JPWO2018159384A1 - Resin composition, resin sheet, cured pattern, semiconductor electronic component or semiconductor device - Google Patents

Abstract

(A-1) an alkali-soluble polyimide resin having a glass transition temperature of 200 ° C to 300 ° C, (a-2) an alkali-soluble polyimide, an alkali-soluble polybenzoxazole having a glass transition temperature of 50 ° C to 150 ° C, A resin composition containing at least one resin selected from an alkali-soluble polyamideimide, a precursor thereof, and a copolymer thereof, and (b) a photosensitizer, wherein the component (a-1) is 100 parts by mass. A resin composition containing the component (a-2) in an amount of 10 parts by mass or more and 40 parts by mass or less based on parts by mass. According to the present invention, even when the maximum temperature of the heat treatment step for curing is 150 ° C. or more and 220 ° C. or less, the obtained cured film has low stress, and the shape change of the cured pattern in the subsequent solder reflow step. Can be obtained.

Description

  The present invention relates to a resin composition, a resin sheet, a cured pattern, and a semiconductor electronic component or a semiconductor device. Specifically, the present invention relates to a resin composition suitably used for a protective film of a semiconductor device, an interlayer insulating film, an insulating layer of an organic electroluminescent device, and the like, and uses thereof.

  Polyimide-based, polybenzoxazole-based, polyamide-imide-based resins with excellent heat resistance and mechanical properties are used for protective films and interlayer insulating films for semiconductor devices, insulating layers for organic electroluminescent devices, and flattening films for TFT substrates. Such heat-resistant resins are widely used. Conventionally, these heat-resistant resins form a coating film in a state of a precursor having high solubility in an organic solvent, and after patterning the coating film using a photoresist based on a novolak resin or the like, A method of converting the precursor into an insoluble and infusible heat-resistant resin by heating and curing the precursor has been adopted. In recent years, the use of a negative or positive photosensitive resin composition capable of pattern processing itself has simplified the process by eliminating the need for a photoresist process. Positive-type and negative-type photosensitive resin compositions have advantages and disadvantages, respectively, and are selectively used depending on applications so as to obtain desired characteristics. A positive type is suitable for applications requiring high resolution with an opening size of 10 μm or less, and a negative type is suitable for applications requiring a step of treatment with a chemical such as a resist stripper.

  In recent years, as the integration of semiconductors and the capacity of semiconductor memories have increased, multilayering and thickening of insulating materials have progressed, and in order to reduce the heat load on semiconductor devices in the production process and the stress on the substrate wafer, Development of an insulating material that can be cured by a heat treatment at a relatively low temperature of 250 ° C. or less, and further at 220 ° C. or less, has been advanced in contrast to a heat curing treatment that conventionally required a high temperature of 300 ° C. or more.

  In this regard, a resin composition containing a heat-resistant resin such as polyimide and a polyfunctional alkoxymethyl crosslinking agent has been proposed (for example, Patent Document 1).

  Further, in order to improve elongation, a resin composition containing a resin having a flexible group in the main chain such as an alkylene glycol has been proposed (for example, Patent Document 2).

JP 2010-72143 A International Publication No. 2014/050558

  However, the resin composition of Patent Literature 1 loses flexibility of a cured film due to crosslinking, and the cured film tends to have high stress and insufficient elongation, causing warpage of a semiconductor chip, physical shock or thermal shock. Cracks tended to occur. Further, when the maximum temperature of the heat treatment for curing (hereinafter, also referred to as baking) step is set to 220 ° C. or lower, these resin compositions may be subjected to a subsequent solder reflow step (about 250 to 270 ° C.). There was a problem that the cured pattern could not maintain the shape and the shape collapsed.

  The present invention has been made in view of the above problems, even if the maximum temperature of the heat treatment step for curing is 150 ° C or more and 220 ° C or less, the obtained cured film has low stress, and It is an object of the present invention to provide a resin composition having a small change in the shape of a cured pattern in the solder reflow step.

In order to solve the above problems, the present invention has the following configurations.
(1) (a-1) an alkali-soluble polyimide resin having a glass transition temperature of 200 ° C. to 300 ° C .; (a-2) an alkali-soluble polyimide having an glass transition temperature of 50 ° C. to 150 ° C. A resin composition containing at least one resin selected from benzoxazole, alkali-soluble polyamideimide, a precursor thereof, and a copolymer thereof, and (b) a photosensitizer,
A resin composition containing 10 parts by mass or more and 40 parts by mass or less of the component (a-2) based on 100 parts by mass of the component (a-1).
(2) A resin sheet comprising the above resin composition.
(3) A cured pattern composed of a cured product of the above resin composition.
(4) A method for producing a cured pattern using the above resin composition, wherein the maximum temperature of the step of heat-treating the developed resin pattern is lower than the glass transition temperature of the component (a-1), A method for producing a cured pattern, which is higher than the glass transition temperature of the component (a-2).
(5) A semiconductor electronic component or a semiconductor device on which the above-described cured pattern is arranged.

  According to the present invention, even if the maximum temperature of the heat treatment step for curing is 150 ° C. or more and 220 ° C. or less, the obtained cured film has low stress, and the shape change of the cured pattern in the subsequent solder reflow step. Can be obtained.

The resin composition of the present invention,
(A-1) an alkali-soluble polyimide resin having a glass transition temperature of 200 ° C. or more and 300 ° C. or less, (a-2) an alkali-soluble polyimide having an glass transition temperature of 50 ° C. or more and 150 ° C. or less, and an alkali-soluble polybenzoxazole; A resin composition containing at least one resin selected from an alkali-soluble polyamideimide, a precursor thereof, and a copolymer thereof, and (b) a photosensitizer,
The component (a-2) is contained in an amount of 10 to 40 parts by mass with respect to 100 parts by mass of the component (a-1).

  The glass transition temperature can be determined using a differential scanning calorimeter (DSC). Details will be described later.

  In the present invention, the inclusion of the resin of the component (a-1) and the resin of the component (a-2) having different glass transition temperatures can improve the elongation of a cured film obtained by firing at a low temperature of 150 to 220 ° C. This is important for reducing stress and improving the resistance of the cured pattern to the solder reflow process.

  The present inventors have failed to achieve the effects of the present invention by using a resin having a glass transition temperature of more than 150 ° C. and less than 200 ° C., which is an intermediate property between them, instead of the above (a-1). It has been found that the effects of the present invention as described above can be achieved only when the component and the component (a-2) are used in combination. Specifically, when only the resin having a glass transition temperature of more than 150 ° C and less than 200 ° C is used instead of the component (a-1) and the component (a-2), the case where only the component (a-2) is used, Similarly, the shape of the cured pattern cannot be maintained in the solder reflow process, and the shape tends to collapse. The estimation mechanism is described below.

  In the resin composition of the present invention, the component (a-1) improves the solder reflow process resistance during low-temperature baking at 150 ° C to 220 ° C, and improves the elongation of the cured film from which the component (a-2) is obtained. Let me. In addition, the component (a-2) has a synergistic effect of alleviating the stress of the obtained cured pattern and suppressing the deformation of the cured pattern in the solder reflow step when used in combination with the component (a-1). These effects make it possible to achieve high elongation, low stress, and resistance to a solder reflow process of a cured pattern obtained by baking at a low temperature of 150 ° C. or more and 220 ° C. or less.

  The glass transition temperature of the component (a-1) is 200 ° C. or higher and 300 ° C. or lower, but is preferably 220 ° C. or higher, and more preferably 240 ° C. or higher, from the viewpoint of the solder reflow process resistance of the cured pattern. Further, from the viewpoint of storage stability of the resin composition, the glass transition temperature of the component (a-1) is more preferably 280 ° C or lower, further preferably 270 ° C or lower, and particularly preferably 260 ° C or lower.

  The glass transition temperature of the component (a-2) is 50 ° C. or higher and 150 ° C. or lower, but is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, and particularly preferably, from the viewpoint of the solder reflow process resistance of the cured pattern. 100 ° C. or higher. Further, from the viewpoint of improving the elongation of the cured film and reducing the stress, the glass transition temperature of the component (a-2) is more preferably 140 ° C. or lower, further preferably 130 ° C. or lower, and particularly preferably 120 ° C. or lower.

  The stress of the cured film or cured pattern obtained by thermally curing the resin composition of the present invention at 210 ° C. is preferably 10 MPa or more and 30 MPa or less. The stress of the cured film or the cured pattern can be measured by a stress measuring device. Details will be described later. The stress of the cured film or the cured pattern is preferably 30 MPa or less, more preferably 25 MPa or less, further preferably 20 MPa or less, and particularly preferably 18 MPa or less, from the viewpoint of suppressing the warpage of the semiconductor chip. The stress of the cured film or cured pattern is preferably 3 MPa or more, more preferably 5 MPa or more, and particularly preferably 10 MPa or more, for maintaining the pattern shape.

  The “alkali-soluble” resin in the present invention refers to a resin having an alkali dissolution rate of 60 nm / min or more and 1,000,000 nm / min or less measured by the following method.

  The resin to be measured is dissolved in γ-butyrolactone so as to have a solid content of 35% by mass. This solution is applied on a 6-inch silicon wafer and prebaked on a hot plate at 120 ° C. for 4 minutes to form a resin film having a thickness of 10 μm ± 0.5 μm. This was immersed in an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide at 23 ± 1 ° C. for 1 minute, and the thickness of the resin film dissolved per minute was determined from the change in the thickness of the resin film before and after immersion. The alkali dissolution rate is used. If the resin film completely dissolves in less than 1 minute, measure the time required for dissolution and determine the film thickness per minute from this and the film thickness of the resin film before immersion. The alkali dissolution rate is used.

  The content of the component (a-2) in the resin composition of the present invention is 10 parts by mass or more and 40 parts by mass or less based on 100 parts by mass of the component (a-1). When the content of the component (a-2) is less than 10 parts by mass, effects of improving the elongation and reducing the stress of the obtained cured film cannot be sufficiently obtained. When the content of the component (a-2) is more than 40 parts by mass, the resistance to the solder reflow process is impaired. The content of the component (a-2) is more preferably 12 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more, from the viewpoint of improving the elongation of the cured film and reducing the stress. The content of the component (a-2) is more preferably 37 parts by mass or less, further preferably 34 parts by mass or less, and particularly preferably 30 parts by mass or less, from the viewpoint of improving the resistance of the cured pattern to the solder reflow process. .

  The difference between the glass transition temperature of the component (a-1) and the glass transition temperature of the component (a-2) is preferably 100 ° C. or higher, and more preferably 130 ° C. or higher, from the viewpoint of reducing the stress of the obtained cured film. . Further, the difference in the glass transition temperature is preferably 220 ° C. or less, more preferably 190 ° C. or less, from the viewpoint of improving the elongation of the cured film.

