Adhesive composition, laminate, and method for producing processed semiconductor substrate or processed electronic device layer

Abstract

Provided is an adhesive composition containing: an adhesive component, and a polyorganosiloxane having, in a side chain, a secondary hydroxyl group and a branched aliphatic hydrocarbon group having 6 or more carbon atoms.

Description

Adhesive composition, laminate, and method for manufacturing a processed semiconductor substrate or processed electronic device layer

[0001] The present invention relates to an adhesive composition, a laminate, and a method for manufacturing a processed semiconductor substrate or a processed electronic device layer.

[0002] Conventionally, semiconductor wafers have been integrated in a two-dimensional planar direction. To achieve even greater integration, there is a need for semiconductor integration technology that integrates (stacks) in a three-dimensional direction as well. This three-dimensional stacking is a technology that integrates in multiple layers while connecting them with through-silicon vias (TSVs). When integrating in multiple layers, the side opposite to the circuit surface (i.e., the back surface) of each wafer to be integrated is thinned by polishing, and the thinned semiconductor wafers are stacked.

[0003] Before thinning, the semiconductor wafer (also simply called a wafer here) is bonded to a support in order to be polished using a polishing device. This bonding is called temporary bonding because it must be easily removed after polishing. This temporary bonding must be easily removed from the support, as applying too much force during removal can cause the thinned semiconductor wafer to cut or deform. To prevent this, it must be easily removed. However, it is undesirable for the temporary bonding to detach or shift due to polishing stress during back-side polishing of the semiconductor wafer. Therefore, the required performance of the temporary bonding is to withstand the stress during polishing and to be easily removed after polishing.

[0004] As temporary adhesives used for such temporary bonding, adhesives containing polydimethylsiloxane (Patent Document 1) and temporary adhesives containing epoxy-modified polysiloxane (Patent Document 2) have been proposed.

[0005] International Publication No. 2017 / 221772 Brochure International Publication No. 2018 / 216732 Brochure

[0006] Temporary adhesives contain an adhesive component and a release agent component. For a temporary adhesive to maintain a stable composition, good compatibility (solubility) between the adhesive component and the release agent component is required. The present invention has been made in view of the above circumstances, and aims to provide an adhesive composition that can form an adhesive layer with excellent release properties and has good compatibility between the adhesive component and the release agent component, a laminate using the adhesive composition, and a method for manufacturing a processed semiconductor substrate or a processed electronic device layer using the laminate.

[0007] The inventors of the present invention conducted diligent studies to solve the aforementioned problems and, as a result, found that they could solve the aforementioned problems, and completed the present invention having the following gist.

[0008] In other words, the present invention encompasses the following: [1] An adhesive composition comprising an adhesive component and a polyorganosiloxane having a secondary hydroxyl group and a branched aliphatic hydrocarbon group having 6 or more carbon atoms in its side chains. [2] The adhesive composition according to [1], wherein the polyorganosiloxane has a substructure represented by the following formula (Cg-1) or the following formula (Cg-2). (In formulas (Cg-1) and (Cg-2), R １ R represents an alkylene group having 1 to 10 carbon atoms, which may be interrupted by an oxygen atom. ２ X represents a branched aliphatic hydrocarbon group with 6 or more carbon atoms, １∫ represents -O-, -COO-, -OCO-, -NH-, -S-, or -CONOC-. * represents a bond that binds to a silicon atom.) [3] The adhesive composition according to [1] or [2], wherein the content of the polyorganosiloxane in the nonvolatile content of the adhesive composition is 0.01% to 30% by mass. [4] The adhesive composition according to any one of [1] to [3], wherein the adhesive component is a component that hardens by a hydrosilylation reaction. [5] The adhesive composition according to [4], wherein the component that hardens by a hydrosilylation reaction contains a component (A-1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, a component (A-2) having a Si-H group, and a platinum group metal catalyst (A-3). [6] The adhesive composition according to [5], wherein component (A-1) is a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom. [7] The adhesive composition according to [5] or [6], wherein component (A-2) is a polyorganosiloxane having a Si-H group. [8] A laminate comprising a semiconductor substrate or an electronic device layer, a light-transmitting support substrate, and an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate, wherein the adhesive layer is an adhesive layer formed from any of the adhesive compositions according to [1] to [7]. [9] A method for manufacturing a processed semiconductor substrate or a processed electronic device layer, comprising: a fifth A step in which the semiconductor substrate of the laminate described in [8] is processed, or a fifth B step in which the electronic device layer of the laminate described in [8] is processed; a sixth A step in which the semiconductor substrate processed in the fifth A step is separated from the support substrate, or a sixth B step in which the electronic device layer processed in the fifth B step is separated from the support substrate.

[0009] According to the present invention, it is possible to provide an adhesive composition that can form an adhesive layer with excellent peelability and has good compatibility between the adhesive component and the release agent component, a laminate using the adhesive composition, and a method for manufacturing a processed semiconductor substrate or a processed electronic device layer using the laminate.

[0010] Figure 1 is a schematic cross-sectional view of an example of a laminate in the first embodiment. Figure 2 is a schematic cross-sectional view of another example of a laminate in the first embodiment. Figure 3A is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the first embodiment (part 1). Figure 3B is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the first embodiment (part 2). Figure 4 is a schematic cross-sectional view of an example of a laminate in the second embodiment. Figure 5 is a schematic cross-sectional view of another example of a laminate in the second embodiment. Figure 6A is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the second embodiment (part 1). Figure 6B is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the second embodiment (part 2). Figure 6C is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the second embodiment (part 3). Figure 7A is a schematic cross-sectional view illustrating a method for processing a laminate in an example of the first embodiment (part 1). Figure 7B is a schematic cross-sectional view illustrating a method for processing a laminate in an example of the first embodiment (part 2). Figure 7C is a schematic cross-sectional view illustrating an example of a laminate processing method in the first embodiment (part 3). Figure 7D is a schematic cross-sectional view illustrating an example of a laminate processing method in the first embodiment (part 4). Figure 8A is a schematic cross-sectional view illustrating an example of a laminate processing method in the second embodiment (part 1). Figure 8B is a schematic cross-sectional view illustrating an example of a laminate processing method in the second embodiment (part 2). Figure 8C is a schematic cross-sectional view illustrating an example of a laminate processing method in the second embodiment (part 3). Figure 8D is a schematic cross-sectional view illustrating an example of a laminate processing method in the second embodiment (part 4). Figure 8E is a schematic cross-sectional view illustrating an example of a laminate processing method in the second embodiment (part 5). Figure 8F is a schematic cross-sectional view illustrating an example of a laminate processing method in the second embodiment (part 6).

[0011] (Adhesive Composition) The adhesive composition of the present invention contains an adhesive component and a polyorganosiloxane having a secondary hydroxyl group and a branched aliphatic hydrocarbon group having 6 or more carbon atoms in its side chain. The adhesive composition may contain other components. In this specification, "hydroxyl group" and "hydroxyl group" are synonymous.

[0012] Examples of adhesive compositions include, but are not limited to, polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenol resin-based adhesives. Among these, polysiloxane-based adhesives are preferred because they exhibit suitable adhesive properties during processing of semiconductor substrates and the like, are readily removable after processing, have excellent heat resistance, and can be readily removed with cleaning agent compositions.

[0013] <Adhesive Components> The adhesive components are not particularly limited, but are preferably components that harden, and are more preferably components that harden by a hydrosilylation reaction. The components that harden by a hydrosilylation reaction are not particularly limited, but are preferably components that contain an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom (hereinafter sometimes referred to as "component (A-1)"), a component having a Si-H group (hereinafter sometimes referred to as "component (A-2)"), and a platinum group metal catalyst (A-3).

[0014] <<Components (A-1) and (A-2)>> The adhesive composition preferably contains component (A-1). The adhesive composition preferably contains component (A-2). Hereinafter, the combination of component (A-1), component (A-2), and platinum group metal catalyst (A-3) may be referred to as "curing component (A)" or "component (A)".

[0015] From the viewpoint of suitably obtaining the effect of the present invention, component (A-1) preferably contains a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom. From the viewpoint of suitably obtaining the effect of the present invention, component (A-2) preferably contains a polyorganosiloxane (a2) having a Si-H group. 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 carboxy group, an aryl group, a heteroaryl group and the like.

[0016] In another preferred embodiment, the adhesive composition curable by hydrosilylation reaction is SiO ２ siloxane unit (Q unit) represented by, R １ R ２ R ３ SiO １／２ siloxane unit (M unit) represented by, R ４ R ５ SiO ２／２ siloxane unit (D unit) represented by and R ６ SiO ３／２ a polysiloxane (A1) comprising one or more units selected from the group consisting of siloxane units (T units) represented by and a platinum group metal catalyst (A-3), wherein the polysiloxane (A1) is SiO ２ siloxane unit (Q' unit) represented by, R １ 'R ２ 'R ３ 'SiO １／２ siloxane unit (M' unit) represented by, R ４ 'R ５ 'SiO ２／２ siloxane unit (D' unit) represented by and R ６ 'SiO ３／２ contains one or more units selected from the group consisting of siloxane units (T' units) represented by, and a polyorganosiloxane (a1') containing at least one unit selected from the group consisting of M' units, D' units and T' units, and SiO ２ siloxane unit (Q'' unit) represented by, R １ ''R ２ ''R３ "SiO １／２ Siloxane units (M'' units) expressed as R ４ "R ５ "SiO ２／２ Siloxane units (D'' units) and R ６ "SiO ３／２ The polyorganosiloxane (a2') contains one or more units selected from the group consisting of siloxane units (T'' units) represented by , and also contains 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).

[0017] R １ ~R ６ This group or atom is bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0018] R １ '~R ６ ' represents a group that bonds to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, R １ '~R ６ At least one of the ' is an alkenyl group which may be substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0019] R １ "~R ６ " represents a group or atom bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or hydrogen atom, R １ "~R ６ At least one of the atoms is a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0020] The alkyl group may be linear, branched, or cyclic, but linear or branched alkyl groups are preferred. 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.

[0021] Specific examples of substituted linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, and 4-methyl-n-pentyl group. Examples of methyl groups include, but are not limited to, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group. The number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among these, the methyl group is particularly preferred.

[0022] Specific examples of cyclic alkyl groups, whether substituted or not, include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, and 3,3-dimethyl-cyclobutyl group. Examples of cycloalkyl groups include cycloalkyl groups such as 2-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl; bicycloalkyl groups such as bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl. However, the number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0023] The alkenyl group may be linear or branched, and its number of carbon atoms is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0024] Specific examples of substituted linear or branched alkenyl groups include, but are not limited to, vinyl groups, allyl groups, buttenyl groups, and pentenyl groups. The number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among these, ethenyl groups and 2-propenyl groups are particularly preferred. Specific examples of substituted cyclic alkenyl groups include, but are not limited to, cyclopentenyl and cyclohexenyl groups. The number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0025] As described above, polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'). The alkenyl groups in polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) in polyorganosiloxane (a2') form a cross-linked structure through a hydrosilylation reaction with a platinum group metal catalyst (A-3), and then harden. As a result, a hardened film is formed.

[0026] 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. As polyorganosiloxane (a1'), two or more polyorganosiloxanes that satisfy these conditions may be used in combination.

[0027] Two or more preferred combinations 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).

[0028] Furthermore, when polyorganosiloxane (a1') contains two or more polyorganosiloxanes, 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.

[0029] 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. As polyorganosiloxane (a2'), two or more polyorganosiloxanes that satisfy these conditions may be used in combination.

[0030] Two or more preferred combinations 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).

[0031] Polyorganosiloxane (a1') is composed of siloxane units in which an alkyl group and / or an alkenyl group is bonded to the silicon atom, R １ '~R ６ The proportion of alkenyl groups in the total substituents represented by ' is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, and the remaining R １ '~R ６ ' can be an alkyl group.

[0032] Polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom are bonded to the silicon atom, R １ "~R ６ The proportion of hydrogen atoms in all substituents and substituted atoms represented by " is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remaining R １ "~R ６ " can be an alkyl group.

[0033] When the adhesive composition includes (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of the alkenyl group contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bond contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0034] 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 each, and is preferably 5,000 to 50,000 from the viewpoint of reproducibly realizing the effects of the present invention. In this invention, the weight-average molecular weight, number-average molecular weight, and degree of dispersion of polyorganosiloxane can be measured, for example, using a GPC instrument (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex, manufactured by Resona Corporation) as the standard sample.

[0035] The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 10 to 1,000,000 (mPa·s), and is preferably 50 to 10,000 (mPa·s) from the viewpoint of reproducibly realizing the effects of the present invention. The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is the value measured with an E-type rotational viscometer at 25°C.

[0036] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via hydrosilylation. Therefore, the mechanism of curing is different from that mediated by, for example, silanol groups, and thus neither siloxane needs to contain a silanol group or a functional group that forms a silanol group through hydrolysis, such as an alkyloxy group.

[0037] <<Platinum Group Metal Catalysts (A-3)>> Platinum group metal catalysts are platinum-based metal catalysts. Such platinum-based metal catalysts are catalysts that promote the hydrosilylation reaction between alkenyl groups and Si-H groups.

[0038] Specific examples of platinum-based metal catalysts include known platinum-based compounds (platinum or compounds containing platinum). Specific examples include platinum powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with diolefins, platinum-olefin complexes, platinum-carbonyl complexes (e.g., platinum-bis(acetacetate), platinum-bis(acetylacetonate)), chloroplatinic acid-alkenylsiloxane complexes (e.g., chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex), platinum-alkenylsiloxane complexes (e.g., platinum-divinyltetramethyldisiloxane complex, platinum-tetravinyltetramethylcyclotetrasiloxane complex), and complexes of chloroplatinic acid with acetylene alcohols. Among these, platinum-alkenylsiloxane complexes are particularly preferred due to their high efficacy in promoting hydrosilylation reactions. These hydrosilylation catalysts may be used individually or in combination of two or more.

[0039] The alkenylsiloxane used in the platinum-alkenylsiloxane complex is not particularly limited, but examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxane oligomers obtained by substituting some of the methyl groups of these alkenylsiloxanes with ethyl groups, phenyl groups, etc., and alkenylsiloxane oligomers obtained by substituting the vinyl groups of these alkenylsiloxanes with allyl groups, hexenyl groups, etc. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because the resulting platinum-alkenylsiloxane complex has good stability.

[0040] The content of the platinum group metal catalyst (A-3) in the adhesive composition is not particularly limited, but is, for example, in the range of 0.1 to 50.0 ppm relative to the total mass of component (A-1) and component (A-2).

[0041] The content of adhesive components in the adhesive composition is not particularly limited, but is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, relative to the nonvolatile content of the adhesive composition. The upper limit is not particularly limited, but for example, is preferably 97% by mass or less, more preferably 96% by mass or less, and even more preferably 95% by mass or less. The nonvolatile content of the adhesive composition refers to components other than the solvent in the adhesive composition.

[0042] <Polyorganosiloxane having a secondary hydroxyl group and a branched aliphatic hydrocarbon group having 6 or more carbon atoms in its side chain> By containing a polyorganosiloxane having a secondary hydroxyl group and a branched aliphatic hydrocarbon group having 6 or more carbon atoms in its side chain (hereinafter also referred to as "polyorganosiloxane (b)") in the adhesive composition, the adhesive layer formed from the adhesive composition exhibits excellent release properties. Polyorganosiloxane (b) is a release agent component.

