JP7131133B2 - resin composition - Google Patents

Description

The present invention relates to resin compositions. More particularly, the present invention relates to a photosensitive resin composition suitable for surface protective films of semiconductor elements, interlayer insulating films, insulating layers and planarizing layers of organic electroluminescence (organic EL) elements, and the like.

Conventionally, polyimide resins, polybenzoxazole resins, and the like, which are excellent in heat resistance and mechanical properties, have been widely used for surface protective films and interlayer insulating films of semiconductor elements of electronic devices (see Patent Document 1). When polyimide or polybenzoxazole is used as a surface protective film or an interlayer insulating film, one method for forming through holes and the like is etching using a positive photoresist. However, this method requires the steps of coating and stripping the photoresist, which poses a problem that the steps are complicated. Therefore, for the purpose of streamlining the work process, studies have been made on heat-resistant materials imparted with photosensitivity (see Patent Document 2).

On the other hand, the diameter of a silicon wafer, which is a substrate, is increasing year by year, and in recent years, fan-out wafer level packages, in which a fine rewiring structure is formed on a sealing resin substrate or the like, are expanding.

For this reason, by adding a copper discoloration inhibitor to the photosensitive resin, a photosensitive resin composition that suppresses copper corrosion of the underlying copper wiring (see Patent Document 3), polybenzoxazole having an aliphatic group, A photosensitive resin composition has been disclosed (see Patent Literature 4), in which adhesion to copper and high elongation can be obtained by adding a cyclic compound. In addition, studies have also been conducted to improve the elongation by adding an antioxidant and an epoxy resin to the polyimide resin (see Patent Document 5).

JP-A-11-199557 JP-A-11-24271 JP 2011-169980 A JP 2010-96927 A JP 2010-77382 A

However, the cured films of these resin compositions have problems in adhesiveness when forming barrier metals necessary for forming wiring and bumps and in etching properties of barrier methyl, resulting in poor uniformity of wiring width within the substrate. was there.

For this reason, thick metal wiring and copper posts are used for power applications that require a structure that can withstand high voltages, and for fan-out wafer level packages on glass substrates that aim to reduce costs by using large substrates. In the structure used, the application was difficult.

The present invention has been made in view of the problems associated with the prior art as described above, and provides a resin composition capable of obtaining a cured film with high elongation capable of forming wiring with excellent dimensional uniformity. is. The resin composition of the present invention can be suitably used for surface protective films of semiconductor elements, interlayer insulating films, insulating layers and planarizing layers of organic electroluminescence (organic EL) elements, and the like.

In order to solve the above problems, the present invention is characterized by the following configurations.
[1] A resin composition comprising (a) a resin and (c) a solvent,
(a) The resin has structural units represented by general formulas (1), (2) and (3), and the sum of the structural units represented by general formulas (1) to (3) 100 mol % of the resin composition having 5 mol % or more and less than 50 mol % of the structural unit represented by the general formula (2).

(In general formulas (1) to (3), Y ¹ to Y ³ each independently represent a divalent organic group, and X ¹ to X ³ each independently represent a tetravalent organic group. R ¹ is carbon Indicates a monovalent organic group of numbers 1 to 20. * indicates a chemical bond.)
[2] The resin composition of [1], wherein ^R1 in the general formula (2) is an alkyl group having a molecular weight of 100 or less.
[3] The diamine residue having a fluorine atom is 20 mol% or more and 80 mol% or less when the total amount of diamine residues in the resin (a) is 100 mol%. Resin composition.
[4] Furthermore, (b) contains a resin,
(b) resin has a structural unit represented by the following general formula (4), general formula (5) and general formula (6), and the structural unit represented by general formulas (4) to (6) The resin composition according to any one of [1] to [3], having 60 mol% or more and less than 98 mol% of the structural unit represented by the general formula (5) with a total of 100 mol%.

(In general formulas (4) to (6), Y ⁴ to Y ⁶ each independently represent a divalent organic group, and X ⁴ to X ⁶ each independently represent a tetravalent organic group. R ² is a carbon Indicates a monovalent organic group of numbers 1 to 20. * indicates a chemical bond.)
[5] The (a) resin and the (b) resin have alkali water solubility,
(b) The resin composition according to [4], wherein the dissolution rate of the resin in the alkaline aqueous solution is 0.5 to 2 times the dissolution rate of the (a) resin in the alkaline aqueous solution.
[6] The resin according to [4] or [5], wherein the resin (b) contains 25 parts by weight or more and 75 parts by weight or less with respect to the total amount of 100 parts by weight of the resin (a) and the resin (b). Composition.
[7] The resin composition according to any one of [1] to [6], further comprising (d) a photosensitive compound and (e) a compound having an alkoxymethyl group.
[8] The resin composition according to any one of [1] to [7], further comprising (f) an acrylic polymer surfactant.
[9] A step of applying the resin composition according to any one of [1] to [8] onto a substrate and then drying it to form a resin film, and partially eluting or removing the resin film with an alkaline aqueous solution. and developing, and a step of heat-treating the resin film that has undergone the developing step to obtain a cured film.
[10] The method for producing a cured film according to [9], further comprising the step of subjecting the cured film obtained by the heat treatment to a dry etching treatment.
[11] A cured film obtained by curing the resin composition according to [1] to [8].
[12] An organic EL display device in which the cured film according to [11] is disposed on either the flattening layer on the drive circuit or the insulating layer on the electrode.
[13] An electronic component or semiconductor device in which the cured film of [11] is arranged as an interlayer insulating film between rewirings.
[14] The electronic component or semiconductor device according to Claim 13, wherein the rewiring is a copper metal wiring, and the width of the copper metal wiring and the spacing between adjacent wirings are 5 µm or less.
[15] An electronic component or a semiconductor device, wherein the cured film according to claim 11 is disposed as an interlayer insulating film between rewirings on a sealing resin substrate on which a silicon chip is disposed.
[16] A step of disposing the cured film, the silicon chip, and the sealing resin according to claim 11 as an interlayer insulating film between rewirings on the support substrate on which the temporary attachment material is disposed;
After that, including a step of peeling off the support substrate on which the temporary attachment material is arranged,
Methods of manufacturing electronic components or semiconductor devices.

Provided is a resin composition capable of obtaining a cured film with high elongation capable of forming wiring excellent in dimensional uniformity.

FIG. 3 is a schematic diagram showing an enlarged cross-section of a pad portion of a semiconductor device having bumps; It is the figure which showed the detailed manufacturing method of the semiconductor device which has a bump. 1 is an enlarged cross-sectional view of a structure called a fan-out wafer level package (fan-out WLP) showing an embodiment of the present invention; FIG. 1 is a cross-sectional view of a coil component of an inductor device showing an embodiment of the present invention; FIG. It is the figure which showed the semiconductor device manufacturing method in RDL first. 1 is a cross-sectional view of an example of a TFT substrate; FIG.

The present invention will be described in detail below.
The present invention is a resin composition comprising (a) a resin and (c) a solvent,
(a) the resin has structural units represented by general formulas (1), (2) and (3);
Assuming that the total of the structural units represented by the general formulas (1) to (3) is 100 mol%,
It is a resin composition having 5 mol % or more and less than 50 mol % of structural units represented by the general formula (2).

In general formulas (1) to (3), Y ¹ to Y ³ each independently represent a divalent organic group, and X ¹ to X ³ each independently represent a tetravalent organic group. R ¹ represents a monovalent organic group having 1 to 20 carbon atoms. * indicates a chemical bond.

The structure represented by general formula (1) is polyamic acid, and the structure represented by general formula (2) is polyamic acid ester, both of which mean a polyimide precursor structure. General formula (3) means a polyimide structure in which they are ring-closed. Y ¹ to Y ³ are diamine residues, and X ¹ to X ³ are acid dianhydride or tetracarboxylic acid residues. (a) The resin may be copolymerized with structures other than those represented by the general formulas (1) to (3). Specifically, polyamide, polybenzoxazole, polybenzimidazole, polybenzothiazole, Precursors thereof are included.

By having 5 mol % or more and less than 50 mol % of the structural unit represented by the general formula (2), it is possible to obtain a highly elongating cured film capable of forming wiring with excellent dimensional uniformity. This is because (a) the resin has a polyimide structure, a polyamic acid structure, and a polyamic acid ester structure, and by having a polyamic acid ester structure within the scope of the present invention, the resin composition has moderate phase separation and high wettability. It is because it has a nature. As a result, it is presumed that a cured film having high surface energy, fine surface roughness and high wettability uniformly in the plane can be obtained. From this, it is considered that the adhesiveness of the barrier metal due to the anchor effect and the uniform wet etching property within the surface of the barrier metal can be obtained, and wiring excellent in dimensional uniformity can be formed.

