Silicone-based resin-containing temporary adhesive and method for processing circuit boards with circuits

Abstract

The present invention is a temporary adhesive containing a silicone-based resin that contains a silicone-based resin, and temporarily adheres a semiconductor substrate and a support, wherein, when the semiconductor substrate and the support are bonded together via a temporary adhesive layer formed by the temporary adhesive, and then the semiconductor substrate and the support are peeled off from each other after heating for two hours at 260°C, followed by dissolving the temporary adhesive layer remaining on the semiconductor substrate or the support in a 50°C dimethylpropionamide solution containing 3% by mass of tetrabutylammonium fluoride, the measurement of the dissolution speed of the temporary adhesive layer formed by the temporary adhesive performed at this time is 20 μm / minute or greater.

Description

[Technical Field]

[0001] The present invention relates to a temporary adhesive containing a silicone-based resin and a method for processing a substrate with a circuit. [Background Art]

[0002] Three-dimensional semiconductor packaging has become essential for achieving further higher density and larger capacity. Three-dimensional packaging technology is a semiconductor fabrication technology in which individual semiconductor chips are thinned and then stacked in multiple layers while being connected by through silicon vias (TSVs). To realize this, it is necessary to thin a substrate on which semiconductor circuits are formed by grinding the non-circuit-formed surface (also referred to as the "back surface"), and then form electrodes including TSVs on the back surface. Conventionally, in the back surface grinding step of a silicon substrate, a back surface protection tape is attached to the side opposite to the grinding surface to prevent wafer damage during grinding. However, this tape uses an organic resin film as a support substrate, and while it has flexibility, its strength and heat resistance are insufficient, making it unsuitable for performing the TSV forming step and the wiring layer forming step on the back surface.

[0003] Accordingly, systems have been proposed in which a semiconductor substrate is bonded to a support such as silicon or glass via an adhesive layer, so as to sufficiently withstand the steps of back surface grinding, TSV formation, and back electrode formation. What is important at this time is the adhesive layer for bonding the substrate to the support. It is required that the adhesive layer can bond the substrate to the support without gaps, have sufficient durability to withstand subsequent steps, and furthermore, allow the thinned wafer to be easily peeled off from the support finally. Since the adhesive layer is peeled off at the final step, this adhesive layer is referred to as a temporary adhesive layer (or temporary adhesive layer) in the present specification.

[0004] As a conventionally known temporary adhesive layer and a peeling method therefor, there has been proposed a technique that uses a heat-meltable hydrocarbon-based compound as an adhesive and performs bonding and peeling in a heated molten state (Patent Document 1). However, although this technique is simple because it is controlled only by heating, its application range is narrow because the thermal stability at high temperatures exceeding 200°C is insufficient.

[0005] Furthermore, when exposed to high temperatures, the cleanability of the adhesive layer is significantly reduced due to thermal oxidation and the like, which sometimes leads to a decrease in cleaning speed and the generation of cleaning residues. Prior Art Documents Patent Documents

[0006] Patent Document 1 Japanese Unexamined Patent Application Publication No. 2003-177528 Summary of the Invention Problems to be Solved by the Invention

[0007] The present invention has been made in view of the above problems, and provides a silicone resin-containing temporary adhesive and a method for processing a substrate with a circuit, wherein bonding between a support and a substrate is easy, a film with uniform thickness can be formed even on a high-step substrate, the process compatibility with TSV formation and wafer backside wiring processes is high, peeling of the substrate from the support is easy, the adhesive layer can be favorably removed without contaminating the substrate, and the productivity of thin substrates can be improved. Means for Solving the Problems

[0008] In order to solve the above problems, the present invention provides a silicone resin-containing temporary adhesive that contains a silicone resin and is used for temporarily bonding a semiconductor substrate and a support, wherein when measuring the dissolution rate of a temporary adhesive layer formed of the temporary adhesive, the measurement is performed by: bonding the semiconductor substrate and the support via the temporary adhesive layer formed of the temporary adhesive, heating at 260°C for 2 hours, then peeling the semiconductor substrate and the support, and dissolving the temporary adhesive layer remaining on the semiconductor substrate or the support in a 50°C dimethylpropionamide solution containing 3 mass% of tetrabutylammonium fluoride, the dissolution rate is 20 µm / min or more.

[0009] Such a silicone-based resin-containing temporary adhesive can be applied to a wide range of semiconductor film deposition processes due to the flexibility and excellent heat resistance of the silicone resin, and it also has excellent CVD (chemical vapor deposition) resistance. Furthermore, it can form a temporary adhesive layer with high film thickness uniformity even on wafers with steps, and this film thickness uniformity makes it easy to produce uniform thin wafers of 50 μm or less. In addition, after thin wafer production, the wafer can be easily peeled off the support, for example, at room temperature. Moreover, with a silicone-based resin-containing temporary adhesive having the above dissolution rate, the adhesive layer can be removed cleanly without contaminating the substrate, thereby increasing the productivity of thin substrates.

[0010] In this case, it is preferable that the proportion of dimethylsiloxane units in the nonvolatile components of the silicone resin-containing temporary adhesive is 20% by mass or more.

[0011] By using this proportion of dimethylsiloxane units, the dissolution rate of the temporary adhesive layer formed with the temporary adhesive can be increased.

[0012] Furthermore, it is preferable that the silicone resin-containing temporary adhesive of the present invention contains a heat resistance improver.

[0013] By including a heat-resistant enhancer in this way, the silicone resin-containing temporary adhesive can maintain a high dissolution rate in the solvent even after being subjected to high-temperature treatment.

[0014] Furthermore, the silicone resin is a curable silicone resin, and the curable silicone resin is (A) Organopolysiloxanes having two or more alkenyl groups in one molecule, (B) Organohydrogenpolysiloxanes containing two or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule, and (C) platinum-based catalyst, Preferably, the composition contains such an amount that the molar ratio of Si-H groups in component (B) to alkenyl groups in component (A) is 0.3 to 10.

[0015] By using such a curable silicone resin as a temporary adhesive containing silicone resin, it is possible to more effectively maintain a high rate of dissolution into the solvent after high-temperature processing.

[0016] Furthermore, it is preferable that the semiconductor substrate and the support be used in combination with a laser release agent when temporarily bonding them together.

[0017] In this way, temporary bonding using a laser release agent makes it easier to remove the adhesive using a laser.

[0018] Furthermore, the present invention relates to a method for processing a circuit board, (a) A step of preparing a laminate including a circuit board and a support as the semiconductor substrate, which is temporarily bonded by a silicone resin layer using the silicone resin-containing temporary adhesive described above and a laser release layer using the laser release agent, (b) A step of processing the back surface of the laminate, (c) A step of separating the support from the laminate by laser irradiation from the support side, (d) A step of removing the silicone resin layer and the laser release layer from the separated laminate with a cleaning solution having a temperature of 40°C to 60°C to extract only the circuit board, The present invention provides a method for processing circuit boards with a circuit, characterized by including the following:

[0019] With this circuit board processing method, as described above, since a temporary adhesive containing a silicone resin with a high melting rate is used even after high-temperature processing, the adhesive layer can be removed cleanly without contaminating the substrate, thereby increasing the productivity of thin substrates. [Effects of the Invention]

[0020] The present invention, due to the flexibility and excellent heat resistance of the silicone resin, can be applied to a wide range of semiconductor film deposition processes, exhibits excellent CVD (chemical vapor deposition) resistance, and can form a temporary adhesive layer with high film thickness uniformity even on wafers with steps. This film thickness uniformity makes it possible to easily produce uniform thin wafers of 50 μm or less. Furthermore, after thin wafer production, the wafer can be easily peeled off the support, for example, at room temperature. In addition, if a temporary adhesive containing a silicone resin with the above-mentioned dissolution rate is used, the adhesive layer can be removed cleanly without contaminating the substrate, thereby increasing the productivity of thin substrates. [Modes for carrying out the invention]

[0021] As described above, there was a need for a silicone-based resin-containing temporary adhesive that facilitates bonding between the support and the substrate, enables the formation of high-step substrates with a uniform film thickness, offers high process compatibility with TSV formation and wafer back-side wiring processes, allows for easy peeling of the substrate from the support, and enables the removal of the adhesive layer without contaminating the substrate, thereby increasing the productivity of thin substrates.

[0022] The inventors of the present invention conducted diligent studies to achieve the above objective and found that the objective can be achieved by using a silicone-containing temporary adhesive, characterized in that, after bonding a semiconductor substrate and a support via a temporary adhesive layer formed with a temporary adhesive, and then peeling the semiconductor substrate and support apart after heating at 260°C for 2 hours, the temporary adhesive layer remaining on the semiconductor substrate or support has a dissolution rate of 20 μm / min or more in a dimethylpropionamide solution containing 3% by mass of tetramethylammonium fluoride at 50°C. Thus, the present invention was completed.

[0023] In other words, the present invention relates to a silicone resin-containing temporary adhesive for temporarily bonding a semiconductor substrate and a support, characterized in that the dissolution rate of the temporary adhesive layer formed with the temporary adhesive is measured when the semiconductor substrate and the support are bonded together via the temporary adhesive layer formed with the temporary adhesive, heated at 260°C for 2 hours, the semiconductor substrate and the support are peeled off, and the temporary adhesive layer remaining on the semiconductor substrate or the support is dissolved in a dimethylpropionamide solution containing 3% by mass of tetrabutylammonium fluoride at 50°C, and the dissolution rate is 20 μm / min or more.

