JP2013197441A - Method of manufacturing circuit board with cured material layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-reliability alkaline soluble curable resin composition such that the alkaline soluble curable resin composition can be formed on a circuit board with bump electrodes by a coating method or laminating method, then the formed alkaline soluble curable resin composition can have a thickness controlled by alkali etching, and the alkaline soluble curable resin composition is suitable for formation of a permanent film to be used as an insulating material which is insoluble in an alkali etching solution and has superior chemical resistance by curing the alkaline soluble curable resin composition, and to provide a method of manufacturing a circuit board using the same.SOLUTION: There is provided a method of manufacturing a circuit board with a cured material layer that is characterized in: forming a layer of an alkaline soluble curable resin composition 103 on a circuit board with bump electrodes and adjusting a layer of the alkaline soluble curable resin composition 103 to an arbitrary thickness through alkali etching; and then curing the layer of the alkaline soluble curable resin composition 103.

Description

  The present invention relates to a method for manufacturing a circuit board with a cured product layer. More specifically, an alkali-soluble thermosetting resin composition formed by forming an alkali-soluble thermosetting resin composition layer on a circuit board with bump electrodes by a coating method or a laminating method and then performing alkali etching. The layer is controlled to an arbitrary thickness. Thereafter, the layer of the alkali-soluble thermosetting resin composition was cured to form a cured product layer of the alkali-soluble thermosetting resin composition suitable for forming a permanent film used as an insulating material. The present invention relates to a method of manufacturing a circuit board with bump electrodes.

  Alkali-soluble thermosetting resin compositions marketed as positive-type or negative-type photosensitive resists are used in applications such as surface protection films for semiconductor elements, interlayer insulation films, and wiring protection insulation films for circuit boards. Yes.

  In particular, a polyimide-containing photosensitive resist is said to be useful because it is excellent in electrical and mechanical properties and has high heat resistance of 300 ° C. or higher. In general, polyimide-containing photosensitive resist materials include liquid and film-like materials. Compared with a liquid material, a film-like material has advantages that a thick film can be produced and that production efficiency is high. An insulating film using these photosensitive resists is manufactured as follows. When it is liquid, it is applied on the circuit board, and when it is film, it is laminated to form a photosensitive resist layer. Thereafter, an insulating film made of a photosensitive resist is formed on the circuit board by performing exposure and development.

  So far, polyimide-containing photosensitive resist films have been proposed, for example, forming a film with excellent heat resistance containing a closed ring polyimide that does not cure and shrink due to the ring closing reaction from the polyimide precursor to the polyimide. There are polyimide-containing photosensitive resist films that can be used (see, for example, Patent Documents 1 and 2).

JP 2008-281597 A JP 2011-180472 A

  However, a semiconductor element or a wiring board obtained by using a photosensitive resist and a polyimide-containing photosensitive resist film as a permanent film has cracks in the resist itself by a high-temperature and high-humidity test and a thermal cycle test in an environment of −50 ° C. to 125 ° C. Or a gap is formed between the resist and a substrate such as a semiconductor wafer or glass epoxy, resulting in poor adhesion and a decrease in reliability as a semiconductor package. These problems are caused by the fact that photopolymerization initiators such as photo radical generators and photo acid generators present in the permanent film promote discoloration and corrosion of bump electrodes and wiring.

  In view of such a situation, the present invention is capable of forming an alkali-soluble thermosetting resin composition on a circuit board with bump electrodes by a coating method or a laminating method, and then performing alkali etching to perform alkali etching. As an insulating material that can control the thickness of the thermosetting resin composition, and is then insoluble in an alkali etchant and excellent in chemical resistance by curing the alkali-soluble thermosetting resin composition It is an object of the present invention to provide a method for producing a circuit board with bump electrodes on which a cured layer of a highly reliable alkali-soluble thermosetting resin composition suitable for forming a permanent film to be used is formed.

  That is, the present invention, after forming a layer of an alkali-soluble thermosetting resin composition on a circuit board with bump electrodes, and adjusting the thickness of the alkali-soluble thermosetting resin composition to an arbitrary thickness by alkali etching, A method for producing a circuit board with a cured product layer, wherein the layer of the alkali-soluble thermosetting resin composition is cured.

  According to the present invention, an alkali-soluble thermosetting resin formed by performing alkali etching after forming a layer of an alkali-soluble thermosetting resin composition on a circuit board with a bump electrode by a coating method or a laminating method. The layer of the composition is controlled to an arbitrary thickness. Thereafter, the layer of the alkali-soluble thermosetting resin composition was cured to form a cured product layer of the alkali-soluble thermosetting resin composition suitable for forming a permanent film used as an insulating material. A circuit board with bump electrodes can be obtained.

An example of the manufacturing method of the circuit board with a bump electrode which formed the permanent film using the alkali-soluble thermosetting resin composition of this invention is shown.

  In the present invention, an alkali-soluble thermosetting resin composition layer is formed on a circuit board with a bump electrode, the alkali-soluble thermosetting resin composition layer is alkali-etched and adjusted to an arbitrary thickness, A method for producing a circuit board with a cured product layer, comprising curing a layer of an alkali-soluble thermosetting resin composition.

  The alkali-soluble thermosetting resin composition in the present invention has (A) the structural unit represented by the general formula (1), and the general formula (2) and / or (3) at least at one end of the main chain. It is preferable to contain an alkali-soluble polyimide having a structure represented by: (B) a thermosetting resin and (C) a curing agent.

  The alkali-soluble thermosetting resin composition in the present invention is not limited in its shape before curing, and examples thereof include a varnish shape, a film shape, and a sheet shape coated on a support substrate.