  The polyimide preferably used in the resin composition of the present invention is obtained, for example, by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, a tetracarboxylic diester dichloride and the like with a diamine, a corresponding diisocyanate compound, and a trimethylsilylated diamine. The obtained polyamic acid (polyimide precursor) can be obtained by dehydration and ring closure by heat treatment or chemical treatment such as acid or base.

  The polybenzoxazole preferably used in the resin composition of the present invention is, for example, a polyhydroxyamide (polybenzoxazole precursor) obtained by reacting bisaminophenol with dicarboxylic acid, corresponding dicarboxylic acid chloride, dicarboxylic acid active ester, or the like. ) Can be obtained by dehydration and ring closure by heat treatment or chemical treatment with phosphoric anhydride, a base, a carbodiimide compound, or the like.

  Polyamide imide preferably used in the resin composition of the present invention, for example, tricarboxylic acid, corresponding tricarboxylic anhydride, tricarboxylic anhydride halide and the like, a polyamideimide precursor obtained by reacting with diamine or diisocyanate, heat treatment, Alternatively, it can be obtained by dehydration and ring closure by a chemical treatment with an acid or a base.

  Further, the resin of the component (a-1) and the resin of the component (a-2) may be obtained by precipitating in a poor solvent for the polymer such as methanol or water after completion of the polymerization, and then washing and drying. More preferred. By this operation, the low molecular weight component of the polymer can be removed, so that the mechanical properties of the resin composition after heat curing are improved.

  As the component (a-1), a resin having a structural unit represented by the general formula (1) is preferable. The number of structural units represented by the general formula (1) contained in one molecule of the resin is preferably 3 or more, more preferably 10 or more, and particularly preferably 15 or more. Further, from the viewpoint of alkali solubility, the number of structural units is preferably 500 or less, more preferably 200 or less, further preferably 100 or less, further preferably 70 or less, and particularly preferably 50 or less.

In the general formula (1), R ¹ represents a tetravalent organic group, R ² represents a divalent to hexavalent organic group, and p represents an integer of 0 to 4.

  It is particularly preferable that the component (a-1) has a structural unit represented by the general formula (4) from the viewpoint of improving adhesion to a metal wiring containing a copper element or a metal electrode. The number of structural units represented by the general formula (4) contained in one molecule of the resin is preferably 2 or more, more preferably 3 or more, and particularly preferably 5 or more. Further, from the viewpoint of alkali solubility, the number of structural units is preferably 100 or less, more preferably 50 or less, further preferably 20 or less, and particularly preferably 10 or less.

In the general formula (4), R ⁹ represents a tetravalent organic group, and Z represents one or more groups selected from the following group (Z-1).

In the formula, R ¹⁰ represents a hydrogen atom, a hydroxyl group, a mercapto group, or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

  As the component (a-2), any resin of polyimide, polybenzoxazole, polyamideimide, a precursor thereof, and a copolymer thereof is preferably used. From the viewpoint of mechanical properties of a cured film obtained by firing at a low temperature of 150 ° C. or more and 220 ° C. or less, a resin having a structural unit represented by the general formula (1) is particularly preferable. The structural unit of the general formula (1) preferably contains 30% or more, more preferably 50% or more, even more preferably 70% or more, and more preferably 90% of the total number of the structural units of the component (a-2). It is particularly preferable to include the above.

In the general formula (1), R ¹ represents a tetravalent organic group, R ² represents a divalent to hexavalent organic group, and p represents an integer of 0 to 4.

  The component (a-2) is one or more types of structures selected from structural units represented by general formulas (2) and (3) from the viewpoint of setting the glass transition temperature to 50 ° C. or higher and 150 ° C. or lower. It is preferred to have units. The number of the structural units represented by the general formula (2) or (3) contained in one molecule of the resin is preferably 3 or more, more preferably 3 or more, from the viewpoint of setting the glass transition temperature to 50 ° C or more and 150 ° C or less. It is 5 or more, more preferably 10 or more, and particularly preferably 15 or more. Further, the number of structural units is preferably 100 or less, more preferably 80 or less, further preferably 50 or less, and particularly preferably 30 or less, from the viewpoint of maintaining high heat resistance of the cured pattern. The structural units represented by the general formulas (2) and (3) may be any of diamine compound residue, dicarboxylic acid compound residue, tricarboxylic acid compound residue, and tetracarboxylic acid compound residue in the resin. May be included, but it is preferable that it is included as a diamine compound residue from the viewpoint of elongation of the cured film.

In the general formulas (2) and (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and are the same. But they may be different. r represents an integer of 4 to 20, and s represents an integer of 2 to 20.

R ¹ , R ² (OH) _p and R ⁹ in the general formulas (1) and (4) can include a phenolic hydroxyl group, a sulfonic acid group, a thiol group, and the like in the skeleton. By using a resin having an appropriate amount of a phenolic hydroxyl group, a sulfonic acid group or a thiol group, a photosensitive resin composition excellent in alkali solubility and pattern formability can be obtained.

In the general formulas (1) and (4), R ¹ and R ⁹ represent a tetracarboxylic acid compound residue. Acid components containing R ¹ and R ⁹ include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′ , 3,3'-biphenyltetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 2,2', 3,3'-benzophenonetetracarboxylic acid, 2,2-bis (3,4 -Dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2 , 3-Dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, bis 3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, And aromatic tetracarboxylic acids such as 4,9,10-perylenetetracarboxylic acid, and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. it can. These acid components can be used as they are, or as acid anhydrides, active esters and the like. Further, these two or more acid components may be used in combination.

In the general formula (1), R ² (OH) _p represents a diamine compound residue. Examples of the diamine component containing R ² (OH) _p include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, and bis (3-amino-4). -Hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino- Hydroxyl group-containing diamines such as 4-hydroxyphenyl) fluorene; sulfonic acid-containing diamines such as 3-sulfonic acid-4,4'-diaminodiphenyl ether; thiol group-containing diamines such as dimercaptophenylenediamine; 3,4'-diaminodiphenyl ether , 4,4'-diaminodiphenyl ether 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenyl Sulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, 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'-bis (trifluoromethyl) -4,4 ' Aromatic diamines such as diaminobiphenyl, and compounds in which hydrogen atoms of these aromatic rings are partially substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, and the like; 2,4-diamino- 1,3,5-triazine (guanamine), 2,4-diamino-6-methyl-1,3,5-triazine (acetoguanamine), 2,4-diamino-6-phenyl-1,3,5-triazine (Benzoguanamine) 2,4-diamino-6-vinyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3,3 5-triazine, 2,4-diaminopyrimidine, 2,4-diamino-6-methylpyrimidine, 2,4-diamino-6-phenylpyrimidine, 2,4-diamino-6-vinylpyrimidine, 2,4-diamino- 6-hydroxypyrimidine, 2,4-diamino-6-mercaptopyrimidine, 4,6-diaminopyrimidine, 4,6-diamino-2-methylpyrimidine, 4,6-diamino-2-phenylpyrimidine, 4,6-diamino Nitrogen-containing heteroaromatics such as -2-vinylpyrimidine, 4,6-diamino-2-hydroxypyrimidine, 4,6-diamino-2-mercaptopyrimidine Diamine having a ring; 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (p-aminophenyl) -1,1,3,3- Tetramethyldisiloxane, 1,3-bis (p-aminophenethyl) -1,1,3,3-tetramethyldisiloxane, 1,7-bis (p-aminophenyl) -1,1,3,3 Silicone diamines such as 5,5,7,7-octamethyltetrasiloxane; alicyclic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine; and aliphatic diamines. As a diamine containing a long-chain aliphatic group or a polyalkylene oxide group, a polyethylene oxide group-containing “Jeffamine” (registered trademark) KH-511, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, Jeffamine EDR-148, Jeffamine EDR-176, Jeffamine D-200 of polyoxypropylenediamine, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000 (Available from HUNTSMAN Co., Ltd.). These diamines can be used as they are or as the corresponding diisocyanate compound or trimethylsilylated diamine. Further, these two or more kinds of diamine components may be used in combination.

  The component (a-2) preferably has a diamine residue containing a long-chain aliphatic group or polyalkylene oxide group, because the glass transition temperature of the resin can be lowered. Therefore, as the component (a-2), a component having a diamine residue having a structural unit selected from the structural units of the general formula (2) and the general formula (3) is particularly preferably used. On the other hand, the component (a-1) preferably does not contain these structural units from the viewpoint of maintaining a high glass transition temperature of the resin.

  Further, it is preferable that a fluorine atom is contained in the structural unit of the component (a-1) and / or the component (a-2). The fluorine atom imparts water repellency to the surface of the obtained resin film, and can suppress the infiltration of the developer from the resin film surface during alkali development. The fluorine atom content in the component (a-1) and the component (a-2) is preferably 10% by mass or more in order to sufficiently obtain the effect of preventing seepage, and 20% by mass or less from the viewpoint of solubility in an aqueous alkaline solution. Is preferred.

In the component (a-1) and / or the component (a-2), an aliphatic diamine having a siloxane structure may be copolymerized as R ² (OH) _p as long as the heat resistance is not reduced. Adhesion with the substrate can be improved. Specifically, as the diamine component, 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane or the like is copolymerized.

  In order to improve the storage stability of the resin composition, the component (a-1) and the component (a-2) have a main chain terminal of a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a mono-active compound. It is preferable to seal with a terminal blocking agent such as an ester compound. For the purpose of improving the chemical resistance of the obtained cured resin film, as these terminal blocking agents, monoamines having at least one alkenyl group or alkynyl group, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive compounds Ester compounds and the like can also be used.

  When a monoamine is used as a terminal blocking agent, its introduction ratio is preferably at least 0.1 mol%, particularly preferably at least 5 mol%, based on all amine components. Further, it is preferably at most 60 mol%, particularly preferably at most 50 mol%, based on all amine components. When an acid anhydride, a monocarboxylic acid, a monoacid chloride compound or a monoactive ester compound is used as a terminal blocking agent, the introduction ratio thereof is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, based on the diamine component. Mol% or more. On the other hand, in order to maintain the molecular weight of the resin high, the introduction ratio of the terminal blocking agent is preferably 100 mol% or less, particularly preferably 90 mol% or less, based on the diamine component. A plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

  Monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1- Hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-amino Naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-amino Benzoic acid, 3-aminobenzoic acid, -Aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxy Preferred are pyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more of these may be used.

  Examples of the acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride. Anhydride; 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxy Monocarboxylic acids such as naphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, and 4-carboxybenzenesulfonic acid. And monocarboxylic acid compounds in which these carboxyl groups are acid chlorides; terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, Monoacid chloride compound in which only one carboxyl group of dicarboxylic acids such as 2,6-dicarboxynaphthalene is acid chloride; monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3- Active ester compounds obtained by reaction with dicarboximide are preferred. Two or more of these may be used.