[0024] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0025] First, we will describe the support and semiconductor substrate (wafer) that are temporarily bonded using the silicone resin-containing temporary adhesive of the present invention.

[0026] [Support] Examples of supports to be temporarily bonded using the silicone resin-containing temporary adhesive of the present invention include transparent substrates, silicon wafers, and ceramic substrates. However, transparent substrates are preferred from the viewpoint of laser transparency when irradiating the support during peeling. Typically, glass substrates or quartz substrates are used as the transparent substrate, and their thickness is usually preferably 300 to 1,000 μm, and more preferably 500 to 800 μm.

[0027] [Semiconductor substrates (wafers)] A semiconductor substrate is also called a semiconductor wafer or simply a wafer. Examples of such wafers include silicon wafers, germanium wafers, gallium-arsenide wafers, gallium-phosphorus wafers, and gallium-arsenide-aluminum wafers. The thickness of the wafer is not particularly limited, but is usually preferably 600 to 800 μm, and more preferably 625 to 775 μm. Circuit-equipped substrates are manufactured by processing such wafers to form circuits.

[0028] The silicone resin-containing temporary adhesive of the present invention is preferably used in combination with a laser release agent when temporarily bonding a semiconductor substrate and a support. This laser release agent will be described below.

[0029] [Laser stripping agent] The laser-extracted layer formed using the laser-extracting agent is a light-shielding resin layer (light-shielding layer) containing a resin with a condensed ring in its main chain, and preferably has a transmittance of 20% or less, more preferably 18% or less, and even more preferably 0-15% for light with a wavelength of 355 nm. Furthermore, the laser-extracted layer preferably has an absorption maximum wavelength of 300-500 nm, more preferably 300-400 nm. Moreover, it is preferable that the laser-extracted layer has a transmittance of 20% or less for light with a wavelength of 300-500 nm.

[0030] From the viewpoint of heat resistance, adhesion, chemical resistance, etc., it is preferable that the resin contained in the laser release layer (hereinafter also referred to as "resin layer I") is made of 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") that contains repeating units represented by the following formula (1). The repeating units represented by formula (1) may consist of only one type or may consist of two or more types.

[0031] [ka]

[0032] In formula (1), R 1 ~R 3 Each of these 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. However, R 1 ~R 3 At least one of them is a hydroxyl group.

[0033] Examples of the monovalent organic groups include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-icosyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group, cyclopentylethyl group, cyclohexylethyl group, cyclopentylbutyl group, cyclohexylbutyl group, and adamantyl group; linear, branched, or cyclic alkoxy groups having 1 to 5 carbon atoms, such as methoxy group; epoxy group-containing groups, such as glycidyloxy group; and aryl groups, such as phenyl group and naphthyl group. 1 ~R 3 Preferred elements include hydrogen atoms, hydroxyl groups, methyl groups, and the like.

[0034] In formula (1), R 4 R is a monovalent organic group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, which may have a hydrogen atom or substituents. 4 Examples of monovalent organic groups represented by include alkyl groups, phenyl groups, naphthyl groups, anthracenyl groups, norbornyl groups, and some of their hydrogen atoms may be substituted with alkyl groups, aryl groups, aldehyde groups, halogen atoms, nitro groups, nitrile groups, hydroxyl groups, etc.

[0035] Resin I can usually be obtained by polycondensation reaction of naphthol or its derivatives with an aldehyde compound at room temperature or, if necessary, under cooling or heating conditions, using an acid or base as a catalyst, either in a solvent-free environment or in a solvent.

[0036] Examples of the naphthol or derivative thereof include 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 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, and 2-hydroxymethylnaphthalene. The naphthol or derivative thereof may be used alone or in combination of two or more thereof.

[0037] Examples of the aldehyde compound include those represented by the following formula (2). R 4 -CHO (2) (wherein, R 4 is the same as defined above.)

[0038] Examples of aldehyde compounds represented by formula (2) include formaldehyde, trioxane, paraformaldehyde, acetaldehyde, propylaldehyde, adamantane carbolaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde. Examples include aldehydes, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, 1-naphthylaldehyde, 2-naphthylaldehyde, anthracenecarbaldehyde, pyrenecarbaldehyde, furfural, methylal, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, naphthalenedicarbaldehyde, anthracenedicarbaldehyde, and pyrenedicarbaldehyde. The aldehyde compounds can be used individually or in combination of two or more.

[0039] Examples of solvents used in the polycondensation reaction include alcohols such as methanol, ethanol, isopropyl alcohol, 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 methylene chloride, 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 hexamethylphosphoric triamide. These solvents can be used individually or in combination of two or more. These solvents can be used in an amount of preferably 0 to 2,000 parts by mass, more preferably 10 to 2,000 parts by mass, relative to 100 parts by mass of the total amount of naphthol or its derivative and the aldehyde compound.

[0040] 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, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide, and titanium(IV) oxide.

[0041] 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 ethylmagnesium 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.

[0042] The amount of catalyst used is preferably 0.001 to 100 parts by mass, more preferably 0.005 to 50 parts by mass, per 100 parts by mass of the total amount of naphthol or its derivative and the aldehyde compound. The reaction temperature is preferably from -50°C to the boiling point of the solvent, and more preferably from room temperature to 100°C.

[0043] Polycondensation reaction methods include charging naphthol or its derivatives, aldehydes, and a catalyst all at once, or adding naphthol or its derivatives and aldehydes dropwise in the presence of a catalyst.

[0044] The ratio of naphthol or its derivatives to the aldehyde compound used is preferably 0.01 to 5, more preferably 0.05 to 2, even more preferably 0.05 to 1, and most preferably 0.1 to 0.9, of the aldehyde compound relative to the total amount of naphthol or its derivatives.

[0045] After the polycondensation reaction is complete, in order to remove unreacted raw materials, catalysts, etc., the temperature of the reaction vessel may be raised to 130-230°C and volatile components removed at a temperature of 1-50 mmHg, or the polymer may be fractionated by adding an appropriate solvent or water, or the polymer may be dissolved in a good solvent and then reprecipitation in a poor solvent. These methods can be selected depending on the properties of the resulting reaction product.

[0046] The weight-average molecular weight (Mw) of resin I is preferably 500 to 500,000, and more preferably 1,000 to 100,000. The degree of dispersion of the polymer (Mw / Mn, Mn: number-average molecular weight) is preferably in the range of 1.2 to 20, and more preferably 1 to 10. However, by removing monomer components, oligomer components, or low molecular weight components with Mw less than 500, volatile components during baking can be suppressed, and Mn is preferably set to 500 to 100,000. This prevents contamination around the bake cup and the occurrence of surface defects due to the fall of volatile components. In this invention, Mw and Mn are polystyrene-converted values ​​measured by gel permeation chromatography (GPC) using THF as the solvent.

[0047] The resin composition I preferably contains a crosslinking agent that crosslinks the resin I by a thermal reaction. Suitable crosslinking agents include epoxy compounds having two or more functional groups in their molecules, epoxy resins, amino resins such as methylolmelamine, and it is preferable to further add a catalyst to promote the crosslinking reaction between these crosslinking agents and the polymer.

[0048] Examples of the epoxy compounds and epoxy resins mentioned above include bifunctional, trifunctional, tetrafunctional or more polyfunctional epoxy resins, such as EOCN-1020 (see formula below), EOCN-102S, XD-1000, NC-2000-L, EPPN-201, GAN, NC6000, and those represented by the formula below, all manufactured by Nippon Kayaku Co., Ltd. [ka]

[0049] When the epoxy compound or epoxy resin is used as a crosslinking agent, the amount blended is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, and even more preferably 1 to 30 parts by mass, per 100 parts by mass of the polymer having repeating units represented by formula (1). The crosslinking agent can be used alone or in combination of two or more types. If the blending amount is within the above range, a sufficient crosslinking density can be obtained, and the resulting cured product will function properly.

[0050] 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 carried out appropriately and uniformly.

[0051] Epoxy resin curing accelerators include, for example, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and ethyl isocyanate compounds 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]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), organic salts of DBU, D Examples include DBU compounds such as phenolic resin salts of BU and tetraphenylborate salts of DBU derivatives, triorganophosphines such as triphenylphosphine, tributylphosphine, tris(p-methylphenyl)phosphine, tris(p-methoxyphenyl)phosphine, tris(p-ethoxyphenyl)phosphine, triphenylphosphine-triphenylborate, and tetraphenylphosphine-tetraphenylborate, quaternary phosphonium salts, tertiary amines such as triethyleneammonium-triphenylborate, and their tetraphenylborate salts. The epoxy resin curing accelerator may be used alone or in combination of two or more types.

[0052] The amount of epoxy resin curing accelerator added is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of resin I.

[0053] Furthermore, examples of amino resins such as methylolmelamine used in the present invention include one or more compounds selected from the group consisting of amino condensates modified with formalin or formalin-alcohol and phenolic compounds having an average of two or more methylol groups or alkoxymethylol groups per molecule.

[0054] The amino resin is preferably one with a weight-average molecular weight Mw of 150 to 10,000, and more preferably one with a weight-average molecular weight Mw of 200 to 3,000. If Mw is within the above range, sufficient curability can be obtained, and the heat resistance of the composition after curing is also good.

[0055] Examples of amino condensates modified with formalin or formalin-alcohol include melamine condensates modified with formalin or formalin-alcohol, or urea condensates modified with formalin or formalin-alcohol.

