JP7730456B2 - Stripping composition, laminate, method for manufacturing laminate, and method for manufacturing semiconductor substrate - Google Patents

Description

The present invention relates to a stripping agent composition, a laminate, a method for manufacturing a laminate, and a method for manufacturing a semiconductor substrate.

Semiconductor wafers have traditionally been integrated in a two-dimensional plane, but for the purpose of further integration, semiconductor integration technology is required that integrates (stacks) the plane in a three-dimensional plane as well. This three-dimensional stacking is a technology that integrates multiple layers while connecting them using through silicon vias (TSVs). When integrating multiple layers, each wafer to be integrated is thinned by polishing the side opposite the circuit surface (i.e., the backside), and the thinned semiconductor wafers are stacked.
An unthinned semiconductor wafer (also referred to herein simply as a wafer) is bonded to a support for polishing in a polishing apparatus.
The adhesive used in this process must be easily peeled off after polishing, and is therefore called a temporary adhesive. This temporary adhesive must be easily removed from the support; applying a large force to remove it can cause the thinned semiconductor wafer to break or deform, so it must be easily removed to prevent this from happening. However, it is undesirable for the adhesive to become dislodged or shifted due to the polishing stress during polishing of the backside of the semiconductor wafer. Therefore, the performance required of the temporary adhesive is that it can withstand the stress during polishing and be easily removed after polishing.
For example, the performance required is high stress (strong adhesive strength) in the planar direction during polishing, and low stress (weak adhesive strength) in the vertical direction during removal.

As one example of such an adhesion process, a wafer support structure has been proposed, which has, from the wafer (1) side, a silicone oil layer, a separation layer (4) which is a plasma polymer layer, and a layer (5) of a partially cured or curable elastomer material between a semiconductor wafer (1) and a support layer (6) which is a support, and the adhesive bond between the support layer system and the separation layer (4) after the elastomer material has fully cured is greater than the adhesive bond between the wafer (1) and the separation layer (4) (see, for example, the examples in Patent Document 1).

Patent No. 5335443

The thinned wafer may be heated to a temperature exceeding 200° C. before being separated from the support. The heating temperature varies depending on the processing to be performed on the wafer, and in some cases may be as high as 280° C. or higher.
However, the inventors have found that when a semiconductor substrate wafer is heated to a high temperature, even if an attempt is made to subsequently separate the semiconductor substrate and the support substrate using a peeling layer interposed therebetween, a force stronger than when the heating temperature is low is required for separation, and in some cases, such a force is required that the semiconductor substrate after thinning cracks.

The present invention aims to provide a laminate that does not peel when the semiconductor substrate and supporting substrate are temporarily bonded together, even after the semiconductor substrate has been exposed to high temperatures, and that allows for easy peeling when an attempt is made to peel the semiconductor substrate and supporting substrate, a method for manufacturing a semiconductor substrate using the laminate, a method for manufacturing the laminate, and a release agent composition for use with the laminate.

The inventors conducted extensive research to solve the above-mentioned problems, and as a result, discovered that the above-mentioned problems could be solved, leading to the completion of the present invention, which has the following gist:

That is, the present invention includes the following.
[1] 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;
an adhesive layer interposed between the support substrate and the release layer;
A laminate having
A 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)
A polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom,
a polyorganosiloxane (a2) having Si—H groups;
a platinum group metal catalyst (A2);
The laminate according to [4] or [5],
[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 polymerization of an organosilicon compound.
[9] The laminate according to any one of [1] to [8], wherein the semiconductor substrate is used in a treatment in which the semiconductor substrate is heated to 280° C. or higher.
[10] A step of processing the semiconductor substrate in the stack according to any one of [1] to [8];
separating the support substrate from the processed semiconductor substrate;
A method for manufacturing a semiconductor substrate, comprising:
[11] The method for manufacturing a semiconductor substrate according to [10], wherein the processing step includes a process of polishing a surface of the semiconductor substrate opposite to a surface in contact with the release layer, thereby thinning the semiconductor substrate.
[12] The method for manufacturing a semiconductor substrate according to [10] or [11], wherein the processing step includes a treatment in which the semiconductor substrate is heated to 280° C. or higher.
[13] A method for producing a laminate according to any one of [1] to [9],
forming an adhesive coating layer that provides the adhesive layer;
a step of heating the adhesive coating layer to form the adhesive layer while the support substrate and the semiconductor substrate are in contact with each other with the release layer and the adhesive coating layer interposed therebetween;
A method for producing a laminate, comprising:
[14] A release agent composition used to form a release layer in contact with a semiconductor substrate heated to 280°C or higher, comprising:
A release agent composition containing a polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000.
[15] The release agent composition according to [14], wherein the polyorganosiloxane is polydimethylsiloxane.
[16] The release agent composition according to [14] or [15], which is used to form the release layer of a laminate having a support substrate, the semiconductor substrate, the 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 which is in contact with the semiconductor substrate that is heated to 280°C or higher when the semiconductor substrate of the laminate is processed.

The present invention provides a laminate that does not peel when the semiconductor substrate and the support substrate are temporarily bonded together, even after the semiconductor substrate has been exposed to high temperatures, and that allows the semiconductor substrate and the support substrate to be easily peeled from each other when an attempt is made to peel them apart; a method for manufacturing a semiconductor substrate using the laminate; and a release agent composition for use with the laminate.

FIG. 1 is a schematic cross-sectional view of an example of a laminate.

(Laminate)
The laminate of the present invention comprises a support substrate, a semiconductor substrate, a release layer, an adhesive layer, and, if necessary, an inorganic material layer.
The release layer is interposed between the support substrate and the semiconductor substrate and is in contact with the semiconductor substrate.
The adhesive layer is interposed between the support substrate and the release layer.

<Support substrate>
The support substrate is not particularly limited as long as it is a member that can support the semiconductor substrate when the semiconductor substrate is processed, and examples thereof include a glass support substrate and a silicon support substrate.

The shape of the support substrate is not particularly limited, but may be, for example, a disk shape. Note that the disk-shaped support substrate does not need to have a perfectly circular surface, and for example, the outer periphery of the support substrate may have a straight line portion called an orientation flat or a notch.
The thickness of the disk-shaped support substrate may be appropriately determined depending on 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 depending on the size of the semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.

An example of a support substrate is a glass wafer or silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 700 μmm.

<Semiconductor substrate>
The main material constituting the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, but examples thereof include silicon, silicon carbide, and compound semiconductors.
The shape of the semiconductor substrate is not particularly limited, but may be, for example, a disk shape. Note that the disk-shaped semiconductor substrate does not need to have a perfectly circular surface, and for example, the outer periphery of the semiconductor substrate may have a straight line portion called an orientation flat or a notch.
The thickness of the disk-shaped semiconductor substrate may be appropriately determined depending on the intended use of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 μm.
The diameter of the disk-shaped semiconductor substrate may be appropriately determined depending on the intended 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, which are protruding terminals.
In the laminate, when the semiconductor substrate has bumps, the semiconductor substrate has the bumps on the support substrate side.
In a semiconductor substrate, bumps are usually formed on the surface on which a circuit is formed. The circuit may be a single layer or a multilayer. There are no particular limitations on the shape of the circuit.
In the semiconductor substrate, the surface opposite to the surface having the bumps (back surface) is the surface to be processed.
The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited.
Examples of the bumps include ball bumps, printed bumps, stud bumps, and plated bumps.
Normally, the height, diameter and pitch of the bumps are appropriately determined based on the conditions of a bump height of about 1 to 200 μm, a bump diameter of 1 to 200 μm and a bump pitch of 1 to 500 μm.
Examples of materials for the bumps include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bumps may be composed of a single component or multiple components. More specifically, alloy platings mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps, may be used.
The bump may also have a laminated structure including a metal layer made of at least one of these components.

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

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

<<Removal Agent Composition>>
The release agent composition contains a polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000, and may further contain other components as required.
That is, the weight average molecular weight of the polyorganosiloxane contained in the release agent composition is 22,000 to 68,000.
The release layer may be composed only of polyorganosiloxane, or may contain other components. For example, when the release agent composition is composed only of polyorganosiloxane and a volatile component, the volatile component usually volatilizes due to heating when forming the release layer, and therefore the release layer formed from the release agent composition contains only polyorganosiloxane.

By having the weight-average molecular weight of the polyorganosiloxane contained in the release agent composition be 22,000 or more, even after the semiconductor substrate is exposed to high temperatures (e.g., 280 ° C. or higher) during processing of the semiconductor substrate of the laminate, the semiconductor substrate and the support substrate of the laminate can be easily peeled off when attempting to peel them off using a peeling device, etc. On the other hand, by having the weight-average molecular weight of the polyorganosiloxane contained in the release agent composition be 68,000 or less, even after the semiconductor substrate is exposed to high temperatures during processing of the semiconductor substrate of the laminate, the semiconductor substrate and the support substrate can be maintained in a temporary adhesive state, and the semiconductor substrate and the support substrate can be maintained in a state where they are difficult to peel off until an attempt is made to peel them off using a peeling device, etc.
If the weight-average molecular weight of the polyorganosiloxane contained in the release agent composition is less than 22,000, after the semiconductor substrate is exposed to high temperatures during processing of the semiconductor substrate of the laminate, the semiconductor substrate and the support substrate of the laminate cannot be easily peeled off when an attempt is made to peel them off using a peeling device, etc., and in some cases, the semiconductor substrate may crack when trying to peel it off from the support substrate. If the weight-average molecular weight of the polyorganosiloxane contained in the release agent composition is more than 68,000, the adhesive strength of the release layer is weak after the semiconductor substrate is exposed to high temperatures during processing of the semiconductor substrate of the laminate, etc., and peeling occurs even when temporary adhesion between the semiconductor substrate and the support substrate is required.

