together with the component (A) that cures. By including such a component (B) in the thermosetting adhesive component, 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, and 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-mentioned 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 thermosetting adhesive component used in the present invention contains a component (A) that cures and a component (B) that does not undergo a curing reaction. Contains organosiloxanes.

An example of the thermosetting adhesive component used in the present invention can contain component (A) and component (B) in any ratio. ) to component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75 by mass ratio [(A):(B)]. :25.
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 thermosetting adhesive component used in the present invention is not particularly limited, it is usually 500 to 20,000 mPa·s, preferably 1,000 to 1,0000 mPa·s at 25°C.

In the present invention, the curing initiation temperature Tc (°C) of the thermosetting adhesive component can be measured by the following method.
5 mg of the thermosetting adhesive component is weighed into an aluminum pan, and the calorific value is measured using a DSC (for example, TA Instruments Co., Ltd. Differential Scanning Calorimeter Q-2000). , and the temperature at which the peak of the calorific value is confirmed can be obtained as the curing start temperature Tc (°C) of the thermosetting adhesive component. The temperature rising condition at this time can be, for example, from room temperature (23° C.) to 300° C. at 10° C./min.

<Thermal expandable particles>
The adhesive composition of the present invention contains thermally expandable particles in an amount of 3.5 mass % or less based on the thermosetting adhesive component.
For example, thermally expandable particles are microcapsules that contain a volatile substance enclosed within a shell composed of a thermoplastic resin that expands when heated.
Specifically, for example, a microcapsule (shell) with a film thickness of 2 to 15 μm encloses an organic solvent as a swelling agent (volatile substance).
Examples of thermoplastic resins forming the shell of this component include vinyl polymers such as polyethylene, polystyrene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polymethyl methacrylate, polybutadiene, polychloroprene, and the like. copolymers; polyamides such as nylon 6, nylon 66; and polyethylene terephthalate, polyacetal, and blends thereof.
Among them, vinyl polymers such as polyethylene, polystyrene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polymethyl methacrylate, polybutadiene, and polychloroprene are used because they are well mixed with organic solvents and thermosetting adhesive components. and copolymers thereof are preferred, and polyacrylonitrile-based copolymers are more preferred.
Volatile substances encapsulated in thermally expandable particles include, for example, hydrocarbons such as butane, isobutene and propane; alcohols such as methanol and ethanol; halogenated hydrocarbons such as dichloroethane, trichloroethane and trichloroethylene; Organic solvents such as ethers and the like are included, but hydrocarbons are preferred as they contribute to good stability within the capsule and excellent thermal expansibility.
Volatile substances in the capsule are typically liquid at 1.01×10 ⁵ Pa and 25°C.

The shape of the thermally expandable particles is not particularly limited and can be appropriately selected depending on the intended purpose.

The maximum expansion ratio of the thermally expandable particles is appropriately set in consideration of other physical properties of the thermally expandable particles so as to obtain a porous structure capable of reducing the adhesive ability necessary for peeling. It is greater than 1, and in some embodiments, it is 3 to 15 from the viewpoint of achieving good releasability with good reproducibility.

The average particle size of the thermally expandable particles before expansion is not particularly limited as long as it is smaller than the thickness of the adhesive layer to be formed and is well mixed with the adhesive component, but is usually 3 to 100 μm. , in some embodiments from 5 to 50 μm.
In the present invention, the average particle diameter of the thermally expandable particles can be obtained as the average particle diameter of the D50 value using a particle size distribution meter (for example, Shimadzu Corporation laser diffraction particle size distribution analyzer SALD-3100). can.

The expansion start temperature Ts (° C.) of the thermally expandable particles can be measured, for example, by the following method. Using dynamic viscoelasticity measurement (DMA) (for example, DMA Q800 type manufactured by TA Instruments), 0.5 mg of particles are placed in an aluminum cup with a diameter of 6.0 mm (inner diameter of 5.65 mm) and a depth of 4.8 mm, and the particles are An aluminum lid (diameter 5.6 mm, thickness 0.1 mm) was placed on the upper part of the layer to prepare a measurement sample, and a force of 0.01 N was applied to the measurement sample from above with a pressurizer, and the height of the sample was measured. Measured, heated from 20 ° C. to 300 ° C. at a temperature increase rate of 10 ° C./min with a force of 0.01 N applied by the presser, and measured the amount of displacement in the vertical direction of the presser. The expansion start temperature (Ts) can be obtained as the displacement start temperature in the direction, and the maximum expansion temperature (Tm) can be obtained as the temperature indicating the maximum amount of displacement at this time.
The expansion initiation temperature (° C.) of the thermally expandable particles is preferably 50 to 120° C. from the viewpoint of realizing good peeling with good reproducibility.

In the present invention, the maximum expansion ratio Ms of the thermally expandable particles is based on the true specific gravity of the thermally expandable particles "at the time of maximum expansion", and the average true specific gravity of the particle group before thermal expansion is Db, The maximum expansion ratio of the thermally expandable particles is represented by Db/Da (times), where Da is the average true specific gravity when the particle group is heated and expanded to have the minimum average true specific gravity. be.
That is, the maximum expansion ratio can be calculated using the true specific gravity Db of the thermally expandable particles and the true specific gravity Da of the thermally expandable particles after heating (expanded). The true specific gravity can be measured by a liquid immersion method (Archimedes method) using isopropyl alcohol in an atmosphere with an ambient temperature of 25° C. and a relative humidity of 50%.
As for the heating conditions, 1 g of the thermally expandable particles is heated in an oven in a range from the expansion start temperature (Ts) to a temperature 100° C. higher than the maximum expansion temperature (Tm) for 2 minutes at each temperature, and the true specific gravity is the lowest. The value is defined as the maximum expansion giving Df, and the maximum expansion ratio Ms of the thermally expandable particles is calculated from the formula Ms=(Db/Df).