The terminal blocking agent introduced into the component (a-1) and the component (a-2) can be detected by the following method. For example, a resin into which an endcapping agent has been introduced is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component, which are constituent units, and this is subjected to gas chromatography (GC) or nuclear magnetic resonance (NMR). By performing the measurement, the terminal blocking agent can be easily detected. Separately, it can be easily detected by directly measuring the resin component into which the terminal blocking agent has been introduced by pyrolysis gas chromatography (PGC), infrared spectrum and ¹³ C-NMR spectrum. It is.

In the component (a-1), when the molar ratio of the imide-closed unit to the total amount of all the imide and imide precursor units is defined as an imide ring-closure ratio (R _IM (%)), R _IM is 220 ° C. or lower. From the viewpoint of mechanical properties and chemical resistance of the cured film at the time of low-temperature firing, it is preferably at least 30%, more preferably at least 50%, further preferably at least 70%, particularly preferably at least 90%. Similarly, when polyimide is used as the component (a-2), the imide ring closure ratio _RIM is preferably 30% or more from the viewpoints of mechanical properties and chemical resistance of the cured film at the time of low-temperature firing at 220 ° C. or lower. It is more preferably at least 50%, further preferably at least 70%, particularly preferably at least 90%.

The imide ring closure rate (R _IM (%)) can be determined, for example, by the following method. 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 confirmed the presence of, determine the peak intensity at around 1377 cm ^-1 (X) . Next, the polymer is heat-treated at 350 ° C. for 1 hour to completely close the imide ring, and then the infrared absorption spectrum is measured to determine the peak intensity (Y) near 1377 cm ⁻¹ . The peak intensity ratio obtained by dividing the peak intensity (X) by the peak intensity (Y) corresponds to the molar ratio of the imide-closed units in the polymer before the heat treatment, that is, the imide ring-closure ratio (R _IM = X / Y × 100 (%) )).

  From the viewpoint of shortening the development time, the components (a-1) and (a-2) have an alkali dissolution rate measured by the above-described method of preferably 100 nm / min or more, more preferably 200 nm / min or more, and furthermore It is preferably at least 500 nm / min, particularly preferably at least 1,000 nm / min. In addition, from the viewpoint of improving the pattern shape of the obtained pattern, the alkali dissolution rate is preferably 200,000 nm / min or less, more preferably 100,000 nm / min or less, even more preferably 50,000 nm / min or less. It is preferably at most 20,000 nm / min, particularly preferably at most 15,000 nm / min.

  The weight average molecular weight of the component (a-1) and the component (a-2) is preferably 1,000 or more, more preferably 1,500 or more, and still more preferably 5,000 or more, from the viewpoint of the mechanical properties of the cured film. And particularly preferably 10,000 or more. The weight average molecular weight is preferably 100,000 or less, more preferably 50,000 or less, further preferably 40,000 or less, and particularly preferably 30,000 or less, from the viewpoint of alkali solubility. The weight average molecular weight in the present invention is a value determined by gel permeation chromatography (GPC) in terms of polystyrene. Details will be described later.

  The resin composition of the present invention may contain a phenol-containing resin as needed. The phenol-containing resin in the present invention is a resin having a phenol group as a structural unit, and includes, for example, a polyhydroxystyrene resin, an alkali-soluble novolak resin, a resole resin, and a benzyl ether type phenol resin, but is not limited thereto. Not done. Two or more of these may be used. Among these, it is particularly preferable to contain (a-3) a polyhydroxystyrene resin (hereinafter, sometimes abbreviated as the component (a-3)) from the viewpoint of the reliability of the cured film.

  (A-3) The polyhydroxystyrene resin can be obtained by, for example, addition polymerization of a phenol derivative having an unsaturated bond by a known method. Examples of the phenol derivative having an unsaturated bond include hydroxystyrene, dihydroxystyrene, allylphenol, coumaric acid, 2′-hydroxychalcone, N-hydroxyphenyl-5-norbornene-2,3-dicarboxylic imide, resveratrol , 4-hydroxystilbene and the like, and two or more of these may be used. Further, a copolymer with a monomer having no phenolic hydroxyl group such as styrene may be used. This facilitates adjustment of the alkali dissolution rate.

  (A-3) The polyhydroxystyrene resin is preferably a copolymer having a hydroxystyrene residue and a styrene residue from the viewpoint of adjusting the alkali dissolution rate. The content of the styrene residue is preferably at least 5 mol%, more preferably at least 10 mol%, particularly preferably at least 15 mol%, based on 100 mol% of the hydroxystyrene residue. The content of the styrene residue is preferably 60 mol% or less, more preferably 40 mol% or less, more preferably 30 mol% or less, particularly preferably 25 mol% or less, based on 100 mol% of the hydroxystyrene residue. It is.

  Novolak resins, resole resins, and benzyl ether type phenol resins are obtained by polycondensing phenols and aldehydes such as formalin by a known method.

  Examples of phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 2,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylene Bisphenol, methylenebis (p-cresol), resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butyl Alkoxy phenol, o- ethylphenol, m- ethylphenol, p- ethylphenol, 2,3-diethyl phenol, 2,5-diethyl phenol, p- isopropylphenol, alpha-naphthol, such as β- naphthol. Two or more of these may be used.

  Examples of aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and chloroacetaldehyde. Two or more of these may be used.

  The weight average molecular weight of the phenol-containing resin is preferably 500 or more, more preferably 700 or more, further preferably 1,000 or more, and preferably 50,000 or less, more preferably 50,000 or less, from the viewpoint of chemical resistance. Is 40,000 or less, more preferably 30,000 or less, and particularly preferably 20,000 or less. The weight average molecular weight is a value determined in terms of polystyrene by gel permeation chromatography (GPC).

  The glass transition temperature of the phenol-containing resin can be determined using a differential scanning calorimeter (DSC). The glass transition temperature is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and even more preferably 100 ° C. or higher, from the viewpoint of the solder reflow process resistance of the cured pattern. Further, the glass transition temperature is preferably 200 ° C. or lower, more preferably 170 ° C. or lower, and particularly preferably 150 ° C. or lower, from the viewpoint of elongation of the cured film.

  The content of the phenol-containing resin is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, with respect to 100 parts by mass of the component (a-1), from the viewpoint of improving sensitivity when used as a photosensitive resin composition. It is more preferably at least 15 parts by mass, particularly preferably at least 18 parts by mass. The content of the phenol-containing resin is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and still more preferably 200 parts by mass with respect to 100 parts by mass of the component (a-1) from the viewpoint of heat resistance of the cured film. Parts by mass, more preferably 100 parts by mass or less, particularly preferably 50 parts by mass or less.

  The alkali dissolution rate of the phenol-containing resin is preferably 100 nm / min or more, more preferably 200 nm / min or more, further preferably 500 nm / min or more, particularly preferably 1,000 nm / min or more, from the viewpoint of making the development time appropriate. It is. In addition, it is preferably 200,000 nm / min or less, more preferably 100,000 nm / min or less, further preferably 50,000 nm / min or less, further preferably 20,000 nm / min or less, and particularly preferably 15,000 nm / min or less. It is.

  The resin composition of the present invention contains (b) a photosensitizer. (B) By containing a photosensitive agent, the solubility of an ultraviolet-exposed portion in an alkali developing solution or an organic developing solution changes, so that a resin pattern can be obtained by developing with a developing solution after exposure to ultraviolet light.

  In a preferred embodiment of the resin composition of the present invention, (b-1) a quinonediazide compound is used as the photosensitizer (b). When the resin composition contains the (b-1) quinonediazide compound, an acid is generated in the UV-exposed area, and the solubility of the exposed area in an aqueous alkaline solution is increased. Can be obtained. Two or more quinonediazide compounds can also be used. This makes it possible to further increase the ratio of the dissolution rate between the exposed part and the unexposed part, and to obtain a highly sensitive photosensitive resin composition.

  (B-1) Examples of the compound include a polyhydroxy compound in which sulfonic acid of quinonediazide is ester-bonded, a polyamino compound in which sulfonic acid of quinonediazide is sulfonamide-bonded, and a polyhydroxypolyamino compound in which sulfonic acid of quinonediazide is esterified. And one or more types selected from a bond and a sulfonamide bond. All the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, but it is preferable that 50 mol% or more of all the functional groups are substituted with quinonediazide. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition which is sensitive to i-line (365 nm), h-line (405 nm), or g-line (436 nm) of a mercury lamp which is a common ultraviolet ray. it can.

  As the quinonediazide compound, both a 5-naphthoquinonediazidosulfonyl group and a 4-naphthoquinonediazidosulfonyl group are preferably used. A compound having both of these groups in the same molecule may be used, or a compound using different groups may be used in combination.

  The quinonediazide compound can be synthesized by a known method. For example, there is a method in which 5-naphthoquinonediazidosulfonyl chloride is reacted with a polyhydroxy compound in the presence of triethylamine.

  The content of the compound (b-1) in the resin composition is preferably 1 to 60 parts by mass based on 100 parts by mass of the component (a-1). By setting the content of the quinonediazide compound in this range, the sensitivity of the resin composition can be increased, and mechanical properties such as elongation of the obtained cured film can be maintained. For higher sensitivity, the content of the compound (b-1) is preferably at least 3 parts by mass. In order not to impair the mechanical properties of the cured film, the content of the compound (b-1) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less. Further, a sensitizer and the like may be contained as needed.

  In another preferred embodiment of the resin composition of the present invention, (b-2) a photopolymerization initiator is used as the photosensitizer (b). When the resin composition contains (b-2) a photopolymerization initiator and (d) a compound having a polymerizable unsaturated bond described below, the exposed portion is exposed to an alkali developer or an organic developer by ultraviolet exposure and subsequent heat treatment. Since it is insoluble in the developer, a negative pattern can be formed.

  (B-2) Examples of the photopolymerization initiator include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like. Benzophenones; benzylidenes such as 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone and 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone; 7-diethylamino-3- Tenonyl coumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1-methylmethylbenzimidazolyl) coumarin, 3- (2-benzothiazolyl ) Coumarins such as -7-diethylaminocoumarin Anthraquinones such as 2-t-butylanthraquinone, 2-ethylanthraquinone and 1,2-benzanthraquinone; benzoins such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; ethylene glycol bis (3-mercaptopropionate); ), 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, mercapto such as 2-mercaptobenzimidazole; N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- (p-chlorophenyl) glycine Glycines such as N- (4-cyanophenyl) glycine; 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o (Methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, bis (α- Isonitrosopropiophenone oxime) isophthal, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), OXE02 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Oximes such as "ADEKA ARKULS" (registered trademark) NCI-831 (trade name, manufactured by ADEKA Corporation); 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- Α-alkyl such as on, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc. Roh alkylphenones; 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, and the like. Two or more of these may be contained.

