TW201522045A - Element-processing layered structure, method for manufacturing element-processing layered structure, and method for manufacturing thin element using same - Google Patents

Abstract

To provide an element-processing layered structure in which there is no generation of volatile compounds or occurrence of cracking in a substrate due to separation or the like during the steps for polishing the back surface and forming the back-surface circuits of a semiconductor circuit formation substrate, separation being possible in mild conditions at room temperature, and essentially no temporary adhesive remaining on the semiconductor circuit formation substrate side after separation. An element-processing layered structure in which an element-processing substrate is layered on a support substrate with temporary adhesive layers interposed therebetween, wherein the element-processing layered structure is characterized in that: the temporary adhesive layers are layered in the order of heat-resistant resin layer (A), heat-resistant resin layer (B), from the support substrate side; and 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).

Description

Multilayer laminate for component processing, method for producing laminate for component processing, and method for manufacturing thin component using same

The present invention relates to an adhesive for temporary attachment which is excellent in heat resistance and which is not changed by a manufacturing process of a semiconductor device or a video display device, and which can be peeled off at room temperature and mildly thereafter. Next, the layered body for element processing for the temporary attaching adhesive, the method for producing the laminated body for processing the element, and the method for producing the thin element using the laminated body for the element processing are used.

In recent years, the weight and thickness of semiconductor devices and video display devices have been increasing. In particular, in semiconductor devices, in order to obtain high integration and high density of semiconductor elements, technology development by connecting through electrodes (TSV, Through Silicon Via) and laminating semiconductor wafers has been advanced. Further, it is necessary to make the thickness of the semiconductor circuit-formed substrate thinner than 100 μm and to process it. In this step, the non-circuit forming surface (back surface) of the semiconductor circuit forming substrate is polished and thinned to form a back surface electrode on the back surface thereof. In order to prevent cracking of the semiconductor circuit forming substrate in the step of polishing or the like, the semiconductor circuit forming substrate is fixed to a supporting substrate such as a germanium wafer or a glass substrate, and is subjected to polishing, back surface forming processing, or the like, and then processed. The semiconductor circuit forming substrate is peeled off from the supporting substrate. In order to fix the semiconductor circuit on the support substrate, a temporary adhesive material is used, and the heat resistance which can withstand the semiconductor step is required for the adhesive which can be used as the temporary adhesive material, and is required to be completed after the processing step. Easily peeled off.

As such a temporary adhesive, it has been proposed to use a bismuth-based material and to perform peeling by heat treatment (for example, refer to Patent Document 1), or to use a polyamide or a polyimide-based material to heat and peel off (for example, refer to a patent). Literature 2) and so on. In addition, there has been proposed a material in which a tetrazolium compound having excellent heat resistance is decomposed by ultraviolet irradiation to cause bubbles to be peeled off (for example, see Patent Document 3). In addition, it has been proposed that the temporary adhesive is formed into a two-layer structure of a thermoplastic organopolysiloxane and a curable modified siloxane, and is peeled off at room temperature (for example, see Patent Document 4).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2012-144616 (Application No.)

Patent Document 2: Japanese Patent Laid-Open Publication No. 2010-254808 (Application No.)

Patent Document 3: Japanese Patent Laid-Open Publication No. 2012-67317 (Application No.)

Patent Document 4: Japanese Patent Laid-Open Publication No. 2013-48215 (Application No.)

However, the temporary adhesive which is peeled off by the heat treatment has a problem in that the solder bump is melted in the heating step for peeling off, or the adhesion force in the semiconductor processing step is lowered to peel off in the middle of the step, or the force is increased. Stripping, etc. Further, when the adhesive is photosensitive, there is a problem in that a volatile component or the like is generated in a step under high-temperature vacuum conditions by adding a photopolymerization initiator or a photosensitizer.

When the peeling is performed at room temperature, there is no problem as described above. However, since the temporary attaching material adheres to the semiconductor circuit forming substrate after peeling, it is necessary to use a washing and removing step such as a solvent, in order to completely remove the temporary attaching material. , there is a phase in the steps When the big burden is a problem.

In view of the above circumstances, an object of the present invention is to provide a back surface polishing of a semiconductor circuit forming substrate, a non-volatile component in the step of forming a back surface circuit, and no cracking of the substrate due to peeling or the like, and at room temperature and mild conditions. In the semiconductor circuit forming substrate side after the peeling, the layered body for element processing for which a temporary adhesive agent is hardly left remains, and a method for producing the laminated body for processing the element and a method for producing the thin element using the same are provided.

In other words, the present invention is a laminate for element processing, in which a substrate for element processing is laminated on a support substrate via a temporary adhesive layer, and a temporary adhesive layer is sequentially laminated with a heat resistant resin layer from the side of the support substrate. A. The heat resistant resin layer B, and the adhesive force of the heat resistant resin layer B and the element processing substrate is lower than the adhesive force of the heat resistant resin layer A and the support substrate, and the adhesion between the heat resistant resin layer B and the heat resistant resin layer A.

According to the present invention, it is possible to provide a layered body for element processing which does not generate a volatile component in the element processing step and which has sufficient heat resistance, and which does not cause cracks in the substrate for element processing in the polishing step. In addition, the substrate for element processing can be peeled off from the support substrate at room temperature and under mild conditions, and there is almost no temporary adhesive attached to the substrate for element processing after peeling, so that productivity is improved.

1‧‧‧Support substrate

2‧‧‧Parts for component processing

3‧‧‧ Temporary layer

4‧‧‧Heat Resin Layer A

5‧‧‧Heat Resin Layer B

Fig. 1 is a schematic view showing a laminate for component processing of the present invention.

As shown in FIG. 1, the layered body for component processing of the present invention is formed by sequentially bonding a substrate for element processing and a supporting substrate via a temporary bonding layer, and temporarily laminating the layer by a heat-resistant tree. The lipid layer A and the heat resistant resin layer B are composed of two layers. The support substrate functions to support the substrate for element processing when processing the substrate for component processing.

The substrate for component processing is usually a germanium wafer. On the surface in contact with the heat-resistant resin layer B, a bump for circuit and external connection is formed, and the opposite surface is a surface on which no circuit is formed. Further, a through-electrode for forming a circuit and an external connection may be formed on a surface on which no circuit is formed, and a through electrode for conducting the front and back circuits may be formed. The thickness of the substrate for component processing is not particularly limited and is 600 to 800 μm, preferably 625 to 775 μm.

A substrate such as a germanium wafer or a glass or a quartz wafer can be used as the support substrate. The thickness of the support substrate is not particularly limited and is 600 to 800 μm, preferably 625 to 775 μm.

The temporary bonding layer temporarily fixes the element processing substrate to the support substrate. It is important that the processed substrate for component processing is easily peeled off from the support substrate in the peeling step after the processing step of the device is not peeled off in the device processing step of the substrate for processing the substrate. Further, it is also important that not only the resin is easily peeled off but also the resin of the temporary adhesive layer remains on the substrate for component processing after peeling. If the resin remains, a step of washing off the resin with an organic solvent or the like is required, resulting in an increase in the burden in the production step.