From the perspective of achieving the effects of the present invention with good reproducibility, the weight-average molecular weight of the polyorganosiloxane is preferably 25,000 to 65,000, and more preferably 30,000 to 60,000.

The weight-average molecular weight and number-average molecular weight of polyorganosiloxane can be measured, for example, using a GPC apparatus (HLC-8320GPC, manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H, manufactured by Tosoh Corporation), setting the column temperature to 40°C, using tetrahydrofuran as the eluent (elution solvent), setting the flow rate (flow rate) to 0.35 mL/min, and using polystyrene (manufactured by Shodex) as the standard sample.

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

In the present invention, the volatile silicone oils described below are not included in the polyorganosiloxanes.

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

Another example of polyorganosiloxane is polydimethylsiloxane. This 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. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
The epoxy group in the epoxy group-containing organic group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group.
Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.
In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but is not limited thereto.

The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane units ( ^D10 units), but may also 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 D ¹⁰ units, a polyorganosiloxane containing D ¹⁰ units and Q units, a polyorganosiloxane containing D ¹⁰ units and M units, a polyorganosiloxane containing D ¹⁰ units and T units, a polyorganosiloxane containing D ¹⁰ units, Q units, and M units, a polyorganosiloxane containing D ¹⁰ units, M units, and T units, and a polyorganosiloxane containing D ¹⁰ units, Q units, M units, and T units.

The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane with an epoxy value of 0.1 to 5.

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

( _m1 and _n1 represent the number of each repeating unit and are positive integers.)

( _m2 and _n2 each represent the number of repeating units and are positive integers, and R represents an alkylene group having 1 to 10 carbon atoms.)

(m ₃ , n ₃ and o ₃ each represent the number of repeating units 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 siloxane units (D ²⁰⁰ units) represented by R ²¹⁰ R ²²⁰ SiO _2/2 , preferably those containing siloxane units (D ²⁰ units) represented by R ²¹ R ²¹ SiO _2/2 .

R ²¹⁰ and R ²²⁰ are groups bonded to a silicon atom, and each independently represents an alkyl group, with at least one being a methyl group. Specific examples of the alkyl group include those listed above.
^R21 is a group bonded to a silicon atom and represents an alkyl group, specific examples of which include those listed above, with a methyl group being preferred as ^R21 .
In the present invention, a preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.

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

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

Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1):

( _n4 represents the number of repeating units and is a positive integer of 4 or more.)

The methyl group-containing polyorganosiloxane represented by formula (M1) is a polydimethylsiloxane, but it is not denied that there exists polydimethylsiloxane in the bulk of the polydimethylsiloxane that contains trace amounts of other groups as impurity structures at the terminals or in the middle of the repeating units, other than the -Si(CH ₃ ) ₃ group and the -Si(CH ₃ ) ₂ -O- group.

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

^R31 is a group bonded to a silicon atom and represents a phenyl group or an alkyl group, ^R32 is a group bonded to a silicon atom and represents a phenyl group, and specific examples of the alkyl group include those listed above, with a methyl group being preferred.

The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane units ( ^D30 units), but may also 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, a polyorganosiloxane containing ^D30 units and M units, a polyorganosiloxane containing ^D30 units and T units, a polyorganosiloxane containing ^D30 units, Q units, and M units, a polyorganosiloxane containing ^D30 units, M units, and T units, and a polyorganosiloxane containing ^D30 units, Q units, M units, and T units.

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

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

( _m6 and _n6 represent the number of each repeating unit and are positive integers.)

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

When the weight average molecular weight of a commercially available polyorganosiloxane is the desired value, it may be used alone. Alternatively, for example, two or more types of polyorganosiloxanes 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 is the desired value.
In addition, when the synthesized polyorganosiloxane has a desired weight average molecular weight, it may be used alone.In addition, for example, two or more types of polyorganosiloxanes having different weight average molecular weights, each synthesized separately, may be used in combination so that the weight average molecular weight of the polyorganosiloxane in the release layer has a desired value.
Furthermore, a combination of a commercially available product and a synthesized product may be used.

The stripper composition may contain a solvent.
Such a solvent is not particularly limited as long as it can dissolve polyorganosiloxane well, but specific examples of such a good solvent include linear or branched aliphatic hydrocarbons such as linear or branched aliphatic saturated hydrocarbons such as hexane, heptane, octane, nonane, decane, undecane, dodecane, and isododecane; cyclic aliphatic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, isopropylcyclohexane, and p-menthane; and cyclic aliphatic unsaturated hydrocarbons such as limonene. hydrogen chloride; aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, cumene, 1,4-diisopropylbenzene, and p-cymene; aliphatic saturated hydrocarbon ketones such as MIBK (methyl isobutyl ketone), ethyl methyl ketone, acetone, diisobutyl ketone, 2-octanone, 2-nonanone, and 5-nonanone, dialkyl ketones such as cycloalkyl ketones such as cyclohexanone, and aliphatic unsaturated hydrocarbon ketones such as alkenyl ketones such as isophorone. Ketones; ethers such as dialkyl ethers such as diethyl ether, di(n-propyl) ether, di(n-butyl) ether, and di(n-pentyl) ether, and cyclic alkyl ethers such as tetrahydrofuran and dioxane; sulfides such as dialkyl sulfides such as diethyl sulfide, di(n-propyl) sulfide, and di(n-butyl) sulfide; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; nitriles such as acetonitrile and 3-methoxypropionitrile; glycol monohydrocarbon ethers such as glycol monoalkyl ethers such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and dipropylene glycol monomethyl ether, and glycol monoaryl ethers such as diethylene glycol monophenyl ether; alkyl alcohols such as cyclic alkyl alcohols such as cyclohexanol, and diacetone alcohol Monoalcohols other than alkyl alcohols such as benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; glycols such as glycol monoalkyl ethers such as 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, and tripropylene glycol monobutyl ether; and glycol monoaryl ethers such as 2-phenoxyethanol. Monoethers; glycol diethers such as glycol dialkyl ethers such as 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, and tetraethylene glycol dimethyl ether; glycol ether acetates such as glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate; cyclic carbonates such as ethylene carbonate, propylene carbonate, and vinylene carbonate; and esters such as butyl acetate and pentyl acetate.
Volatile silicone oil may also be used as the solvent. In the present invention, the volatile silicone oil 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 alone 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 purposes such as adjusting viscosity and surface tension, as long as the polyorganosiloxane does not precipitate. Specific examples include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; linear or branched alkyl monoalcohols such as methanol, ethanol, and propanol; and glycols such as 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 stripper composition contains a solvent, the amount of solvent is typically 70% to 99.9% by weight based on the total composition, and therefore the amount of polyorganosiloxane is 0.1% to 30% by weight based on the total composition.

The release agent composition may contain components other than polyorganosiloxane and solvent as long as the effects of the present invention are not impaired. However, from the perspective of reproducibly obtaining a film with excellent uniformity and avoiding the need for complicated composition preparation, it is preferable that the release agent composition contain only polyorganosiloxane and solvent.

The release agent composition can be produced, for example, by mixing a polyorganosiloxane with a solvent.
The order of mixing is not particularly limited, but examples of a method that can easily and reproducibly produce a release agent composition include, but are not limited to, a method of dissolving the polyorganosiloxane in a solvent at once, or a method of dissolving a part of the polyorganosiloxane in a solvent and the rest in a separate solvent, and then mixing the resulting solutions. When preparing the release agent composition, heating may be performed as appropriate within a range that does not cause the components to decompose or deteriorate.

In the present invention, in order to remove foreign matter, the solvents, solutions, etc. used may be filtered using a filter during the production of the stripping composition or after all components have been mixed.

The above-described stripping agent composition is also a subject of the present invention, and the relevant conditions (preferable conditions, manufacturing conditions, etc.) are as described above. By using the stripping agent composition of the present invention, it is possible to reproducibly manufacture a film suitable as a release layer that can be used, for example, in the manufacture of semiconductor devices.

The stripping composition is used, for example, to form a release layer that comes into contact with a semiconductor substrate that is heated to 280° C. or higher.
The release agent composition is used to form a release layer in a laminate having, 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 which is in contact with the 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. A release layer containing 100% polyorganosiloxane means that the release layer is composed only of components intentionally included as polyorganosiloxane. However, this does not exclude the presence of solvents used to dissolve the polyorganosiloxane or impurities contained in the bulk polyorganosiloxane.

The thickness of the release layer provided in the laminate of the present invention is not particularly limited, but is typically 10 to 500 nm. From the viewpoint of maintaining film strength, it is preferably 50 nm or more, more preferably 80 nm or more, and even more preferably 100 nm or more. From the viewpoint of avoiding non-uniformity due to a thick film, it is preferably 400 nm or less, more preferably 350 nm or less, even more preferably 300 nm or less, and even more preferably 250 nm or less.

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

The adhesive layer is not particularly limited, but it is preferably a layer formed from an adhesive composition.

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

In a preferred embodiment, the adhesive composition contains a polyorganosiloxane.
In another preferred embodiment, the thermosetting adhesive composition includes a component that cures 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>>.
Furthermore, a more specific embodiment of the thermoplastic adhesive composition used in the present invention is, for example, the <<fourth embodiment>>.