  The content of the photopolymerization initiator (b-2) in the resin composition is preferably from 0.1 to 40 parts by mass per 100 parts by mass of the resin (a-1). When two or more kinds are combined, the total amount is preferably 0.2 to 60 parts by mass.

  It is preferable that the resin composition of the present invention further contains (c) a thermal crosslinking agent. As the thermal crosslinking agent, a compound having at least two of one or more groups selected from an alkoxymethyl group and a methylol group, or a compound having at least two groups of one or more selected from an epoxy group and an oxetanyl group Are preferably used, but are not limited thereto. When the resin composition contains the thermal crosslinking agent (c), when the resin pattern formed by using the resin composition is fired, the components (a-1) and (a-2) and the component (c) are fired. The thermal crosslinking agent reacts to form a crosslinked structure, and the resulting cured film has improved solder reflow process resistance. In addition, two or more types of thermal crosslinking agents may be used, which enables a wider design.

  Preferred examples of the compound having at least two of one or more groups selected from an alkoxymethyl group and a methylol group include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML -PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC , DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML -BPAF, TML-BPAP, MOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), “NIKALAC” (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (trade names, manufactured by Sanwa Chemical Co., Ltd.) And are available from each company. Two or more of these may be contained.

  Preferred examples of the compound having at least two of one or more groups selected from an epoxy group and an oxetanyl group include, for example, bisphenol A epoxy resin, bisphenol A oxetanyl resin, bisphenol F epoxy resin, and bisphenol F Oxetanyl resins, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, epoxy group-containing silicones such as polymethyl (glycidyloxypropyl) siloxane, and the like, but are not limited thereto. Specifically, "EPICLON" (registered trademark) 850-S, HP-4032, HP-7200, HP-820, HP-4700, EXA-4710, HP-4770, EXA-859CRP, EXA-1514, EXA- 4880, EXA-4850-150, EXA-4850-1000, EXA-4816, EXA-4822 (both trade names, manufactured by DIC Corporation), "Rikaresin" (registered trademark) BEO-60E (trade name, Shin-Nippon Rika) EP-4003S, EP-4000S (trade name, manufactured by ADEKA Corporation), "TECHMORE" (registered trademark) VG3101L, VG3101M80 (trade name, manufactured by Printtech Co., Ltd.), and the like. Available from each company. Two or more of these may be contained.

  The content of the thermal crosslinking agent (c) in the resin composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 10 parts by mass, per 100 parts by mass of the component (a-1). Not less than parts by mass. From the viewpoint of maintaining mechanical properties such as elongation, the content of (c) the thermal crosslinking agent is preferably 300 parts by mass or less, more preferably 200 parts by mass or less.

  In an embodiment in which (b) the photosensitive agent is (b-2) a photopolymerization initiator, the resin composition preferably further contains (d) a compound having a polymerizable unsaturated bond group. By containing the (b-2) photopolymerization initiator and (d) a compound having a polymerizable unsaturated bond group, the exposed portion is insolubilized in an alkali or organic developer by ultraviolet exposure and subsequent heat treatment. Therefore, a negative pattern can be formed.

  In the component (d), examples of the polymerizable unsaturated bond group include an unsaturated double bond group such as a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group, and an unsaturated triple bond group such as a propargyl group. . You may have these two or more types. Among these, a group selected from a conjugated vinyl group, an acryloyl group, and a methacryloyl group is preferable in terms of polymerizability. Further, from the viewpoint of stability, it is preferable to have 1 to 4 of these groups in one molecule.

  Examples of the component (d) include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylol Methylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate Isooctyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butane Diol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate Acrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 2-hydroxyethyl alcohol Acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2, 2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl -2,2,6,6-tetramethylpiperidinyl acrylate and the like.

  The content of the component (d) in the resin composition is preferably from 5 to 200 parts by mass, and more preferably from 5 to 150 parts by mass from the viewpoint of compatibility with respect to 100 parts by mass of the component (a-1). .

  In the embodiment in which (b) the photosensitive agent is (b-2) a photopolymerization initiator, the resin composition preferably further contains (e) a polymerization inhibitor. (E) The polymerization inhibitor stops radical polymerization by capturing a radical generated at the time of exposure or a radical at a polymer growing terminal of a polymer chain obtained by the radical polymerization at the time of exposure and holding it as a stable radical. Refers to compounds that can

  In the embodiment in which (b) the photosensitizer is (b-2) a photopolymerization initiator, the resin composition contains an appropriate amount of (e) a polymerization inhibitor, thereby suppressing generation of residues after development and after development. Resolution can be improved. This is presumed to be because the polymerization inhibitor traps an excessive amount of radicals generated at the time of exposure or a radical at the growing end of a high-molecular-weight polymer chain, thereby suppressing excessive radical polymerization.

  (E) As the polymerization inhibitor, a phenol-based polymerization inhibitor is preferable. Examples of the phenolic polymerization inhibitor include 4-t-butylphenol, 4-methoxyphenol, 1,4-hydroquinone, 1,4-benzoquinone, 2-t-butyl-4-methoxyphenol, and 3-t-butyl- 4-methoxyphenol, 4-tert-butylcatechol, 2-tert-butyl-1,4-hydroquinone, 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2,6- Di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-1,4-hydroquinone, 2,5-di-tert- Amyl-1,4-hydroquinone, 2-nitroso-1-naphthol, "IRGANOX" (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330 The 1726, the 1425, the 1520, the 245, the 259, the 3114, the 565, or the 295 (all manufactured by BASF) and the like.

  The content of the polymerization inhibitor (e) in the resin composition is preferably at least 0.01 part by mass, more preferably at least 0.03 part by mass, based on 100 parts by mass of the compound having a polymerizable unsaturated bond group (d). Is more preferably, more preferably 0.05 part by mass or more, and particularly preferably 0.1 part by mass or more. When the content is within the above range, the resolution after development and the heat resistance of the cured film can be improved. On the other hand, the content of the polymerization inhibitor (e) is preferably at most 10 parts by mass, more preferably at most 8 parts by mass, further preferably at most 5 parts by mass, particularly preferably at most 3 parts by mass. When the content is within the above range, the sensitivity at the time of exposure can be improved.

  The resin composition of the present invention may contain a solvent as needed. Preferred examples of the solvent include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide; tetrahydrofuran, dioxane, propylene glycol Ethers such as monomethyl ether and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl Esters such as acetate; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol and 3-methyl-3-methoxybutanol; fragrances such as toluene and xylene Such as hydrocarbons. Two or more of these may be contained.

  The content of the solvent in the resin composition is preferably 70 parts by mass or more, more preferably 100 parts by mass or more, from the viewpoint of dissolving the resin, based on 100 parts by mass of the component (a-1). From the viewpoint of obtaining an appropriate film thickness, the content of the solvent is preferably 1800 parts by mass or less, more preferably 1500 parts by mass or less.

  The resin composition of the present invention preferably contains (f) a solvent having an ester structure (hereinafter, sometimes abbreviated as (f) solvent) among the above-mentioned solvents. Although the detailed reason is unknown because a small amount of the solvent (f) is contained in the cured pattern obtained by heat-treating the resin pattern formed using the resin composition, the elongation of the cured pattern is improved. Alternatively, it is preferable because it has a stress reducing effect. (F) Preferred examples of the solvent having an ester structure include γ-butyrolactone, δ-valerolactone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate. , Ethyl lactate, methyl lactate and the like.

  The content of the solvent (f) contained in the cured pattern is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass, relative to the cured pattern. %, Particularly preferably 0.015% by mass or more. Further, the content of the solvent (f) is preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, further preferably 0.05% by mass or less, and particularly preferably. Is 0.03% by mass or less.

  The resin composition of the present invention may further contain a thermal acid generator as needed. The thermal acid generator generates an acid by heating, accelerates the crosslinking reaction of (c) the thermal crosslinking agent, and forms an unclosed imide ring structure and / or oxazole ring structure of the components (a-1) and (a-2). Has the effect of promoting these cyclizations and further improving the mechanical properties of the resulting cured film even when calcined at a lower than usual 150 to 300 ° C.

  The thermal decomposition start temperature of the thermal acid generator is preferably from 50 ° C to 270 ° C, more preferably 220 ° C or less, and further preferably 180 ° C or less. Further, when the resin composition is applied to a supporting substrate and dried (prebaked: about 70 to 140 ° C.), no acid is generated, and final heating (curing: aboutcured) after forming a resin pattern through subsequent exposure and development. (100 to 400 ° C.) is preferable because it can suppress the decrease in sensitivity during development. Even if the maximum temperature of the heat treatment step for curing is 150 ° C. or more and 220 ° C. or less, the resin composition of the present invention is excellent in that the shape change of the cured pattern in the solder reflow step is small, and thus the thermal acid generator As the thermal decomposition temperature, those having a thermal decomposition initiation temperature not higher than the maximum temperature of the heat treatment step are preferably used.

  The acid generated from the thermal acid generator is preferably a strong acid, for example, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid, and trifluoromethane. Haloalkylsulfonic acids such as sulfonic acids are preferred. These are used as salts, such as onium salts, or as covalent compounds, such as imidosulfonates.

  The content of the thermal acid generator in the resin composition is preferably 0.01 part by mass with respect to 100 parts by mass of the component (a-1), from the viewpoint of promoting a cross-linking reaction and cyclizing an unring-closed structure of the resin. The amount is more preferably 0.1 part by mass or more. Further, from the viewpoint of electrical insulation of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less.

  The resin composition of the present invention may further contain a low molecular compound having a phenolic hydroxyl group, if necessary. By containing a low molecular weight compound having a phenolic hydroxyl group, the alkali solubility during resin pattern formation can be easily adjusted.

  The content of the low molecular compound having a phenolic hydroxyl group is preferably at least 0.1 part by mass, more preferably at least 1 part by mass, per 100 parts by mass of the component (a-1). Further, from the viewpoint of maintaining mechanical properties such as elongation, the content is preferably 30 parts by mass or less, more preferably 15 parts by mass or less.

  The resin composition of the present invention may contain, if necessary, a surfactant for the purpose of improving wettability with a supporting substrate; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; alcohols such as ethanol; cyclohexanone and methyl isobutyl. Ketones such as ketones; ethers such as tetrahydrofuran and dioxane may be further contained.

  The preferred content of the compound used for the purpose of improving the wettability with the support substrate is 0.001 part by mass or more based on 100 parts by mass of the component (a-1). Further, from the viewpoint of obtaining an appropriate film thickness, the content is preferably 1800 parts by mass or less, more preferably 1500 parts by mass or less.