Further, within the scope of the present invention, having a structural unit represented by the general formula (2) reduces the molecular weight due to depolymerization of the polyimide precursor during heat curing and aggregation of the polyamic acid ester due to excessive phase separation. Since it does not occur, high elongation can be obtained. The ratio of the structural unit represented by the general formula (2) is 5 mol or more and less than 50 mol%, with the total of the structural units represented by the general formulas (1) to (3) being 100 mol%. It is preferably 12 mol % or more, more preferably 15 mol % or more, from the viewpoint of suppressing a decrease in molecular weight due to cleavage of the polyimide precursor during thermosetting. Moreover, from the viewpoint of suppressing aggregation of the polyamic acid ester due to excessive phase separation, it is preferably less than 40 mol %, more preferably less than 35 mol %.

Further, the ratio of the structural unit represented by the general formula (1) is preferably more than 40 mol% and less than 95 mol%, and the ratio of the structural unit represented by (3) is more than 0 mol% and 10 Less than mole % is preferred. These ranges are preferable because a cured film with high elongation that can form wiring with excellent dimensional uniformity can be obtained.

R ¹ in the general formula (2) is preferably an alkyl group having a molecular weight of 100 or less. By using a low-molecular-weight and easily volatile alkyl group, excessive phase separation does not occur in the resin composition, and the shrinkage rate during curing is small, so wiring with excellent dimensional uniformity can be formed, which is preferable. Specifically, in general formula (2) above, R ¹ is preferably a methyl group, an ethyl group, or a butyl group.

Assuming that the total amount of diamine residues in the resin (a) is 100 mol %, the content of diamine residues having a fluorine atom is preferably 20 to 80 mol %.
By partially having a diamine residue having a bulky fluorine atom, the rigidity of the cured film caused by excessive packing between resin chains is alleviated, and a cured film with high elongation is obtained. Preferably, 40 mol % or more is more preferable. Moreover, since a cured film with high elongation can be obtained by obtaining an appropriate interaction between resin chains, it is preferably 80 mol % or less, more preferably 60 mol % or less.
Partially containing a diamine residue having a bulky fluorine atom is preferable because the rigidification of the cured film caused by excessive packing is suppressed, and a cured film with high elongation can be obtained.

Specific examples of the diamine residue having a fluorine atom include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2′-ditrifluoromethyl-5,5′-dihydroxyl-4,4 '-diaminobiphenyl, 2'-bis (trifluoromethyl)-5,5'-dihydroxybenzidine, 2,2'-bis (trifluoromethyl)-4,4'-diaminobiphenyl, bis (3-amino- 4-hydroxyphenyl)sulfone, 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-4-hydroxyphenyl)fluorene, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 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, ethylenediamine, 1,3-diaminopropane, 2-methyl-1 ,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino Octane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl) Cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,2-bis(2-aminoethoxy)ethane , KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE -600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, HT-1100, HT-1700, (manufactured by Co., Ltd.) in which some of the hydrogen atoms of aromatic rings and hydrocarbons are substituted with fluoroalkyl groups, and diamines having the structures shown below, but are not limited to these. . Moreover, you may use combining these 2 or more types of diamine components.

Among these, 2,2′-ditrifluoromethyl-5,5′-dihydroxyl-4,4′-diaminobiphenyl, 2′-bis(trifluoromethyl)-5,5′-dihydroxybenzidine, 2,2′ -Bis(trifluoromethyl)-4,4'-diaminobiphenyl is more preferable because it provides high strength and elongation due to proper packing.

Other diamine residues in the resin (a) include bis(3-amino-4-hydroxyphenyl)sulfone, 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-4-hydroxyphenyl)fluorene, 3,4′-diaminodiphenyl ether, 4 , 4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfide, 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-amino phenoxy)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, ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane , 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1 ,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl) ) cyclohexane, 4,4′-methylenebis(cyclohexy leamine), 4,4′-methylenebis(2-methylcyclohexylamine), 1,2-bis(2-aminoethoxy)ethane, KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP- 2005, RP-2009, RT-1000, HE-1000, HT-1100, HT-1700 (all trade names, manufactured by HUNTSMAN Co., Ltd.), and some of the hydrogen atoms of these aromatic rings and hydrocarbons , alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms, compounds substituted with halogen atoms, diamines having the structures shown below, and the like, but are not limited thereto. Moreover, you may use combining these 2 or more types of diamine components.

Here, each n is independently an integer of 1-10, preferably 1-5.

Furthermore, in order to improve adhesion to the silicon substrate, the (a) resin may copolymerize a structure having both a siloxane structure and an aliphatic structure. Specific examples of the diamine component include copolymers of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-amino-phenyl)octamethylpentasiloxane, and the like in an amount of 1 to 10 mol %.

Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4'-diaminobiphenyl have fluorine atoms. The combined use with a diamine is preferable because a cured film with high elongation can be obtained by obtaining an appropriate interaction between resin chains.

In general formulas (1) to (3), X ¹ to X ³ are acid dianhydrides or tetracarboxylic acid residues, specifically pyromellitic dianhydride, 3,3′,4 ,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3, 3′,4,4′-benzophenonetetracarboxylic dianhydride, 2,2′,3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3 -dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) Sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl) Fluoric dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluoric dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3 ,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, etc. aromatic tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3 ,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid di anhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3, 5,6-tricarboxy-2-norbor Nanacetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione and Acid dianhydrides having the structures shown in the following formulas, compounds in which some of the hydrogen atoms of these aromatic rings or hydrocarbons are substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, etc. can include, but are not limited to.

Among these, bis(3,4-dicarboxyphenyl) ether dianhydride, pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′ ,4'-biphenyltetracarboxylic dianhydride and 2,2',3,3'-biphenyltetracarboxylic dianhydride are more preferred because they provide high strength and elongation.

The resin composition of the present invention preferably contains (b) a resin. (b) The resin has structural units represented by general formulas (4), (5) and (6), and the sum of the structural units represented by general formulas (4) to (6) is 100 mol %, and the structural unit represented by the general formula (5) is preferably contained in an amount of 60 mol % or more and less than 98 mol %.

In general formulas (4) to (6), Y ⁴ to Y ⁶ each independently represent a divalent organic group, and X ⁴ to X ⁶ each independently represent a tetravalent organic group. R ¹ represents a monovalent organic group having 1 to 20 carbon atoms.

The structure represented by general formula (4) is polyamic acid, and the structure represented by general formula (5) is polyamic acid ester, both of which mean a polyimide precursor structure. General formula (6) means a polyimide structure in which they are ring-closed. Y ¹ to Y ³ are diamine residues, and X ¹ to X ³ are acid dianhydride or tetracarboxylic acid residues. (b) The resin may be copolymerized with structures other than those represented by general formulas (4) to (6). Specifically, polyamide, polybenzoxazole, polybenzimidazole, polybenzothiazole, Precursors thereof are included.

(b) Inclusion of a resin is preferable because the adhesion of the barrier metal can be improved. This is probably because the (a) resin and the (b) resin have similar structures with different esterification rates, so that the resin composition has moderate phase separation and a slight surface roughness can be obtained.

The ratio of the structural unit represented by the general formula (5) is preferably 60 mol% or more, more preferably 65 mol% or more, and even more preferably 70 mol% or more, from the viewpoint of obtaining appropriate phase separation. From the viewpoint of not causing significant phase separation, it is preferably less than 98 mol%, more preferably less than 90 mol%, and even more preferably less than 85 mol%.

Further, the ratio of the structural unit represented by the general formula (4) is preferably 2 mol% or more and less than 35 mol%, and the ratio of the structural unit represented by (6) is more than 0 mol% and 35 mol%. Less than is preferred. If the resin (b) is within these ranges, it is possible to form wiring with excellent dimensional uniformity while maintaining the elongation obtained by the resin (a), which is preferable.

In general formulas (4) to (6), Y ⁴ to Y ⁶ are diamine residues, specifically bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4 -hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino -4-hydroxy)biphenyl, 2,2′-ditrifluoromethyl-5,5′-dihydroxyl-4,4′-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, 2,2′- bis(trifluoromethyl)-5,5'-dihydroxybenzidine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4 '-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 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'-diaminobiphenyl, Ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diamino Hexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1 , 11-diaminoundecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis (Aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,2-bis(2- aminoethoxy)ethane, KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, THF-100, THF-140, THF -170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, HT-1100, HT-1700 (manufactured by HUNTSMAN Co., Ltd.), and compounds in which some of the hydrogen atoms of these aromatic rings or hydrocarbons are substituted with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, etc., and the following and the like, but are not limited to these. Moreover, you may use combining these 2 or more types of diamine components.

Here, each n is independently an integer of 1-10, preferably 1-5.

Among these, it is preferable to use a diamine having an amide structure. When the (b) resin is derived from a diamine residue having an amide structure, the surface energy of the (a) resin is improved, which is preferable because the adhesion to the barrier metal can be improved.

Furthermore, in order to improve adhesion to the silicon substrate, the heat-resistant resin of the present invention may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include copolymers of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-amino-phenyl)octamethylpentasiloxane, and the like in an amount of 1 to 10 mol %.