  (A) The structural unit represented by the general formula (1) preferably used in the alkali-soluble thermosetting resin composition of the present invention, and the general formula (2) and / or at least one end of the main chain The alkali-soluble polyimide having the structure represented by (3) has an alkali-soluble functional group for etching with an alkaline aqueous solution. The alkali-soluble functional group is a functional group having acidity, and specifically includes a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a thiol group. The term “alkali-soluble” as used herein refers to a substance that dissolves 0.1 g or more at 25 ° C. with respect to 100 g of a 2.38% aqueous solution of tetramethylammonium hydroxide. Among the above alkali-soluble groups, the alkali-soluble group is a phenolic hydroxyl group because of problems such as storage stability of the alkali-soluble thermosetting resin composition and corrosion to copper wiring, aluminum wiring, and solder bumps as conductors. Preferably there is. The introduction of the alkali-soluble group into the polyimide can be carried out by imparting an alkali-soluble group to the diamine, tetracarboxylic dianhydride, or terminal blocker. In addition, when the imidation ratio of polyimide is less than 100%, a carboxyl group derived from tetracarboxylic dianhydride remains, but the carboxyl group is not included in the alkali-soluble group here.

  (A) preferably used in the present invention has a structural unit represented by the general formula (1) and has a structure represented by the general formula (2) and / or (3) at least at one end of the main chain. The alkali-soluble polyimide has the following structure.

  In the formula, Y represents a monovalent organic group having at least one group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group, and Z represents a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group. And a divalent organic group having at least one group selected from the group consisting of thiol groups. Y preferably has an aromatic group, and Z preferably has an aromatic group. Among them, Y and Z preferably have a phenolic hydroxyl group or a thiol group.

R ¹ represents a 4- to 14-valent organic group, R ² represents a ^2- to 12-valent organic group, R ³ and R ⁴ each independently represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and It represents at least one group selected from the group consisting of thiol groups. Moreover, (alpha) and (beta) represent the integer of 0-10 each independently.

  (A) preferably used in the present invention has a structural unit represented by the general formula (1) and has a structure represented by the general formula (2) and / or (3) at least at one end of the main chain. The weight average molecular weight of the alkali-soluble polyimide is preferably 10,000 or more and 100,000 or less. When two or more kinds of soluble polyimides are contained, at least one of the weight average molecular weights may be in the above range. When the weight average molecular weight is 10,000 or more, the mechanical strength of the cured film is improved, crack generation in the thermal cycle test is suppressed, and high reliability can be obtained. On the other hand, when the weight average molecular weight is 100,000 or less, compatibility with (B) thermosetting resin and (C) curing agent described later is improved. Furthermore, it is preferable that it is 50,000 or less from the point which etchability improves. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography method (GPC method), and is computed by polystyrene conversion.

  (A) preferably used in the present invention has a structural unit represented by the general formula (1) and has a structure represented by the general formula (2) and / or (3) at least at one end of the main chain. The glass transition temperature (Tg) of the alkali-soluble polyimide is preferably 160 ° C. or higher. Tg is more preferably 180 ° C. or higher. When Tg is within this range, the occurrence of cracks in the thermal cycle test is suppressed. The Tg in the present invention is measured by the differential scanning calorimetry (DSC method), and the temperature at which the curve obtained by differentiating the caloric change curve when measured for the polyimide powder shows the maximum value is Tg. It is.

(A) An alkali-soluble polyimide having a structural unit represented by the general formula (1) and having a structure represented by the general formula (2) and / or (3) at least at one end of the main chain is tetra Obtained by reaction of carboxylic dianhydride and diamine. In the general formula (1), R ¹ is a residue of tetracarboxylic dianhydride. R ¹ is preferably an organic group having 8 to 40 carbon atoms containing an aromatic group or a cyclic aliphatic group.

  Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetra. Carboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3 '-Benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1, 1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride , Screw (2,3- Carboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic dianhydride, 2 , 3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2 -Aromatic tetracarboxylic dianhydrides such as bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4- B pentanoic acid dianhydride aliphatic tetracarboxylic dianhydrides such as, and structures and the like of the acid dianhydride shown below. These are used alone or in combination of two or more.

Here, R ²² is an oxygen atom, a group selected from C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , CO, COO and SO ₂ , and R ²³ and R ²⁴ are a hydrogen atom, a hydroxyl group and a thiol, respectively. Represents a group selected from groups.

In the general formula (1), R ² is a diamine residue. R ² is preferably an organic group having 5 to 40 carbon atoms containing an aromatic group or a cyclic aliphatic group.

  Specific examples of the diamine include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4 , 4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diamino Diphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl- 4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4′-diaminobiphenyl, 3,3 ′, 4 , 4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, 9,9-bi (4-aminophenyl) fluorene, or and compounds substituted with alkyl group or halogen atom in the aromatic ring, aliphatic cyclohexyl diamine, such as diamines having the structure shown in methylene bis cyclohexylamine and are given below. These are used alone or in combination of two or more.

Here, R ²⁵ is a group selected from an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , CO, COO and SO ₂ , and R ^{26 to} R ²⁹ are each selected from a hydroxyl group and a thiol group. Represents a group.

  Among these, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino Diphenylmethane, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, m -Phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, diamine having the structure shown below, and the like are preferable.

Here, R ²⁵ represents a group selected from an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ and SO ₂ , and R ^{26 to} R ²⁹ each represents a group selected from a hydroxyl group and a thiol group.

