JP2022144612A - Release agent composition, laminate, manufacturing method of laminate, and manufacturing method of semiconductor substrate - Google Patents

Abstract

To provide a release agent composition, a laminate, a manufacturing method of the laminate, and a manufacturing method of a semiconductor substrate, in which the semiconductor substrate and a support substrate are not separated from each other at the time of temporary adhesion even when the semiconductor substrate is exposed to high temperatures during processing of the semiconductor substrate, and the semiconductor substrate and the support substrate can be separated easily from each other when attempting to separate the semiconductor substrate and the support substrate.SOLUTION: A laminate includes a support substrate 5, a semiconductor substrate 1, a release layer 2 interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate, and an adhesive layer 4 interposed between the support substrate and the release layer. The release layer is a layer formed of a release agent composition containing polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a release agent composition, a laminate, a method for producing a laminate, and a method for producing a semiconductor substrate.

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 (herein simply referred to as a wafer) before thinning is bonded to a support for polishing with a polishing apparatus.
The adhesion at that time is called temporary adhesion because it must be easily peeled off after polishing. This temporary adhesion must be easily removed from the support, and if a large force is applied to the removal, the thinned semiconductor wafer may be cut or deformed. easily removed. However, it is not preferable that the back surface of the semiconductor wafer is removed or displaced due to polishing stress. Therefore, the performance required for the temporary adhesion is to withstand the stress during polishing and to be easily removed after polishing.
For example, it is required to have high stress (strong adhesion) in the planar direction during polishing and low stress (weak adhesion) in the vertical direction during removal.

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

Japanese Patent No. 5335443

The thinned wafer may be heated to temperatures in excess of 200° C. before separation from the support. The heating temperature varies depending on the processing applied to the wafer, and in some cases can be as high as 280° C. or higher.
However, when the wafer, which is a semiconductor substrate, is heated to a high temperature, even if the semiconductor substrate and the support substrate are subsequently separated using the peeling layer interposed therebetween, the force required for separation is the heating. The inventors have found that a stronger force is required than when the temperature is low, and in some cases, a force strong enough to crack the thinned semiconductor substrate.

Therefore, according to the present invention, even after the semiconductor substrate is exposed to a high temperature, the semiconductor substrate and the support substrate are not separated when temporarily bonded, and can be easily separated when the semiconductor substrate and the support substrate are to be separated. An object of the present invention is to provide a laminate, a method for producing a semiconductor substrate using the laminate, a method for producing the laminate, and a release agent composition used for the laminate.

In order to solve the above problems, the present inventors conducted intensive studies, and as a result, found that the above problems can be solved, and completed the present invention having the following gist.

That is, the present invention includes the following.
[1] a support substrate;
a semiconductor substrate;
a peeling layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate;
an adhesive layer interposed between the support substrate and the release layer;
A laminate having
The laminate, wherein the release layer is a layer formed from a release agent composition containing a polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000.
[2] The laminate according to [1], wherein the polyorganosiloxane is polydimethylsiloxane.
[3] The laminate according to [1] or [2], wherein the adhesive layer is a layer formed from an adhesive composition.
[4] The laminate according to [3], wherein the adhesive composition contains a curable component (A).
[5] The laminate according to [4], wherein the component (A) is a component that cures by a hydrosilylation reaction.
[6] The component (A) is
A polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom;
a polyorganosiloxane (a2) having a Si—H group;
a platinum group metal-based catalyst (A2);
The laminate according to [4] or [5], containing
[7] The laminate according to any one of [1] to [6], which has an inorganic material layer interposed between the release layer and the adhesive layer.
[8] The laminate according to [7], wherein the inorganic material layer is a layer obtained by plasma-polymerizing an organosilicon compound.
[9] The laminate according to any one of [1] to [8], which is used in a process in which the semiconductor substrate is heated to 280° C. or higher.
[10] A step of processing the semiconductor substrate in the laminate according to any one of [1] to [8];
separating the support substrate from the processed semiconductor substrate;
A method of manufacturing a semiconductor substrate, comprising:
[11] Manufacture of a semiconductor substrate according to [10], wherein the processing step includes polishing the surface of the semiconductor substrate opposite to the surface in contact with the release layer to thin the semiconductor substrate. Method.
[12] The method of manufacturing a semiconductor substrate according to [10] or [11], wherein the processing step includes heating the semiconductor substrate to 280° C. or higher.
[13] A method for manufacturing a laminate for manufacturing the laminate according to any one of [1] to [9],
forming an adhesive coating layer providing said adhesive layer;
a step of heating the adhesive coating layer in a state in which the support substrate and the semiconductor substrate are in contact with each other with the release layer and the adhesive coating layer interposed therebetween to form the adhesive layer;
A method of manufacturing a laminate, comprising:
[14] A release agent composition used for forming a release layer in contact with a semiconductor substrate heated to 280° C. or higher,
A release agent composition containing a polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000.
[15] The release agent composition of [14], wherein the polyorganosiloxane is polydimethylsiloxane.
[16] A supporting substrate, the semiconductor substrate, the peeling layer interposed between the supporting substrate and the semiconductor substrate and in contact with the semiconductor substrate, and an adhesive layer interposed between the supporting substrate and the peeling layer. and used for forming the release layer in contact with the semiconductor substrate that is heated to 280° C. or higher when the semiconductor substrate of the laminate is processed, [14 ] or the release agent composition according to [15].

According to the present invention, even after the semiconductor substrate is exposed to a high temperature, the semiconductor substrate and the support substrate are not separated when temporarily bonded, and can be easily separated when the semiconductor substrate and the support substrate are to be separated. A laminate, a method for producing a semiconductor substrate using the laminate, a method for producing the laminate, and a release agent composition used for the laminate can be provided.

It is a schematic sectional drawing of an example of a laminated body.

(Laminate)
The laminate of the present invention has a supporting substrate, a semiconductor substrate, a release layer, an adhesive layer, and optionally an inorganic material layer.
The peeling layer is interposed between the supporting substrate and the semiconductor substrate and is in contact with the semiconductor substrate.
The adhesive layer is interposed between the supporting substrate and the release layer.

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

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

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

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

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

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

<Release layer>
The peeling layer is interposed between the supporting substrate and the semiconductor substrate and is in contact with the semiconductor substrate.
A release layer is a layer formed from a release agent composition.

<<Removing agent composition>>
The release agent composition contains polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000, and further contains other components as necessary.
That is, the polyorganosiloxane contained in the release agent composition has a weight average molecular weight of 22,000 to 68,000.
The release layer may consist of only polyorganosiloxane, or may contain other components. For example, when the release agent composition is composed only of polyorganosiloxane and volatile components, the volatile components are usually volatilized by heating during the formation of the release layer. Contains only polyorganosiloxane.