In general formulas (4) to (6), X ⁴ to X ⁶ are acid dianhydrides or tetracarboxylic acid residues, specifically pyromellitic dianhydride, 3,3′,4 ,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3, 3′,4,4′-benzophenonetetracarboxylic dianhydride, 2,2′,3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3 -dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) Sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl) Fluoric dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluoric dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3 ,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, etc. aromatic tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3 ,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid di anhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3, 5,6-tricarboxy-2-norbor Nanacetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione and Acid dianhydrides having the structures shown in the following formulas, compounds in which some of the hydrogen atoms of these aromatic rings or hydrocarbons are substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, etc. can include, but are not limited to.

Further, the (a) resin and the (b) resin have alkaline water solubility, and the dissolution rate of the (b) resin in the alkaline aqueous solution is 0.5 of the dissolution rate of the (a) resin in the alkaline aqueous solution. It is preferably more than twice and less than twice. Since the dissolution rates of (a) resin and (b) resin are close to each other, it is possible to improve uniform wettability in the plane with minute surface roughness after the development process with an alkaline aqueous solution. It is preferable because it is possible to form excellent wiring. The dissolution rate is preferably 0.5 times or more, more preferably 0.7 times or more, from the viewpoint of obtaining minute surface roughness after the developing step with an alkaline aqueous solution. In addition, the dissolution rate is preferably 2 times or less, more preferably 1.6 times or less, because uniform wettability can be improved in the plane.
The rate of dissolution in an alkaline aqueous solution is determined by (a) the diamine having fluorine and rigid diamines such as m-phenylenediamine, p-phenylenediamine, and 3,3′-dimethyl-4,4′-diaminobiphenyl in the resin. The above range can be achieved by using them together and setting the ratio of general formula (5) to 70 mol % or more and less than 90 mol % in the resin (b).

Further, it is preferable that the resin (b) is contained in an amount of 25 parts by weight or more and 75 parts by weight or less with respect to 100 parts by weight of the total amount of the resin (a) and the resin (b). 40 parts by weight or more is more preferable from the viewpoint of obtaining higher elongation than the (a) resin alone due to the mutual network structure. Moreover, from the viewpoint of obtaining a higher elongation than the (a) resin alone due to the mutual network structure, it is more preferably less than 60 parts by weight. When the content ratio of (b) the resin is within the above range, a mutual network structure is obtained, and a higher elongation than that of the (a) resin alone is obtained, which is preferable.

The (a) resin and (b) resin may be capped with other end capping agents such as monoamines, monocarboxylic acids, acid anhydrides and monoactive ester compounds.

The introduction ratio of the terminal blocking agent is preferably 0.00 to the total diamine component in order to prevent the weight average molecular weight of the resin (a) or the resin (b) from increasing and the solubility in an alkaline solution from decreasing. It is 1 mol % or more, more preferably 5 mol % or more. Also, in order to suppress deterioration of the mechanical properties of the cured film obtained due to a decrease in the weight average molecular weight of the resin (a) or the resin (b), it is preferably 60 mol% or less, more preferably 50 mol% or less. is. Also, a plurality of terminal blocking agents may be reacted to introduce a plurality of different terminal groups.

Specific examples of monoamines as terminal blockers include M-600, M-1000, M-2005, and M-2070 (trade names, manufactured by HUNTSMAN Co., Ltd.), aniline, 2-ethynylaniline, and 3-ethynyl. Aniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-amino naphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid , 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2- Aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be used. You may use 2 or more types of these.

Monocarboxylic acids and monoactive ester compounds as terminal blockers include 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy -6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4 -Monocarboxylic acids such as carboxybenzenesulfonic acid and active ester compounds in which the carboxyl group is esterified, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, etc. acid anhydrides, dicarboxylic acids phthalic acid, maleic acid, nadic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, and tricarboxylic acids trimellitic acid, trimesin acid, diphenyl ether tricarboxylic acid, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene Active ester compounds obtained by reacting one carboxyl group of dicarboxylic acids such as N-hydroxybenzotriazole, imidazole, N-hydroxy-5-norbornene-2,3-dicarboximide, aromatic rings and carbonization thereof A compound in which part of the hydrogen atoms of hydrogen is substituted with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like can be used. You may use 2 or more types of these.

Structures in which the resin terminals and resin side chains of (a) resin and (b) resin are blocked with imide precursors such as amic acid or amic acid esters and imides are phthalic anhydride, maleic anhydride, and nadic anhydride. , cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride and other acid anhydrides, dicarboxylic acids phthalic acid, maleic acid, nadic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3 - the dicarboxylic and tricarboxylic acids trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, One carboxyl group of dicarboxylic acids such as 1,7-dicarboxynaphthalene and 2,6-dicarboxynaphthalene and N-hydroxybenzotriazole, imidazole, and N-hydroxy-5-norbornene-2,3-dicarboximide It can be obtained from an active ester compound obtained by reaction, a compound obtained by substituting a part of the hydrogen atoms of these aromatic rings or hydrocarbons with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, etc. It is not limited to these.

The terminal blocking agent used for terminal blocking of (a) resin and (b) resin can be detected by the following method. For example, the (a) resin or (b) resin into which a terminal blocker has been introduced is dissolved in an acid solution such as nitric acid or aqua regia, decomposed into the amine component and the acid anhydride component, which are structural units, and The terminal blocking agent can be detected by gas chromatography (GC) or NMR analysis. Apart from this, the (a) resin or (b) resin into which the end blocking agent has been introduced can also be directly measured by pyrolysis gas chromatography (PGC), infrared spectrum, and ¹³ C-NMR spectrum. can do.

(a) resin and (b) resin are not particularly limited and can be polymerized by a known method. For example, it can be synthesized by the following method.

First, an acid dianhydride, a diamine compound, and optionally other copolymerization components are dissolved in an organic solvent at room temperature, optionally at elevated temperature, and then polymerized by heating. From the viewpoint of the stability of the solution during the reaction, it is preferable that the diamine compound having high solubility be dissolved first. Thereafter, a terminal blocking agent is added and reacted to obtain a resin having a polyamic acid structure and a polyimide structure. In some cases, the imidization rate may be adjusted by adding an imidization accelerator such as pyridine and stirring at 40 to 150°C.

After that, an esterifying agent is added to esterify a part of the carboxylic acid sites of the polyamic acid structure, whereby a resin having a polyamic acid structure, a polyamic acid ester structure and a polyimide structure can be obtained. As the esterifying agent, a method using a catalyst such as triethylamine or dimethylaminopyridine and a compound having an alcohol group such as 2-hydroxyethyl methacrylate, methanol or ethanol, or a method using N,N-dialkylformamide dimethylacetal without using a catalyst. There is (a) In order to obtain a resin, it is preferable to add 1 mol % or more and less than 120 mol % of an esterification agent, with the total acid dianhydride being 100 mol %. Further, in order to obtain the resin (b), it is preferable to add 150 mol % or more and 250 mol % or less of the esterification agent, with the total acid dianhydride being 100 mol %.

In the present invention, the resin obtained by the above method may be mixed with other additives to form a resin composition, but the resin composition may be prepared by adding a large amount of water or a mixture of methanol and water, etc., and precipitating, filtering and drying. However, it is preferable to add other additives after isolating the resin. The drying temperature is preferably 40-100°C, more preferably 50-80°C. By this operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and the film properties after thermal curing can be improved.

The molar ratios of the structures represented by the general formulas (1) to (3) and the general formulas (4) to (6) in the present invention are obtained using a nuclear magnetic resonance spectrometer (NMR). It can be confirmed by a method for detecting peaks of a polyamide structure, an imide precursor structure, or an imide structure in a resin composition or a cured film. If the molar ratio of the monomers used in the polymerization is known, it can be calculated from the blending molar ratio of the monomers. is preferably within the range of Within this range, moderate solubility in an alkaline developer can be obtained, so a high contrast between exposed and unexposed areas can be obtained, and a desired pattern can be formed. From the viewpoint of solubility in an alkaline developer, it is more preferably 100,000 or less, and more preferably 50,000 or less. Moreover, from the aspect of elongation improvement, 1.0000 or more is preferable. Here, the molecular weight can be obtained by measuring by gel permeation chromatography (GPC) and converting from a standard polystyrene calibration curve.

The imidization ratios of (a) resin and (b) resin can be obtained by the following method. First, the infrared absorption spectrum of the polymer is measured to confirm the presence of absorption peaks (near 1780 cm ⁻¹ and 1377 cm ⁻¹ ) of the imide structure due to polyimide. Next, the polymer was heat-treated at 350 ° C. for ¹ hour, and the infrared absorption spectrum was measured as a sample with an imidization rate of 100%. The imidization ratio is determined by calculating the content of imide groups in the pre-resin.