[0043] The polyorganosiloxane (b) contained in the adhesive composition is not particularly limited. Polyorganosiloxane (b) is a polyorganosiloxane having a hydroxyl group directly bonded to a secondary carbon atom and a branched aliphatic hydrocarbon group having six or more carbon atoms in its side chain. Polyorganosiloxane (b) does not usually undergo hydrosilylation reactions.

[0044] Polyorganosiloxane (b) is, for example, a polydimethylsiloxane having a secondary hydroxyl group and a branched aliphatic hydrocarbon group having 6 or more carbon atoms in its side chain.

[0045] The number of hydroxyl groups directly bonded to the secondary carbon atoms in polyorganosiloxane (b) is not particularly limited and may be one or two or more.

[0046] The branched aliphatic hydrocarbon group of polyorganosiloxane (b) has 6 or more carbon atoms, preferably 8 or more, and more preferably 10 or more. The upper limit of the number of carbon atoms of the branched aliphatic hydrocarbon group is not particularly limited, but for example, 40 or less is preferred. The branched aliphatic hydrocarbon group of polyorganosiloxane (b) may or may not have unsaturated bonds such as carbon-carbon double bonds or carbon-carbon triple bonds. In the adhesive composition of this embodiment, the branching of the aliphatic hydrocarbon group of polyorganosiloxane (b) improves the compatibility (solubility) between the adhesive component and the release agent component, and suppresses clouding (phase separation) caused by mixing the adhesive component and the release agent component. Therefore, the adhesive composition can be maintained as a stable composition.

[0047] Polyorganosiloxane (b) has a hydroxyl group directly bonded to a secondary carbon atom in its side chain. In this case, even a small amount of polyorganosiloxane (b) can impart good release properties to the adhesive layer formed from the adhesive composition.

[0048] Polyorganosiloxane (b) has a substructure represented by, for example, the following formula (Cg-1) or formula (Cg-2). (In formulas (Cg-1) and (Cg-2), R １ R represents an alkylene group having 1 to 10 carbon atoms, which may be interrupted by oxygen atoms. ２ X represents a branched aliphatic hydrocarbon group with 6 or more carbon atoms. １ The symbols represent -O-, -COO-, -OCO-, -NH-, -S-, or -CONOC-. * represents a bond to a silicon atom.

[0049] R １ The alkylene group may be linear, branched, or cyclic. １ The number of carbon atoms is preferably 1 to 6, and more preferably 1 to 4.

[0050] R ２ The number of carbon atoms is 6 or more, preferably 8 or more, and more preferably 10 or more. ２The upper limit of the number of carbon atoms is not particularly limited, but for example, 40 or less is preferred. ２ It may or may not have unsaturated bonds such as carbon-carbon double bonds or carbon-carbon triple bonds. ２ It may or may not have a ring structure.

[0051] Examples of substructures represented by formulas (Cg-1) and (Cg-2) include the following substructures. (In the formula, R １ represents an alkylene group with 1 to 10 carbon atoms, which may be interrupted by an oxygen atom. * represents a bond to a silicon atom. (In the formula, R １ represents an alkylene group with 1 to 10 carbon atoms, which may be interrupted by an oxygen atom. * represents a bond to a silicon atom.

[0052] Polyorganosiloxane (b) is represented, for example, by the following formula (CPS-1) or the following formula (CPS-2). (In formula (CPS-1), R ３ Each of these independently represents a hydrocarbon group. １ , R ２ and X １ R in the above formula (Cg-1) or (Cg-2) is １ , R ２ and X １ This is equivalent to: m1 represents an integer greater than or equal to 0. n1 represents an integer greater than or equal to 1. In equation (CPS-2), R ３ Each of these independently represents a hydrocarbon group. １ , R ２ and X １ R in the above formula (Cg-1) or (Cg-2) is １ , R ２ and X １ This is synonymous. m² represents an integer greater than or equal to 0. n² represents an integer greater than or equal to 1.

[0053] R ３Examples of the hydrocarbon group in include alkyl groups having 1 to 8 carbon atoms. A methyl group is preferable as the alkyl group having 1 to 8 carbon atoms. That is, the polyorganosiloxane (b) is preferably polydimethylsiloxane represented by the following formula (CPS-1a) or formula (CPS-2a). (In formula (CPS-1a), R １ , R ２ , X １ , m1 and n1 have the same definitions as R １ , R ２ , X １ , m1 and n1 in the above formula (CPS-1). In formula (CPS-2a), R １ , R ２ , X １ , m2 and n2 have the same definitions as R １ , R ２ , X １ , m2 and n2 in the above formula (CPS-2).)

[0054] In the polyorganosiloxane (b) represented by formula (CPS-1), when n1 is 2 or more, -Si(R ３ )(R １ CH(OH)CH ２ X １ R ２ )-O- siloxane units represented by this formula may be adjacent to each other to form blocks, or may be arranged randomly. In the polyorganosiloxane (b) represented by formula (CPS-2), when n2 is 2 or more, the siloxane units having a cyclohexane ring may be adjacent to each other to form blocks, or may be arranged randomly. Furthermore, in the polydimethylsiloxane (b) represented by formula (CPS-1a), when n1 is 2 or more, -Si(CH ３ )(R １ CH(OH)CH ２ X １ R ２The siloxane units represented by )-O- may be arranged adjacently to form blocks, or they may be arranged randomly. In the polyorganosiloxane (b) represented by formula (CPS-2a), when n2 is 2 or more, the siloxane units having a cyclohexane ring may be arranged adjacently to form blocks, or they may be arranged randomly.

[0055] The weight-average molecular weight of polyorganosiloxane (b) is not particularly limited, but is usually 500 to 1,000,000, and is preferably 5,000 to 50,000 from the viewpoint of reproducibly achieving the effects of the present invention. Furthermore, the degree of dispersion is not particularly limited, but is usually 1.0 to 10.0, and is preferably 1.5 to 5.0, more preferably 2.0 to 3.0, from the viewpoint of reproducibly achieving suitable peeling. The viscosity of polyorganosiloxane (b) is not particularly limited, but is usually 100 to 200,000 mm². ２ The viscosity is given by / s. Note that the viscosity value of polyorganosiloxane (b) is given by kinematic viscosity, centistokes (cSt) = mm ２ It is / s. Viscosity (mPa·s) is compared to density (g / cm³). ３ It can also be obtained by dividing by ). In other words, the value can be obtained from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm²) ２ / s)=viscosity (mPa・s) / density (g / cm ３ It can be calculated using the formula:

[0056] The side-chain functional value of polyorganosiloxane (b) is preferably 0.05 to 2.00 mol / kg, and more preferably 0.10 to 1.90 mol / kg. The side-chain functional value of polyorganosiloxane (b) is the amount of side-chain functional groups obtained by functional group transformation by adding an active proton compound to the epoxy groups in an epoxy-modified polyorganosiloxane having epoxy groups in the side chains of the polyorganosiloxane. The side-chain functional value of polyorganosiloxane (b) can be measured using a nuclear magnetic resonance spectrometer (hereinafter abbreviated as NMR in this specification) by the method described in the examples.

[0057] Polyorganosiloxane (b) may be a commercially available product or a synthesized product. Examples of synthesized products include epoxy-modified polyorganosiloxane having epoxy groups in its side chains and H-X １ -R ２ (X １ and R ２ This refers to X in equations (Cg-1) and (Cg-2). １ and R ２ This is synonymous with polyorganosiloxanes obtained by addition reaction with compounds represented by ). Examples of commercially available epoxy-modified polyorganosiloxanes having epoxy groups in the side chains include KF-101, KF-102, KF-1001, KF-1002, KF-1005, X-22-343, X-22-2000, X-22-2046, X-22-4741 from Shin-Etsu Chemical Co., Ltd., and DOWSIL® SF8413 Fluid, DOWSIL® SF8411 Fluid, DOWSIL® BY16-839 Fluid from Dow Toray Industries, Inc. Examples include DOWSIL® FZ-3736 Fluid, DOWSIL® SF8421EG Fluid, DOWSIL® BY16-870 Fluid, DOWSIL® BY16-876 Fluid, DOWSIL® BY16-869 Fluid, DOWSIL® BY16-760 Fluid, and TSF4730 and YF3965 manufactured by Momentive Performance Materials Japan LLC.

[0058] The content of polyorganosiloxane (b) in the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more, relative to the nonvolatile content of the adhesive composition. The upper limit is not particularly limited, but it is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less, relative to the nonvolatile content of the adhesive composition. The nonvolatile content of the adhesive composition refers to components other than the solvent in the adhesive composition.

[0059] The adhesive composition used in the present invention may contain a release agent component other than polyorganosiloxane (b) (second release component) as a release agent component. Examples of the second release component include polydimethylsiloxane and polyorganosiloxane having a functional group other than a secondary hydroxyl group in its side chain. Examples of functional groups other than a secondary hydroxyl group include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups (primary or tertiary), carboxyl groups, epoxy groups, aryl groups, heteroaryl groups, etc.

[0060] The adhesive composition used in the present invention may contain a solvent for purposes such as adjusting viscosity. Specific examples of such solvents include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.

[0061] More specifically, examples of solvents include, but are not limited to, hexane, heptane, octane, nonane, isononane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, cyclohexanone, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. Such solvents can be used individually or in combination of two or more.

[0062] If the adhesive composition used in the present invention contains a solvent, its content is appropriately determined considering the viscosity of the desired composition, the application method used, the thickness of the film to be produced, etc., but is in the range of approximately 10 to 90% by mass of the total composition.

[0063] The viscosity of the adhesive composition used in the present invention is not particularly limited, but at 25°C it is usually 1 to 20,000 mPa·s, preferably 1 to 5,000 mPa·s, more preferably 1 to 1,000 mPa·s, and most preferably 1 to 500 mPa·s. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the type of solvent used, their ratios, the concentration of film components, etc., taking into consideration various factors such as the application method used and the desired film thickness.

[0064] An example of an adhesive composition used in the present invention can be produced by mixing component (A), a release agent component (B), and a solvent. The mixing order is not particularly limited, but examples of methods that can easily and reproducibly produce an adhesive composition include, for example, dissolving component (A) and release agent component (B) in a solvent, or dissolving a portion of component (A) and release agent component (B) in a solvent, dissolving the remainder in a solvent, and then mixing the resulting solutions. However, the method is not limited to these. When preparing the adhesive composition, heating may be applied as appropriate, as long as the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the solvent or solution used may be filtered using a filter or the like during the production of the adhesive composition or after all components have been mixed.

[0065] (Laminate) The laminate according to the present invention comprises a semiconductor substrate or an electronic device layer, a support substrate, and an adhesive layer. The laminate according to the present invention may further have a release agent layer, in which case it has a configuration comprising a semiconductor substrate or an electronic device layer, a support substrate, a release agent layer, and an adhesive layer.

[0066] The adhesive layer is provided between the semiconductor substrate or electronic device layer and the support substrate.

[0067] The laminate of the present invention is used for temporary bonding when processing a semiconductor substrate or an electronic device layer, and is suitably used for processing such as thinning of the semiconductor substrate or electronic device layer. While the semiconductor substrate is being processed such as thinning, the semiconductor substrate is supported by the support substrate. On the other hand, after the semiconductor substrate has been processed, the support substrate and the semiconductor substrate are separated. Similarly, while the electronic device layer is being processed such as thinning, the electronic device layer is supported by the support substrate. On the other hand, after the electronic device layer has been processed, the support substrate and the electronic device layer are separated. After the semiconductor substrate or electronic device layer is separated from the support substrate, any residue of the release agent layer or adhesive layer remaining on the semiconductor substrate, electronic device layer, or support substrate can be removed, for example, by a cleaning agent composition for cleaning semiconductor substrates, etc.

[0068] The following will be a detailed explanation, divided into two cases: when the laminate has a semiconductor substrate and when it has an electronic device layer. The case where the laminate has a semiconductor substrate will be described in <First Embodiment> below, and the case where the laminate has an electronic device layer will be described in <Second Embodiment> below.

[0069] <First Embodiment> A laminate having a semiconductor substrate is used for processing the semiconductor substrate. While the semiconductor substrate is being processed, the semiconductor substrate is bonded to a support substrate. After processing the semiconductor substrate, the semiconductor substrate is separated from the support substrate.

[0070] <<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 include silicon, silicon carbide, compound semiconductors, and glass substrates with organic resin. The shape of the semiconductor substrate is not particularly limited, but for example it is disc-shaped. Note that the surface shape of the disc-shaped semiconductor substrate does not need to be a perfect circle; for example the outer edge of the semiconductor substrate may have a straight section called an orientation flat or a notch. The thickness of the disc-shaped semiconductor substrate is not particularly limited and can be appropriately determined according to the intended use of the semiconductor substrate, but for example it is 500 to 1,000 μm. The diameter of the disc-shaped semiconductor substrate is not particularly limited and can be appropriately determined according to the intended use of the semiconductor substrate, but for example it is 100 to 1,000 mm.

[0071] A semiconductor substrate may have bumps. A bump is a protruding terminal. In a laminate, if 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 circuits are formed. The circuits may be single-layer or multi-layer. The shape of the circuits is not particularly limited. In a semiconductor substrate, the surface opposite to the surface with bumps (the back surface) is the surface used for processing. The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited. Examples of bumps include ball bumps, printed bumps, stud bumps, and plated bumps. Typically, the height, radius, and pitch of the bumps are appropriately determined from conditions such as a bump height of about 1 to 200 μm, a bump radius of 1 to 200 μm, and a bump pitch of 1 to 500 μm. Examples of bump materials include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bump may consist of a single component or multiple components. More specifically, examples include Sn-based alloy plating such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. The bump may also have a laminated structure including a metal layer made of at least one of these components.

[0072] An example of a semiconductor substrate is a silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 770 μm.

[0073] <<Support Substrate>> The support substrate is not particularly limited as long as it is a material that can support the semiconductor substrate when the semiconductor substrate is being processed, but examples include glass support substrates and silicon support substrates.

[0074] The shape of the support substrate is not particularly limited, but for example, it can be disc-shaped. The disc-shaped support substrate does not need to have a perfectly circular surface; for example, the outer circumference of the support substrate may have a straight section called an orientation flat, or a notch. The thickness of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and is not particularly limited, but for example, it is 500 to 1,000 μm. The diameter of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and is not particularly limited, but for example, it is 100 to 1,000 mm.

[0075] An example of a support substrate is a glass wafer with a diameter of approximately 300 mm and a thickness of approximately 700 μm.

[0076] Furthermore, when delamination in a laminate is performed by light irradiation, a substrate that is light-transmitting to the light used is used as the support substrate.

[0077] <<Adhesive Layer>> The adhesive layer is provided between the support substrate and the semiconductor substrate. The adhesive layer is in contact with the semiconductor substrate, for example. The adhesive layer may also be in contact with the support substrate, for example. The adhesive layer is an adhesive layer formed from an adhesive composition.

[0078] The thickness of the adhesive layer in the laminate of the present invention is not particularly limited, but is usually 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 caused by thick films, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and still more preferably 100 μm or less.

[0079] The method for forming an adhesive layer from the adhesive composition will be described in detail below in the section titled "<>".

[0080] <<Release Agent Layer>> The laminate may have a release agent layer. In a laminate having a release agent layer, separation of the semiconductor substrate and the support substrate is performed, for example, by light irradiation of the release agent layer. The release agent layer is formed, for example, from a release agent composition.