<<First embodiment>>
In a preferred embodiment, the adhesive composition used in the present invention contains a polyorganosiloxane.
For example, the adhesive composition used in the present invention contains a curable component (A) that becomes an adhesive component. The adhesive composition used in the present invention may contain a curable component (A) that becomes an adhesive component and a component (B) that does not undergo a curing reaction. Here, an example of the component (B) that does not undergo a curing reaction is polyorganosiloxane. In the present invention, "does not undergo a curing reaction" does not mean that any curing reaction does not occur, but rather that the curing reaction occurring in the curable component (A) does not occur.
In another preferred embodiment, component (A) may be a component that cures via a hydrosilylation reaction, or may be a polyorganosiloxane component (A') that cures via a hydrosilylation reaction.
In another preferred embodiment, component (A) contains, for example, a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, as an example of component (A'), a polyorganosiloxane (a2) having a Si—H group, and a platinum group metal catalyst (A2). Here, the alkenyl group having 2 to 40 carbon atoms may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.
In another preferred embodiment, the polyorganosiloxane component (A') that cures via a hydrosilylation reaction comprises a polysiloxane ( ^A1 ) containing one ^or more units selected from the _group consisting of siloxane units represented by _SiO2 (Q units), siloxane units represented by ^{R1R2R3SiO1 /} ₂ (M units), siloxane units represented by R4R5SiO2 ^/ 2 (D units), and siloxane units represented by ^R6SiO3 _/2 (T units), and a platinum group metal catalyst (A2). The polysiloxane (A1) contains siloxane units represented by _SiO2 (Q' units), siloxane units represented by ^{R1'R2'R3'SiO1} / ² (M' units), siloxane units represented by ^{R4'R5'SiO2 / 2} ₍ D' units), and siloxane units represented by ^R6'SiO3 / ₂ (T units). and a polyorganosiloxane (a2') containing one or more units selected from the group consisting of siloxane units (T' units) represented _{by SiO 2} (Q" units), siloxane units (M _" units) represented by R ⁴ _{"R 5 "SiO 2/2 (D" units) and siloxane units (T" units) represented by R 6 "SiO 3/2} ^{, and containing} _at least one unit 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 the silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

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, provided that at least one of R ¹ ' to R ⁶ ' is an optionally substituted alkenyl group. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

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

The alkyl group may be linear, branched, or cyclic, but linear or branched alkyl groups are preferred. There are no particular restrictions on the number of carbon atoms, but it is typically 1 to 40, 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, s-butyl, tertiary butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, and 4-methyl-n-pentyl. Examples of such alkyl groups include, but are not limited to, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl groups. The number of carbon atoms is typically 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Of these, a methyl group is particularly preferred.

Specific examples of optionally substituted cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, Examples of cycloalkyl groups include 1-ethyl-2-methylcyclopropyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-i-propylcyclopropyl, 2-i-propylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, and 2-ethyl-3-methylcyclopropyl; and bicycloalkyl groups such as bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl. These groups typically contain 3 to 14 carbon atoms, preferably 4 to 10, and more preferably 5 to 6.

The alkenyl group may be either linear or branched, and although there are no particular limitations on the number of carbon atoms, it is typically 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

Specific examples of the optionally substituted linear or branched alkenyl group include, but are not limited to, a vinyl group, an allyl group, a butenyl group, and a pentenyl group, and the number of carbon atoms therein is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Of these, 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 and cyclohexenyl, and the number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

As described above, polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'). The alkenyl groups contained in polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in polyorganosiloxane (a2') undergo a hydrosilylation reaction in the presence of a platinum group metal catalyst (A2) to form a crosslinked structure and cure. 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 also contains at least one unit selected from the group consisting of M' units, D' units, and T' units. Two or more polyorganosiloxanes satisfying these conditions may be used in combination as polyorganosiloxane (a1').

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

Furthermore, when polyorganosiloxane (a1') contains two or more types of polyorganosiloxane, combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but are 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 also contains at least one unit selected from the group consisting of M" units, D" units, and T" units. Two or more polyorganosiloxanes satisfying these conditions may be used in combination as polyorganosiloxane (a2').

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

The polyorganosiloxane (a1') is composed of siloxane units in which alkyl and/or alkenyl groups are bonded to the silicon atoms thereof, and the proportion of alkenyl groups in all the substituents represented by R ¹ ' to R ⁶ ' 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.

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

When component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in polyorganosiloxane (a1) to hydrogen atoms constituting Si-H bonds 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 is usually 500 to 1,000,000, and from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000.
In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of the polyorganosiloxane can be measured using, for example, a GPC apparatus (HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (manufactured by Shodex) as a standard sample.

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

Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via a hydrosilylation reaction to form a film. Therefore, the curing mechanism is different from that via, for example, silanol groups, and therefore neither siloxane needs to contain a silanol group or a functional group that forms a silanol group upon hydrolysis, such as an alkyloxy group.

In a preferred embodiment of the present invention, the adhesive composition contains a platinum group metal catalyst (A2) together 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, but are not limited to, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, and platinum bisacetoacetate.
Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum.
The amount of the platinum group metal catalyst (A2) is not particularly limited, but is usually in the range of 1.0 to 50.0 ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

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

An example of the adhesive composition used in the present invention may contain a component (B) that does not undergo a curing reaction to become a release agent component in addition to the curable component (A). By including such component (B) in the adhesive composition, the resulting adhesive layer can be suitably peeled with good reproducibility.
Such component (B) typically includes polyorganosiloxanes, and specific examples thereof include epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes, but are not limited to these.
Component (B) may also include polydimethylsiloxane. The polydimethylsiloxane may be modified. Examples of the optionally modified polydimethylsiloxane include, but are not limited to, epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, and phenyl group-containing polydimethylsiloxane.

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

The weight average molecular weight of the polyorganosiloxane of component (B) is not particularly limited, but is typically 100,000 to 2,000,000. From the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000. Furthermore, its dispersity is not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable release, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight average molecular weight and dispersity can be measured using the methods described above for the polyorganosiloxane contained in the release agent composition.
The viscosity of the polyorganosiloxane, component (B), is not particularly limited, but is usually 1,000 to 2,000,000 ^{mm 2} /s. The viscosity value of the polyorganosiloxane, component (B), is expressed as kinematic viscosity, where centistokes (cSt) = mm ² /s. It can also be determined by dividing the viscosity (mPa·s) by the density (g/cm ³ ). That is, this value can be determined from the viscosity and density measured using an E-type rotational viscometer at 25°C, and can be calculated from the formula kinematic viscosity (mm ² /s) = viscosity (mPa·s) / density (g/cm ³ ).

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 include those listed above.
The epoxy group in the epoxy group-containing organic group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group.
Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.
In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but is not limited thereto.

The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane units ( ^D10 units), but may also 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 D ¹⁰ units, a polyorganosiloxane containing D ¹⁰ units and Q units, a polyorganosiloxane containing D ¹⁰ units and M units, a polyorganosiloxane containing D ¹⁰ units and T units, a polyorganosiloxane containing D ¹⁰ units, Q units, and M units, a polyorganosiloxane containing D ¹⁰ units, M units, and T units, a polyorganosiloxane containing D ^{10 units, Q units, M units, and T units, and a polyorganosiloxane containing D 10} units, Q units, M units, and T units.

The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane with an epoxy value of 0.1 to 5. Its weight average molecular weight is not particularly limited, but is typically 1,500 to 500,000, and is preferably 100,000 or less from the standpoint of suppressing precipitation in the composition.

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

( _m1 and _n1 represent the number of each repeating unit and are positive integers.)

( _m2 and _n2 each represent the number of repeating units and are positive integers, and R represents an alkylene group having 1 to 10 carbon atoms.)

(m ₃ , n ₃ and o ₃ each represent the number of repeating units 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 siloxane units (D ²⁰⁰ units) represented by R ²¹⁰ R ²²⁰ SiO _2/2 , preferably those containing siloxane units (D ²⁰ units) represented by R ²¹ R ²¹ SiO _2/2 .

R ²¹⁰ and R ²²⁰ are groups bonded to a silicon atom, and each independently represents an alkyl group, with at least one being a methyl group. Specific examples of the alkyl group include those listed above.
^R21 is a group bonded to a silicon atom and represents an alkyl group, specific examples of which include those listed above, with a methyl group being preferred as ^R21 .
In the present invention, a preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.

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

In a preferred aspect 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, a polyorganosiloxane containing ^D20 units and M units, a polyorganosiloxane containing ^D20 units and T units, a polyorganosiloxane containing ^D20 units, Q units, and M units, a polyorganosiloxane containing ^D20 units, M units, and T units, and a polyorganosiloxane containing ^D20 units, Q units, M units, and T units.

Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1):

( _n4 represents the number of repeating units and is a positive integer.)

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, and specific examples of the alkyl group include those listed above, with a methyl group being preferred.

The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane units ( ^D30 units), but may also 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, a polyorganosiloxane containing ^D30 units and M units, a polyorganosiloxane containing ^D30 units and T units, a polyorganosiloxane containing ^D30 units, Q units, and M units, a polyorganosiloxane containing ^D30 units, M units, and T units, and a polyorganosiloxane containing ^D30 units, Q units, M units, and T units.

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

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

( _m6 and _n6 represent the number of each repeating unit and are positive integers.)

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

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

The viscosity of the adhesive composition used in the present invention is not particularly limited, but is typically 500 to 20,000 mPa·s, and 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.
The curable adhesive material may be selected from, for example, polyarylene oligomers, cyclic olefin oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, and mixtures thereof.
The release additive may, for example, be a polyether compound.
Preferably, the polyether compound comprises end 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 copolymer, and mixtures thereof.
Preferably, 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, the temporary bonding composition described in JP 2014-150239 A can be used.
The adhesive composition of the second embodiment will be described in more detail below.