Since the polyorganosiloxane contained in the release agent composition has a weight average molecular weight of 22,000 or more, the semiconductor substrate is exposed to high temperatures (e.g., 280° C. or more) when processing the semiconductor substrate of the laminate. Even after the lamination, the semiconductor substrate and the support substrate of the laminate can be easily separated by a peeling device or the like. On the other hand, since the weight average molecular weight of the polyorganosiloxane contained in the release agent composition is 68,000 or less, even after the semiconductor substrate is exposed to high temperatures such as when processing the semiconductor substrate of the laminate, the semiconductor substrate and the support substrate can be maintained in a temporarily bonded state, and a state in which the semiconductor substrate and the support substrate are difficult to peel off can be maintained until the semiconductor substrate and the support substrate of the laminate are to be peeled off by a peeling device or the like.
When the weight-average molecular weight of the polyorganosiloxane contained in the release agent composition is less than 22,000, the semiconductor substrate of the laminate is exposed to high temperatures such as when the semiconductor substrate of the laminate is processed. When an attempt is made to separate the semiconductor substrate from the supporting substrate by using a separating device or the like, the semiconductor substrate cannot be easily separated, and in some cases, the semiconductor substrate may crack when the semiconductor substrate is separated from the supporting substrate. When the weight average molecular weight of the polyorganosiloxane contained in the release agent composition exceeds 68,000, the adhesive strength of the release layer after the semiconductor substrate is exposed to high temperatures such as when processing the semiconductor substrate of the laminate is reduced. It is weak, and peeling occurs even when temporary bonding between the semiconductor substrate and the supporting substrate is required.

The weight average molecular weight of the polyorganosiloxane is preferably 25,000 to 65,000, more preferably 30,000 to 60,000, from the viewpoint of achieving the effects of the present invention with good reproducibility.

The weight average molecular weight and number average molecular weight of the polyorganosiloxane are determined, for example, using a GPC apparatus (HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), and the column temperature is 40° C., tetrahydrofuran is used as an eluent (elution solvent), the flow rate (flow rate) is 0.35 mL/min, and polystyrene (manufactured by Shodex) is used as a standard sample.

The polyorganosiloxane dispersity (weight average molecular weight (Mw)/number average molecular weight (Mn)) is not particularly limited, but is preferably 1.50 to 20.0, more preferably 2.00 to 15.0.

In the present invention, the volatile silicone oil described later is not included in the polyorganosiloxane.

Examples of polyorganosiloxane include, but are not limited to, epoxy group-containing polyorganosiloxane, methyl group-containing polyorganosiloxane, phenyl group-containing polyorganosiloxane, and the like.

Moreover, polydimethylsiloxane is mentioned as polyorganosiloxane. The polydimethylsiloxane may be modified. Therefore, examples of polydimethylsiloxane include, but are not limited to, epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, and phenyl group-containing polydimethylsiloxane.

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, and R ¹² is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group.
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.
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.

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.)

Examples of the methyl group-containing polyorganosiloxane include those containing a siloxane unit ( ^D200 unit) represented by R ²¹⁰ R ²²⁰ SiO _2/2 , preferably a siloxane unit represented by R ²¹ R ²¹ SiO _2/2 (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 a polyorganosiloxane consisting only of ^D20 units, a polyorganosiloxane containing ^D20 units and Q units, and a 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、４以上の正の整数である。）

(n4 indicates the number of repeating units and is a positive integer of ₄ or more.)

The methyl group-containing polyorganosiloxane represented by the formula (M1) is polydimethylsiloxane, but in the bulk of polydimethylsiloxane, —Si(CH ₃ ) ₃ groups and —Si( It is undeniable that polydimethylsiloxanes containing groups other than CH ₃ ) ₂ --O-- groups exist as trace impurity structures.

Examples of phenyl group-containing polyorganosiloxanes include those containing siloxane units ( ^D30 units) represented by R ³¹ R ³² SiO _2/2 .

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 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.)

The polyorganosiloxane may be a commercial product or a synthesized one.
Examples of commercially available polyorganosiloxanes include trade names AK 50, AK 350, AK 1000, AK 10000 and AK 1000000 manufactured by Wacker Chemie.

A commercially available polyorganosiloxane may be used alone as it is when the weight average molecular weight thereof is a desired value. Further, for example, two or more types having different weight average molecular weights may be used in combination so that the weight average molecular weight of the polyorganosiloxane in the release layer becomes a desired value.
Also, the synthesized polyorganosiloxane may be used singly as it is when the weight average molecular weight thereof is a desired value. Further, for example, two or more types of separately synthesized polyorganosiloxanes having different weight average molecular weights may be used in combination so that the release layer has a desired weight average molecular weight.
Furthermore, a commercially available product and a synthesized product may be used in combination.

The release agent composition may contain a solvent.
Such a solvent is not particularly limited as long as it can dissolve polyorganosiloxane well. Specific examples of such a good solvent include hexane, heptane, octane, nonane, decane, and undecane. Linear or branched chain aliphatic hydrocarbons such as linear or branched saturated aliphatic hydrocarbons such as dodecane and isododecane; cyclohexane, cycloheptane, cyclooctane, isopropylcyclohexane, p-menthane cycloaliphatic hydrocarbons such as saturated hydrocarbons, unsaturated cyclic aliphatic hydrocarbons such as limonene; benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, Aromatic hydrocarbons such as cumene, 1,4-diisopropylbenzene and p-cymene; Dialkyl ketones such as MIBK (methyl isobutyl ketone), ethyl methyl ketone, acetone, diisobutyl ketone, 2-octanone, 2-nonanone and 5-nonanone , Aliphatic saturated hydrocarbon ketones such as cycloalkyl ketones such as cyclohexanone, ketones such as aliphatic unsaturated hydrocarbon ketones such as alkenyl ketones such as isophorone; diethyl ether, di (n-propyl) ether, di (n-butyl) ) ether, dialkyl ether such as di(n-pentyl) ether, ether such as cyclic alkyl ether such as tetrahydrofuran, dioxane; dialkyl sulfide such as diethyl sulfide, di(n-propyl) sulfide, di(n-butyl) sulfide, etc. sulfide; N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, amides such as 1,3-dimethyl-2-imidazolidinone; acetonitrile, 3-methoxy Nitriles such as propionitrile; glycol monohydrocarbons such as glycol monoalkyl ethers such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and glycol monoaryl ethers such as diethylene glycol monophenyl ether; Ether; Alkyl alcohol such as cyclic alkyl alcohol such as cyclohexanol, diacetone alcohol, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, tetrahydrofurfury monoalcohols other than alkyl alcohol such as diol alcohol; ethylene glycol monohexyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, dipropylene glycol Monomethyl ether, diethylene glycol monopropyl ether (propyl carbitol), diethylene glycol monohexyl ether, 2-ethylhexyl carbitol, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, diethylene glycol monomethyl ether, tripropylene glycol monobutyl ether, etc. Alkyl ethers, glycol monoethers such as glycol monoaryl ethers such as 2-phenoxyethanol; ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dibutyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol dimethyl ether , dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, glycol dialkyl ether such as tetraethylene glycol dimethyl ether; dipropylene glycol monomethyl ether acetate, diethylene glycol mono glycol ether acetates such as ethyl ether acetate, diethylene glycol monobutyl ether acetate, glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate; cyclic carbonates such as ethylene carbonate, propylene carbonate and vinylene carbonate; esters such as butyl acetate and pentyl acetate; mentioned.
Volatile silicone oil may also be used as the solvent. Volatile silicone oil in the present invention refers to the following compounds having 2 to 5 silicon atoms.
Hexamethyldisiloxane, heptamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethylcyclotetrasiloxane, and pentamethylcyclopentasiloxane These solvents can be used singly or in combination of two or more.