[0081] <<<Release Agent Composition>>> The release agent composition contains, for example, at least an organic resin or a polynuclear phenol derivative, and optionally other components. The organic resin is preferably one that can exhibit suitable release ability, and when the semiconductor substrate and the support substrate are separated by light irradiation of the release agent layer, the organic resin preferably absorbs light and undergoes a change, such as decomposition, necessary to improve the release ability.

[0082] A laminate having a release agent layer formed from a release agent composition can be peeled off without applying excessive load for peeling by, for example, irradiating the release agent layer with a laser. The release agent layer of the laminate has a reduced adhesive strength compared to before irradiation, for example, when irradiated with a laser. That is, in the laminate, for example, while a semiconductor substrate is being processed such as thinning, the semiconductor substrate is suitably supported on a laser-transmitting support substrate via an adhesive layer and a release agent layer. After processing is complete, by irradiating a laser from the support substrate side, the laser that has passed through the support substrate is absorbed by the release agent layer, causing alteration (e.g., separation) of the release agent layer at the interface between the release agent layer and the adhesive layer, at the interface between the release agent layer and the support substrate, or within the release agent layer itself. As a result, suitable peeling (separation) can be achieved without applying excessive load for peeling.

[0083] Examples of organic resins include novolac resins. Further details will be provided later.

[0084] In a preferred embodiment, the release agent composition contains at least a novolac resin and optionally other components such as a crosslinking agent, an acid generator, an acid, a surfactant, or a solvent. In another preferred embodiment, the release agent composition contains at least a polynuclear phenol derivative and a crosslinking agent, and optionally other components such as an acid generator, an acid, a surfactant, or a solvent. In yet another preferred embodiment, the release agent composition contains at least an organic resin and a branched polysilane, and optionally other components such as a crosslinking agent, an acid generator, an acid, a surfactant, or a solvent.

[0085] <<<<<Novolac resin>>>> Novolac resin is a resin obtained by condensing at least one of a phenolic compound, a carbazole compound, and an aromatic amine compound with at least one of an aldehyde compound, a ketone compound, and a divinyl compound under acid catalyst.

[0086] Examples of phenolic compounds include phenols, naphthols, antrols, and hydroxypyrenes. Examples of phenols include phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis(4-hydroxyphenyl)fluorene, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Examples of naphthols include 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 9,9-bis(6-hydroxynaphthyl)fluorene. Examples of antrols include 9-antrol. Examples of hydroxypyrenes include 1-hydroxypyrene and 2-hydroxypyrene. Examples of carbazole compounds include carbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'-bis(9H-carbazole-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, and 9-(1H-benzotriazole-1-yl) Examples include (9-ethylcarbazole-9H-carbazole, 9-acetyl-3,6-diiodocarbazole, 9-benzoylcarbazole, 9-benzoylcarbazole-6-dicarboxyaldehyde, 9-benzylcarbazole-3-carboxyaldehyde, 9-methylcarbazole, 9-phenylcarbazole, 9-vinylcarbazole, potassium carbazole, carbazole-N-carbonyl chloride, N-ethylcarbazole-3-carboxyaldehyde, and N-((9-ethylcarbazole-3-yl)methylene)-2-methyl-1-indolinylamine. Examples of aromatic amine compounds include diphenylamine and N-phenyl-1-naphthylamine. These can be used individually or in combination of two or more. They may also have substituents.For example, these may have substituents on the aromatic ring.

[0087] Examples of aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, caproaldehyde, 2-methylbutyraldehyde, hexylaldehyde, undecanealdehyde, 7-methoxy-3,7-dimethyloctylaldehyde, cyclohexanealdehyde, 3-methyl-2-butyraldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, and azipi Examples of suitable aldehydes include saturated aliphatic aldehydes such as ammonium aldehydes, unsaturated aliphatic aldehydes such as acrolein and methacrolein, heterocyclic aldehydes such as furfural and pyridine aldehyde, and aromatic aldehydes such as benzaldehyde, naphthyl aldehyde, anthryl aldehyde, phenanthryl aldehyde, salicyl aldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolyl aldehyde, (N,N-dimethylamino)benzaldehyde, and acetoxybenzaldehyde. Among these, aromatic aldehydes are preferred. Examples of suitable ketone compounds include diaryl ketone compounds such as diphenyl ketone, phenylnaphthyl ketone, dinaphthyl ketone, phenyltolyl ketone, and ditolyl ketone. Examples of divinyl compounds include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnoborna-2-ene, divinylpyrene, limonene, and 5-vinylnorbornadiene. These can be used individually or in combination of two or more.

[0088] Novolac resin is a type of novolac resin that absorbs and alters upon exposure to light irradiated from the support substrate side. This alteration is, for example, photodegradation.

[0089] Novolac resin includes, for example, at least one of the structural units represented by the following formula (C1-1), the following formula (C1-2), and the following formula (C1-3).

[0090]

[0091] In the formula, C １ This represents a group derived from an aromatic compound containing a nitrogen atom, C ２ This represents a group containing a tertiary carbon atom having at least one selected from the group consisting of secondary carbon atoms, quaternary carbon atoms, and aromatic rings in its side chain, C ３ This represents a group derived from an aliphatic polycyclic compound, C ４ This represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.

[0092] In other words, novolac resin contains, for example, one or more of the following structural units: • A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring as a side chain (Formula (C1-1)) • A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound (Formula (C1-2)) • A structural unit having a bond between a group derived from phenol, bisphenol, naphthol, biphenyl, or biphenol and a group containing a tertiary carbon atom having at least one selected from the group consisting of a quaternary carbon atom and an aromatic ring as a side chain (Formula (C1-3))

[0093] In a preferred embodiment, the novolac resin comprises either or both of the following structural units: a structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in its side chain (formula (C1-1)); and a structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound (formula (C1-2)).

[0094] C １ The group derived from an aromatic compound containing a nitrogen atom can be, for example, a group derived from carbazole, a group derived from N-phenyl-1-naphthylamine, a group derived from N-phenyl-2-naphthylamine, etc., but is not limited to these.２ A group comprising a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring as a side chain can be, for example, a group derived from 1-naphthaldehyde, a group derived from 1-pyrenecarboxyaldehyde, a group derived from 4-(trifluoromethyl)benzaldehyde, a group derived from acetaldehyde, etc., but is not limited to these. ３ The group derived from the aliphatic polycyclic compound may be, but is not limited to, a group derived from dicyclopentadiene. ４ This group is derived from phenol, bisphenol, naphthol, biphenyl, or biphenol.

[0095] In a preferred embodiment, the novolac resin includes, for example, a structural unit represented by the following formula (C1-1-1) as a structural unit represented by formula (C1-1-1).

[0096]

[0097] In formula (C1-1-1), R ９０１ and R ９０２ R represents a substituent that substitutes for the ring, and each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９０３ R represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９０４ R represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ９０５ R represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ９０４ The base and R ９０５The groups may bond with each other to form a divalent group. Examples of substituents on alkyl and alkenyl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, and heteroaryl groups. Examples of substituents on aryl and heteroaryl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, alkyl groups, and alkenyl groups. １ and h ２ Each of these independently represents an integer between 0 and 3.

[0098] The number of carbon atoms in the optionally substituted alkyl groups and optionally substituted alkenyl groups is usually 40 or less, preferably 30 or less, and more preferably 20 or less, from the viewpoint of solubility. The number of carbon atoms in the optionally substituted aryl groups and heteroaryl groups is usually 40 or less, preferably 30 or less, and more preferably 20 or less, from the viewpoint of solubility.

[0099] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0100] Specific examples of substituted alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, and 3-methyl-n-pentyl group. Examples include, but are not limited to, the following groups: 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, etc.

[0101] Specific examples of alkenyl groups that may be substituted include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, and 1-methyl-3-butenyl group. Nyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group Xenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-tert-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group Examples include, but are not limited to, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0102] Specific examples of aryl groups that may be substituted include, but are not limited to, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-nitrophenyl group, 4-cyanophenyl group, 1-naphthyl group, 2-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, and 9-phenanthryl group.

[0103] Specific examples of heteroaryl groups that may be substituted include, but are not limited to, 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, and 5-isothiazolyl groups.

[0104] The following are specific examples of structural units represented by formula (C1-1-1), but are not limited to these.

[0105]

[0106] In a preferred embodiment, the novolac resin includes, for example, a structural unit represented by formula (C1-1-2) below, as a structural unit represented by formula (C1-1).

[0107]

[0108] In formula (C1-1-2), Ar ９０１ and Ar ９０２ Each of these independently represents an aromatic ring such as a benzene ring or a naphthalene ring, and R ９０１ ~R ９０５ and h １ and h ２ This expresses the same meaning as above.

[0109] The following are specific examples of structural units represented by formula (C1-1-2), but are not limited to these.

[0110]

[0111] In a preferred embodiment, the novolac resin includes structural units represented by formula (C1-2), for example, structural units represented by the following formulas (C1-2-1) or (C1-2-2).

[0112]

[0113] In the above formula, R ９０６ ~R ９０９ is a substituent bonded to the ring, each independently representing a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. Specific examples and preferred carbon number configurations of the halogen atom, optionally substituted alkyl group, optionally substituted alkenyl group, and optionally substituted aryl group are the same as those described above. ３ ~h ６ Each of these independently represents an integer from 0 to 3, and R ９０１ ~R ９０３ and h １ and h ２ This expresses the same meaning as above.

[0114] The following are specific examples of structural units represented by formulas (C1-2-1) and (C1-2-2), but are not limited to these.

[0115]

[0116] The following are specific examples of structural units represented by formula (C1-3), but are not limited to these.

[0117]

[0118] As mentioned above, novolac resins are resins obtained by condensing at least one of a phenolic compound, a carbazole compound, and an aromatic amine compound with at least one of an aldehyde compound, a ketone compound, and a divinyl compound under an acid catalyst. In this condensation reaction, for example, an aldehyde compound or ketone compound is usually used in a ratio of 0.1 to 10 equivalents per equivalent of the benzene ring constituting the ring of the carbazole compound.

[0119] In the above condensation reaction, an acid catalyst is usually used. Examples of acid catalysts include, but are not limited to, mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid. The amount of acid catalyst is determined appropriately depending on the type of acid used and cannot be specified in general terms, but it is usually set appropriately from the range of 0.001 to 10,000 parts by mass per 100 parts by mass of the carbazole compound.

[0120] The above condensation reaction can sometimes be carried out without a solvent if either the starting compound or the acid catalyst is a liquid, but it is usually carried out with a solvent. Such solvents are not particularly limited as long as they do not inhibit the reaction, but typical examples include ether compounds such as tetrahydrofuran and cyclic ether compounds such as dioxane.

[0121] The reaction temperature is usually determined appropriately within the range of 40°C to 200°C, and the reaction time cannot be specified in general terms as it varies depending on the reaction temperature, but it is usually determined appropriately within the range of 30 minutes to 50 hours.

[0122] After the reaction is complete, if necessary, the novolac resin is purified and isolated according to standard procedures and used in the preparation of the release agent composition. A person skilled in the art can determine the production conditions for the novolac resin without undue burden based on the above description and common technical knowledge, and therefore can produce the novolac resin.

[0123] The weight-average molecular weight of organic resins such as novolac resin is usually 500 to 200,000. From the viewpoint of ensuring solubility in solvents and ensuring good mixing with branched polysilanes when formed into a film to obtain a uniform film, it is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, still more preferably 5,000 or less, and still more preferably 3,000 or less. From the viewpoint of improving the strength of the film, it is preferably 600 or more, more preferably 700 or more, even more preferably 800 or more, still more preferably 900 or more, and still more preferably 1,000 or more. In this invention, the weight-average molecular weight, number-average molecular weight, and degree of dispersion of organic resins such as novolac resins, which are polymers, can be measured, for example, using a GPC instrument (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (manufactured by Sigma-Aldrich) as the standard sample.

[0124] The organic resin contained in the above-mentioned release agent composition is preferably novolac resin. Therefore, the above-mentioned release agent composition preferably contains novolac resin alone as the organic resin. However, other polymers may be included together with the novolac resin for purposes such as adjusting the film properties. Examples of such other polymers include polyacrylic acid ester compounds, polymethacrylic acid ester compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydride, and polyacrylonitrile compounds.

[0125] The content of novolac resin in the release agent composition is not particularly limited, but it is preferably 70% by mass or more relative to the total amount of polymer contained in the release agent composition. The content of novolac resin in the release agent composition is not particularly limited, but it is preferably 50 to 100% by mass relative to the film constituent components. In this invention, film constituent components refer to components other than the solvent contained in the composition.

[0126] <<<<<Polynuclear phenol derivatives>>>>> A polynuclear phenol derivative is represented, for example, by the following formula (P).

[0127] In formula (P), Ar represents an arylene group, and the number of carbon atoms is not particularly limited, but is usually 6 to 60. From the viewpoint of preparing a release agent composition with excellent uniformity and obtaining a release agent layer with higher flatness with good reproducibility, the number of carbon atoms is preferably 30 or less, more preferably 20 or less, even more preferably 18 or less, and still more preferably 12 or less.

[0128] Specific examples of such arylene groups include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,2-anthracenediyl, 1,3-anthracenediyl, 1,4-anthracenediyl, 1,5-anthracenediyl, 1,6-anthracenediyl, 1,7-anthracenediyl, 1,8-anthracenediyl, and 2,3-anthracenediyl. Examples include, but are not limited to, groups derived by removing two hydrogen atoms from the aromatic ring of fused ring aromatic hydrocarbon compounds such as diyl, 2,6-anthracenediyl, 2,7-anthracenediyl, 2,9-anthracenediyl, 2,10-anthracenediyl, and 9,10-anthracenediyl groups; and groups derived by removing two hydrogen atoms from the aromatic ring of ring-linked ring aromatic hydrocarbon compounds such as biphenyl-4,4'-diyl group and paraterphenyl-4,4''-diyl group.

[0129] From the viewpoint of obtaining a laminate that exhibits good peelability as a release agent layer and allows for good separation of the support substrate with good reproducibility, the polynuclear phenol derivative represented by formula (P) is preferably a polynuclear phenol derivative represented by formula (P-1), more preferably a polynuclear phenol derivative represented by formula (P-1-1), and even more preferably a polynuclear phenol derivative represented by formula (P1).

[0130]

[0131] The content of the polynuclear phenol derivative in the release agent composition is not particularly limited, but it is preferably 50 to 100% by mass relative to the film components.

[0132] << Although the reason is not entirely clear, depending on the type of end groups (end substituents (atoms)) of the polysilane, the polysilane can react with organic resins and crosslink. Furthermore, since branched polysilanes have more end groups (end substituents (atoms)) than linear polysilanes, it is thought that branched polysilanes have more crosslinking points than linear polysilanes. It is presumed that moderate and suitable curing via these more crosslinking points in branched polysilanes makes it possible to achieve both the property of being unsuitably removed by organic solvents, acids, and chemicals used in the manufacture of semiconductor devices (alkaline developers, hydrogen peroxide, etc.) and the property of being suitablely removed by cleaning agent compositions.

[0133] The branched polysilane preferably contains a structural unit represented by formula (B).

[0134]

[0135] In formula (B), R Ｂ The group represents a hydrogen atom, a hydroxyl group, a silyl group, or an organic group. Specific examples of such organic groups include hydrocarbon groups (optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted aryl groups, optionally substituted aralkyl groups), and ether groups corresponding to these hydrocarbon groups (optionally substituted alkoxy groups, optionally substituted aryloxy groups, optionally substituted aralkyloxy groups, etc.). However, the organic group in question is usually a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, or aralkyl group. Furthermore, hydrogen atoms, hydroxyl groups, alkoxy groups, silyl groups, etc., are often substituted at their terminal ends.

