Temporary adhesive containing silicone resin and method for processing circuit-equipped substrate

Abstract

The present invention is a temporary adhesive agent containing a silicone-based resin, which contains a silicone-based resin and temporarily bonds a semiconductor substrate and a support body, and is characterized in that: the temporary adhesive agent contains a silicone-based resin; the semiconductor substrate and the support body are bonded and heated at 260 DEG C for 2 hours through a temporary adhesive layer formed by the temporary adhesive, and then the semiconductor substrate and the support body are peeled off. And then dissolving the temporary adhesive layer remaining on the semiconductor substrate or the support in a dimethylpropionamide solution at 50 DEG C containing 3% by mass of tetrabutylammonium fluoride to measure the dissolution rate of the temporary adhesive layer formed from the temporary adhesive agent, wherein the dissolution rate is 20 [mu] m / min or more.

Description

Technical Field

[0001] This invention relates to a temporary adhesive containing silicone resin and a method for processing a substrate with circuitry. Background Technology

[0002] To achieve further high density and high capacity, three-dimensional semiconductor mounting is required. Three-dimensional mounting technology refers to the process of thinning a single semiconductor chip, further connecting it via through-silicon vias (TSVs), and simultaneously stacking multiple semiconductor layers. To achieve this, the substrate with the semiconductor circuitry formed needs to be thinned by grinding the non-circuit-forming surface (also known as the "back side"), followed by the formation of electrodes containing TSVs on the back side. Previously, during the back-side grinding process of the silicon substrate, a protective back-side tape was applied to the opposite side of the grinding surface to prevent wafer breakage during grinding. However, this tape, which uses an organic resin film to support the substrate, while flexible, lacks sufficient strength and heat resistance, making it unsuitable for TSV formation or back-side wiring layer formation processes.

[0003] Therefore, a system has been proposed that bonds a semiconductor substrate to a support such as silicon or glass using an adhesive layer, thereby enabling it to withstand back-side grinding, TSV, or back-side electrode formation processes. The adhesive layer used to bond the substrate to the support is crucial here. It needs to be able to bond the substrate to the support without gaps, possess sufficient durability to withstand only subsequent processes, and also allow for easy peeling of the thin wafer from the support at the end. Therefore, since it will be peeled off last, this adhesive layer is referred to as a temporary adhesive layer (or temporary bonding layer) in this specification.

[0004] To date, as a known temporary adhesive layer and its peeling method, a technique has been proposed that uses a thermally molten hydrocarbon compound as an adhesive to bond and peel the layers in a heated molten state (Patent Document 1). However, although this technique is relatively simple and can be controlled by heating alone, its thermal stability at high temperatures above 200°C is insufficient, thus limiting its applicability.

[0005] In addition, if exposed to high temperatures, the cleanability of the adhesive layer will decrease significantly due to thermal oxidation, which may sometimes lead to a decrease in cleaning speed or the generation of cleaning residue.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2003-177528 Summary of the Invention

[0009] (1) Technical issues to be resolved

[0010] The present invention was made in view of the above-mentioned problems, and provides a method for processing a substrate with circuitry and a temporary adhesive containing an organosilicon resin. The method for processing a substrate with circuitry and a temporary adhesive containing an organosilicon resin facilitates the bonding of the support and the substrate, can form a uniform film thickness on substrates with high step differences, has high process suitability for TSV formation and wafer back-side wiring processes, facilitates easy peeling of the substrate from the support, and can effectively remove the adhesive layer without contaminating the substrate, thereby improving the productivity of thin substrates.

[0011] (2) Technical solution

[0012] To solve the above-mentioned technical problems, the present invention provides a temporary adhesive containing an organosilicon resin. This temporary adhesive, containing an organosilicon resin, temporarily bonds a semiconductor substrate to a support. Its characteristic is that, after bonding the semiconductor substrate and the support together with a temporary adhesive layer formed by the temporary adhesive and heating at 260°C for 2 hours, the semiconductor substrate and the support are peeled off. Then, the temporary adhesive layer remaining on the semiconductor substrate or the support is dissolved in a 50°C dimethylpropionamide solution containing 3% by mass tetrabutylammonium fluoride. When measuring the dissolution rate of the temporary adhesive layer formed by the temporary adhesive, the dissolution rate is 20 μm / min or higher.

[0013] If the temporary adhesive contains silicone resin, its flexibility and excellent heat resistance make it suitable for a wide range of semiconductor film deposition processes. It also exhibits excellent CVD (chemical vapor deposition) resistance and can form a temporary adhesive layer with high film thickness uniformity even on wafers with stepped surfaces. This uniformity allows for the easy fabrication of uniform thin wafers with a thickness of 50 μm or less. Furthermore, after fabricating the thin wafer, the wafer self-support can be easily peeled off at, for example, room temperature. Additionally, if the temporary adhesive contains silicone resin with the aforementioned dissolution rate, the adhesive layer can be removed effectively without contaminating the substrate, thus improving the productivity of thin substrates.

[0014] At this point, it is preferable that the proportion of dimethylsiloxane units in the non-volatile component of the temporary adhesive containing organosilicon resin is 20% by mass or more.

[0015] By setting the proportion of dimethylsiloxane units in this way, the dissolution rate of the temporary adhesive layer formed by the temporary adhesive can be further improved.

[0016] Furthermore, the temporary adhesive containing organosilicon resin of the present invention preferably includes a heat resistance enhancer.

[0017] By including heat-resistant enhancers, temporary adhesives containing silicone resins can maintain a high dissolution rate in the solvent even after being subjected to high-temperature treatment.

[0018] Furthermore, the silicone resin is preferably a curable silicone resin, which is a composition containing the following components:

[0019] (A) An organopolysiloxane having two or more alkenyl groups in one molecule;

[0020] (B) Organohydropolysiloxanes containing two or more hydrogen atoms bonded to silicon atoms (Si-H groups) in one molecule, and

[0021] (C) Platinum-based catalysts,

[0022] And the amount contained is such that the molar ratio of Si-H groups in component (B) to alkenes in component (A) is 0.3 to 10.

[0023] By using such curable silicone resin as a temporary adhesive containing silicone resin, it is possible to further and effectively maintain the dissolution rate in the solvent after treatment at high temperatures.

[0024] Furthermore, it is preferable to use it in combination with a laser stripping agent when temporarily bonding the semiconductor substrate to the support.

[0025] If a temporary adhesive is formed in this way in combination with a laser stripping agent, laser-assisted stripping can be performed more easily.

[0026] Furthermore, the present invention provides a method for processing a substrate with circuitry, which is a method for processing a substrate with circuitry, characterized in that it includes:

[0027] (a) A process of preparing a laminate containing a substrate with circuitry as the semiconductor substrate and the support body, which is temporarily bonded by using a silicone resin layer containing a silicone resin temporary adhesive and a laser release layer using the laser release agent described above.

[0028] (b) A process of processing the back side of the laminate;

[0029] (c) The step of separating the support from the laminate by irradiating the support with a laser from the support side; and

[0030] (d) A process of removing the silicone resin layer and the laser lift-off layer from the separated laminate using a cleaning solution with a temperature of 40°C to 60°C, and removing only the substrate with circuitry.

[0031] If this is the processing method for a circuit-containing substrate, as described above, since a temporary adhesive containing silicone resin with a high dissolution rate is used even after being treated at high temperatures, the adhesive layer can be removed well without contaminating the substrate, thus improving the productivity of thin substrates.

[0032] (3) Beneficial effects

[0033] This invention utilizes the flexibility and excellent heat resistance of silicone resins, making them suitable for a wide range of semiconductor film deposition processes. It also exhibits excellent CVD (chemical vapor deposition) resistance and can form a temporary adhesive layer with high film thickness uniformity even on wafers with stepped surfaces. This film thickness uniformity allows for the easy fabrication of uniform thin wafers of 50 μm or less. Furthermore, after fabricating the thin wafer, it can be easily peeled off from the support at, for example, room temperature. Moreover, if the temporary adhesive is a silicone-based resin with the aforementioned dissolution rate, the adhesive layer can be easily removed without contaminating the substrate, thus improving the productivity of thin substrates. Detailed Implementation

[0034] As described above, there is a need for a temporary adhesive containing an organosilicon resin that facilitates bonding between the support and the substrate, enables the formation of a uniform film thickness on high-step substrates, has high process suitability for TSV formation and wafer back-side wiring processes, facilitates easy peeling of the substrate from the support, and allows for good removal of the adhesive layer without contaminating the substrate, thereby improving the productivity of thin substrates.

[0035] The inventors of this application conducted in-depth research to achieve the above-mentioned objectives, and as a result, the objectives were achieved by using a temporary adhesive containing organosilicon, thus completing the present invention. The temporary adhesive containing organosilicon is characterized in that, after the semiconductor substrate and the support are bonded together by the temporary adhesive layer formed by the temporary adhesive and heated at 260°C for 2 hours, and after the semiconductor substrate and the support are peeled off, the dissolution rate of the temporary adhesive layer remaining on the semiconductor substrate or the support relative to the dimethylpropionamide solution containing 3% by mass tetrabutylammonium fluoride at 50°C is 20 μm / min or more.

[0036] That is, the present invention is a temporary adhesive containing an organosilicon resin, which is a temporary adhesive containing an organosilicon resin that temporarily bonds a semiconductor substrate to a support. The invention is characterized in that, after bonding the semiconductor substrate and the support with a temporary adhesive layer formed by the temporary adhesive and heating at 260°C for 2 hours, the semiconductor substrate and the support are peeled off. Then, the temporary adhesive layer remaining on the semiconductor substrate or the support is dissolved in a dimethylpropionamide solution containing 3% by mass tetrabutylammonium fluoride at 50°C to measure the dissolution rate of the temporary adhesive layer formed by the temporary adhesive. The dissolution rate is 20 μm / min or higher.

[0037] The present invention will now be described in detail, but it is not limited thereto.

[0038] First, a support and a semiconductor substrate (wafer) temporarily bonded using the temporary adhesive material containing an organosilicon resin of the present invention will be described.

[0039] [Support]

[0040] Examples of supports for temporary bonding using the silicone-based resin-containing temporary adhesive material of the present invention include transparent substrates, silicon wafers, and ceramic substrates. From the perspective of the transmissivity of the laser irradiated when the support is peeled off, a transparent substrate is preferred. As the transparent substrate, a glass substrate or a quartz substrate can generally be used, and its thickness is generally preferably 300 to 1,000 μm, more preferably 500 to 800 μm.

