JPWO2015053132A1 - LAMINATE FOR ELEMENT PROCESSING, METHOD FOR PRODUCING LAMINATE FOR ELEMENT PROCESSING, AND METHOD FOR PRODUCING THIN ELEMENT USING THE SAME - Google Patents

Abstract

There is no generation of volatile components in the backside polishing and backside circuit forming process of a semiconductor circuit forming substrate, and there is no occurrence of cracking of the substrate due to peeling, and the semiconductor circuit after peeling is possible under mild conditions at room temperature. Provided is an element processing laminate in which almost no temporary adhesive remains on the formation substrate side. In an element processing laminate in which an element processing substrate is stacked on a support substrate via a temporary adhesive layer, the temporary adhesive layer is stacked in the order of the heat resistant resin layer A and the heat resistant resin layer B from the support substrate side. The adhesive strength between the heat resistant resin layer B and the element processing substrate is lower than the adhesive strength between the heat resistant resin layer A and the support substrate and the adhesive strength between the heat resistant resin layer B and the heat resistant resin layer A. The laminated body for element processing characterized. [Selection] Figure 1

Description

  The present invention is excellent in heat resistance, and does not change the adhesive force even during the manufacturing process of a semiconductor device, an image display device, etc., and can then be temporarily bonded at a room temperature and a temporary bonding adhesive The present invention relates to an element processing laminate used for a layer, a method for manufacturing the element processing laminate, and a thin element manufacturing method using the element processing laminate.

  In recent years, semiconductor devices and image display devices have been reduced in weight and thickness. In particular, for semiconductor devices, in order to achieve high integration and high density of semiconductor elements, technology development is progressing in which semiconductor chips are stacked while being connected by through silicon vias (TSV). Further, it is necessary to make the package thinner, and it has been studied to reduce the thickness of the semiconductor circuit formation substrate to 100 μm or less and process it. In this step, the non-circuit formation surface (back surface) of the semiconductor circuit formation substrate is polished to reduce the thickness, and a back electrode is formed on the back surface. In order to prevent cracking of the semiconductor circuit formation substrate during polishing, etc., after fixing the semiconductor circuit formation substrate to a support substrate such as a supportable silicon wafer or glass substrate, and after polishing, back surface circuit formation processing, etc. Then, the processed semiconductor circuit forming substrate is peeled off from the support substrate. Temporary sticking material is used to fix the semiconductor circuit forming substrate to the support substrate, but the adhesive used as the temporary sticking material is required to have heat resistance enough to withstand the semiconductor process. It must be easily peelable.

  As such a temporary adhesive, a silicon-based material is used for peeling by heat treatment (see, for example, Patent Document 1), or a polyamide or polyimide-based material is used for heating and peeling. (For example, refer patent document 2) etc. are proposed. In addition, a material that decomposes a tetrazole compound having excellent heat resistance when irradiated with ultraviolet rays to generate bubbles to peel off (for example, see Patent Document 3) has been proposed. Further, there has been proposed a temporary adhesive having a two-layer structure of a thermoplastic organopolysiloxane type and a curable modified siloxane type, which peels at room temperature (see, for example, Patent Document 4).

JP 2012-144616 A (Claims) JP 2010-254808 A (Claims) JP 2012-67317 A (Claims) JP 2013-48215 A (Claims)

  However, the temporary adhesive that is peeled off by heat treatment dissolves the solder bumps in the heating process for peeling, or the adhesive strength in the semiconductor processing process is reduced, and it is peeled off in the middle of the process, or the adhesive force is increased and peeled off. There were problems such as disappearing. Further, when the adhesive is made photosensitive, since a photopolymerization initiator and a photosensitizer are added, there is a problem that volatile matter is generated in a process under high temperature vacuum conditions.

  If it is peeled off at room temperature, the above problems will not occur. However, since the temporary adhesive is attached to the semiconductor circuit formation substrate after peeling, a cleaning removal step with a solvent is necessary, and the temporary adhesive is completely removed. In order to do so, there was a problem that a considerable burden was placed on the process.

  In view of such a situation, the object of the present invention is to remove the volatile component in the backside polishing process of the semiconductor circuit forming substrate and the generation of volatile components in the backside circuit forming process, and to prevent the substrate from being cracked due to peeling, and to peel off under mild conditions at room temperature. It is possible to provide a laminated body for element processing capable of leaving almost no temporary adhesive on the semiconductor circuit forming substrate side after peeling, and a manufacturing method of the laminated body for element processing, and a thin element using the same It is to provide a manufacturing method.

  That is, according to the present invention, in the element processing laminate in which the element processing substrate is laminated on the support substrate via the temporary adhesion layer, the temporary adhesion layer is formed in the order of the heat resistant resin layer A and the heat resistant resin layer B from the support substrate side. The adhesive strength between the heat resistant resin layer B and the element processing substrate is lower than the adhesive strength between the heat resistant resin layer A and the support substrate and the adhesive strength between the heat resistant resin layer B and the heat resistant resin layer A. It is the laminated body for element processing characterized by this.

  According to the present invention, there is provided an element processing laminate that has sufficient heat resistance without generation of volatile components in an element processing step, and that does not generate cracks in the element processing substrate even in a polishing step. be able to. In addition, the element processing substrate can be peeled off from the support substrate under mild conditions at room temperature, and productivity is improved because there is almost no temporary adhesive adhering to the element processing substrate after peeling.

It is the schematic of the laminated body for element processing of this invention.

  In the element processing laminate of the present invention, as shown in FIG. 1, the element processing substrate and the support substrate are bonded via a temporary adhesive layer, and the temporary adhesive layer is composed of a heat resistant resin layer A and a heat resistant resin layer B. It consists of two layers. The support substrate plays a role of supporting the element processing substrate when processing the element processing substrate.

  The element processing substrate is usually a silicon wafer. Circuits and bumps for external connection are formed on the surface in contact with the heat-resistant resin layer B, and the opposite surface is a surface on which no circuit is formed. In addition, a circuit and a bump for external connection may be formed on the surface where the circuit is not formed, and a through electrode for conducting the front and back circuits may be formed. The thickness of the element processing substrate is not particularly limited, but is 600 to 800 μm, preferably 625 to 775 μm.

  A substrate such as a silicon wafer, glass, or quartz wafer can be used as the support substrate. Although there is no restriction | limiting in particular in the thickness of a support substrate, it is 600-800 micrometers, Preferably it is 625-775 micrometers.

  The temporary adhesive layer temporarily fixes the element processing substrate to the support substrate. It is important that the element processing substrate processed in the peeling step after the device processing step is easily peeled off from the support substrate without being peeled off in the device processing step of the element processing substrate. It is also important that the resin for the temporary adhesive layer does not remain on the element processing substrate after the peeling, in addition to the easy peeling. If the resin remains, a process of washing off the resin with an organic solvent becomes necessary, which increases the burden on the production process.