The adhesive composition used in the present invention comprises a curable adhesive material, a release additive, and optionally an organic solvent. Typically, the curable adhesive material has a modulus of >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 moiety, such as a fluorine-containing group, to provide additional hydrophobicity, provided that such moiety does not adversely affect the mechanical properties of the cured adhesive material. Preferably, the curable adhesive material is selected from polyarylene oligomers, cyclic olefin oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, and mixtures thereof, more preferably one or more of arylcyclobutene oligomers, vinyl aromatic oligomers, or mixtures thereof. When a mixture of different curable adhesive materials is used in the present invention, such materials are selected to cure together during the curing process. When a mixture of different curable materials is used, the curable materials are used in a mass ratio of 99:1 to 1:99, preferably 95:5 to 5:95, more preferably 90:10 to 10:90, and even more preferably 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 can be synthesized from precursors, such as ethynyl aromatic compounds of the following formula:

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; L is a covalent bond or a group linking one Ar to at least one other Ar; n and m are integers of at least 2; and q is an integer of at least 1. As such, ethynyl aromatic compounds typically have four or more ethynyl groups (e.g., tetraethynyl aromatic compounds).

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:

where 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. Polyarylene copolymers useful in the present invention include, as polymerized units, monomers having the following formula:

wherein Ar′ and R are as defined above.

Exemplary polyarylenes include those in which Ar-L-Ar is: biphenyl; 2,2-diphenylpropane; 9,9'-diphenylfluorene;2,2-diphenylhexafluoropropane; diphenyl sulfide; oxydiphenylene; diphenyl ether; bis(phenylene)diphenylsilane; bis(phenylene)phosphine oxide; bis(phenylene)benzene; bis(phenylene)naphthalene; bis(phenylene)anthracene; thiodiphenylene; 1,1,1-triphenyleneethane; 1,3,5-triphenylene phenylbenzene; 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;anthracene; or bis(phenylene)naphthacene; more preferably biphenylene; naphthylene; p,p'-(2,2-diphenylenepropane) (or C _{6H4 -} C( _CH3 ) _{2 - C6H4-} ); p,p'-(2,2-diphenylene- _{1,1,1,3,3,3hexafluoropropene} ) and ( _-C6H4 -C( _CF3 ) ₂ - _C6H4- ). Useful bisphenyl derivatives include 2,2-diphenylpropane; 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 at one of the two positions ortho to the phenolic hydroxyl group; (b) selectively brominating the phenolic hydroxyl groups on the resulting poly(ortho-halophenol) with a leaving group (e.g., a sulfonate ester) reactive with and displaced by a terminal ethynyl compound, preferably in a solvent. (e.g., trifluoromethanesulfonate ester prepared from trifluoromethanesulfonyl halide or trifluoromethanesulfonic anhydride), and (c) reacting the reaction product of step (b) with an ethynyl-containing compound or ethynyl synthon in the presence of an aryl ethynylation catalyst, preferably a palladium catalyst, and an acid acceptor to simultaneously replace the halogen and trifluoromethylsulfonate with an ethynyl-containing group (e.g., 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. While the specific conditions for polymerization will depend on various factors, including the specific ethynyl aromatic monomer(s) being polymerized and the desired properties of the resulting polymer, general polymerization conditions are detailed in 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 those disclosed in WO 00/31183, WO 98/11149, WO 97/10193, WO 91/09081, EP 755957, and U.S. Pat. Nos. 5,115,082; 5,155,175; 5,179,188; 5,874,516; and 6,093,636.

A suitable cyclic olefin material is a poly(cyclic olefin), which may be thermoplastic and preferably has a weight average molecular weight (Mw) of 2000 to 200,000 daltons, more preferably 5000 to 100,000 daltons, and even more preferably 2000 to 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 to 200°C, and most preferably 75 to 160°C.

Preferred poly(cyclic olefins) comprise repeating monomers of cyclic and acyclic olefins, or ring-opened polymers based on cyclic olefins. Cyclic olefins suitable for use in the present invention are selected from norbornene-based olefins, tetracyclododecene-based olefins, dicyclopentadiene-based olefins, Diels-Alder polymers such as those derived from furan and maleimide, and derivatives thereof. Derivatives include alkyl (preferably _C1 - _C20 alkyl, more preferably _C1 - _C10 alkyl), alkylidene (preferably _C1 - _C20 alkylidene, more preferably _C1 - _C10 alkylidene), aralkyl (preferably _C6 - _C30 aralkyl, more preferably _C6 - _C18 aralkyl), cycloalkyl (preferably _C3 - _C30 cycloalkyl, more preferably _C3 - _C18 cycloalkyl), ether, acetyl, aromatic, ester, hydroxy, alkoxy, cyano, amide, imide, and silyl-substituted derivatives. Particularly preferred cyclic olefins for use in the present invention include those selected from the following and combinations thereof:

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 selected from 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, more preferably C ₃ -C ₁₈ cycloalkyl), aralkyl groups (preferably C ₆ -C ₃₀ aralkyl, more preferably C ₆ -C ₁₈ aralkyl, e.g., 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 _C2 - _C20 alkenes (preferably _C2 - _C10 alkenes). More preferably, the acyclic olefin has the structure ( ^R4 ) _2C =C( ^R4 ) ₂ , where each ^R4 is independently selected from H and an alkyl group (preferably _C1 - _C20 alkyl, more preferably _C1 - _C10 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 for producing cyclic olefin copolymers are known in the art. For example, cyclic olefin copolymers can be produced by chain polymerization of cyclic and acyclic monomers. When norbornene is reacted with ethene under these conditions, an ethene-norbornene copolymer containing alternating norbornanediyl and ethylene units is obtained. Examples of copolymers produced 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 producing these copolymers is disclosed in U.S. Pat. No. 6,008,298. Cycloolefin copolymers can also be produced by ring-opening metathesis polymerization of various cyclic monomers, followed by hydrogenation. The polymer resulting from this type of polymerization can be conceptualized as a copolymer of ethene and a cyclic olefin monomer (e.g., 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™ (manufactured by JSR Corporation) brands. A suitable method for producing these copolymers by this ring-opening method is disclosed in U.S. Pat. No. 5,191,026.

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

wherein B is an n-valent linking group; Ar is a polyvalent aryl group, wherein a carbon atom of the cyclobutene ring is bonded to an adjacent carbon atom on the same aromatic ring of Ar; m is an integer of 1 or greater; n is an integer of 1 or greater; and ^R5 is a monovalent group. Preferably, the polyvalent aryl group Ar may be composed of 1 to 3 aromatic carbocyclic or heteroaromatic rings. Preferably, the aryl group contains a single aromatic ring, more preferably a phenyl ring. The aryl group is optionally substituted with 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 one or more of (C ₁ -C ₃ ) alkyl, tri(C ₁ -C ₃ ) alkylsilyl and (C ₁ -C ₃ ) alkoxy. Preferably, the aryl group is unsubstituted. Preferably, n=1 or 2, more preferably n=1. Preferably, m=1 to 4, more preferably m=2 to 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 selected from 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 selected from H, (C ₁ -C ₆ )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 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 selected from H, (C ₁ -C ₆ ) alkyl, aryl, aralkyl, and alkaryl; p is an integer greater than or equal to 1. 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 following formula:

wherein each R ⁶ is independently selected from H and (C ₁ -C ₆ )alkyl, preferably 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. Preferably, each R ⁶ is 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 selected from (C ₁ -C ₃ )alkyl, tri(C ₁ -C ₃ )alkylsilyl and (C ₁ -C ₃ )alkoxy. Preferably, each ^R8 is independently selected from (C ₂ -C ₆ )alkenyl, more preferably each ^R8 is -CH=CH-. Each ^R9 is preferably selected from (C ₁ -C ₃ )alkyl, more preferably each ^R9 is methyl. Preferably, p=1 to 5, more preferably p=1 to 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 following formula:

Arylcyclobutene oligomers may be prepared by any suitable means, such as those described in U.S. Pat. Nos. 4,812,588; 5,136,069; 5,138,081 and International Publication WO 94/25903. Suitable arylcyclobutene oligomers are also commercially available under the CYCLOTENE™ brand, available from Dow Electronic Materials. The arylcyclobutene oligomers may be used as is or may be further purified by any suitable means.

Curable vinyl aromatic oligomers can be used as curable adhesive materials in the present invention. Such vinyl aromatic oligomers are typically oligomers of one or more reactive ethylenically unsaturated comonomers and a vinyl aromatic monomer. Preferably, the vinyl aromatic monomer contains one vinyl group. Suitable vinyl aromatic monomers include unsubstituted vinyl aromatic monomers and substituted vinyl aromatic monomers in which one or more hydrogens are replaced with a substituent selected from the group consisting of (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkoxy, halo, and amino. Exemplary vinyl aromatic monomers include, but are not limited to, styrene, vinyl toluene, vinyl xylene, vinyl anisole, vinyl dimethoxy benzene, vinyl aniline, halostyrenes such as fluorostyrene, α-methyl styrene, β-methoxy styrene, ethyl vinyl benzene, vinyl pyridine, vinyl imidazole, vinyl pyrrole, and mixtures thereof. Preferred vinyl aromatic monomers are styrene, vinyl toluene, vinyl xylene, vinyl anisole, ethyl vinyl benzene, and mixtures thereof. Preferred reactive comonomers are those that contain a reactive moiety, i.e., a moiety capable of further polymerization (or crosslinking) after formation of the vinyl aromatic oligomer, such as an allyl moiety or vinyl group, in addition to the olefinic (or ethylenically unsaturated) moiety used to form the vinyl aromatic oligomer. Such reactive comonomers may suitably be any asymmetric diene or triene that can be further polymerized by a Diels-Alder reaction after oligomerization with the vinyl aromatic monomer. More preferably, the reactive comonomer contains an allyl moiety in addition to the ethylenic unsaturation used to form the vinyl aromatic oligomer, and even more preferably, contains an allyl ester moiety in addition to this ethylenic unsaturation. Exemplary reactive comonomers useful for forming vinyl aromatic oligomers include, but are not limited to, vinylcyclohexene, vinyl ethers, asymmetric dienes or trienes such as terpene monomers, dicyclopentadiene, diallyl maleate, allyl acrylate, allyl methacrylate, allyl cinnamate, 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 vinyl aromatic oligomers. Such second comonomers are ethylenically unsaturated but do not contain reactive moieties. Exemplary second comonomers include, but are not limited to, (meth)acrylic acid, (meth)acrylamide, (C1-C10) alkyl (meth)acrylates, aromatic (meth)acrylates, substituted ethylene monomers, and poly(alkylene oxide) monomers.