[0041] [Semiconductor substrate (wafer)]

[0042] Semiconductor substrates are also referred to as semiconductor wafers or simply wafers. Examples of such wafers include silicon wafers, germanium wafers, gallium-arsenic wafers, gallium-phosphorus wafers, and gallium-arsenic-aluminum wafers. The thickness of the wafer is not particularly limited, but is typically preferred to be 600-800 μm, more preferably 625-775 μm. Circuit-containing substrates are fabricated by forming circuits on such wafers and performing processing.

[0043] The temporary adhesive material containing an organosilicon resin of the present invention is preferably used in combination with a laser release agent when temporarily bonding a semiconductor substrate to a support. The laser release agent will be described below.

[0044] [Laser stripping agent]

[0045] The laser release layer formed using a laser release agent comprises a resin with condensation rings in its main chain and is a light-shielding resin layer (light-shielding layer). The transmittance of light with a wavelength of 355 nm is preferably 20% or less, more preferably 18% or less, and even more preferably 0-15%. Furthermore, the maximum absorption wavelength of the laser release layer is preferably 300-500 nm, more preferably 300-400 nm. Further, the transmittance of light with a wavelength of 300-500 nm in the laser release layer is preferably 20% or less.

[0046] From the perspectives of heat resistance, adhesion, and chemical resistance, the resin contained in the laser release layer (hereinafter also referred to as "resin layer I") is preferably formed from a cured product of a resin composition (laser release agent, hereinafter also referred to as "resin composition I") containing a resin (hereinafter also referred to as "resin I") containing repeating units represented by the following formula (1). The repeating units represented by formula (1) may contain only one type or two or more types.

[0047] [Chemical Formula 1]

[0048]

[0049] In equation (1), R 1 ~R 3 Each is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Wherein, R 1 ~R 3 At least one of them is a hydroxyl group.

[0050] Examples of monovalent organic groups include alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-pentadecanyl, n-eicosyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclohexylmethyl, cyclopentylethyl, cyclohexylethyl, cyclopentylbutyl, cyclohexylbutyl, adamantyl, etc., which are straight-chain, branched, or cyclic; alkoxy groups with 1 to 5 carbon atoms, such as methoxy; epoxy groups, such as glycidyl etheroxy; and aryl groups, such as phenyl and naphthyl. As R 1 ~R 3 Preferably, hydrogen atoms, hydroxyl groups, methyl groups, etc.

[0051] In equation (1), R 4 It is a hydrogen atom, or optionally a monovalent organic group with 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, having a substituent. As R 4The monovalent organic groups represented can be alkyl, phenyl, naphthyl, anthraceneyl, norbornyl, etc., and some of their hydrogen atoms can be replaced by alkyl, aryl, aldehyde, halogen, nitro, nitrile, hydroxyl, etc.

[0052] Resin I is typically obtained by polycondensation of naphthol or its derivatives with aldehyde compounds in the absence of solvent or with an acid or base as a catalyst, at room temperature or under cooling or heating as needed.

[0053] Examples of naphthol or its derivatives include 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol, 1,2-dihydroxynaphthol, 1,3-dihydroxynaphthol, 2,3-dihydroxynaphthol, 1,4-dihydroxynaphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, 1,7-dihydroxynaphthol, 2,7-dihydroxynaphthol, 1, 8-Dihydroxynaphthalene, 5-amino-1-naphthol, 2-methoxycarbonyl-1-naphthol, 1-(4-hydroxyphenyl)naphthalene, 6-(4-hydroxyphenyl)-2-naphthol, 6-(cyclohexyl)-2-naphthol, 1,1'-bi-2-naphthol, 6,6'-bi-2-naphthol, 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 6-hydroxy-2-vinylnaphthalene, 1-hydroxymethylnaphthalene, 2-hydroxymethylnaphthalene, etc. The naphthols or their derivatives may be used alone or in combination of two or more.

[0054] Examples of aldehyde compounds include substances represented by the following formula (2).

[0055] R 4 -CHO (2)

[0056] (where R is in the formula) 4 With the above R 4 same.)

[0057] Examples of aldehyde compounds represented by formula (2) include formaldehyde, paraformaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, adamantane formaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, anthracene formaldehyde, pyrene formaldehyde, furfural, methyl acetal, o-phthalaldehyde, m-phthalaldehyde, terephthalaldehyde, naphthalene diacetal, anthracene diacetal, pyrene diacetal, etc. The aldehyde compounds may be used alone or in combination of two or more.

[0058] Examples of solvents used in the polycondensation reaction include alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran (THF), and 1,4-dioxane; chlorinated solvents such as dichloromethane, chloroform, dichloroethane, and trichloroethylene; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; lactones such as γ-butyrolactone; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoryltriamine. These solvents can be used alone or in combination of two or more. These solvents are preferably used in the range of 0 to 2,000 parts by mass, more preferably 10 to 2,000 parts by mass, relative to a total of 100 parts by mass of naphthol or its derivatives and aldehyde compounds.

[0059] Examples of acid catalysts used in the polycondensation reaction include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyldimethoxytin, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, methyl phthalate, tetraethyl phthalate, tetraisopropyl phthalate, and titanium dioxide.

[0060] Furthermore, examples of base catalysts used in the polycondensation reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, and calcium hydride; alkyl metals such as methyllithium, n-butyllithium, methylmagnesium chloride, and ethyl magnesium bromide; alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; and organic bases such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, and 4-dimethylaminopyridine.

[0061] The amount of catalyst used is preferably 0.001 to 100 parts by mass relative to 100 parts by mass of naphthol or its derivatives and aldehyde compounds, more preferably 0.005 to 50 parts by mass. The reaction temperature is preferably from -50°C to about the boiling point of the solvent, and more preferably room temperature to 100°C.

[0062] As a method for polycondensation reaction, methods include adding naphthol or its derivatives, aldehydes, and catalysts together, or adding naphthol or its derivatives and aldehydes dropwise in the presence of a catalyst.

[0063] The ratio of naphthol or its derivatives to aldehyde compounds, relative to the total amount of naphthol or its derivatives, is 0.01 to 5 molar ratio, preferably 0.05 to 2, more preferably 0.05 to 1, and most preferably 0.1 to 0.9.

[0064] After the polycondensation reaction is complete, in order to remove unreacted raw materials, catalysts, etc., present in the system, the temperature of the reactor is raised to 130~230℃, and volatile components are removed at a rate of about 1~50 mmHg. Alternatively, a suitable solvent or water is added to fractionate the polymer, or the polymer is dissolved in a good solvent and then precipitated in a poor solvent. These methods can be used depending on the properties of the resulting reaction products.

[0065] The weight-average molecular weight (Mw) of resin I is preferably 500 to 500,000, more preferably 1,000 to 100,000. The polymer dispersion (Mw / Mn, Mn: number-average molecular weight) is preferably 1.2 to 20, more preferably in the range of 1 to 10. Removing monomer components, oligomer components, or low molecular weight components with Mw less than 500 can suppress volatile components during baking. In addition, Mn can be 500 to 100,000. This can prevent surface defects caused by contamination around the baking cup or the falling of volatile components. In addition, in this invention, Mw and Mn are polystyrene conversion values ​​obtained by gel permeation chromatography (GPC) using THF as a solvent.

[0066] Resin composition I preferably includes a crosslinking agent that crosslinks resin I through a thermal reaction. As the crosslinking agent, epoxy compounds, epoxy resins, amino resins such as hydroxymethyl melamine, which have two or more functional groups within the molecule, may be appropriately used. To promote the crosslinking reaction between these crosslinking agents and the polymer, a catalyst is preferably further added.

[0067] Examples of epoxy compounds or epoxy resins include difunctional, trifunctional, tetrafunctional or higher multifunctional epoxy resins, such as EOCN-1020 (refer to the formula below), EOCN-102S, XD-1000, NC-2000-L, EPPN-201, GAN, NC6000, and substances represented by the formula below, manufactured by Nippon Kayaku Co., Ltd.

[0068] [Chemical Formula 2]

[0069]

[0070] When the epoxy compound or epoxy resin is used as a crosslinking agent, the amount of the epoxy compound or epoxy resin blended relative to 100 parts by weight of a polymer having repeating units represented by formula (1) is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 30 parts by weight, and even more preferably 1 to 30 parts by weight. One crosslinking agent may be used alone or in combination of two or more. If the blending amount is within the range described, sufficient crosslinking density can be obtained, and the resulting cured product fully performs its function.

[0071] Furthermore, when the epoxy resin is used as a crosslinking agent, it is preferable to add a curing accelerator as a catalyst. By including an epoxy resin curing accelerator, the curing reaction can be promoted appropriately and uniformly.

[0072] Examples of epoxy resin curing accelerators include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and ethyl isocyanates of these compounds; imidazole compounds such as 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole; 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); 1,5-diazabicyclo[4.3.0]non-5-ene (DBN); and D... The epoxy resin curing accelerator includes DBU organic acid salts, DBU phenolic resin salts, DBU derivatives such as tetraphenylborate, triphenylphosphine, tributylphosphine, tris(p-methylphenyl)phosphine, tris(p-methoxyphenyl)phosphine, tris(p-ethoxyphenyl)phosphine, triphenylphosphine-triphenylboronic acid ester, tetraphenylphosphine-tetraphenylboronic acid ester, quaternary phosphonium salts, triethylammonium-triphenylborate, and other tertiary amines, as well as their tetraphenylborates. One type of epoxy resin curing accelerator may be used alone, or two or more may be used simultaneously.

[0073] The amount of epoxy resin curing accelerator incorporated relative to 100 parts by weight of resin I is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight.

[0074] Furthermore, as amino resins such as hydroxymethyl melamine used in this invention, one or more compounds selected from the group consisting of amino condensates modified with formaldehyde or formaldehyde-alcohol and phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups in one molecule can be listed.

[0075] The weight-average molecular weight (Mw) of the amino resin is preferably 150 to 10,000, more preferably 200 to 3,000. If Mw is within this range, sufficient curability can be obtained, and the cured composition also has good heat resistance.

[0076] Examples of the formaldehyde- or formaldehyde-alcohol-modified amino condensates include melamine condensates modified with formaldehyde or formaldehyde-alcohol, or urea condensates modified with formaldehyde or formaldehyde-alcohol.

[0077] The formaldehyde- or formaldehyde-alcohol-modified melamine condensate can be prepared by, for example, by modifying the melamine monomer with formaldehyde by hydroxymethylation using a known method, or by further modifying it by alkoxylation with an alcohol, thereby producing the modified melamine represented by the following formula. Furthermore, lower alcohols, such as alcohols having 1 to 4 carbon atoms, are preferred as the alcohol.