[0136] The substituted alkyl groups may be linear, branched, or cyclic. Specific examples of substituted linear or branched alkyl groups include: methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, and 4-methyl-n-pentyl group. Examples include, but are not limited to, tyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group. The number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6.Specific examples of cyclic alkyl groups, whether substituted or not, include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, and 3,3-dimethyl-cyclobutyl group. Examples of cycloalkyl groups include methyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, and other cycloalkyl groups, as well as bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group, but are not limited to these. The number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0137] The alkenyl group may be linear, branched, or cyclic. Specific examples of linear or branched alkenyl groups that may be substituted include, but are not limited to, vinyl, allyl, butyl, and pentenyl groups. The number of carbon atoms is typically 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Specific examples of cyclic alkenyl groups that may be substituted include, but are not limited to, cyclopentenyl and cyclohexenyl. The number of carbon atoms is typically 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0138] Specific examples of substituted aryl groups include, but are not limited to, phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 3,5-dimethylphenyl, 1-naphthyl, and 2-naphthyl groups. The number of carbon atoms is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 12.

[0139] Specific examples of substituted aralkyl groups include, but are not limited to, benzyl, phenethyl, and phenylpropyl groups. Preferably, a substituted aralkyl group is a group in which one hydrogen atom of an alkyl group having 1 to 4 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms.

[0140] The substituted alkoxy group may have a linear, branched, or cyclic alkyl moiety. Specific examples of substituted linear or branched alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, and pentyloxy groups, and their carbon atoms are typically 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Specific examples of substituted cyclic alkoxy groups include, but are not limited to, cyclopentyloxy and cyclohexyloxy, and their carbon atoms are typically 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0141] Specific examples of substituted aryloxy groups include, but are not limited to, phenoxy, 1-naphthyloxy, and 2-naphthyloxy. The number of carbon atoms is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 10.

[0142] Specific examples of substituted aralkyloxy groups include, but are not limited to, benzyloxy, phenethyloxy, and phenylpropyloxy. Preferably, a substituted aralkyloxy group is a group in which one hydrogen atom of an alkyloxy group having 1 to 4 carbon atoms is replaced by an aryl group having 6 to 20 carbon atoms.

[0143] Specific examples of silyl groups include silyl groups, disilanyl groups, and trisilanyl groups, but are not limited to these. The silicon number is usually 1 to 10, preferably 1 to 6.

[0144] R Ｂ However, in the case of the above-mentioned organic group or silyl group, at least one of its hydrogen atoms may be substituted with a substituent. Specific examples of such substituents include hydroxyl groups, alkyl groups, aryl groups, and alkoxy groups.

[0145] From the viewpoint of suppressing unintended peeling when the laminate is brought into contact with an organic solvent, an acid, or a chemical solution used in the manufacture of semiconductor devices (such as an alkaline developer or hydrogen peroxide), and from the viewpoint of suitably removing the residue of the release agent layer on the substrate when the semiconductor substrate and support substrate of the laminate are separated and then washed with a cleaning agent composition, R Ｂ The group is preferably an alkyl group or an aryl group, more preferably an aryl group, even more preferably a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and even more preferably a phenyl group.

[0146] The branched-chain polysilane may contain structural units represented by formula (B), as well as structural units represented by formula (S) and formula (N). However, from the viewpoint of suppressing unintended peeling when the laminate is brought into contact with an organic solvent, an acid, or a chemical solution used in the manufacture of semiconductor devices (such as an alkaline developer or hydrogen peroxide), and from the viewpoint of suitably removing residue of the release agent layer on the substrate when the semiconductor substrate and support substrate of the laminate are separated and then washed with a cleaning agent composition, the content of structural units represented by formula (B) in the branched-chain polysilane is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more of the total structural units.

[0147] (R Ｓ１ and R Ｓ２ R Ｂ (This expresses the same meaning.)

[0148] The terminal groups (terminal substituents (atoms)) of branched polysilanes are usually hydrogen atoms, hydroxyl groups, halogen atoms (such as chlorine atoms), alkyl groups, aryl groups, alkoxy groups, silyl groups, etc. Among these, hydroxyl groups, methyl groups, and phenyl groups are most common, with methyl groups being preferred, and the terminal group may be a trimethylsilyl group.

[0149] In one embodiment, the average degree of polymerization of the branched polysilane is typically 2 to 100, preferably 3 to 80, more preferably 5 to 50, and even more preferably 10 to 30, in terms of silicon atoms (i.e., the average number of silicon atoms per molecule). In another embodiment, the upper limit of the weight-average molecular weight of the branched polysilane is typically 30,000, preferably 20,000, more preferably 10,000, even more preferably 5,000, still more preferably 2,000, and even more preferably 1,500, and the lower limit is typically 50, preferably 100, more preferably 150, even more preferably 200, even more preferably 300, and even more preferably 500. The average degree of polymerization and weight-average molecular weight of branched polysilanes can be measured, for example, using a GPC instrument (EcoSEC, HLC-8220GPC manufactured by Tosoh Corporation) and a GPC column (Shodex KF-803L, KF-802, and KF-801 manufactured by Showa Denko K.K., used in this order), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate of 1.00 mL / min, and polystyrene (manufactured by Sigma-Aldrich) as the standard sample. If the degree of polymerization and weight-average molecular weight of the branched polysilane used are too low, heating during the formation of the release agent layer or during processing of the laminate containing the obtained release agent layer may cause the branched polysilane to vaporize or lead to defects due to insufficient film strength. If the degree of polymerization and molecular weight of the branched polysilane used are too high, depending on the type of solvent used to prepare the release agent composition, sufficient solubility may not be ensured, leading to precipitation in the composition or insufficient mixing with the resin, which may prevent the reproducibility of a highly uniform film. Therefore, from the viewpoint of obtaining a laminate containing a release agent layer that contributes to the suitable manufacture of semiconductor devices with even greater reproducibility, it is desirable that the degree of polymerization and weight-average molecular weight of the branched polysilane meet the above-mentioned range.

[0150] The 5% weight loss temperature of branched polysilane is typically 300°C or higher, preferably 350°C or higher, more preferably 365°C or higher, even more preferably 380°C or higher, even more preferably 395°C or higher, and even more preferably 400°C or higher, from the viewpoint of obtaining a release agent layer with excellent heat resistance and good reproducibility. The 5% weight loss temperature of branched polysilane can be measured, for example, by using a NETZSCH 2010SR under air conditions and raising the temperature from room temperature (25°C) to 400°C at a rate of 10°C / min.

[0151] When the semiconductor substrate and support substrate of a laminate are separated and then each substrate is washed with a cleaning agent composition, from the viewpoint of suitably removing residue from the release agent layer on the substrate and from the viewpoint of preparing a release agent composition with excellent uniformity and reproducibility, it is preferable that the branched-chain polysilane dissolves in any of the following: ether compounds such as tetrahydrofuran, aromatic compounds such as toluene, glycol ether ester compounds such as propylene glycol monomethyl ether acetate, ketone compounds such as cyclohexanone and methyl ethyl ketone, and glycol ether compounds such as propylene glycol monomethyl ether. In this case, dissolution means that when dissolution is attempted using a shaker at room temperature (25°C) to obtain a 10% by mass solution, it can be visually confirmed that dissolution has occurred within one hour.

[0152] The branched polysilane may be in either a solid or liquid state at room temperature.

[0153] Branched-chain polysilanes can be manufactured by referring to known methods described in, for example, Japanese Patent Publication No. 2011-208054, Japanese Patent Publication No. 2007-106894, Japanese Patent Publication No. 2007-145879, WO2005 / 113648, etc., or they can be obtained as commercially available products. Specific examples of commercially available products include, but are not limited to, the silicon material polysilanes OGSOL SI-20-10 and SI-20-14 manufactured by Osaka Gas Chemical Co., Ltd.

[0154] Suitable examples of branched polysilanes include, but are not limited to, the following. (Ph represents the phenyl group, R ＥEach of these independently represents a terminal substituent, an atom or a group, and n ｂ (This indicates the number of repeating units.)

[0155] The branched polysilane content in the above-mentioned stripping agent composition is usually 10 to 90% by mass relative to the film components. However, from the viewpoint of reproducibly achieving a film that cannot be suitably removed by organic solvents, acids, or chemicals used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.) but can be suitably removed by the cleaning agent composition, the content is preferably 15 to 80% by mass, more preferably 20 to 70% by mass, even more preferably 25 to 60% by mass, and still more preferably 30 to 50% by mass.

[0156] <<<<<Crosslinking Agent>>>> The release agent composition may contain a crosslinking agent. The crosslinking agent may undergo a crosslinking reaction by self-condensation, but if crosslinkable substituents are present in the novolac resin, it can undergo a crosslinking reaction with those crosslinkable substituents.

[0157] Specific examples of crosslinking agents are not limited to those mentioned above, but typically include phenolic crosslinking agents, melamine crosslinking agents, urea crosslinking agents, thiourea crosslinking agents, etc., which have crosslinking groups such as hydroxymethyl groups, methoxymethyl groups, butoxymethyl groups, and other alkoxymethyl groups in their molecules. These may be low molecular weight compounds or high molecular weight compounds. The crosslinking agent contained in the release agent composition usually has two or more crosslinking groups, but from the viewpoint of achieving more suitable curing with good reproducibility, the number of crosslinking groups contained in the crosslinking agent compound is preferably 2 to 10, more preferably 2 to 6. From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the release agent composition preferably has an aromatic ring (e.g., a benzene ring, a naphthalene ring) in its molecule, and typical examples of such crosslinking agents, though not limited to those mentioned above, include phenolic crosslinking agents.

[0158] A phenolic crosslinking agent having a crosslinking group is a compound having a crosslinking group bonded to an aromatic ring, and having at least one of a phenolic hydroxyl group and an alkoxy group derived from a phenolic hydroxyl group. Examples of such alkoxy groups derived from a phenolic hydroxyl group include, but are not limited to, methoxy groups and butoxy groups. The aromatic ring to which the crosslinking group is bonded and the aromatic ring to which the phenolic hydroxyl group and / or the alkoxy group derived from a phenolic hydroxyl group are bonded are not limited to non-fused aromatic rings such as benzene rings, but may also be fused aromatic rings such as naphthalene rings and anthracene rings. When multiple aromatic rings exist within the molecule of a phenolic crosslinking agent, the crosslinking group and the phenolic hydroxyl group and the alkoxy group derived from a phenolic hydroxyl group may be bonded to the same aromatic ring or to different aromatic rings within the molecule. The aromatic ring to which the crosslinking group, the phenolic hydroxyl group and the alkoxy group derived from a phenolic hydroxyl group are bonded may be further substituted with alkyl groups such as methyl groups, ethyl groups and butyl groups, hydrocarbon groups such as aryl groups such as phenyl groups, halogen atoms such as fluorine atoms, etc.

[0159] For example, specific examples of phenolic crosslinking agents having crosslinking groups include compounds represented by any of the formulas (L1) to (L4).

[0160]

[0161] In each formula, each R' independently represents a fluorine atom, an aryl group, or an alkyl group, and each R'' independently represents a hydrogen atom or an alkyl group, L １ and L ２ Each of these independently represents a single bond, a methylene group, or a propane-2,2-diyl group, L ３t11, t12 and t13 are integers satisfying 2≦t11≦5, 1≦t12≦4, 0≦t23≦2, and t21+t22+t23≦5, t24, t25 and t26 are integers satisfying 2≦t24≦4, 1≦t25≦3, 0≦t26≦2, and t24+t25+t26≦5, and t27, t28 and t29 are integers satisfying 0≦t27≦4, 0≦t28≦ 4 is an integer satisfying 0 ≤ t29 ≤ 4 and t27 + t28 + t29 ≤ 4, t31, t32 and t33 are integers satisfying 2 ≤ t31 ≤ 4, 1 ≤ t32 ≤ 3, 0 ≤ t33 ≤ 2 and t31 + t32 + t33 ≤ 5, t41, t42 and t43 are integers satisfying 2 ≤ t41 ≤ 3, 1 ≤ t42 ≤ 2, 0 ≤ t43 ≤ 1 and t41 + t42 + t43 ≤ 4, q1 is 2 or 3, q2 represents the number of repetitions and is an integer of 0 or more, specific examples of aryl groups and alkyl groups are the same as the specific examples below, but phenyl groups are preferred as aryl groups and methyl groups and t-butyl groups are preferred as alkyl groups.

[0162] The following are specific examples of compounds represented by formulas (L1) to (L4), but are not limited to these. These compounds may be synthesized by known methods, and can also be obtained as products from companies such as Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd.

[0163]

[0164]

[0165]

[0166]

[0167] A melamine-based crosslinking agent having a crosslinking group is a melamine derivative, a 2,4-diamino-1,3,5-triazine derivative, or a 2-amino-1,3,5-triazine derivative in which at least one hydrogen atom of the amino group bonded to the triazine ring is substituted with a crosslinking group, and the triazine ring may further have substituents such as aryl groups such as phenyl groups. Specific examples of melamine-based crosslinking agents having crosslinking groups include, but are not limited to, mono, bis, tris, tetrakiss, pentakiss, or hexakisalkoxymethyl melamine such as N,N,N',N',N'',N''-hexakis(butoxymethyl)melamine, mono, bis, tris, or tetrakisalkoxymethyl benzoguanamine such as N,N,N',N'-tetrakis(methoxymethyl)benzoguanamine, and N,N,N',N'-tetrakis(butoxymethyl)benzoguanamine.

[0168] A urea-based crosslinking agent having a crosslinking group is a derivative of a urea bond-containing compound having a structure in which at least one hydrogen atom of the NH group constituting the urea bond is substituted with a crosslinking group. Specific examples of urea-based crosslinking agents having a crosslinking group include, but are not limited to, mono, bis, tris, or tetrakisalkoxymethyl glycoluryls such as 1,3,4,6-tetrakis(methoxymethyl) glycoluryl and 1,3,4,6-tetrakis(butoxymethyl) glycoluryl, and mono, bis, tris, or tetrakisalkoxymethylureas such as 1,3-bis(methoxymethyl)urea and 1,1,3,3-tetrakismethoxymethylurea.

[0169] A thiourea-based crosslinking agent having a crosslinking group is a derivative of a thiourea bond-containing compound having a structure in which at least one hydrogen atom of the NH group constituting the thiourea bond is substituted with a crosslinking group. Specific examples of thiourea-based crosslinking agents having a crosslinking group include, but are not limited to, mono, bis, tris, or tetrakisalkoxymethylthioureas such as 1,3-bis(methoxymethyl)thiourea and 1,1,3,3-tetrakismethoxymethylthiourea.

[0170] The amount of crosslinking agent contained in the release agent composition cannot be specified in general terms as it varies depending on the coating method adopted, the desired film thickness, etc. However, it is usually 0.01 to 50% by mass relative to the organic resin or polynuclear phenol derivative. From the viewpoint of achieving suitable curing and obtaining a laminate in which the semiconductor substrate and the support substrate can be separated well with good reproducibility, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, still more preferably 5% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and still more preferably 30% by mass or less.

[0171] <<

[0172] Examples of acid generators include thermal acid generators and photoacid generators. Thermal acid generators are not particularly limited as long as they generate acid with heat, and specific examples include, but are not limited to, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE® CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic alkyl sulfonates.