  The resin composition of the present invention may further include inorganic particles. Preferred specific examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, and talc.

  The primary particle diameter of these inorganic particles is preferably 100 nm or less, particularly preferably 60 nm or less, from the viewpoint of maintaining sensitivity. As a method for obtaining the primary particle diameter of the inorganic particles, a calculation method for obtaining the number average particle diameter from the specific surface area may be mentioned. The specific surface area is defined as the sum of the surface areas contained in a unit mass of powder. As a method for measuring the specific surface area, a BET method can be used, and the specific surface area can be measured using a specific surface area measuring device (such as HMmodel-1201 manufactured by Mounttech).

  Further, in order to enhance the adhesiveness with the silicon substrate, the resin composition may further contain a silane coupling agent such as trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, and trimethoxythiolpropylsilane. Good.

  The preferable content of the compound used for enhancing the adhesion to the silicon substrate is 0.01 part by mass or more based on 100 parts by mass of the component (a-1). From the viewpoint of maintaining mechanical properties such as elongation, the content is preferably 5 parts by mass or less.

  The viscosity of the resin composition is preferably from 2 to 5000 mPa · s. By adjusting the solid content concentration so that the viscosity becomes 2 mPa · s or more, it becomes easy to obtain a desired film thickness using the resin composition. On the other hand, if the viscosity is 5000 mPa · s or less, it becomes easy to obtain a coating film with high uniformity. A resin composition having such a viscosity can be easily obtained, for example, by setting the solid content concentration to 5 to 60% by mass.

  Next, a method for forming a cured pattern using the resin composition of the present invention will be described.

  The cured pattern of the present invention is obtained by curing a resin pattern formed into a predetermined shape using the resin composition of the present invention. That is, the cured pattern of the present invention comprises a cured product of the resin composition of the present invention.

  The cured pattern is a step of applying and drying the resin composition of the present invention on a supporting substrate to obtain a resin film, a step of exposing the resin film obtained in the above step, and a step of subjecting the exposed resin film to an alkaline aqueous solution. And a step of heat-treating the resin pattern after the development to form a resin pattern. In addition, the cured pattern is obtained by applying the resin composition of the present invention onto a base material, removing an organic solvent, and obtaining a resin sheet, and attaching the resin sheet obtained in the above step to another supporting substrate. A step of bonding, a step of exposing the resin sheet after the bonding, a step of developing the resin sheet after the exposure using an alkaline aqueous solution to form a resin pattern, and a step of heat-treating the resin pattern after the development. It can also be manufactured by a method including:

  The method for forming the cured pattern is described in more detail below. First, the resin composition of the present invention is applied to a supporting substrate. As the support substrate, a wafer made of silicon, ceramics, gallium arsenide, or the like, or a substrate on which a metal is formed as an electrode and / or a wiring is used, but is not limited thereto. However, since the resin composition of the present invention also has excellent adhesion to a metal surface containing a copper element, the support substrate is formed with at least one or more of a metal wiring containing a copper element and a metal electrode containing a copper element. It is preferable that the substrate has a high durability from the viewpoint of obtaining a semiconductor element having high durability.

  Examples of the coating method include spin coating using a spinner, spray coating, slit coating, and roll coating. The thickness of the coating film obtained by applying the resin composition varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but usually, the thickness after drying is 0.1 to 150 μm. Applied to.

  In order to enhance the adhesion between the support substrate and the resin composition, the support substrate may be pretreated with the above-mentioned silane coupling agent. For example, a silane coupling agent was dissolved at a concentration of 0.5 to 20% by mass in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. Using the solution, the surface treatment of the support substrate is performed by a technique such as spin coating, dipping, spray coating, or steam treatment. If necessary, a heat treatment at 50 to 300 ° C. is then performed to allow the reaction between the support substrate and the silane coupling agent to proceed.

  Next, the support substrate coated with the resin composition is dried to obtain a resin film. Drying is preferably performed using an oven, a hot plate, infrared rays or the like at a temperature of 50 to 150 ° C. for 1 minute to several hours.

  Next, the resin film obtained in the above step is irradiated with actinic radiation through a mask having a desired pattern to expose the resin film. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i-rays (365 nm), h-rays (405 nm), or g-rays (436 nm) of a mercury lamp, or these rays are used. Is preferably used.

  If necessary, after irradiation with actinic radiation, post-exposure baking may be performed. By performing post-exposure baking, effects such as improvement in resolution after development or increase in the allowable width of development conditions can be expected. The post-exposure bake can be performed using an oven, a hot plate, an infrared ray, a flash annealing apparatus, a laser annealing apparatus, or the like. The post-exposure bake temperature is preferably from 50 to 180 ° C, more preferably from 60 to 150 ° C. The post-exposure bake time is preferably from 10 seconds to several hours. If the post-exposure bake time is within the above range, the reaction may proceed favorably, and the development time may be shortened.

  A desired resin pattern is formed by developing the exposed resin film using a developing solution. As the developer, an alkaline aqueous solution is preferable. Examples of the alkaline aqueous solution include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, and dimethylamine. An aqueous solution of a compound exhibiting alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferred. In some cases, a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, or dimethylacrylamide is added to these aqueous alkali solutions; 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 May be. After the development, it is preferable to perform a rinsing treatment with water. Here, rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

  By heating the resin pattern after development, the resin pattern is cured to obtain a cured pattern. The curing of the resin pattern is preferably performed by applying a temperature of 150 to 500 ° C. to the resin pattern to allow a thermal crosslinking reaction, an imide ring-closing reaction, an oxazole ring-closing reaction, and the like to proceed. Chemical resistance can be improved. Even if the maximum temperature of the heat treatment step for curing is 150 ° C. or more and 220 ° C. or less, the resin composition of the present invention is excellent in that the shape change of the cured pattern in the solder reflow step is small. Is preferably 150 ° C. or more and 220 ° C. or less. Further, by setting the maximum temperature of the heat treatment step lower than the glass transition temperature of the component (a-1) and higher than the glass transition temperature of the component (a-2), only the component (a-2) at the time of curing is obtained. Fluidity can be increased, which is preferable from the viewpoint of improving elongation. The heat treatment is preferably performed for 5 minutes to 5 hours while selecting a temperature and increasing the temperature stepwise, or while selecting a certain temperature range and continuously increasing the temperature. As an example, there is a method of performing heat treatment at 110 ° C., 160 ° C., and 200 ° C. for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 200 ° C. over 1 hour may be used. In such a heat treatment step, the temperature at which the temperature becomes the highest is defined as the maximum temperature.

  Next, a method for producing a resin sheet using the resin composition of the present invention and forming a cured pattern using the resin sheet will be described.

  The resin sheet of the present invention is obtained by molding the resin composition of the present invention into a sheet. However, when the resin composition contains a solvent, the resin sheet of the present invention is obtained by removing the solvent from the resin composition of the present invention. A resin sheet can be produced by applying the above-mentioned resin composition on a substrate. When the resin composition contains a solvent, the resin sheet is obtained by removing the solvent contained in the resin composition after coating on a substrate.

  As a substrate on which the resin composition is applied, a polyethylene terephthalate (PET) film or the like can be used. When it is necessary to peel and remove the PET film as the base material after bonding the resin sheet of the present invention to a supporting substrate such as a silicon wafer, a PET film having a surface coated with a release agent such as a silicone resin is used. It is preferable to use it as a base material because the resin sheet and the base material can be easily peeled off. The thickness of the substrate is not particularly limited, but is preferably in the range of 30 to 80 μm from the viewpoint of workability.

  Screen printing, spray coater, bar coater, blade coater, die coater, spin coater and the like can be used as a method of applying the resin composition onto the base material.

  Examples of the method for removing the organic solvent contained in the resin composition include heating with an oven or a hot plate, vacuum drying, and heating with electromagnetic waves such as infrared rays and microwaves. It is preferable to perform the treatment in an oven at 50 to 140 ° C. for 1 minute to 1 hour. Here, if the removal of the organic solvent is insufficient, the cured product obtained by the next curing treatment may be in an uncured state or may have poor thermomechanical properties.

  In order to protect the surface of the resin sheet from dust and the like in the atmosphere, a cover film may be attached to the surface of the resin sheet. When the thickness of the obtained resin sheet is smaller than a desired thickness, two or more resin sheets may be bonded to each other to obtain a desired thickness.

  When laminating the resin sheet prepared by the above method on another support substrate, even if using a laminating device such as a roll laminator or a vacuum laminator, using a rubber roller on the support substrate heated on a hot plate It may be pasted manually. After bonding the resin sheet to the support substrate, the substrate is peeled off after sufficiently cooling, whereby a laminate in which the resin sheet is laminated on the support substrate is obtained.

  A step of irradiating a resin sheet on a supporting substrate with actinic radiation through a mask having a desired pattern in the same manner as in the method of forming a cured pattern using the resin composition on the obtained laminate, which is necessary Baking after exposure after exposure to actinic radiation, forming a resin pattern by removing exposed or unexposed parts using a developing solution, and curing the resin pattern by applying a temperature of 150 to 500 ° C. Through these steps, a cured pattern can be obtained.

  The resin composition of the present invention can be suitably used for applications such as semiconductor electronic components and semiconductor devices. Specifically, the cured pattern formed using the resin composition of the present invention as described above is suitably used for applications such as an interlayer insulating film and a semiconductor protective film. In detail, a cured pattern composed of a cured product of the resin composition of the present invention is used as a passivation film of a semiconductor, a protective film of a semiconductor element, an interlayer insulating film of a multilayer wiring for high-density mounting, an insulating layer of an organic electroluminescent element, and the like. The arranged semiconductor electronic components or semiconductor devices are suitably used.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. First, the evaluation method in each example and comparative example will be described. In the evaluation of the resin composition (hereinafter, referred to as varnish), a varnish filtered in advance with a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) was used.

(1) Film Thickness The thickness of the resin film on the support substrate was measured using a light interference type film thickness measuring device (Lambda Ace VM-1030 manufactured by SCREEN Holdings Co., Ltd.). The refractive index of the resin film was measured as 1.629 for polyimide.

(2) Glass transition temperature of resin Using a differential scanning calorimeter (DSC-50, manufactured by Shimadzu Corporation), the resin powder was heated at a rate of 10 ° C / min under a nitrogen gas flow at a measurement temperature of 30 to 350 ° C. Measurement was performed to determine the glass transition temperature. In this case, the glass transition temperature is a midpoint glass transition temperature calculated from a change in calorific value by a method based on JIS K 7121-2012 “Method of measuring transition temperature of plastic”.