  Furthermore, in order to improve the adhesion to the substrate, a diamine having a siloxane structure may be copolymerized as long as the heat resistance is not lowered. Specific examples include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

  (A) preferably used in the present invention has a structural unit represented by the general formula (1) and has a structure represented by the general formula (2) and / or (3) at least at one end of the main chain. In the alkali-soluble polyimide, at least a part of the main chain terminal is sealed with a primary monoamine or dicarboxylic acid anhydride. By this terminal blocking agent, the weight average molecular weight of the alkali-soluble polyimide can be adjusted to an appropriate range. Furthermore, it is preferable that a terminal blocker has an alkali-soluble group from the viewpoint of improving alkali solubility.

  In the general formula (2), Y is derived from a primary monoamine which is a terminal blocking agent. Specific examples of the end-capping agent include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5 as primary monoamine. Aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1- Carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3 -Aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, -Aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable.

  Moreover, in General formula (3), Z originates in the dicarboxylic anhydride which is a terminal blocker. As the dicarboxylic acid anhydride, 4-carboxyphthalic acid anhydride, 3-hydroxyphthalic acid anhydride, cis-aconitic acid anhydride and the like are preferable. These are used alone or in combination of two or more.

  (A) preferably used in the present invention has a structural unit represented by the general formula (1) and has a structure represented by the general formula (2) and / or (3) at least at one end of the main chain. Alkali-soluble polyimide is prepared by replacing a part of the diamine with a primary monoamine that is a terminal blocking agent, or by replacing tetracarboxylic dianhydride with a dicarboxylic acid anhydride that is a terminal blocking agent. Is synthesized. For example, a method of reacting tetracarboxylic dianhydride, diamine compound and monoamine at low temperature, a method of reacting tetracarboxylic dianhydride, dicarboxylic anhydride and diamine compound at low temperature, tetracarboxylic dianhydride and Diester is obtained with alcohol, and then a polyimide precursor is obtained using a method such as a method of reacting diamine, monoamine and a condensing agent. Thereafter, a polyimide can be synthesized using a known imidization reaction method.

  (A) preferably used in the present invention has a structural unit represented by the general formula (1) and has a structure represented by the general formula (2) and / or (3) at least at one end of the main chain. The alkali-soluble polyimide may be composed only of the structural unit represented by the general formula (1), or may be a copolymer with another structural unit. In that case, it is preferable to contain the structural unit represented by General formula (1) 50 mol% or more of the whole polyimide, and it is more preferable to contain 70 mol% or more. The type and amount of structural units used for copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the polyimide obtained by the final heat treatment.

Further, (A) an alkali-soluble polyimide having a structural unit represented by the general formula (1) and having a structure represented by the general formula (2) and / or (3) at least at one end of the main chain The imidization rate can be easily determined by the following method, for example. Here, the imidation ratio means how many mol% of the polyimide precursor is converted to polyimide when the polyimide is synthesized through the polyimide precursor as described above. First, measuring the infrared absorption spectrum of the polymer, absorption peaks of an imide structure caused by a polyimide (1780 cm around ^-1, 1377 cm around ^-1) to confirm the presence of. Next, after heat-treating the polymer at 350 ° C. for 1 hour, the infrared absorption spectrum is measured again, and the peak intensities near 1377 cm ⁻¹ before and after the heat treatment are compared. The imidation rate of the polymer before heat treatment is determined by setting the imidation rate of the polymer after heat treatment to 100%. The imidization ratio of the polymer is preferably 90% or more.

The end-capping agent introduced into the alkali-soluble polyimide (A) can be detected by the following method. For example, a polyimide having an end-capping agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and a carboxylic anhydride component, which are constituent units of the polyimide, and this is analyzed by gas chromatography (GC) or NMR measurement. To do. Separately from this, it is also possible to detect the polyimide having the end-capping agent introduced by directly measuring it using a pyrolysis gas chromatograph (PGC), infrared spectrum and ¹³ CNMR spectrum.

  (A) preferably used in the present invention has a structural unit represented by the general formula (1) and has a structure represented by the general formula (2) and / or (3) at least at one end of the main chain. The content of the alkali-soluble polyimide is preferably 10% by weight or more from the viewpoint that the alkali etching property is expressed with respect to the total amount of the organic matter of the alkali-soluble thermosetting resin composition. Preferably they are 20 weight% or more and 50 weight% or less. By using in this range, it is excellent in alkali etching property, and the characteristics such as chemical resistance, heat resistance and moisture resistance of the cured film are improved.

  The alkali-soluble thermosetting resin composition of the present invention preferably contains (B) a thermosetting resin. Examples of the thermosetting resin include epoxy resin, resol resin, melamine resin, xylene resin, furan resin, and cyanate ester resin. Among these, the epoxy resin can be preferably used because it increases the crosslink density after curing of the alkali-soluble thermosetting resin composition, and improves reflow resistance, adhesion, and insulation reliability under high temperature conditions. .

  As the epoxy compound, a liquid epoxy compound and a solid epoxy compound can be used.

Here, the liquid epoxy compound shows a viscosity of 150 Pa · s or less at 25 ° C. and 1.013 × 10 ⁵ N / m ² , and the solid epoxy compound shows a viscosity exceeding 150 Pa · s at 25 ° C. Is. Examples of the liquid epoxy compound include JER828, JER1750, JER152, JER630, YL980 (above trade name, manufactured by Mitsubishi Chemical Corporation), Epiklon HP-4032 (above trade name, manufactured by DIC Corporation), and the like. It is not limited to these. Two or more of these may be combined. Moreover, as a solid epoxy compound, JER1002, JER1001, YX4000H, JER4004P, JER5050, JER154, JER157S70, JER180S70, YX4000H (above trade name, manufactured by Mitsubishi Chemical Corporation), Tepic S, Tepic G, Tepic P (above trade names) , Nissan Chemical Industries, Ltd.), Epototo YH-434L (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), EPPN502H, NC3000 (above, trade name, manufactured by Nippon Kayaku Co., Ltd.), Epicron N695, Epicron HP -7200 (trade name, manufactured by DIC Corporation) and the like, but is not limited thereto. Two or more of these may be combined.