[0078] [Chemical Formula 3]

[0079]

[0080] (where R is in the formula) 5 ~R 10 Each of the following is independently a hydroxymethyl group, an alkoxymethyl group containing a linear, branched, or cyclic alkoxy group with 1 to 4 carbon atoms, or a hydrogen atom, with at least one being a hydroxymethyl group or an alkoxymethyl group.

[0081] Examples of modified melamine include trimethoxymethyl melamine, dimethoxymethyl melamine, trimethylol melamine, hexamethylol melamine, and hexamethoxymethylol melamine. Next, the modified melamine or its polymers (e.g., dimers, trimers, or oligomers) are subjected to addition polymerization with formaldehyde to the desired molecular weight using conventional methods, thereby obtaining a melamine condensate modified with formaldehyde or formaldehyde-alcohol. Furthermore, one or more of the modified melamine and its condensates can be used as crosslinking agents.

[0082] In addition, urea condensates modified with formaldehyde or formaldehyde-alcohol can be prepared by, for example, by modifying the urea condensate of the desired molecular weight with formaldehyde by hydroxymethylation according to known methods, or by further modifying it by alkoxylation with an alcohol.

[0083] Specific examples of the modified urea condensate include methoxymethylated urea condensate, ethoxymethylated urea condensate, and propoxymethylated urea condensate. Furthermore, one or more of these modified urea condensates may be used.

[0084] Among them, phenolic compounds that have an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups per molecule include, for example, (2-hydroxy-5-methyl)-1,3-benzyldiethanol and 2,2',6,6'-tetramethoxymethylbisphenol A.

[0085] These amino condensates or phenolic compounds can be used alone or in combination of two or more.

[0086] The amount of crosslinking agent incorporated relative to 100 parts by weight of resin I is preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight. If it is within this range, composition I is fully cured, and the resulting cured product fully performs its function.

[0087] Furthermore, when using amino resins such as hydroxymethyl melamine as crosslinking agents, it is preferable to add a thermally generated acid agent as a catalyst. This thermally generated acid agent is not particularly limited; for example, ammonium salts represented by the following formula can be listed.

[0088] [Chemical Formula 4]

[0089]

[0090] (where R is in the formula) 11 ~R 14 Each group independently represents a hydrogen atom, a linear, branched, or cyclic alkyl or oxoalkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl or oxoalkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl or aryloxoalkyl group having 7 to 12 carbon atoms, wherein some or all of the hydrogen atoms in these groups may be substituted with alkoxy groups. (Selected from R) 11 ~R 14 The two atoms in X can form a ring with the nitrogen atoms they are bonded to. This ring is either an aliphatic ring with 3 to 10 carbon atoms containing the nitrogen atoms in the formula, or a heteroaromatic ring with 5 to 10 carbon atoms containing the nitrogen atoms in the formula. - (At least one fluorinated sulfonic acid, perfluoroalkylimide acid, or perfluoroalkylmethylated acid at the α-position.)

[0091] As X - Specifically, examples include perfluoroalkyl sulfonate ions such as trifluoromethanesulfonate ion and nonafluorobutyrate ion, sulfonate anions formed by at least one fluorine substitution at the α-position, bis(trifluoromethylsulfonyl)imide anion, bis(perfluoroethylsulfonyl)imide anion, bis(perfluorobutylsulfonyl)imide anion, and methane anions such as tri(trifluoromethylsulfonyl)methane anion and tri(perfluoroethylsulfonyl)methane anion.

[0092] The amount of thermally generated acid agent incorporated relative to 100 parts by weight of resin I is preferably 0.1 to 15 parts by weight, more preferably 0.2 to 10 parts by weight. If it is within the range described above, composition I is fully cured and has good storage stability.

[0093] Laser stripping agents (laser stripping compositions) may contain solvents. Examples of such solvents include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, and γ-butyrolactone. These solvents may be used alone or in combination of two or more. The amount of solvent incorporated relative to 100 parts by weight of resin I is preferably 100 to 5,000 parts by weight, more preferably 150 to 2,500 parts by weight.

[0094] Laser stripping agents (laser stripping compositions) may contain surfactants or antioxidants as needed to further improve heat resistance.

[0095] As a surfactant, there are no particular limitations. Examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oil ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate; and polyoxyethylene sorbitan monolaurate. Nonionic surfactants for polyoxyethylene sorbitan fatty acid esters, including polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by TOKEM PRODUCTS Co., Ltd.); MEGAFACE (registered trademark) F171, F172, F173 (DIC). Fluorinated surfactants such as CORPORATION (manufactured), Fluorad (registered trademark) FC430, FC431 (manufactured by 3M), AsahiGuard AG710, Surflon (registered trademark) S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfynol (registered trademark) E1004, KH-10, KH-20, KH-30, KH-40 (AGC Inc.), organosiloxane polymer P341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic POLYFLOW No. 75, No. 95 (manufactured by KYOEISHA CHEMICAL Co.,LTD.) can be used alone or in combination of two or more.

[0096] As an antioxidant, it is preferably selected from at least one of hindered phenolic compounds, hindered amine compounds, organophosphorus compounds and organosulfur compounds, with particularly preferred hindered phenolic compounds.

[0097] The hindered phenolic compound is not particularly limited, but the following substances are preferred. Examples include 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (trade name: IRGANOX 1330), 2,6-di-tert-butyl-4-methylphenol (trade name: Sumilizer BHT), 2,5-di-tert-butylhydroquinone (trade name: Nocrac NS-7), 2,6-di-tert-butyl-4-ethylphenol (trade name: Nocrac M-17), 2,5-di-tert-pentylhydroquinone (trade name: Nocrac DAH), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (trade name: Nocrac NS-6), 3,5-di-tert-butyl-4-hydroxybenzyl phosphate diethyl ester (trade name: IRGANOX 1222), and 4,4'-thiobis(3-methyl-6-tert-butylphenol) (trade name: Nocrac). 300), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (trade name: Nocrac NS-5), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol) (trade name: ADK STAB AO-40), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (trade name: Sumilizer GS), 2,2'-methylenebis[4-methyl-6-(α-methyl-cyclohexyl)phenol], 4,4'-methylenebis(2,6-di-tert-butylphenol) (trade name: seenox 226M), 4,6-bis(octylthiomethyl)-o-cresol (trade name: IRGANOX) 1520L), 2,2'-Ethylenebis(4,6-di-tert-butylphenol), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1076), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (trade name: ADK STAB AO-30), tetra[methylene-(3,5-di-tert-butyl-4-hydroxycinnamate)]methane (trade name: ADK STAB AO-60), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 245), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine (trade name: IRGANOX) 565), N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoamide) (trade name: IRGANOX 1098), 1,6-Hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 259), 2,2-thio-diethylidene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1035), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: Sumilizer GA-80), tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114), bis(3,5-di-tert-butyl-4-hydroxybenzyl phosphate ethyl ester) calcium / polyethylene paraffin mixture (50:50) (trade name: IRGANOX) 1425WL), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1135), 4,4'-thiobis(6-tert-butyl-3-methylphenol) (trade name: Sumilizer WX-R), 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxophosphorus-heptanane (trade name: Sumilizer GP), etc.

[0098] The hindered amine compound is not particularly limited, but the following substances are preferred. Examples include p,p'-dioctyldiphenylamine (trade name: IRGANOX 5057), phenyl-α-naphthylamine (Nocrac PA), poly(2,2,4-trimethyl-1,2-dihydroquinoline) (trade names: Nocrac 224, 224-S), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (trade name: Nocrac AW), N,N'-diphenyl-p-phenylenediamine (trade name: Nocrac DP), N,N'-di-β-naphthyl-p-phenylenediamine (trade name: Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine (trade name: Nocrac 810NA), N,N'-diallyl-p-phenylenediamine (trade name: Nonflex TP), and 4,4'-(α,α-dimethylbenzyl)diphenylamine (trade name: Nocrac). CD), p,p-toluenesulfonylaminodiphenylamine (trade name: NocracTD), N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine (trade name: Nocrac G1), N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (trade name: Ozonon 35), N,N'-disec-butyl-p-phenylenediamine (trade name: Sumilizer BPA), N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (trade name: Antigene 6C), alkylated diphenylamine (trade name: Sumilizer 9A), dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine condensate (trade name: Tinuvin) 622LD), poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (trade name: CHIMASSORB 944), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-6-chloro-1,3,5-triazine condensate (trade name: CHIMASSORB 119FL), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (trade name: TINUVIN) 123), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (trade name: TINUVIN 770), 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-Pentamethyl-4-piperidinyl (trade name: TINUVIN 144), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (trade name: TINUVIN) 765), tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate (trade name: LA-57), tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate (trade name: LA-52), a mixed ester of 1,2,3,4-butanetetracarboxylate with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecyl alcohol (trade name: LA-62), a mixed ester of 1,2,3,4-butanetetracarboxylate with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecyl alcohol (trade name: LA-67), 1,2,3,4 A mixed ester of butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxellaspiro[5.5]undecane (trade name: LA-63P), a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxellaspiro[5.5]undecane (trade name: LA-68LD), (2,2,6,6-tetramethylene-4-piperidinyl)-2-propenylcarboxylate (trade name: ADK STAB LA-82), (1,2,2,6,6-pentamethyl-4-piperidinyl)-2-propenylcarboxylate (trade name: ADK STAB LA-87), etc.