The thermally expandable particles are prepared by a known method (e.g., WO2020/017361, WO2019/150951, WO2019/124233, WO2018/092554, WO2017/141653, WO2017/002659, WO2016/190178, WO2016/16016/WO28/WO204080, 178329, JP2016-169274, JP2015-129290, WO2015/098586, WO2015/060086, WO2015/029916, JP2015-3951, WO2013/111688, JP2013-173945, JP2012-136695, JP2012-136695 2012-17453, JP-A-2011-195813, JP-A-2012-144820, JP-A-2012-122025, JP-A-2011-32626, JP-A-2011-256224, WO2010/143512, JP-A-2011-68890, WO2009/050863, WO2008/ 142849, JP-A-2008-291067, WO2007/058379, WO2007/046273, JP-A-2006-213930, WO2005/049698, JP-A-2004-323854, WO2004/074396, WO2004/058910, JP-A-2014-108153 169443, JP 2013-28818, JP 2013-32542, JP 2009-299071, JP 2009-113037, WO2003/099955, WO2001/072410, WO2001/023081, WO1999/046320, WO1999/0423758, WO1999/0423758 24488, JP-A-11-2615, JP-A-5-329360, JP-A-5-309262, JP-A-5-285376, JP-A-9-19635, JP-A-62-286534, JP-A-59-173132, JP-A-56 -113338, etc.), or can be obtained as a commercial product. Such commercial products include Matsumoto Microsphere (registered trademark) F-30, HF-30D, F-35, F-35D, HF-36, HF-36D, F-36LV manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd. , F-36LVD, HF-48, HF-48D, FN-80GS, FN-80GSD, HF-50, F-50D, F-65, F-65D, FN-100SS, FN-100SSD, FN-100S, FN -100SD, F-100M, F-100MD, FN-78, FN-78D, FN-100M, FN-100MD, FN-105, FN-105D, FN-180SS, FN-180SSD, FN-180S, FN-180SD , FN-180, FN-180D, FN-190SSD, F-190D, F-260D, F-2800D, F-2830D, F-2860D, and the like.

In the present invention, the content of the thermally expandable particles is 3.5% by mass or less with respect to the thermosetting adhesive component, from the viewpoint of achieving both the peelability of the adhesive layer and the storage stability of the adhesive composition. It is preferably 3.4% by mass or less, more preferably 3.3% by mass or less, still more preferably 3.2% by mass or less, and still more preferably 3.1% by mass or less. The lower limit of the content of the thermally expandable particles is not particularly limited as long as the amount of gas that can contribute to the porosity that can reduce the adhesive ability necessary for peeling is generated, but the thermosetting adhesive It is usually 0.05% by mass, preferably 0.1% by mass, based on the component.
Since the adhesive composition of the present invention contains a predetermined amount of heat-expandable particles, the heat-expandable particles are added to the heat-expandable particles in the process of heating the adhesive coating layer and curing the thermosetting adhesive component to produce the adhesive layer. This causes the layer to cure with voids (porosity) in the layer, and these voids cause a decrease in the adhesive ability of the adhesive layer compared to the case without voids. As a result, good releasability is achieved, and the amount of thermally expandable particles is suitably adjusted, so that the adhesive composition is excellent in storage stability.
The porosity of the adhesive layer can be observed with an optical microscope. If no porosity can be confirmed, the adhesive layer cannot be peeled off, so part of the adhesive layer must be made porous.

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

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 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 10,000 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 adhesive composition of the present invention, it is preferable that the components contained in the composition are uniformly mixed and that fluidity to the extent that it can be applied is secured. A solvent may be contained in the adhesive composition for the purpose of adjusting the viscosity and surface tension of the adhesive composition. The adhesive composition of the present invention does not necessarily contain a solvent, as long as at least the fluidity to allow application is ensured, and preferably the components are uniformly mixed.

<Method for producing adhesive composition>
As a preferred embodiment of the method for producing an adhesive composition, for example, the adhesive composition of the present invention can be produced by mixing a thermosetting adhesive component and thermally expandable particles. The mixing order is not particularly limited.
In the present invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the adhesive composition or after all the components have been mixed.

(Laminate)
A laminate of the present invention includes a semiconductor substrate, a support substrate, and an adhesive layer.
The adhesive layer is interposed between the semiconductor substrate and the support substrate and in contact with the semiconductor substrate.
The adhesive layer is a layer formed from the adhesive composition of the present invention described above.
The laminated body is used for temporary adhesion for processing the semiconductor substrate, and is used for applications in which the support substrate and the semiconductor substrate are separated after processing the semiconductor substrate in the laminated body.
In the laminate of the present invention, the number of adhesive layers is not particularly limited and is appropriately selected according to the purpose. For example, in the laminate, the adhesive layer may be a single layer or multiple layers of two or more layers.
As a preferred embodiment of the laminate of the present invention, a second adhesive layer formed using a second adhesive composition containing no thermally expandable particles is provided separately from the adhesive layer made of the adhesive composition of the present invention. A laminate having In this case, the laminate has a semiconductor substrate, an adhesive layer made of the adhesive composition of the present invention, a second adhesive layer made of a second adhesive composition containing no thermally expandable particles, and a supporting substrate. It is preferable that the laminate including the second adhesive layer is laminated in the order of the semiconductor substrate, the adhesive layer, the second adhesive layer, and the support substrate.

As shown in the following examples, the laminate of the present invention satisfies releasability such that the adhesive layer is peeled off when the semiconductor substrate and the support substrate are separated, and the semiconductor substrate can be easily separated from the adhesive layer. Furthermore, the laminate of the present invention has an adhesive layer formed using an adhesive composition with good storage stability, as shown in the following examples. By forming using an adhesive composition with good storage stability, an adhesive layer with good performance can be stably produced, and a laminate in which the quality stability of the adhesive layer is ensured can be obtained. .
Therefore, the laminate of the present invention is a laminate that satisfies both peelability and quality stability.

An example of the laminate will be described below with reference to the drawings.
FIG. 1A is a schematic cross-sectional view of an example of a laminate.
Note that FIG. 1A (similar to FIG. 1B) will explain an example in which a semiconductor substrate with bumps is used as the semiconductor substrate.
The laminate of FIG. 1A has a semiconductor substrate 1 having bumps 1a, an adhesive layer 2, 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.
FIG. 1B is a schematic cross-sectional view of another example of the laminate.
The laminate of FIG. 1B has a semiconductor substrate 1 having bumps 1a, an adhesive layer 2, a second adhesive layer 3, 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 second adhesive layer 3 is interposed between the adhesive layer 2 and the support substrate 4 . The second adhesive layer 3 is in contact with the adhesive layer 2 and the support substrate 4 .
Each structure of the laminate of the present invention will be described in detail below.