The molar ratio of vinyl aromatic monomer to comonomer in such vinyl aromatic oligomers is preferably 99:1 to 1:99, more preferably 95:5 to 5:95, and even more preferably 90:10 to 10:90. Such vinyl aromatic oligomers may be prepared by any suitable method, including any method known in the art. Typically, vinyl aromatic oligomers are 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 the adhesive material under storage and use conditions and are non-curable under the conditions used to cure the adhesive material. Additionally, the release additive should be compatible with the temporary bonding composition; i.e., the release additive must be dispersible, miscible, or otherwise substantially compatible with the adhesive material and any other components used in the temporary bonding composition, such as organic solvents. If an organic solvent (or mixed solvent system) is used in the temporary bonding composition, the release additive and curable adhesive material must be soluble in such solvent. In the present invention, the release additives are sufficiently nonvolatile so that they do not substantially evaporate under use conditions; i.e., they do not substantially evaporate during the deposition process, e.g., spin coating, or any subsequent heating step used to remove the organic solvent or cure the adhesive material. When a film or layer of the temporary bonding composition is cast, e.g., by spin coating, much (or all) of the solvent evaporates. Preferably, the release additive is soluble in any organic solvent used, but not completely soluble in the curable adhesive material. The release additive is predominantly hydrophilic relative to 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 (a more hydrophilic surface relative to the carrier surface). The use of an appropriate hydrophilic moiety in the release additive allows for complete dispersion, or preferably dissolution, of the release additive in the temporary bonding composition and allows for phase separation of the release additive during curing of the adhesive material, with migration of the release additive toward the more hydrophilic surface. Any material that does not phase separate from the adhesive material during curing will not function as a release additive in accordance with the present invention.

Generally, the release additive will contain one or more relatively hydrophilic moieties, such as one or more oxygen-, nitrogen-, phosphorus-, and sulfur-containing moieties. Suitable release 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 release 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 amine, secondary amine, and tertiary amine, with preferred end groups selected from (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 selected from (C ₁ -C ₆ )alkoxy, (C ₆ -C ₁₀ )aryloxy, hydroxy, carboxylate, and (C 1 -C 6 )alkoxycarbonyl, and 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 release additive is silicone-free.

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

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

One or more organic solvents are preferably used in the temporary bonding composition. Any solvent or mixture of solvents that dissolves or disperses, preferably dissolves, the curable adhesive material and release additive may be suitable for use 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 methyl isobutylcarbinol; 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 from The Dow Chemical Company as PROGLYDE™ DMM); ketones such as cyclohexanone and methylcyclohexanone; and mixtures thereof.

<<Third embodiment>>
In 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, the thermosetting polymer described in Japanese Patent No. 6,528,747 can be used.
The thermosetting polymer is not particularly limited, but a preferred example is a siloxane bond-containing polymer (hereinafter also referred to as silicone A) that is composed of a repeating unit represented by the following formula (3) and, if necessary, a repeating unit represented by the following formula (4) and has a weight average molecular weight of 3,000 to 500,000:

[In the formula, R ⁶ to R ⁹ each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms. Furthermore, m represents an integer from 1 to 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).

(wherein A ¹ is a single bond or a group represented by the following formula:

R ¹⁰ and R ¹¹ each independently represent an alkyl group or alkoxy group having 1 to 4 carbon atoms. h each independently represents 0, 1, or 2.

Examples of monovalent hydrocarbon groups represented by ^R6 to ^R9 include alkyl groups such as methyl and ethyl groups, and aryl groups such as phenyl groups. m is preferably an integer of 3 to 60, more preferably 8 to 40. Furthermore, A is preferably 0.3 to 0.8, and B is preferably 0.2 to 0.7, with A/B preferably satisfying the range of 0.1 to 20, and more preferably satisfying the range of 0.5 to 5.

Another preferred example of a thermosetting polymer is a siloxane bond-containing polymer (hereinafter also referred to as "silicone B") having a weight-average molecular weight of 3,000 to 500,000, which comprises a repeating unit represented by the following formula (6) and, if necessary, a repeating unit represented by the following formula (7):

[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 that satisfy 0<C≦1, 0≦D<1, and C+D=1. ^{T 3} and T ⁴ are divalent organic groups represented by the following formula (8).

(Wherein ^A2 is a single bond or a group represented by the following formula:

^{R 16} and R ¹⁷ are each independently an alkyl group or alkoxy group having 1 to 4 carbon atoms. Each k is independently 0, 1, or 2.

In this case, examples of the monovalent hydrocarbon groups represented by R ¹¹ to R ¹⁴ include the same groups as those exemplified as those represented by R ⁵ to R ^8. p is preferably an integer of 3 to 60, more preferably 8 to 40. Furthermore, 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 preferably a layer of a cured product of a thermosetting resin composition whose main component is silicone A or silicone B. Silicone A and silicone B can be used in combination. In this case, the ratio (polymerization ratio) of silicone A:silicone B is preferably 0.1:99.9 to 99.9:0.1, and more preferably silicone A:silicone B is 20:80 to 80:20.

Thermosetting resin compositions containing silicone A as a main component contain, for thermal curing, one or more crosslinking agents selected from an amino condensate modified with formalin or formalin-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, and an epoxy compound having an average of two or more epoxy groups per molecule.

On the other hand, the thermosetting resin composition containing silicone B as the main component contains, for thermal curing, one or more crosslinking agents selected from phenolic compounds having an average of two or more phenolic groups per molecule and epoxy compounds having an average of two or more epoxy groups per molecule.

The thermosetting resin composition containing silicone A and silicone B also contains, for thermal curing, one or more crosslinking agents selected from epoxy compounds having an average of two or more epoxy groups per molecule.

Examples of the amino condensates include melamine resins and urea resins. Examples of melamine resins modified with formalin or formalin-alcohol include those obtained by subjecting modified melamine monomers (e.g., trimethoxymethyl monomethylol melamine) or their polymers (e.g., oligomers such as dimers and trimers) to addition-condensation polymerization with formaldehyde according to known methods until the desired molecular weight is reached. These can be used alone or in combination of two or more types.

Examples of urea resins modified with formalin or formalin-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, and propoxymethylated urea condensates. These can be used alone or in combination of two or more. Urea resins modified with formalin or formalin-alcohol can be prepared, for example, by modifying a urea condensate of the desired molecular weight with formalin using a known method, or by further modifying the urea condensate by alkoxylation with an alcohol.

Furthermore, examples of phenol compounds having an average of two or more methylol groups or alkoxymethylol groups per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2',6,6'-tetramethoxymethylbisphenol A. These can be used alone or in combination of two or more.

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

Examples of phenolic compounds containing an average of two or more phenolic groups per molecule include m- or p-cresol novolac resins (e.g., EP-6030G manufactured by Asahi Organic Chemicals Co., Ltd.), trifunctional phenolic compounds (e.g., Tris-P-PA manufactured by Honshu Chemical Industry Co., Ltd.), and tetrafunctional phenolic compounds (e.g., TEP-TPA manufactured by Asahi Organic Chemicals Co., Ltd.).

The amount of crosslinking agent in the thermosetting resin composition is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and even more preferably 1 to 20 parts by mass, per 100 parts by mass of the thermosetting polymer. Crosslinking agents can be used alone or in combination of two or more types.

The thermosetting resin composition may also contain a curing catalyst such as an acid anhydride in an amount of up to 10 parts by mass per 100 parts by mass of the thermosetting polymer.

<<Fourth embodiment>>
In a preferred embodiment, the adhesive composition used in the present invention is a thermoplastic composition, for example, 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") can be used.
The bonding composition is not particularly limited, but a preferred example is one that is dispersed or dissolved in a solvent system and contains a compound selected from the group consisting of imide, amide-imide, and amide-imide-siloxane polymers and oligomers.
The compound is selected from the group consisting of polymers and oligomers having repeating units of at least one of the following formula (I) and formula (II):
Formula (I):
wherein R is
wherein R ₁ is alkyl-substituted phenyl;
) is selected from the group consisting of

Formula (II):
wherein Z is selected from the group consisting of siloxanes and moieties having ether bridges.

Preferred alkyl-substituted phenyls are C ₁ -C ₆ alkyl-substituted phenyls. Particularly preferred examples of alkyl-substituted phenyls include:
Examples include those selected from the group consisting of:

In formula (I), X is selected from the group consisting of phenyl sulfone, aromatic compounds (preferably _C6 - _C60 , more preferably _C6 - _C30 , even more preferably _C6 - _C24 ), aliphatic compounds (preferably _C2 - _C15 , more preferably _C2 - _C10 , even more preferably _C2 - _C6 ), and alicyclic compounds (preferably _C4 - _C60 , more preferably _C4 - _C20 , even more preferably _C4 - _C12 ).

