Thermosetting siloxane polymer composition for processing circuit-mounted board, method for manufacturing circuit-mounted board laminate, and method for manufacturing thin circuit-mounted board

Abstract

To provide a temporary adhesive composition that allows selective peeling between a substrate and a temporary adhesive layer or between the temporary adhesive layer and a support, in particular even when applied to a circuit-mounted board.SOLUTION: A thermosetting siloxane polymer composition for processing circuit-mounted board comprises (A-1) an organopolysiloxane having two or more alkenyl groups per molecule but not having any aryl group, (A-2) an organopolysiloxane having two or more alkenyl groups and one or more aryl groups per molecule, (A-3) an organohydrogen polysiloxane including two or more Si-H groups, which are each a hydrogen atom bonded to a silicon atom, per molecule, (A-4) a detachment additive, and (A-5) a platinum-based catalyst, in amounts such that the mole ratio of the Si-H groups in the (A-3) component with respect to the alkenyl groups in the (A-1) and (A-2) components is 0.3-10.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermosetting siloxane polymer composition for processing circuitized substrates, a method for producing a circuitized substrate laminate, and a method for producing a thin circuitized substrate. [Background technology]

[0002] Three-dimensional semiconductor packaging is becoming essential for achieving ever-increasing density and capacity. 3D packaging technology is a semiconductor manufacturing technology that thins individual semiconductor chips and then stacks them in multiple layers while connecting them with through-silicon vias (TSVs). To achieve this, a substrate with semiconductor circuits formed on it must be thinned by grinding the non-circuit-forming side (also called the "backside"), followed by the process of forming electrodes, including TSVs, on the backside. Conventionally, during the backside grinding process of silicon substrates, protective tape is applied to the side opposite the grinding surface to prevent wafer damage during grinding. However, this tape uses an organic resin film as its base material, which, while flexible, lacks strength and heat resistance, making it unsuitable for the TSV formation process or the backside wiring layer formation process.

[0003] Therefore, a system has been proposed in which a semiconductor substrate serving as a circuit board is bonded to a support such as silicon or glass via an adhesive layer, thereby enabling the substrate to withstand the processes of backside grinding, TSV formation, and backside electrode formation. The adhesive layer used to bond the substrate to the support is crucial in this process. It must be able to bond the substrate to the support without gaps, be durable enough to withstand subsequent processes, and also allow the thin wafer to be easily peeled from the support. Because this process involves peeling the substrate off at the end, this adhesive layer will be referred to as a temporary adhesive layer (or temporary adhesive layer) in this specification.

[0004] Previously known methods for producing temporary adhesive layers and their removal include a technique in which high-intensity light is irradiated onto an adhesive containing a light-absorbing substance to decompose the adhesive layer and thereby remove it from the support (Patent Document 1), and a technique in which a heat-melting hydrocarbon compound is used as the adhesive and bonding and removal are performed in a heated, molten state (Patent Document 2). The former technique requires expensive equipment such as a laser, and also requires a light-transmitting glass substrate as the support, which is more expensive than a silicon substrate and cannot be recycled by polishing, making it particularly cost-intensive. On the other hand, the latter technique is simple because it can be controlled by heating alone, but its thermal stability at temperatures above 200°C is insufficient, limiting its range of application. Furthermore, these temporary adhesive layers are not suitable for forming a uniform film thickness on high-step substrates or for complete adhesion to the support.

[0005] Furthermore, a technology has been proposed for a wafer processing method that uses a silicone adhesive as a temporary adhesive layer (Patent Document 3). In this method, a substrate is bonded to a support using an addition-curing silicone adhesive, and when peeling, the substrate is separated from the support by immersing it in a chemical that dissolves or decomposes the silicone resin. Therefore, peeling takes an extremely long time, making it difficult to apply to actual manufacturing processes.

[0006] Another known method involves mechanically peeling a substrate from a wafer in which the substrate and substrate are temporarily bonded using a thermosetting silicone resin composition containing a nonfunctional organopolysiloxane (Patent Document 4). However, depending on the type of circuitized substrate, selective peeling from between the substrate and the temporary adhesive layer is not possible, and some of the temporary adhesive remains on the substrate, resulting in problems such as the need for a long time to clean the residue. Furthermore, when this method is applied to a circuitized substrate having metal pads such as copper, and exposed to high temperatures after the laminate is produced, the metal pads are oxidized and deteriorated, making it particularly inapplicable to hybrid bonding, a next-generation wafer-to-wafer technology that directly bonds metal pads together. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-64040 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-328104 [Patent Document 3] U.S. Patent No. 7,541,264 [Patent Document 4] International Publication No. WO2021 / 112070 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in view of the above circumstances, and has an object to provide a temporary adhesive composition that, particularly when applied to a circuitized substrate, enables selective peeling between the substrate and the temporary adhesive layer or between the temporary adhesive layer and the support, and a method for producing a circuitized substrate laminate and a method for producing a thin circuitized substrate using the same. [Means for solving the problem]

[0009] In order to solve the above problems, the present invention provides: (A-1) an organopolysiloxane having two or more alkenyl groups and no aryl groups in one molecule; (A-2) an organopolysiloxane having two or more alkenyl groups and one or more aryl groups in one molecule; (A-3) an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms (Si-H groups) per molecule; (A-4) release additive, (A-5) platinum-based catalyst, Contains The present invention provides a thermosetting siloxane polymer composition for processing circuitized substrates, characterized in that the molar ratio of Si-H groups in component (A-3) to alkenyl groups in components (A-1) and (A-2) is 0.3 to 10.

[0010] Such a thermosetting siloxane polymer composition for processing circuitized substrates can be used as a temporary adhesive for processing circuitized substrates, and particularly when applied to circuitized substrates, it allows selective peeling between the circuitized substrate / temporary adhesive layer or between the temporary adhesive layer / support. In the latter case, the temporary adhesive layer can be easily removed from the substrate in a subsequent step. As a result, no residue of the temporary adhesive layer remains on the circuitized substrate in either peel pattern, making it possible to carry out a subsequent substrate cleaning process easily and at low cost. Furthermore, when applied to a circuitized substrate having metal pillars on its surface, it is possible to suppress oxidative degradation of the metal pillars even after a specified thermal process, thereby enabling application to next-generation hybrid bonding.

[0011] Preferably, the thermosetting siloxane polymer composition has an initial viscosity of 500 mPa·s to 100,000 mPa·s at 25°C, and exhibits a viscosity increase of 20% or less when stored sealed at 40°C for 7 days.

[0012] Such an initial viscosity is preferable from the viewpoint of coatability and workability, and if the viscosity increase rate is low as described above, the viscosity increase is unlikely to progress and the initially set film thickness is likely to be maintained.

[0013] Furthermore, the component (A-4) is preferably a thermoplastic dimethylpolysiloxane having a viscosity of 100 to 500,000 mPa·s in a 30% toluene solution at 25°C.

[0014] Thermoplastic dimethylpolysiloxanes of such viscosities are preferred as release additives.

[0015] It is also preferred that the thermosetting siloxane polymer composition contains an (A-6) organic solvent, and that the thermosetting siloxane polymer composition contains the (A-6) component in an amount such that the nonvolatile components in the composition account for 10 to 90 wt %.

[0016] By including such an organic solvent, the composition can be easily spin-coated.

[0017] The thermosetting siloxane polymer composition may also be a composition containing (A-7) a reaction inhibitor.

[0018] Such a reaction inhibitor can be added as needed to prevent thickening or gelation.

[0019] Furthermore, the thermosetting siloxane polymer composition for processing circuitized boards of the present invention is preferably such that, after being formed as a film on a circuitized board, the formed thermosetting siloxane polymer composition exhibits a peel force (R1) of 10 gf / 25 mm or more when peeled from the circuitized board after curing in a 180° peel test at 23°C, and the thermosetting siloxane polymer composition formed on a support to which the circuitized board is to be joined via the cured product of the thermosetting siloxane polymer composition exhibits a peel force (R2) of 10 gf / 25 mm or more when peeled from the support after curing in a 180° peel test at 23°C, and that when formed as a film on the circuitized board, R1 / R2≦1.0 and when formed as a film on the support, R1 / R2≧1.0.

[0020] When the peel strength (R1) on the circuitized substrate side and the peel strength (R2) on the support side satisfy the above relationship, the support can be peeled from the laminate with a low peel strength, and the peel interface can be made selective, which is preferable because when a film is formed on the circuitized substrate, residue of the temporary adhesive layer is less likely to remain.Furthermore, even when a film is formed on the support, it is possible to make the peel interface selective.

[0021] In addition, it is preferable that the thermosetting siloxane polymer composition has a solution prepared so that the non-volatile component content is 5% by mass, and the solution has a light transmittance of 50% or less at a wavelength of 265 nm.

[0022] If the transmittance of a solution prepared so that the non-volatile components are 5% by mass is within this range, it will be possible to peel the support from the laminate with low peeling force and selectively at the interface in a circuit-equipped substrate, and when applied to a circuit-equipped substrate having metal pads on its surface, it will be possible to suppress oxidative degradation of the metal pads even if they undergo a heat-resistant process after forming the laminate.

[0023] The present invention also provides (a) forming a temporary adhesive layer by spin coating any one of the thermosetting siloxane polymer compositions on the surface of a circuitized substrate having a circuit surface on the front surface and a back surface to be processed, followed by pre-baking; (b) bonding a support and the circuit-forming surface of the circuit-equipped board on which the temporary adhesive layer is formed under heat and reduced pressure to produce a circuit-equipped board processed body; (c) heating the circuitized substrate body to harden the temporary adhesive layer; The present invention provides a method for manufacturing a circuit-equipped substrate laminate, comprising:

[0024] The present invention also provides (d) grinding and / or polishing the rear surfaces of the circuit-mounted substrates in the circuit-mounted substrate laminate manufactured by the above-mentioned method for manufacturing a circuit-mounted substrate laminate; (e) further processing the back surface of the circuitized board; (f) peeling the circuitized board laminate from the interface between the surface of the circuitized board and the temporary adhesive layer, separating the support body and the temporary adhesive layer together, and removing only the circuitized board; The present invention provides a method for manufacturing a thin circuit board, comprising:

[0025] The present invention also provides (g) forming a film of any one of the thermosetting siloxane polymer compositions on a support by spin coating and pre-baking to form a temporary adhesive layer; (h) bonding a circuit-equipped board having a circuit surface on its front surface and a back surface to be processed under heat and reduced pressure so that the front surface is in contact with the temporary adhesive layer, thereby producing a circuit-equipped board processed body; (i) heating the circuitized board processed body to harden the temporary adhesive layer; The present invention provides a method for manufacturing a circuit-equipped substrate laminate, comprising:

[0026] The present invention also provides (j) grinding and / or polishing the rear surfaces of the circuit-mounted substrates in the circuit-mounted substrate laminate manufactured by the above-mentioned method for manufacturing a circuit-mounted substrate laminate; (k) further processing the back surface of the circuitized board; (l) peeling the circuitized substrate laminate from the interface between the support and the temporary adhesive layer to separate the support; (m) removing the temporary adhesive layer from the circuitized board and taking out only the circuitized board; The present invention provides a method for manufacturing a thin circuit board, comprising:

[0027] The method for producing a circuitized board laminate and the method for producing a thin circuitized board of the present invention can be any of these embodiments. That is, the surface on which the temporary adhesive layer is formed and the surface on which it is peeled can be selectively formed. [Effects of the Invention]

[0028] The thermosetting siloxane polymer composition for processing circuitized boards of the present invention can be used as a temporary adhesive for processing circuitized boards. In particular, when applied to circuitized boards, selective peeling is possible between the circuitized board / temporary adhesive layer or between the temporary adhesive layer / support. In the latter case, the temporary adhesive layer can be easily removed from the substrate in a subsequent step. As a result, no residue of the temporary adhesive layer remains on the circuitized board in either peel pattern, making it possible to carry out the subsequent substrate cleaning process easily and at low cost. Furthermore, when applied to circuitized boards having metal pillars on their surfaces, oxidation degradation of the metal pillars can be suppressed even after undergoing a specified thermal process, thereby enabling application to next-generation hybrid bonding. DETAILED DESCRIPTION OF THE INVENTION

[0029] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a thermosetting siloxane polymer composition containing an organopolysiloxane having two or more alkenyl groups and one or more aryl groups in one molecule as a thermosetting siloxane polymer composition for processing circuitized boards in a temporary adhesive layer, and have thus completed the present invention.