[0056] The melamine condensate modified with formalin or formalin-alcohol can be prepared, for example, by methylolating a melamine monomer with formalin according to a known method, or by further modifying it by alkoxylation with an alcohol to obtain a modified melamine represented by the following formula. A lower alcohol, such as an alcohol having 1 to 4 carbon atoms, is preferred as the alcohol. [ka] (In the formula, R 5 ~R 10 Each of these is independently a methylol group, an alkoxymethyl group containing a linear, branched, or cyclic alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, but at least one is either a methylol group or an alkoxymethyl group.

[0057] Examples of the modified melamine include trimethoxymethylmonomethylolmelamine, dimethoxymethylmonomethylolmelamine, trimethylolmelamine, hexamethylolmelamine, and hexamethoxymethylolmelamine. Next, the modified melamine or a polymer obtained therefrom (for example, oligomers such as dimers and trimers) is subjected to addition-condensation polymerization with formaldehyde according to a conventional method until a desired molecular weight is reached, thereby obtaining a melamine condensate modified with formalin or formalin-alcohol. One or more of the modified melamine and its condensates can be used as crosslinking agents.

[0058] Furthermore, urea condensates modified with formalin or formalin-alcohol can be prepared, for example, by methylolating a urea condensate of a desired molecular weight with formalin according to a known method, or by further modifying it by alkoxylation with alcohol.

[0059] Specific examples of the modified urea condensate include, for example, methoxymethylated urea condensate, ethoxymethylated urea condensate, and propoxymethylated urea condensate. One or more of these modified urea condensates can be used.

[0060] Among these, examples of phenol compounds having an average of two or more methylol groups or alkoxymethylol groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2',6,6'-tetramethoxymethylbisphenol A.

[0061] These amino condensates or phenolic compounds can be used individually or in combination of two or more.

[0062] The amount of the crosslinking agent is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass, per 100 parts by mass of resin I. Within this range, composition I will cure sufficiently, and the resulting cured product will function properly.

[0063] Furthermore, when using an amino resin such as methylolmelamine as a crosslinking agent, it is preferable to add a thermal acid generator as a catalyst. This thermal acid generator is not particularly limited, but examples include ammonium salts represented by the following formula. [ka] (In the formula, R 11 ~R 14 Each of these independently represents a hydrogen atom, a linear, branched, or cyclic C1-C12 alkyl or oxoalkyl group, a linear, branched, or cyclic C2-C12 alkenyl or oxoalkenyl group, a C6-C20 aryl group, or a C7-C12 aralkyl or aryloxoalkyl group, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy groups. 11 ~R 1 4 Two selected from these may form a ring with the nitrogen atom to which they are bonded, and this ring is either an aliphatic ring having 3 to 10 carbon atoms and containing the nitrogen atom in the formula, or a heteroaromatic ring having 5 to 10 carbon atoms and containing the nitrogen atom in the formula. - (This refers to a sulfonic acid, perfluoroalkylimide acid, or perfluoroalkylmethidic acid in which at least one of the α-positions is fluorinated.)

[0064] X - Specifically, examples include perfluoroalkanesulfonic acid anions such as triflate anions and nonaflate anions, sulfonate anions in which at least one of the α positions is fluorosubstituted, imid anions such as bis(trifluoromethylsulfonyl)imid anions, bis(perfluoroethylsulfonyl)imid anions, and bis(perfluorobutylsulfonyl)imid anions, and metanide anions such as tris(trifluoromethylsulfonyl)methanide anions and tris(perfluoroethylsulfonyl)methanide anions.

[0065] The amount of the thermal acid generator added is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 10 parts by mass, per 100 parts by mass of resin I. Within this range, composition I hardens sufficiently and has good storage stability.

[0066] The laser stripping agent (laser stripping composition) may contain a solvent. Examples of the solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl 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; 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 mono-tert-butyl ether acetate, and γ-butyrolactone. These can be used individually or in combination of two or more. The amount of solvent blended is preferably 100 to 5,000 parts by mass, more preferably 150 to 2,500 parts by mass, per 100 parts by mass of resin I.

[0067] The laser stripping agent (laser stripping composition) may, if necessary, contain surfactants and antioxidants, etc., for the purpose of further improving heat resistance.

[0068] The surfactant is not particularly limited, but examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene olein ether; polyoxyethylene alkylaryl 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; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan trioleate. Nonionic surfactants such as polyoxyethylene sorbitan tristearate and other polyoxyethylene sorbitan fatty acid esters, F-Top® EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megafac® F171, F172, F173 (manufactured by DIC Corporation), Florard® FC430, FC431 (manufactured by 3M Company), Asahi Guard AG Examples include 710, fluorine-based surfactants such as Surflon® S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol® E1004, KH-10, KH-20, KH-30, KH-40 (Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic acid-based or methacrylic acid-based polyflow No. 75, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.). These can be used individually or in combination of two or more.

[0069] The antioxidant is preferably at least one selected from hindered phenol compounds, hindered amine compounds, organophosphorus compounds, and organosulfur compounds, but is particularly preferably a hindered phenol compound.

[0070] The hindered phenol compounds are not particularly limited, but the following are preferred. For example, 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), and 2,5-di-tert-butyl-hydroquinone (trade name: Nocrac). NS-7), 2,6-di-tert-butyl-4-ethylphenol (product name: Nocrac M-17), 2,5-di-tert-amylhydroquinone (product name: Nocrac DAH), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (product name: Nocrac NS-6), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester (product name: IRGANOX 1222), 4,4'-thiobis(3-methyl-6-tert-butylphenol) (product name: Nocrac 300), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (product name: Nocrac NS-5), 4,4'-Butylidenebis(3-methyl-6-tert-butylphenol) (Product name: Adekastab AO-40), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (Product name: Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (Product name: Sumilizer GS), 2,2'-Methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 4,4'-Methylenebis(2,6-di-tert-butylphenol) (Product name: C-NOX 226M), 4,6-bis(octylthiomethyl)-o-cresol (Product name: IRGANOX 1520L), 2,2'-ethylenebis(4,6-di-tert-butylphenol), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (product name: IRGANOX 1076), 1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (product name: Adekastab AO-30), tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane (product name: Adekastab AO-60), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (product name: IRGANOX 245), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-Triazine (Trade name: IRGANOX 565), N,N'-Hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide) (Trade name: IRGANOX 1098), 1,6-Hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Trade name: IRGANOX 259), 2,2-Thio-diethylenebis[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) Examples include GA-80), tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114), bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl) calcium / polyethylene wax 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-butyldibenz[d,f][1,3,2]dioxaphosfepine (trade name: Sumilizer GP), etc. ,

[0071] The hindered amine compound is not particularly limited, but the following are preferred. For example, p,p'-dioctyldiphenylamine (product name: IRGANOX 5057), phenyl-α-naphthylamine (Nocrac PA), poly(2,2,4-trimethyl-1,2-dihydroquinoline) (product names: Nocrac 224, 224-S), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (product name: Nocrac AW), N,N'-diphenyl-p-phenylenediamine (product name: Nocrac DP), N,N'-di-β-naphthyl-p-phenylenediamine (product name: Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine (product name: Nocrac 810NA), N,N'-diallyl-p-phenylenediamine (product name: Nonflex TP), 4,4'-(α,α-dimethylbenzyl)diphenylamine (product name: Nocrac CD), p,p-toluenesulfonylaminodiphenylamine (product name: Nocrac TD), N-phenyl-N'-(3-methchlorolyloxy-2-hydroxypropyl)-p-phenylenediamine (product name: Nocrac G1), N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (product name: Ozonon 35), N,N'-di-sec-butyl-p-phenylenediamine (product name: Sumilizer BPA), N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (product name: Antigene 6C), alkylated diphenylamine (product name: Sumilizer 9A), dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (product name: Tinuvin 622LD), poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]](product name: CHIMASSORB 944), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-Triazine condensate (product name: CHIMASSORB 119FL), bis(1-octyroxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (product name: TINUVIN, 123), Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (product name: TINUVIN 770), 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl) (product name: TINUVIN 144), Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (product name: TINUVIN 765), Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate (product name: LA-57), Tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate (product name: LA-52), Mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol (product name: LA-62), Mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol (product name: LA-67), 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol Examples include 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-tetraoxaspiro[5.5]undecane (product 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-tetraoxaspiro[5.5]undecane (product name: LA-68LD), (2,2,6,6-tetramethylene-4-piperidyl)-2-propylene carboxylate (product name: Adekastab LA-82), (1,2,2,6,6-pentamethyl-4-piperidyl)-2-propylene carboxylate (product name: Adekastab LA-87), etc.