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

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

In the embodiment where Z in formula (II) is a siloxane, preferred siloxanes are of the formula:
wherein each ^R3 is independently selected from the group consisting of hydrogen, alkyl (preferably _C1 - _C10 , more preferably _C1 - _C2 ), and phenyl;
m is 1 to 6;
and p is 1 to 50, preferably 1 to 20, and more preferably 1 to 10.

In formula (II), preferred moieties of Z having an ether bridge are
is selected from the group consisting of:

In the embodiment of Formula (I) or the embodiment of Formula (II), it is preferred that the polymer or oligomer further comprises an end-capping group. Preferred end-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 (preferably _C1 - _C15 , more preferably _C1 - _C10 , and even more preferably _C1 - _C6 ) alkyl,
wherein R ₄ is alkyl (preferably C ₁ -C ₁₅ , more preferably C ₁ -C ₁₀ , even more preferably C ₁ -C ₆ ), and R ₅ is an alicyclic group (preferably C ₃ -C ₁₂ , more preferably C ₅ -C ₆ );
and k is 0 to 20, preferably 0 to 10, more preferably 0 to 5.

The bonding composition is, for example, a compound dispersed or dissolved in a solvent system. This compound may be a polymer or oligomer, and is present in the composition at a level of preferably about 1% to about 70% by weight, more preferably about 5% to about 50% by weight, and even more preferably about 15% to about 40% by weight, where the total weight of the film-constituting components in the composition is 100% by weight.

The polymeric or oligomeric compounds are thermoplastic and preferably have a weight average molecular weight of about 3,000 Daltons to about 300,000 Daltons, more preferably about 6,000 Daltons to about 50,000 Daltons. Preferred compounds have a softening temperature (at a melt viscosity of 3,000 Pa·s) of at least about 150°C, more preferably at least about 200°C, and even more preferably about 200°C to about 250°C.

Preferred compounds dissolve at least about 95% by mass, preferably at least about 98% by mass, and more preferably about 100% by mass, when left at room temperature for about 1 to 24 hours in a medium such as N-methyl-2-pyrrolidone, xylene, dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, or a mixture thereof.

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

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

The amount of film constituent components in the bonding composition should be at least about 10% by mass, preferably about 10% to about 40% by mass, and more preferably about 10% to about 30% by mass, with the total mass of the composition being 100% by mass.

The adhesive composition used in the present invention may contain a solvent for purposes such as adjusting viscosity. Specific examples of solvents include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.

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

When the adhesive composition used in the present invention contains a solvent, the content of the solvent is set appropriately taking into consideration the desired viscosity of the composition, the application method to be used, the thickness of the film to be produced, etc., but is generally in the range of approximately 10 to 90% by mass of the total composition.

The viscosity of the adhesive composition used in the present invention is not particularly limited, but is typically 500 to 20,000 mPa·s, and 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 type of solvent used, their ratio, the concentration of the film-constituting components, etc., taking into consideration various factors such as the application method used and the desired film thickness. In this invention, film-constituting components refer to components contained in the composition other than the solvent.

An example of an adhesive composition for use in the present invention can be prepared by mixing component (A) with component (B), if used, and a solvent.
The order of mixing is not particularly limited, but examples of methods that can easily and reproducibly produce an adhesive composition include, but are not limited to, a method of dissolving component (A) and component (B) in a solvent, or a method of dissolving a portion of component (A) and a portion of component (B) in a solvent and the remaining portions in a solvent, and then mixing the resulting solutions. When preparing the adhesive composition, heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components.
In the present invention, in order to remove foreign matter, the solvent, solution, etc. used may be filtered using a filter during the production of the adhesive composition or after all of the components have been mixed.

The thickness of the adhesive layer provided in the laminate of the present invention is not particularly limited, but is typically 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity 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 include an inorganic material layer.
The inorganic material layer is usually interposed between the release layer and the adhesive layer, and the inorganic material layer prevents the release layer and the adhesive layer from intermixing.

The inorganic material layer is not particularly limited as long as it is a layer made of an inorganic material, and examples thereof include layers formed from compounds such as oxides, nitrides, and carbides of at least one element selected from the group consisting of silicon, boron, titanium, zirconium, and aluminum, 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 chemical vapor deposition (CVD), which may involve, for example, plasma polymerization coating.
Examples of materials used in plasma polymerization coating include organosilicon compounds. For example, by performing plasma polymerization coating of an organosilicon compound on a release layer or an adhesive layer, a source gas containing the organosilicon compound is decomposed, and an inorganic material layer, which is a thin film containing Si—O bonds, can be formed on the release layer or the adhesive layer.
It is preferable to blend a gas containing oxygen, such as _O2 or _N2O , into the raw material gas containing the organosilicon compound. Alternatively, a rare gas, such as argon or helium, may be blended into the raw material gas as a carrier gas. In a preferred example of a method for decomposing the raw material gas, a plasma generator is used to generate plasma under appropriate pressure conditions, and the raw material gas is decomposed by the plasma. The technique of using plasma to decompose the raw material gas and form a film (layer) is generally referred to as plasma polymerization.

Examples of the organosilicon compound include a siloxane compound, a disilazane compound, and a silane compound.
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, and 1,1,1,3,5,7,7,7-octamethyl Examples of the siloxane include linear siloxanes such as tetrasiloxane, decamethyltetrasiloxane, and 1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane; and cyclic siloxanes such as hexamethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane.
Examples of disilazane compounds include 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, heptamethyldisilazane, hexamethylcyclotrisilazane, and 1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane.
Examples of silane compounds include methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, trimethoxysilane, triethylsilane, trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, tetramethoxysilane, trimethoxymethylsilane, ethyltrimethoxysilane, dimethoxydimethylsilane, methoxytrimethylsilane, tetraethoxysilane, triethoxymethylsilane, triethoxyethylsilane, diethoxydimethylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethoxydimethylsilane, acetoxytrimethylsilane, allyloxytrimethylsilane, allyltrimethylsilane, butoxytrimethylsilane, butyltrimethoxysilane, diacetoxydimethylsilane, dimethoxydiphenylsilane, and diethoxytrimethylsilane. Examples of the silane include diphenylsilane, dimethoxymethylphenylsilane, ethoxydimethylvinylsilane, diphenylsilanediol, triacetoxymethylsilane, triacetoxyethylsilane, 3-glycidyloxypropyltrimethoxysilane, hexyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, octadecyltriethoxysilane, triethoxyoctylsilane, triethoxyphenylsilane, trimethylphenylsilane, propoxytrimethylsilane, triethoxypropylsilane, tetraacetoxysilane, tetrabutoxysilane, tetrapropoxysilane, triacetoxyvinylsilane, triethoxyvinylsilane, trimethoxyvinylsilane, triphenylsilanol, trimethylvinylsilane, and tris(2-methoxyethoxy)vinylsilane.

The thickness of the inorganic material layer is not particularly limited, but is typically 1 to 1,000 nm, and 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 includes 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.
1 has an 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 does not have to be used, and the inorganic material layer 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. Furthermore, the laminate of Fig. 1 has an adhesive layer 4 in contact with the support substrate 5 and the inorganic material layer 3, but in the laminate of the present invention, the adhesive layer 4 may be in contact with only one of the support substrate 5 and the inorganic material layer 3, or may be in contact with neither.

The laminate of the present invention can be suitably produced, for example, by the following method for producing the laminate of the present invention.

(Method for manufacturing laminate)
The method for producing the 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 may further include other steps such as an inorganic material layer forming step and a laminating step, as necessary.

<Release layer forming step>
The release layer forming step is a step in which a release layer is formed.
When the release agent composition used does not contain a solvent, a release layer is formed, for example, by applying the release agent composition to a semiconductor substrate. If necessary, the layer may be heated during the layer formation process in order to soften the layer and improve its adhesion to the substrate, for example.
When the release agent composition used contains a solvent, the release layer is formed, for example, by applying the release agent composition to a semiconductor substrate to form a release agent coating layer, and then heating the release agent coating layer to remove the solvent. However, if not necessary, heating may not be performed in the process of forming the layer, for example, because the solvent is also removed during film formation by spinning.
The coating method is not particularly limited, but is usually a spin coating method.
The heating temperature is determined appropriately depending on the boiling point of the solvent and the purpose of heating, but is usually 50 to 250°C. The heating time is determined appropriately depending on the heating temperature, but is usually 30 seconds to 1 hour.
Heating can be carried out using, for example, an oven or a hot plate.

<Inorganic material layer formation process>
The inorganic material layer forming step is not particularly limited as long as it is a step in which an inorganic material layer is formed, and examples thereof include a step including the inorganic material layer forming method described above in the description of the 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, and examples thereof include a step in which an adhesive composition is applied onto a release layer, an inorganic material layer, or a support substrate, and then heated (preheat treatment) to form an adhesive coating layer that is an uncured or incompletely cured adhesive layer. In this way, the adhesive coating layer is formed, for example, on the release layer or inorganic material layer, or on the support substrate.

The coating method is not particularly limited, but is usually a spin coating method. Alternatively, a method may be employed in which a coating film is formed separately by a spin coating method or the like, and the sheet-like coating film is attached as an adhesive coating layer.
The thickness of the adhesive coating layer is determined appropriately taking into consideration the thickness of the adhesive layer in the laminate, etc.
When the adhesive composition contains a solvent, the applied adhesive composition is usually heated.
The heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components 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, but is typically 80 to 150°C, and the heating time is typically 30 seconds to 5 minutes.
Heating can be carried out using a hot plate, an oven, or the like.