Therefore, it is important that the temporary adhesive layer in the present invention is composed of two layers of the heat resistant resin layer A and the heat resistant resin layer B, and the adhesive force of the heat resistant resin layer B and the substrate for substrate processing is lower than that of the heat resistant resin layer A and the support substrate. Then, the force and the adhesion of the heat resistant resin layer B and the heat resistant resin layer A are obtained. The adhesion between the heat resistant resin layer B and the substrate for processing the substrate, the adhesion between the heat resistant resin layer A and the support substrate, and the adhesion between the heat resistant resin layer B and the heat resistant resin layer A are 10 g/cm or more, preferably 50 g/cm. the above. By using such a subsequent property, it is not peeled off in the device processing step of the element processing substrate, and peeling is likely to occur between the heat resistant resin layer B and the element processing substrate in the peeling step, and is not formed on the element processing substrate. Residual resin.

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 substrate for element processing is not peeled off and ruptured in the processing step, and can be easily peeled off at room temperature in the peeling step. Further, the adhesion between the heat resistant resin layer A and the support substrate and the adhesion 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, and more preferably 100 g/cm or more. When the adhesive force is 20 g/cm or more, the substrate for processing the substrate can be processed without being broken during the processing step. Here, the adhesion force can be obtained by measuring the stress applied when the adherend is drawn at a fixed angle and a fixed speed. The adhesive force of the present invention is an adhesion at the time of peeling at an angle of 90 ° C and a stretching speed of 50 mm/min.

Acrylic resin, acrylic resin, butadiene resin, urethane resin, polyester resin A polymer resin such as a guanamine resin, a polyamidene resin, a polyamidoximine resin, an epoxy resin, or a phenol resin is preferably a polyimide resin having high heat resistance.

The term "heat resistance" means a temperature defined by a thermal decomposition onset temperature at which a volatile component is generated by decomposition or the like. A preferred thermal decomposition initiation temperature is 250 ° C or higher, and more preferably 300 ° C or higher. If the thermal decomposition initiation temperature is 250 ° C or more, no volatile component is generated in the heat treatment step in the component processing step, thereby improving the reliability of the component. The thermal decomposition onset temperature of the present invention can be measured using a thermogravimetric analyzer (TGA, Thermo Gravimetric Analyzer). The measurement method will be specifically described. A specific amount of the resin was added to the TGA, and the moisture absorbed by the resin was removed by holding at 60 ° C for 30 minutes. Then, the temperature was raised to 500 ° C at 5 ° C / min. From the obtained weight reduction curve, the temperature at which the weight reduction is started is set as the thermal decomposition initiation temperature.

The heat resistant resin layer A of the present invention preferably contains a residue having at least an acid dianhydride residue and a diamine residue and containing at least a polyoxyalkylene-based diamine represented by the formula (1) in the diamine residue. The polyimine resin is a heat resistant resin A.

In the formula (1), n is a natural number, and the average value calculated from the average molecular weight of the polyoxyalkylene-based diamine is 1 or more. R ¹ and R ² may be the same or different, and represent an alkylene group having a carbon number of 1 to 30 or a phenyl 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.

Further, the average molecular weight of the polyoxyalkylene-based diamine can be determined by calculating the amine equivalent by performing neutralization and titration of an amine group of a polyoxyalkylene-based diamine, and the amine is prepared. The base equivalent is doubled. For example, a specific amount of a polyoxyalkylene-based diamine to be a sample may be added to a beaker, and dissolved in a 1:1 mixed solution of a specific amount of isopropyl alcohol (hereinafter referred to as IPA) and toluene while stirring. To the solution, a 0.1 N aqueous hydrochloric acid solution was added dropwise, and the amine equivalent was calculated from the dropwise addition amount of a 0.1 N aqueous hydrochloric acid solution which became a neutralization point. The value obtained by doubling the amine equivalent is the average molecular weight.

On the other hand, the molecular weight of the polyoxyalkylene-based diamine used in the case of n=1 and the case of n=10 can be calculated according to the chemical structural formula, and the value and molecular weight of n can be obtained in the form of a linear relationship. Relationship. The above average molecular weight can be substituted into the relationship to obtain an average value of the above n.

Further, the polyoxyalkylene-based diamine represented by the formula (1) has n which is not a single In the case of a mixture of a plurality of n, therefore, 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 polyoxyalkylene-based diamine represented by the formula (1) include bis(3-aminopropyl)tetramethyldioxane and α,ω-bis(3-amino group). Propyl)polydimethyloxane, α,ω-bis(3-aminopropyl)polydimethoxydecane, α,ω-bis(3-aminopropyl)polydipropylanthracene Oxyalkane, α,ω-bis(3-aminopropyl)polydibutyloxane, α,ω-bis(3-aminopropyl)polydiphenoxydecane, α,ω- Bis(2-aminoethyl)polydimethyloxane, α,ω-bis(2-aminoethyl)polydiphenoxydecane, α,ω-bis(4-aminobutyl) Polydimethyl methoxy oxane, α,ω-bis(4-aminobutyl)polydiphenoxy siloxane, α,ω-bis(5-aminopentyl)polydimethyl hydrazine Oxyalkane, α,ω-bis(5-aminopentyl)polydiphenoxydecane, α,ω-bis(4-aminophenyl)polydimethyloxane, α,ω- Bis(4-aminophenyl)polydiphenoxynonane and the like. The polyoxyalkylene-based diamine may be used singly or in combination of two or more.

The polyimide-based resin contained in the heat-resistant resin A of the present invention preferably contains 40 mol% or more of the residue of the polyoxyalkylene-based diamine represented by the general formula (1) in the total diamine residue. More preferably, it is 60 mol% or more and 99 mol% or less. By containing 40 mol% or more of the residue of the polyoxyalkylene-based diamine represented by the formula (1), the glass transition temperature of the heat-resistant resin layer A can be 60 ° C or less, and the support substrate and the component can be processed. The substrate can exhibit good adhesion at a low temperature of 200 ° C or less by a temporary adhesion layer and subsequent steps. When the content of the residue of the polyoxyalkylene-based diamine represented by the formula (1) is increased, the glass transition temperature of the heat-resistant resin A is lowered, preferably 40 ° C or lower, more preferably 20 ° C or lower.