(3) Alkali dissolution rate The resin was dissolved in γ-butyrolactone (hereinafter referred to as GBL) so as to have a solid concentration of 35% by mass. This solution was applied on a 6-inch silicon wafer, and prebaked at 120 ° C. for 4 minutes using a hot plate to form a resin film having a thickness of 10 μm ± 0.5 μm. This was immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at a temperature of 23 ± 1 ° C. for 1 minute, and the thickness of the resin film dissolved per minute was determined from the change in the thickness of the resin film before and after immersion. And the alkali dissolution rate. When the resin film was completely dissolved in less than 1 minute, the time required for dissolution was measured, and the thickness of the resin film dissolved per minute was determined from this and the thickness of the resin film before immersion. This was taken as the alkali dissolution rate.

(4) Weight-average molecular weight The molecular weight of the resin was measured using a gel permeation chromatography (GPC) apparatus (Waters 2690-996, manufactured by Nippon Waters Co., Ltd.), and using N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as a developing solvent. And the weight average molecular weight (Mw) in terms of polystyrene was calculated.

(5) Ring closing ratio of imide ring (R _IM (%))
An imide or a resin having an imide precursor structure was dissolved in GBL to a concentration of 35% by mass. This solution was applied on a 4-inch silicon wafer by spin coating using a spinner (1H-DX manufactured by Mikasa Corporation), and then baked on a hot plate at 120 ° C. for 3 minutes to obtain a resin having a thickness of 4 to 5 μm. A film was prepared. This wafer with a resin film is divided into two parts, and one of them is divided by using a clean oven (CLH-21CD-S manufactured by Koyo Thermo System Co., Ltd.) at 140 ° C. for 30 minutes under a nitrogen stream (oxygen concentration 20 ppm or less), and then further. The temperature was raised and the mixture was cured at 320 ° C. for 1 hour to completely close the imide ring. The transmission infrared absorption spectra of the resin film before and after curing were each measured using an infrared spectrophotometer (FT-720 manufactured by Horiba, Ltd.), and the absorption peak of the imide structure due to polyimide (around 1780 cm ⁻¹ , 1377 cm ^-1 nearby) the presence on the confirmation, 1377 cm ^-1 peak intensity in the vicinity (before curing: X, after cure: Y) was determined. The peak intensity ratio obtained by dividing the peak intensity (X) by the peak intensity (Y) was calculated, and the content of the imide group in the polymer before the heat treatment, that is, the imide ring closure ratio was determined (R _IM = X / Y × 100 (%) )).

(6) Elongation at Break of Cured Film A varnish was applied on an 8-inch silicon wafer by a spin coating method using a coating and developing apparatus (ACT-8, manufactured by Tokyo Electron Limited). The coating was performed such that the thickness of the resin film after prebaking the obtained resin film at 120 ° C. for 3 minutes was 11 μm. Next, prebaking was performed on a hot plate at 120 ° C. for 3 minutes.

When a negative type varnish is used, the i-line, h-line, and g-line of a mercury lamp are applied to a silicon wafer with a resin film after prebaking using an exposure apparatus (Mask Aligner PEM-6M manufactured by Union Optical Co., Ltd.). A step of irradiating the entire surface of the wafer with an actinic ray having a wavelength including the g-ray at an exposure amount of 5,000 J / m ² was added.

  Using a clean oven CLH-21CD-S, the silicon wafer with the resin film is subjected to a heat treatment at 120 ° C. for 30 minutes and then at 180 ° C. for 1 hour under a nitrogen stream (oxygen concentration: 20 ppm or less). Was. Thereafter, when the temperature dropped to 50 ° C. or lower, the wafer was taken out and immersed in 45% by mass of hydrofluoric acid for 5 minutes to peel the cured film from the wafer. This cured film was cut into strips having a width of 1 cm and a length of 9 cm, and pulled at 23 ° C. at a tensile speed of 50 mm / min using a universal testing machine (Tensilon RTM-100 manufactured by Orientec) to elongate at break. The degree was measured. The measurement was performed on ten strips per sample, and the average value of the top five points was determined. Very good when the value of elongation at break is 15% or more (3), good when 5% or more and less than 15% (2), poor when less than 5% or when film strength is insufficient to measure ( 1).

(7) Stress Measurement of Cured Film A varnish was applied on an 8-inch silicon wafer by a spin coating method using a coating and developing apparatus (ACT-8 manufactured by Tokyo Electron Limited). The coating was performed such that the thickness of the resin film after prebaking the obtained resin film at 120 ° C. for 3 minutes was 11 μm. Next, prebaking was performed on a hot plate at 120 ° C. for 3 minutes.

When a negative type varnish is used, the i-line, h-line, and g-line of a mercury lamp are applied to a silicon wafer with a resin film after prebaking using an exposure apparatus (Mask Aligner PEM-6M manufactured by Union Optical Co., Ltd.). A step of irradiating the entire surface of the wafer with an actinic ray having a wavelength including the g-ray at an exposure amount of 5,000 J / m ² was added.

  Using a clean oven CLH-21CD-S, this silicon wafer with a resin film is heated at 120 ° C. for 30 minutes and then further heated at 210 ° C. for 1 hour under a nitrogen stream (oxygen concentration: 20 ppm or less). Was. The wafer with the cured film after the heat treatment was measured with a stress measurement device (FLX2908 manufactured by KLA Tencor). As a result, those having a stress value of 30 MPa or more were determined to be insufficient (1), those having a stress value of 20 MPa to less than 30 MPa were rated good (2), and those having a stress value of less than 20 MPa were rated extremely good (3).

(8) Resistance of Solder Reflow Step of Cured Pattern A varnish was applied on an 8-inch silicon wafer by a spin coating method using a coating and developing apparatus ACT-8. The coating was performed such that the thickness of the obtained resin film after prebaking at 120 ° C. for 3 minutes was 5 to 7 μm. Next, prebaking was performed on a hot plate at 120 ° C. for 3 minutes.

In the subsequent exposure step, when using a positive type varnish, the mask with the pattern cut is set on an exposure machine i-line stepper (NSR-2005i9C manufactured by Nikon Corporation), and the silicon wafer with the resin film after the pre-baking is set. It was exposed while changing the exposure amount in 10 mJ / cm ² steps in a range of 100~900mJ / cm ^2.

On the other hand, when a negative type varnish is used, a mask with a pattern cut is set in an exposure apparatus (a mask aligner PEM-6M manufactured by Union Optical Co., Ltd.), and a silicon wafer with a resin film after pre-baking is applied with a mercury lamp. An actinic ray having a wavelength including i-line, h-line, and g-line is exposed to g-line at an exposure amount of 5,000 J / m ^2. Bake for minutes.

  After the exposure, the developing process was performed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) (NMD-3 manufactured by Tokyo Ohka Kogyo Co., Ltd.) using an ACT-8 developing device. Then, a resin pattern was formed. In the developing step, paddle (time was adjusted appropriately) development was repeated twice under the condition of a developing solution discharge time of 5 seconds using a paddle method, followed by rinsing with pure water and then shaking off and drying.

  The resin-patterned silicon wafer after development is cured using a clean oven CLH-21CD-S under a nitrogen stream (oxygen concentration: 20 ppm or less) at 120 ° C. for 30 minutes, and then further heated to 180 ° C. for 1 hour. Then, the resin pattern was cured to obtain a cured pattern. Thereafter, when the temperature dropped to 50 ° C. or lower, the silicon wafer was taken out, and the thickness of the cured pattern was measured.

  The thickness of the resin film and the development paddle time were adjusted so that the thickness of the cured pattern after curing became 5 μm. Two silicon wafers were processed for each level, and one of them was baked on a hot plate at 250 ° C. for 5 minutes, then lowered from the hot plate and allowed to cool to room temperature, and this process was repeated three times. These silicon wafers with a cured pattern were cut with a diamond pen, and the cross section of a trench pattern having a width of 20 μm was observed using a scanning electron microscope (SEM, S-4800 manufactured by Hitachi High-Technologies Corporation). Check the exposure amount when the opening is 20.0 to 20.5 μm in the cured pattern without baking at 250 ° C., and observe the cross section of the corresponding part of the cured pattern with baking at 250 ° C. under the same exposure conditions, The two shapes were compared. It is very good that the pattern shape is not changed depending on the presence or absence of the 250 ° C. baking (4), and that the taper angle is reduced by less than 20 ° although the taper angle is reduced by the 250 ° C. baking ( 3) If the taper angle is reduced by baking at 250 ° C. and the amount of change of the taper angle is 20 ° or more, the pattern shape is remarkably changed by baking at 250 ° C. Those having an opening narrowed to 15 μm or less and those having cracks in a cured pattern by baking at 250 ° C. were regarded as extremely defective (1).

(9) Measurement of Solvent Content in Cured Film In the same manner as in (6), a silicon wafer with a cured film having a cured film thickness of 10 μm was prepared and cut into small pieces 1 cm long and 2 cm wide using a diamond pen. It was cut and used as a sample. Using a thermal desorption mass spectrometer (TPD-MS), the temperature was raised from room temperature to 300 ° C at a rate of 10 ° C / min under a helium air flow of 50 mL / min, and then maintained at 300 ° C for 60 minutes. The gas was analyzed. The peak was assigned from the m / z of the obtained measurement spectrum and the molecular weight of the solvent, and the amount of gas generated corresponding to the solvent was determined. Separately, a sample piece different from that used for the measurement was immersed in 45% by mass of hydrofluoric acid for 5 minutes to peel off the cured film from the wafer, and the weight of the cured film was measured. The solvent content in the cured film was calculated from the weight of the cured film having a length of 1 cm and a width of 2 cm and the amount of generated gas.

(10) Measurement of adhesion strength of cured film Adhesion strength measurement with copper was performed by the following method.

  First, copper was sputtered on a silicon wafer to prepare a sputtered substrate on which copper was formed with a thickness of 200 nm. A varnish was applied on the substrate by a spin coat method using a spinner (manufactured by Mikasa Corporation), and then baked at 120 ° C. for 3 minutes using a hot plate to prepare a prebaked film having a thickness of 5 to 7 μm.

In the subsequent exposure step, when using a positive type varnish, the mask with the pattern cut is set on an exposure machine i-line stepper (NSR-2005i9C manufactured by Nikon Corporation), and the silicon wafer with the resin film after the pre-baking is set. It was exposed while changing the exposure amount in 10 mJ / cm ² steps in a range of 100~900mJ / cm ^2.

On the other hand, when a negative type varnish is used, a mask with a pattern cut is set in an exposure apparatus (a mask aligner PEM-6M manufactured by Union Optical Co., Ltd.), and a silicon wafer with a resin film after pre-baking is applied with a mercury lamp. An actinic ray having a wavelength including i-line, h-line, and g-line was exposed to g-line at an exposure amount of 5,000 J / m ² , and after exposure, baked on a hot plate at 100 ° C. for 1 minute.