[0099] There are no particular limitations on the organophosphorus compounds mentioned above, but the following substances are preferred. Examples include bis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name: SANKO-HCA), triethyl phosphite (trade name: JP302), tri-n-butyl phosphite (trade name: JP304), triphenyl phosphite (trade name: ADK STAB TPP), diphenyl monooctyl phosphite (trade name: ADK STAB C), tris(p-tolyl) phosphite (trade name: Chelex-PC), diphenyl monodecyl phosphite (trade name: ADK STAB 135A), diphenyl mono(tridecyl) phosphite (trade name: JPM313), tris(2-ethylhexyl) phosphite (trade name: JP308), phenyl didecyl phosphite (trade name: ADK STAB517), and tridecyl phosphite (trade name: ADK STAB 3010), Tetraphenyl dipropylene glycol diphosphite (trade name: JPP100), Bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (trade name: ADK STAB PEP-24G), Tris(tetrazyl) phosphite (trade name: JP333E), Bis(nonylphenyl) pentaerythritol diphosphite (trade name: ADK STAB PEP-4C), Bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name: ADK STAB PEP-36), Bis[2,4-di(1-phenylisopropyl)phenyl] pentaerythritol diphosphite (trade name: ADKSTAB PEP-45), Trilauryl trithiophosphite (trade name: JPS312), Tris(2,4-di-tert-butylphenyl) phosphite (trade name: IRGAFOS) 168), Tris(nonylphenyl) phosphite (trade name: ADK STAB 1178), Distearate pentaerythritol diphosphite (trade name: ADK STAB PEP-8), Tris(mono- or dinonylphenyl) phosphite (trade name: ADK STAB 329K), Trioleyl phosphite (trade name: Chelex-OL), Tristearate phosphite (trade name: JP318E), 4,4'-Butylenebis(3-methyl-6-tert-butylphenyl bis(tetrazyl)) phosphite (trade name: JPH1200), Tetra(C 12 -C 15Mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite (trade name: ADK STAB1500), tetra(tridecyl)-4,4'-butylidene bis(3-methyl-6-tert-butylphenol) diphosphite (trade name: ADKSTAB 260), hexa(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane-triphosphite (trade name: ADK STAB) 522A), hydrogenated bisphenol A phosphite polymer (HBP), tetrakis(2,4-di-tert-butylphenoxy)4,4'-biphenyl-di-phosphine (trade name: P-EPQ), tetrakis(2,4-di-tert-butyl-5-methylphenoxy)4,4'-biphenyl-di-phosphine (trade name: GSY-101P), 2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxophosphazenecyclohepta-6-yl]oxy]-N,N-bis[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxophosphazenecyclohepta-6-yl]oxy]-ethyl]ethylamine (trade name: IRGAFOS) 12), 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite (trade name: ADK STAB HP-10), etc.

[0100] The organosulfur compound is not particularly limited, but the following substances are preferred. Examples include dilauryl-3,3'-thiodipropionate (trade name: Sumilizer TPL-R), dimyristyl-3,3'-thiodipropionate (trade name: Sumilizer TPM), distearate-3,3'-thiodipropionate (trade name: Sumilizer TPS), pentaerythritol tetra(3-lauryl thiopropionate) (trade name: Sumilizer TP-D), ditridecyl-3,3'-thiodipropionate (trade name: Sumilizer TL), 2-mercaptobenzimidazole (trade name: Sumilizer MB), ditridecyl-3,3'-thiodipropionate (trade name: ADK STAB AO-503A), 1,3,5-tris-β-stearylthiopropionyloxyethyl isocyanurate, and didodecyl 3,3'-thiodipropionate (trade name: IRGANOX). Products such as PS800FL, 3,3'-thiodipropionate dioctadecyl ester (trade name: IRGANOX PS 802FL), etc.

[0101] Of the antioxidants, tetramethyl[methylene-(3,5-di-tert-butyl-4-hydroxycinnamate)]methane is particularly preferred. The amount of the antioxidant added relative to 100 parts by weight of resin I is preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight. Within this range, sufficient heat resistance and compatibility can be obtained. Furthermore, one antioxidant may be used alone or in combination of two or more.

[0102] When the resin composition I is a solution, it can be coated onto the support by methods such as spin coating, roller coating, mold coating, printing, or dip coating. Depending on the solvent evaporation conditions, it is preferably pre-baked at a temperature of 80~200°C, more preferably at 100~180°C, to evaporate the solvent, thereby forming the resin composition layer I'.

[0103] On the other hand, when the resin composition I (laser release layer) is a film composition, the resin composition layer I' can be formed on the support by lamination.

[0104] The resin composition layer I' formed on the support functions as resin layer I (laser release layer) by further heating and curing. Heating and curing can be carried out using a heating plate or oven, typically at 100–350°C for 5–10 minutes, preferably at 150–300°C for 3–8 minutes. This curing reaction can also be achieved by heating the entire wafer stack after forming an uncured wafer stack without curing the resin composition layer I'.

[0105] The thickness of the resin layer I (laser exfoliation layer) formed on the support is preferably 0.1 to 50 μm, more preferably 0.3 to 30 μm. If the film thickness is within the range described above, the light-shielding properties are sufficient, and the flatness of the film is also good.

[0106] [Temporary adhesives containing silicone resins]

[0107] The temporary adhesive containing organosilicon resin of the present invention satisfies the above-mentioned dissolution rate requirement, and preferably contains a curable organosilicon resin containing the following components.

[0108] (A) An organopolysiloxane having two or more alkenyl groups in one molecule;

[0109] (B) Organohydropolysiloxanes containing two or more hydrogen atoms bonded to silicon atoms (Si-H groups) in one molecule, and

[0110] (C) Platinum-based catalysts.

[0111] Preferably, the composition contains an amount in which the molar ratio of the Si-H group in component (B) to the alkenyl group in component (A) is 0.3 to 10.

[0112] The temporary adhesive containing an organosilicon resin of the present invention is preferably an adhesive that further contains component (D) and includes components (A) to (D) below:

[0113] (A) An organopolysiloxane having two or more alkenyl groups in one molecule, in 100 parts by mass;

[0114] (B) An organohydrogen polysiloxane containing two or more hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, wherein the total amount of SiH groups in component (B) is in a molar ratio of 0.3 to 10 to the total amount of alkenes in component (A).

[0115] (C) Platinum group catalyst (hydrosilylation reaction catalyst), in terms of metal atomic weight, has a mass of 0.1 to 5,000 ppm relative to the total mass of components (A), (B), and (D); and

[0116] (D) Non-functional organopolysiloxane, in the form of 0.1 to 200 parts by mass.

[0117] The temporary adhesive containing silicone resin is a resin used to form a silicone resin layer (hereinafter also referred to as "resin layer II").

[0118] [(A) ingredient]

[0119] (A) is an organopolysiloxane having two or more alkenyl groups per molecule. Examples of component (A) include linear or branched diorganopolysiloxanes containing two or more alkenyl groups per molecule, and organopolysiloxanes with a three-dimensional network structure having two or more alkenyl groups per molecule and siloxane units (Q units) represented by SiO4 / 2. Preferably, diorganopolysiloxanes or organopolysiloxanes with a three-dimensional network structure and an alkenyl group content of 0.6 to 9 mol% are used. Furthermore, in this invention, the alkenyl group content refers to the ratio (mol%) of the number of alkenyl groups in the molecule to the number of Si atoms.

[0120] Examples of such organopolysiloxanes include substances represented by formulas (A-1), (A-2), or (A-3). Furthermore, they can be used alone or in combination of two or more.

[0121] [Chemical Formula 5]

[0122]

[0123] In equations (A-1) to (A-3), R 21 ~R 36 Each is an independent monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group. X 1 ~X 5Each is an independent monovalent organic group containing an alkenyl group.

[0124] In equation (A-1), a and b are each independent integers from 0 to 3. In equations (A-1) and (A-2), c 1 c 2 d 1 and d 2 To satisfy 0≤c 1 ≤10、2≤c 2 ≤10、0≤d 1 ≤100 and 0≤d 2 Integers ≤ 100. Where a + b + c 1 ≥2. a, b, c 1 c 2 d 1 and d 2 Preferably, the alkenyl content is a combination of 0.6 to 9 mol%.

[0125] In equation (A-3), e is an integer from 1 to 3. 1 f 2 and f 3 In order to make (f 2 +f 3 ) / f 1 The value is 0.3~3.0 and f 3 / (f 1 +f 2 +f 3 () is a number between 0.01 and 0.6.

[0126] As the monovalent hydrocarbon group other than the aliphatic unsaturated hydrocarbon group, it is preferred to be a hydrocarbon group with 1 to 10 carbon atoms, and examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and aryl groups such as phenyl and tolyl. Among them, alkyl groups such as methyl or phenyl are preferred.

[0127] As the alkenyl-containing monovalent organic group, organic groups with 2 to 10 carbon atoms are preferred, such as vinyl, allyl, hexenyl, octene, and other alkenyl groups; (meth)acryloylalkyl groups such as acryloylpropyl, acryloylmethyl, and methacryloylpropyl; (meth)acryloyloxyalkyl groups such as acryloyloxypropyl, acryloyloxymethyl, methacryloyloxypropyl, and methacryloyloxymethyl; and alkenylalkylalkyl groups such as cyclohexenylethyl and vinyloxypropyl. From an industrial perspective, vinyl groups are preferred.

[0128] In formula (A-1), a and b are each an independent integer from 0 to 3. If a is 1 to 3, the molecular chain end is capped by an alkenyl group, thus the reaction can be completed in a short time through the highly reactive alkenyl group at the molecular chain end, which is preferred. Furthermore, from a cost perspective, industrially, a is preferred to be 1. The alkenyl-containing diorganopolysiloxane represented by formula (A-1) or (A-2) is preferably in an oily or raw rubber form.

[0129] The organopolysiloxane represented by formula (A-3) contains SiO₂ 4 / 2 The unit has a three-dimensional mesh structure. In equation (A-3), e is an independent integer from 1 to 3, and from a cost perspective, 1 is preferred industrially. Furthermore, the average value of e and f... 3 The product of (f1 + f2 + f3) is preferably 0.02 to 1.5, more preferably 0.03 to 1.0. The organopolysiloxane represented by formula (A-3) can be dissolved in an organic solvent and used as a solution.

[0130] (A) The number-average molecular weight (Mn) of the organopolysiloxane in component (A) is preferably 100 to 1,000,000, more preferably 1,000 to 100,000. If Mn falls within this range, it is preferred from the perspective of operability associated with the viscosity of the composition or processability associated with the storage modulus after curing. Furthermore, in this invention, Mn is a polystyrene equivalent value obtained by gel permeation chromatography using toluene as a solvent.

[0131] (A) Components may be used alone or in combination of two or more. It is particularly preferred to use a combination of the organopolysiloxane represented by formula (A-1) and the organopolysiloxane represented by formula (A-3). In this case, the amount of organopolysiloxane represented by formula (A-3) used is preferably 1 to 1,000 parts by mass relative to 100 parts by mass of the organopolysiloxane represented by formula (A-1), more preferably 10 to 500 parts by mass.

[0132] [(B) Component]

[0133] (B) Component is a crosslinking agent, which is an organohydrogen polysiloxane having at least two, preferably three or more, hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule. The organohydrogen polysiloxane can be linear, branched, or cyclic. Furthermore, the organohydrogen polysiloxane can be used alone or in combination of two or more.