In the present invention, in addition to the residue of the polyoxyalkylene-based diamine, the residue of the aromatic diamine and/or the residue of the alicyclic diamine may be contained. Specific examples of the aromatic diamine and/or the alicyclic diamine include p-phenylenediamine, m-phenylenediamine, and 2,5-diaminomethyl group. Benzene, 2,4-diaminotoluene, 2-methoxy-1,4-phenylenediamine, 4,4'-diaminobenzimidamide, 3,4'-diaminobenzimidamide , 3,3'-diaminobenzimidamide, 3,3'-dimethyl-4,4'-diaminobenzimidamide, 9,9-bis(4-aminophenyl)anthracene 9,9-bis(3-aminophenyl)anthracene, 9,9-bis(3-methyl-4-aminophenyl)anthracene, 9,9,-bis(3,5-dimethyl 4-aminophenyl)anthracene, 9,9-bis(3-methoxy-4-aminophenyl)anthracene, 9,9-bis(4-aminophenyl)indole-4-methyl 9,9-bis(4-aminophenyl)indole-4-methoxy, 9,9-bis(4-aminophenyl)indole-4-ethyl, 9,9-bis (4- Aminophenyl) 茀-4-碸, 9,9-bis(4-aminophenyl)indole-3-methyl, 1,3-diaminocyclohexane, 2,2'-dimethyl Benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,4-diaminopyridine, 2,6-diaminopyridine, 1,5-diamine Naphthyl, 2,7-diaminoguanidine, p-aminobenzylamine, m-aminobenzylamine, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino Diphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiyl Phenylhydrazine, 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-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 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]anthracene, bis[4-(3-aminophenoxy)phenyl] Bismuth, 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'-Dimethyldicyclohexane, benzidine, and the like. The above aromatic diamine or alicyclic diamine may be used singly or in combination of two or more.

Among these aromatic diamines or alicyclic diamines, it is preferred to have flexibility A higher structural aromatic diamine, specifically, 1,3-bis(3-aminophenoxy)benzene, 3,3'-diaminodiphenylanthracene, 4,4' -diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,3'-diaminobenzophenone.

Further, in the present invention, the total diamine residue contains 1 mol% or more, preferably 5 mol% or more of a residue of an aromatic diamine having a hydroxyl group or a carboxyl group, and contains 40 mol% or less. Preferably, it contains 30 mol% or less. The solvent resistance is improved by containing a residue of 1 mol% or more and 40 mol% or less of an aromatic diamine having a hydroxyl group or a carboxyl group. Further, by using a crosslinking agent in combination, an effect of greatly improving solvent resistance can be obtained.

Specific examples of the aromatic diamine having a hydroxyl group include 2,5-diaminophenol, 3,5-diaminophenol, 3,3'-dihydroxybenzidine, and 4,4'-dihydroxyl group. -3,3'-diaminophenylpropane, 4,4'-dihydroxy-3,3'-diaminophenylhexafluoropropane, 4,4'-dihydroxy-3,3'-diamine Phenyl phenyl, 4,4'-dihydroxy-3,3'-diaminophenyl ether, 3,3'-dihydroxy-4,4'-diaminophenyl ether, 4,4'-dihydroxy -3,3'-diaminophenylpropylmethane, 4,4'-dihydroxy-3,3'-diaminobenzophenone, 1,3-bis(4-amino-3-hydroxyl) Phenyl)benzene, 1,3-bis(3-amino-4-hydroxyphenyl)benzene, bis(4-(4-amino-3-hydroxyphenoxy)benzene)propane, bis(4-( 3-Amino-4-hydroxyphenoxy)benzene)indole, 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, and 4,4'-. Dihydroxy-3,3'-diaminophenylpropane, 4,4'-dihydroxy-3,3'-diaminophenylhexafluoropropane, 4,4'-dicarboxy-3,3'- Diaminophenyl hydrazine, 4,4'-dicarboxy-3,3'-diaminophenyl ether, 3,3'-dicarboxy-4,4'-diaminophenyl ether, 4,4'- Dicarboxy-3,3'-diaminophenylpropylmethane, 4,4'-dicarboxy-3,3'-diaminobenzophenone, 3,5-diaminobenzoic acid, 2, 6-Diaminobenzoic acid, 9,9-bis(4-aminophenyl)indole-4-carboxylic acid, 9,9-bis(4-aminophenyl)indole-3-carboxylic acid, 2- Carboxy-4,4'-diaminodiphenyl ether and the like.

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

The polyimine-based resin contained in the heat-resistant resin A of the present invention preferably contains a residue of an aromatic tetracarboxylic dianhydride as an acid dianhydride residue. Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, and 2,2' dimethyl-3. 3',4,4'-biphenyltetracarboxylic dianhydride, 5,5' dimethyl-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4 '-Biphenyltetracarboxylic 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 IV Carboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3'4'-benzophenonetetracarboxylic dianhydride, 3,3',4 , 4'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-diphenylarylene Carboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethylenetetracarboxylic dianhydride, 4,4 '-Isopropyl phthalic anhydride, 4,4'-(hexafluoroisopropylidene) dicarboxylic anhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 2,3,6,7- Naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3", 4,4"-para-triphenyl Tetracarboxylic dianhydride, 3,3",4,4"-m-triphenyltetracarboxylic dianhydride, 2,3,6,7 - fluorene tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, and the like. The above aromatic tetracarboxylic dianhydride may be used singly or in combination of two or more.

Further, in the present invention, the tetracarboxylic dianhydride having an aliphatic ring can be contained to the extent that the heat resistance of the polyimide resin is not impaired. Specific examples of the tetracarboxylic dianhydride having an aliphatic ring include 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,2,3,4-cyclobutane tetracarboxylic dianhydride. 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-dicyclohexenetetracarboxylic acid Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxa-3- Furyl)-naphthalene [1,2-C]furan-1,3-dione. The above tetracarboxylic dianhydride may be used singly or in combination of two or more.

The heat resistant resin A of the present invention can be an epoxy crosslinking agent or an isocyanate system. Various crosslinking agents such as a crosslinking agent, a methylol crosslinking agent, a maleimide crosslinking agent, and an acrylic crosslinking agent. Among them, the hydroxymethyl-based crosslinking agent is particularly preferred because it is a compound which is crosslinked by a polyimide-based resin and incorporated into a polyimide-based resin during thermosetting. Solvent resistance can be improved by introducing a crosslinked structure into the resin. Specific examples of the methylol-based crosslinking agent include the following melamine derivatives or urea derivatives (manufactured by Sanwa Chemical Co., Ltd.).

Since the heat resistant resin layer B of the present invention is in contact with the substrate for element processing, 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 it is further preferred that the glass transition temperature is not detected before the temperature at which the heat resistant resin starts to thermally decompose. If the glass transition temperature of the heat resistant resin B is 300 ° C or more, the glass transition temperature becomes higher than the temperature in the heat treatment step in the component processing step, so the adhesion force in the step does not rise, so that it can be easily used in the peeling step. The substrate for processing the component is peeled off.

The heat resistant resin B is preferably a polyimide-based resin having a thermal decomposition initiation temperature of at least 250 ° C or higher. The thermal decomposition initiation temperature is preferably 350 ° C or higher, and more preferably 450 ° C or higher. When the thermal decomposition initiation temperature of the heat resistant resin B is 250 ° C or more, no volatile component is generated in the heat treatment step in the component processing step, and the reliability of the component is improved.