  The content of the (B) thermosetting resin preferably used in the present invention is preferably 20% by weight or more from the viewpoint of developing adhesive strength with respect to the total amount of organic matter of the alkali-soluble thermosetting resin composition, and is alkali-soluble. In order to form a network structure having a high density by reacting with polyimide and a curing agent (C) described later, 30% by weight or more is more preferable. 80 weight% or less is preferable from the point of the reflow resistance after hardening and the insulation reliability in high temperature conditions.

  The alkali-soluble thermosetting resin composition of the present invention preferably contains (C) a curing agent. When using an epoxy resin for (B) thermosetting resin as a curing agent, it is preferable to use an epoxy resin curing agent or a curing accelerator, and it is more preferable to use these in combination. Examples of the curing agent include phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, dicyandiamide, and organic acid dihydrazides. , Boron trifluoride amine complexes, imidazoles, tertiary amines, phenolic compounds having at least two phenolic hydroxyl groups in the molecule, and the like. These curing agents may be used alone or in combination.

  Among these curing agents, phenolic compounds having at least two phenolic hydroxyl groups in the molecule increase the crosslink density after curing, and improve reflow resistance, adhesion, and insulation reliability under high temperature conditions. Can be preferably used. Examples of the phenolic compound having at least two phenolic hydroxyl groups in the molecule include phenol novolak resin, cresol novolak resin, t-butylphenol novolak resin, dicyclopentagen cresol novolak resin, dicyclopentagen phenol novolak. Examples include resins, xylylene-modified phenol novolak resins, naphthol novolak resins, trisphenol novolak resins, tetrakisphenol novolak resins, bisphenol A novolak resins, poly-p-vinylphenol resins, phenol aralkyl resins, and the like. In addition, the phenolic compound having at least two phenolic hydroxyl groups in these molecules may be a liquid or solid compound alone or in combination.

  The content of the curing agent (C) preferably used in the present invention is preferably 5% by weight or more with respect to the total amount of organic matter of the alkali-soluble thermosetting resin composition, from the viewpoint of improving the curing rate, and (B) thermosetting. 10% by weight or more is more preferable for forming a network structure having a high density by reacting with the functional resin. From the viewpoint of reflow resistance after curing and insulation reliability under high temperature conditions, it is preferably 40% by weight or less.

  The content ratio of the liquid compound of (B) thermosetting resin and (C) curing agent is preferably 5% by weight to 60% by weight with respect to the total amount of the alkali-soluble thermosetting resin composition. Further, the content ratio is more preferably 10% by weight or more and 40% by weight or less. By containing a liquid compound in the range of this content ratio, moderate plasticity and flexibility can be imparted to the alkali-soluble thermosetting resin composition.

  The alkali-soluble thermosetting resin composition of the present invention preferably contains (D) inorganic particles. By containing inorganic particles, the alkali etching rate can be adjusted. Moreover, there exists an effect which suppresses tackiness when it is set as an alkali-soluble thermosetting resin composition film. Furthermore, there is an effect of improving characteristics such as chemical resistance, heat resistance and moisture resistance of the cured film.

  The average particle diameter of the inorganic particles (D) preferably used in the present invention is preferably 20 nm or more and 1 μm or less. The inorganic particles in the alkali-soluble thermosetting resin composition include those in a state of primary particles in which aggregation is completely loosened and those in a state in which a plurality of primary particles are aggregated. Here, the particle diameter of the inorganic particles is the particle diameter of the primary particles that are not aggregated, and the diameter of the primary particles constituting the aggregate is the aggregate of the primary particles. Examples of the method for measuring the average particle size of the inorganic particles in the resist composition include a method in which the particles are directly observed by SEM (scanning electron microscope) or TEM (transmission electron microscope) and the average particle size is calculated. It is done. (D) When the average particle diameter of the inorganic particles is 20 nm or more, the specific surface area with respect to the volume of the particles is reduced, so that the dispersibility of the particles is improved, and furthermore, surface irregularities and pinholes after application are suppressed. And the applicability | paintability at the time of producing an alkali-soluble thermosetting resin composition film can be improved. On the other hand, when the average particle size is 1 μm or less, the precipitation of inorganic particles in the alkali-soluble thermosetting resin composition solution is suppressed, and furthermore, the surface irregularities and pinholes after coating are suppressed, The applicability | paintability at the time of producing a soluble thermosetting resin composition film can be improved. Moreover, from the point which the chemical resistance of a cured film improves, More preferably, it is 0.5 micrometer or less, More preferably, it is 0.1 micrometer or less. Furthermore, it is preferable that it is a spherical inorganic particle from the point which the alkali-etching property of an alkali-soluble thermosetting resin composition improves.

  (D) Examples of inorganic particles include silicates such as talc, fired clay, unfired clay, mica and glass, oxides such as titanium oxide, alumina and silica, carbonates such as calcium carbonate and magnesium carbonate, and water. Hydroxides such as aluminum oxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, aluminum borate, calcium borate, boric acid Examples thereof include borates such as sodium, nitrides such as aluminum nitride, boron nitride, and silicon nitride. A plurality of these inorganic particles may be contained, but silica and titanium oxide are preferable from the viewpoint of reliability and cost. These inorganic particles are more preferably those that have been surface-treated with a silane coupling agent or the like in order to improve dispersibility and sedimentation. The silane coupling agent is not particularly limited as long as it has good compatibility with the resin component of the alkali-soluble thermosetting resin composition film, and is preferably a vinyl, methacrylic, acrylic, epoxy or amino silane. A vinyl, methacrylic, acrylic or epoxy type is more preferred from the viewpoint that when the alkali-soluble thermosetting resin composition film is a coupling agent and is heat-cured, the resin and inorganic particles are covalently bonded.