Examples of organic solvents used for polymerization of (a) resin and (b) resin include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2- Imidazolidinone, N,N'-dimethylpropylene urea, N,N-dimethylisobutyric acid amide, amides of methoxy-N,N-dimethylpropionamide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ- Cyclic esters such as caprolactone, ε-caprolactone and α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone , 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethylsulfoxide, tetrahydrofuran, dimethylsulfoxide, propylene glycol monomethyl ether acetate, ethyl lactate, and the like.

The resin composition of the present invention may contain other resins in addition to the resins (a) and (b). Specifically, polyimide, polyamide, polybenzoxazole, polybenzimidazole, polybenzothiazole, precursors thereof, copolymers thereof, polyamideimide resin, siloxane resin, acrylic polymer copolymerized with acrylic acid, novolac Examples include resins, resol resins, polyhydroxystyrene resins, modified products obtained by introducing cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups, and copolymers thereof.

The resin composition of the present invention contains (c) a solvent. Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2 - polar aprotic solvents such as imidazolidinone, N,N'-dimethylpropylene urea, N,N-dimethylisobutyamide, methoxy-N,N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene ethers such as glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. You may contain 2 or more types of these.

The content of the solvent is preferably 100 parts by weight or more per 100 parts by weight of the resin (a) in order to dissolve the (a) resin. It is preferably contained in parts by weight or less.

The resin composition of the present invention preferably further contains (d) a photosensitive compound and (e) a compound having an alkoxymethyl group.
(d) A resin composition containing a photoacid generator as a photosensitive compound can be used as a positive photosensitive resin composition (positive photosensitive varnish). Moreover, the resin composition containing a photopolymerizable compound and an initiator as the (d) photosensitive compound can be used as a negative photosensitive resin composition (negative photosensitive varnish).

By using (a) the resin and (d) the photosensitive compound in combination, it is possible to improve the uniform wettability in the plane even with minute surface roughness, so that it is possible to form wiring excellent in dimensional uniformity, which is preferable.

Since the positive photosensitive composition is superior to the negative photosensitive resin composition in resolution, it is suitable for use in forming fine processed patterns.

A quinonediazide compound is preferably contained as the photoacid generator of the positive photosensitive resin composition.

The quinonediazide compound includes polyhydroxy compounds in which quinonediazide sulfonic acid is ester-bonded, polyamino compounds in which quinonediazide sulfonic acid is sulfonamide-bonded, and polyhydroxypolyamino compounds in which quinonediazide sulfonic acid is ester-bonded and/or sulfonamide. and the like. Although not all the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may be substituted with quinonediazide, it is preferred that 40 mol % or more of all functional groups on average be substituted with quinonediazide. . By containing such a quinonediazide compound, the positive photosensitive resin composition is sensitive to i-line (wavelength: 365 nm), h-line (wavelength: 405 nm), and g-line (wavelength: 436 nm) of a mercury lamp, which are general UV rays. can be obtained.

Specific examples of polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP -IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade names, manufactured by Honshu Chemical Industry), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade names, manufactured by Asahi Organic Chemical Industry), 2 ,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylenebisphenol, BisP-AP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), novolac resin, etc., but not limited thereto.

Specific examples of polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4 '-diaminodiphenyl sulfide and the like, but are not limited thereto.

Specific examples of polyhydroxypolyamino compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3′-dihydroxybenzidine, but are not limited to these. .

Among these, the quinonediazide compound preferably contains a phenolic compound and an ester with a 4-naphthoquinonediazide sulfonyl group. This makes it possible to obtain high sensitivity and higher resolution in i-line exposure.

The content of the quinonediazide compound contained in the resin composition of the present invention is preferably 1 part by weight or more, more preferably 10 parts by weight or more, and preferably 50 parts by weight or less with respect to 100 parts by weight of all resins in the resin composition. , 40 parts by weight or less. By setting the content of the quinonediazide compound within this range, the difference in the dissolution rate in the developer between the exposed and unexposed areas increases, making it possible to achieve higher sensitivity, and the residue generated when the content is high. It is preferable because it does not show Furthermore, a sensitizer or the like may be added as necessary.

When the resin composition of the present invention contains a photopolymerizable compound, it becomes a resin composition having negative photosensitivity that is rendered insoluble by light. A photopolymerizable compound contains a polymerizable unsaturated functional group. Examples of the polymerizable unsaturated functional group include unsaturated double bond functional groups such as vinyl group, allyl group, acryloyl group and methacryloyl group, and unsaturated triple bond functional groups such as propargyl. Among these, groups selected from conjugated vinyl groups, acryloyl groups and methacryloyl groups are preferred from the standpoint of polymerizability.

The number of functional groups contained is preferably 1 to 4 from the viewpoint of stability, and each group may not be the same. The photopolymerizable compound preferably has a number average molecular weight of 30-800. If the number average molecular weight is in the range of 30 to 800, the compatibility with the polyamide is good and the stability of the resin composition solution is good.

Preferred photopolymerizable compounds include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylol. Propane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2 - vinyl naphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate , neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate methacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate , 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, N-methylol acrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpi Peridinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide-modified bisphenol A diacrylate , ethylene oxide-modified bisphenol A dimethacrylate, N-vinylpyrrolidone, N-vinylcaprolactam and the like. These are used alone or in combination of two or more.

Among these, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, and pentaerythritol tri Acrylates, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 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, ethylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified bisphenol A dimethacrylate, N-vinylpyrrolidone, N-vinylcaprolactam and the like.

The content of the photopolymerizable compound in the resin composition of the present invention is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the total resin, and is preferably 5 to 150 parts by weight from the viewpoint of compatibility. more preferred. By setting the content of the photopolymerizable compound to 5 parts by weight or more, it is possible to prevent elution of the exposed area during development and obtain a resin composition having a high residual film ratio after development. Also, by setting the content of the photopolymerizable compound to 200 parts by weight or less, whitening of the film during film formation can be suppressed.
Furthermore, the resin composition of the present invention preferably contains (e) a compound having an alkoxymethyl group.
Alkoxymethyl group-containing compounds include, but are not limited to, the following compounds.

It is preferable to use (a) the resin and (e) the compound having an alkoxymethyl group in combination, because it is possible to improve the adhesion of the barrier metal by improving minute surface roughness.

(e) The amount of the compound having an alkoxymethyl group added is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, relative to 100 parts by weight of the total resin. Moreover, 60 parts by weight or less is preferable, and 40 parts by weight or less is more preferable. Within the above range, since the cross-linking density by the thermal cross-linking agent is high, the chemical resistance of the cured film can be improved, and since sufficient flexibility can be obtained, high elongation can be obtained, which is preferable.

Moreover, the resin composition of the present invention may contain a thermal cross-linking agent having an epoxy group, acrylic group, oxetane group or methylol group in order to improve chemical resistance and heat resistance.
Among these, it is preferable to contain a thermal cross-linking agent having a structural unit represented below, since it is possible to further improve the elongation and reduce the stress.

In the formula, n is an integer of 1-5 and m is an integer of 1-20.
Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and elongation improvement.

In addition, if necessary, a low-molecular-weight compound having a phenolic hydroxyl group other than the above may be contained within a range that does not reduce the residual film shrinkage ratio after curing. Thereby, development time can be shortened.

These compounds include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP , BIR-BIPC-F (these are trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.), and the like. You may contain 2 or more types of these.

The content of the low-molecular-weight compound having a phenolic hydroxyl group is preferably 1 to 40 parts by weight per 100 parts by weight of the total resin.

The resin composition of the present invention contains surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, for the purpose of improving wettability with a substrate. , tetrahydrofuran, dioxane, and other ethers.

Among these, the resin composition of the present invention preferably contains (f) an acrylic polymer surfactant. (f) The acrylic polymer surfactant has low compatibility with the (a) resin, so that it tends to be unevenly distributed on the surface of the cured film, and as a result, the wettability of the cured film can be improved. Therefore, it is possible to wet-etch the barrier metal uniformly in the plane, and wiring excellent in dimensional uniformity can be formed, which is preferable.

Specific examples include Polyflow manufactured by Kyoeisha Chemical Co., Ltd., and the like. (f) The acrylic polymer surfactant is preferably contained in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the resin (a).

Further, as other surfactants, Sumitomo 3M Co., Ltd. "Florado" (registered trademark), D
Fluorinated surfactants such as "Megafac" (registered trademark) manufactured by IC Co., Ltd., "Sulfuron" (registered trademark) manufactured by Asahi Glass Co., Ltd., KP341 manufactured by Shin-Etsu Chemical Co., Ltd., Chisso Corporation DBE manufactured by Kyoeisha Chemical Co., Ltd., "Polyflow" (registered trademark) and "Granol" (registered trademark) manufactured by Kyoeisha Chemical Co., Ltd., and organic siloxane surfactants such as BYK manufactured by BYK-Chemie.