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

In the formula (2), R ⁷ represents an alkyl group selected from the group consisting of 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a halogen group, a carboxyl group, a carboxylate group, and a fluorine having 1 to 30 carbon atoms. a group of an alkyl group, a phenyl group, a sulfonic acid group, a nitro group, and a cyano group.

In the formula (3), R ⁸ and R ⁹ may be the same or different, and each represents an alkyl group selected from the group consisting of a C 1 to 30 alkyl group, an alkoxy group having 1 to 30 carbon atoms, and a fluoroalkane having 1 to 30 carbon atoms. a group of a hydroxyl group, a hydroxyl group, a halogen group, a carboxyl group, a carboxylate group, a phenyl group, a sulfonic acid group, a nitro group and a cyano group. Y represents a direct bond, a carbonyl group, a isopropylidene group, an ether group, a hexafluoropropylene group, a sulfonyl group, a phenylene group, a methylene group, a fluoromethylene group, a decylamino group, an ester group, an ethyl group, and a fluorine group. Ethyl, phenyl diether, bis(phenyl) isopropylidene.

In the formula (4), R ¹⁰ represents an alkyl group selected from the group consisting of 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 group, a carboxyl group, and a carboxylic acid. a group of an ester group, a phenyl group, a fluorenyl group, a nitro group, and a cyano group.

In the formula (5), R ¹¹ and R ¹² may be the same or different, and each represents an alkyl group selected from the group consisting of a C 1 to 30 alkyl group, an alkoxy group having 1 to 30 carbon atoms, and a fluoroalkane having 1 to 30 carbon atoms. a group of a hydroxy group, a halogen group, a carboxyl group, a carboxylate group, a phenyl group, a fluorenyl group, a nitro group and a cyano group. X represents a direct bond, a carbonyl group, a isopropylidene group, an ether group, a hexafluoropropylene group, a sulfonyl group, a phenylene group, a methylene group, a fluoromethylene group, a decylamino group, an ester group, an ethyl group, and a fluorine group. Ethyl, phenyl diether, bis(phenylene) isopropylidene, fluorenyl.

The term "halogen" as used herein means fluorine, chlorine, bromine or iodine.

In the present invention, it is selected from the group consisting of pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid An acid anhydride residue in a tetracarboxylic dianhydride of an anhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, and a selected from the group consisting of p-phenylenediamine and 4,4'-diamine Residues of aromatic diamines in diphenyl ether, 2,2'-dimethyl-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)anthracene The polyimine-based resin of the component is preferable in terms of heat resistance and high glass transition temperature.

The molecular weight of the polyamidene-based resin used in the heat-resistant resin layer A and the heat-resistant resin layer B of the present invention can be adjusted by using a synthetic tetracarboxylic acid component or a diamine component to be a molar or any component. Excessively. Any one of the tetracarboxylic acid component or the diamine component may be used in excess, and the terminal of the polymer chain may be blocked with an acid component or an amine component. seal. As the blocking agent for the acid component, a dicarboxylic acid or an anhydride thereof can be preferably used, and as the terminal blocking agent for the amine component, a monoamine can be preferably used. In this case, it is preferred that the acid equivalent of the tetracarboxylic acid component including the blocking component of the acid component or the amine component and the amine equivalent of the diamine component are equal to each other.

When the molar ratio is adjusted in excess of the tetracarboxylic acid component or the excess of the diamine component, a dicarboxylic acid such as benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride or aniline or an anhydride thereof, or a monoamine may be added as a capping agent. Agent.

In the present invention, the molar ratio of the tetracarboxylic acid component/diamine component of the polyimine-based resin can be appropriately adjusted so that the viscosity of the resin solution is easily used in the coating step or the like, and is usually tetracarboxylic acid. The molar ratio of the acid component/diamine component is adjusted in the range of 100/95 to 100/100 or 95/100 to 100/100. However, if the molar balance is broken, the molecular weight of the resin is lowered, and the mechanical strength of the formed film tends to be low and the adhesive force is also weakened. Therefore, it is preferred to adjust the molar ratio within a range in which the adhesive force is not weakened.

The method of synthesizing the polyimine-based resin used for the heat-resistant resin layer A and the heat-resistant resin layer B of the present invention is not particularly limited. For example, when polylysine which is a precursor of a polyimine-based resin is polymerized, a tetracarboxylic dianhydride and a diamine are stirred in an organic solvent at 0 to 100 ° C for 1 to 100 hours to obtain a poly-proline resin. Solution. When the composition of the polyimine resin is soluble in an organic solvent, the polyglycine is directly polymerized to a temperature of 120 to 300 ° C and stirred for 1 to 100 hours to be converted into polyimine. A polyamidene resin solution was obtained. At this time, toluene, o-xylene, m-xylene, p-xylene or the like may be added to the reaction solution to remove the water generated in the oxime imidization reaction from the solvent.

Examples of the solvent for synthesizing the polyamic acid as the polyimide or polyimine precursor include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N. , N- A guanamine-based polar solvent such as dimethylformamide; and β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, etc. The lactone is a polar solvent, and examples thereof include methyl sirloin, serotonin methicillin, ethyl celecoxib, acesulfame acetate, methyl carbitol, ethyl carbitol, and Ethylene glycol dimethyl ether (diglyme), ethyl lactate and the like. These may be used alone or in combination of two or more. The concentration of the polyimine resin solution or the polyaminic acid resin solution is usually preferably from 10 to 80% by weight, and more preferably from 20 to 70% by weight.

In the case of a polyaminic acid resin solution, it is applied onto a substrate such as a film or glass and dried to form a coating film, which is then subjected to heat treatment to be converted into polyimine. The conversion of the polyimine precursor to the polyimide needs a temperature of 240 ° C or higher, but by lowering the temperature and the shorter temperature by containing the ruthenium catalyst in the polyphthalic acid resin composition. In the meantime, the hydrazine is imidized. Specific examples of the ruthenium-based catalyst include pyridine, trimethylpyridine, β-methylpyridine, quinoline, isoquinoline, imidazole, 2-methylimidazole, and 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 , but not limited to aminophenol, p-aminobenzoic acid, and the like.

The ruthenium-imidation catalyst is preferably 3 parts by mass or more, and 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 ruthenium imidization catalyst, it is also possible to carry out the imidization by a heat treatment at a lower temperature. Further, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. By setting the content of the ruthenium-imiding catalyst to 10 parts by mass or less, the amount of the ruthenium-imidazole catalyst remaining in the polyimide-based resin layer after heat treatment can be minimized, and generation of volatile components can be suppressed.