  Accordingly, the temporary adhesive layer in the present invention has a two-layer configuration of the heat resistant resin layer A and the heat resistant resin layer B, and the adhesive force between the heat resistant resin layer B and the element processing substrate is the adhesion between the heat resistant resin layer A and the support substrate. It is important that the strength is lower than the adhesive strength between the heat-resistant resin layer B and the heat-resistant resin layer A. The difference between the adhesive force between the heat-resistant resin layer B and the element processing substrate, the adhesive force between the heat-resistant resin layer A and the support substrate, and the adhesive force between the heat-resistant resin layer B and the heat-resistant resin layer A is preferably 10 g / cm or more. Is 50 g / cm or more. By having such adhesive properties, the element processing substrate is not peeled off in the device processing step, and in the peeling step, the heat-resistant resin layer B and the element processing substrate are easily peeled off, and the element processing substrate is resinated. Does not remain.

  The adhesive force between the heat-resistant resin layer B and the element processing substrate is 1 g / cm or more and 70 g / cm or less, preferably 10 g / cm or more and 40 g / cm or less. When the adhesive force is 1 g / cm or more and 70 g / cm or less, the element processing substrate is not peeled and cracked during the processing step, and can be easily peeled at room temperature in the peeling step. The adhesive strength between the heat-resistant resin layer A and the support substrate and the adhesive strength between the heat-resistant resin layer B and the heat-resistant resin layer A are 20 g / cm or more, preferably 50 g / cm or more, more preferably 100 g / cm or more. is there. If the adhesive force is 20 g / cm or more, processing is possible without cracking the element processing substrate during the processing step. The adhesive force here can be determined by measuring the stress applied when pulling up the adherend at a constant angle and a constant speed. The adhesive force of the present invention is an adhesive force when peeled off at an angle of 90 ° and a pulling speed of 50 mm / min.

  Resins that can be used for the heat-resistant resin layer A and the heat-resistant resin layer B constituting the temporary adhesive layer are acrylic resin, acrylonitrile resin, butadiene resin, urethane resin, polyester resin, polyamide resin, polyimide resin. Polymer resins such as polyamide imide resins, epoxy resins, and phenol resins can be used, but polyimide resins with high heat resistance are preferred.

  The heat resistance is defined by the thermal decomposition start temperature at which volatile matter is generated by decomposition or the like. The preferred thermal decomposition starting temperature is 250 ° C. or higher, more preferably 300 ° C. or higher. When the thermal decomposition starting temperature is 250 ° C. or higher, there is no generation of volatile components in the heat treatment step during the device processing step, and the device reliability is improved. The thermal decomposition starting temperature of the present invention can be measured using a thermogravimetric analyzer (TGA). The measurement method will be specifically described. A predetermined amount of resin is charged into TGA and held at 60 ° C. for 30 minutes to remove moisture absorbed by the resin. Next, the temperature is raised to 500 ° C. at 5 ° C./min. The temperature at which weight reduction starts from the obtained weight reduction curve was defined as the thermal decomposition start temperature.

  The heat-resistant resin layer A of the present invention has at least an acid dianhydride residue and a diamine residue, and the diamine residue contains at least a polysiloxane diamine residue represented by the general formula (1). It is preferable to contain the heat resistant resin A which is.

In the general formula (1), n is a natural number, and the average value calculated from the average molecular weight of the polysiloxane diamine is 1 or more. R ¹ and R ² may be the same or different and each represents an alkylene group having 1 to 30 carbon atoms or a phenylene group. R ^{3 to} R ⁶ may be the same or different and each represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group.

  The average molecular weight of the polysiloxane diamine can be determined by calculating the amino group equivalent by neutralizing titration of the amino group of the polysiloxane diamine and doubling the amino group equivalent. For example, a predetermined amount of polysiloxane diamine as a sample is collected and placed in a beaker, and this is dissolved in a predetermined amount of a 1: 1 mixed solution of isopropyl alcohol (hereinafter referred to as IPA) and toluene, and this solution is stirred. The 0.1N hydrochloric acid aqueous solution was dropped while the amino group equivalent was calculated from the amount of the 0.1N hydrochloric acid aqueous solution dropped when the neutralization point was reached. A value obtained by doubling this amino group equivalent is the average molecular weight.

  On the other hand, when the polysiloxane diamine used is n = 1 and n = 10, the molecular weight is calculated from the chemical structural formula, and the relation between the numerical value of n and the molecular weight is obtained as a relational expression of a linear function. Can do. The average molecular weight can be obtained by applying the average molecular weight to this relational expression.

  In addition, since the polysiloxane diamine represented by the general formula (1) may be a mixture having a plurality of n instead of a single n, n in the present invention represents an average value. n is 1 or more, preferably 5 to 100, and more preferably 7 to 50.

  Specific examples of the polysiloxane diamine represented by the general formula (1) include bis (3-aminopropyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis. (3-aminopropyl) polydiethylsiloxane, α, ω-bis (3-aminopropyl) polydipropylsiloxane, α, ω-bis (3-aminopropyl) polydibutylsiloxane, α, ω-bis (3-aminopropyl) ) Polydiphenoxysiloxane, α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (2-aminoethyl) polydiphenoxysiloxane, α, ω-bis (4-aminobutyl) polydimethylsiloxane, α, ω-bis (4-aminobutyl) polydiphenoxysiloxane, α, ω-bis (5-aminopentyl) poly Ridimethylsiloxane, α, ω-bis (5-aminopentyl) polydiphenoxysiloxane, α, ω-bis (4-aminophenyl) polydimethylsiloxane, α, ω-bis (4-aminophenyl) polydiphenoxysiloxane, etc. Can be mentioned. The polysiloxane diamine may be used alone or in combination of two or more.

  The polyimide resin contained in the heat-resistant resin A of the present invention preferably contains 40 mol% or more of the polysiloxane diamine residue represented by the general formula (1) in all diamine residues, 60 mol% or more, 99 mol% or less is more preferable. By including 40 mol% or more of the residue of the polysiloxane diamine represented by the general formula (1), the glass transition temperature of the heat-resistant resin layer A can be reduced to 60 ° C. or less, and the support substrate, the element processing substrate, In the step of adhering via a temporary adhesive layer, good tackiness can be exhibited at a low temperature of 200 ° C. or lower. As the content of the residue of the polysiloxane diamine represented by the general formula (1) is increased, the glass transition temperature of the heat resistant resin A is decreased, preferably 40 ° C. or less, more preferably 20 ° C. or less.