<Semiconductor substrate>
The semiconductor substrate may have bumps. A bump is a projecting terminal.
When the semiconductor substrate to be used has bumps, the semiconductor substrate has bumps on the supporting substrate side in the laminate.
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 main material that constitutes the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, and examples thereof include silicon, silicon carbide, compound semiconductors, and the like.
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 perfectly circular surface shape. 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 depending on the purpose of use of the semiconductor substrate, and is not particularly limited.

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

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.

<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 disk-shaped support substrate does not need to have a perfectly circular surface shape. For example, the periphery of the support substrate may have a linear portion called an orientation flat or a notch. It may have notches.
The thickness 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, 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.

<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 formed using the adhesive composition of the present invention described above, more specifically, by curing the adhesive composition.
Although the thickness of the adhesive layer is not particularly limited, it is preferably 0.1 to 30 μm, more preferably 1 to 10 μm, from the viewpoint of obtaining good peelability.
In particular, when the adhesive layer in the laminate consists only of an adhesive layer formed using the adhesive composition of the present invention, the thickness of the adhesive layer is preferably 10 to 70 μm, more preferably 30 μm. ~60 μm. On the other hand, when the adhesive layer in the laminate includes a second adhesive layer in addition to the adhesive layer formed using the adhesive composition of the present invention, the thickness of the adhesive layer is preferably 0.1. ~30 μm, more preferably 1-10 μm.
The method for forming the adhesive layer from the adhesive composition will be described in detail in the description of <Method for producing laminate> below.

<Second adhesive layer>
The laminate of the invention may comprise a second adhesive layer.
When the laminate has a second adhesive layer, the second adhesive layer is interposed between the support substrate and the adhesive layer. The second adhesive layer is preferably in contact with the support substrate and the adhesive layer.

The second adhesive layer is formed using the second adhesive composition, more specifically, by curing the second adhesive composition.
The second adhesive composition includes a thermosetting adhesive component. However, the second adhesive composition does not contain thermally expandable particles.
The thermosetting adhesive component contained in the second adhesive composition is not particularly limited, but the thermosetting adhesive component contained in the adhesive composition of the present invention has been described above. The same thermosetting adhesive component can be used, as described in the section <Thermosetting adhesive component> in (Adhesive composition) above, and other thermosetting adhesive components below. A flexible adhesive component can also be used. The amount of the thermosetting adhesive component contained in the second adhesive composition, suitable conditions, etc. are also the same as those described above regarding the adhesive composition.
The thermosetting adhesive component contained in the adhesive composition and the thermosetting adhesive component contained in the second adhesive composition are different types even if the same type of thermosetting adhesive component is used. It does not matter if the thermosetting adhesive component is used.
In addition to the thermosetting adhesive component, the second adhesive composition may contain other components such as a solvent in the same manner as the adhesive composition of the present invention. is the same as above.

Although the thickness of the second adhesive layer provided in the laminate according to the present invention is not particularly limited, it is usually 5 to 500 μm, and from the viewpoint of maintaining the film strength, it is preferably 10 μm or more, more preferably 20 μm or more. , more preferably 30 μm or more, and from the viewpoint of avoiding non-uniformity due to a thick film, preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 70 μm or less.

The film thickness ratio between the adhesive layer and the second adhesive layer provided in the laminate according to the present invention is not particularly limited, but a laminate having good peelability and electrode (bump) protection can be obtained with good reproducibility. From the viewpoint of obtaining, the thickness of the second adhesive layer is usually 0.5 to 30, preferably 1 to 20, more preferably 2 to 15, and even more preferably 3 to 10 with respect to the thickness 1 of the adhesive layer. , more preferably 4-8.

<<Other Thermosetting Adhesive Components>>
The second adhesive composition may contain, as a thermosetting adhesive component, for example, a curable adhesive material as 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 thermosetting adhesive component, for example, a temporary bonding composition described in JP-A-2014-150239 can be used.
The thermosetting adhesive component is described in more detail below.

The thermoset adhesive component includes a curable adhesive material and a release additive. 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 temporary bonding compositions as the thermoset adhesive component 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 such curable adhesive materials 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 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 a repeat unit, 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.

The second adhesive composition may contain, for example, a thermosetting polymer as described below as a thermosetting adhesive component.
As the thermosetting adhesive component, 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 having 1 to 4 carbon atoms or an alkoxy group. 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 having 1 to 4 carbon atoms or an alkoxy group. 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 a thermosetting polymer as the thermosetting adhesive component is preferably a layer of a cured thermosetting resin composition containing silicone A or silicone B as a main component. . 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.

<Method for manufacturing laminate>
When the adhesive layer in the laminate consists of only the adhesive layer formed using the adhesive composition of the present invention and a single layer, the method for producing the laminate of the present invention includes the step of forming the adhesive layer (adhesion agent coating layer forming step and adhesive layer forming step) and, if necessary, other steps such as a bonding step. A method for producing a laminate in this case will be described in detail in the section <<first embodiment>> below.
Further, when the adhesive layer in the laminate has two or more (multiple layers) adhesive layers formed using the adhesive composition of the present invention, the method for producing the laminate of the present invention includes the adhesive layer. It includes a forming step (adhesive coating layer forming step and adhesive layer forming step) and, if necessary, other steps such as a bonding step. The method for manufacturing the laminate in this case will be described in detail in the section <<second embodiment>> below. However, in the second embodiment, the case where the adhesive layer is two layers will be described as an example.
Furthermore, when the adhesive layer in the laminate includes a second adhesive layer in addition to the adhesive layer formed using the adhesive composition of the present invention, the method for producing the laminate of the present invention includes adhesion In addition to the step of forming a layer (adhesive coating layer forming step and adhesive layer forming step), the step of forming a second adhesive layer (second adhesive coating layer forming step and second adhesive layer forming step), and further Other steps such as a bonding step are included as necessary. A method for producing a laminate in this case will be described in detail in the section <<third embodiment>> below.

<<First Embodiment>>
An adhesive layer is formed through an adhesive coating layer forming step and an adhesive layer forming step.

<<<Adhesive Coating Layer Forming Step>>>
In the adhesive coating layer forming step, an adhesive composition is applied to a semiconductor substrate with bumps to form an adhesive coating layer.
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 desired thickness of the adhesive layer in the laminate.
When the adhesive composition contains a solvent, preheating may be performed after the composition is applied when forming the adhesive coating layer for the purpose of removing the solvent. The preheating temperature is usually 90 to 130° C. for 1 to 5 minutes in consideration of the boiling point of the solvent, the film thickness, the curing initiation temperature of the thermosetting adhesive component, and the thermal expansion temperature of the thermally expandable particles. Determined as appropriate.