<Adhesive layer formation process>
The adhesive layer forming step is not particularly limited as long as it is a step in which the adhesive coating layer is heated to form an adhesive layer (post-heat treatment).
For example, a semiconductor substrate having a release layer and an adhesive coating layer formed thereon and a support substrate may be used to arrange the two substrates (semiconductor substrate and support substrate) so as to sandwich the two layers (release layer and adhesive coating layer) so that the support substrate and the adhesive coating layer come into contact with each other, and then a heat treatment may be performed. Alternatively, a semiconductor substrate having a release layer formed thereon and a support substrate having an adhesive coating layer may be used to arrange the two substrates (semiconductor substrate and support substrate) so as to sandwich the two layers (release layer and adhesive coating layer) so that the release layer and the adhesive coating layer come into contact with each other, and then a heat treatment may be performed.
For example, a semiconductor substrate having a release layer, an inorganic material layer, and an adhesive coating layer formed thereon and a support substrate may be used to arrange the two substrates (semiconductor substrate and support substrate) so as to sandwich the three layers (release layer, inorganic material layer, and adhesive coating layer) so that the support substrate and the adhesive coating layer come into contact with each other, and then a heat treatment may be performed. Alternatively, a semiconductor substrate having a release layer and an inorganic material layer formed thereon and a support substrate having an adhesive coating layer formed thereon may be used to arrange the two substrates (semiconductor substrate and support substrate) so as to sandwich the three layers (release layer, inorganic material layer, and adhesive coating layer) so that the inorganic material layer and the adhesive coating layer come into contact with each other, and then a 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 an adhesive layer.
The heating temperature is preferably 120°C or higher from the viewpoint of realizing a sufficient curing rate, and is preferably 260°C or lower from the viewpoint of preventing deterioration of each layer (including the support substrate and semiconductor substrate) constituting the laminate.
The heating time is preferably 1 minute or more, more preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of each layer (including the support substrate and semiconductor substrate) constituting the laminate, and is preferably 180 minutes or less, more preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating.
Heating can be carried out using a hot plate, an oven, or the like.
Heating may be carried out in stages.

<Lamination process>
Between the adhesive coating layer forming step and the adhesive layer forming step, a bonding step is preferably carried out to ensure sufficient bonding between the semiconductor substrate and the support substrate.
The bonding step is not particularly limited as long as it allows the substrate and the layer to be bonded together and does not damage the substrate or the layer, but is typically a step in which a load is applied in the thickness direction of the support substrate and the semiconductor substrate, and more preferably a step in which a load is applied in the thickness direction of the support substrate and the semiconductor substrate under reduced pressure.
The load is not particularly limited as long as it allows the substrate and layer to be bonded together and does not damage the substrate or layer, but is, for example, 10 to 1,000 N.
The degree of reduced pressure is not particularly limited as long as it allows the substrate and layer to be bonded together and does not damage the substrate or layer, but is, for example, 10 to 10,000 Pa.

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

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

<<Polishing process>>
The polishing process is not particularly limited as long as it is a process for polishing the surface of the semiconductor substrate opposite to the surface on which the bumps are present, thereby thinning the semiconductor substrate. For example, physical polishing using an abrasive or a grinding stone may be used.
The polishing process can be carried out using a general polishing device used for polishing semiconductor substrates.
The polishing process reduces the thickness of the semiconductor substrate, resulting in a semiconductor substrate thinned 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 formation process>>
In some cases, through electrodes are formed in the polished semiconductor substrate to realize electrical continuity between the thinned semiconductor substrates when a plurality of thinned semiconductor substrates are stacked.
Therefore, the method for manufacturing a semiconductor substrate may include a through electrode forming process for forming a through electrode in the polished semiconductor substrate after the polishing process and before the peeling step.
The method for forming a through electrode in a semiconductor substrate is not particularly limited, but may include, for example, forming a through hole and filling the formed through hole with a conductive material.
The through holes are formed by, for example, photolithography.
The through holes are filled with a conductive material by, for example, plating techniques.

<Peeling process>
The peeling step is not particularly limited as long as it is a step in which the support substrate and the processed semiconductor substrate are separated after the processing step.
For example, mechanical peeling can be performed using a device with a sharp part (a so-called debonder). Specifically, for example, a sharp part is inserted between the semiconductor substrate and the support substrate, and then the semiconductor substrate and the support substrate are separated. Usually, peeling occurs at the interface between the release layer and the semiconductor substrate or the inorganic material layer.

<Removal process>
The removal step is not particularly limited as long as it is a step in which the release layer is removed after the peeling step, and examples thereof include dissolution removal. Removal may also be performed using a removal tape or the like. Note that, if there is a residue of the adhesive layer on the semiconductor substrate via the release layer after the peeling step, the residue is also removed in the removal step.
When using the cleaning composition, for example, the semiconductor substrate with the release layer can be immersed in the cleaning composition or 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 is used for this type of application.
Such quaternary ammonium cations typically include tetra(hydrocarbon)ammonium cations, while their counter anions include, but are not limited to, hydroxide ion (OH ⁻ ), halogen ions such as fluoride ion (F ⁻ ), chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), and iodide ion (I ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ), and hexafluorophosphate ion (PF ₆ ⁻ ).

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 either the cation or the anion, but is preferably contained in the anion.

In a preferred embodiment, the fluorine-containing quaternary ammonium salt is a tetra(hydrocarbon)ammonium fluoride.
Specific examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms.
In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride.
Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also called tetrabutylammonium fluoride), etc. Among these, tetrabutylammonium fluoride is preferred.

The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of a hydrate. The 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 based on the detergent composition.

The solvent contained in the cleaning composition used in the present invention is not particularly limited, as long as it is suitable for this type of application and dissolves salts such as the quaternary ammonium salt. However, from the perspective of reproducibly obtaining a cleaning composition with excellent cleaning properties and of obtaining a cleaning composition with excellent uniformity by satisfactorily dissolving salts such as the quaternary ammonium salt, the cleaning composition used in the present invention preferably contains one or more amide solvents.

A suitable example of the amide 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, with an ethyl group being preferred. ^{R A} and R ^B each independently represent an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, and a cyclobutyl group. Of these, a methyl group or an ethyl group is preferred as R ^A and R ^B.

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, and N-ethyl-N-methylisobutyric acid amide. Of these, N,N-dimethylpropionamide is particularly preferred.

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

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

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

Specific examples of lactam compounds represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, and δ-lactam compounds, which can be used alone or in combination of two or more.

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

The cleaning composition used in the present invention may contain one or more other organic solvents different from the above-mentioned amide compound.
Such other organic solvents are not particularly limited as long as they are used for this type of application and are compatible with the above-mentioned amide compounds.
Other preferred solvents include, but are not limited to, alkylene glycol dialkyl ethers, aromatic hydrocarbon compounds, and ether compounds containing a ring structure.
The amount of the organic solvent other than the amide compound is usually determined appropriately so as to be 95 mass % or less of the solvent contained in the cleaning composition, as long as the quaternary ammonium salt contained in the cleaning composition does not precipitate or separate and is uniformly mixed with the amide compound.
The cleaning composition used in the present invention may contain water as a solvent, but usually only an organic solvent is used as the solvent from the viewpoint of avoiding corrosion of the substrate, etc. In this case, it is not excluded that the cleaning composition may contain water of hydration of salts or trace amounts of water contained in the organic solvent. The water content of the cleaning composition used in the present invention is usually 5 mass% or less.

The present invention will be explained in more detail below using examples, but the present invention is not limited to the following examples. The equipment used is as follows:

(1) Mixer: Thinky Corporation, Planetary Planetary Mixer ARE-500
(2) Vacuum bonding device: XBS300 manufactured by SUSS MicroTec Co., Ltd.
(3) Manual peeling device: Manual debonder manufactured by SUSS Microtec Co., Ltd. (4) Vacuum heating device: VJ-300-S manufactured by Ayumi Industries Co., Ltd.

[Measurement of molecular weight]
The weight average molecular weight and number average molecular weight of polydimethylsiloxane were measured using a GPC apparatus (HLC-8320GPC manufactured by Tosoh Corporation) and GPC columns (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H manufactured by Tosoh Corporation) at a column temperature of 40°C, using tetrahydrofuran as an eluent (elution solvent) at a flow rate (flow rate) of 0.35 mL/min, and using polystyrene (manufactured by Shodex) as a standard sample.

[1] Preparation of adhesive composition [Preparation Example 1]
Into a 600 mL stirring vessel dedicated to the planetary centrifugal mixer, 80 g of MQ resin (manufactured by Wacker Chemie) containing a polysiloxane skeleton and vinyl groups, 2.52 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 100 mPa s, 5.89 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 70 mPa s, and 0.22 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) were placed, and the mixture was stirred with a stirrer for 5 minutes to obtain mixture (I).
0.147 g of platinum catalyst (manufactured by Wacker Chemie) and 5.81 g of vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 1,000 mPa·s were stirred for 5 minutes with a stirrer to obtain a mixture (II).
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 obtained mixture (III) was filtered through a 300 mesh nylon filter to obtain an adhesive composition.

[2] Preparation of Stripping Composition [Preparation Example 2-1]
In a 250 mL stirring vessel, 1.81 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 50), which is a polydimethylsiloxane having a weight average molecular weight of 7120 and a dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.41, and 98.19 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.

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

[Preparation Example 2-3]
A 250 mL stirring vessel was charged with 1.81 g of a polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is a polydimethylsiloxane having a weight average molecular weight of 34,550 and a dispersity of 2.24, and 98.19 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65), and the resulting mixture was stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.