[0173] Examples of photoacid generators include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0174] Specific examples of onium salt compounds include, but are not limited to, iodonium salt compounds such as diphenyliodonium hexafluorophosphonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium nitrate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0175] Specific examples of sulfonimide compounds include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0176] Specific examples of disulfonyl diazomethane compounds include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0177] Specific examples of acids include, but are not limited to, aryl sulfonic acids and pyridinium salts such as p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid (pyridinium p-toluenesulfonate), pyridinium trifluoromethanesulfonate, pyridinium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, and 1-naphthalenesulfonic acid, as well as their salts; aryl carboxylic acids and their salts such as salicylic acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid; linear or cyclic alkyl sulfonic acids and their salts such as trifluoromethanesulfonic acid and camphorsulfonic acid; and linear or cyclic alkyl carboxylic acids and their salts such as citric acid.

[0178] The amounts of acid generator and acid contained in the release agent composition cannot be specified in general terms, as they vary depending on the type of crosslinking agent used, the heating temperature when forming the film, etc., but are usually 0.01 to 5% by mass relative to the film components.

[0179] <<<<<Surfactants>>>>> The stripping agent composition may contain surfactants for purposes such as adjusting the liquid properties of the composition itself and the film properties of the resulting film, or for reproducibly preparing a highly uniform stripping agent composition. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as Eftop EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafac F171, F173, R-30, R-30N (manufactured by DIC Corporation, trade name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). Surfactants can be used individually or in combination of two or more. The amount of surfactant is usually 2% by mass or less relative to the film components of the stripping agent composition.

[0180] <<<<Solvent>>>> The release agent composition preferably contains a solvent. As such a solvent, for example, a highly polar solvent that can well dissolve the film components such as the aforementioned organic resins, polynuclear phenol derivatives, branched polysilanes, and crosslinking agents can be used, and if necessary, a low-polarity solvent may be used for the purpose of adjusting viscosity, surface tension, etc. In this invention, a low-polarity solvent is defined as one with a relative permittivity of less than 7 at a frequency of 100 kHz, and a highly polar solvent is defined as one with a relative permittivity of 7 or more at a frequency of 100 kHz. The solvent can be used alone or in combination of two or more types.

[0181] Examples of highly polar solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; cyano solvents such as acetonitrile and 3-methoxypropionitrile; polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and sulfoxide solvents such as dimethyl sulfoxide.

[0182] Examples of low-polarity solvents include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon solvents such as alkylbenzenes such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene; aliphatic alcohol solvents such as 1-octanol, 1-nonanol, and 1-decanol; ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; and ester-based solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0183] The solvent content is determined appropriately considering the viscosity of the desired composition, the coating method used, the thickness of the film to be produced, etc., but is 99% by mass or less of the total composition, preferably 70 to 99% by mass of the total composition, that is, the amount of film components in that case is 1 to 30% by mass of the total composition.

[0184] The viscosity and surface tension of the release agent composition are appropriately adjusted by changing the type of solvent used, their ratios, and the concentration of film components, taking into consideration various factors such as the application method used and the desired film thickness.

[0185] In one aspect of the present invention, the release agent composition contains a glycol-based solvent, from the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with good storage stability with good reproducibility, and a composition that provides a highly uniform film with good reproducibility. The term "glycol-based solvent" as used herein refers to a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0186] An example of a preferred glycol-based solvent is represented by formula (G).

[0187]

[0188] In formula (G), R Ｇ１ Each of these independently represents a linear or branched alkylene group having 2 to 4 carbon atoms, R Ｇ２ and R Ｇ３ Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkylacyl group in which the alkyl portion is a linear or branched alkyl group having 1 to 8 carbon atoms, n ｇ is an integer between 1 and 6.

[0189] Specific examples of linear or branched alkylene groups having 2 to 4 carbon atoms include, but are not limited to, ethylene groups, trimethylene groups, 1-methylethylene groups, tetramethylene groups, 2-methylpropane-1,3-diyl groups, pentamethylene groups, and hexamethylene groups. In particular, linear or branched alkylene groups having 2 to 3 carbon atoms are preferred from the viewpoint of obtaining highly uniform compositions with good reproducibility, compositions with good storage stability with good reproducibility, and compositions that provide highly uniform films with good reproducibility, and linear or branched alkylene groups having 3 carbon atoms are more preferred.

[0190] Specific examples of linear or branched alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl Examples of suitable groups include, but are not limited to, ru-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group. In particular, methyl groups and ethyl groups are preferred, and methyl groups are more preferred, from the viewpoint of obtaining a highly homogeneous composition with good reproducibility, a composition with high storage stability with good reproducibility, and a composition that gives a highly homogeneous film with good reproducibility.

[0191] Specific examples of the alkyl acyl group in which the alkyl portion is a linear or branched alkyl group having 1 to 8 carbon atoms include the same examples as described above. Among these, from the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with good storage stability with good reproducibility, and a composition that gives a highly uniform film with good reproducibility, methyl carbonyl group and ethyl carbonyl group are preferred, and the methyl carbonyl group is more preferred.

[0192] n ｇ From the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with high storage stability with good reproducibility, and a composition that gives a highly uniform film with good reproducibility, the ratio is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and most preferably 1.

[0193] From the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with high storage stability with good reproducibility, and a composition that gives a highly uniform film with good reproducibility, in formula (G), preferably, R Ｇ２ and R Ｇ３ At least one of them is a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably R Ｇ２ and R Ｇ３ One of the components is a linear or branched alkyl group having 1 to 8 carbon atoms, and the other is an alkylacyl group in which the hydrogen atom or the alkyl portion is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0194] From the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with good storage stability with good reproducibility, and a composition that provides a highly uniform film with good reproducibility, the content of the glycol-based solvent is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to the solvent contained in the release agent composition. From the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with good storage stability with good reproducibility, and a composition that provides a highly uniform film with good reproducibility, the film components in the release agent composition are uniformly dispersed or dissolved in the solvent, preferably dissolved.

[0195] A release agent composition can be produced, for example, by mixing an organic resin or a polynuclear phenol derivative with a solvent and, if necessary, a crosslinking agent. The mixing order is not particularly limited, but examples of methods that can easily and reproducibly produce a release agent composition include, but are not limited to, a method in which the organic resin or polynuclear phenol derivative and the crosslinking agent are dissolved in the solvent at once, or a method in which a portion of the organic resin or polynuclear phenol derivative and the crosslinking agent are dissolved in the solvent, the remainder is dissolved separately in the solvent, and the resulting solutions are mixed. Furthermore, when preparing the release agent composition, heating may be appropriately applied, as long as the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the solvent or solution used may be filtered using a filter or the like during the production of the release agent composition or after all components have been mixed.

[0196] The thickness of the release agent layer is not particularly limited, but is usually 5 nm to 100 μm, 10 nm to 10 μm in one embodiment, 50 nm to 1 μm in another embodiment, and 100 nm to 700 nm in yet another embodiment.

[0197] There are no particular limitations on the method for forming a release agent layer from a release agent composition, but one example is a method of forming a release agent layer by coating the release agent composition. There are no particular limitations on the method of coating the release agent composition, but it is usually a spin coating method. The heating temperature of the coated release agent composition cannot be specified in general terms as it varies depending on the type and amount of release agent components contained in the release agent composition, the desired thickness of the release agent layer, etc. However, from the viewpoint of reproducibly achieving a suitable release agent layer, it is 80°C to 300°C, and the heating time is usually appropriately determined in the range of 10 seconds to 10 minutes depending on the heating temperature. The heating temperature is preferably 100°C to 280°C, and more preferably 150°C to 250°C. The heating time is preferably 30 seconds to 8 minutes, and more preferably 1 minute to 5 minutes. Heating can be carried out using a hot plate, oven, etc.

[0198] The following describes an example of the configuration of the laminate according to the first embodiment, using the figures. Figure 1 shows a schematic cross-sectional view of an example of the laminate according to the first embodiment. The laminate in Figure 1 has a semiconductor substrate 1, an adhesive layer 2, and a support substrate 4 in this order. That is, the adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1 and the support substrate 4.

[0199] The following describes another example of the configuration of the laminate according to the first embodiment, using the figures. Figure 2 shows a schematic cross-sectional view of another example of the laminate according to the first embodiment. The laminate in Figure 2 has a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4 in this order. The adhesive layer 2 and the release agent layer 3 are provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1. The release agent layer 3 is in contact with the adhesive layer 2 and the support substrate 4.

[0200] <<Example of Manufacturing Method for a Laminate in the First Embodiment>> The manufacturing method for a laminate will be described below, using the laminate shown in Figure 1 as an example from the laminates in the first embodiment. An example of the laminate of the present invention can be manufactured by a method including the following first and second steps. First step: A step of applying an adhesive composition onto a semiconductor substrate to form an adhesive coating layer. Second step: A step of heating the adhesive coating layer to form an adhesive layer.

[0201] The method of applying the adhesive composition is not particularly limited, but is usually done by spin coating. Alternatively, a method can be adopted in which a coating film is formed separately by spin coating or the like to form a sheet-like coating film, and this sheet-like coating film is then applied as the adhesive coating layer. The heating temperature of the applied adhesive composition cannot be specified in general terms, as it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is included, the boiling point of the solvent used, and the desired thickness of the adhesive layer, but is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes. If the adhesive composition contains a solvent, the applied adhesive composition is usually heated. The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it if necessary is usually about 5 to 500 μm, and is ultimately determined appropriately so that it falls within the aforementioned range of adhesive layer thickness.

[0202] In this invention, the laminate can be obtained by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing heat treatment, vacuum treatment, or both, and then performing post-heat treatment. The choice of which treatment conditions to adopt—heat treatment, vacuum treatment, or a combination of both—is determined appropriately after considering various factors such as the type of adhesive composition, film thickness, and desired adhesive strength.

[0203] The heat treatment is usually determined appropriately from a range of 20 to 160°C, from the viewpoint of removing solvents from the composition. In particular, from the viewpoint of suppressing or avoiding excessive hardening or unwanted deterioration of the adhesive components, it is preferably 150°C or lower, more preferably 130°C or lower. The heating time is appropriately determined depending on the heating temperature and the type of adhesive, but from the viewpoint of reliably achieving suitable adhesion, it is usually 30 seconds or more, preferably 1 minute or more, but from the viewpoint of suppressing deterioration of the adhesive layer and other components, it is usually 10 minutes or less, preferably 5 minutes or less.

[0204] The vacuum treatment can be performed by exposing the adhesive coating layers that are in contact with each other to a pressure of 10 to 10,000 Pa. The vacuum treatment time is usually 1 to 30 minutes.

[0205] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate and the layers between them, and can firmly adhere them together, but it is usually in the range of 10 to 50,000 N.

[0206] The post-heating temperature is preferably 120°C or higher from the viewpoint of achieving a sufficient curing rate, and preferably 260°C or lower from the viewpoint of preventing deterioration of the substrate and each layer. The post-heating time is usually 1 minute or more, preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of the substrate and layers constituting the laminate, and usually 180 minutes or less, 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, oven, etc. When post-heating using a hot plate, heating may be done with either the semiconductor substrate or the support substrate of the laminate facing downwards, but it is preferable to post-heat with the semiconductor substrate facing downwards from the viewpoint of achieving suitable peeling with good reproducibility. One of the purposes of the post-heating treatment is to realize an adhesive layer that is a more suitable self-supporting film, and in particular to suitably achieve curing by hydrosilylation reaction.

[0207] Figures 3A to 3C illustrate one method of manufacturing a laminate. First, a laminate is prepared in which an adhesive coating layer 2a is formed on a semiconductor substrate 1 (Figure 3A). This laminate can be obtained, for example, by applying an adhesive composition to the semiconductor substrate 1 and heating it. Next, the laminate shown in Figure 3A and the support substrate 4 are bonded together so that the adhesive coating layer 2a and the support substrate 4 are in contact. Then, after applying a load in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure, a heating device (not shown; hot plate) is placed on the side of the semiconductor substrate 1 opposite to the side where the adhesive coating layer 2a is in contact, and the adhesive coating layer 2a is heated and cured by the heating device to convert it into an adhesive layer 2 (Figure 3B). The laminate shown in Figure 1 is obtained by the process shown in Figures 3A to 3B.

[0208] <Second Embodiment> A laminate having an electronic device layer is used for processing the electronic device layer. While the electronic device layer is being processed, the electronic device layer is bonded to a support substrate. After processing the electronic device layer, the electronic device layer is separated from the support substrate.

[0209] <<Electronic Device Layer>> The electronic device layer refers to a layer having an electronic device, and in the present invention, it refers to a layer in which a plurality of semiconductor chip substrates are embedded in a sealing resin, that is, a layer consisting of a plurality of semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates. Here, "electronic device" means a component that constitutes at least a part of an electronic component. The electronic device is not particularly limited and may have various mechanical structures or circuits formed on the surface of a semiconductor substrate. Preferably, the electronic device is a composite of a component made of metal or semiconductor and a resin that seals or insulates the component. The electronic device may have a redistribution layer and / or semiconductor elements or other elements that are sealed or insulated with a sealing material or insulating material, and may have a single-layer or multi-layer structure.

[0210] <<Support Substrate>> An example of a support substrate is the same as the one described in the <<Support Substrate>> section of the <<First Embodiment>> above.

[0211] <<Release Agent Layer>> The release agent layer is formed, for example, using the release agent composition described above. A detailed description of the release agent layer is as described in the <<Release Agent Layer>> section of the <<First Embodiment>> above.

[0212] <<Adhesive Layer>> The adhesive layer is formed using the adhesive composition described above. A detailed description of the adhesive layer is as described in the <<Adhesive Layer>> section of the <<First Embodiment>> above.

[0213] The following describes an example of the configuration of the laminate according to the second embodiment, using the figures. The laminate in Figure 4 has a support substrate 24, an adhesive layer 22, and an electronic device layer 26 in that order. The electronic device layer 26 has a plurality of semiconductor chip substrates 21 and a sealing resin 25, which is a sealing material, disposed between the semiconductor chip substrates 21. The adhesive layer 22 is provided between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device layer 26 and the support substrate 24.

[0214] Figure 5 shows a schematic cross-sectional view of another example of the laminate of the second embodiment. The laminate of Figure 5 has a support substrate 24, a release agent layer 23, an adhesive layer 22, and an electronic device layer 26 in this order. The electronic device layer 26 has a plurality of semiconductor chip substrates 21 and a sealing resin 25 which is a sealing material disposed between the semiconductor chip substrates 21. The adhesive layer 22 and the release agent layer 23 are provided between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device layer 26. The release agent layer 23 is in contact with the adhesive layer 22 and the support substrate 24.

[0215] <<Example of a manufacturing method for a laminate in the second embodiment>> The manufacturing method for a laminate will be described below using the laminate shown in Figure 4 as an example from the laminates in the second embodiment. The laminate of the present invention can be manufactured by a method including the following first to fourth steps. First step: Apply an adhesive composition to the surface of the support substrate to form an adhesive coating layer (and if necessary, further heat to form an adhesive layer) Second step: Place a semiconductor chip substrate on the adhesive coating layer or adhesive layer and bond the semiconductor chip substrate to the adhesive coating layer or adhesive layer while performing at least one of a heat treatment and a vacuum treatment Third step: Harden the adhesive coating layer by post-heat treatment to form an adhesive layer Fourth step: Seal the semiconductor chip substrate fixed on the adhesive layer using a sealing resin A more detailed explanation of the second step is, for example, the step of the embodiment in (i) below. (i) A semiconductor chip substrate is placed on the adhesive coating layer or adhesive layer, and while performing at least one of a heat treatment and a reduced pressure treatment, a load is applied in the thickness direction to the semiconductor chip substrate and the support substrate to bring them into close contact, thereby bonding the semiconductor chip substrate to the adhesive coating layer or adhesive layer.