[0030] Therefore, the present invention provides the following thermosetting siloxane polymer composition for processing circuitized boards, a method for producing a circuitized board laminate, and a method for producing a thin circuitized board.

[0031] The thermosetting siloxane polymer composition for processing circuitized boards of the present invention comprises: (A-1) an organopolysiloxane having two or more alkenyl groups and no aryl groups in one molecule; (A-2) an organopolysiloxane having two or more alkenyl groups and one or more aryl groups in one molecule; (A-3) an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms (Si-H groups) per molecule; (A-4) release additive, (A-5) platinum-based catalyst, Contains The thermosetting siloxane polymer composition for processing circuitized substrates is characterized in that it contains an amount of component (A-3) such that the molar ratio of Si-H groups in component (A-1) and component (A-2) to the alkenyl groups in components (A-2) is 0.3 to 10.

[0032] The present invention will now be described in more detail.

[0033] The thermosetting siloxane polymer composition for processing circuitized substrates as a temporary adhesive in the present invention is thermosetting. After forming a laminate and curing the temporary adhesive layer, the laminate can be peeled off to remove the circuitized substrate alone. Peeling can be performed selectively from either the circuitized substrate side or the support side interface. In the latter case, the temporary adhesive layer remains on the circuitized substrate as a thick film. However, since the temporary adhesive layer can be easily removed from the substrate in a subsequent process, no temporary adhesive layer remains on the circuitized substrate in either peeling pattern. Furthermore, by making the temporary adhesive thermosetting, sufficient heat resistance can be obtained even when the backside of the circuitized substrate is ground to thin it or when it is subjected to a heating process such as CVD, making it possible to easily produce thin circuitized substrates.

[0034] A circuitized substrate having a circuit surface on its front surface and a back surface to be processed is a circuitized substrate having a circuit-forming surface on its front surface and a non-circuit-forming surface on its back surface. The circuitized substrate used in the present invention is usually a semiconductor wafer. Examples of the semiconductor wafer include not only silicon wafers but also germanium wafers, gallium-arsenide wafers, gallium-phosphorus wafers, and gallium-arsenide-aluminum wafers. The thickness of the wafer is not particularly limited, but is typically 600 to 800 μm, more typically 625 to 775 μm.

[0035] As described above, the substrate to which the circuit board is bonded is the substrate via the cured product of the thermosetting siloxane polymer composition of the present invention. Substrates such as silicon wafers, glass plates, quartz wafers, and various metal plates can be used as the substrate, and there are no limitations other than process compatibility.

[0036] When the circuit-mounted substrate is a wafer, the support is preferably a circular plate with the same diameter as the wafer. When laminating a temporary adhesive layer, it is preferable to form a film of a liquid temporary adhesive by spin coating. This method makes it easy to form a temporary adhesive layer with a uniform thickness, and even if the surface of the circuit-mounted substrate is uneven, it is possible to easily fill these unevennesses and form a uniform film. This makes it less likely for voids to form at the adhesive interface between the temporary adhesive layer and the surface of the support or circuit-mounted substrate when forming an integrated laminate via the temporary adhesive layer, and further enables the thickness of the integrated laminate to be more uniform. Even when the circuit-mounted substrate is not a wafer, it can be formed into a film by existing methods such as spin coating, slit coating, spray coating, and film lamination, depending on its shape. In this case, it is preferable for the support shape to be the same as the circuit-mounted substrate and the same size except for the thickness.

[0037] In the present invention, the temporary adhesive layer is a cured product obtained by curing the thermosetting siloxane polymer composition for processing a circuitized board of the present invention. Hereinafter, the thermosetting siloxane polymer (A) in the thermosetting siloxane polymer composition for processing a circuitized board of the present invention will be also referred to as the thermosetting siloxane polymer (A), and the thermosetting siloxane polymer (A) and its cured product will be described in detail.

[0038] -Thermosetting siloxane polymer (A)- The thermosetting siloxane polymer composition for processing circuitized boards of the present invention is a thermosetting siloxane polymer (A) composition that is a component of a processed circuitized board, and contains the following components: (A-1) an organopolysiloxane having two or more alkenyl groups and no aryl groups in one molecule; (A-2) an organopolysiloxane having two or more alkenyl groups and one or more aryl groups in one molecule; (A-3) an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms (Si-H groups) per molecule; (A-4) release additive, (A-5) Platinum-based catalyst.

[0039] Furthermore, the thermosetting siloxane polymer composition for processing circuitized boards of the present invention contains an amount of component (A-3) such that the molar ratio of Si-H groups to alkenyl groups in components (A-1) and (A-2) is 0.3 to 10.

[0040] The thermosetting siloxane polymer composition for processing a circuitized board of the present invention may also contain, as optional components, one or more of (A-6) an organic solvent and (A-7) a reaction inhibitor.

[0041] Components (A-1) to (A-7) will be explained below.

[0042] Component (A-1) The component (A-1) is an organopolysiloxane that contains two or more alkenyl groups in one molecule and no aryl groups, for example, an organopolysiloxane that contains two or more alkenyl groups in one molecule and has no R 13 R 13 SiO 2 / 2 Siloxane units (D units), expressed in units of R 13 SiO 3 / 2 Siloxane units (T units) or SiO 4 / 2 The organopolysiloxane is an organopolysiloxane having one or more siloxane units (Q units) represented by units. In particular, it is preferable that the alkenyl group content per molecule is 0.0001 to 3.0 mol / 100 g, and that the organopolysiloxane is a diorganopolysiloxane containing D units, a monoorganopolysiloxane containing T units, or a resin-structured organopolysiloxane containing Q units.

[0043] Specific examples of such organopolysiloxanes include those represented by the following formulas (1), (2), and (3), which may be used alone or in combination of two or more. R 13 (3-a1) X a1 SiO-(R 13 XSiO) m1 -(R 13 2SiO) n1-SiR 13 (3-a1) X a1 (1) R 13 2(HO)SiO-(R 13 XSiO) p1+2 -(R 13 2SiO) q1 -SiR 13 2(OH) (2) (SiO 4 / 2 ) b1 (R 13 3SiO 1 / 2 ) c1 (R 13 (3-e1) X e1 SiO 1 / 2 ) d1 (3) (In the formula, R 13 are each independently a monovalent hydrocarbon group free of aliphatic unsaturated bonds, X are each independently an alkenyl-containing monovalent organic group, a1 is an integer from 0 to 3, m1 and n1 are numbers such that 2a1 + m1 results in an alkenyl group content per molecule of 0.0001 to 3.0 mol / 100 g, p1 and q1 are numbers such that p1 + 2 results in an alkenyl group content per molecule of 0.0001 to 3.0 mol / 100 g, e1 is each independently an integer from 1 to 3, b1, c1, and d1 are numbers such that (c1 + d1) / b1 is 0.3 to 3.0 and d1 / (b1 + c1 + d1) is 0.01 to 0.6.

[0044] In the above formula, R 13 As the alkyl group, a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferred, and examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; and cycloalkyl groups such as a cyclohexyl group, with alkyl groups such as a methyl group being particularly preferred.

[0045] The alkenyl-containing monovalent organic group for X is preferably an organic group having 2 to 10 carbon atoms, and examples thereof include alkenyl groups such as vinyl, allyl, hexenyl, and octenyl; (meth)acryloylalkyl groups such as acryloylpropyl, acryloylmethyl, and methacryloylpropyl; (meth)acryloxyalkyl groups such as acryloxypropyl, acryloxymethyl, methacryloxypropyl, and methacryloxymethyl; and alkenyl-containing monovalent hydrocarbon groups such as cyclohexenylethyl and vinyloxypropyl, with vinyl being particularly preferred from an industrial perspective.

[0046] In the general formula (1), a1 is an integer of 0 to 3. When a1 is 1 to 3, the molecular chain terminals are blocked with alkenyl groups, and the highly reactive alkenyl groups at the molecular chain terminals allow the reaction to be completed in a short time, which is preferable. Furthermore, from an industrial standpoint, a1 = 1 is preferable in terms of cost. The properties of this alkenyl group-containing diorganopolysiloxane are preferably oily or rubber-like. This alkenyl group-containing diorganopolysiloxane may be linear or branched.

[0047] The above general formula (3) is SiO 4 / 2 In the formula, e1 is independently an integer of 1 to 3, but from an industrial standpoint, e1 = 1 is preferred in terms of cost. Furthermore, the product of the average value of e1 and the alkenyl group content is preferably 0.001 to 7.0 mol / 100 g, and more preferably 0.001 to 2.3 mol / 100 g. This resin-structured organopolysiloxane may be used as a solution dissolved in an organic solvent.

[0048] The component (A-1) is distinguished from the component (A-2) by the absence of an aryl group.

[0049] Ingredient (A-2) Component (A-2) is an organopolysiloxane having two or more alkenyl groups and one or more aryl groups in one molecule. Component (A-2) may, for example, contain two or more alkenyl groups and one or more aryl groups in one molecule, and R 3 R 3 SiO 2 / 2 Siloxane units (D units) represented by (where R 3 each independently represents an unsubstituted or substituted monovalent hydrocarbon group, R 3 SiO 3 / 2 Siloxane units (T units) represented by (where R 3 each independently represents an unsubstituted or substituted monovalent hydrocarbon group, SiO 4 / 2 Siloxane units (Q units) represented by and R 3 Among these, those having two or more alkenyl groups and one or more aryl groups in one molecule.

[0050] Among these, diorganopolysiloxanes containing D units, monoorganopolysiloxanes containing T units, or organopolysiloxanes with a resin structure containing Q units, each of which has an alkenyl group content of 0.0001 to 3.0 mol / 100 g and an aryl group content of 0.0001 to 1.5 mol / 100 g per molecule, are particularly preferred.