  In the present invention, in addition to the polysiloxane diamine residue, an aromatic diamine residue and / or an alicyclic diamine residue may be included. Specific examples of the aromatic diamine and / or alicyclic diamine include p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,4-diaminotoluene, 2-methoxy-1,4-phenylenediamine. 4,4′-diaminobenzanilide, 3,4′-diaminobenzanilide, 3,3′-diaminobenzanilide, 3,3′-dimethyl-4,4′-diaminobenzanilide, 9,9-bis ( 4-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (3-methyl-4-aminophenyl) fluorene, 9,9-bis (3,5-dimethyl-4) -Aminophenyl) fluorene, 9,9-bis (3-methoxy-4-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fur Oren-4-methyl, 9,9-bis (4-aminophenyl) fluorene-4-methoxy, 9,9-bis (4-aminophenyl) fluorene-4-ethyl, 9,9-bis (4-aminophenyl) ) Fluorene-4-sulfone, 9,9-bis (4-aminophenyl) fluorene-3-methyl, 1,3-diaminocyclohexane, 2,2′-dimethylbenzidine, 3,3′-dimethylbenzidine, 3,3 '-Dimethoxybenzidine, 2,4-diaminopyridine, 2,6-diaminopyridine, 1,5-diaminonaphthalene, 2,7-diaminofluorene, p-aminobenzylamine, m-aminobenzylamine, 4,4'- Bis (4-aminophenoxy) biphenyl, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4 -Diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3 '-Diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 1,3-bis (4-aminophenoxy) benzene, 1 , 3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 2,2-bis [4- (4-amino Phenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propyl Bread, bis [4- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3 -Aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 3,3′-methylenebis (cyclohexylamine), 4,4′-diamino-3,3′-dimethyldicyclohexylmethane 4,4′-diamino-3,3′-dimethyldicyclohexyl, benzidine and the like can be mentioned. The said aromatic diamine or alicyclic diamine may be used independently and may use 2 or more types.

  Among these aromatic diamines or alicyclic diamines, aromatic diamines having a highly flexible structure are preferable. Specifically, 1,3-bis (3-aminophenoxy) benzene and 3,3′-diaminodiphenyl are preferred. Sulfone, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, and 3,3′-diaminobenzophenone are particularly preferred.

  In the present invention, the aromatic diamine residue having a hydroxyl group or a carboxyl group in all diamine residues is 1 mol% or more, preferably 5 mol% or more, and 40 mol% or less, preferably 30 mol. % Or less. By including 1 mol% or more and 40 mol% or less of an aromatic diamine residue having a hydroxyl group or a carboxyl group, the solvent resistance is improved. Furthermore, the effect of greatly improving the solvent resistance can be obtained by using a crosslinking agent in combination.

  Specific examples of the aromatic diamine having a hydroxyl group include 2,5-diaminophenol, 3,5-diaminophenol, 3,3′-dihydroxybenzidine, 4,4′-dihydroxy-3,3′-diaminophenylpropane, 4,4′-dihydroxy-3,3′-diaminophenyl hexafluoropropane, 4,4′-dihydroxy-3,3′-diaminophenyl sulfone, 4,4′-dihydroxy-3,3′-diaminophenyl ether, 3,3′-dihydroxy-4,4′-diaminophenyl ether, 4,4′-dihydroxy-3,3′-diaminophenylpropanemethane, 4,4′-dihydroxy-3,3′-diaminobenzophenone, 1, 3-bis (4-amino-3-hydroxyphenyl) benzene, 1,3-bis (3-amino-4-hydroxyphenyl) benzene Bis (4- (4-amino-3-hydroxyphenoxy) benzene) propane, bis (4- (3-amino-4-hydroxyphenoxy) benzene) sulfone, bis (4- (3-amino-4-hydroxyphenoxy) )) Biphenyl and the like.

  Specific examples of the aromatic diamine having a carboxyl group include 4,4′-dicarboxy-3,3′-diaminophenylmethane, 3,3′-dicarboxybenzidine, 4,4′-dihydroxy-3,3 ′. -Diaminophenylpropane, 4,4'-dihydroxy-3,3'-diaminophenylhexafluoropropane, 4,4'-dicarboxy-3,3'-diaminophenylsulfone, 4,4'-dicarboxy-3, 3'-diaminophenyl ether, 3,3'-dicarboxy-4,4'-diaminophenyl ether, 4,4'-dicarboxy-3,3'-diaminophenylpropanemethane, 4,4'-dicarboxy- 3,3′-diaminobenzophenone, 3,5-diaminobenzoic acid, 2,6-diaminobenzoic acid, 9,9-bis (4-aminophenyl) fluorene-4-carbene Bon acid, 9,9-bis (4-aminophenyl) fluorene-3-carboxylic acid, 2-carboxy-4,4'-diaminodiphenyl ether and the like.

  The aromatic diamine having a hydroxyl group or a carboxyl group may be used alone or in combination of two or more.

  The polyimide resin contained in the heat-resistant resin A of the present invention preferably contains an aromatic tetracarboxylic dianhydride residue as an acid dianhydride residue. Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2′dimethyl-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5′dimethyl-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4 ′ -Diphenyl ether tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3′-benzophenonetetracarboxylic dianhydride, 2,3, ', 4'-Benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyl sulfone tetracarboxylic dianhydride 3,3 ′, 4,4′-diphenylsulfoxide tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfide tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl Methylenetetracarboxylic dianhydride, 4,4′-isopropylidene diphthalic anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride 3,3 ", , 4 "-paraterphenyl tetracarboxylic dianhydride, 3,3", 4,4 "-metaterphenyl tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride and the like. The said aromatic tetracarboxylic dianhydride may be used independently and may use 2 or more types.

  Moreover, in this invention, the tetracarboxylic dianhydride which has an aliphatic ring can be contained to such an extent that the heat resistance of a polyimide-type resin is not impaired. Specific examples of the tetracarboxylic dianhydride having an aliphatic ring include 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 1,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexene tetracarboxylic dianhydride, 2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- C] furan-1,3-dione. The said tetracarboxylic dianhydride may be used independently and may use 2 or more types.

  In the heat-resistant resin A of the present invention, various crosslinking agents such as an epoxy crosslinking agent, an isocyanate crosslinking agent, a methylol crosslinking agent, a maleimide crosslinking agent, and an acrylic crosslinking agent can be used. Among these, a methylol-based crosslinking agent is particularly preferable because it is a compound that crosslinks a polyimide resin at the time of thermosetting and is taken into the polyimide resin. By introducing a crosslinked structure into the resin, the solvent resistance can be improved. Specific examples of the methylol-based crosslinking agent include the following melamine derivatives and urea derivatives (manufactured by Sanwa Chemical Co., Ltd.).

  Since the heat-resistant resin layer B of the present invention is in contact with the element processing substrate, high heat resistance is required. Therefore, the heat resistant resin B contained in the heat resistant resin layer B is preferably a polyimide resin having a glass transition temperature of 300 ° C. or higher. The glass transition temperature is preferably 400 ° C. or higher, and more preferably the glass transition temperature is not detected before the temperature at which the heat resistant resin reaches thermal decomposition. If the glass transition temperature of the heat-resistant resin B is 300 ° C. or higher, the glass transition temperature becomes higher than the temperature in the heat treatment step in the element processing step, so there is no increase in the adhesive force in the step, and the element in the peeling step The processing substrate can be easily peeled off.

  The heat resistant resin B is preferably a polyimide resin having a thermal decomposition starting temperature of 250 ° C. or higher. The thermal decomposition starting temperature is preferably 350 ° C. or higher, more preferably 450 ° C. or higher. If the thermal decomposition start temperature of the heat-resistant resin B is 250 ° C. or higher, there is no generation of volatile components in the heat treatment step during the device processing step, and the device reliability is improved.