[0216] Furthermore, the third step may be performed after the semiconductor chip substrate has been bonded to the adhesive coating layer in the second step, or it may be performed in conjunction with the second step. For example, the semiconductor chip substrate may be placed on the adhesive coating layer, and while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, the adhesive coating layer may be heated and cured to simultaneously achieve adhesion between the semiconductor chip substrate and the adhesive coating layer and curing from the adhesive coating layer to the adhesive layer, thereby bonding the adhesive layer to the semiconductor chip substrate. Alternatively, the third step may be performed before the second step, in which case the semiconductor chip substrate may be placed on the adhesive layer, and while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, the adhesive layer and the semiconductor chip substrate may be bonded together.

[0217] The application method, the heating temperature of the applied adhesive composition, the heating means, etc., are as described in the section "<<Example of manufacturing method of laminate in the first embodiment>>" in the first embodiment above.

[0218] The method for manufacturing the laminate according to the second embodiment will be described in more detail below with reference to the figures. In this manufacturing method, the laminate shown in Figure 4 is manufactured. As shown in Figure 6A, an adhesive coating layer 22' made of an adhesive composition is formed on the support substrate 24. At this time, the adhesive coating layer 22' may be heated to form the adhesive layer 22. Next, as shown in Figure 6B, a semiconductor chip substrate 21 is placed on the adhesive layer 22 or adhesive coating layer 22', and while performing at least one of a heat treatment and a vacuum treatment, a load in the thickness direction is applied to the semiconductor chip substrate 21 and the support substrate 24 to bring them into close contact, thereby bonding the semiconductor chip substrate 21 to the adhesive layer 22 or adhesive coating layer 22'. If the semiconductor chip substrate 21 is bonded to the adhesive coating layer 22', the adhesive coating layer 22' is cured by post-heat treatment to become an adhesive layer 22, and the semiconductor chip substrate 21 is fixed to the adhesive layer 22. Next, as shown in Figure 6C, the semiconductor chip substrate 21 fixed on the adhesive layer 22 is sealed using a sealing resin 25. In Figure 6C, multiple semiconductor chip substrates 21, temporarily bonded to a support substrate 24 via an adhesive layer 22, are sealed with a sealing resin 25. An electronic device layer 26 is formed on the adhesive layer 22, having the semiconductor chip substrates 21 and the sealing resin 25 placed between them. Thus, the electronic device layer 26 is a substrate layer in which multiple semiconductor chip substrates are embedded in the sealing resin.

[0219] <<<Sealing Process>>> The semiconductor chip substrate 21 is sealed using a sealing material. The sealing material used to seal the semiconductor chip substrate 21 is a material that can insulate or seal a component made of metal or semiconductor. In the present invention, for example, a resin composition (sealing resin) is used as the sealing material. The type of sealing resin is not particularly limited as long as it can seal and / or insulate metal or semiconductor, but for example, epoxy resin or silicone resin is preferred. In addition to the resin component, the sealing material may also contain other components such as fillers. Examples of fillers include spherical silica particles. In the sealing process, for example, a sealing resin heated to 130 to 170°C is supplied onto the adhesive layer 22 so as to cover the semiconductor chip substrate 21 while maintaining a high viscosity state, and is compression molded to form a layer made of sealing resin 25 on the adhesive layer 22. At that time, the temperature condition is, for example, 130 to 170°C. The pressure applied to the semiconductor chip substrate 21 is, for example, 50 to 500 N / cm ２ That is the case.

[0220] (Method for manufacturing a processed semiconductor substrate or a processed electronic device layer) By using the laminate according to the present invention, a method for manufacturing a processed semiconductor substrate or a method for manufacturing a processed electronic device layer can be provided. The "method for manufacturing a processed semiconductor substrate" uses the laminate described in the <First Embodiment> section above (Laminate). The "method for manufacturing a processed electronic device layer" uses the laminate described in the <Second Embodiment> section above (Laminate). The "method for manufacturing a processed semiconductor substrate" will be explained in the <Third Embodiment> below, and the "method for manufacturing a processed electronic device layer" will be explained in the <Fourth Embodiment> below.

[0221] <Third Embodiment> The method for manufacturing a processed semiconductor substrate of the present invention includes the following step 5A and step 6A. The method for manufacturing a processed semiconductor substrate may further include the following step 7A. Here, step 5A is a step of processing the semiconductor substrate in the laminate described in the section <First Embodiment> above. Step 6A is a step of separating the semiconductor substrate processed in step 5A from the support substrate. Step 7A is a step of cleaning the processed semiconductor substrate after step 6A.

[0222] The processing performed on the semiconductor substrate in step 5A includes, for example, processing on the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the back surface. Subsequently, for example, through-silicon electrodes (TSVs) are formed, and then the thinned wafer is peeled off the support substrate to form a wafer laminate for three-dimensional mounting. Alternatively, for example, back-side electrodes may be formed before or after this. During the wafer thinning and TSV processes, heat of approximately 250 to 350°C is applied while the wafer is bonded to the support substrate. The laminate of the present invention typically includes an adhesive layer and possesses heat resistance to this load. The processing is not limited to those described above and also includes, for example, the implementation of a semiconductor component mounting process when the substrate is temporarily bonded to the support substrate to support the substrate for mounting semiconductor components.

[0223] In step 6A, the method for separating (peeling) the semiconductor substrate from the support substrate is not particularly limited. For example, a method of mechanical peeling using equipment with a sharp part (a so-called debonder) can be used. Specifically, for example, the sharp part is inserted between the semiconductor substrate and the support substrate, and then the semiconductor substrate and the support substrate are separated. Also, if the laminate has a release agent layer, the method for separating (peeling) the semiconductor substrate from the support substrate in step 6A may be peeling by irradiating the release agent layer with light and then tearing the semiconductor substrate and support substrate apart. By irradiating the release agent layer with light from the support substrate side, the release agent layer is altered as described above (for example, separation or decomposition of the release agent layer), and then, for example, one of the substrates can be easily lifted up to separate the semiconductor substrate and the support substrate.

[0224] Irradiation of the release agent layer with light does not necessarily have to be performed over the entire surface of the release agent layer. Even if there is a mixture of irradiated and unirradiated areas, if the overall release ability of the release agent layer is sufficiently improved, the semiconductor substrate and the support substrate can be separated by a small external force, such as lifting the support substrate. The ratio and positional relationship between the irradiated and unirradiated areas will vary depending on the type and specific composition of the adhesive used, the thickness of the adhesive layer, the thickness of the release agent layer, the intensity of the irradiated light, etc., but those skilled in the art can set the conditions appropriately without requiring excessive testing. For these reasons, according to the manufacturing method of the processed semiconductor substrate of the present invention, for example, when the support substrate of the laminate used is light-transmitting, it is possible to shorten the light irradiation time when peeling is performed by light irradiation from the support substrate side. As a result, not only is an improvement in throughput expected, but the semiconductor substrate and the support substrate can be easily and efficiently separated by light irradiation alone, avoiding physical stress for peeling. Typically, the amount of light irradiation for peeling is 50 to 3,000 mJ / cm². ２ The irradiation time is determined appropriately according to the wavelength and irradiation dose.

[0225] The wavelength of light used for peeling is preferably, for example, 250 to 600 nm, and more preferably 250 to 370 nm. More preferred wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The amount of light required for peeling is an amount that can induce a suitable alteration, such as decomposition, of the specific compound and polymer. The light used for peeling may be laser light or non-laser light emitted from a light source such as an ultraviolet lamp.

[0226] The substrates can be cleaned by spraying the cleaning agent composition onto at least one of the surfaces of the separated semiconductor substrate and the support substrate, or by immersing the separated semiconductor substrate or the support substrate in the cleaning agent composition. Alternatively, the surface of the processed semiconductor substrate may be cleaned using a removal tape or the like. As an example of substrate cleaning, step 7A, in which the processed semiconductor substrate is cleaned, may be performed after step 6A. Examples of cleaning agent compositions used for cleaning include the following.

[0227] Detergent compositions typically contain a solvent. Examples of solvents include lactones, ketones, polyhydric alcohols, compounds having ester bonds, derivatives of polyhydric alcohols, cyclic ethers, esters, and aromatic organic solvents. Examples of lactones include γ-butyrolactone. Examples of ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Examples of compounds having ester bonds include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. Examples of derivatives of polyhydric alcohols include monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether, or compounds having ether bonds such as monophenyl ether, which are monomethyl ethers, monoethyl ether, monopropyl ether, and monobutyl ether of the above polyhydric alcohols or compounds having ester bonds. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred. Examples of cyclic ethers include tetrahydrofuran, dioxolane, tetrahydropyran, methyltetrahydropyran, and dioxane. Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene. These can be used individually or in combination of two or more.Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0228] Furthermore, a mixed solvent obtained by mixing PGMEA and a polar solvent is also preferred. The mixing ratio (mass ratio) can be appropriately determined considering the compatibility of PGMEA and the polar solvent, but it is preferably in the range of 1:9 to 9:1, more preferably 2:8 to 8:2. For example, when EL is used as the polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. When PGME is used as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. When PGME and cyclohexanone are used as the polar solvent, the mass ratio of PGMEA:(PGME + cyclohexanone) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.

[0229] The cleaning agent composition may or may not contain salt, but it is preferable that it does not contain salt, as this increases its versatility when processing semiconductor substrates using laminates and reduces costs.

[0230] An example of a detergent composition containing a salt is a detergent 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. Typical examples of such quaternary ammonium cations include tetra(hydrocarbon)ammonium cations. On the other hand, the anion that pairs with it is the hydroxide ion (OH) － ); fluoride ion (F － ), chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halogen ions; tetrafluoroborate ions (BF４ － ); Hexafluorophosphate ion (PF ６ － Examples include, but are not limited to, these.

[0231] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, and more preferably a fluorine-containing quaternary ammonium salt. In the quaternary ammonium salt, the halogen atom may be contained in the cation or in the anion, but is preferably contained in the anion.

[0232] In one preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. Specific examples of hydrocarbon groups 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, tetra(hydrocarbon)ammonium fluoride includes tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluoride include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also called tetrabutylammonium fluoride). Among these, tetrabutylammonium fluoride is preferred.

[0233] Quaternary ammonium salts such as tetraammonium fluoride may be used in hydrate form. Furthermore, quaternary ammonium salts such as tetraammonium fluoride may be used alone or in combination of two or more types. The amount of 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 relative to the detergent composition.

[0234] When a detergent composition contains a salt, the solvent used in combination is not particularly limited as long as it is used for this type of application and dissolves salts such as quaternary ammonium salts. However, from the viewpoint of obtaining a detergent composition with excellent cleaning properties with good reproducibility, and from the viewpoint of dissolving salts such as quaternary ammonium salts well and obtaining a detergent composition with excellent uniformity, the detergent composition preferably contains one or more amide-based solvents.

[0235] A suitable example of an amide solvent is an acid amide derivative represented by formula (Z).

[0236] In the formula, R ０ R represents an ethyl group, a propyl group, or an isopropyl group, with ethyl and isopropyl groups being preferred, and ethyl group being more preferred. Ａ and R Ｂ Each of these independently represents 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 methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, and cyclobutyl groups. Of these, R Ａ and R Ｂ The groups are preferably methyl or ethyl, more preferably both are methyl or ethyl, and even more preferably both are methyl.

[0237] Examples of acid amide derivatives represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyrate amide, N,N-diethylbutyrate amide, N-ethyl-N-methylbutyrate amide, N,N-dimethylisobutyrate amide, N,N-diethylisobutyrate amide, and N-ethyl-N-methylisobutyrate amide. Of these, N,N-dimethylpropionamide and N,N-dimethylisobutylamide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

[0238] The acid amide derivative represented by formula (Z) may be synthesized by substitution reaction of the corresponding carboxylic acid ester with an amine, or a commercially available product may be used.

[0239] Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

[0240] In equation (Y), R １０１ R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. １０２ The symbol represents an alkylene group having 1 to 6 carbon atoms. Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, and n-butyl groups, while 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.

[0241] Specific examples of lactam compounds represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc., which can be used individually or in combination of two or more.

[0242] In one preferred embodiment, the lactam compound represented by formula (Y) comprises 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in one more preferred embodiment, comprises N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in one even more preferred embodiment, comprises N-methylpyrrolidone (NMP).

[0243] The cleaning agent composition used in this invention may contain water as a solvent, but from the viewpoint of avoiding corrosion of the substrate, etc., only organic solvents are usually intentionally used as solvents. However, in this case, it is not ruled out that trace amounts of water from the salt hydration solution or contained in the organic solvent may be included in the cleaning agent composition. The water content of the cleaning agent composition used in this invention is usually 5% by mass or less.

[0244] The components and method elements relating to the above-described steps of the method for manufacturing a processed semiconductor substrate of the present invention may be modified in various ways, as long as they do not depart from the spirit of the present invention. The method for manufacturing a processed semiconductor substrate of the present invention may also include steps other than those described above.

[0245] One example of the delamination method of the present invention involves separating the semiconductor substrate and the support substrate of a laminate by irradiating the release agent layer with light from either the semiconductor substrate side or the support substrate side, when the semiconductor substrate or support substrate of the laminate is light-transmitting. In one example of the laminate of the present invention, the semiconductor substrate and the support substrate are suitably temporarily bonded together by an adhesive layer and a release agent layer. For example, if the support substrate is light-transmitting, the semiconductor substrate and the support substrate can be easily separated by irradiating the release agent layer with light from the support substrate side of the laminate. Typically, delamination is performed after processing has been carried out on the semiconductor substrate of the laminate.

[0246] An example of a third embodiment will be described using Figures 7A to 7D. This example is an example of manufacturing a thinned semiconductor substrate. First, a laminate is prepared (Figure 7A). This laminate is the same laminate as the laminates shown in Figures 1 and 3B. Next, the surface of the semiconductor substrate 1 opposite to the surface in contact with the adhesive layer 2 is polished using a polishing device (not shown) to thin the semiconductor substrate 1 (Figure 7B). The thinned semiconductor substrate 1 may also be subjected to the formation of through electrodes, etc. Next, the thinned semiconductor substrate 1 and the support substrate 4 are separated using a peeling device (not shown) (Figure 7C). This results in a thinned semiconductor substrate 1 (Figure 7D). At this point, residue of the adhesive layer 2 may remain on the thinned semiconductor substrate 1. Therefore, it is preferable to wash the thinned semiconductor substrate 1 using a cleaning agent composition to remove the residue of the adhesive layer 2 from the semiconductor substrate 1.

[0247] <Fourth Embodiment> The method for manufacturing a processed electronic device layer of the present invention includes the following fifth B step and sixth B step. The method for manufacturing a processed electronic device layer may further include the following seventh B step. Here, fifth B step is a step of processing the electronic device layer in the laminate described in the <Second Embodiment> section above. Sixth B step is a step of separating the electronic device layer processed in fifth B step from the support substrate. Seventh B step is a step of cleaning the processed electronic device layer after sixth B step. Hereinafter, specific examples of the fourth embodiment will be described with reference to Figures 8A to 8F.

[0248] The processing applied to the electronic device layer in step 5B includes, for example, grinding and wiring layer formation processes.