[0134] The viscosity of the organohydrogen polysiloxane in component (B) at 25°C is preferably 1 to 5,000 mPa·s, more preferably 5 to 500 mPa·s. Furthermore, in this invention, the viscosity is the value measured at 25°C using a rotational viscometer. Similar to component A, the Mn content of component B is also determined using GPC.

[0135] (B) The Mn of the organohydrogen polysiloxane is preferably 100 to 100,000, more preferably 500 to 10,000. If Mn is in the range described above, it is preferred from the perspective of operability associated with the viscosity of the composition or processability associated with the storage modulus after curing.

[0136] Component (B) is incorporated such that the total SiH groups in component (B) relative to the total alkenyl groups in component (A) is preferably in the range of 0.3 to 10, more preferably in the range of 1.0 to 8.0, in a molar ratio (SiH groups / alkenyl groups). If the molar ratio is 0.3 or higher, the crosslinking density will not decrease, and problems such as the temporary adhesive layer (silicone resin layer) not curing will not occur. Furthermore, if the molar ratio is 10 or lower, the crosslinking density will not become too high, sufficient adhesion and tack can be obtained, and the usable time of the treatment solution can be extended.

[0137] [(C) Component]

[0138] Component (C) functions as a catalyst for the hydrosilylation reaction, preferably a platinum group metal-based catalyst, and more preferably a platinum-based catalyst as described above. Component (C) is a catalyst that promotes the addition reaction between the alkenyl group in component (A) and the hydrosilylation group in component (B). This hydrosilylation reaction catalyst is usually a compound of a noble metal; due to its high cost, platinum or platinum compounds, which are relatively easy to obtain, are often used.

[0139] Examples of platinum compounds include chloroplatinic acid or its complexes with olefins such as ethylene, complexes with alcohols or vinylsiloxanes, and metallic platinum supported on silica, alumina, carbon, etc. Other platinum group metal catalysts besides platinum compounds include rhodium, ruthenium, iridium, and palladium compounds, such as RhCl(PPh3)3, RhCl(CO)(PPh3)2, and Ru3(CO). 12 Examples include IrCl(CO)(PPh3)2 and Pd(PPh3)4. Additionally, in these formulas, Ph represents a phenyl group.

[0140] When using these catalysts, if they are solid catalysts, they can be used in solid form. In order to obtain a more uniform cured product, it is preferable to dissolve the chloroplatinic acid or complex in a suitable solvent and use the resulting solution in a way that is compatible with component (A).

[0141] The amount of component (C) added is an effective amount, typically calculated relative to the total mass of components (A), (B), and (D) using metal atomic weights. The amount of component (C) added is 0.1 to 5,000 ppm, preferably 1 to 1,000 ppm. If it is 0.1 ppm or more, the curability of the composition will not decrease, the crosslinking density will not decrease, and the holding power will not decrease. If it is 5,000 ppm or less, side reactions such as dehydrogenation during curing can be suppressed, and the usable time of the treatment solution can be extended.

[0142] [(D) component]

[0143] (D) The component is a non-functional organopolysiloxane. Here, "non-functional" means that the molecule does not have reactive groups such as hydrogen atoms, halogen atoms, hydroxyl groups, alkoxy groups, etc. that are directly bonded to silicon atoms, nor does it have reactive groups such as alkenyl groups, epoxy groups, etc. that are directly bonded to silicon atoms or bonded to silicon atoms through any group.

[0144] Examples of such nonfunctional organopolysiloxanes include organopolysiloxanes having a monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group, with 1 to 12, preferably 1 to 10, unsubstituted or substituted carbon atoms. Examples of such monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; and aralkyl groups such as benzyl and phenethyl. Furthermore, some or all of the hydrogen atoms in these groups can be substituted with halogen atoms such as chlorine, fluorine, and bromine atoms; examples of such groups include chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl halogenated alkyl groups. Alkyl and aryl groups are preferred as the monovalent hydrocarbon group, and methyl and phenyl groups are more preferred.

[0145] (D) The molecular structure of the nonfunctional organopolysiloxane of the component is not particularly limited, and can be any of the following: linear, branched, cyclic, etc. It is preferred to be a linear or branched organopolysiloxane, and particularly preferred to be a linear or branched diorganopolysiloxane in which the main chain is basically composed of repeating diorganosiloxane units and the ends of the molecular chain are capped by triorganosiloxy groups.

[0146] From the perspectives of workability, coating properties on substrates, mechanical properties of cured products, and peelability of the support, the viscosity of a 30% by mass toluene solution of the nonfunctional organopolysiloxane in component (D) at 25°C is preferably 100-500,000 mPa·s, more preferably 200-100,000 mPa·s. Within this range, it has a suitable molecular weight, thus avoiding volatilization during heat curing of the silicone resin composition, preventing wafer breakage during wafer thermal processes such as CVD, and providing good workability and coating properties, making it preferred. Furthermore, the viscosity of component D was measured using a rotational viscometer (25°C).

[0147] Examples of linear, nonfunctional organopolysiloxanes include trimethylsiloxy-terminated dimethylsiloxane polymers, trimethylsiloxy-terminated diphenylpolysiloxanes, trimethylsiloxy-terminated 3,3,3-trifluoropropylmethylsiloxane polymers, trimethylsiloxy-terminated dimethylsiloxane-diphenylsiloxane copolymers, and trimethylsiloxy-terminated dimethylsiloxane-3,3,3-trifluoropropylmethylsiloxane copolymers. Copolymers, trimethylsiloxy-terminated diphenylsiloxane-3,3,3-trifluoropropylmethyl copolymers, trimethylsiloxy-terminated dimethylsiloxane-3,3,3-trifluoropropylmethylsiloxane-diphenylsiloxane copolymers, triphenylsiloxy-terminated dimethylpolysiloxanes, triphenylsiloxy-terminated diphenylpolysiloxanes, and triphenylsiloxy-terminated dimethylsiloxane-diphenylsiloxane copolymers, etc.

[0148] Examples of branched, nonfunctional organopolysiloxanes include the following substances.

[0149] [Chemical Formula 6]

[0150]

[0151] [Chemical Formula 7]

[0152]

[0153] (In the formula, g1, g2, g3, g4, g5, g1', g2', g3', g4', g5', and g6' are each independently an integer within the range that makes the viscosity of a 30% by mass toluene solution of the compound at 25°C equal to the viscosity of the compound within the range stated above.)

[0154] The amount of nonfunctional organopolysiloxane in component (D) relative to 100 parts by weight of component (A) is 0.1 to 200 parts by weight, preferably 1 to 180 parts by weight, and more preferably 10 to 170 parts by weight. If the amount of component (D) is within the aforementioned range, the wafer self-support can be easily peeled off. One type of nonfunctional organopolysiloxane in component (D) can be used alone, or two or more types can be used in combination. Furthermore, its physical properties are preferably oily or raw rubbery.

[0155] Furthermore, in this invention, it is preferable to adjust the amount of non-functional organopolysiloxane in component (D) to set the proportion of dimethylsiloxane units in the non-volatile component of the temporary adhesive containing organosilicon resin to 20% by mass or more. There is no particular upper limit, but it is approximately 95% by mass. By setting such a proportion of dimethylsiloxane units, the dissolution rate of the temporary adhesive layer formed by the temporary adhesive can be further improved. This dissolution rate is 20 μm / min or more. There is no particular upper limit, but it is approximately 200 μm / min or less. It can also be further set to at least 50 μm / min or more.

[0156] [(E) component]

[0157] The thermosetting silicone resin composition may further include a reaction control agent as component (E). This reaction control agent may be added as needed to prevent tackification or gelation of the composition during preparation or application to a substrate.

[0158] Examples of reaction control agents include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3-methyl-3-trimethylsilaneoxy-1-butyn, 3-methyl-3-trimethylsilaneoxy-1-pentyn, 3,5-dimethyl-3-trimethylsilaneoxy-1-hexyn, 1-ethynyl-1-trimethylsilaneoxycyclohexane, bis(2,2-dimethyl-3-butynoxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane. Among these, 1-ethynylcyclohexanol and 3-methyl-1-butyn-3-ol are preferred.

[0159] When the thermosetting silicone resin composition contains component (E), the controllability varies depending on the chemical structure, therefore its content should be adjusted to the most suitable amount. Considering its influence on curability, storage stability, and post-curing properties, its content is preferably 0.001 to 10 parts by mass relative to a total of 100 parts by mass of components (A), (B), and (D), more preferably 0.01 to 10 parts by mass. If the content of component (E) is within the aforementioned range, the composition has a long shelf life, achieves long-term storage stability, and exhibits good curability or workability.

[0160] The thermosetting silicone composition may further contain RA3SiO0.5 units (where RA is an independent, unsubstituted or substituted monovalent hydrocarbon group with 1 to 10 carbon atoms) and SiO2 units, and the molar ratio of RA3SiO0.5 units to SiO2 units (R... A 3SiO 0.5 The organopolysiloxane has a SiO2 content of 0.3 to 1.8. The preferred addition amount is 0 to 500 parts by weight relative to 100 parts by weight of component (A).

[0161] The temporary adhesive containing organosilicon resin of the present invention preferably includes a heat resistance enhancer. Such a heat resistance enhancer is preferably selected from at least one of hindered phenolic compounds and hindered amine compounds.

[0162] The hindered phenolic compound is not particularly limited, but the following substances are preferred. Examples include 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (trade name: IRGANOX 1330), 2,6-di-tert-butyl-4-methylphenol (trade name: Sumilizer BHT), 2,5-di-tert-butylhydroquinone (trade name: Nocrac NS-7), 2,6-di-tert-butyl-4-ethylphenol (trade name: Nocrac M-17), 2,5-di-tert-pentylhydroquinone (trade name: Nocrac DAH), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (trade name: Nocrac NS-6), 3,5-di-tert-butyl-4-hydroxybenzyl phosphate diethyl ester (trade name: IRGANOX 1222), and 4,4'-thiobis(3-methyl-6-tert-butylphenol) (trade name: Nocrac). 300), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (trade name: Nocrac NS-5), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol) (trade name: ADK STAB AO-40), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (trade name: Sumilizer GS), 2,2'-methylenebis[4-methyl-6-(α-methyl-cyclohexyl)phenol], 4,4'-methylenebis(2,6-di-tert-butylphenol) (trade name: seenox 226M), 4,6-bis(octylthiomethyl)-o-cresol (trade name: IRGANOX) 1520L), 2,2'-Ethylenebis(4,6-di-tert-butylphenol), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1076), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (trade name: ADK STAB AO-30), tetra[methylene-(3,5-di-tert-butyl-4-hydroxycinnamate)]methane (trade name: ADK STAB AO-60), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 245), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine (trade name: IRGANOX) 565), N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoamide) (trade name: IRGANOX 1098), 1,6-Hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 259), 2,2-thio-diethylidene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1035), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: Sumilizer GA-80), tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114), bis(3,5-di-tert-butyl-4-hydroxybenzyl phosphate ethyl ester) calcium / polyethylene paraffin mixture (50:50) (trade name: IRGANOX) 1425WL), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1135), 4,4'-thiobis(6-tert-butyl-3-methylphenol) (trade name: Sumilizer WX-R), 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxophosphorus-heptanane (trade name: Sumilizer GP), etc.