[0051] Specific examples of such organopolysiloxanes include those represented by the following formulas (4), (5), (6), (7), and (8). These may be used alone or in combination of two or more. R 23 (3-a-b) X a Y b SiO-(R 23 XSiO) l -(Y2SiO) m -(R 23 2SiO) n -SiR 23 (3-a-b) X a Yb (4) R 23 2(HO)SiO-(R 23 XSiO) p -(Y2SiO) q -(R 23 2SiO) r -SiR 23 2(OH) (5) (SiO 4 / 2 ) c (R 23 3SiO 1 / 2 ) d (R 23 (3-f) X f SiO 1 / 2 ) e (R 23 (3-g) Y g SiO 1 / 2 ) h (6) (SiO 4 / 2 ) c (R 23 3SiO 1 / 2 ) d (R 23 (3-j-k) X k Y j SiO 1 / 2 )​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​are each independently a monovalent hydrocarbon group having no aliphatic unsaturated bonds, each X is independently an alkenyl group-containing monovalent organic group, each Y is independently an aryl group or an aryl group-containing monovalent organic group, a and b are integers of 0 to 3, and l, m, and n are numbers such that 2a+l results in an alkenyl group content of 0.0001 to 3.0 mol / 100 g per molecule, and 2b+2m results in an aryl group content of 0.0001 to 1.5 mol / 100 g per molecule. p, q, and r are such that p is a number that gives an alkenyl group content in one molecule of 0.0001 to 1.0 mol / 100 g, and q is a number that gives an aryl group content in one molecule of 0.0001 to 1.0 mol / 100 g. f and g are each independently an integer of 1 to 3, and ef / (c+d+e+h) is a number such that the alkenyl group content per molecule is 0.001 to 2.3 mol / 100 g, and gh / (c+d+e+h) is a number such that the aryl group content per molecule is 0.001 to 1.5 mol / 100 g. k and j are each independently an integer of 1 or greater and 2≦k+j≦3, ki / (c+d+i) is a number such that the alkenyl group content per molecule is 0.001 to 2.3 mol / 100 g, and ji / (c+d+i) is a number such that the aryl group content per molecule is 0.001 to 1.5 mol / 100 g. l and s are each independently an integer of 0 to 3, and 1≦l+s≦6, provided that when l+s is 6, n≧1, and (l m + su) / (c + d + m + o + u) is a number such that the alkenyl group content per molecule is 0.001 to 2.3 mol / 100 g. n and t are each independently an integer of 0 to 3, and 1≦n+t≦6, provided that when n+t is 6, l≧1, and (n0+tu) / (c+d+m+o+u) is a number such that the aryl group content per molecule is 0.001 to 1.5 mol / 100 g.

[0052] In the above formula, R 23 As the alkyl group, a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferred, and examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; and cycloalkyl groups such as a cyclohexyl group, with alkyl groups such as a methyl group being particularly preferred.

[0053] The alkenyl-containing monovalent organic group for X is preferably an organic group having 2 to 10 carbon atoms, and examples thereof include alkenyl groups such as vinyl, allyl, hexenyl, and octenyl; (meth)acryloylalkyl groups such as acryloylpropyl, acryloylmethyl, and methacryloylpropyl; (meth)acryloxyalkyl groups such as acryloxypropyl, acryloxymethyl, methacryloxypropyl, and methacryloxymethyl; and alkenyl-containing monovalent hydrocarbon groups such as cyclohexenylethyl and vinyloxypropyl, with vinyl being particularly preferred from an industrial perspective.

[0054] The aryl group or aryl group-containing monovalent organic group for Y is preferably an organic group having 6 or more carbon atoms, such as a phenyl group, a tolyl group, a naphthyl group, an anthracenyl group, a benzyl group, or a phenethyl group, with a phenyl group being industrially preferred.

[0055] In the general formula (4), a is an integer of 0 to 3. When a is 1 to 3, the molecular chain terminals are blocked with alkenyl groups, and the highly reactive alkenyl groups at the molecular chain terminals allow the reaction to be completed in a short time, which is preferable. Furthermore, from an industrial standpoint, a = 1 is preferable in terms of cost. The di(mono)organopolysiloxane containing alkenyl groups and aryl groups is preferably oily or rubber-like in nature. This alkenyl-group-containing di(mono)organopolysiloxane may be composed of only D units, or may also contain T units.

[0056] The above general formula (6) is SiO 4 / 2 In the formula, f and g are each independently an integer of 0 to 3, and k and j are each independently an integer of 1 to 2 that satisfies 2≦k+j≦3, but from an industrial standpoint, f=g=0 and k=j=1 are preferred. This resin-structured organopolysiloxane may be used as a solution dissolved in an organic solvent.

[0057] The amount of component (A-2) added can be any ratio with component (A-1), which also contains alkenyl groups in its molecule. The effective amount varies depending on the amount of aryl groups in component (A-2), making it impossible to define a generalized optimal amount. For example, it is added in an amount of 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, per 100 parts by weight of component (A-1). An amount of 0.1 parts by weight or more is preferred because it is likely to reduce debonding force, improve selectivity of the peel interface, and inhibit oxidation degradation of the metal pad due to the aryl group content. An amount of 100 parts by weight or less is preferred because it is likely to produce a homogeneous cured film without separation from other components.

[0058] Ingredient (A-3) Component (A-3) is a crosslinking agent, which is an organohydrogenpolysiloxane having at least two, and preferably three or more, silicon-bonded hydrogen atoms (Si-H groups) per molecule. Linear, branched, or cyclic organohydrogenpolysiloxanes can be used.

[0059] The viscosity of the organohydrogenpolysiloxane of component (A-3) at 25°C is preferably 1 to 5,000 mPa·s, and more preferably 5 to 500 mPa·s. The viscosity here was measured at 25°C in accordance with JIS Z 8803. The viscometer used can be selected appropriately depending on the viscosity, but an E-type viscometer (RE-85R manufactured by Toki Sangyo Co., Ltd.) is a suitable example.

[0060] This organohydrogenpolysiloxane may be a mixture of two or more types. The amount of component (A-3) is adjusted so that the molar ratio of SiH groups in component (A-3) to the amount of alkenyl groups in components (A-1) and (A-2) (SiH groups / alkenyl groups) is 0.3 to 10. This ratio is preferably adjusted to be in the range of 1.0 to 8.0. When the molar ratio of SiH groups to alkenyl groups is 0.3 or higher, the crosslink density does not decrease, and problems such as the adhesive layer not curing do not occur. When the molar ratio is 10 or lower, the crosslink density does not become too high, and sufficient adhesive strength and tackiness are obtained. Furthermore, when the molar ratio is 10 or lower, the usable life of the treatment solution can be extended.

[0061] The molar ratio (SiH group / alkenyl group) was calculated from the measured value of SiH per 100 g (mol / 100 g) and the measured value of alkenyl group per 100 g (mol / 100 g). The molar ratio (SiH group / alkenyl group) in the preparation examples is calculated using the following formula. [(SiH group content of POHS / 100) x amount of POHS added] / {[(Alkenyl group content of PDMS / 100) × Amount of PDMS added] + [(Alkenyl group content of PVMS / 100) × Amount of PVMS added]} (In the above formula, POHS: organohydrogenpolysiloxane, PDMS: dimethylpolysiloxane, PVMS: vinylmethylpolysiloxane with a resin structure)

[0062] Ingredient (A-4) Component (A-4) is a release additive that is effective in adjusting the release force when peeling the support or circuit board from the laminate (circuit-equipped board laminate) and stabilizing the peel interface, which in turn helps to suppress the generation of residue after peeling.

[0063] As component (A-4), a substance with particularly excellent release properties is selected. Specific examples include thermoplastic alkylpolysiloxanes such as dialkylpolysiloxanes, phenyl-modified alkylpolysiloxanes, and fluorine-modified alkylpolysiloxanes, with dimethylpolysiloxane being particularly preferred.

[0064] The release additive (A-4) preferably has a viscosity of 100 to 500,000 mPa·s in a 30% toluene solution at 25°C. A thermoplastic dimethylpolysiloxane having such a viscosity is particularly preferred. The viscosity was measured at 25°C in accordance with JIS Z 8803. The viscometer used may be selected appropriately depending on the viscosity, but an E-type viscometer (RE-85R manufactured by Toki Sangyo Co., Ltd.) is preferably used, for example.

[0065] The amount of component (A-4) is typically in the range of 1 to 200 parts by weight per 100 parts by weight of the total of components (A-1), (A-2), and (A-3), preferably 5 to 100 parts by weight, and particularly preferably 10 to 70 parts by weight. If the amount is 200 parts by weight or less, the mechanical strength of the cured product and the adhesion between the substrate (circuited board) and the support are not excessively reduced, allowing the circuited board to be stably held on the support during backside processing and thermal processing. If the amount is 1 part by weight or more, it is possible to more reliably adjust the peel force and select the peel interface, thereby suppressing the generation of residue on the substrate after peeling the temporary adhesive layer.

[0066] Ingredient (A-5) Component (A-5) is a platinum catalyst (i.e., a platinum group metal catalyst) that promotes the addition reaction between components (A-1), (A-2), and (A-3). Examples of such catalysts include chloroplatinic acid, alcohol solutions of chloroplatinic acid, reaction products of chloroplatinic acid and alcohol, reaction products of chloroplatinic acid and olefin compounds, and reaction products of chloroplatinic acid and vinyl group-containing siloxanes.

[0067] The amount of component (A-5) added is an effective amount, typically 1 to 500 ppm, preferably 2 to 100 ppm, of platinum group metal (by mass) relative to the total of components (A-1), (A-2), and (A-3). A content of 1 ppm or more does not impair the curability of the silicone temporary adhesive composition, nor does it lower the crosslink density or the holding power. Furthermore, a content of less than 500 ppm facilitates control so as to obtain a long pot life and shelf life of the pre-cured composition. This is also preferred because it also leads to suppression of foaming during heat curing and during the heat-resistance process of the cured product.

[0068] Ingredient (A-6) Component (A-6) is an organic solvent. The thermosetting siloxane polymer (A) is formed on a substrate by spin coating or other methods using a solution of the pre-cured composition (i.e., a solution of the thermosetting siloxane polymer composition for processing circuit-equipped boards of the present invention). When forming the polymer layer (A) on a substrate by spin coating or other methods, it is preferable to coat the resin as a solution. The organic solvent used here is not particularly limited as long as it is capable of dissolving components (A-1) to (A-5) and (A-7). Preferred examples include hydrocarbon solvents such as pentane, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene, xylene, mesitylene, isooctane, nonane, decane, p-menthane, pinene, isododecane, and limonene, as well as silicone solvents. The solvent content is 10 to 900 parts by mass, preferably 25 to 400 parts by mass, and more preferably 40 to 300 parts by mass, per 100 parts by mass of the resin. In particular, the nonvolatile components in the composition may be contained in an amount of 10 to 90 wt %.

[0069] Ingredient (A-7) Component (A-7) is a reaction inhibitor that is optionally added as needed to prevent thickening or gelation of the pre-cure composition solution when the silicone temporary adhesive composition is formulated or applied to a substrate.