In addition, the resin composition of the present invention can improve the elongation characteristics of the film after curing after reliability evaluation and the adhesion to metal materials by containing the compounds represented below. preferable.

The amount of the compound represented by the above is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, relative to the heat-resistant resin. If the amount added is less than 0.1 parts by weight, it is difficult to obtain the effect of improving elongation characteristics after reliability and adhesion to metal materials. , the sensitivity of the resin composition may be lowered.

Further, in order to improve adhesion to the substrate, trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, trimethoxythiolpropylsilane, trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, and trimethoxythiolpropyl as silicon components are added to the resin composition of the present invention within a range that does not impair storage stability. It may contain a silane coupling agent such as silane. A preferred content of the silane coupling agent is 0.01 to 5 parts by weight per 100 parts by weight of the resin (a).

Furthermore, the resin composition of the present invention may contain a dissolution modifier within a range that does not increase the shrinkage ratio after curing. As the dissolution modifier, any compound such as a polyhydroxy compound, a sulfonamide compound, a urea compound, etc., which is generally used as a dissolution modifier for a positive resist, can be preferably contained. In particular, polyhydroxy compounds, which are raw materials for synthesizing quinonediazide compounds, are preferably used.

The viscosity of the resin composition of the present invention is preferably 2 to 5,000 mPa·s at 25°C. Viscosity can be measured using an E-type rotational viscometer. A desired film thickness can be easily obtained by adjusting the solid content concentration so that the viscosity is 2 mPa·s or more. On the other hand, if the viscosity is 5,000 mPa·s or less, it becomes easy to obtain a highly uniform coating film. A resin composition having such a viscosity can be easily obtained, for example, by adjusting the solid content concentration to 5 to 60% by weight.

A method for producing the resin composition of the present invention will be exemplified. For example, (a) resin, (c) solvent, and if necessary, components (b), (d) to (f), and other components are placed in a glass flask or stainless steel container and stirred and dissolved with a mechanical stirrer or the like. method, a method of dissolving with ultrasonic waves, a method of stirring and dissolving with a planetary stirring and degassing device, and the like. Among them, a method of stirring and dissolving with a mechanical stirrer or the like is preferable. In addition, when the resin composition contains (b) resin, (a) resin and (b) resin are separately produced (polymerization, esterification), (a) mixing the resin, (b) ) mixing a resin and (c) mixing a solvent.
After that, it is preferable to filter with a filter having a pore size of 0.1 μm to 5 μm in order to remove foreign substances.

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

First, the resin composition of the present invention is applied to a substrate. Substrates include silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, composite substrates of silicon wafers and sealing resin such as epoxy resin, sealing resin substrates, and circuit configurations on these substrates. Examples include, but are not limited to, those in which materials are arranged. Examples of organic circuit boards include glass substrate copper-clad laminates such as glass cloth and epoxy copper-clad laminates, composite copper-clad laminates such as glass non-woven fabric and epoxy copper-clad laminates, temporary carrier substrates, and polyetherimide. Examples include heat-resistant/thermoplastic substrates such as resin substrates, polyetherketone resin substrates and polysulfone resin substrates, and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates. Examples of inorganic circuit substrates include ceramic substrates such as glass substrates, alumina substrates, aluminum nitride substrates and silicon carbide substrates, and metal substrates such as aluminum base substrates and iron base substrates. Examples of circuit constituent materials include conductors containing metals such as silver, gold, and copper; resistors containing inorganic oxides; low dielectric materials containing glass materials and/or resins; Examples include high dielectric materials containing dielectric inorganic particles and the like, and insulators containing glass-based materials and the like. Application methods include spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater. methods such as tar. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but the coating is usually applied so that the film thickness after drying is 0.1 to 150 μm. When used as a photosensitive uncured sheet, it is then dried and peeled off.

In order to improve the adhesion between a substrate such as a silicon wafer and the resin composition, the substrate can be pretreated with the silane coupling agent described above. For example, a solution obtained by dissolving 0.5 to 20% by weight of a silane coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. , spin coating, dipping, spray coating, vapor treatment, etc. In some cases, a heat treatment is then performed at 50° C. to 300° C. to advance the reaction between the substrate and the silane coupling agent.

Next, the substrate obtained by coating or laminating the resin composition or uncured sheet on the substrate is dried to obtain a resin film. Drying is preferably carried out using an oven, hot plate, infrared rays, or the like, at a temperature of 50° C. to 150° C. for 1 minute to several hours.

Then, the resin film is exposed to actinic rays through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm) and g-rays (436 nm) of a mercury lamp. .

To form a pattern, after exposure, a developer is used to remove the exposed area in the case of a positive type, and the unexposed area in the case of a negative type. Developers include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl Solutions of alkaline compounds such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine are preferred.

In the present invention, it is particularly preferable to use an alkaline aqueous solution as the developer. After the alkali development step, uniform wettability is improved within the surface due to minute surface roughness, and wiring with excellent dimensional uniformity can be formed, which is preferable.

In some cases, the alkaline solution may be added with a polar solvent such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, isopropanol, or the like. alcohols, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone, may be added singly or in combination. Development can be carried out by a method such as spraying the above developer onto the film surface, immersing the substrate in the developer, applying ultrasonic waves while immersed, or spraying the developer while rotating the substrate. It is preferable to rinse with water after development. Also here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing. After development, a temperature of 150° C. to 500° C. is applied to promote a thermal cross-linking reaction, thereby curing the resin film and obtaining a cured film. Crosslinking can improve heat resistance and chemical resistance. As a method for this heat treatment, a method in which the temperature is increased stepwise, or a method in which a certain temperature range is selected and the temperature is continuously increased for 5 minutes to 5 hours can be selected. As an example of the former, there is a method of heat-treating at 130° C. and 200° C. for 30 minutes each. An example of the latter is a method of linearly raising the temperature from room temperature to 400° C. over 2 hours. The curing conditions in the present invention are preferably 150° C. or higher and 350° C. or lower.

Furthermore, the method for producing a cured film of the present invention preferably includes a step of subjecting the cured film obtained by the heat treatment to a dry etching treatment. By applying the dry etching process, minute surface roughness on the cured film can be improved, and adhesion to the barrier metal can be improved by the anchor effect.

The dry etching process of the present invention includes plasma etching, reactive ion etching, and the like. Reactive ion etching is preferable in terms of obtaining a high anchoring effect because highly anisotropic etching is possible in the cured film. The reactive gas used for dry etching is not particularly limited, and reactive gases such as tetrafluoromethane, trifluoromethane, oxygen, nitrogen, tetrachloromethane, carbon monoxide, and carbon dioxide are used alone or in combination of two or more. be done. Also, an inert gas such as helium or argon may be mixed. Among these, the reactive gas preferably contains oxygen because it can improve the surface energy of the cured film and improve the adhesion to the barrier metal. Also, the RF output is preferably 200 W or more and 1500 W or less, and the pressure is preferably 5 to 80 Pa.

The thickness of the cured film etched by the dry etching process is preferably 0.1 to 0.5 μm.

A cured film formed from the resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards, and organic EL display devices. Specifically, semiconductor passivation films, surface protection films for semiconductor elements, interlayer insulation films, interlayer insulation films for multilayer wiring for high-density mounting, interlayer insulation films for electronic components such as inductors and SAW filters, organic electroluminescence devices ( Although it is suitably used for applications such as an insulating layer and a flat layer for organic EL), it is not limited to this and can take various structures.

Next, an example of application of the resin composition of the present invention to a semiconductor device having bumps will be described with reference to drawings (Application Example 1). FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having bumps according to the present invention. As shown in FIG. 1, a silicon wafer 1 has a passivation film 3 formed on an input/output aluminum (hereinafter referred to as Al) pad 2 and a via hole formed in the passivation film 3 . Further, an insulating film 4 is formed thereon as a pattern of the resin composition of the present invention, and a metal (Cr, Ti, etc.) film 5 as a barrier metal is formed so as to be connected to the Al pad 2, followed by electroplating. A metal wiring (Al, Cu, etc.) 6 is formed by, for example. The metal film 5 is etched around the solder bumps 10 to insulate the pads. A barrier metal 8 and a solder bump 10 are formed on the insulated pad. The resin composition of the insulating film 7 can be processed into a thick film at the scribe line 9 .