[0249] <<Grinding Process>> The grinding process involves grinding the resin portion of the sealing resin 25 layer in the electronic device layer 26 so that a portion of the semiconductor chip substrate 21 is exposed. The grinding of the sealing resin portion is performed, for example, as shown in Figure 8B, by grinding the sealing resin 25 layer of the laminate shown in Figure 8A until it is approximately the same thickness as the semiconductor chip substrate 21. Note that the laminate shown in Figure 8A is the same laminate as the laminates shown in Figures 4 and 6C.

[0250] <<Wiring Layer Formation Process>> The wiring layer formation process is a process in which a wiring layer is formed on the exposed semiconductor chip substrate 21 after the grinding process described above. In Figure 8C, a wiring layer 28 is formed on an electronic device layer 26 consisting of a semiconductor chip substrate 21 and a sealing resin 25 layer. The wiring layer 28 is also called an RDL (Reduction Layer) and is a thin film wiring body that constitutes wiring connected to the substrate, and may have a single-layer or multi-layer structure. The wiring layer is made of dielectric material (silicon oxide (SiO2) ｘThe wiring may be formed by a conductor (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloy) between layers of photosensitive resins such as photosensitive epoxy, etc., but is not limited to this. For example, the following method can be used to form the wiring layer 28. First, silicon oxide (SiO2) is formed on the layer of sealing resin 25. ｘ ), a dielectric layer such as a photosensitive resin is formed. The dielectric layer made of silicon oxide can be formed by, for example, sputtering or vacuum deposition. The dielectric layer made of a photosensitive resin can be formed by, for example, applying the photosensitive resin onto the layer of sealing resin 25 by methods such as spin coating, dipping, rollerblade coating, spray coating, or slit coating. Subsequently, wiring is formed on the dielectric layer using a conductor such as a metal. As a method for forming the wiring, known semiconductor process methods such as lithography (photolithography) or etching can be used. Examples of such lithography processes include lithography using positive-type resist materials and lithography using negative-type resist materials. In the manufacturing method of the laminate according to the fourth embodiment, bumps can be formed on the wiring layer 28, or elements can be mounted. Elements can be mounted on the wiring layer 28 using, for example, a chip mounter. The laminate according to the fourth embodiment may be a laminate manufactured in a process based on fan-out technology, in which terminals provided on a semiconductor chip substrate are mounted on a wiring layer that extends outside the chip area.

[0251] In step 6B, the method for separating (peeling) the electronic device layer from the support substrate includes, but is not limited to, mechanical peeling using equipment with sharp parts, or peeling the support from the electronic device layer. If the laminate has a release agent layer, for example, by irradiating the release agent layer with light from the support substrate side, the release agent layer is altered as described above (for example, separation or decomposition of the release agent layer), and then, for example, one of the substrates can be lifted up to easily separate the electronic device layer from the support substrate.

[0252] Figures 8D to 8E are schematic cross-sectional views illustrating a method for separating the laminate, and Figure 8F is a schematic cross-sectional view illustrating a cleaning method after separation of the laminate. Figures 8D to 8F illustrate one embodiment of a method for manufacturing a semiconductor package (electronic component). The step of separating the laminate is to separate the electronic device layer 26 and the support substrate 24 using a peeling device (not shown), as shown in Figures 8D and 8E.

[0253] The substrate can be cleaned by spraying the cleaning agent composition onto at least one of the surfaces of the separated electronic device layer and the support substrate, or by immersing the separated electronic device layer or the support substrate in the cleaning agent composition. Alternatively, the surface of the processed electronic device layer may be cleaned using a removal tape or the like. For example, in Figure 8E, after the separation step, the adhesive layer 22 is attached to the electronic device layer 26, but the adhesive layer 22 can be removed by decomposing the adhesive layer 22 using a cleaning agent composition such as an acid or alkali. By removing the adhesive layer, a processed electronic device layer (electronic component) as shown in Figure 8F can be suitably obtained.

[0254] The components and method elements relating to the above-described steps of the method for manufacturing a processed electronic device layer of the present invention may be modified in various ways, as long as they do not depart from the spirit of the present invention. The method for manufacturing a processed electronic device layer of the present invention may also include steps other than those described above.

[0255] The present invention will be described in more detail below with reference to synthesis examples and embodiments, but the present invention is not limited to the embodiments described below.

[0256] The compounds shown in the following synthesis examples in this specification are as follows. The side-chain epoxy-modified polyorganosiloxane (product name: X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd.)) is represented as (B'-1) below, and its epoxy value was 2.27 mol / kg. Hereinafter, R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0257]

[0258] The side-chain epoxy-modified polyorganosiloxane (product name: KF-1001 (manufactured by Shin-Etsu Chemical Co., Ltd.)) is represented as (B'-2) below, and its epoxy value was 0.29 mol / kg. R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0259]

[0260] The side-chain epoxy-modified polyorganosiloxane (product name: KF-102 (manufactured by Shin-Etsu Chemical Co., Ltd.)) is represented as (B'-3) below, and its epoxy value was 0.25 mol / kg. ２ is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0261]

[0262] The epoxy value of the side-chain alicyclic epoxy-modified polyorganosiloxane (product name: DOWSIL® BY16-839 (manufactured by Dow-Toray Industries, Inc.)) was 0.27 mol / kg.

[0263] The side-chain functional value shown in the synthesis example below is the molal concentration (mol / kg) of the side-chain functional group obtained by adding an active proton compound to the epoxy group in an epoxy-modified polyorganosiloxane having an epoxy group in the side chain, and was calculated using a nuclear magnetic resonance spectrometer (hereinafter abbreviated as NMR in this specification). An NMR spectrometer (JNW-ECA500) (manufactured by JEOL Ltd.) was used for the measurement, and the measurement conditions were as follows: Measurement temperature: room temperature Measurement solvent: deuterated chloroform (CDCl ３ )

[0264] First, a dimethyl sulfone standard (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) or a trimethoxybenzene standard (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in deuterated chloroform to prepare a deuterated chloroform solution of the standard. The analytical sample was dissolved in this deuterated chloroform solution of the standard to prepare an NMR measurement sample. From the NMR measurement, the proton derived from the methyl group of dimethyl sulfone or the benzene ring of trimethoxybenzene in the measurement sample was used as the reference proton, and the peak integrated value of the reference proton and the peak integrated value derived from the side chain functional group in the analytical sample were used to calculate the value. Side-chain functional value (mol / kg) = {a・(b / c) / (d / e)} / (f / 100)・1000 In the above formula, a is the molal concentration (mol / kg) of the reference substance in the measurement sample, b is the cumulative value of proton peaks derived from the functional group, c is the number of protons derived from the functional group, d is the cumulative value of proton peaks of the reference substance, e is the number of protons of the reference substance, and f is the mass percentage concentration (wt%) of the sample in the measurement sample.

[0265] [1] Synthesis of the release agent component <Synthesis Example 1> Synthesis of side-chain modified polyorganosiloxane (B-1) 22.12 g of X-22-343, 7.24 g of 2-ethylhexanoic acid, 0.64 g of tetrabutylphosphonium bromide, and 70.00 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 23 hours. 30 g each of cation exchange resin and anion exchange resin were added to the resulting reaction solution and stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the obtained concentrate and concentrated under reduced pressure again, and this process was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B-1), which will be the release agent component. NMR (CDCl ３ The side-chain functional value was 1.81 mol / kg. The structure of the side-chain modified polyorganosiloxane (B-1) is shown below.

[0266] In formula (B-1), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0267] <Synthesis Example 2> Synthesis of Side-Chain Modified Polyorganosiloxane (B-2) 18.63 g of X-22-343, 18.63 g of isopalmitic acid KS (manufactured by Nissan Chemical Corporation), 0.54 g of tetrabutylphosphonium bromide, and 70.00 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 24 hours. 30 g each of cation exchange resin and anion exchange resin were added to the resulting reaction solution and stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the obtained concentrate, and the concentration process was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B-2), which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 1.48 mol / kg. The structure of the side-chain modified polyorganosiloxane (B-2) is shown below.

[0268] In formula (B-2), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0269] <Synthesis Example 3> Synthesis of Side-Chain Modified Polyorganosiloxane (B-3) 17.92 g of X-22-343, 11.56 g of isostearate T (manufactured by Nissan Chemical Corporation), 0.52 g of tetrabutylphosphonium bromide, and 70.00 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 24 hours. 30 g each of cation exchange resin and anion exchange resin were added to the resulting reaction solution and stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the obtained concentrate, and the concentration process was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B-3), which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 1.45 mol / kg. The structure of the side-chain modified polyorganosiloxane (B-3) is shown below.

[0270] In formula (B-3), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0271] <Synthesis Example 4> Synthesis of Side-Chain Modified Polyorganosiloxane (B-4) 17.92 g of X-22-343, 11.56 g of isostearic acid (manufactured by Nissan Chemical Corporation), 0.52 g of tetrabutylphosphonium bromide, and 70.00 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 24 hours. 30 g each of cation exchange resin and anion exchange resin were added to the resulting reaction solution and stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the obtained concentrate, and the concentration process was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B-4), which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 1.39 mol / kg. The structure of the side-chain modified polyorganosiloxane (B-4) is shown below.

[0272] In formula (B-4), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0273] <Synthesis Example 5> Synthesis of Side-Chain Modified Polyorganosiloxane (B-5) 17.27 g of X-22-343, 12.23 g of isoarachiate EC (manufactured by Nissan Chemical Corporation), 0.50 g of tetrabutylphosphonium bromide, and 70.00 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 24 hours. 30 g each of cation exchange resin and anion exchange resin were added to the resulting reaction solution and stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the obtained concentrate, and the concentration process was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B-5), which serves as a release agent component. NMR (CDCl ３The side-chain functional value was 1.53 mol / kg. The structure of the side-chain modified polyorganosiloxane (B-5) is shown below.

[0274] In formula (B-5), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0275] <Synthesis Example 6> Synthesis of Side-Chain Modified Polyorganosiloxane (B-6) 27.17 g of KF-1001, 2.70 g of isostearate T (manufactured by Nissan Chemical Corporation), 0.13 g of tetrabutylphosphonium bromide, and 12.86 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 23 hours. 57.14 g of p-menthane was added to the resulting reaction solution to dilute it, 30 g each of cation exchange resin and anion exchange resin were added, and the mixture was stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the resulting concentrate, and this process of concentration under reduced pressure was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B-6), which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 0.26 mol / kg. The structure of the side-chain modified polyorganosiloxane (B-6) is shown below.

[0276] In formula (B-6), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0277] <Synthesis Example 7> Synthesis of Side-Chain Modified Polyorganosiloxane (B-7) 27.17 g of KF-1001, 2.70 g of isostearic acid (manufactured by Nissan Chemical Corporation), 0.13 g of tetrabutylphosphonium bromide, and 12.86 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 23 hours. 57.14 g of p-menthane was added to the resulting reaction solution to dilute it, 30 g each of cation exchange resin and anion exchange resin were added, and the mixture was stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the resulting concentrate, and this process of concentration under reduced pressure was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B-7), which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 0.27 mol / kg. The structure of the side-chain modified polyorganosiloxane (B-7) is shown below.

[0278] In formula (B-7), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0279] <Synthesis Example 8> Synthesis of Side-Chain Modified Polyorganosiloxane (B-8) 28.71 g of KF-102, 1.18 g of 2-ethylhexanoic acid, 0.12 g of tetrabutylphosphonium bromide, and 12.86 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 23 hours. 57.14 g of p-menthane was added to the resulting reaction solution to dilute it, 30 g each of cation exchange resin and anion exchange resin were added, and the mixture was stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the resulting concentrate, and this process of concentration under reduced pressure was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B-8), which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 0.18 mol / kg. The structure of the side-chain modified polyorganosiloxane (B-8) is shown below.

[0280] In formula (B-8), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0281] <Synthesis Example 9> Synthesis of Side-Chain Modified Polyorganosiloxane (B-9) 27.86 g of KF-102, 2.03 g of isopalmitic acid KS (manufactured by Nissan Chemical Corporation), 0.11 g of tetrabutylphosphonium bromide, and 12.86 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 23 hours. 57.14 g of p-menthane was added to the resulting reaction solution to dilute it, 30 g each of cation exchange resin and anion exchange resin were added, and the mixture was stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the resulting concentrate, and this process of concentration under reduced pressure was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B-9), which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 0.19 mol / kg. The structure of the side-chain modified polyorganosiloxane (B-9) is shown below.

[0282] In formula (B-9), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0283] <Synthesis Example 10> Synthesis of Side-Chain Modified Polyorganosiloxane (B-10) 69.14 g of KF-102, 5.59 g of isostearate T (manufactured by Nissan Chemical Corporation), 0.28 g of tetrabutylphosphonium bromide, and 32.14 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 24 hours. 142.86 g of p-menthane was added to the resulting reaction solution to dilute it, 75 g each of cation exchange resin and anion exchange resin were added, and the mixture was stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the obtained concentrate, and the concentration under reduced pressure was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B-10), which serves as a release agent component. NMR (CDCl ３The side-chain functional value was 0.21 mol / kg. The structure of the side-chain modified polyorganosiloxane (B-10) is shown below.

[0284] In formula (B-10), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0285] <Synthesis Example 11> Synthesis of Side-Chain Modified Polyorganosiloxane (B-11) 69.14 g of KF-102, 5.59 g of isostearic acid (manufactured by Nissan Chemical Corporation), 0.28 g of tetrabutylphosphonium bromide, and 32.14 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 24 hours. 142.86 g of p-menthane was added to the resulting reaction solution to dilute it, 75 g each of cation exchange resin and anion exchange resin were added, and the mixture was stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the resulting concentrate, and this process of concentration under reduced pressure was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B-11), which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 0.20 mol / kg. The structure of the side-chain modified polyorganosiloxane (B-11) is shown below.

[0286] In formula (B-11), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0287] <Synthesis Example 12> Synthesis of Side-Chain Modified Polyorganosiloxane (B-12) 27.45 g of KF-102, 2.44 g of isoarachiate EC (manufactured by Nissan Chemical Corporation), 0.11 g of tetrabutylphosphonium bromide, and 12.86 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 23 hours. 57.14 g of p-menthane was added to the resulting reaction solution to dilute it, 30 g each of cation exchange resin and anion exchange resin were added, and the mixture was stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the resulting concentrate, and this process of concentration under reduced pressure was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B-12), which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 0.13 mol / kg. The structure of the side-chain modified polyorganosiloxane (B-12) is shown below.

[0288] In formula (B-12), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0289] <Synthesis Example 13> Synthesis of Side-Chain Modified Polyorganosiloxane (B-13) 27.32 g of DOWSIL® BY16-839, 2.55 g of isostearate T (manufactured by Nissan Chemical Corporation), 0.13 g of tetrabutylphosphonium bromide, and 12.86 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 23 hours. 57.14 g of p-menthane was added to the resulting reaction solution to dilute it, 30 g each of cation exchange resin and anion exchange resin were added, and the mixture was stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the resulting concentrate, and this process of concentration under reduced pressure was repeated twice to obtain a p-menthane solution of the side-chain modified polyorganosiloxane that would serve as the release agent component. NMR (CDCl ３ The side-chain functional value was 0.22 mol / kg.

[0290] <Synthesis Example 14> Synthesis of Side-Chain Modified Polyorganosiloxane (B-14) 27.32 g of DOWSIL® BY16-839, 2.55 g of isostearic acid (manufactured by Nissan Chemical Corporation), 0.13 g of tetrabutylphosphonium bromide, and 12.86 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 23 hours. 57.14 g of p-menthane was added to the resulting reaction solution to dilute it, 30 g each of cation exchange resin and anion exchange resin were added, and the mixture was stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the resulting concentrate, and this process of concentration under reduced pressure was repeated twice to obtain a p-menthane solution of the side-chain modified polyorganosiloxane, which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 0.23 mol / kg.