In addition, the release agent composition may contain one or more poor solvents in addition to the good solvent for the purpose of adjusting the viscosity and surface tension, as long as the polyorganosiloxane does not precipitate. Examples include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 2,3-butanediol; linear or branched chains such as methanol, ethanol, propanol, etc. Alkyl monoalcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, triethylene glycol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1 , 4-butanediol and 1,5-pentanediol.

When the release agent composition contains a solvent, the amount of the solvent can be generally 70% by weight to 99.9% by weight based on the total composition. 0.1% by mass to 30% by mass.

The release agent composition may contain other components other than the polyorganosiloxane and the solvent as long as the effects of the present invention are not impaired. From the viewpoint of avoiding complicated preparation, the release agent composition preferably contains only polyorganosiloxane and solvent.

The release agent composition can be produced, for example, by mixing polyorganosiloxane and a solvent.
The mixing order is not particularly limited, but examples of methods for easily and reproducibly producing a release agent composition include a method of dissolving polyorganosiloxane in a solvent at once, and a method of dissolving polyorganosiloxane in a solvent. Examples include, but are not limited to, a method of dissolving a part in a solvent, separately dissolving the remainder in a solvent, and mixing the resulting solutions. When preparing the release agent composition, it may be appropriately heated within a range in which the components are not decomposed or deteriorated.

In the present invention, for the purpose of removing foreign matter, the solvent, solution, or the like used may be filtered using a filter or the like during production of the release agent composition or after all the components are mixed.

The release agent composition described above is also the object of the present invention, and the related conditions (preferred conditions, manufacturing conditions, etc.) are as described above. By using the release agent composition of the present invention, a film suitable as a release layer that can be used, for example, in the production of semiconductor devices can be produced with good reproducibility.

The release agent composition is used, for example, to form a release layer in contact with a semiconductor substrate heated to 280° C. or higher.
Further, the release agent composition includes, for example, a support substrate, a semiconductor substrate, a release layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate, and an adhesive layer interposed between the support substrate and the release layer. and is used to form a release layer in contact with a semiconductor substrate that is heated to 280° C. or higher when the semiconductor substrate of the laminate is processed.

The content of polyorganosiloxane in the release layer is not particularly limited, but is preferably 95% by mass or more, more preferably 99% by mass or more, and most preferably 100% by mass. The content of polyorganosiloxane in the release layer of 100% by mass means that the release layer is composed only of components intentionally included as polyorganosiloxane. and the presence of impurities contained in the bulk polyorganosiloxane cannot be denied.

The thickness of the release layer included in the laminate of the present invention is not particularly limited, but is usually 10 to 500 nm. The thickness is preferably 100 nm or more, and is preferably 400 nm or less, more preferably 350 nm or less, even more preferably 300 nm or less, still more preferably 250 nm or less from the viewpoint of avoiding non-uniformity due to a thick film.

<Adhesive layer>
The adhesive layer is interposed between the supporting substrate and the release layer.
The adhesive layer is usually in contact with the support substrate.

Although the adhesive layer is not particularly limited, it is preferably a layer formed from an adhesive composition.

<<Adhesive Composition>>
Examples of adhesive compositions include polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, phenolic resin-based adhesives, and the like. but not limited to these.
Among these, polysiloxane-based adhesives are preferred as the adhesive composition because they exhibit suitable adhesive properties during processing of semiconductor substrates, etc., can be peeled off after processing, and are also excellent in heat resistance. preferable.
Also, the adhesive composition may be a thermosetting adhesive or a thermoplastic adhesive.

In a preferred embodiment, the adhesive composition contains polyorganosiloxane.
Also, in another preferred embodiment, the thermosetting adhesive composition includes components that cure via a hydrosilylation reaction.
More specific embodiments of the thermosetting adhesive composition used in the present invention include, for example, the following <<first embodiment>> to <<third embodiment>>.
Further, as a more specific embodiment of the thermoplastic adhesive composition used in the present invention, for example, <<fourth embodiment>> can be mentioned.

<<First Embodiment>>
As a preferred embodiment, the adhesive composition used in the present invention contains polyorganosiloxane.
For example, the adhesive composition used in the present invention contains a curable component (A) that serves as an adhesive component. The adhesive composition used in the present invention may contain a component (A) that cures as an adhesive component and a component (B) that does not cause a curing reaction. Here, examples of the component (B) that does not cause a curing reaction include polyorganosiloxane. In the present invention, "does not cause a curing reaction" does not mean that no curing reaction occurs, but rather means that the component (A) to be cured does not cause a curing reaction.
In another preferred embodiment, component (A) may be a component that cures by a hydrosilylation reaction or a polyorganosiloxane component (A') that cures by a hydrosilylation reaction.
In another preferred embodiment, the component (A) comprises, for example, a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, as an example of the component (A'), and Si- It contains a polyorganosiloxane (a2) having an H group 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 a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2- methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group , 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n -propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1 , 2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl -Cycloalkyl groups such as 2-methyl-cyclopropyl group and 2-ethyl-3-methyl-cyclopropyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, Examples include, but are not limited to, bicycloalkyl groups such as bicyclodecyl group, and the number of carbon atoms thereof is usually 3-14, preferably 4-10, more preferably 5-6.

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

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

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

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

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

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

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

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

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

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

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

The weight-average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but each is usually 500 to 1,000,000, and the effects of the present invention are realized with good reproducibility. From the viewpoint of doing, it is preferably 5,000 to 50,000.
In the present invention, the weight-average molecular weight, number-average molecular weight, and degree of dispersion of the polyorganosiloxane are determined, for example, by a GPC apparatus (manufactured by Tosoh Corporation, HLC-8320GPC) and a GPC column (manufactured by Tosoh Corporation, TSKgel SuperMultiporeHZ-N, TSKgel SuperMultipore HZ-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, polystyrene (manufactured by Shodex) was used as a standard sample, can be measured.

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

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

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

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

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

The weight-average molecular weight of the polyorganosiloxane, which is the component (B), is not particularly limited, but is usually 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 degree of dispersion can be measured by the above-described methods for the polyorganosiloxane contained in the release agent composition.
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 which is 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 precipitation in the composition.

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.)

Examples of the methyl group-containing polyorganosiloxane include those containing a siloxane unit ( ^D200 unit) represented by R ²¹⁰ R ²²⁰ SiO _2/2 , preferably a siloxane unit represented by R ²¹ R ²¹ SiO _2/2 (D ²⁰ units).

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

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

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

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

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

（ｎ_４は、繰り返し単位の数を示し、正の整数である。）

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

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

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

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

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

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

（ｍ₅及びｎ₅は、各繰り返し単位の数を示し、正の整数である。）

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

（ｍ₆及びｎ₆は、各繰り返し単位の数を示し、正の整数である。）

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

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

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

Although the viscosity of the adhesive composition used in the present invention is not particularly limited, it is usually 500 to 20,000 mPa·s, preferably 1,000 to 1,0000 mPa·s at 25°C.

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

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

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

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

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

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

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

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

式中、Ａｒ’及びＲは前記で定義される通りである。

wherein Ar' and R are as defined above.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Polyethers are preferred release additives. Polyether compounds include alkylene oxide homopolymers and alkylene oxide copolymers, and such copolymers may be random or block. Polyalkylene oxide release additives may have a variety of polar end groups, preferably such polar end groups are hydroxy, (C ₁ -C ₆ )alkoxy, and (C ₁ -C ₆ )alkoxycarbonyl. , more preferably hydroxy, (C ₁ -C ₃ )alkoxy, and acetoxy. Preferred polyether compounds are polyglycols (or polyalkylene oxides), such as poly(C ₁ -C ₄ ) alkylene oxide compounds, which 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.