Next, FIG. 2 shows a detailed manufacturing method of the semiconductor device. As shown in FIG. 2a, an input/output Al pad 2 and a passivation film 3 are formed on a silicon wafer 1, and an insulating film 4 is formed as a pattern of the resin composition of the present invention. The surface of the film is dry etched. Subsequently, as shown in 2b of FIG. 2, a metal (Cr, Ti, etc.) film 5 is formed as a barrier metal so as to be connected to the Al pad 2 and processed with a resist. is removed, and the barrier metal is wet-etched with an etchant to form a metal wiring 6 (so-called rewiring) as shown in 2c of FIG. At this time, if there is a problem with the adhesion of the barrier metal or wet etching, it becomes difficult to peel off the wiring or to form a uniform wiring.
Next, as shown in 2d' of FIG. 2, the resin composition of the present invention is applied, and an insulating film 7 is formed in a pattern as shown in 2d of FIG. 2 through a photolithography process. A metal wiring can be further formed on the insulating film 7 . In the case of forming a multilayer wiring structure of two or more layers, the above steps are repeated to form a multilayer wiring structure in which two or more rewiring layers are separated by an interlayer insulating film obtained from the resin composition of the present invention. Structures can be formed. Although there is no upper limit to the number of layers in the multilayer wiring structure, 10 layers or less are often used.

Next, as shown in 2e and 2f of FIG. 2, barrier metal 8 and solder bumps 10 are formed. Then, it is diced along the last scribe line 9 to cut into chips.

Next, Application Example 2 to a semiconductor device having bumps using the resin composition of the present invention will be described with reference to the drawings. FIG. 3 is an enlarged cross-sectional view of a pad portion of a semiconductor device having an insulating film according to the present invention, and has a structure called a fan-out wafer level package (fan-out WLP). The silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed is diced in the same manner as in Application Example 1 described above, and after the chips are cut into chips, the chips are sealed with a resin 11 . An insulating film 4 is formed as a pattern of the resin composition of the present invention over the sealing resin 11 and the chip, and a metal (Cr, Ti, etc.) film 5 and metal wiring 6 are formed as barrier metal. Thereafter, barrier metal 8 and solder bumps 10 are formed in openings of insulating film 7 formed on the sealing resin outside the chip. The fan-out WLP uses sealing resin such as epoxy resin to provide an extended portion around the semiconductor chip, rewires from the electrodes on the semiconductor chip to the extended portion, and mounts solder balls on the extended portion. It is a semiconductor package that secures the required number of terminals. In the fan-out WLP, wiring is installed so as to straddle the boundary formed by the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a substrate made of two or more kinds of materials such as a semiconductor chip with metal wiring and a sealing resin, and wiring is formed on the interlayer insulating film.

In addition, the fan-out WLP is arranged as an interlayer insulating film between rewirings on a support substrate on which a temporary attachment material is arranged. There is a type of package that is produced by a process called RDL-first in which the substrate and rewiring are separated. In this type of package, a glass substrate or the like that warps more easily than a silicon wafer is often used as the support substrate, so it is preferable that the insulating film has a low stress.

A method for manufacturing a semiconductor device in RDL-first will be described with reference to FIGS. In 3a of FIG. 5, a barrier metal such as Ti is formed on the support substrate 20 by a sputtering method, a Cu seed (seed layer) is formed thereon by a sputtering method, and then an electrode pad 21 is formed by a plating method. Then, in step 3b, the photosensitive resin composition of the present invention is applied, and a patterned insulating film 22 is formed through a photolithography step. Then, in step 3c, a seed layer is again formed by sputtering, and a metal wiring 23 (rewiring layer) is formed by plating. Thereafter, in order to match the pitch of conductive portions of the semiconductor chip with the pitch of metal wiring, the steps 3b and 3c are repeated to form a multilayer wiring structure as shown in 3d. Next, in step 3e, the photosensitive resin composition of the present invention is applied again, a patterned insulating film is formed through a photolithography step, and Cu posts 24 are formed by plating. Here, the pitch of the Cu posts is equal to the pitch of the conducting portions of the semiconductor chip. That is, in order to increase the number of layers of the rewiring layer while narrowing the metal wiring pitch, the film thickness of the interlayer insulating film is as follows: interlayer insulating film 1>interlayer insulating film 2>interlayer insulating film 3>, as shown in 3e of FIG. Interlayer insulating film 4>. Then, in the process of 3f, the semiconductor chip 26 is connected through the solder bumps 25 to obtain the RDL-first semiconductor device having the multilayer wiring structure.

In addition to this, in a type of semiconductor package in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is installed so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. . Also in this aspect, an interlayer insulating film is formed on a substrate made of two or more materials, and wiring is formed on the interlayer insulating film.

Further, in the fan-out WLP, miniaturization of rewiring is progressing. The cured film of the resin composition of the present invention has high metal adhesion to wiring having a width of metal wiring and an interval between adjacent wirings of 5 μm or less, and is therefore suitably used for fine rewiring. In this structure, the closer the rewiring layer is to the semiconductor chip, the narrower the width of the metal wiring and the spacing between the adjacent wirings, and the thinner the thickness of the interlayer insulating film is, the closer it is to the semiconductor chip. It is compatible with high integration of chips. Therefore, wiring uniformity has become an important issue as the resolution has increased.

Next, an application example 3 to a coil component of an inductor device using the resin composition of the present invention will be described with reference to the drawings. FIG. 4 is a cross-sectional view of a coil component having an insulating film according to the present invention. As shown in FIG. 4, an insulating film 13 is formed on a substrate 12, and an insulating film 14 is formed thereon as a pattern. Ferrite or the like is used as the substrate 12 . The resin composition of the present invention may be used for either insulating film 13 or insulating film 14 . A metal (Cr, Ti, etc.) film 15 is formed as a barrier metal in the opening of this pattern, and a metal wiring (Ag, Cu, etc.) 16 is plated thereon. A metal wiring 16 (Ag, Cu, etc.) is formed in a spiral. By repeating the process of forming the insulating film 13 to the metal wiring (Ag, Cu, etc.) 16 a plurality of times and stacking them, it is possible to impart a function as a coil. Finally, metal wiring 16 (Ag, Cu, etc.) is connected to electrode 18 by metal wiring 17 (Ag, Cu, etc.) and sealed with sealing resin 19 .

The resin composition of the present invention is also suitable for use in organic EL display devices. The organic EL display device has a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light emitting layer and a second electrode on a substrate, and the planarizing layer and/or the insulating layer is formed from the cured film of the present invention. Become. Organic EL light-emitting materials are susceptible to deterioration due to moisture, and may have adverse effects such as a decrease in the area ratio of light-emitting portions to the area of light-emitting pixels. properties are obtained. Taking an example of an active-matrix display device, a substrate made of glass, various plastics, or the like is provided with TFTs and wirings located on the sides of the TFTs and connected to the TFTs, and unevenness is covered thereon. A planarization layer is thus provided, and a display element is provided on the planarization layer. The display element and the wiring are connected through a contact hole formed in the planarization layer.

FIG. 6 shows a cross-sectional view of an example of a TFT substrate. Bottom gate type or top gate type TFTs (thin film transistors) are provided in a matrix on the substrate 32 , and an insulating layer 29 is formed to cover the TFTs 27 . A wiring 28 connected to the TFT 27 is provided on the insulating layer 29 . Furthermore, a planarizing layer 30 is provided on the insulating layer 29 so as to bury the wiring 28 therein. A contact hole 33 reaching the wiring 28 is provided in the planarization layer 30 . An ITO (transparent electrode) 31 is formed on the planarization layer 30 in a state of being connected to the wiring 28 through the contact hole 33 . Here, the ITO 31 becomes a first electrode of a display element (for example, an organic EL element). An insulating layer 34 is formed to cover the periphery of the ITO 31 . The organic EL element may be of a top emission type that emits light from the side opposite to the substrate 32, or may be of a bottom emission type that emits light from the substrate 32 side. Thus, an active matrix type organic EL display device is obtained in which TFTs 27 for driving the organic EL elements are connected to the respective organic EL elements.

The insulating layer 29, the planarizing layer 30 and/or the insulating layer 34 are formed by the steps of forming a photosensitive resin film made of the resin composition or resin sheet of the present invention, exposing the photosensitive resin film, and It can be formed by a step of developing the exposed photosensitive resin film and a step of heat-treating the developed photosensitive resin film. An organic EL display device can be obtained by a manufacturing method including these steps.

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

(1) Polyamic acid ester ratio (ratio of structure represented by general formula (2) or (5)), polyimide ratio (ratio of structure represented by general formula (3) or (6)), polyamic acid ratio (The ratio of the structure represented by the general formula (1) or (4) in each resin, for the polyamic acid ester ratio, 400 MHz, ¹ H-NMR (nuclear magnetic resonance) device (AL-400 manufactured by JEOL Ltd.) was measured in a deuterated dimethyl sulfoxide solution with 16 integration times, and calculated based on the integrated value of the protons of the esterified substituents.

Regarding the polyimide ratio (imidation ratio) of the resin, a solution of the resin dissolved in n-methylpyrrolidone was spin-coated on a silicon wafer, dried at 120 ° C. for 3 minutes, and inert oven CLH-21CD-S (Koyo Thermo System Co., Ltd.), the temperature was raised to 170° C. at 3.5° C./min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 170° C. for 1 hour. Furthermore, an infrared absorption spectrum was measured to confirm the presence of absorption peaks of the imide structure (around 1780 cm ⁻¹ and around 1377 cm ⁻¹ ). Next, the coating film was heat-treated at 350 ° C. for ¹ hour, and the infrared absorption spectrum was measured as a sample with an imidization rate of 100%. The imidization rate was determined by calculating the content of imide groups in the resin before heat treatment. For the measurement of the infrared absorption spectrum, "FT-720" (trade name, manufactured by HORIBA, Ltd.) was used as a measuring device.