In addition to the polyimine-based resin and the crosslinking agent, the heat-resistant resin layer A and the heat-resistant resin layer B of the present invention may be added with other resins or fillers within the range in which the effects of the present invention are not impaired. Examples of the other resin include an acrylic resin and an acrylonitrile resin. A heat-resistant polymer resin such as a butadiene-based resin, a urethane-based resin, a polyester-based resin, a polyamine-based resin, a polyamidoximine-based resin, an epoxy resin, or a phenol resin. Examples of the filler include fine particles composed of organic or inorganic materials, fillers, and the like. Specific examples of the fine particles and the filler include cerium oxide, aluminum oxide, titanium oxide, quartz powder, magnesium carbonate, potassium carbonate, barium sulfate, mica, and talc. Further, in order to improve properties such as adhesion, heat resistance, coatability, and storage stability, a surfactant, a decane coupling agent, or the like may be added.

Next, a method of producing a laminate for component processing of the present invention will be described. The production of the laminated body for component processing of the present invention includes at least the following steps (manufacturing method 1).

(Step A), after laminating the heat-resistant resin A or the laminated heat-resistant resin A on the support substrate, the precursor is converted into the heat-resistant resin A, and the laminate A of the support substrate and the heat-resistant resin layer A is formed; and the layer is laminated on the substrate for component processing. The heat-resistant resin B or the laminated heat-resistant resin B is converted into the heat-resistant resin B before being driven, and is formed into a layered body B of the element processing substrate and the heat-resistant resin layer B.

(Step B) The layered body A and the layered body B are superposed on each other so that the heat resistant resin layer A and the heat resistant resin layer B face each other.

Further, it may be at least the following steps (manufacturing method 2).

(Step A) The heat-resistant resin B or the laminated heat-resistant resin B is laminated on the element processing substrate and then converted into the heat-resistant resin B to form a layered body B of the element processing substrate and the heat-resistant resin layer B.

(Step B) The heat-resistant resin A or the heat-resistant resin A is laminated on the heat-resistant resin layer B of the layered body B, and then converted into a heat-resistant resin A to form a substrate for component processing, a heat-resistant resin layer B, and a heat-resistant resin layer. A layer of layer C.

(Step C) The support substrate is superposed on the heat-resistant resin layer A of the layered body C and then.

As the coating method of the present invention, a bar coater or a roll type can be used. A method such as a coater, a slit coater, a spin coater, or screen printing. Drying of the organic solvent in the resin composition is performed by heat treatment after coating, and the ruthenium imidization is carried out when the heat resistant resin A and the heat resistant resin B are polyphthalic acid resins. The heat treatment temperature is 100 to 400 ° C, preferably 150 to 250 ° C. The heat treatment time can be appropriately selected within 20 seconds to 2 hours, and can be continuously or intermittently. When the heat resistant resin A or the heat resistant resin B is a polyamic acid resin, a further heat treatment may be further performed. The heat treatment temperature is 160 to 500 ° C, preferably 200 to 350 ° C. The heat treatment time can be appropriately selected within 20 seconds to 4 hours, and can be continuously or intermittently.

The residual volatile component 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, and more preferably 0.01% by weight or less. When the residual volatile component is 1% by weight or less, voids, peeling, and the like can be produced in the element processing step, and the element processing can be performed with good yield.

In the case of the production method 2, when the heat resistant resin B is a polyphthalic acid resin, it may be subjected to heat treatment after coating to imidize, and then the heat resistant resin A may be applied, or the heat resistant resin B may be applied and After drying, the heat-resistant resin A is applied and dried, and then heat-treated to iodide.

The thickness of the heat resistant resin layer A and the heat resistant resin layer B can be appropriately selected. There is a bump for connection on the surface of the substrate for element processing which is in contact with the heat resistant resin B, and the height of the bump is usually 20 to 150 μm. In order to make the thickness of the temporary adhesive layer to which the heat resistant resin layer A and the heat resistant resin layer B are added is thicker than the height of the bump, the thickness is preferably 25 to 200 μm, more preferably 30 to 160 μm. The thickness of each of the heat resistant resin layer A and the heat resistant resin layer B can be appropriately selected in the thickness range of the temporary adhesive layer.

In the production method 1, the surface of the heat-resistant resin layer A of the laminate A and/or the heat-resistant resin layer B of the laminate B may be subjected to a subsequent improvement treatment before the step B. Make For the subsequent improvement treatment, discharge treatment such as normal piezoelectric slurry treatment, corona discharge treatment, and low temperature plasma treatment is preferred.

The step B in the manufacturing method 1 and the subsequent step in the step C of the manufacturing method 2 can be pressed by pressure. It can also be pressed at room temperature or pressed and heated. The temperature at this time is 250 ° C or lower, preferably 200 ° C or lower. Pressing can be carried out in air or in nitrogen. It is preferably in a vacuum.

Next, a method of manufacturing a thin element using the layered body for element processing of the present invention will be described. The method of manufacturing a thin component includes at least the following steps.

(Step A) The substrate for component processing is processed to be thin.

(Step B) The substrate processed into a thin component processing substrate is processed.

(Step C) The component processed substrate processed by the device is peeled off from the support substrate.

The step of processing the substrate for element processing to be thin is a step of polishing and thinning the surface on the opposite side to the surface on which the heat-resistant resin layer B of the substrate for element processing is placed. Thinning is performed so that the thickness of the substrate for element processing is in the range of 10 to 200 μm, preferably 30 to 100 μm.

The layered body for element processing obtained by thinning the element processing substrate in the step A is subjected to various device processing steps on the side of the side polished in the step B. Examples of the electrode formation, the formation of a metal wiring, the formation of a protective film, the formation of a bump for connection, and the like are exemplified. Specific examples thereof include metal sputtering for forming electrodes, wet etching of metal layers, resist coating for forming metal wiring, drying, exposure, development, resist stripping, and metal plating. , dry etching, chemical mechanical polishing (CMP), and the like. Further, there are cases including a ruthenium etching for forming a TSV, and a chemical vapor deposition (CVD) for forming an insulating film.

Next, the component processed substrate subjected to the device processing in the step B is peeled off from the support substrate. As a peeling method, there is a thermal sliding method in which a laminate for processing an element is heated at a temperature of 250 ° C or lower and peeled while sliding in a horizontal direction; a protective film is bonded to a component processing substrate and supported at room temperature. Room temperature peeling method for substrate peeling. In the present invention, a room temperature peeling method can be preferably applied.

Since the element processing substrate of the layered body for component processing of the present invention is temporarily fixed to the temporary adhesive layer with an adhesive force capable of being easily peeled off at room temperature, the peeling interface at the time of peeling is the component processed substrate and the heat resistant resin layer B. between. Therefore, since the heat-resistant resin layer B does not remain on the element processing substrate, the cleaning step is not required after the peeling, but the cleaning step may be performed when a small amount of residue remains. As the solution to be used for washing, an aqueous solution of sodium hydroxide, sodium hydrogencarbonate, potassium hydroxide or tetramethylammonium hydroxide, a mixed solution of ethanolamine and dimethylarylene, or the like can be used.