[0070] Specific examples include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynylcyclohexyl. 3-Methyl-3-trimethylsiloxy-1-butyne, 3-Methyl-3-trimethylsiloxy-1-butyne Siloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne , 1-ethynyl-1-trimethylsiloxycyclohexane, bis(2,2-dimethyl-3 -butynoxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetramethyl Vinylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane Siloxanes and the like are exemplified, and preferred are 1-ethynylcyclohexanol and 3-methylcyclohexanol. It is 1-butyn-3-ol.

[0071] The amount of component (A-7) added is usually 0.1 to 1,000 mol equivalents, preferably 1 to 500 mol equivalents, relative to the metal atoms of the platinum catalyst of component (A-5). An amount within this range is preferred because it does not affect curability and improves storage stability such as pot life and shelf life.

[0072] Furthermore, known antioxidants such as phenolic, quinone, and amine antioxidants can be added to the composition of polymer (A) (the thermosetting siloxane polymer composition for processing circuitized boards of the present invention) to improve heat resistance.Furthermore, fillers such as silica can be added to further increase physical hardness and mechanical strength.

[0073] The thermosetting siloxane polymer (A) is preferably used in a thickness between 10 and 150 μm. A thickness of 10 μm or more is less likely to result in voids or the like at the adhesive interface between the polymer (A) layer and the surface of the support and the circuit-mounted substrate when the support and the circuit-mounted substrate are integrally formed into a laminate. Furthermore, the thickness of the integrally formed laminate can be made more uniform, which allows the polymer (A) to withstand the grinding process used to thin the circuit-mounted substrate. This is also preferred because it allows application to circuit-mounted substrates with large steps. Furthermore, a thickness of 150 μm or less of the polymer (A) layer is preferred because it is less likely to cause resin deformation during heat treatment processes such as the TSV formation process, ensuring practical use.

[0074] The thermosetting siloxane polymer composition for processing circuitized boards of the present invention (thermosetting siloxane polymer (A) composition) preferably has an initial viscosity at 25°C of 500 to 100,000 mPa·s, more preferably 1,000 to 10,000 mPa·s, from the viewpoint of coatability. A viscosity of 100 mPa·s or more is preferred because it is easy to obtain the above-mentioned film thickness, while a viscosity of 100,000 mPa·s or less is preferred from the viewpoint of workability, because it allows the use of a dispensing device.

[0075] Furthermore, it is preferable that the increase in viscosity at 25°C after storage at 40°C for 7 days in a sealed container be 20% or less; if it is 20% or less, it can be considered to have sufficient storage stability. If this viscosity increase rate is 20% or less, it is preferable that thickening does not progress during use at room temperature, for example, and the initially set film thickness is easily maintained. Note that the initial viscosity at 25°C and the viscosity at 25°C after storage at 40°C for 7 days in a sealed container were measured in accordance with JIS Z 8803 using an E-type viscometer (RE-85R, manufactured by Toki Sangyo Co., Ltd.) at 25°C.

[0076] Furthermore, when the thermosetting siloxane polymer composition for processing circuitized boards of the present invention (thermosetting siloxane polymer (A) composition) is used as a temporary adhesive layer, it preferably has the following properties. In particular, it is preferable that the composition satisfies all of these properties.

[0077] First, it is preferable that the thermosetting siloxane polymer composition be formed into a film on a circuit board (particularly a silicon substrate), and the peel force (R1) when peeling the film from the circuit board after curing is 10 gf / 25 mm or more in a 180° peel test at 23°C.

[0078] Furthermore, the peel force (R2) when peeling the cured thermosetting siloxane polymer composition from a support (i.e., a support to which a circuit board is to be bonded via a cured product of the thermosetting siloxane polymer composition) from the support is preferably 10 gf / 25 mm or more in a peel test in a 180° direction at 23°C.

[0079] Furthermore, when the thermosetting siloxane polymer composition is formed into a film on a circuit board, it is preferable that R1 / R2≦1.0, and when the thermosetting siloxane polymer composition is formed into a film on a support, it is preferable that R1 / R2≧1.0.

[0080] When the peel strength (R1) on the circuitized substrate side and the peel strength (R2) on the support side satisfy the above relationship, the support can be peeled from the laminate with a low peel strength, and the peel interface can be made selective, which is preferable because when a film is formed on the circuitized substrate, residue of the temporary adhesive layer is less likely to remain.Furthermore, even when a film is formed on the support, it is possible to make the peel interface selective.

[0081] Furthermore, the thermosetting siloxane polymer composition for processing circuitized boards (thermosetting siloxane polymer (A) composition) of the present invention preferably has a light transmittance of 50% or less at a wavelength of 265 nm when the solution is prepared so that the nonvolatile components are 5% by mass. This solution can be prepared by diluting it with a solvent that does not contain an aryl group, as necessary.

[0082] If the transmittance of the thermosetting siloxane polymer composition for processing circuitized boards of the present invention (thermosetting siloxane polymer (A) composition) is within this range, the effects of the present invention can be easily achieved, which is preferable. That is, in the case of a circuitized board, it becomes possible to peel the support from the laminate with low peeling force and selectively at the interface. Furthermore, when applied to a circuitized board having metal pads on its surface, it becomes possible to suppress oxidative degradation of the metal pads even if the laminate is subjected to a heat-resistant process after formation.

[0083] -Optional ingredients- The temporary adhesive layer used in the present invention can contain any component depending on the purpose, such as a triazole-based or benzophenone-based light stabilizer, a halogen-based or antimony-based flame retardant, or an antistatic agent such as a cationic surfactant, an anionic surfactant, or a nonionic surfactant.

[0084] <Method of manufacturing a circuitized substrate laminate and a thin circuitized substrate> The method for producing a circuitized substrate laminate and a method for producing a thin circuitized substrate of the present invention are methods for producing a laminate of a circuitized substrate, a temporary adhesive layer, and a support using the thermosetting siloxane polymer composition for processing circuitized substrates of the present invention (thermosetting siloxane polymer (A) composition) in a temporary adhesive layer, and are methods for producing a thin circuitized substrate by subjecting the circuitized substrate fixed on the support to various processes including thinning the substrate, and removing only the thinned circuitized substrate after processing is completed. The thickness of the thinned circuitized substrate obtained by the method for processing a circuitized substrate of the present invention is typically 5 to 300 μm, more typically 10 to 100 μm.

[0085] The method for producing a circuit-equipped substrate laminate of the present invention comprises the steps of: (a) forming a temporary adhesive layer by spin coating the thermosetting siloxane polymer composition for processing a circuitized substrate of the present invention on the surface of a circuitized substrate having a circuit surface on the front surface and a back surface to be processed, and pre-baking the composition; (b) bonding a support and the circuit-forming surface of the circuit-equipped board on which the temporary adhesive layer is formed under heat and reduced pressure to produce a circuit-equipped board processed body; (c) heating the circuitized substrate body to harden the temporary adhesive layer; a process comprising: Or in another aspect, (g) forming a film of the thermosetting siloxane polymer composition for processing circuitized substrates of the present invention on a support by spin coating and pre-baking to form a temporary adhesive layer; (h) bonding a circuit-equipped board having a circuit surface on its front surface and a back surface to be processed under heat and reduced pressure so that the front surface is in contact with the temporary adhesive layer, thereby producing a circuit-equipped board processed body; (i) heating the circuitized board processed body to harden the temporary adhesive layer; The method is obtained by any of the processes comprising:

[0086] The method for producing a thin circuit board of the present invention further comprises the steps of: (d) grinding and / or polishing the rear surfaces of the circuit-equipped substrates in the circuit-equipped substrate laminate manufactured by the method for manufacturing a circuit-equipped substrate laminate that has undergone the steps (a), (b), and (c); (e) further processing the back surface of the circuitized board; (f) peeling the circuitized board laminate from the interface between the surface of the circuitized board and the temporary adhesive layer, separating the support body and the temporary adhesive layer together, and removing only the circuitized board; Or in another embodiment, the product is obtained by a process comprising: (j) grinding and / or polishing the rear surfaces of the circuit-equipped substrates in the circuit-equipped substrate laminate manufactured by the method for manufacturing a circuit-equipped substrate laminate that has undergone the steps (g), (h), and (i); (k) further processing the back surface of the circuitized board; (l) peeling the circuitized substrate laminate from the interface between the support and the temporary adhesive layer to separate the support; (m) removing the temporary adhesive layer from the circuitized board and taking out only the circuitized board; The method is obtained by any of the processes comprising:

[0087] The present invention also provides a circuitized substrate laminate and a thin circuitized substrate obtained by these manufacturing methods.

[0088] [Process (a)] Step (a) involves spin-coating the thermosetting siloxane polymer composition for processing circuitized substrates (thermosetting siloxane polymer (A) composition) of the present invention onto the circuit-formed surface of a circuitized substrate having a circuit-formed surface on the front side and a non-circuit-formed surface on the back side, followed by laminating a temporary adhesive layer. When the thermosetting siloxane polymer composition for processing circuitized substrates contains an organic solvent component (A-6), the spin-coating may be followed by pre-baking at a temperature of 50 to 200°C, depending on the volatilization conditions of the solvent. Pre-baking may be performed using either an oven or a hot plate. In the case of a hot plate, the circuitized substrate may be placed in contact with the hot plate and heated, or the support may be placed in contact with the hot plate and heated. The hot plate used may have a heater on only one side of the laminate, or a heater on both sides of the laminate. Any type of heating mechanism may be used. When using a hot plate with heaters on both sides, a temperature difference between the two heaters may or may not be provided.

[0089] [Step (b)] Step (b) is a step of laminating a support on the polymer (A) layer formed on the surface of the circuit-mounted substrate in step (a) and bonding the support and the circuit-mounted substrate via the polymer (A) layer. The process is performed at a temperature of 10 to 200°C, preferably 40 to 150°C, under reduced pressure (particularly under vacuum), and uniformly press-bonding the circuit-mounted substrate and the support, thereby forming a processed circuit-mounted substrate in which the support and the circuit-mounted substrate are bonded via the temporary adhesive layer. Examples of wafer bonding devices for forming the processed circuit-mounted substrate include commercially available wafer bonding devices such as EVG's EVG520IS and 850TB, SUSS's XBC300, and Tokyo Electron's SynapseV. In this series of bonding steps, the circuit-mounted substrate, the support, and the laminated substrate are uniformly heat-treated in a reduced-pressure chamber.

[0090] [Process (c)] Step (c) is a step of thermally curing the polymer (A). After the circuit-equipped substrate processed body is formed, the polymer layer (A) is cured by heating at 60 to 250°C, preferably 80 to 200°C, for 2 minutes to 4 hours, preferably 3 minutes to 1 hour. In this case, if the circuit-equipped substrate processed body is heated directly at a temperature above 150°C, warping may occur and become fixed in the processed body. To prevent warping, a two-stage heating process may be performed, for example, by heating at 60 to 150°C for 1 to 30 minutes and then heating at 170 to 250°C for 5 minutes to 4 hours. In this curing process, heating may be performed using either an oven or a hot plate. In the case of a hot plate, heating may be performed with the circuit-equipped substrate side facing the hot plate, or with the support side facing the hot plate. This is because the peel interface of the thermosetting siloxane polymer (A) composition of the present invention is not affected whether it is heated from the circuit-equipped substrate side or the support side. Therefore, when using a hot plate, any heating specification type can be used, whether it is a type with a heater installed only on the side where the laminate is placed, or a type with heaters installed on both sides of the laminate. When using a hot plate with heaters installed on both sides, it is not necessary to create a temperature difference between the two heaters.