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

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

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

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

（式中、Ａ^１は、単結合、又は下記式

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

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

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

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

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

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

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

（式中、Ａ^２は、単結合、又は下記式

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

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

is a divalent organic group selected from groups represented by R ¹⁶ and R ¹⁷ are each independently an alkyl group 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 the thermosetting polymer as the adhesive composition of the third embodiment is a layer of a cured thermosetting resin composition containing silicone A or silicone B as a main component. is preferred. Silicone A and silicone B can be used in combination. In that case, the ratio (polymerization ratio) is preferably silicone A:silicone B=0.1:99.9 to 99.9:0.1, more preferably silicone A:silicone B=20:80 to 80:20. is.

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

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

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

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

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

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

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

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

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

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

［式中、Ｒは、

（式中、Ｒ_１は、アルキル置換フェニル、

からなる群から選択される。）からなる群から選択される。］ <<Fourth Embodiment>>
In preferred embodiments, the adhesive composition used in the present invention is, for example, a thermoplastic composition as described below.
As the adhesive composition of the fourth embodiment, for example, a thermoplastic composition for forming a bonding composition layer described in Japanese Patent No. 5788173 (hereinafter referred to as "bonding composition") may be used. can be done.
Bonding compositions include, but are not limited to, preferred examples that are dispersed or dissolved in a solvent system and include compounds selected from the group consisting of imide, amideimide and amideimide-siloxane polymers and oligomers.
The compound is, for example, selected from the group consisting of polymers and oligomers having repeating units of at least one of formula (I) and formula (II) below.
Formula (I):

[In the formula, R is

(wherein R ₁ is alkyl-substituted phenyl,

selected from the group consisting of ). ]

（式中、Ｚは、シロキサン、及びエーテル橋かけを有する部分からなる群から選択される。） Formula (II):

(Where Z is selected from the group consisting of siloxanes and moieties with ether bridges.)

からなる群から選択されるものが挙げられる。 Preferred alkyl-substituted phenyls are C ₁ -C ₆ alkyl-substituted phenyls. Particularly preferred examples of alkyl-substituted phenyl are

Those selected from the group consisting of

In formula (I), X is phenylsulfone, (preferably C ₆ -C ₆₀ , more preferably C ₆ -C ₃₀ , more preferably C ₆ -C ₂₄ ) aromatic compound, (preferably C ₂ - C ₁₅ , more preferably C ₂ -C ₁₀ , more preferably C ₂ -C ₆ ) aliphatic compounds and (preferably C ₄ -C ₆₀ , more preferably C ₄ -C ₂₀ , more preferably C _{4 —C12} ) alicyclic compounds.

In one embodiment, X can be an aromatic, aliphatic, or cycloaliphatic group as described above. In other embodiments, X may include aromatic groups with ether bridges (as discussed for Z) or aromatic groups with linking groups and/or —NH ₂ groups in the meta position.

Particularly preferred X groups are selected from the group consisting of alkyl-substituted phenyl (as described above), isopropylidenediphenyl, and hexafluoroisopropylidene.

［式中、各Ｒ^３は個々に、水素、（好ましくはＣ_１－Ｃ_１０、より好ましくはＣ_１－Ｃ_２の）アルキル、及びフェニルからなる群から選択され、
ｍは１～６であり、
ｐは１～５０、好ましくは１～２０、より好ましくは１～１０である。］で表される。 In formula (II), in embodiments where Z is a siloxane, preferred siloxanes have the formula:

wherein each R ³ is individually selected from the group consisting of hydrogen, alkyl (preferably C ₁ -C ₁₀ , more preferably C ₁ -C ₂ ), and phenyl;
m is 1 to 6,
p is 1-50, preferably 1-20, more preferably 1-10. ].

からなる群の中から選択される。 Preferred moieties having an ether bridge of Z in formula (II) are

selected from the group consisting of

［式中、Ｒ_４は、（好ましくはＣ_１－Ｃ_１５、より好ましくはＣ_１－Ｃ_１０、さらに好ましくはＣ_１－Ｃ_６の）アルキルであり、Ｒ_５は、（好ましくはＣ_３－Ｃ_１２、より好ましくはＣ_５－Ｃ_６の）脂環式基であり、
ｋは０～２０、好ましくは０～１０、より好ましくは０～５である。］からなる群から選択される基を有する。 In embodiments of formula (I) or embodiments of formula (II), it is preferred that the polymer or oligomer further comprises terminal capping groups. Preferred capping groups are derived from compounds selected from the group consisting of aromatic monoamines, aliphatic monoamines, cycloaliphatic monoamines and phthalic anhydride. Particularly preferred end capping groups are alkyl (preferably C ₁ -C ₁₅ , more preferably C ₁ -C ₁₀ , more preferably C ₁ -C ₆ ),

[wherein R ₄ is alkyl (preferably C ₁ -C ₁₅ , more preferably C ₁ -C ₁₀ , more preferably C ₁ -C ₆ ) and R ₅ is (preferably C ₃ - C ₁₂ , more preferably C ₅ -C ₆ ) cycloaliphatic groups,
k is 0-20, preferably 0-10, more preferably 0-5. ] and has a group selected from the group consisting of

A bonding composition is, for example, a compound dispersed or dissolved in a solvent system. This compound may be a polymer or an oligomer, and is preferably about 1% to about 70% by mass, more preferably about 5% to about 5% by mass, based on the total mass of membrane constituents in the composition as 100% by mass. It is present in the composition at a level of about 50% by weight, more preferably from about 15% to about 40% by weight.

The polymeric or oligomeric compound is thermoplastic and preferably has a weight average molecular weight of from about 3000 Daltons to about 300000 Daltons, more preferably from about 6000 Daltons to about 50000 Daltons. Preferred compounds have a softening temperature (at a melt viscosity of 3000 Pa·s) preferably of at least about 150°C, more preferably of at least about 200°C, and even more preferably of about 200°C to about 250°C.

Preferred compounds exhibit at least about 95% yield when left at room temperature for about 1-24 hours in media such as N-methyl-2-pyrrolidone, xylene, dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, and mixtures thereof. % by weight, preferably at least about 98% by weight, more preferably about 100% by weight, are dissolved.

The bonding composition comprises at least about 30% by weight solvent system, preferably about 50% to about 90% by weight solvent system, more preferably about 60% by weight, based on the total weight of the bonding composition as 100%. from about 90% by weight solvent system, more preferably from about 70% to about 90% by weight solvent system. The solvent system should have a boiling point of about 100-250°C, preferably 120-220°C.

Suitable solvents include those selected from the group consisting of N-methyl-2-pyrrolidone, xylene, dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, and mixtures thereof.

The amount of the membrane component in the bonding composition is at least about 10% by weight, preferably about 10% to about 40% by weight, more preferably about 10% to about It should be 30% by mass.

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

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

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

An example of the adhesive composition used in the present invention can be produced by mixing component (A) with component (B) and a solvent if used.
The mixing order is not particularly limited, but an example of a method for easily and reproducibly producing an adhesive composition is a method of dissolving component (A) and component (B) in a solvent, or , dissolving a part of component (A) and component (B) in a solvent, dissolving the remainder in a solvent, and mixing the obtained solutions, but not limited thereto. In addition, when preparing the adhesive composition, it may be appropriately heated within a range in which the components are not decomposed or deteriorated.
In the present invention, for the purpose of removing foreign matter, the 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.