The polyamic acid ratio of the resin can be obtained by 100%-(polyamic acid ester ratio+polyimide ratio).

(2) Dissolution rate The resin was dissolved in n-methylpyrrolidone at a solid content of 39% by weight. This was coated on a silicon wafer and prebaked on a hot plate at 120° C. for 4 minutes to form a prebaked film with a film thickness of 10 μm±0.5 μm. This was immersed in a 2.38% by weight tetramethylammonium hydroxide aqueous solution at 23±1° C. for 3 minutes, and the dissolved film thickness was calculated from the change in film thickness before and after immersion. The film thickness dissolved per minute was obtained by dividing the dissolved film thickness by 3, and this was defined as the dissolution rate (μm/min). The film thickness was measured by an optical interferometric film thickness measuring device Lambda Ace STM-602 (Dainippon Screen Mfg. Co., Ltd.).

(3) Evaluation of elongation A varnish was applied on an 8-inch silicon wafer by a spin coating method using a coating and developing apparatus ACT-8 so that the film thickness after prebaking at 120 ° C. for 3 minutes was 11 μm and was prebaked. After that, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised to 300° C. at a rate of 3.5° C./min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at the curing temperature for 1 hour. rice field. When the temperature became 50° C. or less, the wafer was taken out, slowly cooled, and then immersed in 45% by weight hydrofluoric acid for 5 minutes to peel off the resin composition film from the wafer. This film was cut into strips with a width of 1 cm and a length of 3 cm, and a Tensilon RTM-100 (manufactured by Orientec Co., Ltd.) was used at a room temperature of 23.0 ° C. and a humidity of 45.0% RH at a tensile speed of 5 mm /. It was pulled in minutes and measured with elongation at break. Measurement was performed on 10 strips per sample, and the average value of the top 5 points was obtained from the results. Elongation at break value of 70% or more is very good (A), 50% or more and less than 70% is good (B), 30% or more and less than 50% is acceptable (D), less than 30% was judged to be defective (D).

(4) Adhesion to Barrier Metal A varnish was spin-coated on an 8-inch silicon wafer, then baked on a hot plate at 120° C. (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Ltd.) for 3 minutes to obtain a resin. A membrane was obtained. As shown in Table 1, in the case of development, a 2.38% by weight tetramethylammonium aqueous solution (hereinafter referred to as TMAH, manufactured by Tama Chemical Industry Co., Ltd.) was used with an ACT-8 developing device by the paddle method. Development was repeated twice with a developer discharge time of 10 seconds and a puddle time of 40 seconds, followed by rinsing with pure water and drying by shaking off.

Using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the resin film was heated to 300° C. at an oxygen concentration of 20 ppm or less at a rate of 5° C./min, and heat-treated at 300° C. for 1 hour. After that, it was cooled to 50°C at 5°C/min. As shown in Table 1, in the case of dry etching, RIE-10N manufactured by SAMCO Co., Ltd. was used, and the cured 8-inch wafer sample was treated with O2/CF4=0.06/0.02 Pa·m ³ . Dry etching was performed for 60 seconds under the conditions of /S, pressure of 20 Pa, and RF output of 300 W.

After that, a titanium target was set in a sputtering apparatus (SPL-500 manufactured by Nichiden ANELVA), and the substrate was set on a sample holder. An argon gas was mixed with oxygen (gas flow rate: argon 0.03 Pa·m ³ /S/oxygen 0.004 Pa·m ³ /S) and sputtered to a thickness of 100 nm to form a titanium layer. Further, a copper layer was formed to a thickness of 100 nm using a copper target using the same apparatus. After that, a resist of TMMR P-W1000 (manufactured by Tokyo Ohka Co., Ltd.) is applied, a circular pattern with a diameter of 50 μm is formed, and then electrolytic copper plating is performed so that the layer thickness is 4 μm. (manufactured by Tokyo Ohka Co., Ltd.), and copper etching and Ti etching are performed using etching solutions WLC-C2 and WLC-T (manufactured by Mitsubishi Gas Chemical Co., Ltd.), respectively, resulting in a film thickness of 4 μm and a diameter of 50 μm. copper pattern was formed. The copper pattern was shear peeled using a die shear tester (Dage-series 4000 manufactured by Dage Co.), and the strength at that time was defined as barrier metal adhesion. A barrier metal adhesion value of 50 mN or less is defective (D), a value of 100 mN or less but exceeding 50 mN is acceptable (C), a value of 150 mN or less but exceeding 100 mN is acceptable (B), and 150 mN. Those exceeding were evaluated as acceptable (A).

(5) Wiring Uniformity A varnish was spin-coated on an 8-inch silicon wafer, then baked on a hot plate at 120° C. (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Co., Ltd.) for 3 minutes to form a resin film. got As shown in Table 2, in the case of development, a 2.38% by weight aqueous solution of tetramethylammonium (hereinafter referred to as TMAH, manufactured by Tama Chemical Industry Co., Ltd.) was used with a developing device of ACT-8 by the paddle method. Development was repeated twice with a developer discharge time of 10 seconds and a puddle time of 40 seconds, followed by rinsing with pure water and drying by shaking off.

Using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the resin film was heated to 300° C. at an oxygen concentration of 20 ppm or less at a rate of 5° C./min, and heat-treated at 300° C. for 1 hour. After that, it was cooled to 50°C at 5°C/min. As shown in Table 2, in the case of dry etching, using RIE-10N manufactured by SAMCO Co., Ltd., the cured 8-inch wafer sample was treated with O2/CF4=0.06/0.02 Pa·m ³ /. Dry etching was performed for 60 seconds under the conditions of S, pressure of 20 Pa, and RF output of 300 W.

After that, a titanium target was set in a sputtering apparatus (SPL-500 manufactured by Nichiden ANELVA), and the substrate was set on a sample holder. An argon gas was mixed with oxygen (gas flow rate: argon 0.03 Pa·m ³ /S/oxygen 0.004 Pa·m ³ /S) and sputtered to a thickness of 100 nm to form a titanium layer. Further, a copper layer was formed to a thickness of 100 nm using a copper target using the same apparatus. After that, a resist of TMMR P-W1000 (manufactured by Tokyo Ohka Co., Ltd.) is applied, and an L/S pattern of 10 μm is formed at intervals of 2 cm left and right from the center of the 8-inch wafer. Electrolytic copper plating is performed, the resist is stripped with stripping solution ST-120 (manufactured by Tokyo Ohka Co., Ltd.), and copper etching and Ti etching are performed using etching solutions WLC-C2 and WLC-T (manufactured by Mitsubishi Gas Chemical Co., Ltd.), respectively. A copper wiring pattern with a film thickness of 4 μm and a target of 10 μmL/S was formed. Wiring dimensions formed in the wafer surface were measured using a scanning laser microscope 1LM21 (manufactured by Lasertec Co., Ltd.), and the difference between the minimum and maximum dimensions was taken as the wiring uniformity of the pattern. A value of wiring uniformity exceeding 1 μm is defective (D), a value of 1 μm or less but exceeding 0.7 μm is acceptable (C), and a value of 0.7 μm or less but exceeding 0.5 μm is good (B ), those having a thickness of 0.5 μm or less but exceeding 0.2 μm were evaluated as good (A), and those having a thickness of 0.2 μm or less were evaluated as good (S).
The names or structures of the compounds used are shown below.

GBL: γ-butyl lactone DMAC: Dimethylacetamide (F-1): BYK333 (manufactured by BYK Chemie Co., Ltd.)
(F-2): Polyflow 77 (manufactured by Kyoeisha Chemical Co., Ltd., acrylic polymer)
(Synthesis Example 1) Synthesis of resin (A-1) HA (27.2 g, 0.045 mol) was dissolved in 400 g of N-methyl-2-pyrrolidone (hereinafter NMP) under a dry nitrogen stream. 4′-Oxydiphthalic dianhydride (hereinafter ODPA, 15.5 g, 0.05 mol) was added and reacted at 40° C. for 2 hours.

2-Hydroxyethyl methacrylate (hereinafter referred to as HEMA, 5.20 g, 0.04 mol) and 400 ml of γ-butyrolactone were added and reacted at room temperature for 4 hours.

After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (A-1) powder as the resin (a).

(Synthesis Example 2) Synthesis of Resin (A-2) HA (27.2 g, 0.045 mol) was dissolved in 400 g of NMP under a dry nitrogen stream, and then ODPA (15.5 g, 0.05 mol) was added. , and 40° C. for 2 hours.