[Examples]

The invention is illustrated by the following examples, but the invention is not limited to the examples. A method of evaluating the glass transition temperature, the weight reduction rate, and the adhesion force will be described.

(1) Determination of glass transition temperature

The heat-resistant resin solutions (B1 to B9, A1 to A6) described in the following Production Examples 1 to 15 were applied to the shiny surface of the electrolytic copper foil having a thickness of 18 μm so as to have a thickness of 20 μm by a bar coater. The mixture was dried at 80 ° C for 10 minutes, dried at 150 ° C for 10 minutes, and further heated in a nitrogen atmosphere at 250 ° C for 10 minutes to be converted into polyimine to obtain a resin laminated copper foil. Then, the copper foil of the obtained resin laminated copper foil was subjected to full-surface etching using a ferric chloride solution to obtain a single film of a heat resistant resin.

About 10 mg of the obtained single film of the heat-resistant resin was filled in a standard container made of aluminum, and it was measured using a differential scanning calorimeter DSC-50 (manufactured by Shimadzu Corporation) (DSC method), and calculated based on the bending point of the obtained DSC curve. Glass transfer temperature. After pre-drying at 80 ° C for 1 hour, the temperature was raised to 500 ° C at a temperature increase rate of 20 ° C / min.

(2) Determination of the coefficient of thermal linear expansion

The single film of the heat-resistant resin obtained above was cut into a specific width, and rolled into a cylindrical shape, and heated at a temperature of 30 to 200 ° C using a thermomechanical analyzer SS-6100 (manufactured by Seiko Instruments Co., Ltd.). The measurement was carried out by raising the temperature to 250 ° C at a rate of 5 ° C /min. Based on the obtained measurement results, the 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) Substrate force measurement of substrate for component processing - heat resistant resin layer B

The heat-resistant resin solution (B1 to B9) was applied to the element processing substrate by a spin coater so as to have a thickness of 20 μm, and then dried at 80 ° C for 10 minutes, dried at 150 ° C for 10 minutes, and further under a nitrogen atmosphere. The mixture was heat-treated at 250 ° C for 30 minutes to be converted into polyimine, and a heat resistant resin layer B was laminated. The heat-resistant resin layer B was cut at a width of 10 mm, and a 10 mm-width polyimine film was used under the conditions of a tensile speed of 50 mm/min and a peeling degree of 90° using "Tensilon UTM-4-100" manufactured by TOYO BOLDWIN Co., Ltd. The measurement was carried out.

(4) Substrate force measurement of support substrate-heat resistant resin layer A, heat resistant resin layer A-heat resistant resin layer B

After peeling the substrate for element processing in the laminated body for component processing obtained in each of the examples and the comparative examples, the temporary adhesive layer including the heat resistant resin layer B/heat resistant resin layer A was cut at a width of 10 mm, and the TOYO BOLDWIN company was used. The manufactured "Tensilon UTM-4-100" was measured for the heat resistant resin layer B under the conditions of a tensile speed of 50 mm/min and a peeling of 90°.

When the peeling interface is the support substrate-heat resistant resin layer A, the measured value indicates the adhesion force of the support substrate-heat resistant resin layer A. At this time, it is considered that the heat-resistant resin layer A-heat-resistant resin layer B has a larger adhesive force than the support substrate-heat resistant resin. The adhesion of layer A.

(5) Back grinding of the substrate for component processing

The layered body for element processing obtained in each of the examples and the comparative examples was placed in a Grinder DAG810 (manufactured by DISCO), and the substrate for element processing was polished to a thickness of 100 μm. The substrate for component processing after polishing was observed with the naked eye, and the presence or absence of cracks, cracks, and the like was evaluated.

(6) Visual inspection after heat treatment

The back-grinding element-processed laminated body was placed in a hot air oven set at 250 ° C, left for 1 hour, and returned to room temperature, and then the appearance change such as expansion of the substrate side for element processing was visually observed.

(7) Evaluation of solvent resistance

The back-grinded layered component processing body was immersed in a 1N aqueous hydrochloric acid solution, a 1N aqueous sodium hydroxide solution, and acetone at 25 ° C for 10 minutes. After peeling off the substrate for element processing, the heat resistant resin layer was observed with an optical microscope.

The case where no change is observed is evaluated as good (A), and will be received from the temporary The case where the change of the heat-resistant resin such as dissolution or infiltration was observed in the region from the end of the layer to the area of 500 μm was evaluated as (B), and the change was evaluated as not possible (C) from the end portion to the region of more than 500 μm.

(8) Evaluation of the peelability of the substrate for component processing

The dicing protective tape is bonded to the component processing substrate of the back-grinding component processing laminate by the dicing frame, and the dicing protective tape is placed on the adsorption disk by vacuum suction, and the support substrate is lifted by the tweezers at room temperature. At one point, the support substrate is peeled off.

The peeling test was performed using the laminated body for 10 pieces of component processing, and the number of pieces of the substrate for processing the substrate to be 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)polydimethyloxane (average molecular weight: 860, n=9 in formula (1))

PDA: p-phenylenediamine

DAE: 4,4'-diaminophenyl ether

APB: 1,3-bis(3-aminophenoxy)benzene

DABS: 4,4'-dihydroxy-3,3'-diaminophenyl hydrazine

m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl

BAHF: 4,4'-dihydroxy-3,3'-diaminophenylhexafluoropropane

FDA: 9,9-bis(4-aminophenyl)anthracene

100LM: NIKALAC (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)

Add PDA 75.7g (0.7mol), DAE 60.1g (0.3mol) and NMP 2264g to the reaction vessel with thermometer, dry nitrogen inlet, heating/cooling device with warm water/cooling water and stirring device. After the solution was dissolved, 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, followed by reaction at 60 ° C for 5 hours to obtain 15% by weight of polyfluorene. Amino acid resin solution (B-1).

Production Example 2 to 7 (Polymerization of Heat Resistant Resin B Solution)

The same operation as in Production Example 1 was carried out except that the type and amount of the acid dianhydride and the diamine were changed as shown in Table 1, and a 15% by weight poly-lysine resin solution (B-2 to 7) was obtained.

Production Example 8 (Polymerization of Heat Resistant Resin B Solution)

M-TB 127.4g (0.6mol) and BAHF 146.5g (0.4mol) were added together with a thermometer, a dry nitrogen inlet, a heating/cooling device for warm water/cooling water, and a stirring device. NMP 2788g was dissolved in the same manner, and then 218.1 g (1.0 mol) of PMDA was added thereto, and the mixture was reacted at room temperature for 1 hour, followed by reaction at 60 ° C for 3 hours, and then reacted at 180 ° C for 5 hours to obtain 15% by weight. Polyimine resin solution (B-8).