[0291] <Comparative Synthesis Example 1> Synthesis of Side-Chain Modified Polyorganosiloxane (B'-4) 22.98 g of X-22-343, 6.36 g of benzoic acid, 0.64 g of tetrabutylphosphonium bromide, and 70.00 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 23 hours. 30 g each of cation exchange resin and anion exchange resin were added to the resulting reaction solution and stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the obtained concentrate and concentrated under reduced pressure again, repeating this process twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B'-4), which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 1.73 mol / kg. The structure of the side-chain modified polyorganosiloxane (B'-4) is shown below.

[0292] In formula (B'-4), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0293] <Comparative Synthesis Example 2> Synthesis of Side-Chain Modified Polyorganosiloxane (B'-5) 19.91 g of X-22-343, 6.51 g of n-octanoic acid, 0.57 g of tetrabutylphosphonium bromide, and 63.00 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 23 hours. 27 g each of cation exchange resin and anion exchange resin were added to the resulting reaction solution and stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the obtained concentrate and concentrated under reduced pressure again, repeating this process twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B'-5), which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 1.74 mol / kg. The structure of the side-chain modified polyorganosiloxane (B'-5) is shown below.

[0294] In formula (B'-5), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0295] <Comparative Synthesis Example 3> Synthesis of Side-Chain Modified Polyorganosiloxane (B'-6) 17.92 g of X-22-343, 11.56 g of stearic acid, 0.52 g of tetrabutylphosphonium bromide, and 70.00 g of propylene glycol monomethyl ether acetate were added to a three-necked flask and heated and stirred at 100°C for 25 hours. 30 g each of cation exchange resin and anion exchange resin were added to the resulting reaction solution and stirred at room temperature for 4 hours. After filtering the ion exchange resin, 20 g of p-menthane was added to the filtrate and concentrated under reduced pressure. 20 g of p-menthane was added to the obtained concentrate, and the concentration process was repeated twice to obtain a p-menthane solution of side-chain modified polyorganosiloxane (B'-6), which serves as a release agent component. NMR (CDCl ３ The side-chain functional value was 1.35 mol / kg. The structure of the side-chain modified polyorganosiloxane (B'-6) is shown below.

[0296] In formula (B'-6), R is an alkylene group having 1 to 10 carbon atoms, which may contain an ether group, and m and n are the number of repeating units.

[0297] [2] Preparation of adhesive components 10.82 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), 17.28 g of SiH group-containing linear polydimethylsiloxane (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), 0.15 g of 1-ethynyl-1-cyclohexanol, and 0.15 g of 1,1-diphenyl-2-propyne-1-ol were stirred in a rotary-orbit mixer (ARE-500, manufactured by Thinky Co., Ltd.). 102.30 g of vinyl group-containing MQ silicone resin (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), 19.25 g of p-menthane, and 0.06 g of platinum catalyst (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) were added to this mixture in a rotary-orbit mixer, and the mixture was stirred again in the rotary-orbit mixer to prepare adhesive component (A).

[0298] [3] Preparation of adhesive composition <Preparation example 1> Adhesive composition (A-1) was prepared by mixing 0.92 g of the release agent component (B-1, concentration: 90.3% by mass) obtained in Synthesis Example 1 with 19.08 g of adhesive component (A). The ratio of the non-volatile content of release agent component (B-1) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0299] <Preparation Example 2> Adhesive composition (A-2) was prepared by mixing 0.91 g of the release agent component (B-2, concentration: 90.5% by mass) obtained in Synthesis Example 2 with 19.09 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B-2) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0300] <Preparation Example 3> Adhesive composition (A-3) was prepared by mixing 0.88 g of the release agent component (B-3, concentration: 92.2% by mass) obtained in Synthesis Example 3 with 19.11 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B-3) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0301] <Preparation Example 4> Adhesive composition (A-4) was prepared by mixing 0.83 g of the release agent component (B-4, concentration: 92.3% by mass) obtained in Synthesis Example 4 with 19.12 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B-4) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0302] <Preparation Example 5> Adhesive composition (A-5) was prepared by mixing 0.91 g of the release agent component (B-5, concentration: 90.9% by mass) obtained in Synthesis Example 5 with 19.09 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B-5) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0303] <Preparation Example 6> Adhesive composition (A-6) was prepared by mixing 0.91 g of the release agent component (B-6, concentration: 91.2% by mass) obtained in Synthesis Example 6 with 19.09 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B-6) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0304] <Preparation Example 7> Adhesive composition (A-7) was prepared by mixing 0.91 g of the release agent component (B-7, concentration: 90.1% by mass) obtained in Synthesis Example 7 with 19.09 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B-7) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0305] <Preparation Example 8> Adhesive composition (A-8) was prepared by mixing 0.97 g of the release agent component (B-8, concentration: 85.4% by mass) obtained in Synthesis Example 8 with 19.03 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B-8) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0306] <Preparation Example 9> Adhesive composition (A-9) was prepared by mixing 19.11 g of adhesive component (A) with 0.89 g of the release agent component (B-9, concentration: 93.2% by mass) obtained in synthesis example 9. The ratio of the non-volatile content of release agent component (B-9) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0307] <Preparation Example 10> Adhesive composition (A-10) was prepared by mixing 19.10 g of adhesive component (A) with 1.75 g of the release agent component (B-10, concentration: 90.8% by mass) obtained in synthesis example 10. The ratio of the non-volatile content of release agent component (B-7) to the non-volatile content (components other than the solvent) of adhesive component (A) is 10% by mass.

[0308] <Preparation Example 11> Adhesive composition (A-11) was prepared by mixing 0.91 g of the release agent component (B-11, concentration: 91.5% by mass) obtained in Synthesis Example 11 with 19.12 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B-11) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0309] <Preparation Example 12> Adhesive composition (A-12) was prepared by mixing 0.88 g of the release agent component (B-12, concentration: 95.2% by mass) obtained in Synthesis Example 12 with 19.12 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B-12) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0310] <Preparation Example 13> Adhesive composition (A-13) was prepared by mixing 0.90 g of the release agent component (B-13, concentration: 92.7% by mass) obtained in Synthesis Example 13 with 19.10 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B-13) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0311] <Preparation Example 14> Adhesive composition (A-14) was prepared by mixing 0.88 g of the release agent component (B-14, concentration: 92.7% by mass) obtained in Synthesis Example 14 with 19.12 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B-14) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0312] <Comparative Preparation Example 1> Adhesive composition (A-15) was prepared by mixing 19.17 g of adhesive component (A) with 0.83 g of side-chain epoxy-modified polyorganosiloxane (product name: X-22-343) (B'-1) as a release agent component. The non-volatile content ratio of side-chain epoxy-modified polyorganosiloxane X-22-343 (B'-1) relative to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0313] <Comparative Preparation Example 2> Adhesive composition (A-16) was prepared by mixing 19.17 g of adhesive component (A) with 0.83 g of side-chain epoxy-modified polyorganosiloxane (product name: KF-1001) (B'-2) as a release agent component. The non-volatile content ratio of side-chain epoxy-modified polyorganosiloxane KF-1001 (B'-2) relative to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0314] <Comparative Preparation Example 3> Adhesive composition (A-17) was prepared by mixing 19.17 g of adhesive component (A) with 0.83 g of side-chain epoxy-modified polyorganosiloxane (product name: KF-102) (B'-3) as a release agent component. The non-volatile content ratio of side-chain epoxy-modified polyorganosiloxane KF-102 (B'-3) relative to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0315] <Comparative Preparation Example 4> Adhesive composition (A-18) was prepared by mixing 0.86 g of the release agent component (B'-4, concentration: 96.5% by mass) obtained in Comparative Synthesis Example 2 with 19.14 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B'-4) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0316] <Comparative Preparation Example 5> Adhesive composition (A-19) was prepared by mixing 0.89 g of the release agent component (B'-5, concentration: 93.4% by mass) obtained in Comparative Synthesis Example 1 with 19.11 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B'-5) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0317] <Comparative Preparation Example 6> Adhesive composition (A-20) was prepared by mixing 0.90 g of the release agent component (B'-6, concentration: 91.7% by mass) obtained in Comparative Synthesis Example 3 with 19.10 g of adhesive component (A). The ratio of the non-volatile content of the release agent component (B'-6) to the non-volatile content (components other than the solvent) of adhesive component (A) is 5% by mass.

[0318] <Comparative Preparation Example 7> Adhesive composition (A-21) was prepared by mixing 20.00 g of adhesive component (A) with a release agent component.

[0319] [4] Compatibility (solubility) of the adhesive composition The compatibility of the adhesive compositions of Preparation Examples 1 to 14 and Comparative Preparation Examples 4 to 6, obtained by mixing two liquids, the adhesive component (A) and the release agent component, was confirmed. "○" was used when the adhesive composition was transparent and the compatibility between the adhesive component and the release agent component was good, and "×" was used when the adhesive composition became cloudy and the compatibility between the adhesive component and the release agent component was poor. The results of the compatibility of the adhesive compositions are shown in Table 1.

[0320]

[0321] From the results in Table 1, it was confirmed that the adhesive compositions of Examples 1 to 14 had better compatibility (solubility) between the adhesive component and the release agent component compared to the adhesive compositions of Comparative Examples 1 to 3, and that the adhesive compositions prepared by mixing the adhesive component and the release agent component could be maintained as a stable mixture.

[0322] [5] The adhesive compositions of Tape Peelability Preparation Examples 1 to 14 and Comparative Preparation Examples 1 to 3 and 7 were spin-coated onto a 4-inch silicon wafer and baked on a hot plate at 130°C for 90 seconds and 200°C for 60 seconds to form a heat-cured adhesive layer with a thickness of 60 μm. In addition, the adhesive compositions of each example were spin-coated onto a 5 cm x 8 cm square copper wafer (copper plating thickness: 1.5 μm) and baked on a hot plate at 130°C for 90 seconds and 200°C for 60 seconds to form a heat-cured adhesive layer with a thickness of 60 μm. Silicon wafers or copper wafers with the formed adhesive layer were cut into 3 cm x 6 cm pieces. Adhesive tape (polyester adhesive tape for silicone bonding, tape width 30 mm, tape thickness 0.06 mm, manufactured by Nitto Denko Corporation) was attached to the adhesive layer, and the tape peelability was evaluated using a peel analysis device (VPA-2S, manufactured by Kyowa Interface Science Co., Ltd.) at a peel angle of 90° and a peel speed of 300 mm / min. In the tape peelability test, "○" was used to indicate that the adhesive layer was completely peeled from the wafer, "△" was used to indicate that only a part of the adhesive layer was peeled from the wafer, and "×" was used to indicate that the adhesive layer was not peeled from the wafer at all. The results of the tape peelability of the adhesive compositions are shown in Table 2.

[0323]

[0324] As shown in Table 2, the adhesive layers of Examples 15 to 28 exhibited better tape peelability from silicon wafers and copper wafers compared to the adhesive layer of Comparative Example 7, due to the addition of a release agent component. Furthermore, the adhesive layers of Examples 15 to 28 showed better tape peelability from both silicon wafers and copper wafers compared to the release agent components added in Comparative Examples 4 to 6, demonstrating high peelability regardless of the substrate material.

[0325] [6] Wafer detachability of adhesive compositions The adhesive compositions of Preparation Examples 1 to 5, and Comparative Preparation Examples 1 and 7 were spin-coated onto a 12-inch silicon wafer (device side), and baked on a hot plate at 90°C for 90 seconds to form an adhesive layer with a film thickness of 50 µm. This wafer was bonded to a 12-inch silicon wafer (carrier side) under vacuum at 70°C under a load of 500 N using a wafer bonding apparatus (XBS300, manufactured by SUSS Microtec Co., Ltd.) to prepare a laminated substrate including the adhesive layer. Thereafter, baking was performed on a hot plate at 130°C for 5 minutes and then at 200°C for 5 minutes such that the device-side silicon wafer was in contact with the hot plate, to thermally cure the adhesive layer. After inserting a blade into the adhesive layer from the side surface of the obtained laminated substrate, a mechanical load was applied by pulling up the carrier-side silicon wafer upward from the vicinity where the blade was inserted using a manual debonder (manufactured by SUSS Microtec Co., Ltd.), thereby evaluating wafer detachability. In the wafer detachability test, the case where the wafer could be peeled from the laminate with a load of 30 N or less was rated "○", the case where the wafer could be peeled from the laminate with a load of more than 30 N to 50 N or less was rated "△", and the case where the wafer could not be peeled even with a load of more than 50 N was rated "×". The results are shown in Table 3.

[0326]

[0327] From the results in Table 3, compared with the adhesive layers of Comparative Examples 8 and 9, the adhesive layers of Examples 29 to 33 can be easily peeled off with a smaller load even in a laminated wafer obtained by bonding silicon wafers to each other.

[0328] 1 Semiconductor substrate 2 Adhesive layer 2a Adhesive coating layer 3 Release agent layer 4 Support substrate 21 Semiconductor chip substrate 22 Adhesive layer 22' Adhesive coating layer 23 Release agent layer 24 Support substrate 25 Encapsulating resin 26 Electronic device layer 28 Wiring layer

Claims

1. An adhesive composition comprising an adhesive component and a polyorganosiloxane having a secondary hydroxyl group and a branched aliphatic hydrocarbon group having 6 or more carbon atoms in its side chain.

2. The adhesive composition according to claim 1, wherein the polyorganosiloxane has a substructure represented by the following formula (Cg-1) or the following formula (Cg-2). (In formulas (Cg-1) and (Cg-2), R １ R represents an alkylene group having 1 to 10 carbon atoms, which may be interrupted by an oxygen atom. ２ X represents a branched aliphatic hydrocarbon group with 6 or more carbon atoms, １ The symbols represent -O-, -COO-, -OCO-, -NH-, -S-, or -CONOC-. * represents a bond to a silicon atom.

3. The adhesive composition according to claim 1, wherein the content of the polyorganosiloxane in the nonvolatile content of the adhesive composition is 0.01% by mass to 30% by mass.

4. The adhesive composition according to claim 1, wherein the adhesive component is a component that hardens by a hydrosilylation reaction.

5. The adhesive composition according to claim 4, wherein the component that hardens by the hydrosilylation reaction contains a component (A-1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, a component (A-2) having a Si-H group, and a platinum group metal catalyst (A-3).

6. The adhesive composition according to claim 5, wherein the component (A-1) contains a polyorganosiloxane (a1) having alkenyl groups having 2 to 40 carbon atoms bonded to a silicon atom.

7. The adhesive composition according to claim 5, wherein the component (A-2) contains a polyorganosiloxane having a Si-H group.

8. A laminate comprising a semiconductor substrate or an electronic device layer, a light-transmitting support substrate, and an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate, wherein the adhesive layer is formed from the adhesive composition described in any one of claims 1 to 7.

9. A method for manufacturing a processed semiconductor substrate or a processed electronic device layer, comprising: a fifth A step in which the semiconductor substrate of the laminate according to claim 8 is processed, or a fifth B step in which the electronic device layer of the laminate according to claim 8 is processed; a sixth A step in which the semiconductor substrate processed in the fifth A step is separated from the support substrate, or a sixth B step in which the electronic device layer processed in the fifth B step is separated from the support substrate.

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