Although the thickness of the adhesive layer provided in the laminate of 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, and more preferably 20 μm or more. The thickness is preferably 30 μm or more, and from the viewpoint of avoiding nonuniformity due to a thick film, it is 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.

<Inorganic material layer>
The laminate may have an inorganic material layer.
The inorganic material layer is usually interposed between the release layer and the adhesive layer. The inorganic material layer suppresses mixing of the release layer and the adhesive layer.

The inorganic material layer is not particularly limited as long as it is a layer made of an inorganic material. For example, oxides and nitrides of at least one element selected from the group consisting of silicon, boron, titanium, zirconium, and aluminum. , layers formed from compounds such as carbides, and mixtures thereof.
Preferably, the inorganic material layer is a layer obtained by plasma polymerization of an organosilicon compound.

The inorganic material layer is formed, for example, by a chemical vapor deposition method (CVD (Chemical Vapor Deposition)). Chemical vapor deposition, for example, provides a plasma polymerized coating.
Materials used in plasma polymerized coatings include, for example, organosilicon compounds. For example, by performing plasma polymerization coating of an organosilicon compound on the release layer or adhesive layer, the raw material gas containing the organosilicon compound is decomposed to form an inorganic thin film containing Si—O bonds on the release layer or adhesive layer. A material layer can be formed.
It is preferable to mix a gas containing oxygen such as O ₂ or N ₂ O with the raw material gas containing the organosilicon compound. Also, a rare gas such as argon or helium may be used as a carrier gas and blended with the raw material gas. In a preferred example of the method of decomposing the source gas, the source gas is decomposed by plasma generated under appropriate pressure conditions using a plasma generator. A technique of decomposing a raw material gas using plasma to form a film (layer) is generally called a plasma polymerization method.

Examples of organosilicon compounds include siloxane compounds, disilazane compounds, and silane compounds.
Examples of siloxane compounds include 1,1,3,3-tetramethyldisiloxane, pentamethyldisiloxane, hexamethyldisiloxane, 1,1,3,3-tetraphenyl-1,3-dimethyldisiloxane, 1 ,3-divinyltetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, octamethyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, decamethyltetrasiloxane, 1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane, etc. hexamethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1,3,5,7-tetravinyl-1, cyclic siloxanes such as 3,5,7-tetramethylcyclotetrasiloxane;
Disilazane compounds include, for example, 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, heptamethyldisilazane, hexamethylcyclotrisilazane, 1,1,3,3,5,5,7, 7-octamethylcyclotetrasilazane and the like.
Examples of silane compounds include methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, trimethoxysilane, triethylsilane, trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, tetramethoxysilane, trimethoxymethylsilane, and ethyltrimethoxysilane. Silane, dimethoxydimethylsilane, methoxytrimethylsilane, tetraethoxysilane, triethoxymethylsilane, triethoxyethylsilane, diethoxydimethylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethoxydimethylsilane, acetoxytrimethylsilane, allyloxytrimethylsilane , allyltrimethylsilane, butoxytrimethylsilane, butyltrimethoxysilane, diacetoxydimethylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxymethylphenylsilane, ethoxydimethylvinylsilane, diphenylsilanediol, triacetoxymethylsilane, triacetoxyethylsilane , 3-glycidyloxypropyltrimethoxysilane, hexyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, octadecyltriethoxysilane, triethoxyoctylsilane, triethoxyphenylsilane, trimethylphenylsilane, propoxytrimethylsilane, triethoxypropylsilane , tetraacetoxysilane, tetrabutoxysilane, tetrapropoxysilane, triacetoxyvinylsilane, triethoxyvinylsilane, trimethoxyvinylsilane, triphenylsilanol, trimethylvinylsilane, tris(2-methoxyethoxy)vinylsilane, and the like.

The thickness of the inorganic material layer is not particularly limited, but is usually 1 to 1,000 nm, preferably 100 to 500 nm.

An example of the laminate will be described below with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of an example of a laminate.
The laminate in FIG. 1 has a semiconductor substrate 1, a release layer 2, an inorganic material layer 3, an adhesive layer 4, and a support substrate 5 in this order.
The release layer 2 is in contact with the semiconductor substrate 1 .
The adhesive layer 4 is interposed between the support substrate 5 and the release layer 2 . The adhesive layer 4 is in contact with the support substrate 5 and the inorganic material layer 3 .
The inorganic material layer 3 is interposed between the release layer 2 and the adhesive layer 4 . The inorganic material layer 3 is in contact with the release layer 2 and the adhesive layer 4 .
The laminate of FIG. 1 has the inorganic material layer 3 in contact with the release layer 2 and the adhesive layer 4, but in the laminate of the present invention, the inorganic material layer 3 may not be used, and the inorganic material layer may be 3 may be in contact with only one of the release layer 2 and the adhesive layer 4, or may be in contact with neither. 1 has the adhesive layer 4 in contact with the support substrate 5 and the inorganic material layer 3. In the laminate of the present invention, the adhesive layer 4 is one of the support substrate 5 and the inorganic material layer 3. It does not have to be in contact with either of them.

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

(Laminate manufacturing method)
The method for producing a laminate of the present invention includes, for example, a release layer forming step, an adhesive coating layer forming step, and an adhesive layer forming step, and further, if necessary, an inorganic material layer forming step, a bonding step, and the like. Including other steps of

<Peeling layer forming step>
The release layer forming step is a step of forming a release layer.
When the release agent composition used does not contain a solvent, for example, by applying the release agent composition onto a semiconductor substrate, a release layer is formed, but the layer is softened to improve adhesion to the substrate. For such purposes, if necessary, heating may be performed during the process of forming the layer.
When the release agent composition to be used contains a solvent, for example, the release agent composition is applied onto a semiconductor substrate to form a release agent coating layer, and the release agent coating layer is heated to remove the solvent. Although the layer is formed, heating may not be performed during the layer formation process unless necessary because the solvent is also removed during the film formation by spinning.
Although the coating method is not particularly limited, spin coating is usually used.
The heating temperature is appropriately determined according to the boiling point of the solvent and the purpose of heating, but is usually 50 to 250 ° C. The heating time is appropriately determined according to the heating temperature, but is usually 30 seconds to 1 hour.
Heating can be performed, for example, using an oven or a hot plate.

<Inorganic material layer forming step>
The inorganic material layer forming step is not particularly limited as long as it is a step of forming an inorganic material layer.

<Adhesive coating layer forming step>
The adhesive coating layer forming step is not particularly limited as long as it is a step in which an adhesive coating layer is formed. , heating (preheat treatment) to form an adhesive coating layer that is an uncured or incompletely cured adhesive layer. In this way, an adhesive coating layer is formed, for example, on the release layer or inorganic material layer, or on the support substrate.