Production Example 9 (Polymerization of Heat Resistant Resin B Solution)

Except for changing the type and amount of acid dianhydride and diamine as shown in Table 1, In the same manner as in Example 8, a 20% by weight solution of the polyimine resin (B-9) was obtained.

Production Example 10 (Polymerization of Heat Resistant Resin A Solution)

APPS 301g (0.35mol), DAE 130.1g (0.65mol) and NMP 494g were added together with a thermometer, a dry nitrogen inlet, a heating/cooling device of warm water/cooling water and a stirring device. After it was dissolved, 310.2 g (1 mol) of ODPA was added thereto, and the mixture was reacted at room temperature for 1 hour, followed by reaction at 60 ° C for 3 hours, and then reacted at 180 ° C for 5 hours to obtain 60% by weight of polyfluorene. Amine resin solution (A-1).

Production Example 11 to 15 (polymerization of heat resistant resin A solution)

The same operation as in Production Example 10 was carried out except that the type and amount of the acid dianhydride and the diamine were changed as shown in Table 2, and a 60% by weight of the polyimide resin solution (A-2 to 5) was obtained.

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

The glass transition temperature (Tg) of each of the heat resistant resin A and the heat resistant resin B is also shown in Tables 1 and 2.

[Example 1]

For a silicon wafer having a thickness of 0.7 mm, the number of revolutions was adjusted by a spin coater to a thickness of 20 μm after drying and yttrium imidation to a bump of a 6-inch element processing substrate having a bump of a height of 30 μm. The block forming surface was coated with a polyaminic acid resin solution (B-3), heat-treated at 120 ° C for 10 minutes, dried, and then heat-treated at 250 ° C for 30 minutes to be completely imidized to obtain a heat-resistant resin layer B. / Laminate of the substrate for component processing.

The spin coating machine was used to adjust the number of revolutions, and the polyimine resin solution (A-4) was coated on a support substrate having a thickness of 0.7 mm, that is, a 6-inch thick support substrate, to a thickness of 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 the heat resistant resin layer A / the support substrate.

The laminate of the heat-resistant resin layer B/component processing substrate and 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, and the hot press is used at 200 ° C, 0.6. The laminated body for component processing was obtained by pressing at MPa for 90 seconds. The characteristics of the obtained laminated body for component processing are summarized in Table 3.

[Examples 2 to 7]

The same operation as in Example 1 was carried out except that the heat-resistant resin A used for the heat-resistant resin layer A and the heat-resistant resin B used in the heat-resistant resin layer B were changed, and the laminate for element processing was obtained. The characteristics of the obtained laminated body for component processing are summarized in Table 3.

[Comparative Example 1]

The same operation as in Example 1 was carried out except that the heat-resistant resin A used in the heat-resistant resin layer A and the heat-resistant resin B used in the heat-resistant resin layer B were changed as shown in Table 3, A laminated body for component processing is obtained. The characteristics of the obtained laminated body for component processing are summarized in Table 3.

[Comparative Example 2]

For a silicon wafer having a thickness of 0.7 mm, the number of revolutions was adjusted by a spin coater to a thickness of 20 μm after drying and yttrium imidation to a bump of a 6-inch element processing substrate having a bump of a height of 30 μm. The block forming surface was coated with a polyaminic acid resin solution (B-1), heat-treated at 120 ° C for 10 minutes, dried, and then heat-treated at 250 ° C for 30 minutes to be completely imidized to obtain a heat-resistant resin layer B. / Laminate of the substrate for component processing.

The laminate of the heat-resistant resin layer B/component processing substrate was bonded to a 6-inch support substrate having a thickness of 0.7 mm, and was pressed at 200 ° C and 0.6 MPa for 90 seconds using a hot press. , and the laminated body for component processing cannot be obtained.

[Comparative Example 3]

The spin coating machine was used to adjust the number of revolutions, and the polyimine resin solution (A-4) was coated on a support substrate having a thickness of 0.7 mm, that is, a 6-inch thick support substrate, to a thickness of 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 the heat resistant resin layer A / the support substrate.

A 6-inch element processing substrate having a bump having a height of 30 μm is bonded to the laminate of the heat-resistant resin layer A/support substrate and the silicon wafer having a thickness of 0.7 mm so that the heat-resistant resin layer A and the bump-forming surface face each other. Then, it was pressed at 200 ° C and 0.6 MPa for 90 seconds using a hot press to obtain a laminate for component processing. The characteristics of the obtained laminated body for component processing are summarized in Table 3. When the heat resistant resin layer A is a single layer, the heat resistant resin layer A and the element processing substrate have a strong adhesive force, and the heat resistant resin layer A and the element processing substrate cannot be peeled off.

[Examples 8 to 12]

The same operation as in Example 1 was carried out except that the heat-resistant resin A used in the heat-resistant resin layer A and the heat-resistant resin B used in the heat-resistant resin layer B were changed, and the layered body for element processing was obtained. The characteristics of the obtained laminated body for component processing are summarized in Table 4.

According to the embodiment of the present invention, the temporary adhesive layer includes 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 lower than the adhesive force of the support substrate and the heat resistant resin layer A and the heat resistant resin. The bonding force between the layer A and the heat-resistant resin layer B can be favorably peeled off at room temperature after the substrate for element processing is processed by a back surface polishing or the like.

Further, since the element processing substrate is completely peeled off at the interface with the heat resistant resin layer B, there is no residue of the temporary bonding layer on the element processing substrate side, and no additional cleaning step is required.

[Example 13]

For a silicon wafer having a thickness of 0.7 mm, the number of revolutions was adjusted by a spin coater to a thickness of 20 μm after drying and yttrium imidation to a bump of a 6-inch element processing substrate having a bump of a height of 30 μm. The block forming surface was coated with a polyaminic acid resin solution (B-5), heat-treated at 120 ° C for 10 minutes, dried, and then heat-treated at 250 ° C for 30 minutes to be completely imidized to obtain a heat-resistant resin layer B. / Laminate of the substrate for component processing.

The spin coating machine is used to adjust the number of revolutions and apply a polyimine resin solution (A-4) to the heat-resistant resin layer B of the laminate of the heat-resistant resin layer B/component processing substrate so that the thickness after drying becomes 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 the heat resistant resin layer A / the heat resistant resin layer B / the substrate for element processing.

The laminate of the heat-resistant resin layer A/heat-resistant resin layer B/component processing substrate and the tantalum wafer having a thickness of 0.7 mm as the support substrate are bonded to each other with the heat-resistant resin layer A and the support substrate, and a hot press is used. The laminate for component processing was obtained by press-bonding at 200 ° C and 0.6 MPa for 90 seconds. The characteristics of the obtained laminated body for component processing are summarized in Table 5.

[Examples 14 to 15]

The same operation as in Example 13 was carried out, 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, and the layered body for element processing was obtained. The characteristics of the obtained laminated body for component processing are summarized in Table 5.