  The polyimide resin contained in the heat-resistant resin B of the present invention has at least a tetracarboxylic dianhydride residue represented by the general formula (2) and / or (3) as an acid dianhydride residue, The diamine residue has at least an aromatic diamine residue represented by the general formula (4) and / or (5).

In the general formula (2), R ⁷ is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a halogen, a carboxyl group, a carboxylic acid ester group, a fluoroalkyl group having 1 to 30 carbon atoms, A group selected from a phenyl group, a sulfonic acid group, a nitro group and a cyano group is shown.

In the general formula (3), R ⁸ and R ⁹ may be the same or different, and are each an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, A group selected from a hydroxyl group, a halogen, a carboxyl group, a carboxylic acid ester group, a phenyl group, a sulfonic acid group, a nitro group and a cyano group. Y is a direct bond, carbonyl group, isopropylidene group, ether group, hexafluoropropylidene group, sulfonyl group, phenylene group, methylene group, fluoromethylene group, amide group, ester group, ethylene group, fluoroethylene group, phenylenebisether Group represents a bis (phenylene) isopropylidene group.

In the general formula (4), R ¹⁰ is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, a hydroxyl group, a halogen, a carboxyl group, a carboxylic acid ester group, A group selected from a phenyl group, a sulfone group, a nitro group and a cyano group is shown.

In General Formula (5), R ¹¹ and R ¹² may be the same or different from each other, and are an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, A group selected from a hydroxyl group, a halogen, a carboxyl group, a carboxylic acid ester group, a phenyl group, a sulfone group, a nitro group, and a cyano group. X is a direct bond, carbonyl group, isopropylidene group, ether group, hexafluoropropylidene group, sulfonyl group, phenylene group, methylene group, fluoromethylene group, amide group, ester group, ethylene group, fluoroethylene group, phenylenebisether Group, bis (phenylene) isopropylidene group, fluorene group.

  Halogen here means fluorine, chlorine, bromine and iodine.

  In the present invention, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3, An acid dianhydride residue of a tetracarboxylic dianhydride selected from 3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, and p-phenylenediamine, 4,4'-diaminodiphenyl ether, 2, A polyimide resin having a residue of an aromatic diamine selected from 2'-dimethyl-4,4'-diaminobiphenyl and 9,9-bis (4-aminophenyl) fluorene as a main component is heat resistant and has a high glass transition temperature. From the point of view, it is preferable.

  Adjustment of the molecular weight of the polyimide resin used for the heat resistant resin layer A and the heat resistant resin layer B of the present invention is such that the tetracarboxylic acid component or diamine component used in the synthesis is equimolar, or either one component is excessive. This can be done. Either the tetracarboxylic acid component or the diamine component may be excessive, and the polymer chain terminal may be sealed with a terminal blocking agent such as an acid component or an amine component. A dicarboxylic acid or an anhydride thereof is preferably used as the terminal blocking agent for the acid component, and a monoamine is preferably used as the terminal blocking agent for the amine component. At this time, it is preferable that the acid equivalent of the tetracarboxylic acid component including the end-capping agent of the acid component or the amine component and the amine equivalent of the diamine component are equimolar.

  When the molar ratio is adjusted so that the tetracarboxylic acid component is excessive or the diamine component is excessive, dicarboxylic acid such as benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride, aniline or its anhydride, monoamine is terminated. You may add as a sealing agent.

  In the present invention, the molar ratio of the tetracarboxylic acid component / diamine component of the polyimide resin can be appropriately adjusted so that the viscosity of the resin solution is in a range that can be easily used in the coating process, etc. It is common to adjust the molar ratio of the / diamine component to be in the range of 100/95 to 100/100, or 95/100 to 100/100. However, as the molar balance is lost, the molecular weight of the resin decreases and the mechanical strength of the formed film decreases and the adhesive strength also tends to decrease. Therefore, the molar ratio should be adjusted within the range where the adhesive strength does not decrease. Is preferred.

  There is no restriction | limiting in particular in the method of synthesize | combining the polyimide-type resin used for the heat resistant resin layer A and the heat resistant resin layer B of this invention. For example, when polymerizing polyamic acid which is a precursor of polyimide resin, tetracarboxylic dianhydride and diamine are stirred in an organic solvent at 0 to 100 ° C. for 1 to 100 hours to obtain a polyamic acid resin solution. When the composition of the polyimide resin is soluble in the organic solvent, after the polyamic acid is polymerized, the temperature is raised to 120 to 300 ° C. and stirred for 1 to 100 hours to convert to polyimide to obtain a polyimide resin solution. . At this time, toluene, o-xylene, m-xylene, p-xylene or the like may be added to the reaction solution, and water generated in the imidization reaction may be removed by azeotropy with these solvents.

  As a solvent for synthesizing polyimide or polyamic acid which is a polyimide precursor, for example, amide polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Lactone polar solvents such as β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl Examples thereof include cellosolve acetate, methyl carbitol, ethyl carbitol, diethylene glycol dimethyl ether (diglyme), and ethyl lactate. These may be used alone or in combination of two or more. The concentration of the polyimide resin solution or the polyamic acid resin solution is usually preferably 10 to 80% by weight, and more preferably 20 to 70% by weight.

  In the case of a polyamic acid resin solution, it is applied to a substrate such as a film or glass, dried and heat-treated after forming a coating film to convert it into polyimide. The conversion from polyimide precursor to polyimide requires a temperature of 240 ° C. or higher, but by including an imidization catalyst in the polyamic acid resin composition, imidization at a lower temperature and in a shorter time becomes possible. . Specific examples of the imidization catalyst include pyridine, trimethylpyridine, β-picoline, quinoline, isoquinoline, imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2,6-lutidine, triethylamine, m -Hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, p-hydroxyphenylacetic acid, 4-hydroxyphenylpropionic acid, p-phenolsulfonic acid, p-aminophenol, p-aminobenzoic acid, and the like. It is not limited.

  The imidization catalyst is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the polyamic acid solid content. By containing 3 parts by mass or more of the imidization catalyst, imidization can be completed even by a lower temperature heat treatment. Moreover, Preferably it is 10 mass parts or less, More preferably, it is 8 mass parts or less. By setting the content of the imidization catalyst to 10 parts by mass or less, the amount of the imidization catalyst remaining in the polyimide resin layer after the heat treatment can be minimized, and generation of volatile matter can be suppressed.

  In addition to the polyimide resin and the cross-linking agent, other resins and fillers can be added to the heat-resistant resin layer A and the heat-resistant resin layer B of the present invention as long as the effects of the present invention are not impaired. Other resins include heat-resistant polymer resins such as acrylic resins, acrylonitrile resins, butadiene resins, urethane resins, polyester resins, polyamide resins, polyamideimide resins, epoxy resins, and phenol resins. Can be mentioned. Examples of the filler include organic or inorganic fine particles and filler. Specific examples of the fine particles and filler include silica, alumina, titanium oxide, quartz powder, magnesium carbonate, potassium carbonate, barium sulfate, mica and talc. In addition, a surfactant, a silane coupling agent, or the like may be added for the purpose of improving properties such as adhesiveness, heat resistance, coating property, and storage stability.