[Preparation Example 2-4]
A 250 mL stirring vessel was charged with 1.70 g of a polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 10000), which is a polydimethylsiloxane having a weight average molecular weight of 69,980 and a dispersity of 3.66, and 98.3 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65), and the mixture was stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.

[Preparation Example 2-5]
1.34 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000000), which is a polydimethylsiloxane having a weight average molecular weight of 171,860 and a dispersity of 2.18, and 98.66 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed in a 250 mL stirring vessel and stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.

[Preparation Example 2-6]
In a 250 mL stirring vessel, 1.17 g of a polydimethylsiloxane polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 350) having a weight average molecular weight of 21110 and a dispersity of 1.72, 0.52 g of a polydimethylsiloxane polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000) having a weight average molecular weight of 34550 and a dispersity of 2.24, and 98.33 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.
In addition, the weight average molecular weight of the polydimethylsiloxane in the mixture of 1.17 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 350), which is a polydimethylsiloxane having a weight average molecular weight of 21110 and a dispersity of 1.72, and 0.52 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is a polydimethylsiloxane having a weight average molecular weight of 34550 and a dispersity of 2.24, was 25100. The dispersity was 4.04.

[Preparation Example 2-7]
In a 250 mL stirring vessel, 0.50 g of a polydimethylsiloxane (manufactured by Wacker Chemie, trade name AK 350) having a weight average molecular weight of 21110 and a dispersity of 1.72, 1.38 g of a polydimethylsiloxane (manufactured by Wacker Chemie, trade name AK 1000) having a weight average molecular weight of 34550 and a dispersity of 2.24, and 98.32 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.
In addition, the weight average molecular weight of the polydimethylsiloxane in the mixture of 0.50 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 350), which is a polydimethylsiloxane having a weight average molecular weight of 21110 and a dispersity of 1.72, and 1.38 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is a polydimethylsiloxane having a weight average molecular weight of 34550 and a dispersity of 2.24, was 29270. The dispersity was 4.94.

[Preparation Example 2-8]
In a 250 mL stirring vessel, 1.33 g of a polydimethylsiloxane polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000) having a weight average molecular weight of 34,550 and a dispersity of 2.24, 0.57 g of a polydimethylsiloxane polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 10000) having a weight average molecular weight of 69,980 and a dispersity of 3.66, and 98.10 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.
In addition, the weight average molecular weight of the polydimethylsiloxane in the mixture of 1.33 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is a polydimethylsiloxane having a weight average molecular weight of 34550 and a dispersity of 2.24, and 0.57 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 10000), which is a polydimethylsiloxane having a weight average molecular weight of 69980 and a dispersity of 3.66, was 49350. The dispersity was 8.37.

[Preparation Example 2-9]
In a 250 mL stirring vessel, 0.55 g of a polydimethylsiloxane (manufactured by Wacker Chemie, trade name AK 1000) having a weight average molecular weight of 34,550 and a dispersity of 2.24, 1.28 g of a polydimethylsiloxane (manufactured by Wacker Chemie, trade name AK 10000) having a weight average molecular weight of 69,980 and a dispersity of 3.66, and 98.17 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.
In addition, the weight average molecular weight of the polydimethylsiloxane in the mixture of 0.55 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is a polydimethylsiloxane having a weight average molecular weight of 34550 and a dispersity of 2.24, and 1.28 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 10000), which is a polydimethylsiloxane having a weight average molecular weight of 69980 and a dispersity of 3.66, was 68740. The dispersity 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 final laminate was 170 nm, thereby forming a release layer.
Next, a plasma polymer layer, which is an inorganic material layer, was formed on the release layer so that the film thickness in the final laminate was 160 nm. The plasma polymer layer was formed by a chemical vapor deposition (CVD) method. Specifically, the 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 final laminate was 60 μm, to form an adhesive coating layer on the plasma polymer layer.
Then, using a bonding device, a silicon wafer serving as a semiconductor substrate and a 12-inch glass wafer serving as a support substrate were bonded together so as to sandwich the release layer, plasma polymer layer, and adhesive coating layer, and then, with the semiconductor substrate facing downward, they were subjected to heat treatments on a hot plate at 170°C for 7 minutes and then 190°C for 7 minutes, thereby producing a laminate. The bonding was performed at a temperature of 23°C and a reduced pressure of 1,000 Pa.

Examples 1 to 4
Laminates were prepared in the same manner as in Comparative Example 1, except that the release agent composition obtained in Preparation Example 2-1 was replaced with the release agent compositions obtained in Preparation Examples 2-3 and 2-6 to 2-8, respectively.

(Comparative Examples 2 to 5)
Laminates were prepared in the same manner as in Comparative Example 1, except that the release agent composition obtained in Preparation Example 2-1 was replaced with the release agent compositions obtained in Preparation Examples 2-2, 2-4, 2-5, and 2-9, respectively.

[High-temperature treatment of laminate]
The laminate was subjected to a heat treatment using a vacuum heating device according to the following procedure.
The stack was placed with the semiconductor substrate facing downwards on a heating stage set at 300° C. and heated for 10 minutes in a nitrogen atmosphere.
The state of the semiconductor substrate of each laminate after processing was observed using an optical microscope through the glass wafer support substrate, and the presence or absence of voids and delamination was visually confirmed. After the observation, a manual peeling device was used to insert a sharp object between the semiconductor substrate and support substrate of the laminate to confirm whether the semiconductor substrate and support substrate could be easily separated manually. The peelability evaluation results were rated as "possible" if the semiconductor substrate and support substrate could be manually separated at the interface between the release layer and the inorganic material layer without applying a force that felt like a heavy load was being applied to the substrate, and "failed" otherwise. Note that a "failed" evaluation result indicated that even when further force was applied to peel the substrates, they still could not be separated at all, or the substrates could be forcibly separated but cracked.
Here, "voids" refers to a state in which air bubbles exist between the substrate and a layer of the laminate, between two layers, or within a layer, and in such a state where undesirable air bubbles exist, sufficient protection of the semiconductor substrate cannot be expected. "Delamination" refers to a state in which the release layer is partially peeled off from the semiconductor substrate, and in such a state, sufficient protection of the semiconductor substrate cannot be expected.
The results are shown in Table 1 below.

As shown in the table, even in laminates having a film obtained from a release agent composition containing polyorganosiloxane (polydimethylsiloxane) as a release layer, when the weight average molecular weight is outside the specified range of the present invention (Comparative Examples 1 to 5), when heat treatment is performed at high temperatures (300 ° C.), delamination cannot be suppressed during heat treatment, or delamination does not occur during heat treatment. Even if peeling was not possible after heat treatment, when the weight average molecular weight is within the specified range of the present invention (Examples 1 to 4), delamination during heat treatment at high temperatures (300 ° C.) can be suppressed, and in addition, peeling was possible after heat treatment.
In terms of whether peeling is possible, Comparative Example 2 is better than Comparative Example 1, and it is thought that peeling becomes possible when a polyorganosiloxane having a weight average molecular weight slightly larger than that of the polyorganosiloxane of Comparative Example 2 (for example, a polyorganosiloxane having a weight average molecular weight of 22,000) is used.
In terms of the degree of delamination, Comparative Examples 3 and 5 are better than Comparative Example 4, and it is believed that delamination would not occur if a polyorganosiloxane having a weight average molecular weight slightly smaller than that of the polyorganosiloxane of Comparative Example 5 (for example, a polyorganosiloxane having a weight average molecular weight of 68,000) were used.

According to the present invention, the laminate of the present invention is useful for producing processed semiconductor substrates, as it does not peel off when the semiconductor substrate and support substrate are temporarily bonded together, even after the semiconductor substrate has been exposed to high temperatures, and can be easily peeled off when an attempt is made to peel the semiconductor substrate and support substrate.

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

Claims (15)

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;
an adhesive layer interposed between the support substrate and the release layer;
A laminate having
A 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 the polyorganosiloxane is polydimethylsiloxane. The laminate according to claim 1 or 2, wherein the adhesive layer is a layer formed from an adhesive composition. The laminate described in claim 3, wherein the adhesive composition contains a curable component (A). The laminate described in claim 4, wherein component (A) is a component that cures via 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 Si—H groups;
a platinum group metal catalyst (A2);
The laminate according to claim 4 or 5, comprising: The laminate described in any one of claims 1 to 6, which has an inorganic material layer interposed between the release layer and the adhesive layer. The laminate according to claim 7, wherein the inorganic material layer is a layer obtained by plasma polymerization of an organosilicon compound. The laminate described in any one of claims 1 to 8 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 stack according to any one of claims 1 to 8;
separating the support substrate from the processed semiconductor substrate;
A method for manufacturing a semiconductor substrate, comprising: The method for manufacturing a semiconductor substrate according to claim 10, wherein the processing step includes polishing the surface of the semiconductor substrate opposite to the surface in contact with the release layer, thereby thinning the semiconductor substrate. The method for manufacturing a semiconductor substrate according to claim 10 or 11, wherein the processing step includes a treatment in which the semiconductor substrate is heated to 280°C or higher. A method for producing a laminate according to any one of claims 1 to 9, comprising:
forming an adhesive coating layer that provides the adhesive layer;
a step of heating the adhesive coating layer to form the adhesive layer while the support substrate and the semiconductor substrate are in contact with each other with the release layer and the adhesive coating layer interposed therebetween;
A method for producing a laminate, comprising: A release agent composition used in forming the release layer of a laminate having 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, the release layer being in contact with the semiconductor substrate that is heated to 280°C or higher when the semiconductor substrate of the laminate is processed,
A release agent composition containing a polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000. The stripping agent composition according to claim 14, wherein the polyorganosiloxane is polydimethylsiloxane.