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

<Adhesive Layer Forming Step>
The adhesive layer forming step is not particularly limited as long as it is a step in which an adhesive coating layer is heated to form an adhesive layer (post-heat treatment).
For example, using a semiconductor substrate and a supporting substrate on which a peeling layer and an adhesive coating layer are formed, the two substrates (the semiconductor substrate and the supporting substrate) are sandwiched between the two layers (the peeling layer and the adhesive coating layer). After the support substrate and the adhesive coating layer are brought into contact with each other by arranging them, heat treatment may be performed. Alternatively, for example, using a semiconductor substrate on which a release layer is formed and a support substrate on which an adhesive coating layer is formed, two substrates (semiconductor A substrate and a supporting substrate) are placed so that the peeling layer and the adhesive coating layer are in contact with each other, and then heat treatment may be performed.
For example, using a semiconductor substrate and a supporting substrate on which a release layer, an inorganic material layer and an adhesive coating layer are formed, two substrates are used so as to sandwich the three layers (the release layer, the inorganic material layer and the adhesive coating layer). After disposing (semiconductor substrate and supporting substrate) so that the supporting substrate and the adhesive coating layer are brought into contact with each other, heat treatment may be performed. Alternatively, for example, by using a semiconductor substrate on which a peeling layer and an inorganic material layer are formed and a support substrate on which an adhesive coating layer is formed, three layers (a peeling layer, an inorganic material layer, and an adhesive coating layer) are formed. By arranging two substrates (semiconductor substrate and supporting substrate) so as to sandwich them, the inorganic material layer and the adhesive coating layer are brought into contact with each other, and then 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 adhesive coating layer is converted into the adhesive layer.
The heating temperature is preferably 120° C. or higher from the viewpoint of realizing a sufficient curing rate, and is preferably 120° C. or higher from the viewpoint of preventing deterioration of each layer (including the support substrate and the semiconductor substrate) constituting the laminate. 260° C. or less.
The heating time is preferably 1 minute or more, more preferably 5 minutes or more, from the viewpoint of realizing suitable bonding of each layer (including the support substrate and the semiconductor substrate) constituting the laminate. From the viewpoint of suppressing or avoiding adverse effects on each layer due to heating, the time is preferably 180 minutes or less, more preferably 120 minutes or less.
Heating can be performed using a hot plate, an oven, or the like.
Heating may be performed in stages.

<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.
The bonding process is not particularly limited as long as the substrate and the layer can be bonded together and the substrate and the layer are not damaged. can be applied, and more preferably, a load can be applied in the thickness direction of the supporting substrate and the semiconductor substrate under reduced pressure.
The load is not particularly limited as long as the substrate and layer can be bonded together and the substrate and layer are not damaged.
The degree of reduced pressure is not particularly limited as long as the substrate and layer can be bonded together and the substrate and layer are not damaged.

(Method for manufacturing semiconductor substrate)
The method of manufacturing a semiconductor substrate of the present invention includes at least a processing step, a peeling step, and a removing step, and further includes other steps as necessary.

<Processing process>
The processing step is not particularly limited as long as it is a step for processing the semiconductor substrate in the laminate of the present invention, and includes, for example, polishing processing and through electrode forming processing.

<<Polishing process>>
The polishing treatment is not particularly limited as long as it is a treatment for thinning the semiconductor substrate by polishing the surface of the semiconductor substrate opposite to the surface on which the bumps are present. polishing and the like.
The polishing process can be performed using a general polishing apparatus used for polishing semiconductor substrates.
The polishing process reduces the thickness of the semiconductor substrate to obtain a thinned semiconductor substrate to a desired thickness. The thickness of the thinned semiconductor substrate is not particularly limited, but may be, for example, 30 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 a 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 device 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. Delamination usually occurs at the interface between the release layer and the semiconductor substrate or inorganic material layer.

<Removal process>
The removing step is not particularly limited as long as it is a step in which the peeling layer is removed after the peeling step. Alternatively, removal may be performed using a removal tape or the like. After the peeling process, if there is a residue of the adhesive layer on the semiconductor substrate through the peeling layer, the residue is also removed in the removing process.
When using a cleaning composition, for example, a semiconductor substrate with a release layer can be immersed in the cleaning composition, or can be sprayed with the cleaning composition.

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

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

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

Quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used as hydrates. In addition, quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used singly or in combination of two or more.
The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the detergent composition, but is usually 0.1 to 30% by mass of the detergent composition.

The solvent contained in the detergent composition used in the present invention is not particularly limited as long as it is used for this type of application and dissolves salts such as the quaternary ammonium salts. From the viewpoint of obtaining a detergent composition having detergency with good reproducibility, and from the viewpoint of obtaining a detergent composition having excellent uniformity by satisfactorily dissolving a salt such as a quaternary ammonium salt, etc., the present invention is preferably The cleaning composition used contains one or more amide solvents.

A suitable example of the amide-based solvent is an acid amide derivative represented by formula (Z).

In the formula, R ⁰ represents an ethyl group, a propyl group or an isopropyl group, preferably an ethyl group. R ^A and R ^B each independently represent an alkyl group having 1 to 4 carbon atoms. Alkyl groups having 1 to 4 carbon atoms may be linear, branched, or cyclic, and are specifically methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, and isobutyl groups. , s-butyl group, t-butyl group, cyclobutyl group and the like. Among these, R ^A and R ^B are preferably methyl or ethyl groups.

Examples of acid amide derivatives represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N, N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, N-ethyl-N-methylisobutyric acid amide and the like. Among these, N,N-dimethylpropionamide is particularly preferred.

The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

Another example of a preferable amide-based solvent is a lactam compound represented by formula (Y).

In the formula (Y), specific examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group and the like. Specific examples include, but are not limited to, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups.

Specific examples of the lactam compound represented by the formula (Y) include α-lactam compound, β-lactam compound, γ-lactam compound, δ-lactam compound and the like, and these may be used singly or Two or more kinds can be used in combination.

In a preferred aspect of the present invention, the lactam compound represented by the formula (Y) contains 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), and in a more preferred aspect, N- It includes methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, N-methylpyrrolidone (NMP).

The cleaning composition used in the present invention may contain one or more organic solvents different from the amide compounds described above.
Such other organic solvents are used for this type of application, and are not particularly limited as long as they are compatible with the above-mentioned amide compound.
Other preferred solvents include, but are not limited to, alkylene glycol dialkyl ethers, aromatic hydrocarbon compounds, and cyclic structure-containing ether compounds.
The amount of the other organic solvent different from the above-mentioned amide compound is usually about 20 to 20%, as long as the quaternary ammonium salt contained in the cleaning composition does not precipitate or separate and is uniformly mixed with the above-mentioned amide compound. It is appropriately determined at 95% by mass or less in the solvent contained in the detergent composition.
Although the cleaning composition used in the present invention may contain water as a solvent, only an organic solvent is usually intentionally used as a solvent from the viewpoint of avoiding substrate corrosion and the like. In this case, it is not denied that the detergent composition contains hydrated water of the salt and a small amount of water contained in the organic solvent. The water content of the detergent composition used in the present invention is usually 5% by mass or less.

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

(1) Stirrer: Rotation/revolution mixer ARE-500 manufactured by Thinky Co., Ltd.
(2) Vacuum bonding device: XBS300 manufactured by SUSS Microtech Co., Ltd.
(3) Manual peeling device: manual debonder manufactured by Sus Microtec Co., Ltd. (4) Vacuum heating device: VJ-300-S manufactured by Ayumi Industry Co., Ltd.

[Measurement of molecular weight]
The weight average molecular weight and number average molecular weight of polydimethylsiloxane are determined using a GPC apparatus (HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), and the column temperature is adjusted to The temperature was set to 40° C., tetrahydrofuran was used as an eluent (elution solvent), the flow rate (flow rate) was set to 0.35 mL/min, and polystyrene (manufactured by Shodex) was used as a standard sample for measurement.