<<<adhesive layer forming step>>>
In the adhesive layer forming step, the adhesive coating layer is heated to cure the thermosetting adhesive component to form the adhesive layer.
Heating can be performed using a hot plate, an oven, or the like.
In the present invention, the curing initiation temperature Tc (°C) of the thermosetting adhesive component is the curing initiation temperature exhibited by the thermosetting adhesive component used for this type of application, and does not adversely affect the members and materials used together. Although the temperature is not particularly limited as long as it is not too high, it is usually 90 to 160°C, preferably 100 to 150°C.
Further, the expansion start temperature Ts (° C.) of the thermally expandable particles is appropriately determined in consideration of the relationship with the curing start temperature of the thermosetting adhesive component, but is usually 70 to 160° C. It is preferably 80 to 150°C.
The heating temperature in the adhesive layer forming step is appropriately determined in consideration of the curing start temperature of the thermosetting adhesive component so that curing is achieved. From the viewpoint of achieving a curing speed, the temperature is usually 170°C or higher, preferably 200°C or higher, and the upper limit is usually 250°C.
The heating time is preferably 1 to 20 minutes from the viewpoint of improving the throughput of manufacturing semiconductor substrates using the adhesive composition of the present invention.

As the adhesive layer forming step, if the adhesive layer is formed by heating the adhesive layer while the supporting substrate and the adhesive layer are in contact with each other and the adhesive layer and the semiconductor substrate are in contact with each other, the adhesive layer is formed. Not limited.
For example, by using a semiconductor substrate on which an adhesive coating layer is formed and a supporting substrate, and disposing the two substrates (semiconductor substrate and supporting substrate) so as to sandwich the adhesive coating layer, the supporting substrate and the adhesive are applied. After bringing the layers into contact and the adhesive coating layer and the semiconductor substrate into contact, heat treatment may be performed.
The heating temperature and time are not particularly limited as long as the temperature and time are such that the thermosetting adhesive component is cured.
The heating temperature is appropriately determined in consideration of the curing initiation temperature of the thermosetting adhesive component and the heat resistance of the substrate to be used. C. or higher, more preferably 170.degree. C. or higher, still more preferably 200.degree. C. or higher, and preferably 250.degree.
The heating time is appropriately determined according to the heating temperature, but is preferably 1 minute or longer, more preferably 5 minutes or longer, from the viewpoint of sufficiently accelerating the curing of the thermosetting adhesive component. From the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating, the time is preferably 180 minutes or less, more preferably 120 minutes or less, even more preferably 60 minutes or less, and still more preferably 20 minutes or less. is.
Heating can be performed using a hot plate, an oven, or the like.

(Lamination process)
A bonding step is preferably performed between the adhesive coating layer forming step and the adhesive layer forming step in order to ensure sufficient bonding between the semiconductor substrate and the supporting substrate. Better bonding can be realized with good reproducibility by laminating using the adhesive coating layer, which is a film having a certain degree of flexibility before becoming an adhesive layer, which is a cured film.
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.

<<Second Embodiment>>
After forming the first adhesive layer through the adhesive coating layer forming step and the adhesive layer forming step, the second adhesive layer is adhered through the same steps as the adhesive coating layer forming step and the adhesive layer forming step. form a layer.
The first adhesive layer is formed by applying an adhesive composition to a semiconductor substrate with bumps using the same method as the adhesive coating layer forming step described in the above <<first embodiment>>. An adhesive coating layer can be formed.
Next, the adhesive coating layer is heated to cure the thermosetting adhesive component to form the first adhesive layer. Various conditions for forming the adhesive layer from the adhesive coating layer are as described in the <<<adhesive layer forming step>>> section of <<first embodiment>>.

Next, the second adhesive layer is formed through an adhesive coating layer forming step and an adhesive layer forming step.
The coating method used in the second-layer adhesive coating layer forming step is not particularly limited as long as the second-layer adhesive composition is applied so as to be in contact with either the support substrate or the first-layer adhesive layer. Instead, the same coating method as the coating method described in the adhesive coating layer forming step of <<first embodiment>> can be used.
In the second adhesive layer forming step, the adhesive coating layer obtained in the second adhesive coating layer forming step is heated to cure the thermosetting adhesive component, thereby forming the second adhesive layer. do.

In the step of forming the second adhesive layer, the second adhesive layer is formed in a state in which the support substrate and the second adhesive coating layer are in contact with each other and the second adhesive coating layer and the first adhesive layer are in contact with each other. The process is not particularly limited as long as it is a process in which the adhesive coating layer is heated to form a second adhesive layer.
For example, using a semiconductor substrate on which a first adhesive layer and a second adhesive coating layer are formed and a support substrate, or a semiconductor substrate on which a first adhesive layer is formed and a second layer Two substrates (a semiconductor substrate and a supporting substrate) are sandwiched between two layers (the first adhesive layer and the second adhesive layer) by using a supporting substrate on which an adhesive coating layer is formed. By disposing, the support substrate and the second adhesive coating layer are brought into contact with each other, and after the second adhesive coating layer and the first adhesive layer are brought into contact with each other, heat treatment may be performed. .
The heating temperature and time are not particularly limited as long as the temperature and time are such that the thermosetting adhesive component is cured.
As the heating conditions, the same conditions as those described in the adhesive layer forming step of <<first embodiment>> can be used, and the suitable conditions and the like are also the same as those described above.

(Lamination process)
Between the step of forming the second adhesive layer and the step of forming the second adhesive layer, a bonding step may be performed to ensure sufficient bonding between the semiconductor substrate and the support substrate. preferable. By performing the bonding using the adhesive coating layer, which is a film having a certain degree of flexibility before becoming the adhesive layer, which is a cured film, it is possible to achieve better bonding with good reproducibility.
As the bonding step, the same conditions as those described in the above <<first embodiment>> can be used, and the suitable conditions and the like are also the same as those described above.