  The content of (D) inorganic particles preferably used in the present invention is 0% by weight or more and 80% by weight or less with respect to the total amount of the alkali-soluble thermosetting resin composition containing an organic substance and / or an inorganic substance. Preferably they are 40 weight% or more and 70 weight% or less. By using in this range, it is excellent in alkali etching property, and the characteristics such as chemical resistance, heat resistance and moisture resistance of the cured film are improved.

  Furthermore, the alkali-soluble thermosetting resin composition of the present invention includes organic particles, crosslinking accelerators, ion scavengers, antioxidants, colorants, dissolution regulators, surfactants, antifoaming agents, and the like as necessary. Can also be contained. Moreover, in order to improve adhesiveness with base substrates, such as a silicon wafer, a silane coupling agent, a titanium chelating agent, etc. can also be contained.

  Next, a method for producing an alkali-soluble thermosetting resin composition film using the alkali-soluble thermosetting resin composition of the present invention will be described. The alkali-soluble thermosetting resin composition film of the present invention is obtained by applying a solution (varnish) of an alkali-soluble thermosetting resin composition on a peelable support, and then drying it if necessary. The alkali-soluble thermosetting resin composition varnish is obtained by adding an organic solvent to the alkali-soluble thermosetting resin composition. Any organic solvent may be used as long as it dissolves the alkali-soluble thermosetting resin composition.

  As the organic solvent, specifically, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, Acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate , Acetone, methyl ethyl ketone, acetyl acetone, methyl propyl ketone, Ketones such as rubutyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3 Alcohols such as methoxybutanol and diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone and the like can be mentioned.

  Further, the alkali-soluble thermosetting resin composition varnish may be filtered using a filter paper or a filter. The filtration method is not particularly limited, but a method of filtration by pressure filtration using a filter having a reserved particle diameter of 0.4 μm to 10 μm is preferable.

  The alkali-soluble thermosetting resin composition film of the present invention is preferably formed and used on a peelable support. Although the peelable support is not particularly limited, various commercially available films such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film can be used. Surface treatment with silicone, silane coupling agent, aluminum chelating agent, polyurea, etc. on the bonding surface between the peelable support and the alkali-soluble thermosetting resin composition film in order to improve adhesion and peelability May be applied. The thickness of the peelable support is not particularly limited, but is preferably in the range of 10 to 100 μm from the viewpoint of workability.

  Moreover, in order to protect the surface, the alkali-soluble thermosetting resin composition film of the present invention may have a protective film on the film. Thereby, the alkali-soluble thermosetting resin composition film surface can be protected from contaminants such as dust and dust in the atmosphere.

  Examples of the protective film include polyolefin films and polyester films. The protective film preferably has a small adhesive force with the alkali-soluble thermosetting resin composition film.

  As a method for applying the alkali-soluble thermosetting resin composition varnish to the peelable support, spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar Examples of the method include a coater, a roll coater, a comma roll coater, a gravure coater, a screen coater, and a slit die coater. Moreover, although a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is preferable that the film thickness after drying is usually 0.5 μm or more and 100 μm or less.

  An oven, a hot plate, infrared rays, or the like can be used for drying. The drying temperature and the drying time may be within a range where the organic solvent can be volatilized, and may be appropriately set within a range in which the alkali-soluble thermosetting resin composition film is in an uncured or semi-cured state. preferable. Specifically, it is preferable to carry out from 1 minute to several tens of minutes in the range of 40 ° C to 120 ° C. Moreover, you may heat up in steps, combining these temperatures, for example, you may heat-process at 70 degreeC, 80 degreeC, and 90 degreeC for 1 minute each.

  Next, the manufacturing method of the circuit board with a hardened material layer of the present invention is explained. An example thereof will be described with reference to FIG.

  First, a method for forming an alkali-soluble thermosetting resin composition layer on a circuit board with bump electrodes will be described.

  First, a circuit board with bump electrodes is prepared. In FIG. 1, the semiconductor substrate 100 with gold stud bump electrodes in FIG.

  As the layer of the alkali-soluble thermosetting resin composition, an alkali-soluble thermosetting resin composition varnish or an alkali-soluble thermosetting resin composition film using the same is preferably used. If it is a conductive resin composition film, it is more preferable because it is a sheet. In FIG. 1, the alkali-soluble thermosetting resin composition 103 in (b) corresponds to this.

  When using an alkali-soluble thermosetting resin composition varnish, first, the varnish is applied onto a circuit board with bump electrodes. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and screen printing. Moreover, it is preferable to apply the coating film so that the film thickness after drying is equal to or higher than the bump electrode height. Next, the substrate coated with the alkali-soluble thermosetting resin composition varnish is dried to obtain an alkali-soluble thermosetting resin composition film. For drying, an oven, a hot plate, infrared rays, or the like can be used. The drying temperature and the drying time may be within a range where the organic solvent can be volatilized, and may be appropriately set within a range in which the alkali-soluble thermosetting resin composition film is in an uncured or semi-cured state. preferable. Specifically, it is preferably carried out in the range of 50 to 150 ° C. for 1 minute to several hours.