[1] Preparation of adhesive composition [Preparation Example 1]
80 g of MQ resin containing a polysiloxane skeleton and a vinyl group (manufactured by Wacker Chemi) and 2.52 g of SiH group-containing linear polydimethylsiloxane having a viscosity of 100 mPa s (manufactured by Wacker Chemi) were placed in a 600 mL stirring vessel dedicated to the rotation/revolution mixer. , SiH group-containing linear polydimethylsiloxane having a viscosity of 70 mPa s (manufactured by Wacker Chemi) 5.89 g and 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemi) 0.22 g are added and stirred for 5 minutes with a stirrer. A mixture (I) was obtained.
0.147 g of a platinum catalyst (manufactured by Wacker Chemie) and 5.81 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 1,000 mPa s were stirred with a stirrer for 5 minutes to obtain a mixture (II). rice field.
3.96 g of mixture (II) was added to the total amount of mixture (I), and the mixture was stirred for 5 minutes with a stirrer to obtain mixture (III). Finally, the resulting mixture (III) was filtered through a nylon filter of 300 mesh to obtain an adhesive composition.

[2] Preparation of release agent composition [Preparation Example 2-1]
In a 250 mL stirring vessel, polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 50, manufactured by Wacker Chemi Co., Ltd., trade name AK 50 ) and 98.19 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were added and stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a stripper composition.

[Preparation Example 2-2]
In a 250 mL stirring vessel, 1.80 g of polyorganosiloxane (manufactured by Wacker Chemi, trade name AK 350), which is polydimethylsiloxane having a weight average molecular weight of 21110 and a degree of dispersion of 1.72, and hexamethyldisiloxane (manufactured by Wacker Chemi, trade AK 0.65) (98.2 g) was added and stirred with a stirrer for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a stripper composition.

[Preparation Example 2-3]
In a 250 mL stirring container, 1.81 g of polyorganosiloxane (manufactured by Wacker Chemi, trade name AK 1000), which is polydimethylsiloxane having a weight average molecular weight of 34550 and a degree of dispersion of 2.24, and hexamethyldisiloxane (manufactured by Wacker Chemi, trade AK 0.65) (98.19 g) was added and stirred with a stirrer for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a stripper composition.

[Preparation Example 2-4]
1.70 g of polyorganosiloxane (manufactured by Wacker Chemi, trade name AK 10000) and hexamethyldisiloxane (manufactured by Wacker Chemi, trade AK 0.65) (98.3 g) was added and stirred with a stirrer for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a stripper composition.

[Preparation Example 2-5]
1.34 g of polyorganosiloxane (manufactured by Wacker Chemi, trade name AK 1000000) and hexamethyldisiloxane (manufactured by Wacker Chemi, trade AK 0.65) (98.66 g) was added and stirred with a stirrer for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a stripper composition.

[Preparation Example 2-6]
1.17 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 350) having a weight average molecular weight of 21110 and a dispersity of 1.72 and a weight average molecular weight of 34550 and a dispersity of 2.72 were placed in a 250 mL stirring container. 0.52 g of polyorganosiloxane (manufactured by Wacker Chemi Co., trade name AK 1000) and 98.33 g of hexamethyldisiloxane (manufactured by Wacker Chemi Co., trade name AK 0.65), which is polydimethylsiloxane No. 24, were added, and the mixture was stirred with a stirrer. Stir for a minute. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a stripper composition.
In addition, 1.17 g of polyorganosiloxane (manufactured by Wacker Chemi Co., Ltd., trade name AK 350) which is polydimethylsiloxane having a weight average molecular weight of 21110 and a dispersity of 1.72 and a weight average molecular weight of 34550 and a dispersity of 2.24 The weight average molecular weight of polydimethylsiloxane in a mixture with 0.52 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is polydimethylsiloxane, was 25,100. Further, the degree of dispersion was 4.04.

[Preparation Example 2-7]
In a 250 mL stirring vessel, 0.50 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 350), which is polydimethylsiloxane having a weight average molecular weight of 21110 and a dispersity of 1.72, and a weight average molecular weight of 34550 and a dispersity of 2 1.38 g of polyorganosiloxane (manufactured by Wacker Chemi Co., trade name AK 1000) and 98.32 g of hexamethyldisiloxane (manufactured by Wacker Chemi Co., trade name AK 0.65), which is polydimethylsiloxane of No. 24, were added and stirred with a stirrer. Stir for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a stripper composition.
In addition, 0.50 g of polyorganosiloxane (manufactured by Wacker Chemi Co., Ltd., trade name AK 350) which is polydimethylsiloxane having a weight average molecular weight of 21110 and a dispersity of 1.72 and a weight average molecular weight of 34550 and a dispersity of 2.24 The weight average molecular weight of polydimethylsiloxane in a mixture with 1.38 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is polydimethylsiloxane, was 29,270. Further, the degree of dispersion was 4.94.

[Preparation Example 2-8]
In a 250 mL stirring container, 1.33 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is polydimethylsiloxane having a weight average molecular weight of 34550 and a dispersity of 2.24, and a weight average molecular weight of 69980 and a dispersity of 3. 0.57 g of polyorganosiloxane (manufactured by Wacker Chemi Co., trade name AK 10000) and 98.10 g of hexamethyldisiloxane (manufactured by Wacker Chemi Co., trade name AK 0.65), which is a polydimethylsiloxane of No. 66, were added and stirred with a stirrer. Stir for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a stripper composition.
In addition, 1.33 g of polyorganosiloxane (manufactured by Wacker Chemi Co., Ltd., trade name AK 1000) which is polydimethylsiloxane having a weight average molecular weight of 34550 and a dispersity of 2.24 and a weight average molecular weight of 69980 and a dispersity of 3.66 The weight average molecular weight of polydimethylsiloxane in a mixture with 0.57 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 10000), which is polydimethylsiloxane, was 49,350. Further, the degree of dispersion was 8.37.

[Preparation Example 2-9]
In a 250 mL stirring container, 0.55 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is polydimethylsiloxane having a weight average molecular weight of 34550 and a dispersity of 2.24, and a weight average molecular weight of 69980 and a dispersity of 3. 1.28 g of polyorganosiloxane (manufactured by Wacker Chemi Co., trade name AK 10000) and 98.17 g of hexamethyldisiloxane (manufactured by Wacker Chemi Co., trade name AK 0.65), which is a .66 polydimethylsiloxane, were added and stirred with a stirrer. Stir for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a stripper composition.
In addition, 0.55 g of polyorganosiloxane (manufactured by Wacker Chemi Co., Ltd., trade name AK 1000) which is polydimethylsiloxane having a weight average molecular weight of 34550 and a dispersity of 2.24 and a weight average molecular weight of 69980 and a dispersity of 3.66 The weight average molecular weight of polydimethylsiloxane in a mixture with 1.28 g of polyorganosiloxane (manufactured by Wacker Chemi Co., Ltd., trade name AK 10000), which is polydimethylsiloxane, was 68,740. Further, the degree of dispersion was 12.5.