Next, the manufacturing method of the laminated body for element processing of this invention is demonstrated. The production of the element processing laminate of the present invention includes at least the following steps (Production Method 1).
(Process A) Laminating heat-resistant resin A on a support substrate, or converting the precursor of heat-resistant resin A into heat-resistant resin A after laminating to form laminate A of the support substrate and heat-resistant resin layer A, and A step of laminating the heat-resistant resin B on the element processing substrate or converting the precursor of the heat-resistant resin B into the heat-resistant resin B after being laminated to form a laminated body B of the element processing substrate and the heat-resistant resin layer B.
(Process B) The process of laminating | stacking and bonding the said laminated body A and the said laminated body B so that the heat resistant resin layer A and the heat resistant resin layer B may face each other.

Moreover, it may include at least the following process (manufacturing method 2).
(Process A) Heat-resistant resin B is laminated on an element processing substrate, or a precursor of heat-resistant resin B is laminated and then converted to heat-resistant resin B to obtain a laminate B of element processing substrate and heat-resistant resin layer B. Process.
(Step B) On the heat-resistant resin layer B of the laminate B, the heat-resistant resin A is laminated, or the precursor of the heat-resistant resin A is laminated and then converted to the heat-resistant resin A, and the element processing substrate and the heat-resistant resin layer B And a step of forming a laminate C of the heat-resistant resin layer A.
(Step C) A step of superimposing and bonding a support substrate on the heat resistant resin layer A of the laminate C.

  Examples of the coating method of the present invention include a method using a bar coater, a roll coater, a slit die coater, a spin coater, screen printing and the like. After the application, heat treatment is performed to remove the organic solvent in the resin composition, and when the heat-resistant resin A and the heat-resistant resin B are polyamic acid resins, imidization is performed. The heat treatment temperature is 100 to 400 ° C, preferably 150 to 250 ° C. The heat treatment time is usually appropriately selected from 20 seconds to 2 hours, and may be continuous or intermittent. When the heat-resistant resin A and the heat-resistant resin B are polyamic acid resins, another one-step heat treatment may be performed. The heat treatment temperature is 160 to 500 ° C, preferably 200 to 350 ° C. The heat treatment time is usually appropriately selected from 20 seconds to 4 hours, and may be continuous or intermittent.

  The residual volatile content in the heat-resistant resin layer A and the heat-resistant resin layer B after drying and heat treatment is 1% by weight or less, preferably 0.1% by weight or less, more preferably 0.01% by weight or less. If the residual volatile content is 1% by weight or less, element processing can be performed with good yield without occurrence of voids and peeling in the element processing step.

  In the production method 2, when the heat-resistant resin B is a polyamic acid resin, the heat-resistant resin A may be applied after heat treatment and imidization after coating, or the heat-resistant resin B may be applied and dried, and then the heat-resistant resin A After coating and drying, it may be imidized by heat treatment.

  The thickness of the heat resistant resin layer A and the heat resistant resin layer B can be selected as appropriate. There are bumps for connection on the surface of the element processing substrate in contact with the heat-resistant resin B, and the height of the bumps is generally 20 to 150 μm. Since the thickness of the temporary adhesive layer obtained by adding the heat-resistant resin layer A and the heat-resistant resin layer B becomes thicker than the bump height, the thickness is preferably 25 to 200 μm, and more preferably 30 to 160 μm. The thicknesses of the heat-resistant resin layer A and the heat-resistant resin layer B can be appropriately selected within the thickness range of the temporary adhesive layer.

  In the manufacturing method 1, before the process B, you may perform an adhesive improvement process on the surface of the heat resistant resin layer A of the laminated body A and / or the heat resistant resin layer B of the laminated body B. As the adhesion improving treatment, a discharge treatment such as a normal pressure plasma treatment, a corona discharge treatment, a low temperature plasma treatment or the like is preferable.

  The bonding process in the process B of the manufacturing method 1 and the process C of the manufacturing method 2 can be pressure-bonded using a press. Although it may be crimped at room temperature, it may be crimped by heating. The temperature at this time is 250 ° C. or lower, preferably 200 ° C. or lower. The pressure bonding may be performed in air or in nitrogen. Preferably in vacuum.

Next, the manufacturing method of the thin element using the laminated body for element processing of this invention is demonstrated. The method for manufacturing a thin element includes at least the following steps.
(Step A) A step of thinly processing the element processing substrate.
(Process B) The process of device-processing the element processing substrate processed thinly.
(Step C) A step of peeling the device-processed element processing substrate from the support substrate.

  The step of thinly processing the element processing substrate is a step of polishing and thinning the surface opposite to the surface in contact with the heat-resistant resin layer B of the element processing substrate. The thickness of the element processing substrate is reduced to 10 to 200 μm, preferably 30 to 100 μm.

  The device processing laminate in which the device processing substrate is thinned in step A is subjected to various device processing steps on the surface polished in step B. Examples include electrode formation, metal wiring formation, protective film formation, and connection bump formation. Specifically, metal sputtering for forming electrodes, wet etching of metal layers, resist coating for metal wiring formation, drying, exposure, development, resist stripping, metal plating, dry etching, CMP (chemical machinery) Polishing: Chemical Mechanical Polishing). Further, there are cases where steps such as silicon etching for TSV formation and CVD (Chemical Vapor Deposition) for forming an insulating film are included.

  Next, the element processing substrate on which the device processing is performed in the process B is peeled from the support substrate. As a peeling method, the laminated body for element processing is heated at a temperature of 250 ° C. or lower, and a thermal slide method in which the laminate is slid while sliding horizontally, a protective film is attached to the element processing substrate, and the room temperature is released from the support substrate at room temperature. There is a peeling method. In the present invention, the room temperature peeling method is preferably applicable.

  In the element processing laminate of the present invention, since the element processing substrate is temporarily fixed to the temporary adhesive layer with an adhesive force that can be easily peeled off at room temperature, the peeling interface when peeled is the element processing substrate and the heat resistant resin layer. B. Therefore, since the heat-resistant resin layer B does not remain on the element processing substrate, a cleaning process is not necessary after peeling, but if a slight residue remains, the cleaning process may be performed. As a solution used for washing, an aqueous solution of sodium hydroxide, sodium hydrogen carbonate, potassium hydroxide, tetramethylammonium hydroxide, a mixed solution of ethanolamine and dimethyl sulfoxide, or the like can be used.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. A method for evaluating the glass transition temperature, weight reduction rate, and adhesive strength will be described.

(1) Measurement of glass transition temperature A bar coater with the heat resistant resin solutions (B1 to B9, A1 to A6) described in the following Production Examples 1 to 15 having a thickness of 20 μm on the glossy surface of an 18 μm thick electrolytic copper foil After coating, the film was dried at 80 ° C. for 10 minutes and at 150 ° C. for 10 minutes, and further subjected to heat treatment at 250 ° C. for 10 minutes in a nitrogen atmosphere to convert to polyimide to obtain a resin laminated copper foil. Next, the copper foil of the obtained resin laminated copper foil was etched all over with a ferric chloride solution to obtain a single film of heat-resistant resin.