[0072] The organophosphorus compounds are not particularly limited, but the following are preferred: For example, bis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphine, 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: Adekastab TPP), diphenyl mono Octyl phosphite (product name: Adekastab C), tri(p-cresyl) phosphite (product name: Chelex-PC), diphenyl monodecyl phosphite (product name: Adekastab 135A), diphenyl mono(tridecyl) phosphite (product name: JPM313), tris(2-ethylhexyl) phosphite (product name: JP308), phenyl didecyl phosphite (product name: Adekastab 517), tridecyl phosphite (Product name: Adekastab 3010), Tetraphenyldipropylene glycol diphosphite (Product name: JPP100), Bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (Product name: Adekastab PEP-24G), Tris(tridecyl) phosphite (Product name: JP333E), Bis(nonylphenyl) pentaerythritol diphosphite (Product name: Adekastab PEP-4C), Bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (Product name: Adekastab PEP-36), Bis[2,4-di(1-phenylisopropyl)phenyl] pentaerythritol diphosphite (Product name: Adekastab PEP-45), Trilauryl trithiophosphite (Product name: JPS312), Tris(2,4-di-tert-butylphenyl) phosphite (Product name: IRGAFOS 168), Tris(nonylphenyl) phosphite (product name: Adekastab 1178), Distearyl pentaerythritol diphosphite (product name: Adekastab PEP-8), Tris(mono,dinonylphenyl) phosphite (product name: Adekastab 329K), Trioleyl phosphite (product name: Chelex-OL), Tristearyl phosphite (product name: JP318E), 4,4'-Butylidenebis(3-methyl-6-tert-butylphenylditridecyl)phosphite (trade name: JPH1200), tetra(C, 12 -C 15 Mixed alkyl)-4,4'-isopropylidenediphenyl diphosphite (product name: Adekastab 1500), tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-tert-butylphenol) diphosphite (product name: Adekastab 260), hexa(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane-triphosphite (product name: Adekastab 522A), hydrogenated bisphenol A phosphite polymer (HBP), tetrakis(2,4-di-tert-butylphenyloxy)4,4'-bi Examples include phenylene-diphosphine (trade name: P-EPQ), tetrakis(2,4-di-tert-butyl-5-methylphenyloxy)4,4'-biphenylene-diphosphine (trade name: GSY-101P), 2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]-N,N-bis[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]-ethyl]ethanamine (trade name: IRGAFOS 12), and 2,2'-methylenebis(4,6-di-tert-butylphenyl)octylphosphine (trade name: Adekastab HP-10).

[0073] The aforementioned organic sulfur compounds are not particularly limited, but the following are preferred. For example, dilauryl-3,3'-thiodipropionate (product name: Sumilizer TPL-R), dimyristyl-3,3'-thiodipropionate (product name: Sumilizer TPM), distearyl-3,3'-thiodipropionate (product name: Sumilizer TPS), pentaerythritol tetrakis(3-laurylthiopropionate) (product name: Sumilizer TP-D), ditridecyl-3,3'-thiodipropionate (product name: Sumilizer TL), 2-mercaptobenzimidazole (product name: Sumilizer MB), ditridecyl-3,3'-thiodipropionate (product name: Adekastab AO-503A), 1,3,5-tris-β-stearylthiopropionyloxyethyl isocyanurate, 3,3'-thiobispropionate didodecyl ester (product name: IRGANOX PS) Examples include diocdecyl 3,3'-thiobispropionate (trade name: IRGANOX PS 802FL), 800FL, etc.

[0074] Among the antioxidants, tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane is particularly preferred. The amount of antioxidant added is preferably 0.5 to 5 parts by mass, and more preferably 1 to 3 parts by mass, per 100 parts by mass of resin I. Within this range, sufficient heat resistance and compatibility can be obtained. The antioxidant can be used alone or in combination of two or more types.

[0075] If the resin composition I is a solution, it is applied to a support by methods such as spin coating, roll coating, die coating, printing, or dipping, and pre-baking is performed at a temperature of preferably 80 to 200°C, more preferably 100 to 180°C, depending on the evaporation conditions of the solvent, to evaporate the solvent and form the resin composition layer I'.

[0076] On the other hand, if the resin composition I (laser-release layer) is a film-like composition, the resin composition layer I' can be formed on the support by lamination.

[0077] The resin composition layer I' formed on the support can be further heat-cured to function as resin layer I (laser release layer). Heat curing can be performed using a hot plate or oven, and the conditions are typically 100-350°C for 5-10 minutes, preferably 150-300°C for 3-8 minutes. This curing reaction can also be achieved by forming an uncured wafer laminate without curing the resin composition layer I', and then heating the entire laminate.

[0078] The thickness of the resin layer I (laser-release layer) formed on the support is preferably 0.1 to 50 μm, and more preferably 0.3 to 30 μm. When the thickness is within the above range, the light-shielding properties are sufficient and the flatness of the film is also good.

[0079] [Silicone-based resin-containing temporary adhesive] The silicone resin-containing temporary adhesive of the present invention satisfies the above-mentioned dissolution rate requirements, but it is preferable that it contains a curable silicone resin containing the following components. (A) Organopolysiloxanes having two or more alkenyl groups in one molecule, (B) Organohydrogenpolysiloxanes containing two or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule, and (C) Platinum-based catalyst.

[0080] Here, it is preferable that the composition contains an amount such that the molar ratio of Si-H groups in component (B) to alkenyl groups in component (A) is between 0.3 and 10.

[0081] The silicone resin-containing temporary adhesive of the present invention preferably contains the following components (A) to (D), with component (D) added. (A) Organopolysiloxane having two or more alkenyl groups in one molecule: 100 parts by mass, (B) Organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms (Si-H groups) in one molecule: an amount such that the total number of SiH groups in component (B) is 0.3 to 10 in molar ratio to the total number of alkenyl groups in component (A). (C) Platinum-based catalyst (hydrosilylation reaction catalyst): 0.1 to 5,000 ppm in terms of metal atomic weight relative to the total mass of components (A), (B), and (D), and (D) Non-functional organopolysiloxane: 0.1 to 200 parts by mass.

[0082] This silicone resin-containing temporary adhesive is a resin used to form a silicone resin layer (hereinafter also referred to as "resin layer II").

[0083] [(A) component] Component (A) is an organopolysiloxane having two or more alkenyl groups in one molecule. Examples of component (A) include linear or branched diorganopolysiloxanes containing two or more alkenyl groups in one molecule, and organopolysiloxanes with a three-dimensional network structure containing two or more alkenyl groups in one molecule and having siloxane units (Q units) represented by SiO4 / 2 units. Of these, diorganopolysiloxanes or organopolysiloxanes with a three-dimensional network structure having an alkenyl group content of 0.6 to 9 mol% are preferred. In this invention, the alkenyl group content is the ratio (mol%) of the number of alkenyl groups to the number of Si atoms in the molecule.

[0084] Examples of such organopolysiloxanes include those represented by the following formulas (A-1), (A-2), or (A-3). These may be used individually or in combination of two or more. [ka]

[0085] In formulas (A-1) to (A-3), R 21 ~R 36 Each of these is independently a monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group.1 ~X 5 These are, independently, monovalent organic groups containing an alkenyl group.

[0086] In equation (A-1), a and b are each independent integers between 0 and 3. In equations (A-1) and (A-2), c 1 , c 2 d 1 and d 2 is 0≦c 1 ≤10, 2 ≤c 2 ≤10, 0 ≤d 1 ≤100 and ≤0 d 2 It is an integer satisfying ≤ 100, where a + b + c 1 ≥ 2. a, b, c 1 , c 2 d 1 and d 2 The combination of elements is preferably such that the alkenyl group content is 0.6 to 9 mol%.

[0087] In equation (A-3), e is an integer between 1 and 3. 1 ,f 2 and f 3 is, (f 2 +f 3 ) / f 1 The value becomes 0.3 to 3.0, and f 3 / ( f 1 +f 2 +f 3 This is a number such that the result is between 0.01 and 0.6.

[0088] Other than the aliphatic unsaturated hydrocarbon group mentioned above, monovalent hydrocarbon groups having 1 to 10 carbon atoms are preferred, and examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and n-hexyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; and aryl groups such as phenyl and tolyl groups. Of these, alkyl groups such as methyl groups or phenyl groups are preferred.

[0089] The aforementioned monovalent organic group containing an alkenyl group is preferably one having 2 to 10 carbon atoms, and examples include alkenyl groups such as vinyl, allyl, hexenyl, and octenyl groups; (meth)acryloylalkyl groups such as acryloylpropyl, acryloylmethyl, and methacryloylpropyl groups; (meth)acryloxyalkyl groups such as acryloxypropyl, acryloxymethyl, methacryloxypropyl, and methacryloxymethyl groups; and monovalent hydrocarbon groups containing an alkenyl group such as cyclohexenylethyl and vinyloxypropyl groups. Of these, vinyl groups are preferred from an industrial standpoint.

[0090] In formula (A-1), a and b are each an integer from 0 to 3, but a is preferable when it is between 1 and 3, because the molecular chain ends are sealed with alkenyl groups, allowing the reaction to be completed in a short time due to the highly reactive molecular chain terminal alkenyl groups. Furthermore, from a cost perspective, a being of 1 is industrially preferable. The properties of the alkenyl group-containing diorganopolysiloxane represented by formula (A-1) or (A-2) are preferably oily or raw rubbery.

[0091] The organopolysiloxane represented by formula (A-3) is SiO 4 / 2 It includes units and has a three-dimensional network structure. In formula (A-3), e is an integer from 1 to 3, but from a cost perspective, it is industrially preferable to be 1. Also, the average value of e and f 3 The product with / (f1+f2+f3) is preferably between 0.02 and 1.5, and more preferably between 0.03 and 1.0. The organopolysiloxane represented by formula (A-3) may be used as a solution dissolved in an organic solvent.

[0092] The number-average molecular weight (Mn) of the organopolysiloxane of component (A) is preferably 100 to 1,000,000, and more preferably 1,000 to 100,000. When Mn is within the above range, it is preferable in terms of workability due to the viscosity of the composition and processability due to the storage modulus after curing. In this invention, Mn is a polystyrene-converted value measured by gel permeation chromatography using toluene as a solvent.

[0093] Component (A) may be used alone or in combination of two or more. In particular, it is preferable 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, and more preferably 10 to 500 parts by mass, per 100 parts by mass of organopolysiloxane represented by formula (A-1).