  On the other hand, when using an alkali-soluble thermosetting resin composition film, if it has a protective film, it is peeled off, the alkali-soluble thermosetting resin composition film and the circuit board with bump electrodes are opposed, Bonding is performed by pressure bonding to obtain an alkali-soluble thermosetting resin composition film. The thickness of the alkali-soluble thermosetting resin composition film is preferably set to be equal to or higher than the bump electrode height from the viewpoint of suppressing deformation due to pressure bonding of the bump electrode or embedding of inorganic fine particles in the bump electrode. Thermocompression bonding can be performed by hot plate pressing, hot vacuum flat plate pressing, hot roll laminating, hot vacuum roll laminating, or the like. These thermocompression bonding can also be processed in combination. When a flat surface is required after bonding, it is preferable to perform hot plate pressing or hot vacuum plate pressing. The bonding temperature is preferably 40 ° C. or higher from the viewpoint of adhesion to the substrate and embedding. In addition, the bonding temperature is preferably 150 ° C. or lower in order to cure the alkali-soluble thermosetting resin composition film at the time of bonding and to prevent a decrease in etching rate and etching unevenness in the etching process. In this way, a circuit board is obtained in which the bump electrodes are buried with the alkali-soluble thermosetting resin composition. In FIG. 1, the circuit board 104 in which the gold stud bump electrode in (c) is buried with an alkali-soluble thermosetting resin composition corresponds to this.

  The circuit board with bump electrodes used in any of the alkali-soluble thermosetting resin composition and the alkali-soluble thermosetting resin composition film is a group IV semiconductor wafer of silicon or germanium, gallium arsenide, SiC, or nitride Examples include compound semiconductor wafers such as gallium, organic circuit boards, inorganic circuit boards, and those in which circuit constituent materials are arranged on these boards, all of which have bump electrodes. Examples of the material of the bump electrode include silver, gold, copper, and solder. Examples of the solder material include those containing Sn—Ag, Sn—Ag—Cu, Sn—Pb, Bi, and the like.

  Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven fabrics / epoxy copper-clad laminates, polyetherimide resin substrates, Examples include heat-resistant / thermoplastic substrates such as ether ketone resin substrates and polysulfone resin substrates, polyester copper-clad film substrates, and polyimide copper-clad film substrates. Examples of the inorganic circuit board include ceramic substrates such as an alumina substrate, an aluminum nitride substrate, a silicon carbide substrate, and a silicon nitride substrate, and metal substrates such as an aluminum base substrate and an iron base substrate. Examples of circuit components include conductors containing metals such as silver, gold and copper, resistors containing inorganic oxides, low dielectrics containing glass materials and / or resins, resins and high Examples thereof include high dielectric materials containing dielectric constant inorganic particles, insulators containing glass-based materials, and the like.

  Next, a method for adjusting the thickness of the alkali-soluble thermosetting resin composition to an arbitrary thickness by alkali etching will be described. When it has a peelable support, this is peeled off and alkali etching of the alkali-soluble thermosetting resin composition is performed. Alkali etching of the alkali-soluble thermosetting resin composition is performed by gradually removing it from the surface of the alkali-soluble thermosetting resin composition film using an alkali etching solution. Alkaline etchants include tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, An aqueous solution of a compound showing alkalinity such as dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Contains alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone alone or in combination of several kinds Good.

  Alkaline etching can be performed by spraying the above-mentioned alkaline etching solution onto the coating surface, immersing in the alkaline etching solution, applying ultrasonic waves while immersing, spraying the alkaline etching solution while rotating the substrate, etc. it can. The thickness of the alkali-soluble thermosetting resin composition by alkali etching can be controlled by changing etching conditions such as processing time and processing solution temperature.

  After alkali etching, rinsing with water may be performed. Here, the rinsing process can be performed by various methods performed by alkali etching. Further, rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

  In order to adjust the speed at the time of alkali etching, a step of baking before alkali etching may be incorporated. As this temperature, the range of 50-180 degreeC is preferable, and the range of 60-120 degreeC is especially more preferable. The time is preferably 5 seconds to several hours.

  From the viewpoint of reducing the solvent, volatile matter, and water remaining in the alkali-soluble thermosetting resin composition film after alkali etching, it is preferable to heat dry in the range of 60 to 200 ° C. The time is preferably 1 minute to several hours. Thus, a circuit board on which an alkali-soluble thermosetting resin composition film after alkali etching is formed is obtained. In FIG. 1, the circuit board 105 on which the alkali-soluble thermosetting resin composition film after alkali etching in (d) is formed corresponds to this.

  Next, a method for curing the layer of the alkali-soluble thermosetting resin composition will be described. The substrate on which the alkali-soluble thermosetting resin composition film controlled to an arbitrary thickness obtained as described above is formed is heated to form a cured film. The temperature is preferably 120 ° C to 400 ° C. This heat treatment is preferably carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C. and 200 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 250 ° C. over 2 hours can be mentioned. At this time, the heating temperature is preferably 150 ° C. or higher and 300 ° C. or lower, and more preferably 180 ° C. or higher and 250 ° C. or lower. The alkali-soluble thermosetting resin composition after such a thermosetting step becomes a cured film that is insoluble in an alkali etching solution and has excellent chemical resistance and chemical resistance. Thus, the circuit board in which the alkali-soluble thermosetting resin composition film after thermosetting is formed is obtained. In FIG. 1, the circuit board 107 on which the alkali-soluble thermosetting resin composition film after thermosetting in (e) is formed corresponds to this.

  The thickness of the cured film can be arbitrarily set, but is preferably 0.5 μm or more and 100 μm or less.

  The substrate on which the obtained cured film is formed is made into a thin plate by back grinding as necessary. In FIG. 1, the circuit board 109 on which the heat-cured alkali-soluble thermosetting resin composition coating film after back grinding in (f) is formed corresponds to this.

  The substrate on which the obtained cured film is formed can obtain individual semiconductor elements and circuit boards by performing blade dicing, laser dicing, or the like. In FIG. 1, the semiconductor element 110 in (g) corresponds to this.