  After exposure, development is performed by a dip method using a tetramethylammonium aqueous solution (manufactured by Tama Chemical Industry Co., Ltd.) diluted with pure water to 0.8% by weight, and then rinsed with pure water to form a film having a thickness of 5%. A resin pattern of about 6 μm was obtained.

  The substrate with the resin pattern was cured using a clean oven CLH-21CD-S in a nitrogen stream (oxygen concentration: 20 ppm or less) at 120 ° C. for 30 minutes, and then further heated to 180 ° C. for 1 hour to cure the resin pattern. It was cured to obtain a cured pattern.

  Using a die shear tester (DAGE SERIES 4000 manufactured by Dage Japan Co., Ltd.), a rectangular convex pattern having a length of 30 μm and a width of 120 μm is sheared in a vertical direction at a test height of 1 μm and a range of 2.5 N. The operation of obtaining the maximum load at the time of peeling was performed for each of the five convex patterns of the same size, and the adhesion strength to the substrate was obtained from the average value and the pattern area. Regarding any of the substrates, adhesion strength of 100 MPa or more was rated as very good (3), 60 MPa or more and less than 100 MPa as good (2), and adhesion strength of less than 60 MPa as poor (1).

[Synthesis Example 1] Synthesis of diamine compound (HA) 164.8 g (0.45 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) was mixed with 900 mL of acetone and propylene. The oxide was dissolved in 156.8 g (2.7 mol) and cooled to -15 ° C. A solution in which 183.7 g (0.99 mol) of 3-nitrobenzoyl chloride was dissolved in 900 mL of acetone was added dropwise. After the completion of the dropwise addition, the reaction was carried out at −15 ° C. for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and dried at 50 ° C. in vacuo.

  270 g of the obtained solid was placed in a 3 L stainless steel autoclave, dispersed in 2400 mL of methyl cellosolve, and 5 g of 5% palladium-carbon was added. Here, hydrogen was introduced using a balloon, and the reduction reaction was performed at room temperature. Two hours later, the reaction was terminated when it was confirmed that the balloon did not deflate any more. After completion of the reaction, the mixture was filtered to remove the palladium compound as a catalyst, and concentrated by a rotary evaporator to obtain a diamine compound (hereinafter, referred to as HA) represented by the following formula.

[Synthesis Example 2] Synthesis of alkali-soluble polyimide resin (A-1) 102.55 g (0.28 mol) of BAHF, 2,4-diamino-6-phenyl-1,3,5-triazine under a stream of dry nitrogen. 23 g (0.06 mol), 4.97 g (0.02 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and 8.73 g (0.4%) of 4-aminophenol as a terminal blocking agent. 08 mol) was dissolved in 1200 g of NMP. To this, 124.09 g (0.4 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added together with 40 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, 40 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropic distillation of water and xylene was performed. After completion of the stirring, the solution was cooled to room temperature, and the solution was poured into 10 L of water to obtain a precipitate. The precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a powder of an alkali-soluble polyimide resin (A-1).

[Synthesis Example 3] Synthesis of alkali-soluble polyimide resin (A-2) 124.53 g (0.34 mol) of BAHF and 4.97 g (0.02) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were used as diamines. Mol), and a polymerization reaction was carried out in the same manner as in Synthesis Example 2 to obtain a powder of an alkali-soluble polyimide resin (A-2).

[Synthesis Example 4] Synthesis of alkali-soluble polyimide resin (A-3) BAHF 54.94 g (0.15 mol), 4,4'-diaminodiphenyl ether 4.00 g (0.02 mol), 2.49 g (0.01 mol) of 3-bis (3-aminopropyl) tetramethyldisiloxane and 4.37 g (0.04 mol) of 4-aminophenol as a terminal blocking agent were dissolved in 600 g of NMP. Here, 62.04 g (0.2 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added together with 20 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, 20 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. After the stirring, the solution was cooled to room temperature, and the solution was poured into 5 L of water to obtain a precipitate. The precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a powder of an alkali-soluble polyimide resin (A-3).

[Synthesis Example 5] Synthesis of alkali-soluble polyimide resin (A-4) The amount of diamine added was 32.96 g (0.09 mol) of BAHF and 34.40 g of Jeffamine D-400 (polyoxypropylene diamine manufactured by HUNTSMAN Co., Ltd.). (0.08 mol) and 2.49 g (0.01 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and the polymerization reaction was carried out in the same manner as in Synthesis Example 4 to obtain an alkali. A powder of the soluble polyimide resin (A-4) was obtained.

Synthesis Example 6 Synthesis of Alkali-Soluble Polyimide Resin (A-5) The amount of diamine added was 47.61 g (0.13 mol) of BAHF, 17.20 g (0.04 mol) of Jeffamine D-400, and 1,3- A polymerization reaction was carried out in the same manner as in Synthesis Example 4 except that bis (3-aminopropyl) tetramethyldisiloxane was changed to 2.49 g (0.01 mol), and a powder of an alkali-soluble polyimide resin (A-5) was obtained. Obtained.

Synthesis Example 7 Synthesis of Alkali-Soluble Polyimide Resin (A-6) BAHF 32.96 g (0.09 mol), 1,3-diaminopropane 5.19 g (0.07 mol) and 1,3-bis ( Synthesis Example 4 except that 3-aminopropyl) tetramethyldisiloxane was changed to 2.49 g (0.01 mol) and the amount of the terminal blocking agent was changed to 6.55 g (0.06 mol) of 4-aminophenol. A polymerization reaction was carried out in the same manner to obtain a powder of an alkali-soluble polyimide resin (A-6).

Synthesis Example 8 Synthesis of Alkali-Soluble Polyimide-Benzoxazole Precursor Resin (A-7) 62.04 g (0.2 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride under a stream of dry nitrogen. It was dissolved in 630 g of NMP. Here, 106.39 g (0.176 mol) of HA and 1.99 g (0.008 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added together with 20 g of NMP, and reacted at 20 ° C. for 1 hour. Then, the reaction was performed at 50 ° C. for 2 hours. Next, 3.49 g (0.032 mol) of 4-aminophenol was added as a terminal blocking agent together with 10 g of NMP, and reacted at 50 ° C. for 2 hours. Thereafter, a solution obtained by diluting 42.90 g (0.36 mol) of N, N-dimethylformamide dimethyl acetal with 80 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50 ° C. for 3 hours. After the stirring, the solution was cooled to room temperature, and the solution was poured into 5 L of water to obtain a precipitate. The precipitate was collected by filtration, washed three times with water, and dried in a vacuum drier at 80 ° C. for 20 hours to obtain a powder of an alkali-soluble polyimide-benzoxazole precursor resin (A-7).

Synthesis Example 9 Synthesis of Alkali-Soluble Polyamideimide Resin (A-8) Under dry nitrogen flow, 47.61 g (0.13 mol) of BAHF, 8.01 g (0.04 mol) of 4,4′-diaminodiphenyl ether, 1 2.49 g (0.01 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 4.37 g (0.04 mol) of 4-aminophenol as a terminal blocking agent were dissolved in 400 g of NMP. . To this, 42.11 g (0.2 mol) of trimellitic anhydride chloride was added together with 20 g of NMP, and the mixture was stirred while cooling so as not to reach 30 ° C. or more. Thereafter, the mixture was stirred at 30 ° C. for 4 hours to obtain an alkali-soluble polyamideimide precursor solution (solid content concentration: 20% by mass). This solution was poured into 5 L of water to obtain a precipitate. The precipitate was collected by filtration and washed three times with water to obtain a powder of an alkali-soluble polyamideimide precursor. This powder was dried at 150 ° C. for 5 hours, and then dried at 200 ° C. for 1 hour and at 220 ° C. for 2 hours to obtain a powder of an alkali-soluble polyamide-imide resin (A-8).

[Synthesis Example 10] Synthesis of alkali-soluble polyimide resin (A-9) Diamine was added in an amount of 51.28 g (0.14 mol) of BAHF, 12.90 g (0.03 mol) of Jeffamine D-400, and 1,3- A polymerization reaction was carried out in the same manner as in Synthesis Example 4 except that bis (3-aminopropyl) tetramethyldisiloxane was changed to 2.49 g (0.01 mol) to obtain a powder of an alkali-soluble polyimide resin (A-9). Obtained.

[Synthesis Example 11] Synthesis of polyhydroxystyrene resin (A-10) A mixed solution of 2,400 g of tetrahydrofuran and 2.56 g (0.04 mol) of sec-butyllithium as an initiator was added to pt-butoxystyrene 84. After adding .60 g (0.48 mol) and 12.50 g (0.12 mol) of styrene and polymerizing while stirring for 3 hours, 12.82 g (0.4 mol) of methanol was added to terminate the polymerization. Was done. The reaction mixture was then poured into 3 L of methanol to purify the polymer and the precipitated polymer was dried. The obtained polymer was dissolved in 1.6 L of acetone, 2 g of concentrated hydrochloric acid was added at 60 ° C., and the mixture was stirred for 7 hours, and pt-butoxystyrene was deprotected and converted to hydroxystyrene. After completion of the reaction, the solution was poured into water to precipitate a polymer, and the obtained precipitate was washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 24 hours. A polyhydroxystyrene resin (A-10) having a styrene residue of 25 mol% was obtained.

[Synthesis Example 12] Synthesis of polyhydroxystyrene resin (A-11) The amount of styrene added was changed to 74.03 g (0.42 mol) of pt-butoxystyrene and 18.75 g (0.18 mol) of styrene. A polymerization reaction was carried out in the same manner as in Synthesis Example 11 except that the reaction was carried out to obtain a polyhydroxystyrene resin (A-11) having 43 mol% of styrene residues with respect to 100 mol% of hydroxystyrene residues.

[Synthesis Example 13] Synthesis of quinonediazide compound (B-1) 42.45 g (0.1 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 5-naphthoquinonediazide sulfonyl chloride under a stream of dry nitrogen 75.23 g (0.28 mol) of NAC-5 (manufactured by Toyo Gosei Co., Ltd.) was dissolved in 1,000 g of 1,4-dioxane. While cooling the reaction vessel with ice, a mixture of 150 g of 1,4-dioxane and 30.36 g (0.3 mol) of triethylamine was added dropwise so that the inside of the system did not reach 35 ° C. or higher. After the dropwise addition, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was removed by filtration, and the filtrate was poured into 7 L of pure water to obtain a precipitate. This precipitate was collected by filtration, and further washed with 2 L of 1% by mass hydrochloric acid. Then, it was further washed twice with 5 L of pure water. The precipitate was dried with a vacuum dryer at 50 ° C. for 24 hours to obtain a quinonediazide compound (B-1) represented by the following formula. On average, 2.8 of the three substituents Q were 5-naphthoquinonediazidosulfonic acid esterified.