[0094] [(B) Component] Component (B) is a crosslinking agent, and is an organohydrogenpolysiloxane having at least two, preferably three or more, hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule. The organohydrogenpolysiloxane may be linear, branched, or cyclic. Furthermore, the organohydrogenpolysiloxane may be used alone or in combination of two or more types.

[0095] The viscosity of component (B), the organohydrogenpolysiloxane, at 25°C is preferably 1 to 5,000 mPa·s, and more preferably 5 to 500 mPa·s. In this invention, viscosity is measured at 25°C using a rotational viscometer. The Mn of component B is measured by GPC in the same way as component A.

[0096] The Mn of component (B), organohydrogenpolysiloxane, is preferably 100 to 100,000, and more preferably 500 to 10,000. When Mn is within the above range, it is preferable in terms of workability due to the viscosity of the composition and processability due to the storage modulus after curing.

[0097] Component (B) is preferably formulated such that the total number of SiH groups in component (B) relative to the total number of alkenyl groups in component (A) is in the range of 0.3 to 10 in molar ratio (SiH groups / alkenyl groups), and more preferably in the range of 1.0 to 8.0. If the molar ratio is 0.3 or higher, the crosslinking density will not be low, and problems such as the temporary adhesive layer (silicone resin layer) not curing will not occur. If the molar ratio is 10 or lower, the crosslinking density will not be too high, sufficient tack and adhesive strength can be obtained, and the usable time of the processing solution can be extended.

[0098] [(C) component] Component (C) can function as a hydrosilylation reaction catalyst, and preferably a platinum group metal hydrosilylation reaction catalyst can be used, but 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 hydrosilyl group in component (B). Since this hydrosilylation reaction catalyst is generally a compound of a precious metal and is expensive, platinum or platinum compounds, which are relatively easy to obtain, are often used.

[0099] Examples of platinum compounds include chloroplatinic acid or complexes of chloroplatinic acid with olefins such as ethylene, complexes with alcohols or vinylsiloxanes, and metallic platinum supported on silica, alumina, carbon, etc. Besides platinum compounds, rhodium, ruthenium, iridium, and palladium-based compounds are also known as platinum group metal catalysts, such as RhCl(PPh3)3, RhCl(CO)(PPh3)2, and Ru3(CO). 12 Examples include IrCl(CO)(PPh3)2 and Pd(PPh3)4. In the above formula, Ph represents a phenyl group.

[0100] When using these catalysts, if they are solid catalysts, they can be used in solid form. However, to obtain a more uniform cured product, it is preferable to dissolve chloroplatinic acid or the complex in a suitable solvent and make it compatible with component (A).

[0101] The amount of component (C) added is an effective amount, which is usually 0.1 to 5,000 ppm in terms of metal atomic weight relative to the total mass of components (A), (B), and (D), but 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 retention strength 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 also be extended.

[0102] [(D) component] Component (D) is a non-functional organopolysiloxane. Here, "non-functional" means that it does not have reactive groups such as hydrogen atoms, halogen atoms, hydroxyl groups, or alkoxy groups directly bonded to the silicon atom within the molecule, nor does it have reactive groups such as alkenyl groups or epoxy groups directly bonded to the silicon atom or via any other group.

[0103] Examples of such non-functional organopolysiloxanes include unsubstituted or substituted organopolysiloxanes having monovalent hydrocarbon groups other than aliphatic unsaturated hydrocarbon groups, with 1 to 12, preferably 1 to 10 carbon atoms. Examples of such monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; and aralkyl groups such as benzyl and phenethyl groups. Furthermore, some or all of the hydrogen atoms of these groups may be substituted with halogen atoms such as chlorine, fluorine, or bromine atoms. Examples of such groups include halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl. The monovalent hydrocarbon group is preferably an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group.

[0104] The molecular structure of the non-functional organopolysiloxane of component (D) is not particularly limited and may be linear, branched, cyclic, etc., but linear or branched organopolysiloxanes are preferred, and in particular, linear or branched diorganopolysiloxanes in which the main chain basically consists of repeating diorganosiloxane units and the molecular chain ends are sealed with triorganosiloxy groups.

[0105] The non-functional organopolysiloxane component (D) is preferably such that the viscosity of a 30% by mass toluene solution thereof at 25°C is 100 to 500,000 mPa·s, and more preferably 200 to 100,000 mPa·s, from the viewpoint of the workability of the composition, the coating properties on the substrate, the mechanical properties of the cured product, and the peelability of the support. Within this range, it has an appropriate molecular weight, so it does not volatilize when the silicone resin composition is heat-cured, making it difficult to obtain the desired effect, nor does it cause wafer cracking in wafer thermal processes such as CVD, and it is also preferable because it has good workability and coating properties. The viscosity of component D is measured using a rotational viscometer (25°C).

[0106] The linear, non-functional organopolysiloxanes include: dimethylsiloxane polymers with trimethylsiloxy groups sealed at both ends of the molecular chain, diphenylpolysiloxanes with trimethylsiloxy groups sealed at both ends of the molecular chain, 3,3,3-trifluoropropylmethylsiloxane polymers with trimethylsiloxy groups sealed at both ends of the molecular chain, dimethylsiloxane / diphenylsiloxane copolymers with trimethylsiloxy groups sealed at both ends of the molecular chain, dimethylsiloxane / 3,3,3-trifluoropropylmethyl copolymers with trimethylsiloxy groups sealed at both ends of the molecular chain, and molecular chains Examples include diphenylsiloxane-3,3,3-trifluoropropylmethyl copolymer with trimethylsiloxy groups sealed at both ends of the molecular chain, dimethylsiloxane-3,3,3-trifluoropropylmethylsiloxane-diphenylsiloxane copolymer with trimethylsiloxy groups sealed at both ends of the molecular chain, dimethylpolysiloxane with triphenylsiloxy groups sealed at both ends of the molecular chain, diphenylpolysiloxane with triphenylsiloxy groups sealed at both ends of the molecular chain, and dimethylsiloxane-diphenylsiloxane copolymer with triphenylsiloxy groups sealed at both ends of the molecular chain.

[0107] Examples of the branched, non-functional organopolysiloxanes include those listed below. [ka]

[0108] [ka] (In the formula, g1, g2, g3, g4, g5, g1', g2', g3', g4', g5', and g6' are each any integer such that the viscosity of a 30% by mass toluene solution of the compound at 25°C falls within the specified range.)

[0109] The amount of the non-functional organopolysiloxane component (D) is 0.1 to 200 parts by mass per 100 parts by mass of component (A), but preferably 1 to 180 parts by mass, and more preferably 10 to 170 parts by mass. If the amount of component (D) is within the above range, the wafer can be easily peeled off the support. The non-functional organopolysiloxane component (D) may be used alone or in combination of two or more types. Furthermore, its properties are preferably oily or rubbery.

[0110] Furthermore, in the present invention, it is preferable to adjust the amount of non-functional organopolysiloxane in component (D) to ensure that the proportion of dimethylsiloxane units in the non-volatile components of the silicone resin-containing temporary adhesive is 20% by mass or more. The upper limit is not particularly limited, but is approximately 95% by mass. By achieving such a proportion of dimethylsiloxane units, the dissolution rate of the temporary adhesive layer formed with the temporary adhesive can be increased. The dissolution rate is 20 μm / min or more. The upper limit is not particularly limited, but is approximately 200 μm / min or less. It is preferable to make it at least 50 μm / min or more.

[0111] [(E) component] The thermosetting silicone resin composition may further contain a reaction control agent as component (E). The reaction control agent is added as needed to prevent the composition from becoming thicker or gelling when preparing the composition or applying it to a substrate.

[0112] Examples of the reaction control agents include 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-ethynylcyclohexanol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, bis(2,2-dimethyl-3-butynyloxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane. Of these, 1-ethynylcyclohexanol and 3-methyl-1-butyne-3-ol are preferred.

[0113] When the thermosetting silicone resin composition contains component (E), its controllability differs depending on its chemical structure, so its content should be adjusted to the optimal amount. However, considering the effects on curability, storage stability, and post-curing properties, the content of component (E) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the total of components (A), (B), and (D). If the content of component (E) is within the above range, the composition has a long usable time, long-term storage stability is obtained, and curability and workability are good.

[0114] The aforementioned thermosetting silicone resin composition further contains R A 3SiO 0.5 Unit (in the formula, R) A Each is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. ) and SiO2 units are included, with a molar ratio of RA3SiO0.5 units to SiO2 units (R A 3SiO 0.5 An organopolysiloxane having a SiO2 content of 0.3 to 1.8 may be added. The amount added is preferably 0 to 500 parts by mass per 100 parts by mass of component (A).

[0115] The silicone resin-containing temporary adhesive of the present invention preferably contains a heat resistance improver. The heat resistance improver is preferably at least one selected from hindered phenol compounds and hindered amine compounds.