  The semiconductor elements and circuit boards obtained in this way are all electro-optical devices, semiconductor circuit boards, and electronic components including these are used in semiconductor devices.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

<Imidation rate of synthesized polyimide>
First, measuring the infrared absorption spectrum of the polymer, the absorption peak (1780 cm around ^-1, 1377 cm around ^-1) of an imide structure caused by a polyimide was confirmed the presence of. Next, after heat-treating the polymer at 350 ° C. for 1 hour, the infrared absorption spectrum was measured again, and the peak intensities near 1377 cm ⁻¹ before and after the heat treatment were compared. The imidation rate of the polymer before heat treatment was determined by setting the imidation rate of the polymer after heat treatment to 100%.

<Tg of synthesized polyimide>
When the polyimide powder is measured with a differential scanning calorimeter (EXSTAR DSC 6220, manufactured by SII Nanotechnology Co., Ltd.) at a heating rate of 20 ° C./min, and the curve obtained by differentiating the caloric change curve shows the maximum value. The temperature was Tg of polyimide.

<Evaluation of alkali solubility of synthesized polyimide>
When 100 g of a 2.38% aqueous solution of tetramethylammonium hydroxide was dissolved, 0.1 g or more of the synthesized polyimide powder was evaluated as alkali-soluble, and the others were evaluated as alkali-insoluble.

<Reliability test>
After maintaining 20 semiconductor elements at −50 ° C. for 5 minutes and maintaining at 125 ° C. for 5 minutes as 1 cycle, 1000 cycles were repeated for 10 and 2000 cycles were repeated for the remaining 10 devices. Next, a semiconductor element was incorporated into a liquid crystal substrate to produce a liquid crystal panel, and a display test was performed. The numbers displayed without problems were examined for each of 1000 cycles and 2000 cycles. The results are shown in Table 1 (1000 cycles, 2000 cycles).

  The polyimide used in each example and comparative example was synthesized by the following method.

Synthesis example 1
Under a nitrogen stream, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) 30.95 g (0.0845 mol), 1,3-bis (3-aminopropyl) ) 1.24 g (0.005 mol) of tetramethyldisiloxane was dissolved in 100 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). Here, 31.02 g (0.1 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride (hereinafter referred to as ODPA) was added together with 30 g of NMP, stirred at 20 ° C. for 1 hour, and then at 50 ° C. Stir for 4 hours. To this, 2.5 g (0.02 mol) of 3-aminophenol was added, stirred at 50 ° C. for 2 hours, and then stirred at 180 ° C. for 5 hours to obtain a resin solution. Next, the resin solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed 3 times with water, and then dried in a vacuum dryer at 80 ° C. for 5 hours. The imidation ratio of the obtained resin powder was 94%, Tg was 197 ° C. and alkali-soluble.

Synthesis example 2
Under a dry nitrogen stream, BAHF 20.14 g (0.055 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1.24 g (0.005 mol), polyoxypropylenediamine (Mitsui Chemical Fine Co., Ltd.) )) 7.14 g (0.03 mol), 2.5 g (0.02 mol) of 3-aminophenol was dissolved in 100 g of NMP as a terminal blocking agent. ODPA 31.02g (0.1mol) was added here with NMP30g, and it stirred at 50 degreeC for 4 hours. Then, it stirred at 180 degreeC for 5 hours, and obtained the resin solution. Next, the resin solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed 3 times with water, and then dried in a vacuum dryer at 80 ° C. for 5 hours. The imidation ratio of the obtained resin powder was 95%, Tg was 140 ° C., and alkali-soluble.

Synthesis example 3
Under a dry nitrogen stream, 11.41 g (0.057 mol) of 4,4′-diaminodiphenyl ether, 1.24 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.005 mol) and end-capping As an agent, 6.98 g (0.075 mol) of aniline was dissolved in 100 g of NMP. To this, 31.02 g (0.1 mol) of ODPA was added together with 30 g of NMP, stirred at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 180 ° C. for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed 3 times with water, and then dried in a vacuum dryer at 80 ° C. for 5 hours. The imidation ratio of the obtained polymer powder was 94%. Tg was 203 ° C. and alkali-insoluble.

Example 1
(A) 25 g of the polyimide obtained in Synthesis Example 1 as the component, (B) 157S70 (trade name, manufactured by Mitsubishi Chemical Corporation, solid epoxy resin) as the component (B), 27 g of YL980 (trade name, manufactured by Mitsubishi Chemical Corporation), (Liquid epoxy resin) 23 g, (C) TD2131 (trade name, manufactured by DIC Corporation, solid phenol resin) 10 g, MEH-8005 (trade name, manufactured by Meiwa Kasei Co., Ltd., liquid phenol resin) 10 g and (D) ) SX009-KJA (trade name, manufactured by Admatechs Co., Ltd., average particle size 50 nm, spherical silica, silica 50 wt% methyl isobutyl ketone dispersion) 300 g, propylene glycol monomethyl acetate 100 g as an organic solvent, Additives other than solvent to solid content, alkali-soluble adjusted so that solid content concentration is 50% To obtain a curable resin composition varnish. Using a comma roll coater (coating machine), the obtained varnish was peeled off from a 50 μm thick polyethylene terephthalate film, Therapy HP2 (S) (trade name, manufactured by Toray Film Processing Co., Ltd. (Silicone-based, heavy release grade) treated surface and dried at 80 ° C. for 10 minutes. The thickness of the alkali-soluble thermosetting resin composition after drying was 50 μm. On top of this, a 25 μm thick polyethylene terephthalate film SR-1 (trade name, manufactured by Oiso Kogyo Co., Ltd., single-sided release treatment) is laminated as a protective film, and a protective film, an alkali-soluble thermosetting resin composition, A sheet A made of a peelable support was obtained.