  About 10 mg of the obtained heat-resistant resin single film is packed in an aluminum standard container and measured using a differential scanning calorimeter DSC-50 (manufactured by Shimadzu Corporation) (DSC method), and the obtained DSC curve is changed. The glass transition temperature was calculated from the inflection point. After preliminary drying at 80 ° C. for 1 hour, the temperature was raised to 500 ° C. at a rate of temperature increase of 20 ° C./min, and measurement was performed.

(2) Measurement of thermal linear expansion coefficient A single film of the heat-resistant resin obtained above is cut into a shape having a specific width and formed into a cylindrical shape, and then thermomechanical analyzer SS-6100 (Seiko Instruments Inc.) The temperature was raised to 250 ° C. at a temperature range of 30 to 200 ° C. and a temperature raising rate of 5 ° C./min. From the obtained measurement results, an average linear thermal expansion coefficient of 30 to 200 ° C. was calculated using the calculation formula (1). Here, L30 is the sample length at 30 ° C., and L200 is the sample length at 200 ° C.
Average linear thermal expansion coefficient = (1 / L30) × [(L200−L30) / (200−30)] (1)
(3) Measurement of Adhesive Force of Element Processing Substrate-Heat Resistant Resin Layer B After applying the heat resistant resin solution (B1 to B9) to the element processing substrate to a thickness of 20 μm with a spin coater, 10 minutes at 80 ° C., 150 The film was dried at 10 ° C. for 10 minutes, further heat-treated at 250 ° C. for 30 minutes in a nitrogen atmosphere, converted to polyimide, and heat-resistant resin layer B was laminated. The heat-resistant resin layer B was cut into a 10 mm width, and a 10 mm width polyimide film was measured with a “Tensilon” UTM-4-100 manufactured by TOYO BOLDWIN at a pulling rate of 50 mm / min and 90 ° peeling.

(4) Measurement of Adhesive Force of Supporting Substrate-Heat Resin Layer A, Heat Resistant Resin Layer A-Heat Resin Layer B After peeling the element processing substrate with the element processing laminate obtained in each Example and Comparative Example, A temporary adhesive layer made of heat-resistant resin layer B / heat-resistant resin layer A is cut into a width of 10 mm, and heat-resistant resin layer B is pulled by TOYO BOLDWIN "Tensilon" UTM-4-100 at a pulling rate of 50 mm / min and 90 ° peeling. Measured with

  When the peeling interface is the support substrate-heat resistant resin layer A, the measured value represents the adhesive force of the support substrate-heat resistant resin layer A. At this time, the adhesive force of the heat resistant resin layer A-heat resistant resin layer B is the support substrate-heat resistant resin layer A. It can be said that it is larger than the adhesive strength of the resin layer A.

(5) Back gliding of the element processing substrate The element processing laminate obtained in each example and comparative example was set in a grinder DAG810 (manufactured by DISCO), and the element processing substrate was polished to a thickness of 100 μm. The element processing substrate after gliding was observed with the naked eye and evaluated for the presence of cracks, cracks, and the like.

(6) Appearance inspection after heat treatment The backgrinded device processing laminate is placed in a hot air oven set at 250 ° C. and left for 1 hour to return to room temperature, and then appearance such as swelling on the device processing substrate side. Changes were observed with the naked eye.

(7) Evaluation of solvent resistance The above-mentioned back-grinded laminate for device processing was immersed in a 1N hydrochloric acid aqueous solution, a 1N sodium hydroxide aqueous solution, and acetone for 10 minutes at 25 ° C., respectively. After peeling off the element processing substrate, the heat resistant resin layer was observed with an optical microscope.

  Good when no change is observed (A), and when the heat resistant resin is dissolved or penetrated into the region within 500 μm from the end of the temporary adhesive layer is acceptable (B), the change Was a region larger than 500 μm from the edge, and was evaluated as impossible (C).

(8) Evaluation of peelability of element processing substrate A dicing tape was attached to the element processing substrate of the element processing laminate that was back-ground as described above, and the surface of the dicing tape was set on a suction plate by vacuum suction. Thereafter, the support substrate was peeled off by lifting one point of the support substrate with tweezers at room temperature.

  A peel test was performed with 10 element processing laminates, and the number of the element processing substrates cracked or cracked was evaluated.

The names of the abbreviations of acid dianhydride and diamine shown in the following production examples are as follows.
BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride PMDA: pyromellitic dianhydride ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride APPS: α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight: 860, n = 9 in formula (1))
PDA: paraphenylenediamine DAE: 4,4′-diaminodiphenyl ether APB: 1,3-bis (3-aminophenoxy) benzene DABS: 4,4′-dihydroxy-3,3′-diaminophenylsulfone m-TB: 2 2,2′-dimethyl-4,4′-diaminobiphenyl BAHF: 4,4′-dihydroxy-3,3′-diaminophenylhexafluoropropane FDA: 9,9-bis (4-aminophenyl) fluorene 100LM: Nicalac ( Registered trademark) MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)
NMP: N-methyl-2-pyrrolidone Production Example 1 (polymerization of heat resistant resin B solution)
In a reaction kettle equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device with hot water / cooling water, and a stirring device, 75.7 g (0.7 mol) of PDA and 60.1 g (0.3 mol) of DAE were added to NMP. After being charged and dissolved together with 2264 g, 176.5 g (0.6 mol) of BPDA and 87.2 g (0.4 mol) of PMDA were added, and the mixture was reacted at room temperature for 1 hour, then at 60 ° C. for 5 hours, and 15 wt. % Polyamic acid resin solution (B-1) was obtained.

Production Examples 2 to 7 (polymerization of heat resistant resin B solution)
The same operation as in Production Example 1 was carried out except that the types and amounts of acid dianhydride and diamine were changed as shown in Table 1 to obtain 15 wt% polyamic acid resin solutions (B-2 to 7).

Production Example 8 (polymerization of heat resistant resin B solution)
In a reaction kettle equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using hot water / cooling water, and a stirring device, m-TB 127.4 g (0.6 mol), BAHF 146.5 g (0.4 mol) Was added together with 2788 g of NMP, dissolved, 218.1 g (1.0 mol) of PMDA was added, reacted at room temperature for 1 hour, then at 60 ° C. for 3 hours, and then reacted at 180 ° C. for 5 hours. A weight% polyimide resin solution (B-8) was obtained.

Production Example 9 (polymerization of heat resistant resin B solution)
The same operation as in Production Example 8 was carried out except that the type and amount of dianhydride and diamine were changed as shown in Table 1 to obtain a 20% by weight polyimide resin solution (B-9).

Production Example 10 (polymerization of heat resistant resin A solution)
APPS 301 g (0.35 mol), DAE 130.1 g (0.65 mol) together with 494 g of NMP were charged into a reaction kettle equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using hot water / cooling water, and a stirring device, After dissolution, 310.2 g (1 mol) of ODPA was added, reacted at room temperature for 1 hour, then at 60 ° C. for 3 hours, and then reacted at 180 ° C. for 5 hours to obtain a 60% by weight polyimide resin solution ( A-1) was obtained.