[0116] The hindered phenol compounds are not particularly limited, but the following are preferred. For example, 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), and 2,5-di-tert-butyl-hydroquinone (trade name: Nocrac). NS-7), 2,6-di-tert-butyl-4-ethylphenol (product name: Nocrac M-17), 2,5-di-tert-amylhydroquinone (product name: Nocrac DAH), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (product name: Nocrac NS-6), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester (product name: IRGANOX 1222), 4,4'-thiobis(3-methyl-6-tert-butylphenol) (product name: Nocrac 300), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (product name: Nocrac NS-5), 4,4'-Butylidenebis(3-methyl-6-tert-butylphenol) (Product name: Adekastab AO-40), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (Product name: Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (Product name: Sumilizer GS), 2,2'-Methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 4,4'-Methylenebis(2,6-di-tert-butylphenol) (Product name: C-NOX 226M), 4,6-bis(octylthiomethyl)-o-cresol (Product name: IRGANOX 1520L), 2,2'-ethylenebis(4,6-di-tert-butylphenol), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (product name: IRGANOX 1076), 1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (product name: Adekastab AO-30), tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane (product name: Adekastab AO-60), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (product name: IRGANOX 245), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-Triazine (Trade name: IRGANOX 565), N,N'-Hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide) (Trade name: IRGANOX 1098), 1,6-Hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Trade name: IRGANOX 259), 2,2-Thio-diethylenebis[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) Examples include GA-80), tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114), bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl) calcium / polyethylene wax 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-butyldibenz[d,f][1,3,2]dioxaphosfepine (trade name: Sumilizer GP), etc. ,

[0117] The hindered amine compound is not particularly limited, but the following are preferred. For example, p,p'-dioctyldiphenylamine (product name: IRGANOX 5057), phenyl-α-naphthylamine (product name: Nocrac PA), poly(2,2,4-trimethyl-1,2-dihydroquinoline) (product name: Nocrac 224, 224-S), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (product name: Nocrac AW), N,N'-diphenyl-p-phenylenediamine (product name: Nocrac DP), N,N'-di-β-naphthyl-p-phenylenediamine (product name: Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine (product name: Nocrac 810NA), N,N'-diallyl-p-phenylenediamine (product name: Nonflex TP), 4,4'-(α,α-dimethylbenzyl)diphenylamine (product name: Nocrac CD), p,p-toluenesulfonylaminodiphenylamine (product name: Nocrac TD), N-phenyl-N'-(3-methchlorolyloxy-2-hydroxypropyl)-p-phenylenediamine (product name: Nocrac G1), N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (product name: Ozonon 35), N,N'-di-sec-butyl-p-phenylenediamine (product name: Sumilizer BPA), N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (product name: Antigene 6C), alkylated diphenylamine (product name: Sumilizer 9A), dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (product name: Tinuvin 622LD), poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]](product name: CHIMASSORB 944), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-Triadine condensate (product name: CHIMASSORB 119FL), bis(1-octyroxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (product name: TINUVIN 123), bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (product name: TINUVIN 770), 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl) (product name: TINUVIN 144), bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (product name: TINUVIN 765), Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate (product name: LA-57), Tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate (product name: LA-52), Mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol (product name: LA-62), Mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol (product name: LA-67), 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol Examples include 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-tetraoxaspiro[5.5]undecane (product 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-tetraoxaspiro[5.5]undecane (product name: LA-68LD), (2,2,6,6-tetramethylene-4-piperidyl)-2-propylene carboxylate (product name: Adekastab LA-82), (1,2,2,6,6-pentamethyl-4-piperidyl)-2-propylene carboxylate (product name: Adekastab LA-87), etc.

[0118] Such a heat-resistant improver is preferably added in an amount of 0.5 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and more preferably 1 to 3 parts by mass, per 100 parts by mass of silicone resin. The heat-resistant improver can be added during the synthesis of the resin or when mixing the resin with other processed materials.

[0119] The thermosetting silicone resin composition may contain fillers such as silica to further enhance the heat resistance of the resulting temporary adhesive layer.

[0120] Thermosetting silicone resin compositions may be used after being dissolved by adding a solvent to improve workability and mixability by lowering the viscosity of the composition, and to adjust the film thickness of the temporary adhesive layer. The solvent used is not particularly limited as long as it can dissolve the above components, but hydrocarbon solvents such as pentane, hexane, cyclohexane, isooctane, nonane, decane, p-menthane, pinene, isododecane, and limonene are preferred.

[0121] Methods for solution formation include preparing the thermosetting silicone resin composition and then adding a solvent to adjust it to the desired viscosity, or pre-diluting the high-viscosity components (A), (B), and / or (D) with a solvent to improve workability and mixability before mixing the remaining components. Furthermore, the mixing method during solution formation can be appropriately selected based on the viscosity of the composition and the desired workability, using methods such as a shaking mixer, magnetic stirrer, or various mixers.

[0122] The amount of solvent added can be set appropriately from the viewpoint of adjusting the viscosity and workability of the composition and the thickness of the temporary adhesive layer, but for example, it is preferably 5 to 900 parts by mass, more preferably 10 to 400 parts by mass, per 100 parts by mass of the thermosetting silicone resin composition.

[0123] The temporary adhesive layer can be formed by applying the thermosetting silicone resin composition onto the substrate by methods such as spin coating or roll coating. When forming the temporary adhesive layer on the substrate by methods such as spin coating, it is preferable to coat the thermosetting silicone resin composition in solution.

[0124] The solution-formed thermosetting silicone resin composition has a viscosity at 25°C that is preferably 1 to 100,000 mPa·s, and more preferably 10 to 10,000 mPa·s, from the viewpoint of coatability.

[0125] The thermosetting silicone resin composition, after curing, typically exhibits a 180° peel strength of 2 to 50 gf for a 25 mm wide test piece (e.g., a glass test piece) at 25°C, preferably 3 to 30 gf, and more preferably 5 to 20 gf. A strength of 2 gf or higher eliminates the risk of wafer displacement during wafer grinding, while a strength of 50 gf or lower facilitates wafer peeling.

[0126] The thermosetting silicone resin composition has a storage modulus at 25°C after curing 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 tough and there is no risk of wafer displacement or resulting wafer cracking during wafer grinding. If it is 1,000 MPa or less, deformation stress during wafer thermal processes such as CVD can be reduced and the wafer remains stable during thermal processing.

[0127] [Circuit board processing method] Next, we will explain a method for processing circuit boards using a temporary adhesive containing silicone resin.

[0128] The method for processing the circuit board of the present invention may include the following steps. (a) A step of preparing a laminate including a circuit board and a support as the semiconductor substrate, which is temporarily bonded by a silicone resin layer using the silicone resin-containing temporary adhesive of the present invention and a laser release layer using the laser release agent, (b) A step of processing the back surface of the laminate, (c) A step of separating the support from the laminate by laser irradiation from the support side, (d) A step of removing the silicone resin layer and the laser release layer from the separated laminate with a cleaning solution having a temperature of 40°C to 60°C, and taking out only the circuit board.

[0129] [Process (a)] As described above, step (a) is a step of preparing a laminate including a circuit board and a support as a semiconductor substrate. More specifically, this step can be carried out as follows, but is not limited to this.

[0130] [Process (a1) or (a1')] Step (a1) is a step of forming a light-shielding resin layer I on a support, and step (a1') is a step of forming a resin composition layer I' on the support. If the resin composition I for forming the resin layer I is a solution, it is applied to the support by methods such as spin coating or roll coating, and pre-baking is performed at a temperature of preferably 80 to 200°C, more preferably 100 to 180°C, depending on the evaporation conditions of the solvent, to evaporate the solvent and form the resin composition layer I'. If the resin composition I is a film-like composition, the resin composition layer I' is formed on the support by a lamination method.

[0131] The resin composition layer I' formed on the support can function as resin layer I by heat curing. Heat curing can be performed using a hot plate or oven, with a temperature typically between 100 and 350°C, preferably between 150 and 300°C. The curing time is typically between 1 and 10 minutes, preferably between 2 and 8 minutes. This curing reaction can also be achieved by forming an uncured wafer laminate without curing the resin composition layer I', and then heating the entire laminate.

[0132] [Step (a2) or (a2')] Step (a2) is a step of forming a resin layer II on the circuit formation surface of a semiconductor substrate (wafer), and step (a2') is a step of forming a resin layer II on top of the resin layer I or resin composition layer I'. If the silicone resin-containing temporary adhesive is a solution, the resin layer II can be formed by applying it to the semiconductor substrate (wafer) using methods such as spin coating, roll coating, die coating, printing, or dipping, and then heating it at 130-190°C using a hot plate or oven.

[0133] On the other hand, if the silicone resin-containing temporary adhesive is a film-like composition, a resin layer II can be formed on the wafer by lamination.

[0134] [Process (a3) ​​or (a3')] 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 formation surface of the wafer under reduced pressure. The reduced pressure conditions are preferably 0.1 to 100 Pa, more preferably 1 to 80 Pa. At this time, it is preferable to uniformly press and bond the substrate under reduced pressure in a temperature range of preferably 40 to 240°C, more preferably 60 to 220°C.

[0135] [Process (a4)] Step (a4) is a step in which the resin composition layer A' of the wafer laminate bonded in step (a3) ​​or (a4') is heat-cured to form resin layer I and bonded to resin layer II. After the wafer laminate is formed, heat curing is performed by heating at 120 to 260°C, preferably 150 to 250°C for 1 minute to 4 hours, preferably 3 minutes to 2 hours.

[0136] As described above, the laminate can be prepared (step a).

[0137] [Step (b)] Step (b) is a process for processing the back surface of the laminate. This step involves processing the non-circuit-formed surface of a semiconductor substrate (wafer) that has been ground, i.e., a wafer that has been thinned by back 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, conventionally known processes include CVD for wafer surface treatment, laser annealing, metal sputtering for electrode formation, vapor deposition, wet etching for etching the metal sputtering layer, application of resist to serve as a mask for metal wiring formation, exposure and development for pattern formation, resist peeling, dry etching, metal plating formation, organic film formation for surface protection, silicon etching for TSV formation, and oxide film formation on the silicon surface. In such processes, it is desirable for the wafer laminate to have resistance over a wide range of high temperatures up to about 400°C, and in particular, it is desirable for the wafer laminate to have strength and lifespan even at temperatures above 300°C.