[0163] The hindered amine compound is not particularly limited, but the following substances are preferred. Examples include p,p'-dioctyldiphenylamine (trade name: IRGANOX 5057), phenyl-α-naphthylamine (trade name: NocracPA), poly(2,2,4-trimethyl-1,2-dihydroquinoline) (trade names: Nocrac 224, 224-S), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (trade name: Nocrac AW), N,N'-diphenyl-p-phenylenediamine (trade name: NocracDP), N,N'-di-β-naphthyl-p-phenylenediamine (trade name: Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine (trade name: Nocrac 810NA), N,N'-diallyl-p-phenylenediamine (trade name: Nonflex TP), and 4,4'-(α,α-dimethylbenzyl)diphenylamine (trade name: Nocrac). CD), p,p-toluenesulfonylaminodiphenylamine (trade name: Nocrac TD), N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine (trade name: Nocrac G1), N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (trade name: Ozonon 35), N,N'-disec-butyl-p-phenylenediamine (trade name: Sumilizer BPA), N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (trade name: Antigene 6C), alkylated diphenylamine (trade name: Sumilizer 9A), dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine condensate (trade name: Tinuvin) 622LD), poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (trade name: CHIMASSORB 944), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-6-chloro-1,3,5-triazine condensate (trade name: CHIMASSORB 119FL), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (trade name: TINUVIN) 123), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (trade name: TINUVIN 770), 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-Pentamethyl-4-piperidinyl (trade name: TINUVIN 144), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (trade name: TINUVIN) 765), tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate (trade name: LA-57), tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate (trade name: LA-52), a mixed ester of 1,2,3,4-butanetetracarboxylate with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecyl alcohol (trade name: LA-62), a mixed ester of 1,2,3,4-butanetetracarboxylate with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecyl alcohol (trade name: LA-67), 1,2,3,4 A mixed ester of butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxellaspiro[5.5]undecane (trade name: LA-63P), a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxellaspiro[5.5]undecane (trade name: LA-68LD), (2,2,6,6-tetramethylene-4-piperidinyl)-2-propenylcarboxylate (trade name: ADK STAB LA-82), (1,2,2,6,6-pentamethyl-4-piperidinyl)-2-propenylcarboxylate (trade name: ADK STAB LA-87), etc. ,

[0164] The heat resistance enhancer is preferably 0.5 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, and even more preferably 1 to 3 parts by weight, relative to 100 parts by weight of the silicone resin. This heat resistance enhancer can be added during resin synthesis or when mixing the resin with other processed materials.

[0165] To further improve the heat resistance of the temporary adhesive layer obtained from the thermosetting silicone resin composition, fillers such as silica may be added to the thermosetting silicone resin composition.

[0166] For reasons such as improving workability by reducing the viscosity of the composition, improving mixability, or adjusting the film thickness of the temporary adhesive layer, thermosetting silicone resin compositions can be used after being solvated with a solvent. The solvent used is not particularly limited as long as it can dissolve the components; for example, hydrocarbon solvents such as pentane, hexane, cyclohexane, isooctane, nonane, decane, p-menthane, pinene, isododecane, and limonene are preferred.

[0167] Examples of solutions include: adding a solvent and adjusting the viscosity to the desired level after preparing the thermosetting silicone resin composition; and pre-diluting the high-viscosity components (A), (B), and / or (D) with a solvent and then mixing the remaining components to improve workability or mixability. Furthermore, as a mixing method during solution preparation, appropriate mixing methods can be selected based on the composition's viscosity and workability, such as using a vibrating mixer, magnetic stirrer, or various other mixers.

[0168] The amount of solvent can be appropriately set by adjusting the viscosity or workability of the composition, the film thickness of the temporary adhesive layer, etc. For example, the amount of solvent is preferably 5 to 900 parts by mass relative to 100 parts by mass of a thermosetting silicone resin composition, and more preferably 10 to 400 parts by mass.

[0169] A temporary adhesive layer can be formed by applying the thermosetting silicone resin composition onto a substrate using methods such as spin coating or roll coating. When forming the temporary adhesive layer on the substrate using methods such as spin coating, it is preferable to apply the thermosetting silicone resin composition in a solution-like manner.

[0170] From the perspective of coatability, the viscosity of the solventized thermosetting silicone resin composition at 25°C is preferably 1 to 100,000 mPa·s, more preferably 10 to 10,000 mPa·s.

[0171] The thermosetting silicone resin composition, after curing at 25°C, typically exhibits a 180° peel force of 2~50 gf on a 25 mm wide test piece (e.g., a glass test piece), preferably 3~30 gf, and more preferably 5~20 gf. If the force is above 2 gf, wafer misalignment will not occur during wafer grinding; if the force is below 50 gf, wafer peeling becomes easier.

[0172] The thermosetting silicone resin composition, after curing, has a storage modulus at 25°C of 1,000 Pa or more and 1,000 MPa or less, preferably 10,000 Pa or more and 100 MPa or less. If the storage modulus is 1,000 Pa or more, the formed film is strong and tough, and will not cause wafer misalignment or wafer breakage associated with misalignment during wafer grinding. If it is 1,000 MPa or less, it can mitigate deformation stress in wafer thermal processes such as CVD, and is stable during wafer thermal processing.

[0173] [Fabrication method for substrates with circuitry]

[0174] Next, a method for processing a circuit-containing substrate using a temporary adhesive containing an organosilicon resin will be described.

[0175] The method for processing a circuit-containing substrate according to the present invention may include the following steps.

[0176] (a) A process of preparing a laminate containing a substrate with circuitry as the semiconductor substrate and the support, which is temporarily bonded by using a silicone resin layer containing a silicone resin temporary adhesive of the present invention and a laser release layer using the laser release agent.

[0177] (b) A process of processing the back side of the laminate;

[0178] (c) The process of separating the support from the laminate by irradiating the support with a laser from the support side; and

[0179] (d) A process of removing the silicone resin layer and the laser lift-off layer from the separated laminate using a cleaning solution with a temperature of 40°C to 60°C, and removing only the substrate with circuitry.

[0180] [Process(a)]

[0181] As described above, step (a) is a step of preparing a laminate comprising a substrate with circuitry as a semiconductor substrate and a support. More specifically, this step may be performed as described below, but is not limited thereto.

[0182] [Process (a1) or (a1')]

[0183] Step (a1) is the step of forming a light-shielding resin layer I on the support, and step (a1') is the step of forming a resin composition layer I' on the support. When the resin composition I used to form the resin layer I is a solution, it is coated onto the support by spin coating, roller coating, or other methods, and pre-baked at a temperature of 80-200°C, more preferably 100-180°C, depending on the solvent evaporation conditions, to evaporate the solvent, thereby forming the resin composition layer I'. Furthermore, when the resin composition I is a film composition, the resin composition layer I' can be formed on the support by lamination.

[0184] The resin composition layer I' formed on the support functions as resin layer I by heat curing. Heat curing can be carried out using a heating plate or oven, with temperatures typically ranging from 100 to 350°C, and preferably from 150 to 300°C. Furthermore, the curing time is typically 1 to 10 minutes, preferably 2 to 8 minutes. This curing reaction can also be achieved by heating the entire wafer stack after forming an uncured wafer stack without curing the resin composition layer I'.

[0185] [Process (a2) or (a2')]

[0186] Step (a2) is the process of forming resin layer II on the circuit forming surface of the semiconductor substrate (wafer), and step (a2') is the process of forming resin layer II on the resin layer I or resin composition layer I'. When the temporary adhesive containing silicone resin is a solution, it can be coated onto the semiconductor substrate (wafer) by methods such as spin coating, roll coating, molding coating, printing, or dip coating, and then heated at 130~190°C using a heating plate or oven to form resin layer II.

[0187] On the other hand, when the temporary adhesive containing silicone resin is a film composition, resin layer II can be formed on the wafer by lamination.

[0188] [Process (a3) ​​or (a3')]

[0189] Step (a3) ​​is a step of bonding resin layer I or resin composition I' to resin layer II under reduced pressure, and step (a3') is a step of bonding resin layer II on the support to the circuit forming surface of the wafer under reduced pressure. The reduced pressure condition is preferably 0.1 to 100 Pa, more preferably 1 to 80 Pa. Furthermore, it is preferable to uniformly press and bond the substrate under reduced pressure in a temperature range of 40 to 240°C, more preferably 60 to 220°C.

[0190] [Process (a4)]

[0191] Step (a4) involves thermally curing the resin composition layer A' of the wafer stack bonded in steps (a3) ​​or (a4') to form resin layer I, while simultaneously bonding it with resin layer II. After forming the wafer stack, thermal curing is performed by heating at 120~260°C, preferably 150~250°C, for 1 minute to 4 hours, preferably 3 minutes to 2 hours.

[0192] The above method can be used to prepare the laminate (process a).

[0193] [Process (b)]

[0194] Step (b) is a process for processing the back side of the laminate. This step involves processing the non-circuit forming surface of a wafer on which the non-circuit forming surface of a semiconductor substrate (wafer) has been ground, i.e., the non-circuit forming surface of a wafer that has been thinned by back-side grinding. This step includes various processes used at the wafer level. Examples include wafer surface treatment, electrode formation, metal wiring formation, and protective film formation. More specifically, examples include conventionally known processes such as CVD for wafer surface treatment, laser annealing, metal sputtering for forming electrodes, evaporation, wet etching to etch metal sputtered layers, resist coating for making masks for forming metal wiring, pattern formation by exposure and development, resist stripping, dry etching, metal plating formation, formation of organic films for surface protection, silicon etching for forming TSVs, and formation of oxide films on silicon surfaces. In such a process, it is expected that the wafer stack will have resistance in a wide range of high-temperature fields up to around 400°C, and especially that it can also have strength and lifespan at temperatures above 300°C.