<Compounds used in other examples>
(B-2) As a photopolymerization initiator, "ADEKA ARKULS" (registered trademark) NCI-831 (trade name, manufactured by ADEKA Corporation, oxime ester-based photopolymerization initiator) (B-2) was used.

  (C) Thermal cross-linking agent HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) (C-1), NIKALAC MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) (C-2), TECHMORE VG3101L (trade name, manufactured by Printec Corporation) (C-3) is shown below.

  (D) a compound having a polymerizable unsaturated bond group, “Blemmer” (registered trademark) PDBE-200A (trade name, manufactured by NOF Corporation) (D-1), dipentaerythritol hexaacrylate (trade name DPHA, Nippon Kayaku Co., Ltd.) (D-2) is shown below.

  (E) The polymerization inhibitor, 2-t-butyl-1,4-hydroquinone (E-1) is shown below.

The alkali-soluble resins (A-1 to 11) obtained in Synthesis Examples 2 to 12 correspond to any of the component (a-1), the component (a-2), the component (a-3), and other resins. Table 1 shows the classification results, the glass transition temperature, the alkali dissolution rate, the weight average molecular weight, and the imide ring closure ratio (R _IM (%)) determined by the above method.

[Preparation of varnish]
Each component was placed in a polypropylene vial having a capacity of 32 mL with the composition shown in Tables 2 to 5, and mixed using a stirring and defoaming device (ARE-310, manufactured by Shinky Corporation) under the conditions of stirring for 10 minutes and defoaming for 1 minute. Thereafter, the mixture was filtered with a 1 μm filter made of polytetrafluoroethylene (manufactured by Sumitomo Electric Industries, Ltd.) to remove minute foreign matters, thereby producing varnishes (W-1 to 69). In the table, “GBL” represents γ-butyrolactone, “EL” represents ethyl lactate, “PGME” represents propylene glycol monomethyl ether, and “DAA” represents diacetone alcohol.

[Examples 1 to 25, Comparative Examples 1 to 15]
Tables 6 and 7 show the results of evaluation of elongation at break, stress measurement, and solder reflow process resistance using the positive varnish prepared as described above and the methods described above. The table also shows whether at least one of the component (a-2) and the other resin contains the structural unit of the general formula (2) or (3). In Table 7, "nd" indicates that measurement was impossible due to insufficient film strength.

  In each of Examples 1 to 25, the elongation at break is 5% or more, the stress value is less than 30 MPa, and the pattern shape in the solder reflow process resistance evaluation shows no change, The taper angle was reduced by less than 20 °, and good or extremely good results were obtained.

  On the other hand, in Comparative Examples 1 to 3 in which the content of the component (a-2) is more than 40 parts by mass with respect to 100 parts by mass of the component (a-1), the elongation at break and the stress value are good. And a decrease in the taper angle of 20 ° or more in the solder reflow process resistance evaluation. Comparative Examples 4 to 6 containing no component (a-2) have insufficient elongation at break, and Comparative Examples 7 to 11 containing no component (a-1) have extremely poor solder reflow process resistance. Was. Neither the component (a-1) nor the component (a-2), but instead, an alkali-soluble polyimide (A-) having a glass transition temperature intermediate between the components (a-1) and (a-2). In Comparative Examples 12 to 15 using 9), the stress value was good, but the elongation at break and the resistance to the solder reflow process were not compatible.

  With respect to the presence or absence of the structural unit of the general formula (2) or (3), for example, W-21 in which the component (a-2) does not include the structural unit of the general formula (2) or (3) , W-22, and W-23, the examples using W-19 and W-20 containing the structural units of general formulas (2) and (3) have higher stress. The result was low.

  Regarding the difference (Tg difference) between the glass transition temperatures of the component (a-1) and the component (a-2), for example, when W-14 (Tg difference: 184 ° C.) is used, W-24 (Tg (Difference: 205 ° C.), the elongation was higher. Examples using W-2 (Tg difference: 130 ° C.), W-20 (Tg difference: 141 ° C.), W-21 (Tg difference: 154 ° C.), and W-23 (Tg difference: 148 ° C.) As compared with the example using W-22 (Tg difference: 124 ° C.), the result was lower stress.

[Examples 26 to 39, Comparative Examples 16 to 30]
Tables 8 and 9 show the results of evaluation of elongation at break, stress measurement, and solder reflow process resistance using the negative varnish prepared as described above and the methods described above. The table also shows whether at least one of the component (a-2) and the other resin contains the structural unit of the general formula (2) or (3).

  In all of Examples 26 to 39, the elongation at break is 5% or more, the stress value is less than 30 MPa, and the pattern shape in the solder reflow process resistance evaluation shows no change, Good or extremely good results were obtained with a taper angle reduction of less than 20 °.

  On the other hand, in Comparative Examples 16 to 18 in which the content of the component (a-2) is more than 40 parts by mass relative to 100 parts by mass of the component (a-1), the elongation at break and the stress value are good. And a decrease in the taper angle of 20 ° or more in the solder reflow process resistance evaluation. Comparative Examples 19 to 22 containing no component (a-2) had high stress values, and Comparative Examples 23 to 27 not containing component (a-1) had poor or extremely poor solder reflow process resistance. Neither the component (a-1) nor the component (a-2), but instead, an alkali-soluble polyimide (A-) having a glass transition temperature intermediate between the components (a-1) and (a-2). Comparative Examples 28 to 30 using 9) resulted in insufficient solder reflow process resistance.

  With respect to the presence or absence of the structural unit of the general formula (2) or the general formula (3), for example, W-51 in which the component (a-2) does not include the structural unit of the general formula (2) or the general formula (3) , W-52, and W-53, the examples using W-49 and W-50 containing the structural units of general formulas (2) and (3) have higher stress. The result was low.

  Regarding the difference (Tg difference) between the glass transition temperatures of the component (a-1) and the component (a-2), for example, when W-49 (Tg difference: 184 ° C.) is used, W-54 (Tg difference) (Difference: 205 ° C.). Examples using W-41 (Tg difference: 130 ° C.), W-50 (Tg difference: 141 ° C.), W-51 (Tg difference: 154 ° C.), and W-53 (Tg difference: 148 ° C.) Stress was lower as compared with the example using W-52 (Tg difference: 124 ° C.).

[Examples 40 to 47]
Table 10 shows the results of measuring the amount of the solvent in the cured film by the above method using the varnish prepared as described above. In Table 10, “GBL” represents γ-butyrolactone, “EL” represents ethyl lactate, “PGME” represents propylene glycol monomethyl ether, and “DAA” represents diacetone alcohol.

  In the case where the solvent of the component (f) shown in Examples 40, 41, 44 and 45 was used, the content of the solvent in the cured film was larger than that in the case where other solvents were used, which was a preferable content. Was. In Table 6, in the examples using W-4 and W-10 corresponding to these, lower stress results were obtained than in the examples using W-11 and W-12. Also, in Table 8 above, the examples using W-42 and W-46 corresponding thereto obtained lower stress results than the examples using W-47 and W-48.

[Examples 48 to 64, Comparative Examples 31 to 47]
Tables 11 and 12 show the results of measuring the adhesion strength to copper using the varnish prepared as described above and the method described above. The table also shows whether the component (a-1) contains the structural unit of the general formula (4).

  In Table 11, Examples 48 to 52 and Comparative Example 31 using a resin containing the structural unit of the general formula (4) as the component (a-1) include a resin containing the structural unit of the general formula (4). In comparison with Examples 53 to 57 and Comparative Examples 32 to 39, the results of the adhesion strength to copper were better. Similarly, in Table 12, Examples 58 and 59 and Comparative Example 40 using the resin containing the structural unit of the general formula (4) as the component (a-1) include the structural unit of the general formula (4). Compared with Examples 60 to 64 and Comparative Examples 41 to 47 containing no resin, the results showed that the adhesion strength to copper was better.

Claims (15)

(A-1) an alkali-soluble polyimide resin having a glass transition temperature of 200 ° C. or more and 300 ° C. or less, (a-2) an alkali-soluble polyimide having an glass transition temperature of 50 ° C. or more and 150 ° C. or less, and an alkali-soluble polybenzoxazole; A resin composition containing at least one resin selected from an alkali-soluble polyamideimide, a precursor thereof, and a copolymer thereof, and (b) a photosensitizer,
A resin composition containing 10 parts by mass or more and 40 parts by mass or less of the component (a-2) based on 100 parts by mass of the component (a-1).   The resin composition according to claim 1, wherein a difference between a glass transition temperature of the component (a-1) and a glass transition temperature of the component (a-2) is 130C or more and 190C or less. The resin composition according to claim 1 or 2, wherein the component (a-2) has a structural unit represented by the general formula (1);

In the general formula (1), R ¹ represents a tetravalent organic group, R ² represents a divalent to hexavalent organic group, and p represents an integer of 0 to 4. The resin according to any one of claims 1 to 3, wherein the component (a-2) has one or more structural units selected from structural units represented by general formulas (2) and (3). Composition;

In the general formulas (2) and (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and are the same. R represents an integer of 4 to 20, and s represents an integer of 2 to 20. The resin composition according to any one of claims 1 to 4, wherein the component (a-1) has a structural unit represented by the general formula (4);

In the general formula (4), R ⁹ represents a tetravalent organic group, and Z represents one or more groups selected from the following group (Z-1);

R ¹⁰ represents a hydrogen atom, a hydroxyl group, a mercapto group or a monovalent hydrocarbon group having 1 to 10 carbon atoms.   The resin composition according to any one of claims 1 to 5, wherein the photosensitizer (b) is a quinonediazide compound (b-1).   The resin composition according to any one of claims 1 to 6, further comprising (a-3) a polyhydroxystyrene resin.   The said (b) photosensitizer is (b-2) a photoinitiator, and further contains (d) the compound which has a polymerizable unsaturated bond group, and (e) a polymerization inhibitor. 5. The resin composition according to any one of 5.   The resin composition according to claim 1, wherein a stress of a cured film obtained by thermally curing the resin composition at 210 ° C. is 10 MPa or more and 30 MPa or less.   The resin composition according to any one of claims 1 to 9, further comprising (f) a solvent having an ester structure.   A resin sheet comprising the resin composition according to claim 1.   A cured pattern comprising a cured product of the resin composition according to claim 1.   13. The cured pattern according to claim 12, wherein the curing pattern contains (f) a solvent having an ester structure in an amount of from 0.01% by mass to 0.1% by mass.   A method for producing a cured pattern using the resin composition according to any one of claims 1 to 10, wherein a maximum temperature of a step of heat-treating the developed resin pattern is a temperature of the component (a-1). A method for producing a cured pattern, which is lower than the glass transition temperature and higher than the glass transition temperature of the component (a-2).   A semiconductor electronic component or a semiconductor device on which the cured pattern according to claim 12 is arranged.