[0091] By carrying out steps (a) to (c), a circuit-equipped substrate laminate can be produced.

[0092] [Step (d)] Step (d) is a step of grinding or polishing the back surface (non-circuit-forming surface) of the circuit-mounted substrate bonded to the support, i.e., a step of grinding or polishing the back surface of the circuit-mounted substrate of the circuit-mounted substrate laminate produced by steps (a) to (c) to reduce the thickness of the circuit-mounted substrate. There are no particular limitations on the method for grinding the back surface of the circuit-mounted substrate, and any known grinding method can be used. Grinding is preferably performed while cooling the circuit-mounted substrate and grinding stone (diamond, etc.) by spraying water on them. Examples of devices for grinding the back surface of the circuit-mounted substrate include the DAG-810 manufactured by Disco Corporation and the TSV300 (product name) manufactured by Okamoto Machine Tools Works, Ltd. Furthermore, the back surface of the circuit-mounted substrate after grinding may be polished by CMP.

[0093] [Step (e)] Step (e) is a process of further processing the back surface (non-circuit surface) of the circuit-equipped substrate processed body after grinding the non-circuit surface, i.e., the circuit-equipped substrate processed body thinned by back grinding or back polishing. This process includes various processes used at the wafer level. Examples include electrode formation, metal wiring formation, and protective film formation. More specifically, this process includes conventionally known processes such as metal sputtering for forming electrodes, wet etching of the metal sputtered layer, pattern formation by applying, exposing, and developing a resist to serve as a mask for metal wiring formation, resist stripping, dry etching, metal plating, silicon etching for TSV formation, and oxide film formation on the silicon surface. Additionally, the back-ground and thinned wafer can be cut into chip size by a method such as dicing.

[0094] [Process (f)] Step (f) is a step of separating the support from the circuit-equipped substrate processed in step (e), i.e., a step of separating the support from the circuit-equipped substrate processed body after various processes have been performed on the thinned circuit-equipped substrate. This step is generally carried out under conditions of about 10° C. to 100° C., and examples of such a step include a method in which one of the circuit-equipped substrate or the support of the circuit-equipped substrate processed body is fixed horizontally and the other is lifted at a certain angle from the horizontal direction, and a method in which a protective film is attached to the ground surface of the ground circuit-equipped substrate and the circuit-equipped substrate, polymer (A) layer, and protective film are peeled off together from the circuit-equipped substrate processed body by a peel method.

[0095] Although any of these peeling methods can be applied to the present invention, a more suitable method is to fix the circuit-mounted board of the circuit-mounted board processed body horizontally and lift the support at a certain angle from the horizontal. These peeling methods are usually carried out at room temperature. The step (f) of separating the support from the processed circuit-equipped board body includes: (f-1) A process of adhering dicing tape to the processed surface of the processed circuit board (f-2) A process of vacuum-adsorbing the dicing tape surface onto the adsorption surface (f-3) peeling the support from the processed circuit-equipped substrate body by peeling off while the temperature of the suction surface is in the range of 10° C. to 100° C. By doing so, the support can be easily peeled from the processed circuit-equipped substrate body, and the subsequent dicing step can be easily performed.

[0096] [Process (g)] In the above step (a), the thermosetting siloxane polymer composition for processing a circuitized board of the present invention (thermosetting siloxane polymer (A) composition) was formed as a film on a circuitized board, but in step (g), this is changed to a process in which the film is formed on a support. In other words, the only difference is the surface on which the film is formed, and the rest can be carried out in the same manner as step (a).

[0097] [Process (h)] Step (h) is a step of laminating the circuit-formed surface of a circuit-equipped substrate having a circuit-formed surface on the front surface and a non-circuit-formed surface on the back surface of the polymer (A) layer formed on the support in step (g), and bonding the support and the circuit-equipped substrate via the polymer (A) layer. The circuit-equipped substrate and the support are uniformly pressure-bonded together under reduced pressure (particularly under vacuum) at a temperature range of 10 to 200 ° C, preferably 40 to 150 ° C, to form a processed circuit-equipped substrate in which the support and the circuit-equipped substrate are bonded via the temporary adhesive layer. Examples of wafer bonding devices for forming the processed circuit-equipped substrate include commercially available wafer bonding devices such as EVG's EVG520IS and 850TB, SUSS's XBC300, and Tokyo Electron's SynapseV. In this series of bonding steps, the circuit-equipped substrate, the support, and the laminated laminate are uniformly heat-treated in a reduced-pressure chamber.

[0098] [Process (i)] Step (i) is a step of thermally curing the polymer (A), and can be carried out in the same manner as step (c).

[0099] By steps (g) to (i), a circuit-equipped substrate laminate can be produced.

[0100] [Process (j)] Step (j) is a step of grinding or polishing the back surface (non-circuit surface) of the circuit-equipped board bonded to the support, i.e., a step of grinding or polishing the back surface side of the circuit-equipped board of the circuit-equipped board laminate produced in steps (g) to (i) to reduce the thickness of the circuit-equipped board. This step (j) can be performed in the same manner as step (d).

[0101] [Process (k)] Step (k) is a step of further processing the back surface (non-circuit surface) of the circuit-equipped substrate processed body whose non-circuit surface has been ground, i.e., the circuit-equipped substrate processed body thinned by back grinding or back polishing. This step (k) can be performed in the same manner as step (e).

[0102] [Process (l)] Step (l) is a step of separating the support from the circuit-equipped substrate processed in step (k), i.e., a step of separating the support from the circuit-equipped substrate processed body after various processes have been performed on the thinned circuit-equipped substrate. This step is generally carried out under conditions of about 10°C to 100°C, and examples of such a step include a method in which one of the circuit-equipped substrate or the support of the circuit-equipped substrate processed body is fixed horizontally and the other is lifted at a certain angle from the horizontal direction, and a method in which a protective film is attached to the ground surface of the ground circuit-equipped substrate and the circuit-equipped substrate, polymer (A) layer, and protective film are peeled off together from the circuit-equipped substrate processed body by a peel method.

[0103] Although any of these peeling methods can be applied to the present invention, a more suitable method is to fix the circuit-mounted board of the circuit-mounted board processed body horizontally and lift the support at a certain angle from the horizontal. These peeling methods are usually carried out at room temperature. The step (l) of separating the support from the processed circuit-equipped board body includes: (l-1) A process of adhering dicing tape to the processed surface of the processed circuit board (l-2) A process of vacuum adsorbing the dicing tape surface onto the adsorption surface (l-3) peeling the support from the processed circuit-equipped board body by peeling it off while the temperature of the suction surface is in the range of 10° C. to 100° C. By doing so, the support can be easily peeled from the processed circuit-equipped board body, and the subsequent dicing step can be easily performed.

[0104] [Process (m)] Step (m) is a step of separating the cured film of the polymer (A) layer from the circuit-equipped substrate processed body from which the support has been separated, and taking out only the circuit-equipped substrate. Methods for separating the cured film of the polymer (A) layer include, for example, a tape peeling method, a method in which the cured film is immersed in a solvent to swell it and then removed by suction together with the solvent, and a method in which the cured film is washed off with a cleaning liquid that can decompose and clean it, and these methods may be performed in combination.

[0105] Among the methods for separating the cured film of the polymer (A) layer, the tape peeling method is the simplest and most cost-effective. This tape peeling process is generally carried out at temperatures of about 10°C to 100°C. The circuit-equipped substrate is fixed horizontally, a peeling tape is applied to the exposed polymer (A) layer, and the tape is peeled off by peeling, thereby peeling the cured film of the polymer (A) layer from the processed circuit-equipped substrate. Any tape material can be used as long as it is releasable, but tapes using silicone adhesives are particularly preferred. For example, polyester film adhesive tapes No. 646S and No. 648 manufactured by Teraoka Seisakusho Co., Ltd. are preferably used.

[0106] In the method of removing the cured film of the polymer (A) layer by decomposition and cleaning, the cleaning solution used may suitably be, for example, SPIS-TA-CLEANER series (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0107] [Process (n)] Furthermore, after performing step (f) or step (m) to separate only the circuit-mounted board from the circuit-mounted board processed body, (n) a step of cleaning the surface of the circuit-mounted board can be performed. The cleaning treatment can be performed by a wet process using an organic solvent, an alkaline solution, an acid solution, or the like, or a dry process such as dry etching.

[0108] In step (n), for example, an organic solvent can be used. Specific examples include hydrocarbon organic solvents such as pentane, hexane, cyclohexane, decane, isononane, p-menthane, pinene, isododecane, limonene, toluene, xylene, and mesitylene; polar solvents such as dimethyl sulfoxide, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, cyclopentanone, cyclohexanone, acetone, and tetrahydrofuran; and alcoholic solvents such as methanol, ethanol, isopropyl alcohol, and butanol. However, the solvent is not limited to these, as long as it is capable of being used for cleaning. These solvents may be used alone or in combination of two or more. Furthermore, to further improve cleaning properties, bases or acids may be added to the solvent. Examples of bases that can be used include amines such as ethanolamine, diethanolamine, triethanolamine, triethylamine, and ammonia; ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; and hydrofluoric acids of the above ammonium salts. Examples of acids that can be used include organic acids such as acetic acid, oxalic acid, benzenesulfonic acid, and dodecylbenzenesulfonic acid. The amount of the additive, expressed as a concentration in the cleaning solution, is 0.01 to 40% by mass, preferably 0.1 to 15% by mass. To improve the removability of residual materials, a conventional surfactant may be added. Possible cleaning methods include paddle cleaning using the above solution, spray cleaning, and immersion in a cleaning solution bath. The cleaning temperature is preferably 10 to 80°C, preferably 15 to 65°C. If necessary, after cleaning with these cleaning solutions, a final rinse with pure water or alcohol and drying treatment can be performed to obtain a thin wafer. [Example]

[0109] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0110] [Preparation Example 1] A solution consisting of 10 parts by mass of a polydimethylsiloxane (component (A-2)) terminated with vinyl groups at both ends, having a number average molecular weight (Mn) of 300,000, a phenyl group content of 0.125 mol / 100 g, an alkenyl group content of 0.0255 mol / 100 g, and 20 parts by mass of xylene, and SiO 4 / 2 Units (Q units) 50 mol%, (CH3)3SiO 1 / 2 Units (M units) 48 mol% and (CH2=CH)(CH3)2SiO 1 / 2 A solution consisting of 90 parts by mass of methylvinylsiloxane (component (A-1)) having a resin structure with an alkenyl group content of 0.0282 mol / 100 g and an Mn of 7,000, consisting of 2 mol% units (Vi units), and 180 parts by mass of xylene; a solution consisting of 20 parts by mass of dimethylpolysiloxane (component (A-4)) having a viscosity of 10,000 mPa s in a 30% toluene solution at 25°C, and 40 parts by mass of xylene; and (CH3)HSiO 2 / 2 Unit (D H 20 parts by mass of an organohydrogenpolysiloxane (component (A-3)) with a SiH group content of 0.209 mol / 100 g (expressed as 16.1 mol%) and an Mn of 2,400 were added and mixed with 0.5 parts by mass of ethynylcyclohexanol. 0.2 parts by mass of platinum catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd.) (component (A-5)) was then added, and the mixture was filtered through a 0.2 μm membrane filter to obtain a thermosetting silicone polymer solution (A1). The nonvolatile content was 54.0%, and the molar ratio of the organohydrogenpolysiloxane containing Si-H groups to the alkenyl groups in the organopolysiloxane containing alkenyl groups in the resin solution was 1.5.