[0195] [Process (c)]

[0196] Step (c) is the process of peeling the support from the thin wafer stack that has been processed in step (b). More specifically, it is a process of separating the support from the stack by irradiating it with a laser from the support side of the stack. This peeling process is typically carried out at a relatively low temperature at around room temperature, and preferably includes:

[0197] (c1) The process of applying dicing tape to the processed surface (back side) of a wafer that has undergone processing.

[0198] (c2) The process of vacuum adsorbing the cut tape surface onto the adsorption surface, and

[0199] (c3) A laser, for example, at 355 nm, is irradiated from the support side of the thin wafer stack, thereby peeling the support from the thin wafer stack. This allows for easy peeling of the support from the wafer stack, and further facilitates subsequent dicing processes. Additionally, known products using polyester, polyethylene film, etc., can be used as the dicing tape.

[0200] [Any process(x)]

[0201] Any step (x) is a step in which, after the support is peeled off in step (c), the resin layer I and resin layer II that are not decomposed by the laser are peeled off from the processed semiconductor substrate (wafer) by means of peeling off tape or the like.

[0202] This stripping process is typically carried out at relatively low temperatures, ranging from room temperature to around 60°C. One example of a stripping method in process (x) is to fix the wafer after process (c) horizontally, apply stripping tape to the exposed undecomposed resin layer I, and peel off the tape by tearing, thereby stripping the undecomposed resin layer I and resin layer II from the processed wafer.

[0203] As for the tape material, any tape material can be used as long as it can be peeled off. Tapes using silicone adhesives are particularly preferred, such as polyester film adhesive tapes No. 646S and No. 648 manufactured by TERAOKA SEISAKUSHO CO.,LTD.

[0204] Furthermore, when peeling off the tape material using a tearing method, it is preferable to perform the peeling while the laminate is heated. The heating temperature is preferably 30°C to 60°C, and more preferably 35°C to 55°C. When the laminate is heated in this manner, the adhesion between resin layer II and the wafer decreases, making it easier to peel off.

[0205] [Process (d)]

[0206] Furthermore, after step (x) or without step (c), it is preferable to perform the following step (d): removing the silicone resin layer (resin layer I) and the laser lift-off layer (resin layer II) from the laminate separated in step (c) using a cleaning solution with a temperature ranging from room temperature to 60°C, not exceeding the flash point, and removing only the substrate with circuitry. That is, this step removes the temporary adhesive material layer remaining on the circuit formation surface of the wafer after lift-off. Sometimes, a small amount of resin layer II may remain on the circuit formation surface of the semiconductor substrate (wafer) after lift-off via step (x). This resin layer II can be removed, for example, by cleaning the wafer. Without step (x), more resin layer II will usually remain.

[0207] The step (d) can use a cleaning solution that dissolves the components in resin layer II. Specifically, examples include pentane, hexane, cyclohexane, decane, isononane, p-menthane, pinene, isododecane, and limonene. These solvents can be used alone or in combination of two or more. Furthermore, if removal is difficult, alkalis or acids can be added to the above solvents. Examples of alkalis include amines such as ethanolamine, diethanolamine, triethanolamine, triethylamine, and ammonia; and ammonium salts such as tetramethylammonium hydroxide. Examples of acids include organic acids such as acetic acid, oxalic acid, benzenesulfonic acid, and dodecylbenzenesulfonic acid. The amount added is 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the concentration in the cleaning solution. In addition, existing surfactants can be added to improve the removal of residues. Cleaning methods include cleaning with a paddle using the above liquid, cleaning by spraying, and immersion in a cleaning solution tank. The suitable temperature is 10~80℃, preferably 15~65℃. If necessary, these solvents can be used to dissolve resin layer II, and then the wafer can be washed with water or alcohol and dried to obtain a thin wafer.

[0208] As described above, a support, a resin layer, and a substrate with circuitry on the surface are combined. The resin layer is peeled off by peeling off the support and cleaning away any remaining resin layer (or by peeling off tape), and finally a thin wafer is obtained.

[0209] Example

[0210] The present invention will now be described in more detail with examples of preparation, embodiments, and comparative examples, but the invention is not limited to these embodiments. In the following examples, parts represent parts by mass. Weight-average molecular weight (Mw) and number-average molecular weight (Mn) are converted values ​​of polystyrene obtained using THF as a solvent and through GPC. Furthermore, the acid-generating agent AG used in the following examples is as described below.

[0211] [Chemical Formula 8]

[0212]

[0213] AG

[0214] [1] Preparation of resin solution

[0215] [Preparation Example 1]

[0216] To 100 parts by mass of (CH2=CH)(CH3)SiO with 2.5 mol% 2 / 2 Unit (D) Vi To a solution formed by dimethyl polysiloxane with a Mn of 30,000 and 200 parts by mass of p-menthane, 15 parts by mass of vinylmethyl polysiloxane with a Mn of 7,000 (made from SiO2) are added.4 / 2 Unit (Q unit) 50 mol%, (CH3)3SiO 1 / 2 Unit (M unit) 48 mol% and (CH2=CH)3SiO 1 / 2 A thermosetting organosilicon resin solution D1 was prepared by mixing 2 mol% of unit (Vi unit) and 70 parts by mass of a solution formed from p-menthane, 2 parts by mass of an organohydrogen polysiloxane with Mn of 2,400 represented by M-6, 3 parts by mass of a solution formed from p-menthane, and 0.6 parts by mass of 1-ethynylcyclohexanol. Then, 0.4 parts by mass of catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd., platinum concentration 1.0 wt%) and 1 part by mass of tetra[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane were added and mixed, followed by filtration through a 1 μm membrane filter. Furthermore, in the resin solution, the molar ratio of Si-H groups in the organohydrogen polysiloxane having Si-H groups to the alkenyl groups in the dimethyl polysiloxane having alkenyl groups was 1.0. Additionally, the viscosity of resin solution D1 at 25°C was 2 Pa·s.

[0217] [Chemical Formula 9]

[0218]

[0219] Furthermore, the molar ratio (Si-H / Si-Vi) of the Si-H group in the organohydrogen polysiloxane having Si-H groups to the alkenyl group in the dimethyl polysiloxane having alkenyl groups in Preparation Example 1 can be calculated by the following formula. (In the following formula, PDMS: dimethyl polysiloxane, POHS: organohydrogen polysiloxane.)

[0220] (1) Amount of Si-Vi from composition (A-1) (moles)

[0221] (PDMS addition amount / PDMS molecular weight) × {PDMS molecular weight / (D unit molecular weight × D unit molar % / 100 + D} Vi Unit molecular weight × D unit molar % / 100)} × D Vi Unit mole % / 100

[0222] (2) Amount of Si-H from component (A-2) (moles)

[0223] (POHS addition amount / POHS molecular weight) × 1 Number of H-bonded siloxane units in a molecule

[0224] (3) The value of Si-H / Si-Vi

[0225] Amount of Si-H (moles) from composition (A-2) / Amount of Si-Vi (moles) from composition (A-1)

[0226] [Preparation Example 2]

[0227] To 80 parts by mass of (CH2=CH)(CH3)SiO with 2.5 mol% 2 / 2 Unit (D) Vi In a solution of dimethyl diphenyl polysiloxane with 3 mol% phenyl groups on the molecular side chain, Mn = 50,000, and 200 parts by mass of p-menthane, 70 parts by mass of vinylmethyl polysiloxane with Mn = 7,000 (made from SiO₂) are added. 4 / 2 Unit (Q unit) 50 mol%, (CH3)3SiO 1 / 2 Unit (M unit) 48 mol% and (CH2=CH)3SiO 1 / 2 A thermosetting organosilicon resin solution D2 was prepared by mixing 2 mol% of unit (Vi unit) and 70 parts by mass of a solution formed from p-menthane, 3 parts by mass of an organohydrogen polysiloxane with Mn of 2,400 represented by M-6, 5 parts by mass of a solution formed from p-menthane, and 0.6 parts by mass of 1-ethynylcyclohexanol. Then, 0.4 parts by mass of catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd., platinum concentration 1.0 wt%) and 1 part by mass of tetra[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane were added and mixed, followed by filtration through a 1 μm membrane filter. Furthermore, in the resin solution, the molar ratio of Si-H groups in the organohydrogen polysiloxane having Si-H groups to the alkenyl groups in the dimethyl polysiloxane having alkenyl groups was 1.0. Additionally, the viscosity of the resin solution (D2) at 25°C was 1.5 Pa·s.

[0228] [Preparation Example 3]

[0229] To 90 parts by mass of (CH2=CH)(CH3)SiO with 2.5 mol% 2 / 2 Unit (D) Vi To a solution consisting of dimethyl polysiloxane (with a unit Mn of 50,000) and 200 parts by mass of p-menthane, 70 parts by mass of (CH2=CH)(CH3)SiO2 with a 5 mol% concentration were added. 2 / 2 Unit (D) ViA solution of dimethyl polysiloxane (with a Mn of 10,000), 100 parts by mass of p-menthane, 5 parts by mass of organohydrogen polysiloxane (represented by M-6 with a Mn of 2,400), and 7 parts by mass of p-menthane, along with 0.6 parts by mass of 1-ethynylcyclohexanol, was prepared. Then, 0.4 parts by mass of catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd., with a platinum concentration of 1.0% by mass) and 1 part by mass of tetra[methylene-(3,5-di-tert-butyl-4-hydroxycinnamate)]methane were added and mixed, followed by filtration through a 1 μm membrane filter to prepare a thermosetting organosilicon resin solution D3. Furthermore, in the resin solution, the molar ratio of the Si-H groups in the organohydrogen polysiloxane having Si-H groups to the alkenyl groups in the dimethyl polysiloxane having alkenyl groups was 1.0. Additionally, the viscosity of the resin solution (D3) at 25°C was 3 Pa·s.

[0230] [Preparation Example 4]

[0231] Twenty parts of resin A1 (with a repeating unit Mw of 3,200 and a dispersion (Mw / Mn) of 2.44), one part of acid-generating agent AG, and four parts of NIKALAC Mw390 (Sanwa Chemical Co., Ltd.) as a crosslinking agent were dissolved in 100 parts of PGMEA containing 0.1% by mass of organosilicon surfactant KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The mixture was filtered through a 0.1 μm fluoropolymer filter to obtain resin composition A1 (laser stripping agent). The transmittance was 1%, measured using a 355 nm UV3600i (SHIMADZU CORPORATION) microscope.