  From the obtained sheet A, the protective film SR-1 was peeled off to expose the alkali-soluble thermosetting resin composition surface, and set in a bonding apparatus (manufactured by Takatori Corporation, VTM-200M). Next, alkali-soluble thermosetting is performed on the bump electrode forming surface of the circuit board with bump electrodes (8 inch silicon wafer, Au stud bump, bump height 40 μm, bump diameter 50 μm, bump pitch 100 μm) fixed on the bonding apparatus stage. The surface of the conductive resin composition was laminated at a temperature of 80 ° C. and a bonding speed of 2 mm / s. The excess alkali-soluble thermosetting resin composition around the wafer was cut with a cutter blade, and the bump electrode was embedded with the alkali-soluble thermosetting resin composition provided with the peelable support body therapy HP2 (S). A circuit board was obtained.

  Next, after peeling off the peelable support body therapy HP2 (S) of the obtained circuit board, dip etching of the alkali-soluble thermosetting resin composition was performed using a 2.38% aqueous solution of tetramethylammonium hydroxide. Went for a minute. Then, after rinsing with water under ultrasonic irradiation, the circuit board was dried at 60 ° C. for 20 minutes. Here, as the alkali etching property, the thickness of the alkali-soluble thermosetting resin before and after the alkali etching was measured, and the case where the thickness decreased due to the etching was evaluated as ◯, and the others were evaluated as ×.

The circuit board on which the alkali-soluble thermosetting resin composition film thus obtained was formed was subjected to alkali-soluble thermosetting in an inert oven at room temperature to 200 ° C. for 1 h and at 200 ° C. for 1 h. The resin composition was cured.

  Next, the obtained circuit board was fixed to a tape frame and a dicing tape. Fixing is performed by attaching a dicing tape (Dintech Co., Ltd., D-650) to the wafer substrate surface opposite to the bump electrode using a wafer mounter (Technovision Co., Ltd., FM-114). went.

Next, blade dicing was performed under the following cutting conditions.
Dicing machine: DAD-3350 (manufactured by DISCO Corporation)
Semiconductor chip size: 7.5 × 7.5mm
Blade: NBC-ZH2040-SE27HDEF
Spindle speed: 30000rpm
Cutting speed: 25 mm / s
Cutting depth: Cut to 10 μm depth of dicing tape Cut: One-pass full cut Cut mode: Down cut Cutting water amount: 3.7 L / min Cutting water and cooling water: Temperature 23 ° C., electric conductivity 0.5 MΩ · cm (extra Carbon dioxide gas is injected into pure water).

  As a result, an individual semiconductor element (7.3 mm square) was obtained. A reliability test of the obtained semiconductor element was performed. The results are shown in Table 1.

Examples 2, 3 and Comparative Example 1
An alkali-soluble thermosetting resin composition was prepared and evaluated in the same manner as in Example 1 except that the mixing ratio of the components (A) to (D) was changed as shown in Table 1. The results are shown in Table 1.

  In Comparative Example 1, since the alkali-soluble thermosetting resin composition was not used, the thickness of the thermosetting resin composition by alkali etching could not be controlled, and the bump electrode was buried in the thermosetting resin composition. The reliability evaluation could not be performed.

100 Semiconductor substrate with gold stud bump electrode 101 Aluminum electrode 102 Gold stud bump 103 Alkali-soluble thermosetting resin composition 104 Circuit board 105 in which gold stud bump electrode is embedded with alkali-soluble thermosetting resin composition 105 After alkali etching The circuit board 106 on which the alkali-soluble thermosetting resin composition film is formed Alkali-soluble thermosetting resin composition film 107 after alkali etching The alkali-soluble thermosetting resin composition film after thermosetting is formed Circuit board 108 Alkali-soluble thermosetting resin composition film 109 after thermosetting Circuit board 110 formed with thermosetting alkali-soluble thermosetting resin composition film after back grinding Semiconductor element

Claims (6)

A layer of an alkali-soluble thermosetting resin composition is formed on a circuit board with a bump electrode, the alkali-soluble thermosetting resin composition layer is alkali-etched and adjusted to an arbitrary thickness, and then the alkali-soluble thermosetting resin is cured. A method for producing a circuit board with a cured product layer, comprising curing a layer of a conductive resin composition. The alkali-soluble thermosetting resin composition has (A) a structural unit represented by the general formula (1) and is represented by the general formula (2) and / or (3) at least at one end of the main chain. 2. The method for producing a circuit board with a cured product layer according to claim 1, comprising an alkali-soluble polyimide having a structure, (B) a thermosetting resin, and (C) a curing agent.

(In the general formulas (1) to (3), Y represents a monovalent organic group having at least one group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group, and Z represents R ¹ represents a divalent organic group having at least one group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group, and R ¹ represents a 4 to 14 valent organic group, R ² Represents a divalent to divalent organic group, and R ³ and R ⁴ each independently represents at least one group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. And β each independently represents an integer of 0 to 10.) The method for producing a circuit board with a cured product layer according to claim 2, wherein the (A) alkali-soluble polyimide has a phenolic hydroxyl group. The glass transition temperature of said (A) alkali-soluble polyimide is 160 degreeC or more, The manufacturing method of the circuit board with a hardened | cured material layer of Claim 2 or 3 characterized by the above-mentioned. Furthermore, (D) inorganic particle is contained, The manufacturing method of the circuit board with a hardened | cured material layer in any one of Claims 2-4 characterized by the above-mentioned. The method for producing a circuit board with a cured product layer according to any one of claims 1 to 5, wherein the layer of the alkali-soluble thermosetting resin composition is in a sheet form.

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