Production Examples 11 to 15 (polymerization of heat resistant resin A solution)
The same operation as in Production Example 10 was carried out except that the types and amounts of acid dianhydride and diamine were changed as shown in Table 2 to obtain a 60% by weight polyimide resin solution (A-2 to 5).

  In Production Example 15, 54.2 g of LM100 (5% by weight based on the solid content of the polyimide resin) was added to the polyimide resin solution obtained in Production Example 14, and the mixture was stirred at room temperature for 3 hours. A-6) was obtained.

  The glass transition temperatures (Tg) of the heat resistant resin A and the heat resistant resin B are also shown in Table 1 and Table 2.

Example 1
A polyamic acid resin solution (B-3) is dried and imidized to a thickness of 20 μm on a bump forming surface of a 6-inch device processing substrate having a bump of 30 μm height on a 0.7 mm thick silicon wafer. Apply by adjusting the number of rotations with a spin coater, heat treatment at 120 ° C. for 10 minutes, dry, then heat treatment at 250 ° C. for 30 minutes to completely imidize, heat resistant resin layer B / for element processing A laminate of the substrate was obtained.

  The polyimide resin solution (A-4) was applied to a 6-inch support substrate, which is a 0.7 mm thick silicon wafer, with a spin coater so that the thickness after drying was 25 μm, and applied at 120 ° C. After heat treatment for 10 minutes and drying, heat treatment was performed at 250 ° C. for 30 minutes to obtain a heat-resistant resin layer A / support substrate laminate.

  The laminate of the heat-resistant resin layer B / element processing substrate and the laminate of the heat-resistant resin layer A / support substrate are bonded so that the heat-resistant resin layer B and the heat-resistant resin layer A face each other. The laminated body for element processing was obtained by pressure bonding at 6 MPa for 90 seconds. Table 3 summarizes the characteristics of the obtained element processing laminate.

Examples 2-7
Except that the heat-resistant resin A used for the heat-resistant resin layer A and the heat-resistant resin B used for the heat-resistant resin layer B were changed as shown in Table 3, the same operation as in Example 1 was performed to obtain a laminated body for element processing. Table 3 summarizes the characteristics of the obtained element processing laminate.

Comparative Example 1
Except that the heat-resistant resin A used for the heat-resistant resin layer A and the heat-resistant resin B used for the heat-resistant resin layer B were changed as shown in Table 3, the same operation as in Example 1 was performed to obtain a laminated body for element processing. Table 3 summarizes the characteristics of the obtained element processing laminate.

Comparative Example 2
A polyamic acid resin solution (B-1) is dried and imidized to a thickness of 20 μm on a bump forming surface of a 6-inch device processing substrate having a bump of 30 μm height on a 0.7 mm thick silicon wafer. Apply by adjusting the number of rotations with a spin coater, heat treatment at 120 ° C. for 10 minutes, dry, then heat treatment at 250 ° C. for 30 minutes to completely imidize, heat resistant resin layer B / for element processing A laminate of the substrate was obtained.

  The laminated body of the heat-resistant resin layer B / element processing substrate and a 6-inch support substrate, which is a 0.7 mm thick silicon wafer, were bonded together, and pressure bonded for 90 seconds at 200 ° C. and 0.6 MPa using a hot press machine. The element processing laminate could not be obtained without bonding.

Comparative Example 3
The polyimide resin solution (A-4) was applied to a 6-inch support substrate, which is a 0.7 mm thick silicon wafer, with a spin coater so that the thickness after drying was 25 μm, and applied at 120 ° C. After heat treatment for 10 minutes and drying, heat treatment was performed at 250 ° C. for 30 minutes to obtain a heat-resistant resin layer A / support substrate laminate.

  A 6-inch element processing substrate having bumps with a height of 30 μm is bonded to a laminate of heat resistant resin layer A / support substrate and a 0.7 mm thick silicon wafer so that the heat resistant resin layer A and the bump forming surface face each other. Using a hot press machine, pressure bonding was performed at 200 ° C. and 0.6 MPa for 90 seconds to obtain a laminated body for device processing. Table 3 summarizes the characteristics of the obtained element processing laminate. In the case of the heat resistant resin layer A single layer, the adhesive force between the heat resistant resin layer A and the element processing substrate was strong, and the heat resistant resin layer A and the element processing substrate could not be peeled off.

Examples 8-12
Except that the heat-resistant resin A used for the heat-resistant resin layer A and the heat-resistant resin B used for the heat-resistant resin layer B were changed as shown in Table 4, the same operation as in Example 1 was performed to obtain a laminated body for element processing. Table 4 summarizes the characteristics of the obtained element processing laminate.

  As is clear from the examples of the present invention, the temporary adhesive layer is composed of the heat-resistant resin layer A and the heat-resistant resin layer B, and the adhesive force between the element processing substrate and the heat-resistant resin layer B is between the support substrate and the heat-resistant resin layer A. By lowering the adhesive strength and the adhesive strength between the heat-resistant resin layer A and the heat-resistant resin layer B, the element processing substrate can be peeled well at room temperature after passing through a processing step such as back grinding.

  Further, since the element processing substrate is peeled off at the adhesive interface with the heat-resistant resin layer B, there is no residue of the temporary adhesive layer on the element processing substrate side, and there is no need for a separate cleaning process.

Example 13
A polyamic acid resin solution (B-5) is dried and imidized to a thickness of 20 μm on the bump forming surface of a 6-inch device processing substrate having a 30 μm-high bump on a 0.7 mm thick silicon wafer. Apply by adjusting the number of rotations with a spin coater, heat treatment at 120 ° C. for 10 minutes, dry, then heat treatment at 250 ° C. for 30 minutes to completely imidize, heat resistant resin layer B / for element processing A laminate of the substrate was obtained.

  On the heat-resistant resin layer B of the laminate of the heat-resistant resin layer B / element processing substrate, the polyimide resin solution (A-4) is applied by adjusting the rotational speed with a spin coater so that the thickness after drying is 25 μm. After heat treatment at 120 ° C. for 10 minutes and drying, heat treatment was performed at 250 ° C. for 30 minutes to obtain a laminate of heat resistant resin layer A / heat resistant resin layer B / element processing substrate.

  A laminate of heat-resistant resin layer A / heat-resistant resin layer B / element processing substrate and a silicon wafer having a thickness of 0.7 mm to be a support substrate are bonded so that the heat-resistant resin layer A and the support substrate face each other, and hot press Using a machine, pressure bonding was performed at 200 ° C. and 0.6 MPa for 90 seconds to obtain a laminated body for device processing. Table 5 summarizes the characteristics of the obtained element processing laminate.

Examples 14-15
Except that the heat-resistant resin A used for the heat-resistant resin layer A and the heat-resistant resin B used for the heat-resistant resin layer B were changed as shown in Table 5, the same operation as in Example 13 was performed to obtain a laminated body for element processing. Table 5 summarizes the characteristics of the obtained element processing laminate.