[0111] [Preparation Example 2] A solution consisting of 20 parts by mass of a polydimethylsiloxane (component (A-2)) terminated with vinyl groups at both ends, having a number average molecular weight (Mn) of 300,000, a phenyl group content of 0.0265 mol / 100 g, an alkenyl group content of 0.0271 mol / 100 g, and 40 parts by mass of xylene, and SiO 4 / 2 Units (Q units) 50 mol%, (CH3)3SiO 1 / 2 Units (M units) 48 mol% and (CH2=CH)(CH3)2SiO 1 / 2A solution consisting of 80 parts by mass of methylvinylsiloxane (component (A-1)) having a resin structure with an alkenyl group content of 0.0282 mol / 100 g and an Mn of 7,000, consisting of 2 mol% units (Vi units), and 160 parts by mass of xylene; a solution consisting of 10 parts by mass of dimethylpolysiloxane (component (A-4)) having a viscosity of 1,000 mPa·s at 25°C in a 30% toluene solution, and 20 parts by mass of xylene; and (CH3)HSiO 2 / 2 Unit (D H 20 parts by mass of an organohydrogenpolysiloxane (component (A-4)) with a SiH group content of 0.209 mol / 100 g (expressed as 16.1 mol%) and an Mn of 2,400 were added and mixed with 0.5 parts by mass of ethynylcyclohexanol (component (A-7)). 0.2 parts by mass of platinum catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd.) (component (A-5)) was then added, and the mixture was filtered through a 0.2 μm membrane filter to obtain a thermosetting silicone polymer solution (A2). The nonvolatile content was 54.3%, and the molar ratio of the organohydrogenpolysiloxane containing Si-H groups to the alkenyl groups in the organopolysiloxane containing alkenyl groups in the resin solution was 1.5.

[0112] [Preparation Example 3] A solution consisting of 5 parts by mass of a polydimethylsiloxane (component (A-2)) terminated with vinyl at both ends, having a phenyl group content of 0.125 mol / 100 g, an alkenyl group content of 0.0255 mol / 100 g, a number average molecular weight (Mn) of 300,000, and 10 parts by mass of xylene, and SiO 4 / 2 Units (Q units) 50 mol%, (CH3)3SiO 1 / 2 Units (M units) 48 mol% and (CH2=CH)(CH3)2SiO 1 / 2 A solution consisting of 90 parts by mass of methylvinylsiloxane (component (A-1)) having a resin structure with an alkenyl group content of 0.0282 mol / 100 g and Mn of 7,000, which is composed of 2 mol% of units (Vi units), and 180 parts by mass of xylene, and SiO 4 / 2 Units (Q units) 50 mol%, (CH3)3SiO 1 / 2 Units (M units) 40 mol%, (CH2=CH)(CH3)2SiO 1 / 2Units (Vi units) 5 mol% and (C6H5)(CH3)2SiO 1 / 2 A solution consisting of 5 parts by mass of methylphenylvinylsiloxane (component (A-2)) having a resin structure with a phenyl group content of 0.0673 mol / 100 g, an alkenyl group content of 0.0673 mol / 100 g, and an Mn of 7,000, consisting of 5 mol% units (Ph units), and 10 parts by mass of xylene; a solution consisting of 25 parts by mass of dimethylpolysiloxane (component (A-4)) having a viscosity of 10,000 mPa s in a 30% toluene solution at 25°C, and 50 parts by mass of xylene; and (CH3)HSiO 2 / 2 Unit (D H 25 parts by mass of an organohydrogenpolysiloxane (component (A-3)) with a SiH group content of 0.209 mol / 100 g (expressed as 16.1 mol%) and an Mn of 2,400 were added and mixed with 0.5 parts by mass of ethynylcyclohexanol. 0.2 parts by mass of platinum catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd.) (component (A-5)) was then added, and the mixture was filtered through a 0.2 μm membrane filter to obtain a thermosetting silicone polymer solution (A3). The nonvolatile content was 54.7%, and the molar ratio of the organohydrogenpolysiloxane containing Si-H groups to the alkenyl groups in the organopolysiloxane containing alkenyl groups in the resin solution was 1.7.

[0113] [Preparation Example 4] A solution consisting of 20 parts by mass of a polydimethylsiloxane (component (A-2)) terminated with vinyl groups at both ends, having a number average molecular weight (Mn) of 300,000, a phenyl group content of 0.0265 mol / 100 g, an alkenyl group content of 0.0271 mol / 100 g, and 40 parts by mass of xylene, and SiO 4 / 2 Units (Q units) 50 mol%, (CH3)3SiO 1 / 2 Units (M units) 48 mol% and (CH2=CH)(CH3)2SiO 1 / 2 A solution consisting of 65 parts by mass of methylvinylsiloxane (component (A-1)) having a resin structure with an alkenyl group content of 0.0282 mol / 100 g and Mn of 7,000, which is composed of 2 mol% of units (Vi units), and 130 parts by mass of xylene, and SiO 4 / 2 Units (Q units) 50 mol%, (CH3)3SiO 1 / 2Units (M units) 25 mol%, (CH2=CH)(CH3)2SiO 1 / 2 Units (Vi units) 5 mol% and (C6H5)(CH3)2SiO 1 / 2 A solution consisting of 15 parts by mass of methylphenylvinylsiloxane (component (A-2)) having a resin structure with a phenyl group content of 0.239 mol / 100 g, an alkenyl group content of 0.0598 mol / 100 g, and an Mn of 8,000, consisting of 20 mol% units (Ph units), and 30 parts by mass of xylene; a solution consisting of 10 parts by mass of dimethylpolysiloxane (component (A-4)) having a viscosity of 1,000 mPa·s at 25°C in a 30% toluene solution, and 20 parts by mass of xylene; and (CH3)HSiO 2 / 2 Unit (D H 15 parts by mass of an organohydrogenpolysiloxane (component (A-3)) with a SiH group content of 0.209 mol / 100 g (expressed as 16.1 mol%) and an Mn of 2,400 were added and mixed with 0.5 parts by mass of ethynylcyclohexanol (component (A-7)). 0.2 parts by mass of platinum catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd.) (component (A-5)) was then added, and the mixture was filtered through a 0.2 μm membrane filter to obtain a thermosetting silicone polymer solution (A4). The nonvolatile content was 53.3%, and the molar ratio of the organohydrogenpolysiloxane containing Si-H groups to the alkenyl groups in the organopolysiloxane containing alkenyl groups in the resin solution was 0.96.

[0114] [Comparative Preparation Example 1] A solution consisting of 15 parts by mass of a polydimethylsiloxane (component (A-1)) having an alkenyl group content in the molecular side chains of 0.00337 mol / 100 g and a number average molecular weight (Mn) of 300,000 vinyl terminated at both ends, and 30 parts by mass of xylene, and SiO 4 / 2 Units (Q units) 50 mol%, (CH3)3SiO 1 / 2 Units (M units) 48 mol% and (CH2=CH)(CH3)2SiO 1 / 2A solution consisting of 85 parts by mass of methylvinylsiloxane (component (A-1)) having a resin structure with an alkenyl group content of 0.0282 mol / 100 g and an Mn of 7,000, consisting of 2 mol% units (Vi units), and 170 parts by mass of xylene; a solution consisting of 20 parts by mass of dimethylpolysiloxane (component (A-4)) having a viscosity of 10,000 mPa s in a 30% toluene solution at 25°C, and 40 parts by mass of xylene; and (CH3)HSiO 2 / 2 Unit (D H 20 parts by mass of an organohydrogenpolysiloxane (component (A-3)) with a SiH group content of 0.209 mol / 100 g (expressed as 16.1 mol%) and a Mn of 2,400 were added and mixed with 0.5 parts by mass of ethynylcyclohexanol (component (A-7)). 0.2 parts by mass of platinum catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd.) (component (A-5)) was then added, and the mixture was filtered through a 0.2 μm membrane filter to obtain a thermosetting silicone polymer solution (CA1). The nonvolatile content was 54.0%, and the molar ratio of the Si-H group-containing organohydrogenpolysiloxane to the alkenyl groups in the alkenyl group-containing organopolysiloxane in the resin solution was 1.7.

[0115] (Examples 1 to 4, Reference Example 1, Comparative Examples 1 and 2) -Viscosity measurement test- The initial viscosity of the resin at 25°C and the viscosity at 25°C after sealed storage at 40°C for 7 days were measured using an E-type viscometer (RE-85R manufactured by Toki Sangyo Co., Ltd.).

[0116] -Transmittance measurement test- The composition was adjusted so that the nonvolatile content was 5% by mass, and the transmittance at 265 nm was measured at 25° C. using an ultraviolet spectrophotometer (Shimadzu Corporation UV-3600i Plus).

[0117] -Heat resistance test using metal pad wafer- The thermosetting silicone polymer solutions (A1) to (A4) obtained from Preparation Examples 1 to 4 and the thermosetting silicone polymer solution (CA1) obtained from Comparative Preparation Example 1 were spin-coated onto a 300 mm diameter silicon wafer (725 μm thick) with copper pillars measuring 9 μm in height and 10 μm in diameter formed all over its surface. The resulting solution was then heated in an oven at 100 °C for 2 minutes to form a layer (A) on the wafer with the copper pillars. The resulting layer was preheated in an oven at 120 °C for 2 minutes and then heated in an oven at 200 °C for 10 minutes to cure the layer (A). The resulting layer was then heated in an oven at 220 °C for 10 minutes, cooled to room temperature, and the cured resin layer was washed with a cleaning solution. The copper pillars were then observed under an optical microscope to evaluate any change in appearance from the initial state. A case in which no change from the initial state was evaluated as good and indicated by a circle (○). A case in which the copper pillars discolored due to oxidative degradation was evaluated as poor and indicated by an x ​​(×).