[0232] [Chemical Formula 10]

[0233]

[0234] [Chemical Formula 11]

[0235]

[0236] [Comparative Preparation Example 1]

[0237] A thermosetting organosilicon resin solution D4 was prepared without the addition of tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxycinnamate)]methane in Preparation Example 1.

[0238] [Comparative Preparation Example 2]

[0239] To 20 parts by mass of (CH2=CH)(CH3)SiO with 2.5 mol% of (CH2=CH)(CH3)SiO2 / 2 Unit (D) Vi To a solution formed by dimethyl polysiloxane with a Mn of 30,000 and 100 parts by mass of p-menthane, 150 parts by mass of vinylmethyl polysiloxane with a Mn of 7,000 (made from SiO2) are added. 4 / 2 Unit (Q unit) 50 mol%, (CH3)3SiO 1 / 2 Unit (M unit) 48 mol% and (CH2=CH)3SiO 1 / 2 A thermosetting organosilicon resin solution D5 was prepared by mixing 2 mol% of unit (Vi unit) and 140 parts by mass of a solution of p-menthane, 3 parts by mass of an organohydrogen polysiloxane with Mn of 2,400 represented by M-6, 5 parts by mass of a solution of p-menthane, and 0.6 parts by mass of 1-ethynylcyclohexanol. Then, 0.4 parts by mass of catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd., platinum concentration 1.0 wt%) and 1 part by mass of tetra[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane were added and mixed, followed by filtration through a 1 μm membrane filter. Furthermore, in the resin solution, the molar ratio of Si-H groups in the organohydrogen polysiloxane having Si-H groups to the alkenyl groups in the dimethyl polysiloxane having alkenyl groups was 1.0. Additionally, the viscosity of the resin solution (D5) at 25°C was 0.9 Pa·s.

[0240] [2] Wafer fabrication and evaluation

[0241] [Examples 1-3, Comparative Examples 1-2]

[0242] After spin-coating resin composition A1 (laser release agent) onto a glass wafer with a diameter of 200 mm (thickness: 700 μm), the material corresponding to resin layer I (laser release layer) is formed into a film with the film thickness shown in Table 1 by heating at 120°C for 2 minutes and then at 250°C for 5 minutes using a heating plate.

[0243] In addition, after spin-coating D1 to D5 onto a 200mm diameter silicon wafer (thickness: 725μm), the wafer is heated at 100°C for 2 minutes using a heating plate, thereby forming resin layer II with the film thickness shown in Table 1.

[0244] To bond the glass plate-resin layer I and the resin layer II-wafer surface, the bonding was performed under reduced pressure of less than 1 Pa in a vacuum bonding apparatus (EVG520IS manufactured by EVG Corporation) under the conditions shown in Table 1, and then heated at 150°C for 10 minutes with a heating plate, thereby producing a wafer stack.

[0245] The following tests were then performed on the bonded substrate. The results are shown in Table 1. Furthermore, the evaluation was conducted in the following order.

[0246] (1) Adhesion test

[0247] 200mm wafers were bonded using the EVG520IS wafer bonding apparatus from EVG Corporation. Bonding was performed at the bonding temperatures listed in Table 1, with chamber pressure below 1 Pa and loads ranging from D1 to D5. After bonding, the wafers were cooled to room temperature, and the bonding condition of the interface was assessed visually and under an optical microscope. Waits without bubbles or other abnormalities were rated as good and marked with "○", while those with abnormalities were rated as poor and marked with "×".

[0248] (2) Heat resistance test

[0249] The bonded wafers were placed in a 260°C hot air circulating oven for 2 hours. Then, they were removed from the oven, cooled to room temperature, and their condition was visually inspected. Wafers without interface bubbles or other abnormalities were rated as good and marked with "○", while those with abnormalities were rated as poor and marked with "×".

[0250] (3) Support peelability test

[0251] The peelability of the support was evaluated using the following method. First, dicing tape was attached to the wafer side of the wafer stack using a dicing frame, and the tape was then placed on an adsorption plate using vacuum adsorption. Next, a 355nm laser was irradiated onto the entire surface from the support side. Cases where peeling was successful without damaging the support or wafer were marked with "○", while cases where peeling was impossible or resulted in cracking or other abnormalities were evaluated as defective and marked with "×".

[0252] (4) Dissolution rate test

[0253] The solvent-based dissolution rate was evaluated using the following method. A 200 mm wafer with a residual resin layer was immersed at 50°C with the resin layer on top using a cleaning solution obtained by dissolving tetrabutylammonium fluoride (3% by mass) in dimethylpropionamide and filtering it through a 1 μm filter. The wafer was then immersed in isopropanol (IPA) for 1 minute, placed on a hot plate at 120°C for 3 minutes, and the film thickness was measured. The dissolution rate was calculated using the following formula.

[0254] Dissolution rate = ((thickness of coating on silicon wafer) - (thickness after cleaning test)) / (immersion time in cleaning solution)

[0255] [Table 1]

[0256]

[0257] As shown in Table 1, it can be seen that in Examples 1-3, temporary bonding and support peeling were easy, the cleaning speed was fast, and the cleaning performance was excellent. On the other hand, it can be seen that in Comparative Example 1, some wafer peeling occurred during the heat resistance evaluation, and in Comparative Example 2, the cleaning speed was slow.

[0258] This manual contains the following solutions.

[0259] [1]: A temporary adhesive containing an organosilicon resin, which is a temporary adhesive containing an organosilicon resin for temporarily bonding a semiconductor substrate to a support, characterized in that,

[0260] After attaching the semiconductor substrate and the support body together by means of a temporary adhesive layer formed by the temporary adhesive and heating at 260°C for 2 hours, the semiconductor substrate and the support body are peeled off. Then, the temporary adhesive layer remaining on the semiconductor substrate or the support body is dissolved in a dimethylpropionamide solution containing 3% by mass tetrabutylammonium fluoride at 50°C. When the dissolution rate of the temporary adhesive layer formed by the temporary adhesive layer is measured, the dissolution rate is 20 μm / min or higher.

[0261] [2]: The temporary adhesive containing organosilicon resin according to [1] above, wherein the proportion of dimethylsiloxane units in the non-volatile components of the temporary adhesive containing organosilicon resin is 20% by mass or more.

[0262] [3]: The temporary adhesive containing organosilicon resin according to [1] or [2] above contains a heat resistance enhancer.

[0263] [4]: A temporary adhesive containing an organosilicon resin according to any one of [1] to [3] above, wherein the organosilicon resin is a curable organosilicon resin, and the curable organosilicon resin is a composition containing the following components:

[0264] (A) An organopolysiloxane having two or more alkenyl groups in one molecule;

[0265] (B) Organohydropolysiloxanes containing two or more hydrogen atoms bonded to silicon atoms (Si-H groups) in one molecule, and

[0266] (C) Platinum-based catalysts,

[0267] Furthermore, the amount contained is such that the molar ratio of the Si-H group in component (B) to the alkenyl group in component (A) is 0.3 to 10.

[0268] [5]: The temporary adhesive containing an organosilicon resin according to any one of [1] to [4] above, wherein when temporarily bonding the semiconductor substrate to the support, the temporary adhesive containing an organosilicon resin is used in combination with a laser stripping agent.

[0269] [6]: A method for processing a substrate with circuitry, characterized in that it includes:

[0270] (a) A process of preparing a laminate containing a substrate with circuitry as the semiconductor substrate and the support body, which is temporarily bonded by using the silicone resin layer containing the silicone resin temporary adhesive described above [5] and the laser release layer using the laser release agent.

[0271] (b) A process of processing the back side of the laminate;

[0272] (c) The step of separating the support from the laminate by irradiating the support with a laser from the support side; and

[0273] (d) A process of removing the silicone resin layer and the laser lift-off layer from the separated laminate using a cleaning solution with a temperature of 40°C to 60°C, and removing only the substrate with circuitry.

[0274] Furthermore, this invention is not limited to the above-described embodiments. The above embodiments are illustrative examples, and any technical solutions having a substantially identical structure and achieving the same effect as the technical concept described in the claims of this invention are included within the scope of protection of this invention.

Claims

1. A temporary adhesive containing an organosilicon resin, characterized in that it is a temporary adhesive containing an organosilicon resin for temporarily bonding a semiconductor substrate to a support, and wherein... After attaching the semiconductor substrate and the support body together by means of a temporary adhesive layer formed by the temporary adhesive and heating at 260°C for 2 hours, the semiconductor substrate and the support body are peeled off. Then, the temporary adhesive layer remaining on the semiconductor substrate or the support body is dissolved in a dimethylpropionamide solution containing 3% by mass tetrabutylammonium fluoride at 50°C. When the dissolution rate of the temporary adhesive layer formed by the temporary adhesive layer is measured, the dissolution rate is 20 μm / min or higher.

2. The temporary adhesive containing an organosilicon resin according to claim 1, characterized in that, The proportion of dimethylsiloxane units in the non-volatile component of the temporary adhesive containing organosilicon resin is 20% by mass or more.

3. The temporary adhesive containing an organosilicon resin according to claim 1, characterized in that, It contains heat resistance improvers.

4. The temporary adhesive containing an organosilicon resin according to any one of claims 1 to 3, characterized in that, The organosilicon resin is a curable organosilicon resin, which is a composition containing the following components: (A) An organopolysiloxane having two or more alkenyl groups in one molecule; (B) Organohydropolysiloxanes containing two or more hydrogen atoms bonded to silicon atoms (Si-H groups) in one molecule, and (C) Platinum-based catalysts, Furthermore, the amount contained is such that the molar ratio of the Si-H group in component (B) to the alkenyl group in component (A) is 0.3 to 10.

5. The temporary adhesive containing an organosilicon resin according to any one of claims 1 to 4, characterized in that, When temporarily bonding the semiconductor substrate to the support, the temporary adhesive containing silicone resin is used in combination with a laser stripping agent.

6. A method for processing a substrate with circuitry, characterized in that, It includes: (a) A process of preparing a laminate containing a substrate with circuitry as the semiconductor substrate and the support, which is temporarily bonded by using a silicone resin layer containing a silicone resin temporary adhesive as described in claim 5 and a laser release layer using the laser release agent. (b) A process of processing the back side of the laminate; (c) The step of separating the support from the laminate by irradiating the support with a laser from the support side; and (d) A process of removing the silicone resin layer and the laser lift-off layer from the separated laminate using a cleaning solution with a temperature of 40°C to 60°C, and removing only the substrate with circuitry.

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