[0138] [Process (c)] Step (c) is the process of peeling the support from the thin wafer laminate processed in step (b). More specifically, it is the process of separating the support from the laminate by irradiating the support from the support side of the laminate. This peeling process is generally carried out under relatively low temperature conditions, around room temperature. (c1) A step of adhering dicing tape to the processed surface (back side) of the processed wafer, (c2) A step of vacuum adsorbing the dicing tape surface onto the adsorption surface, (c3) Preferably, the process includes peeling the support from the thin wafer stack by irradiating it with a 355 nm laser from the support side of the thin wafer stack. This allows the support to be easily peeled from the wafer stack and facilitates the subsequent dicing process. The dicing tape can be a known one made of polyester, polyethylene film, etc.

[0139] [Optional process (x)] An optional step (x) is a step in which, after peeling off the support in step (c), the resin layer I and resin layer II that remain without being decomposed by the laser are peeled off from the processed semiconductor substrate (wafer) by tape peeling or the like.

[0140] This peeling process is generally carried out under relatively low temperature conditions, typically ranging from room temperature to around 60°C. One method of peeling in step (x) is to fix the wafer after step (c) horizontally, apply a peeling tape to the exposed, undisintegrated resin layer I, and then peel off the tape using a peeling method to separate the undisintegrated resin layer I and resin layer II from the processed wafer.

[0141] Any tape material can be used as the tape material as long as it is peelable, but tapes using silicone adhesive are particularly preferred, for example, polyester film adhesive tapes No. 646S and No. 648 manufactured by Teraoka Seisakusho Co., Ltd. are suitably used.

[0142] Furthermore, when peeling off the tape material using a peel method, it is preferable to peel it off 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 way, the adhesive strength between the resin layer II and the wafer decreases, making it easier to peel off.

[0143] [Step (d)] Furthermore, it is preferable to perform a step (d) after step (x) has been performed, or without performing step (x) after step (c), in which the silicone resin layer (resin layer I) and the laser delamination layer (resin layer II) are removed from the laminate separated in step (c) using a cleaning solution having a temperature in the range of room temperature to 60°C and not exceeding the flash point, thereby extracting only the circuit-equipped substrate. That is, this step is a step to remove the temporary adhesive layer remaining on the circuit-forming surface of the delaminated wafer. On the circuit-forming surface of the semiconductor substrate (wafer) delaminated by step (x), a small amount of resin layer II may remain, and this resin layer II can be removed, for example, by cleaning the wafer. If step (x) is not performed, a larger amount of resin layer II often remains.

[0144] In step (d) above, a cleaning solution that dissolves the components in resin layer II can be used, specifically, pentane, hexane, cyclohexane, decane, isononane, p-menthane, pinene, isododecane, limonene, etc. These solvents may be used individually or in combination of two or more. If removal is difficult, bases and acids may be added to the solvent. Examples of bases 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, in terms of concentration in the cleaning solution. In addition, existing surfactants may be added to improve the removal of residual substances. Possible cleaning methods include cleaning with a paddle using the above solution, cleaning by spraying, and immersion in a cleaning solution tank. The temperature is preferably 10 to 80°C, more preferably 15 to 65°C. If necessary, the resin layer II can be dissolved in these dissolving solutions, followed by final washing with water or alcohol, and then drying to obtain a thin wafer.

[0145] As described above, a thin wafer can be obtained by combining a support, a resin layer, and a substrate having a circuit on its surface, and by peeling off the support and then removing the resin layer by cleaning and removing the remaining resin layer (tape peeling may be used). [Examples]

[0146] The present invention will be described in more detail below with reference to preparation examples, examples, and comparative examples, but the present invention is not limited to these examples. In the following examples, parts refer to parts by mass. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) are polystyrene-converted values ​​measured by GPC using THF as the solvent. The acid generator AG used in the following examples is as follows. [ka] AG

[0147] [1] Preparation of resin solution [Preparation Example 1] 2.5 mol% (CH2=CH)(CH3)SiO 2 / 2 Unit (D Vi A solution containing 100 parts by mass of dimethylpolysiloxane with Mn 30,000 and 200 parts by mass of p-menthane, with SiO2 4 / 2 Unit (Q units): 50 mol%, (CH3)3SiO 1 / 2 Units (M units): 48 mol% and (CH2=CH)3SiO 1 / 2A solution consisting of 15 parts by mass of vinylmethylpolysiloxane with a Mn of 7,000 (represented by 2 mol% units of Vi) and 70 parts by mass of p-menthane, a solution consisting of 2 parts by mass of organohydrogenpolysiloxane with a Mn of 2,400 (represented by M-6) and 3 parts by mass of p-menthane, and 0.6 parts by mass of 1-ethynylcyclohexanol were added and mixed. Furthermore, 0.4 parts by mass of catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd., platinum concentration 1.0% by mass) and 1 part by mass of tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane were added and mixed, and the mixture was filtered through a 1 μm membrane filter to prepare thermosetting silicone resin solution D1. In the resin solution, the molar ratio of Si-H groups in the organohydrogenpolysiloxane having Si-H groups to the alkenyl groups in the dimethylpolysiloxane having alkenyl groups was 1.0. Furthermore, the viscosity of resin solution D1 at 25°C was 2 Pa·s. [ka]

[0148] The molar ratio (Si-H / Si-Vi) of the Si-H groups in the organohydrogenpolysiloxane having Si-H groups to the alkenyl groups in the dimethylpolysiloxane having alkenyl groups in this Preparation Example 1 is calculated using the following formula. (In the formula below, PDMS: dimethylpolysiloxane, POHS: organohydrogenpolysiloxane.) (1) Si-Vi amount (moles) from component (A-1) (Amount of PDMS added / Molecular weight of PDMS) × {Molecular weight of PDMS / (Molecular weight per unit of D × Mole% per unit of D / 100 + D Vi (Unit molecular weight × D unit mole % / 100) × D Vi Unit: mole % / 100 (2) Amount of Si-H from component (A-2) (moles) (POHS added amount / POHS molecular weight) × Number of hydrogen-bonded siloxane units in one molecule (3) Si-H / Si-Vi values (A-2) Amount of Si-H from component (moles) / (A-1) Amount of Si-Vi from component (moles)

[0149] [Preparation Example 2] 2.5 mol% (CH2=CH)(CH3)SiO 2 / 2 Unit (D Vi A solution comprising 80 parts by mass of dimethyldiphenylpolysiloxane with Mn 50,000 having 3 mol% phenyl groups in its molecular side chain and SiO2 4 / 2 Unit (Q units): 50 mol%, (CH3)3SiO 1 / 2 Units (M units): 48 mol% and (CH2=CH)3SiO 1 / 2 A solution consisting of 70 parts by mass of vinylmethylpolysiloxane with a Mn of 7,000 and 70 parts by mass of p-menthane, represented as 2 mol% in units (Vi units), a solution consisting of 3 parts by mass of organohydrogenpolysiloxane with a Mn of 2,400 represented as M-6 and 5 parts by mass of p-menthane, and 0.6 parts by mass of 1-ethynylcyclohexanol were added and mixed. Furthermore, 0.4 parts by mass of catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd., platinum concentration 1.0% by mass) and 1.5 parts by mass of tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxyhydrosinnamete)]methane were added and mixed, and the mixture was filtered through a 1 μm membrane filter to prepare thermosetting silicone resin solution D2. Furthermore, in the resin solution, the molar ratio of Si-H groups in the organohydrogenpolysiloxane having Si-H groups to the alkenyl groups in the dimethylpolysiloxane having alkenyl groups was 1.0. Also, the viscosity of resin solution D2 at 25°C was 1.5 Pa·s.

[0150] [Preparation Example 3] 2.5 mol% (CH2=CH)(CH3)SiO 2 / 2 Unit (D Vi A solution consisting of 90 parts by mass of dimethylpolysiloxane having units and Mn of 50,000 and 200 parts by mass of p-menthane, is mixed with 5 mol% (CH2=CH)(CH3)SiO2. 2 / 2 Unit (D ViA solution consisting of 70 parts by mass of dimethylpolysiloxane with Mn 10,000 and 100 parts by mass of p-menthane, 5 parts by mass of organohydrogenpolysiloxane represented by M-6 with Mn 2,400 and 7 parts by mass of p-menthane, and 0.6 parts by mass of 1-ethynylcyclohexanol were added and mixed. Furthermore, 0.4 parts by mass of catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd., platinum concentration 1.0% by mass) and 1 part by mass of tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxyhydrosinnamete)]methane were added and mixed, and the mixture was filtered through a 1 μm membrane filter to prepare thermosetting silicone resin solution D3. In the resin solution, the molar ratio of Si-H groups of the organohydrogenpolysiloxane having Si-H groups to the alkenyl groups of the dimethylpolysiloxane having alkenyl groups was 1.0. Furthermore, the viscosity of resin solution D3 at 25°C was 3 Pa·s.

[0151] [Preparation Example 4] Resin composition A1 (laser stripper) was obtained by dissolving 20 parts of resin A1 (having repeating units of the structure described below, with a Mw of 3,200 and a dispersion degree (Mw / Mn) of 2.44), 1 part of acid generator AG, and 4 parts of Nikalac Mw390 (manufactured by Sanwa Chemical Co., Ltd.) as a crosslinking agent in 100 parts of PGMEA containing 0.1% by mass of silicone surfactant KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and filtering the mixture through a 0.1 μm fluororesin filter. The transmittance was 1%, and the transmittance was measured using a 355 nm UV3600i (Shimadzu Corporation). [ka] [ka]

[0152] [Comparative Preparation Example 1] In Preparation Example 1, a thermosetting silicone resin solution D4 was prepared without the addition of tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxyhydrosinnamete)]methane.