In the examples 13 to 15, since the substrate for element processing can be completely peeled off at the interface with the heat resistant resin layer B, there is no residue of the temporary layer on the substrate side for component processing, so that no additional cleaning step is required. .

[Example 16]

For a wafer having a thickness of 0.7 mm, a bump coating surface was coated on a 6-inch element processing substrate having a height of 30 μm by using a spin coater to adjust the number of revolutions and having a thickness of 20 μm after drying. The polyimine resin solution (B-8) was heat-treated at 120 ° C for 10 minutes, dried, and then heat-treated at 250 ° C for 30 minutes to obtain a laminate of the heat-resistant resin layer B/component processing substrate.

The spin coating machine was used to adjust the number of revolutions and apply a polyimine resin solution (A-5) to a 6-inch support substrate having a thickness of 0.7 mm on the basis of a thickness of 25 μm after drying. After heat treatment for 10 minutes at ° C and drying, heat treatment was performed at 250 ° C for 30 minutes to obtain a laminate of the heat resistant resin layer A / the support substrate.

The laminate of the heat-resistant resin layer B/component processing substrate and 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, and the hot press is used at 200 ° C, 0.6. The laminated body for component processing was obtained by pressing at MPa for 90 seconds. The characteristics of the obtained laminated body for component processing are summarized in Table 6.

[Example 17]

The same operation as in Example 16 was carried out except that the heat-resistant resin B used for the heat-resistant resin layer B was changed as shown in Table 6, and a laminate for element processing was obtained. The characteristics of the obtained laminated body for component processing are summarized in Table 6.

In the examples 16 and 17, the substrate for element processing can be completely peeled off at the interface with the heat resistant resin layer B. Therefore, there is no residue of the temporary layer on the substrate side for component processing, so that no additional cleaning step is required. .

1‧‧‧Support substrate

2‧‧‧Parts for component processing

3‧‧‧ Temporary layer

4‧‧‧Heat Resin Layer A

5‧‧‧Heat Resin Layer B

Claims (8)

A laminated body for component processing, in which a substrate for component processing is laminated on a support substrate via a temporary adhesive layer, wherein a temporary adhesive layer is sequentially laminated with a heat resistant resin layer A and a heat resistant resin layer from the side of the support substrate. B. The adhesion between the heat resistant resin layer B and the element processing substrate is lower than the adhesion between the heat resistant resin layer A and the support substrate and the adhesion between the heat resistant resin layer B and the heat resistant resin layer A. The heat-treated resin layer A contains a heat-resistant resin A containing a polyacrylamide resin having an acid dianhydride residue and a diamine residue, and the heat-resistant resin layer A is a layered product for processing a component according to the first aspect of the invention. a residue having at least a polyoxyalkylene-based diamine represented by the formula (1) as the above-mentioned diamine residue, (n is a natural number, and the average value calculated based on the average molecular weight of the polyoxyalkylene-based diamine is 1 or more; and R ¹ and R ² may be the same or different, and represent an alkylene group or a benzene extending to have a carbon number of 1 to 30. The bases; R ³ to R ⁶ may be the same or different, and represent an alkyl group having 1 to 30 carbon atoms, a phenyl group or a phenoxy group). The laminate for processing a component according to the second aspect of the invention, wherein the residue of the polyoxyalkylene-based diamine represented by the formula (1) is contained in the total diamine residue in an amount of 40 mol% or more as heat resistance. Diamine residue of resin A. The heat-treated resin layer B contains a heat-resistant resin B containing a polyacrylamide resin having an acid dianhydride residue and a diamine residue, and the heat-resistant resin layer B is a layered product for processing a component according to the first aspect of the invention, and The glass transition temperature is 300 ° C or higher. The laminate for processing a component according to claim 4, wherein at least the residue of the tetracarboxylic dianhydride represented by the general formula (2) and/or (3) is used as the acid dianhydride residue of the heat resistant resin B. a residue having at least an aromatic diamine represented by the general formula (4) and/or (5) as a diamine residue, (R ⁷ represents an alkyl group selected from the group consisting of 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a halogen, a carboxyl group, a carboxylate group, a fluoroalkyl group having 1 to 30 carbon atoms, a phenyl group, and a sulfonate. The base of the acid group, the nitro group and the cyano group) (R ⁸ and R ⁹ may be the same or different, and each represents 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 group, and a carboxyl group. a group of a carboxylate 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 hexafluoropropylene group, a sulfonyl group, a phenyl group , methylene, fluoromethylene, decylamino, ester, ethyl, fluoroethyl, phenyl diether, bis(phenyl) isopropylidene) (R ¹⁰ represents an alkyl group selected from the group consisting of 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 group, a carboxyl group, a carboxyl group, a phenyl group, and an anthracene group. Base, nitro and cyano group) (R ¹¹ and R ¹² may be the same or different, and represent 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 group, and a carboxyl group. a carboxyl group, a phenyl group, a fluorenyl group, a nitro group and a cyano group; X represents a direct bond, a carbonyl group, an isopropylidene group, an ether group, a hexafluoropropylene group, a sulfonyl group, a phenyl group, Methylene, fluoromethylene, decylamino, ester, ethyl, fluoroethyl, phenyl diether, bis(phenyl) isopropylidene and fluorenyl). A method for producing a layered body for processing a component, which is a method for manufacturing a laminate for component processing according to any one of claims 1 to 5, which comprises at least the step of laminating a heat resistant resin A or a laminate on a support substrate. The heat-resistant resin A is converted into the heat-resistant resin A after the precursor, and the laminate A of the support substrate and the heat-resistant resin layer A is formed; and the heat-resistant resin B or the laminated heat-resistant resin B is laminated on the substrate for component processing. a step of converting the heat-resistant resin B into a laminate B of the substrate for processing the substrate and the heat-resistant resin layer B; and forming the laminate A and the laminate B with the heat-resistant resin layer A and the heat-resistant resin layer B overlaps in a relative manner and then. A method for producing a laminate for component processing, which is a method for manufacturing a laminate for component processing according to any one of claims 1 to 5, which comprises at least the step of laminating a heat resistant resin B on a substrate for component processing or a step of converting the heat-resistant resin B into a heat-resistant resin B to form a laminate B of the substrate for processing the substrate and the heat-resistant resin layer B; and laminating the heat-resistant resin A or the laminate on the heat-resistant resin layer B of the laminate B The step of converting the heat-resistant resin A into the heat-resistant resin A to form the substrate for component processing, the heat-resistant resin layer B, and the layered body C of the heat-resistant resin layer A; and overlapping the heat-resistant resin layer A of the layered body C Support the substrate and follow the steps. A method of manufacturing a thin component, which is a method of manufacturing a thin component by using a laminate for component processing according to any one of claims 1 to 5, which comprises at least the steps of: processing a substrate for component processing into a thinner a step of performing processing on a substrate processed into a thin component; and a step of separating the component processed substrate processed by the device from the support substrate.