<<Third Embodiment>>
After the adhesive layer is formed through the adhesive coating layer forming step and the adhesive layer forming step, the second adhesive layer is formed.
The second adhesive layer is formed through a second adhesive coating layer forming step and a second adhesive layer forming step.
The coating method used in the second adhesive coating layer forming step is not particularly limited as long as the second adhesive composition containing a thermosetting adhesive component is applied so as to be in contact with either the support substrate or the adhesive layer. Instead, the same coating method as described in the step of forming the adhesive coating layer in the above <<first embodiment>> can be used, and the suitable conditions and the like are also the same as those described above.
The second adhesive layer forming step forms the second adhesive layer by heating the second adhesive coating layer obtained in the second adhesive coating layer forming step to cure the thermosetting adhesive component.

In the second adhesive layer forming step, the second adhesive layer is heated while the support substrate and the second adhesive layer are in contact with each other, and the second adhesive layer and the adhesive layer are in contact with each other. is not particularly limited as long as it is a step in which is formed.
For example, using a semiconductor substrate having an adhesive layer and a second adhesive coating layer formed thereon and a supporting substrate, or using a semiconductor substrate having an adhesive layer formed thereon and a supporting substrate having a second adhesive coating layer formed thereon. By arranging the two substrates (semiconductor substrate and supporting substrate) so as to sandwich the two layers (adhesive layer and second adhesive coating layer), the supporting substrate and the second adhesive coating layer are brought into contact with each other. And, after the second adhesive coating layer and the adhesive layer are brought into contact with each other, the heat treatment may be performed.
The heating temperature and time are not particularly limited as long as the temperature and time are such that the thermosetting adhesive component is cured.
As the heating conditions, the same conditions as those described in the adhesive layer forming step of <<first embodiment>> can be used, and the suitable conditions and the like are also the same as those described above.

(Lamination process)
A bonding step is preferably performed between the second adhesive coating layer forming step and the second adhesive layer forming step in order to ensure sufficient bonding between the semiconductor substrate and the supporting substrate. By performing the bonding using the adhesive coating layer, which is a film having a certain degree of flexibility before becoming the adhesive layer, which is a cured film, it is possible to achieve better bonding with good reproducibility.
As the bonding step, the same conditions as those described in the above <<first embodiment>> can be used, and the suitable conditions and the like are also the same as those described above.

(Method for manufacturing semiconductor substrate)
The laminate of the present invention is used for temporary bonding for processing semiconductor substrates, 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 according to the present invention.

<<Polishing process>>
The polishing process is not particularly limited as long as it is a process 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 stacking a plurality of thinned semiconductor substrates.
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 the conductive material is performed by, for example, a plating technique.

<Peeling process>
The peeling step is not particularly limited as long as it is a step in which the supporting substrate and the processed semiconductor substrate are separated after the processing step.
For example, there is a method of mechanically peeling with a machine having a sharp portion (so-called debonder). Specifically, for example, after inserting the sharp portion between the semiconductor substrate and the support substrate, the semiconductor substrate and the support substrate are separated. Since the first adhesive layer provided in the laminate of the present invention has voids, the first adhesive layer is usually preferably broken, and the processed semiconductor substrate can be preferably separated from the indicator substrate.

<Other processes>
<<Removal process>>
In the removing step, the adhesive layer residue adhering to the processed semiconductor substrate is removed after the peeling step. The removal method is not particularly limited, but for example, dissolution removal with a cleaner containing salt can be mentioned. Alternatively, removal may be performed using a removal tape or the like. At this time, care must be taken not to damage the bumps.

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.
Another 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. 3A to 3H.
2A to 2F are diagrams for explaining one aspect of manufacturing a laminate and manufacturing a thin wafer.
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 10 to form an adhesive coating layer 2a (FIG. 2B).
Next, a support substrate 4 is arranged on the adhesive coating layer 2a (FIG. 2C).
Next, after bonding the wafer 1 and the support substrate 4 together under reduced pressure so as to sandwich the adhesive coating layer, a heating device (hot plate ) 11 is placed, and the adhesive coating layer 2a is heated by the heating device 11 to cure the thermosetting adhesive component and convert it into the 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, a peeling device (not shown) is used to separate the thinned wafer 1 from the support substrate 4 (FIG. 2F). By peeling off the adhesive layer 2, the thinned wafer 1 and the supporting substrate 4 are separated. In addition, when the adhesive layer is peeled off, the adhesive layer may remain on the wafer 1 on which the bumps 1a are present. In this case, the remainder of the adhesive layer can be removed, for example, by the method described in <Removing step> above.
A thinned wafer 1 is thus obtained.

3A to 3H are diagrams for explaining another mode of manufacturing a laminate and manufacturing a thin wafer.
First, a wafer 1 having bumps 1a is prepared (FIG. 3A).
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. 3B).
Next, 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 form a thermosetting adhesive component. hardens and converts to adhesive layer 2 (FIG. 3C).
Next, a second adhesive composition is applied onto the adhesive layer 2 by spin coating using a coating device 14 to form a second adhesive coating layer 3a (FIG. 3D).
Next, a support substrate 4 is arranged on the second adhesive coating layer 3a (FIG. 3E).
Next, after bonding the wafer 1 and the support substrate 4 together under reduced pressure so as to sandwich the adhesive layer and the second adhesive coating layer, on the surface of the wafer 1 opposite to the surface where the bumps 1a are present, A heating device (hot plate) 15 is provided, and the adhesive coating layer 3a is heated by the heating device 15 to cure the thermosetting adhesive component and convert it into the adhesive layer 3 (FIG. 3F).
A laminate is obtained by the steps shown in FIGS. 3A to 3F.
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. 3G). It should be noted that through electrodes may be formed on the thinned wafer 1 .
Next, a peeling device (not shown) is used to separate the thinned wafer 1 from the support substrate 4 (FIG. 3H). By peeling off the adhesive layer 2, the thinned wafer 1 and the supporting substrate 4 are separated. In addition, when the adhesive layer is peeled off, the adhesive layer may remain on the wafer 1 on which the bumps 1a are present. In this case, the remainder of the adhesive layer can be removed, for example, by the method described in <Removing step> above.
A thinned wafer 1 is thus obtained.