[0153] [Comparative Preparation Example 2] 2.5 mol% (CH2=CH)(CH3)SiO 2 / 2 Unit (D Vi A solution comprising 20 parts by mass of dimethylpolysiloxane with Mn 30,000 and 100 parts by mass of p-menthane, containing SiO 4 / 2 Unit (Q units): 50 mol%, (CH3)3SiO 1 / 2 Units (M units): 48 mol% and (CH2=CH)3SiO 1 / 2 A solution consisting of 150 parts by mass of vinylmethylpolysiloxane with a Mn of 7,000 and 140 parts by mass of p-menthane, represented as 2 mol% in units (Vi units), a solution consisting of 3 parts by mass of organohydrogenpolysiloxane with a Mn of 2,400 represented as M-6 and 5 parts by mass of p-menthane, and 0.6 parts by mass of 1-ethynylcyclohexanol were added and mixed. Furthermore, 0.4 parts by mass of catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd., platinum concentration 1.0% by mass) and 1 part by mass of tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxyhydrosinnamete)]methane were added and mixed, and the mixture was filtered through a 1 μm membrane filter to prepare thermosetting silicone resin solution D5. Furthermore, in the resin solution, the molar ratio of Si-H groups in the organohydrogenpolysiloxane having Si-H groups to the alkenyl groups in the dimethylpolysiloxane having alkenyl groups was 1.0. The viscosity of resin solution D5 at 25°C was 0.9 Pa·s.

[0154] [2] Wafer fabrication and evaluation [Examples 1-3, Comparative Examples 1-2] A glass wafer with a diameter of 200 mm (thickness: 700 μm) was spin-coated with resin composition A1 (laser release agent), and then heated on a hot plate at 120°C for 2 minutes and 250°C for 5 minutes to deposit a material corresponding to resin layer I (laser release layer) with the thickness shown in Table 1.

[0155] Furthermore, after spin-coating D1 to D5 onto a 200 mm diameter silicon wafer (thickness: 725 μm), a resin layer II was formed with the thickness shown in Table 1 by heating it on a hot plate at 100°C for 2 minutes.

[0156] A wafer laminate was fabricated by bonding the glass plate-resin layer I and the resin layer II-wafer surface in a vacuum bonding apparatus (EVG520IS, manufactured by EVG Corporation) under reduced pressure conditions of 1 Pa or less, as shown in Table 1, and then heating it on a hot plate at 150°C for 10 minutes.

[0157] Subsequently, the following tests were performed on the bonded substrate. The results are shown in Table 1. The evaluation was carried out in the following order.

[0158] (1) Adhesion test 200mm wafer bonding was performed using EVG520IS wafer bonding equipment from EVG Corporation. The bonding temperature was as shown in Table 1, the chamber pressure during bonding was 1 Pa or less, and the load was D1 to D5. After bonding, the wafers were cooled to room temperature, and the bonding status of the interface was checked visually and with an optical microscope. If no abnormalities such as bubbles occurred at the interface, it was evaluated as good and indicated with "○", and if abnormalities occurred, it was evaluated as poor and indicated with "×".

[0159] (2) Heat resistance test The bonded wafers were placed in a 260°C hot air circulating oven and left for 2 hours. After being removed from the oven and allowed to cool to room temperature, the condition of the wafers was visually inspected. If no abnormalities such as bubbles occurred at the interface, it was evaluated as good and indicated with a "○", and if abnormalities occurred, it was evaluated as poor and indicated with a "×".

[0160] (3) Support peelability test 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 this dicing tape surface was set on an adsorption plate by vacuum adsorption. Then, a 355 nm laser was irradiated over the entire surface from the support side. If the support and wafer could be peeled off without cracking, it was indicated with a "○". If peeling was not possible, or if peeling occurred but cracking or other abnormalities occurred, it was evaluated as defective and indicated with a "×".

[0161] (4) Dissolution rate test The dissolution rate test using solvents was evaluated using the following method. A 200 mm wafer with the resin layer remaining was placed with the resin layer facing upwards and cleaned at 50°C. A cleaning solution was prepared by dissolving 3% by mass of tetrabutylammonium fluoride in dimethylpropionamide as the cleaning solvent, and then filtering it through a 1 μm filter. The wafer was then immersed for 1 minute, followed by immersion in isopropyl alcohol (IPA) for 1 minute, and then placed on a 120°C hot plate for 3 minutes. The film thickness was then measured. The dissolution rate was calculated using the following formula.

[0162] Dissolution rate = ((thickness after coating on silicon wafer) - (thickness after cleaning test)) / (cleaning solution immersion time)

[0163] [Table 1]

[0164] As shown in Table 1, in Examples 1 to 3, temporary bonding and support removal were easy, and the cleaning speed was fast, demonstrating excellent cleaning performance. On the other hand, in Comparative Example 1, some wafer delamination occurred during the heat resistance evaluation, and in Comparative Example 2, the cleaning speed was slow.

[0165] This specification includes the following embodiments: [1]: A silicone resin-containing temporary adhesive for temporarily bonding a semiconductor substrate and a support, A silicone resin-containing temporary adhesive characterized in that, when the dissolution rate of the temporary adhesive layer formed with the temporary adhesive is measured by bonding the semiconductor substrate and the support via the temporary adhesive layer formed with the temporary adhesive, heating at 260°C for 2 hours, peeling off the semiconductor substrate and the support, and then dissolving the temporary adhesive layer remaining on the semiconductor substrate or the support in a dimethylpropionamide solution containing 3% by mass of tetrabutylammonium fluoride at 50°C, the dissolution rate is 20 μm / min or more. [2]: The silicone resin-containing temporary adhesive according to [1], wherein the proportion of dimethylsiloxane units in the nonvolatile components of the silicone resin-containing temporary adhesive is 20% by mass or more. [3]: A silicone resin-containing temporary adhesive according to [1] or [2] above, which includes a heat-resistant agent. [4]: The silicone resin is a curable silicone resin, and the curable silicone resin is (A) Organopolysiloxanes having two or more alkenyl groups in one molecule, (B) Organohydrogenpolysiloxanes containing two or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule, and (C) platinum-based catalyst, A silicone resin-containing temporary adhesive according to any of the above [1] to [3], which is a composition containing such an amount that the molar ratio of Si-H groups in component (B) to alkenyl groups in component (A) is 0.3 to 10. [5] A temporary adhesive containing any of the silicone resins described in [1] to [4] above, which is used in combination with a laser release agent when temporarily bonding the semiconductor substrate and the support. [6]: A method for processing a circuit board, (a) A step of preparing a laminate including a circuit board and the support as the semiconductor substrate, which is temporarily bonded by a silicone resin layer using the silicone resin-containing temporary adhesive described in [5] above and a laser release layer using the laser release agent, (b) A step of processing the back surface of the laminate, (c) A step of separating the support from the laminate by laser irradiation from the support side, (d) A step of removing the silicone resin layer and the laser release layer from the separated laminate with a cleaning solution having a temperature of 40°C to 60°C to extract only the circuit board, A method for processing circuit boards, characterized by including the following:

[0166] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. A silicone-based resin-containing temporary adhesive for temporarily bonding a semiconductor substrate and a support, A silicone resin-containing temporary adhesive characterized in that, when the dissolution rate of the temporary adhesive layer formed with the temporary adhesive is measured by bonding the semiconductor substrate and the support via the temporary adhesive layer formed with the temporary adhesive, heating at 260°C for 2 hours, peeling off the semiconductor substrate and the support, and then dissolving the temporary adhesive layer remaining on the semiconductor substrate or the support in a dimethylpropionamide solution containing 3% by mass of tetrabutylammonium fluoride at 50°C, the dissolution rate is 20 μm / min or more.

2. The silicone resin-containing temporary adhesive according to claim 1, characterized in that the proportion of dimethylsiloxane units in the nonvolatile components of the silicone resin-containing temporary adhesive is 20% by mass or more.

3. The silicone resin-containing temporary adhesive according to claim 1, characterized in that it contains a heat resistance improver.

4. The aforementioned silicone resin is a curable silicone resin, and the curable silicone resin is (A) Organopolysiloxanes having two or more alkenyl groups in one molecule, (B) Organohydrogenpolysiloxanes containing two or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule, and (C) platinum-based catalyst, A silicone resin-containing temporary adhesive according to claims 1 to 3, characterized in that it contains an amount such that the molar ratio of Si-H groups in component (B) to alkenyl groups in component (A) is 0.3 to 10.

5. The silicone resin-containing temporary adhesive according to claim 1, characterized in that it is used in combination with a laser release agent when temporarily bonding the semiconductor substrate and the support.

6. A method for processing circuit boards, (a) A step of preparing a laminate including a circuit board and the support as the semiconductor substrate, which is temporarily bonded by a silicone resin layer using the silicone resin-containing temporary adhesive described in claim 5 and a laser release layer using the laser release agent, (b) A step of processing the back surface of the laminate, (c) A step of separating the support from the laminate by laser irradiation from the support side, (d) A step of removing the silicone resin layer and the laser peeling layer from the separated laminate with a cleaning solution having a temperature of 40°C to 60°C to extract only the circuit board, A method for processing circuit boards, characterized by including the following:

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