[0118] -Adhesion test- The thermosetting silicone polymer solutions (A1) to (A4) obtained in Preparation Examples 1 to 4 and the thermosetting silicone polymer solution (CA1) obtained in Comparative Preparation Example 1 were spin-coated onto a 300 mm diameter silicon wafer (725 μm thick) with 9 μm high, 10 μm diameter copper posts formed on the entire surface of the circuitized substrate, or onto a 300 mm diameter bare silicon wafer. The wafer was then heated in an oven at 100°C for 2 minutes to form the material corresponding to Layer (A) with the film thickness shown in Tables 1 and 2. A 300 mm thick glass substrate (700 μm thick) was bonded to the substrate as a support in a vacuum using a Tokyo Electron Synapse V, facing the Layer (A) deposition surface, to produce a circuitized substrate (laminate). The bonding temperature was 70°C, the chamber pressure during bonding was 10 mbar or less, and the load was 10 kN. After bonding, the laminate was preheated in an oven at 120°C for 2 minutes, then heated in an oven at 200°C for 10 minutes to cure the (A) layer, and then cooled to room temperature. In a reference example, the wafer without the (A) layer was placed on a hot plate heated to 120°C and preheated for 2 minutes, and the wafer without the (A) layer was placed on a hot plate heated to 200°C and heated for 10 minutes to cure the (A) layer, and then cooled to room temperature. The adhesion at the interface was then visually inspected, and if no abnormalities such as bubbles were observed at the interface, it was evaluated as good and indicated by a "○." If abnormalities were observed, it was evaluated as poor and indicated by a "×."

[0119] -Back grinding resistance test- After the adhesion test, the backside of the circuit-equipped substrate was ground using a diamond grinding wheel on a grinder (TSV300 (product name) manufactured by Okamoto Machine Tools Works, Ltd.). After grinding to a final substrate thickness of 50 μm, the presence or absence of abnormalities such as cracks and peeling was examined using an optical microscope (100x magnification). If no abnormalities were found, the result was evaluated as good and indicated by "○", and if abnormalities were found, the result was evaluated as bad and indicated by "×".

[0120] -Heat resistance test- After the backside grindability test, the circuit-equipped board processed body was heated in an oven at 260°C for 10 minutes, and then visually inspected for any abnormalities in appearance. If no abnormalities in appearance were observed, it was evaluated as good and indicated by a "○", if slight distortion was observed in the circuit-equipped board but no abnormalities such as voids, swelling, or breakage were observed, it was evaluated as generally good and indicated by a "△", and if abnormalities in appearance such as voids, swelling, or breakage were observed, it was evaluated as poor and indicated by an "×".

[0121] - Peelability test - After the heat resistance test, dicing tape was applied to the ground surface (non-circuit surface) of the circuit-equipped substrate, which had been thinned to 50 μm, using a dicing frame. The glass substrate, which served as the support, was then lifted using a debonder (Tokyo Electron Synapse), and the glass substrate and layer (A) were peeled off together. Selective interfacial peeling without cracking the 50 μm wafer or tearing the layer (A) was indicated by a "○." Abnormalities such as wafer cracking or tearing of the layer (A) were evaluated as failure and indicated by a "×."

[0122] - Peel strength (R1) test - (evaluation of adhesion between substrate and temporary adhesive layer) The thermosetting silicone polymer solutions (A1) to (A4) obtained in Preparation Examples 1 to 4 and the thermosetting silicone polymer solution (CA1) obtained in Comparative Preparation Example 1 were spin-coated onto a 200 mm diameter silicon wafer (725 μm thick) and then heated in an oven at 100 °C for 2 minutes to form the material corresponding to layer (A) with the film thickness shown in Tables 1 and 2. A 200 mm glass substrate (700 μm thick) pre-coated with an LRL layer was bonded to the layer (A) facing surface in a vacuum using an EVG wafer bonding system (EVG520IS) to produce a silicon substrate laminate. The bonding temperature was 70 °C, the chamber pressure during bonding was 10 mbar or less, and the load was 10 kN. After bonding, the laminate was pre-heated in an oven at 120 °C for 2 minutes and then heated in an oven at 200 °C for 10 minutes to cure layer (A), and then cooled to room temperature. In Reference Example (RA3), the wafer without the (A3) layer was placed on a hot plate heated to 120°C and preheated for 2 minutes. The wafer without the (A3) layer was then placed on a hot plate heated to 200°C and heated for 10 minutes, curing the (A3) layer. The laminate was then cooled to room temperature. A UV laser was then irradiated from the support side to peel the glass substrate, yielding a peeled sample with a temporary adhesive layer laminated on a silicon substrate. Five strips of 150mm long x 25mm wide polyimide tape were then attached to the temporary adhesive layer on the silicon substrate, and the temporary adhesive layer was removed from the untaped areas. Using a Shimadzu Corporation AUTOGRAPH (AG-1) tool, the tape was peeled 120mm from one end at a 180° angle at 25°C and a speed of 300mm / min. The average force (120mm stroke x 5 times) applied at this time was recorded as the peel strength (R1) between the silicon substrate and the temporary adhesive layer.

[0123] - Peel strength (R2) test - (evaluation of adhesion between temporary adhesive layer and support) The thermosetting silicone polymer solutions (A1) to (A4) obtained in Preparation Examples 1 to 4 and the thermosetting silicone polymer solution (CA1) obtained in Comparative Preparation Example 1 were spin-coated onto a 200 mm diameter silicon wafer (725 μm thick) and then heated in an oven at 100 °C for 2 minutes to form the material corresponding to layer (A) with the film thickness shown in Table 1. A 200 mm diameter silicon wafer (725 μm thick) was bonded to the substrate facing the layer (A) using an EVG wafer bonding system (EVG520IS) in vacuum to produce a silicon substrate laminate. The bonding temperature was 70 °C, the chamber pressure during bonding was 10 mbar or less, and the load was 10 kN. After bonding, the laminate was preheated in an oven at 120 °C for 2 minutes and then heated in an oven at 200 °C for 10 minutes to cure layer (A), and then cooled to room temperature. In Reference Example (RA3), the wafer without the (A3) layer was placed on a hot plate heated to 120°C and preheated for 2 minutes. The wafer without the (A3) layer was then placed on a hot plate heated to 200°C and heated for 10 minutes, allowing the (A3) layer to harden. The laminate was then cooled to room temperature. At room temperature, a single point on the silicon substrate support was lifted with tweezers, allowing the silicon substrate support and the (A3) layer to be peeled together. This yielded a peel test sample with a temporary adhesive layer laminated on the silicon substrate support. Next, five strips of 150 mm long x 25 mm wide polyimide tape were attached to the temporary adhesive layer on the silicon substrate support, and the temporary adhesive layer was removed from the areas not covered by the tape. Using Shimadzu Corporation's AUTOGRAPH (AG-1), the tape was peeled off at a 180° angle from one end at a speed of 300 mm / min at 25°C for 120 mm, and the average force applied at this time (120 mm stroke × 5 times) was taken as the peel force (R2) between the silicon substrate support and the temporary adhesive layer.

[0124] The peel strengths R1, R2 and R1 / R2 obtained by the above test method are shown in Tables 1 and 2.

[0125] In Table 1, adhesion, back grindability, heat resistance, and debond force were evaluated using a 300 mm diameter silicon wafer.

[0126] In Table 2, adhesion, back grindability, heat resistance, and debond force were evaluated using a 300 mm diameter silicon wafer (thickness: 725 μm) with copper posts 9 μm high and 10 μm in diameter formed all over its surface.

[0127] [Table 1]

[0128] [Table 2]

[0129] As shown in Tables 1 and 2, Examples 1, 2, 3, and 4 and Reference Example 1 demonstrated satisfactory adhesion of the circuit-mounted substrate, backgrindability of the circuit-mounted substrate, and heat resistance and peelability of the processed circuit-mounted substrate. It was also found that the peeling surface selectively peeled at the interface between the circuit-mounted substrate surface and Layer A, regardless of the heated surface. Furthermore, it was confirmed that discoloration due to oxidation degradation during heat resistance testing of copper pillar wafers was also suppressed. On the other hand, in Comparative Examples 1 and 2, oxidation degradation progressed during the heat resistance test of the copper pillar wafer, and discoloration of the copper pillar was confirmed after the test. The debonding force also showed a high value, confirming the effect of reducing the debonding force in this example. Furthermore, a comparison of the peeling force on the substrate side and the support side showed that the peeling selectivity was inferior to that of this example.

[0130] Example 5 The thermosetting siloxane polymer (A) composition was spin-coated onto a support and evaluated.

[0131] -Adhesion test- The thermosetting silicone polymer solution (A3) obtained in Preparation Example 3 above was spin-coated onto a 300 mm glass substrate (thickness: 700 μm) as a support, and then heated in an oven at 100°C for 2 minutes to form the material corresponding to layer (A) with the film thickness shown in Table 3. A 300 mm diameter silicon wafer (thickness: 725 μm) with 9 μm high, 10 μm diameter copper posts formed on its entire surface was bonded to the circuitized substrate facing the layer (A) deposition surface in a vacuum using a Synapse V from Tokyo Electron, to produce a circuitized substrate processed body (laminate). Bonding was performed at a temperature of 70°C, with a chamber pressure of 10 mbar or less, and a load of 10 kN during bonding. After bonding, the laminate was preheated in an oven at 120°C for 2 minutes, and then heated in an oven at 200°C for 10 minutes to harden layer (A), and then cooled to room temperature.The adhesion condition at the interface was then visually inspected, and if no abnormalities such as air bubbles occurred at the interface, it was evaluated as good and indicated by "○", and if abnormalities occurred, it was evaluated as bad and indicated by "×".

[0132] The back grinding resistance and heat resistance tests were carried out under the same conditions as in the above examples.

[0133] - Peelability test - After the heat resistance test, dicing tape was applied to the ground surface (non-circuit surface) of the circuit-equipped substrate, which had been thinned to 50 μm, using a dicing frame. The glass substrate support was then lifted using a debonder (Tokyo Electron Synapse), allowing the glass substrate to be peeled off. A "○" indicates that the 50 μm wafer was not broken or that the (A) layer remained on the circuit-equipped substrate, allowing selective interfacial peeling. An "×" indicates that abnormalities such as wafer cracking or tearing of the (A) layer occurred, resulting in a failure.

[0134] - Peel strength (R1) test - (evaluation of adhesion between substrate and temporary adhesive layer) The thermosetting silicone polymer solution (A3) obtained in Preparation Example 3 above was spin-coated onto a 200 mm diameter silicon wafer (thickness: 725 μm) used as a support, followed by heating in an oven at 100 °C for 2 minutes to form the material corresponding to the (A) layer with the film thickness shown in Table 3. A 200 mm diameter silicon wafer (thickness: 725 μm) was then bonded in a vacuum using an EVG wafer bonding system (EVG520IS) so that it faced the (A) layer deposition surface, producing a silicon substrate laminate. The bonding temperature was 70 °C, the chamber pressure during bonding was 10 mbar or less, and the load was 10 kN. After bonding, the laminate was preheated in an oven at 120 °C for 2 minutes, then further heated in an oven at 200 °C for 10 minutes to cure the (A) layer, and then cooled to room temperature. Subsequently, at room temperature, a single point on the silicon substrate support was lifted with tweezers to obtain a peeled sample in which a temporary adhesive layer was laminated on a silicon substrate. Next, five pieces of polyimide tape, each 150 mm long and 25 mm wide, were attached to the temporary adhesive layer on the silicon substrate, and the temporary adhesive layer was removed from the areas where no tape was attached. Using an AUTOGRAPH (AG-1) from Shimadzu Corporation, the tape was peeled off at a 180° angle from one end at a speed of 300 mm / min at 25°C for 120 mm, and the average force applied at this time (120 mm stroke x 5 times) was taken as the peel force (R1) between the silicon substrate and the temporary adhesive layer.