The method for improving the storage stability of the adhesive composition of the present invention includes a thermosetting adhesive component containing polyorganosiloxane and thermally expandable particles for temporary bonding for processing semiconductor substrates. A method for improving the storage stability of an adhesive composition used to form an adhesive layer, wherein the content of the thermally expandable particles is 3.5% by mass with respect to the thermosetting adhesive component. It shall be as follows. Suitable conditions for the thermosetting adhesive component, thermally expandable particles, their content, etc. are the same as above.
According to the method for improving the storage stability of the adhesive composition of the present invention, when the adhesive composition is stored at 23° C., usually at least 5 days after storage, preferably at least 10 days after storage, In a more preferred embodiment, even after a storage period of at least 20 days after storage, in a still more preferred embodiment, at least 30 days after storage, and in a further preferred embodiment, at least 60 days after storage, visual inspection Excellent storage stability can be achieved with no precipitation observed in the composition when observed.

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.

[Device]
(1) Stirrer: Rotation/Revolution Mixer ARE-500 manufactured by Thinky Co., Ltd.
(2) Vacuum bonding device: manual bonder manufactured by Sus Microtec Co., Ltd. (3) DSC: Q-2000 differential scanning calorimeter manufactured by TA Instruments Co., Ltd.
(4) Peeling device: manual debonder manufactured by Sus Microtec Co., Ltd.

The physical properties of the thermally expandable particles used (all manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) are shown in Table 1 below. The thermally expandable particles used were all thermally expandable particles in which the thermoplastic resin forming the shell was an acrylonitrile-based copolymer shell and the volatile substance therein was a hydrocarbon.

[1] Preparation of thermosetting adhesive component (hereinafter also referred to as adhesive component) [Preparation Example 1]
In a 600 mL stirring vessel dedicated to the rotation/revolution mixer, 80 g of an MQ resin (manufactured by Wacker Chemi Co., Ltd.) containing a polysiloxane skeleton and a vinyl group as the component (a1), and a linear chain containing SiH groups having a viscosity of 100 mPa s as the component (a2). 2.52 g of polydimethylsiloxane (manufactured by Wacker Chemi Co.), 5.89 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemi Co.) having a viscosity of 70 mPa s as the component (a2), 1- as the component (A3) 0.22 g of ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) was added and stirred for 5 minutes with a stirrer.
To the resulting mixture, 0.147 g of a platinum catalyst (manufactured by Wacker Chemie) as the component (A2) and a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 1,000 mPa s as the component (a1) were added. 5.81 g was stirred with a stirrer for 5 minutes and 3.96 g of the separately obtained mixture was added and stirred with a stirrer for 5 minutes.
Finally, the resulting mixture was filtered through a nylon filter of 300 mesh to obtain an adhesive component.

[2] Preparation of adhesive composition

[Example 1-1]
30 g of the adhesive component obtained in Preparation Example 1, 0.15 g of thermally expandable particles FN-80GSD, and propylene glycol-1-monomethyl ether-2-acetate (Tokyo Chemical Industry Co., Ltd.) were placed in a 600 mL stirring vessel dedicated to the rotation/revolution mixer. The same applies hereinafter) was added, and the mixture was stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a nylon filter of 300 mesh to obtain an adhesive composition.

[Example 1-2]
30 g of the adhesive component obtained in Preparation Example 1, 0.30 g of thermally expandable particles FN-80GSD, and 0.6 g of propylene glycol-1-monomethyl ether-2-acetate were placed in a 600 mL stirring vessel dedicated to the rotation/revolution mixer, and stirred. mechanically agitated for 5 minutes. Finally, the resulting mixture was filtered through a nylon filter of 300 mesh to obtain an adhesive composition.

[Example 1-3]
30 g of the adhesive component obtained in Preparation Example 1, 0.60 g of thermally expandable particles FN-80GSD, and 0.6 g of propylene glycol-1-monomethyl ether-2-acetate were placed in a 600 mL stirring vessel dedicated to the rotation/revolution mixer, and stirred. mechanically agitated for 5 minutes. Finally, the resulting mixture was filtered through a nylon filter of 300 mesh to obtain an adhesive composition.

[Example 1-4]
30 g of the adhesive component obtained in Preparation Example 1, 0.90 g of thermally expandable particles FN-80GSD, and 0.6 g of propylene glycol-1-monomethyl ether-2-acetate were placed in a 600 mL stirring vessel dedicated to the rotation/revolution mixer, and stirred. mechanically agitated for 5 minutes. Finally, the resulting mixture was filtered through a nylon filter of 300 mesh to obtain an adhesive composition.

[Comparative Example 1-1]
30 g of the adhesive component obtained in Preparation Example 1, 1.2 g of thermally expandable particles FN-80GSD, and 0.6 g of propylene glycol-1-monomethyl ether-2-acetate were placed in a 600 mL stirring vessel dedicated to the rotation/revolution mixer, and stirred. mechanically agitated for 5 minutes. Finally, the resulting mixture was filtered through a nylon filter of 300 mesh to obtain an adhesive composition.

[Comparative Example 1-2]
30 g of the adhesive component obtained in Preparation Example 1, 1.5 g of thermally expandable particles FN-80GSD, and 0.6 g of propylene glycol-1-monomethyl ether-2-acetate were placed in a 600 mL stirring vessel dedicated to the rotation/revolution mixer, and stirred. mechanically agitated for 5 minutes. Finally, the resulting mixture was filtered through a nylon filter of 300 mesh to obtain an adhesive composition.

[Comparative Preparation Example 1]
In a 600 mL stirring vessel dedicated to the rotation/revolution mixer, 30 g of a synthetic rubber adhesive, ThreeBond 1521B (ThreeBond Fine Chemical Co., Ltd.), 0.15 g of thermally expandable particles FN-80GSD, and 0% of propylene glycol-1-monomethyl ether-2-acetate. .6 g was added and stirred with a stirrer for 5 minutes. Finally, the resulting mixture was filtered through a nylon filter of 300 mesh to obtain an adhesive composition.

[3] Preparation of sample substrate [Manufacturing Example 1]
A substrate with bumps (wafer) was cut as a device-side wafer (semiconductor substrate) to prepare a sample substrate of 4 cm×4 cm. The number of bumps per sample substrate was 5044, and the bump structure consisted of copper in the pillar portion, tin silver (1.8 wt % silver) in the cap portion, and nickel between the pillar and the cap. ing.

[Production Example 2]
A silicon wafer was cut as a device-side wafer (semiconductor substrate) to prepare a sample substrate of 4 cm×4 cm.