[3] Preparation of laminate for evaluation (Comparative Example 1)
The release agent composition obtained in Preparation Example 2-1 was spin-coated onto a 12-inch silicon wafer, which was a semiconductor substrate, so that the film thickness in the finally obtained laminate was 170 nm to form a release layer. did.
Next, a plasma polymer layer, which is an inorganic material layer, was formed on the release layer so that the film thickness in the finally obtained laminate would be 160 nm. The plasma polymer layer was formed by a CVD (Chemical Vapor Deposition) method. Specifically, CVD was performed under the conditions of 40 W, 65 mTorr, and a hexamethyldisiloxane flow rate of 15 sccm.
Next, the adhesive composition obtained in Preparation Example 1 was spin-coated so that the film thickness in the finally obtained laminate was 60 μm to form an adhesive coating layer on the plasma polymer layer.
Then, using a bonding apparatus, a silicon wafer as a semiconductor substrate and a 12-inch glass wafer as a support substrate are bonded together so as to sandwich the release layer, the plasma polymer layer and the adhesive coating layer, and then the semiconductor substrate is placed face down. Then, heat treatment was performed on a hot plate at 170° C. for 7 minutes and then at 190° C. for 7 minutes to prepare a laminate. Note that the bonding was performed at a temperature of 23° C. and a reduced pressure of 1,000 Pa.

(Examples 1 to 4)
Comparative Example 1 and Comparative Example 1 except that the release agent compositions obtained in Preparation Examples 2-3 and 2-6 to 2-8 were used instead of the release agent composition obtained in Preparation Example 2-1. A laminate was produced in the same manner.

(Comparative Examples 2-5)
Except that the release agent compositions obtained in Preparation Examples 2-2, 2-4, 2-5, and 2-9 were used instead of the release agent compositions obtained in Preparation Example 2-1, A laminate was produced in the same manner as in Comparative Example 1.

[High temperature treatment of laminate]
A heat treatment was applied to the produced laminate using a vacuum heating apparatus. The treatment was performed according to the following procedure.
The semiconductor substrate of the laminate was placed face down on a heating stage set at 300° C. and heated for 10 minutes. Note that the heating was performed in a nitrogen atmosphere.
The state of the semiconductor substrate of each laminated body after the treatment was observed using an optical microscope through the glass wafer as the support substrate, and the presence or absence of voids and delamination was visually confirmed. After the observation, it was confirmed whether or not the semiconductor substrate and the supporting substrate could be preferably manually separated by inserting a sharp tool between the semiconductor substrate and the supporting substrate of the laminate using a manual peeling device. At this time, the semiconductor substrate and the support substrate were manually separated at the interface between the peeling layer and the inorganic material layer without applying enough force to the extent that the substrate felt a strong load as a result of the peelability evaluation. When it was possible, it was evaluated as "possible", and in other cases, it was evaluated as "impossible". In addition, if the evaluation result is "impossible", there are cases where the substrates cannot be separated at all even when more force is applied to separate them, or where cracks occur in the substrates even if the substrates can be forcibly separated. Occurred.
Voids here mean the condition of air bubbles between a substrate and a layer of a laminate, between two layers or in a layer, and in such conditions with undesired air bubbles there is sufficient protection of the semiconductor substrate. can't expect Delamination means a state in which the separation layer is partially separated from the semiconductor substrate, and in this state, sufficient protection of the semiconductor substrate cannot be expected.
The results are shown in Table 1 below.

As shown in the table, even a laminate having a film obtained from a release agent composition containing polyorganosiloxane (polydimethylsiloxane) as a release layer has a weight average molecular weight outside the predetermined range of the present invention. At times (Comparative Examples 1 to 5), when heat treatment is performed at a high temperature (300 ° C.), delamination cannot be suppressed during heat treatment, or peeling occurs after heat treatment even if delamination does not occur during heat treatment. Although it was impossible, when the weight average molecular weight was within the predetermined range of the present invention (Examples 1 to 4), delamination during heat treatment at high temperature (300 ° C.) could be suppressed, In addition, peeling was possible after heat treatment.
Comparative Example 2 is better than Comparative Example 1 in terms of whether or not it can be peeled off. ,000 polyorganosiloxane) is believed to allow release.
In terms of the degree of delamination, Comparative Examples 3 and 5 are better than Comparative Example 4, and polyorganosiloxane having a weight average molecular weight slightly smaller than that of the polyorganosiloxane of Comparative Example 5 (e.g., weight average A polyorganosiloxane having a molecular weight of 68,000 is believed to prevent delamination.

According to the present invention, even after the semiconductor substrate has been exposed to high temperatures, the laminate of the present invention does not separate when the semiconductor substrate and the supporting substrate are temporarily bonded, and when the semiconductor substrate and the supporting substrate are to be separated, It is useful in the production of processed semiconductor substrates that can be easily stripped.

REFERENCE SIGNS LIST 1 semiconductor substrate 2 release layer 3 inorganic material layer 4 adhesion layer 5 support substrate

Claims (16)

a support substrate;
a semiconductor substrate;
a peeling layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate;
an adhesive layer interposed between the support substrate and the release layer;
A laminate having
The laminate, wherein the release layer is a layer formed from a release agent composition containing a polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000. The laminate according to claim 1, wherein said polyorganosiloxane is polydimethylsiloxane. The laminate according to claim 1 or 2, wherein the adhesive layer is a layer formed from an adhesive composition. 4. The laminate according to claim 3, wherein the adhesive composition contains a curable component (A). 5. The laminate according to claim 4, wherein the component (A) is a component that cures by a hydrosilylation reaction. The component (A) is
A polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom;
a polyorganosiloxane (a2) having a Si—H group;
a platinum group metal-based catalyst (A2);
The laminate according to claim 4 or 5, containing 7. The laminate according to claim 1, further comprising an inorganic material layer interposed between said release layer and said adhesive layer. 8. The laminate according to claim 7, wherein the inorganic material layer is a layer obtained by plasma polymerization of an organosilicon compound. 9. The laminate according to any one of claims 1 to 8, wherein the semiconductor substrate is used in a process in which the semiconductor substrate is heated to 280°C or higher. a step of processing the semiconductor substrate in the laminate according to any one of claims 1 to 8;
separating the support substrate from the processed semiconductor substrate;
A method of manufacturing a semiconductor substrate, comprising: 11. The method of manufacturing a semiconductor substrate according to claim 10, wherein said processing step includes a process of thinning said semiconductor substrate by polishing a surface opposite to a surface of said semiconductor substrate in contact with said peeling layer. 12. The method of manufacturing a semiconductor substrate according to claim 10, wherein the step of processing includes heating the semiconductor substrate to 280[deg.] C. or higher. A laminate manufacturing method for producing the laminate according to any one of claims 1 to 9,
forming an adhesive coating layer providing said adhesive layer;
a step of heating the adhesive coating layer in a state in which the support substrate and the semiconductor substrate are in contact with each other with the release layer and the adhesive coating layer interposed therebetween to form the adhesive layer;
A method of manufacturing a laminate, comprising: A release agent composition used for forming a release layer in contact with a semiconductor substrate heated to 280° C. or higher,
A release agent composition containing a polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000. 15. The release agent composition of claim 14, wherein said polyorganosiloxane is polydimethylsiloxane. a support substrate; the semiconductor substrate; the separation layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate; and an adhesive layer interposed between the support substrate and the separation layer. 16. The release layer is used for forming the release layer of the laminate and in contact with the semiconductor substrate heated to 280° C. or higher when the semiconductor substrate of the laminate is processed. The stripper composition according to .

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