  Also in Examples 13 to 15, since the element processing substrate is peeled off cleanly at the adhesive interface with the heat-resistant resin layer B, there is no residue of the temporary adhesive layer on the element processing substrate side, and a separate cleaning process is required. There was no.

Example 16
Spin a polyimide resin solution (B-8) to a thickness of 20 μm on the bump forming surface of a 6-inch device processing substrate having a bump of 30 μm height on a 0.7 mm thick silicon wafer. The coating was performed by adjusting the number of rotations with a coater, heat-treated at 120 ° C. for 10 minutes, dried, and then heat-treated at 250 ° C. for 30 minutes to obtain a heat-resistant resin layer B / element processing substrate laminate.

  The polyimide resin solution (A-5) was applied to a 6-inch support substrate, which is a 0.7 mm thick silicon wafer, at a temperature of 120 ° C. with a spin coater adjusted so that the thickness after drying was 25 μm. After heat treatment for 10 minutes and drying, heat treatment was performed at 250 ° C. for 30 minutes to obtain a heat-resistant resin layer A / support substrate laminate.

  The laminate of the heat-resistant resin layer B / element processing substrate and the laminate of the heat-resistant resin layer A / support substrate are bonded so that the heat-resistant resin layer B and the heat-resistant resin layer A face each other. The laminated body for element processing was obtained by pressure bonding at 6 MPa for 90 seconds. Table 6 summarizes the characteristics of the obtained element processing laminate.

Example 17
Except having changed the heat-resistant resin B used for the heat-resistant resin layer B as shown in Table 6, the same operation as in Example 16 was performed to obtain a laminated body for element processing. Table 6 summarizes the characteristics of the obtained element processing laminate.

  Also in Examples 16 and 17, since the element processing substrate is cleanly peeled off at the adhesive interface with the heat-resistant resin layer B, there is no residue of the temporary adhesive layer on the element processing substrate side, and a separate cleaning process is required. There was no.

1 Support Substrate 2 Element Processing Substrate 3 Temporary Adhesion Layer 4 Heat Resistant Resin Layer A
5 Heat-resistant resin layer B

Claims (8)

In the element processing laminate in which the element processing substrate is laminated on the support substrate via the temporary adhesion layer, the temporary adhesion layer is laminated in the order of the heat resistant resin layer A and the heat resistant resin layer B from the support substrate side. The element processing characterized in that the adhesive force between the heat-resistant resin layer B and the element processing substrate is lower than the adhesive force between the heat-resistant resin layer A and the support substrate and the adhesive force between the heat-resistant resin layer B and the heat-resistant resin layer A. Laminated body. The heat resistant resin layer A is a polyimide resin composed of an acid dianhydride residue and a diamine residue, and the heat resistant resin layer A has at least a polysiloxane diamine residue represented by the general formula (1) as the diamine residue. Resin A is included, The element processing laminated body of Claim 1 characterized by the above-mentioned.

(N is a natural number, and the average value calculated from the average molecular weight of the polysiloxane diamine is 1 or more. R ¹ and R ² may be the same or different, and are alkylenes having 1 to 30 carbon atoms. R ^{3 to} R ⁶ may be the same or different and each represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. The laminated body for element processing of Claim 2 which contains 40 mol% or more of residues of the polysiloxane type diamine represented by General formula (1) as a diamine residue of the heat resistant resin A in all the diamine residues. 2. The element processing element according to claim 1, wherein the heat-resistant resin layer B is a polyimide resin composed of an acid dianhydride residue and a diamine residue, and includes the heat-resistant resin B having a glass transition temperature of 300 ° C. or higher. Laminated body. The acid dianhydride residue of the heat-resistant resin B has at least a tetracarboxylic dianhydride residue represented by the general formula (2) and / or (3), and the diamine residue has at least the general formula (4 And / or (5) and a residue of an aromatic diamine represented by (5).

(R ⁷ is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a halogen, a carboxyl group, a carboxylic acid ester group, a fluoroalkyl group having 1 to 30 carbon atoms, a phenyl group, or a sulfonic acid group. And represents a group selected from a nitro group and a cyano group.)

(R ⁸ and R ⁹ may be the same as or different from each other, and are an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, a hydroxyl group, a halogen, and a carboxyl group. , A carboxylic acid ester group, a phenyl group, a sulfonic acid group, a nitro group, and a cyano group, Y represents a direct bond, a carbonyl group, an isopropylidene group, an ether group, a hexafluoropropylidene group, a sulfonyl group, and a phenylene group. Represents a group, a methylene group, a fluoromethylene group, an amide group, an ester group, an ethylene group, a fluoroethylene group, a phenylenebisether group, or a bis (phenylene) isopropylidene group.)

(R ¹⁰ is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, a hydroxyl group, a halogen, a carboxyl group, a carboxylate group, a phenyl group, a sulfone group, A group selected from a nitro group and a cyano group is shown.)

(R ¹¹ and R ¹² may be the same as or different from each other, and are an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, a hydroxyl group, a halogen, and a carboxyl group. , A carboxylic acid ester group, a phenyl group, a sulfone group, a nitro group and a cyano group, wherein X is a direct bond, a carbonyl group, an isopropylidene group, an ether group, a hexafluoropropylidene group, a sulfonyl group, a phenylene group. , Represents a methylene group, a fluoromethylene group, an amide group, an ester group, an ethylene group, a fluoroethylene group, a phenylene bisether group, a bis (phenylene) isopropylidene group, and a fluorene group.) In the method for producing a laminated body for device processing according to any one of claims 1 to 5,
Laminating the heat-resistant resin A on the support substrate, or converting the precursor of the heat-resistant resin A into the heat-resistant resin A after being laminated, and forming the laminate A of the support substrate and the heat-resistant resin layer A, and an element processing substrate The step of laminating the heat-resistant resin B, or converting the precursor of the heat-resistant resin B into the heat-resistant resin B after being laminated, and forming the laminate B of the element processing substrate and the heat-resistant resin layer B; A process for producing a laminated body for element processing, comprising a step of superposing and bonding the laminated body B so that the heat resistant resin layer A and the heat resistant resin layer B face each other. In the method for producing a laminated body for device processing according to any one of claims 1 to 5,
Laminating the heat-resistant resin B on the element processing substrate, or converting the precursor of the heat-resistant resin B into the heat-resistant resin B after the lamination, and forming the laminated body B of the element processing substrate and the heat-resistant resin layer B,
On the heat-resistant resin layer B of the laminate B, the heat-resistant resin A is laminated, or the precursor of the heat-resistant resin A is laminated and then converted to the heat-resistant resin A, and the element processing substrate, the heat-resistant resin layer B, and the heat-resistant resin layer A method for producing a laminated body for device processing, comprising a step of forming a laminated body C with A, and a step of superposing and bonding a support substrate on the heat resistant resin layer A of the laminated body C. In the method for producing a thin element using the element processing laminate according to any one of claims 1 to 5,
A process of thinning a device processing substrate;
A method for manufacturing a thin element, comprising: a step of processing a device processing substrate processed thinly; and a step of peeling the device processed device processing substrate from a support substrate.

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