[4] Preparation of laminate for evaluation [Comparative Example 2-1]
The adhesive component obtained in Preparation Example 1 was spin-coated onto the bump-existing surface of the sample substrate obtained in Production Example 1 so that the film thickness in the finally obtained laminate would be about 60 μm. , to form an adhesive coating layer.
Then, using a bonding apparatus, a sample substrate (silicon wafer) and a 100 mm glass wafer as a support substrate are bonded so as to sandwich the adhesive coating layer, and then, with the sample substrate facing down, the sample substrate is placed on a hot plate at 200°C. A laminate was produced by heat-treating at °C for 10 minutes. The bonding was performed at a temperature of 23° C. and a reduced pressure of 1,500 Pa.

[Comparative Example 2-2]
The adhesive component obtained in Preparation Example 1 was spin-coated onto the bump-existing surface of the sample substrate obtained in Production Example 1 so that the film thickness in the finally obtained laminate would be about 10 μm. Afterwards, an adhesive layer was formed by heat-treating on a hot plate at 200° C. for 5 minutes.
Furthermore, on the adhesive layer of the sample substrate, the adhesive component obtained in Preparation Example 1 was spin-coated so that the film thickness in the finally obtained laminate was about 50 μm, and the second adhesive was applied onto the adhesive layer. A coating layer was formed.
Then, using a bonding apparatus, the sample substrate (silicon wafer) and the glass wafer are bonded together so as to sandwich the adhesive layer and the second adhesive coating layer, and then, with the sample substrate facing down, the sample substrate is placed at 200°C on a hot plate. A laminate was produced by heat-treating at °C for 10 minutes. The bonding was performed at a temperature of 23° C. and a reduced pressure of 1,500 Pa.

[Example 2-1]
The adhesive composition obtained in Example 1-1 was applied to the bump-existing surface of the sample substrate obtained in Production Example 1 so that the film thickness in the finally obtained laminate was about 60 μm. An adhesive coating layer was formed on the sample substrate by spin coating.
Then, using a bonding apparatus, a sample substrate (silicon wafer) and a 100 mm glass wafer as a support substrate are bonded so as to sandwich the adhesive coating layer, and then, with the sample substrate facing down, the sample substrate is placed on a hot plate at 200°C. A laminate was produced by heat-treating at °C for 10 minutes. The bonding was performed at a temperature of 23° C. and a reduced pressure of 1,500 Pa.

[Example 2-2]
The adhesive composition obtained in Example 1-1 was applied to the bump-existing surface of the sample substrate obtained in Production Example 1 so that the film thickness in the finally obtained laminate was about 30 μm. After spin coating, an adhesive layer was formed on the sample substrate by heat treatment on a hot plate at 200° C. for 5 minutes.
Furthermore, on the adhesive layer of the sample substrate, the adhesive component obtained in Preparation Example 1 was spin-coated so that the film thickness in the finally obtained laminate was about 30 μm, and the second adhesive was applied onto the adhesive layer. A coating layer was formed.
Then, using a bonding apparatus, a sample substrate (silicon wafer) and a 100 mm glass wafer as a support substrate are bonded so as to sandwich the adhesive layer and the second adhesive coating layer, and then the sample substrate is placed downward. A laminate was produced by heat-treating on a hot plate at 200° C. for 10 minutes. The bonding was performed at a temperature of 23° C. and a reduced pressure of 1,500 Pa.

[Example 2-3]
The adhesive composition obtained in Example 1-1 was applied to the bump-existing surface of the sample substrate obtained in Production Example 1 so that the film thickness in the finally obtained laminate was about 10 μm. After spin coating, an adhesive layer was formed on the sample substrate by heat treatment on a hot plate at 200° C. for 5 minutes.
Furthermore, on the adhesive layer of the sample substrate, the adhesive component obtained in Preparation Example 1 was spin-coated so that the film thickness in the finally obtained laminate was about 50 μm, and the second adhesive was applied onto the adhesive layer. A coating layer was formed.
Then, using a bonding apparatus, a sample substrate (silicon wafer) and a 100 mm glass wafer as a support substrate are bonded so as to sandwich the adhesive layer and the second adhesive coating layer, and then the sample substrate is placed downward. A laminate was produced by heat-treating on a hot plate at 200° C. for 10 minutes. The bonding was performed at a temperature of 23° C. and a reduced pressure of 1,500 Pa.

[Example 2-4]
The adhesive composition obtained in Example 1-2 was applied to the bump-existing surface of the sample substrate obtained in Production Example 1 so that the film thickness in the finally obtained laminate was about 60 μm. An adhesive coating layer was formed on the sample substrate by spin coating.
Then, using a bonding apparatus, a sample substrate (silicon wafer) and a 100 mm glass wafer as a support substrate are bonded so as to sandwich the adhesive coating layer, and then, with the sample substrate facing down, the sample substrate is placed on a hot plate at 200°C. A laminate was produced by heat-treating at °C for 10 minutes. The bonding was performed at a temperature of 23° C. and a reduced pressure of 1,500 Pa.

[Example 2-5]
The adhesive composition obtained in Example 1-2 was applied to the bump-existing surface of the sample substrate obtained in Production Example 1 so that the film thickness in the finally obtained laminate was about 30 μm. After spin coating, an adhesive layer was formed on the sample substrate by heat treatment on a hot plate at 200° C. for 5 minutes.
Furthermore, on the adhesive layer of the sample substrate, the adhesive component obtained in Preparation Example 1 was spin-coated so that the film thickness in the finally obtained laminate was about 30 μm, and the second adhesive was applied onto the adhesive layer. A coating layer was formed.
Then, using a bonding apparatus, a sample substrate (silicon wafer) and a 100 mm glass wafer as a support substrate are bonded so as to sandwich the adhesive layer and the second adhesive coating layer, and then the sample substrate is placed downward. A laminate was produced by heat-treating on a hot plate at 200° C. for 10 minutes. The bonding was performed at a temperature of 23° C. and a reduced pressure of 1,500 Pa.

[Example 2-6]
The adhesive composition obtained in Example 1-2 was applied to the bump-existing surface of the sample substrate obtained in Production Example 1 so that the film thickness in the finally obtained laminate was about 10 μm. After spin coating, an adhesive layer was formed on the sample substrate by heat treatment on a hot plate at 200° C. for 5 minutes.
Furthermore, on the adhesive layer of the sample substrate, the adhesive component obtained in Preparation Example 1 was spin-coated so that the film thickness in the finally obtained laminate was about 50 μm, and the second adhesive was applied onto the adhesive layer. A coating layer was formed.
Then, using a bonding apparatus, a sample substrate (silicon wafer) and a 100 mm glass wafer as a support substrate are bonded so as to sandwich the adhesive layer and the second adhesive coating layer, and then the sample substrate is placed downward. A laminate was produced by heat-treating on a hot plate at 200° C. for 10 minutes. The bonding was performed at a temperature of 23° C. and a reduced pressure of 1,500 Pa.