[0135] - Peel strength (R2) test - (evaluation of adhesion between temporary adhesive layer and support) The thermosetting silicone polymer solution (A3) obtained in Preparation Example 3 above was spin-coated onto a 200 mm glass substrate (700 μm thick) as a support, followed by heating in an oven at 100°C for 2 minutes to form the material corresponding to layer (A) with the thickness shown in Table 3. A 200 mm glass substrate (700 μm thick) pre-coated with an LRL layer was bonded in a vacuum using an EVG520IS wafer bonding system from EVG, facing the layer (A) deposition surface, to produce a glass substrate laminate. The bonding temperature was 70°C, the chamber pressure during bonding was 10 mbar or less, and the load was 10 kN. After bonding, the laminate was preheated in an oven at 120°C for 2 minutes, then further heated in an oven at 200°C for 10 minutes to cure layer (A), and then cooled to room temperature. The glass substrate was peeled off using a UV laser from the glass wafer side coated with the LRL layer, yielding a peeled sample in which a temporary adhesive layer was laminated on the glass substrate. Next, five pieces of polyimide tape, each 150 mm long and 25 mm wide, were attached to the temporary adhesive layer on the glass substrate support, and the temporary adhesive layer was removed from the areas where no tape was attached. Using an AUTOGRAPH (AG-1) manufactured by Shimadzu Corporation, the tape was peeled off at a 180° angle from one end at a speed of 300 mm / min at 25°C for 120 mm, and the average force applied at this time (120 mm stroke x 5 times) was taken as the peel force (R2) between the glass substrate support and the temporary adhesive layer.

[0136] The peel strengths R1, R2 and R1 / R2 obtained by the above test method are shown in Table 3.

[0137] [Table 3]

[0138] As shown in Table 3, in Example 5, the adhesion of the circuit board, the backside grindability of the circuit board, the heat resistance of the circuit board processed body, and the peelability were all satisfactory, and it was also found that the peeling surface selectively peeled at the interface between the support substrate and Layer (A).

[0139] The present specification includes the following aspects. [1]: (A-1) an organopolysiloxane having two or more alkenyl groups and no aryl groups in one molecule; (A-2) an organopolysiloxane having two or more alkenyl groups and one or more aryl groups in one molecule; (A-3) an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms (Si-H groups) per molecule; (A-4) release additive, (A-5) platinum-based catalyst, Contains A thermosetting siloxane polymer composition for processing circuitized substrates, characterized in that the molar ratio of Si-H groups in component (A-3) to alkenyl groups in components (A-1) and (A-2) is 0.3 to 10. [2]: The thermosetting siloxane polymer composition for processing a circuitized board according to [1] above, wherein the thermosetting siloxane polymer composition has an initial viscosity of 500 mPa·s to 100,000 mPa·s, and exhibits a viscosity increase rate of 20% or less when stored in a sealed state at 40°C for 7 days. [3]: The thermosetting siloxane polymer composition for processing a circuitized board according to [1] or [2] above, wherein the component (A-4) is a thermoplastic dimethylpolysiloxane having a viscosity of 100 to 500,000 mPa·s in a 30% toluene solution at 25°C. [4]: the thermosetting siloxane polymer composition is a composition containing (A-6) an organic solvent, The thermosetting siloxane polymer composition for processing a circuitized board according to any one of [1] to [3] above, wherein the thermosetting siloxane polymer composition contains the component (A-6) in an amount such that the non-volatile components in the composition account for 10 to 90 wt %. [5]: The thermosetting siloxane polymer composition for processing a circuitized board according to any one of [1] to [4] above, wherein the thermosetting siloxane polymer composition contains (A-7) a reaction inhibitor. [6]: The thermosetting siloxane polymer composition is formed into a film on a circuit board, and after curing, the peel force (R1) when peeled from the circuit board is 10 gf / 25 mm or more in a 180° peel test at 23°C; and the peel force (R2) when peeling the circuitized board from a support to which the cured product of the thermosetting siloxane polymer composition formed on the support is to be bonded via the cured product of the thermosetting siloxane polymer composition after curing is 10 gf / 25 mm or more in a 180° peel test at 23°C; and When the film is formed on the circuit board, R1 / R2≦1.0. The thermosetting siloxane polymer composition for processing a circuitized board according to any one of [1] to [5] above, which satisfies R1 / R2≧1.0 when formed into a film on the support. [7]: The thermosetting siloxane polymer composition for processing a circuitized board according to any one of [1] to [6] above, wherein a solution of the thermosetting siloxane polymer composition prepared so that the non-volatile components are 5% by mass has a light transmittance of 50% or less at a wavelength of 265 nm. [8]: (a) forming a temporary adhesive layer by spin-coating any one of the thermosetting siloxane polymer compositions [1] to [7] on the surface of a circuit-equipped substrate having a circuit surface on the front surface and a back surface to be processed, and pre-baking the composition; (b) bonding a support and the circuit-forming surface of the circuit-equipped board on which the temporary adhesive layer is formed under heat and reduced pressure to produce a circuit-equipped board processed body; (c) heating the circuitized substrate body to harden the temporary adhesive layer; A method for manufacturing a circuit-equipped substrate laminate, comprising: [9]: (d) grinding and / or polishing the rear surfaces of the circuit-mounted substrates in the circuit-mounted substrate laminate manufactured by the method for manufacturing a circuit-mounted substrate laminate according to [8] above; (e) further processing the back surface of the circuitized board; (f) peeling the circuitized board laminate from the interface between the surface of the circuitized board and the temporary adhesive layer, separating the support body and the temporary adhesive layer together, and removing only the circuitized board; A method for manufacturing a thin circuit board, comprising:

[10] : (g) forming a film of the thermosetting siloxane polymer composition according to any one of [1] to [7] on a support by a spin coating method and pre-baking to form a temporary adhesive layer; (h) bonding a circuit-equipped board having a circuit surface on its front surface and a back surface to be processed under heat and reduced pressure so that the front surface is in contact with the temporary adhesive layer, thereby producing a circuit-equipped board processed body; (i) heating the circuitized board processed body to harden the temporary adhesive layer; A method for manufacturing a circuit-equipped substrate laminate, comprising:

[11] : (j) grinding and / or polishing the rear surfaces of the circuit-mounted substrates in the circuit-mounted substrate laminate manufactured by the method for manufacturing a circuit-mounted substrate laminate according to

[10] above; (k) further processing the back surface of the circuitized board; (l) peeling the circuitized substrate laminate from the interface between the support and the temporary adhesive layer to separate the support; (m) removing the temporary adhesive layer from the circuitized board and taking out only the circuitized board; A method for manufacturing a thin circuit board, comprising:

[0140] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. (A-1) an organopolysiloxane having two or more alkenyl groups and no aryl groups in one molecule; (A-2) an organopolysiloxane having two or more alkenyl groups and one or more aryl groups in one molecule; (A-3) an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms (Si—H groups) per molecule; (A-4) release additive, (A-5) platinum-based catalyst, Contains A thermosetting siloxane polymer composition for processing circuitized substrates, characterized in that the molar ratio of Si-H groups in component (A-3) to alkenyl groups in components (A-1) and (A-2) is 0.3 to 10.

2. 2. The thermosetting siloxane polymer composition for processing circuitized boards according to claim 1, wherein the thermosetting siloxane polymer composition has an initial viscosity at 25°C of 500 mPa·s to 100,000 mPa·s, and exhibits a viscosity increase rate at 25°C of 20% or less when stored in a sealed container at 40°C for 7 days.

3. 2. The thermosetting siloxane polymer composition for processing circuitized boards according to claim 1, wherein component (A-4) is a thermoplastic dimethylpolysiloxane having a viscosity of 100 to 500,000 mPa·s in a 30% toluene solution at 25°C.

4. the thermosetting siloxane polymer composition is a composition containing (A-6) an organic solvent, The thermosetting siloxane polymer composition for processing circuitized boards according to claim 1, characterized in that the thermosetting siloxane polymer composition contains the component (A-6) in an amount such that the nonvolatile components in the composition account for 10 to 90 wt %.

5. The thermosetting siloxane polymer composition for processing a circuitized board according to claim 1, characterized in that the thermosetting siloxane polymer composition is a composition containing (A-7) a reaction inhibitor.

6. The thermosetting siloxane polymer composition is formed into a film on a circuit board, and after curing, the peel force (R1) when peeled from the circuit board is 10 gf / 25 mm or more in a 180° peel test at 23°C; and the peel force (R2) when peeling the circuitized board from a support to which the cured product of the thermosetting siloxane polymer composition formed on the support is to be bonded via the cured product of the thermosetting siloxane polymer composition after curing is 10 gf / 25 mm or more in a 180° peel test at 23°C; and When the film is formed on the circuit board, R1 / R2≦1.

0.

2. The thermosetting siloxane polymer composition for processing circuitized boards according to claim 1, wherein when formed into a film on said support, R1 / R2 ≥ 1.

0.

7. 2. The thermosetting siloxane polymer composition for processing circuit-equipped boards according to claim 1, wherein a solution of the thermosetting siloxane polymer composition prepared so that the non-volatile components are 5% by mass has a light transmittance of 50% or less at a wavelength of 265 nm.

8. (a) forming a temporary adhesive layer by spin coating the thermosetting siloxane polymer composition according to any one of claims 1 to 7 on the surface of a circuit-equipped substrate having a circuit surface on the front surface and a back surface to be processed, and pre-baking the composition; (b) bonding a support and the circuit-forming surface of the circuit-equipped board on which the temporary adhesive layer is formed under heating and reduced pressure to produce a circuit-equipped board processed body; (c) heating the circuitized board processed body to harden the temporary adhesive layer; A method for manufacturing a circuit-equipped substrate laminate, comprising:

9. (d) grinding and / or polishing the rear surfaces of the circuit-mounted substrates in the circuit-mounted substrate laminate manufactured by the method for manufacturing a circuit-mounted substrate laminate according to claim 8; (e) further processing the back surface of the circuitized board; (f) peeling the circuitized board laminate from the interface between the surface of the circuitized board and the temporary adhesive layer, separating the support body and the temporary adhesive layer together, and removing only the circuitized board; A method for manufacturing a thin circuit board, comprising:

10. (g) forming a film of the thermosetting siloxane polymer composition according to any one of claims 1 to 7 on a support by a spin coating method and pre-baking to form a temporary adhesive layer; (h) bonding a circuit-equipped board having a circuit surface on its front surface and a back surface to be processed under heating and reduced pressure so that the front surface is in contact with the temporary adhesive layer, thereby producing a circuit-equipped board processed body; (i) heating the circuitized substrate processed body to harden the temporary adhesive layer; A method for manufacturing a circuit-equipped substrate laminate, comprising:

11. (j) grinding and / or polishing the rear surfaces of the circuit-mounted substrates in the circuit-mounted substrate laminate manufactured by the method for manufacturing a circuit-mounted substrate laminate according to claim 10; (k) further processing the back surface of the circuitized board; (l) peeling the circuitized substrate laminate from the interface between the support and the temporary adhesive layer, and separating the support; (m) removing the temporary adhesive layer from the circuitized board and taking out only the circuitized board; A method for manufacturing a thin circuit board, comprising:

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