[5] Peeling Test of Laminate Using a hot plate, the laminates obtained in Comparative Examples 2-1 to 2-2 and Examples 2-1 to 2-6 were subjected to high temperature treatment. The treatment was performed according to the following procedure. The support substrate of the laminate was placed face down on a hot plate set at 300° C. and heated for 5 minutes. After standing to cool, a wedge-shaped material was placed between the semiconductor substrate and the supporting substrate using a peeling device, and it was confirmed whether the semiconductor substrate (substrate with bumps) could be peeled from the laminate. Table 2 shows the results.

As shown in Table 2, the substrate could not be peeled off from the laminate having an adhesive layer obtained only from an adhesive component that did not contain thermally expandable particles (Comparative Examples 2-1 and 2-2). , the substrate could be peeled off from the laminates (Examples 2-1 to 2-6) having adhesive layers obtained from adhesive compositions containing thermally expandable particles.

[6] Adhesive Composition Storage Test The adhesive compositions obtained in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-2 were stored in glass screw tubes at 23° C. for 5 days. It was left to stand for days and stored, and the presence or absence of precipitation after storage was visually confirmed. Table 3 shows the results. In addition, in all adhesive compositions, no precipitation was confirmed immediately after preparation.

As shown in Table 3, precipitation was confirmed in adhesive compositions in which the amount of thermally expandable particles relative to the adhesive component exceeded 3.5% by mass, while the amount of thermally expandable particles relative to the adhesive component was No sedimentation was observed with the adhesive composition of 3.5% by mass or less.

[7] Observation of adhesive layer (film after heating) [Reference Examples 1 and 2 and Comparative Reference Examples 1 and 2]
The adhesive compositions obtained in Examples 1-1 and 1-2, the adhesive component obtained in Preparation Example 1, and the adhesive composition obtained in Comparative Preparation Example 1 were each obtained in Production Example 2. After spin-coating on the sample substrate so that the final film thickness is about 10 μm, the sample substrate is placed downward and subjected to heat treatment on a hot plate at 200° C. for 5 minutes. An adhesive layer was formed. Then, the adhesive layer on the sample substrate was observed with an optical microscope. At this time, if the porous state can be confirmed in approximately 30% or more of the area in the field of view observed with the optical microscope, "good" is indicated, and if the porous state can be confirmed in approximately less than 30% of the area, "not". "good", and "bad" when the porous state could not be confirmed at all. Table 4 shows the results.
In Table 4, the results using the adhesive compositions obtained in Examples 1-1 and 1-2 are shown in Reference Examples 1 and 2, and the results using the adhesive component obtained in Preparation Example 1 are for comparative reference. The results obtained using the adhesive composition obtained in Comparative Preparation Example 1 correspond to Example 1 and Comparative Reference Example 2, respectively.

As shown in Table 4, the adhesive layer (Reference Examples 1 and 2) obtained from an adhesive composition containing thermally expandable particles, which is provided in a laminate that can be peeled well, has an area of approximately 30% or more. While a porous state could be confirmed in , the adhesive layer (Comparative Reference Example 1) obtained from an adhesive component that does not contain thermally expandable particles, which is included in the laminate that could not be peeled, was about 30%. Porous state could be confirmed only in less area. Further, when a synthetic rubber-based adhesive component was used instead of the curable adhesive component (Comparative Reference Example 2), no porous state could be confirmed at all.
Since the adhesive composition of the present invention contains thermally expandable particles together with a thermosetting adhesive component, heat Evolution of gas from the inflatable particles occurs, which results in curing with voids (porosification) in the adhesive layer, and these voids reduce the adhesive ability of the adhesive layer compared to the case without voids. is presumed to cause a decrease in the thickness, and as a result, good peelability can be realized.

[8] Confirmation of curing start temperature Tc (° C.) of thermosetting adhesive component [Reference Example 3]
5 mg of the adhesive component obtained in Preparation Example 1 was put into an aluminum pan, and the calorific value was measured using DSC. The temperature was raised from room temperature (23°C) to 300°C at a rate of 10°C/min. The vertical axis represents the amount of heat generated, and the horizontal axis represents the temperature. As a result of the measurement, the curing initiation temperature Tc (°C) of the adhesive component obtained in Preparation Example 1 was 125°C.

According to the present invention, the semiconductor substrate can be easily peeled off from the adhesive layer when separating the semiconductor substrate and the support substrate after processing the semiconductor substrate while reducing the number of layers interposed between the semiconductor substrate and the support substrate, Moreover, since it is possible to obtain a laminated body in which the quality stability of the adhesive layer is ensured, it is useful for manufacturing processed semiconductor substrates.

1 Wafer 1a Bump 2 Adhesive Layer 2a Adhesive Application Layer 3 Second Adhesive Layer 3a Second Adhesive Application Layer 4 Support Substrate 10 Coating Device 11 Heating Device 12 Coating Device 13 Heating Device 14 Coating Device 15 Heating Device

Claims (4)

An adhesive composition used for forming an adhesive layer for temporary bonding to process a semiconductor substrate,
including a thermosetting adhesive component and thermally expandable particles,
The thermosetting adhesive component contains polyorganosiloxane,
An adhesive composition in which the thermally expandable particles are contained in an amount of 3.5% by mass or less with respect to the thermosetting adhesive component. The adhesive composition of Claim 1, wherein the thermosetting adhesive component is a component that cures by a hydrosilylation reaction. A laminate comprising an adhesive layer interposed between a semiconductor substrate and a supporting substrate and in contact with the semiconductor substrate,
A laminate, wherein the adhesive layer is a layer formed from the adhesive composition according to claim 1 or 2. Preservation of an adhesive composition used for forming an adhesive layer for temporary adhesion for processing a semiconductor substrate, comprising a thermosetting adhesive component containing polyorganosiloxane and thermally expandable particles A method of improving stability, comprising:
A method for improving the storage stability of an adhesive composition, characterized in that the content of the thermally expandable particles is 3.5% by mass or less with respect to the thermosetting adhesive component.

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