Then, a solution of N,N-dimethylformamide dimethylacetal (4.76 g, 0.04 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40°C for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (A-2) powder as the resin (a).

(Synthesis Example 3) Synthesis of resin (A-3) 4,4'-diaminodiphenyl ether (hereinafter referred to as DAE, 9.0 g, 0.045 mol) was dissolved in 400 g of NMP under a stream of dry nitrogen, and then ODPA (15.0 g) was dissolved. 5 g, 0.025 mol) and pyromellitic dianhydride (hereinafter PMDA, 7.75 g, 0.025 mol) were added and reacted at 40° C. for 2 hours.

Then, a solution of N,N-dimethylformamide dimethylacetal (4.76 g, 0.04 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40°C for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (A-3) powder as the resin (a).

(Synthesis Example 4) Synthesis of Resin (A-4) Under a dry nitrogen stream, HA (18.1 g, 0.03 mol) and DAE (2.0 g, 0.01 mol) were dissolved in 400 g of NMP, then PMDA. (10.91 g, 0.05 mol) was added and reacted at 40° C. for 2 hours.
Then, a solution of N,N-dimethylformamide dimethylacetal (4.76 g, 0.04 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40°C for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (A-4) powder as the resin (a).

(Synthesis Example 5) Synthesis of Resin (A-5) Under a dry nitrogen stream, HA (6.05 g, 0.01 mol) and DAE (6.0 g, 0.03 mol) were dissolved in 400 g of NMP, then PMDA. (10.91 g, 0.05 mol) was added and reacted at 40° C. for 2 hours.
Then, a solution of N,N-dimethylformamide dimethylacetal (4.76 g, 0.04 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40°C for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (A-5) powder as the resin (a).

(Synthesis Example 6) Synthesis of Resin (A-6) DAE (4.5 g, 0.023 mol), 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl ( Thereafter TFMB, 7.2 g, 0.023 mol) was dissolved in 400 g of NMP, then PMDA (10.91 g, 0.05 mol) was added and reacted at 40° C. for 2 hours.
Then, a solution of N,N-dimethylformamide dimethylacetal (4.76 g, 0.04 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40°C for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (A-6) powder as the resin (a).

(Synthesis Example 7) Synthesis of resin (A-7) Under dry nitrogen stream, TFMB (7.2 g, 0.023 mol), 3,3′-dimethyl-4,4′-diaminobiphenyl (hereinafter mTB, 4. 78 g, 0.023 mol) was dissolved in 400 g NMP, then PMDA (10.91 g, 0.05 mol) was added and allowed to react at 40° C. for 2 hours.
Then, a solution of N,N-dimethylformamide dimethylacetal (4.76 g, 0.04 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40°C for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (A-7) powder as the resin (a).

(Synthesis Example 8) Synthesis of resin (A-8) TFMB (7.2 g, 0.023 mol), p-phenylenediamine (hereinafter referred to as PDA, 2.43 g, 0.023 mol), NMP 400 g under dry nitrogen stream and PMDA (10.91 g, 0.05 mol) was added and allowed to react at 40° C. for 2 hours.
Then, a solution of N,N-dimethylformamide dimethylacetal (4.76 g, 0.04 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40°C for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (A-8) powder as the resin (a).

(Synthesis Example 9) Synthesis of resin (A-9) TFMB (7.2 g, 0.023 mol), p-phenylenediamine (hereinafter referred to as PDA, 2.43 g, 0.023 mol), NMP 400 g under dry nitrogen stream 3,3′,4,4′-biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA, 14.71 g, 0.05 mol) was then added and reacted at 40° C. for 2 hours.
Then, a solution of N,N-dimethylformamide dimethylacetal (4.76 g, 0.04 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40°C for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (A-9) powder as the resin (a).

(Synthesis Example 10) Synthesis of Resin (B-1) Under dry nitrogen stream, HA (27.2 g, 0.045 mol) was dissolved in NMP 400 g, and then ODPA (15.5 g, 0.05 mol) was added. , and 40° C. for 2 hours.
Then, a solution of N,N-dimethylformamide dimethylacetal (11.9 g, 0.10 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40°C for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (B-1) powder as the resin (b).

(Synthesis Example 11) Synthesis of Resin (B-2) HA (27.2 g, 0.045 mol) was dissolved in 400 g of NMP under a dry nitrogen stream, and then ODPA (15.5 g, 0.05 mol) was added. , and 40° C. for 2 hours.
Then, a solution of N,N-dimethylformamide dimethylacetal (10.72 g, 0.09 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40°C for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (B-2) powder as the resin (b).

(Synthesis Example 12) Synthesis of resin (AB-1) Under a dry nitrogen stream, TFMB (14.4 g, 0.045 mol) was dissolved in NMP 400 g, then PMDA (10.91 g, 0.05 mol) was added. , and 40° C. for 2 hours.
Then, a solution of N,N-dimethylformamide dimethylacetal (11.9 g, 0.10 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40°C for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (AB-1) powder as a resin that is neither (a) resin nor (b) resin.

(Synthesis Example 13) Synthesis of Resin (AB-2) HA (27.2 g, 0.045 mol) was dissolved in 400 g of NMP under a stream of dry nitrogen, and then ODPA (15.5 g, 0.05 mol) was added. , and 40° C. for 2 hours.

After completion of the reaction, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a resin (AB-2) powder as a resin that was neither (a) resin nor (b) resin.

(Synthesis Example 14) Synthesis of Resin (AB-3) BAHF (16.47 g, 0.045 mol) was dissolved in 100 g of NMP under a dry nitrogen stream. 4,4′-Diphenyletherdicarboxylic acid dichloride (hereinafter referred to as DPEC, 14.7 g, 0.05 mol) was added together with 10 g of NMP at 5° C. or lower and reacted at 5° C. or lower for 3 hours. After completion of the reaction, the solution was poured into 1.5 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and dried in a ventilation dryer at 50° C. for 3 days. got

Table 1 shows the raw materials, formulations, and properties of the resins in each synthesis example; Table 2 shows the resin compositions, weight ratios, and processes in Examples and Comparative Examples; and Table 3 shows the evaluation results of the obtained resin compositions.

INDUSTRIAL APPLICABILITY The present invention can be preferably used for electronic parts such as semiconductor devices and multilayer wiring boards, and organic EL display devices. Specifically, semiconductor passivation films, surface protection films for semiconductor elements, interlayer insulation films, interlayer insulation films for multilayer wiring for high-density mounting, interlayer insulation films for electronic components such as inductors and SAW filters, organic electroluminescence devices ( It can be used for applications such as insulating layers of organic EL).

When comparing Examples 1 to 20 with Comparative Examples 1 to 6, Examples 1 to 20 are resin compositions containing (a) a resin and (c) a solvent, and (a) the resin is represented by the following general formula (1 ) and a structural unit represented by general formula (2) and general formula (3), and the total of general formulas (1) to (3) is 100 mol%, represented by general formula (2) It is a resin composition having 5 mol % or more and less than 50 mol % of the structural unit, and the results of elongation, barrier metal adhesion, and wiring uniformity are improved.
Comparing Example 1 and Example 2, Example 2 uses a resin composition in which R ¹ in the general formula (2) is an alkyl group having a molecular weight of 100 or less, and results in improved wiring uniformity. there is

Comparing Examples 2 to 3 with Examples 4 to 6, Examples 4 to 6 contain 20 to 20 diamine residues having a fluorine atom when the total amount of diamine residues in the resin (a) is 100 mol%. 80 mol % resin composition with improved elongation results.
Comparing Example 7 and Example 8, Example 8 further contains (b) resin, and (b) resin is the following general formula (4), general formula (5) and general formula (6) and the structural unit represented by general formula (5) is 60 mol% or more and less than 98 mol%, with the total of general formulas (4) to (6) being 100 mol%. , the result of barrier metal adhesion is improved.

Comparing Examples 8-9 with Examples 10-11, Examples 10-11 show that the resin (a) and the resin (b) have alkali water solubility,
(b) The dissolution rate of the resin in the alkaline aqueous solution is 0.5 to 2 times the dissolution rate of the (a) resin in the alkaline aqueous solution, resulting in improved wiring uniformity.
Comparing Examples 13 and 14 with Examples 10 and 11, Examples 13 and 14 had 25 parts by weight of the resin (b) with respect to 100 parts by weight of the total amount of the resin (a) and the resin (b). Since the resin composition is blended in an amount of 75 parts by weight or more, the elongation results are improved.

Comparing Example 15 and Example 16, Example 16 is a resin composition further containing (d) a photosensitive compound and (e) a compound having an alkoxymethyl group, and the result of barrier metal adhesion is is improving.
Comparing Example 17 and Example 18, Example 18 is a resin composition further comprising (f) an acrylic polymer surfactant, resulting in improved wiring uniformity.
Comparing Example 18 and Example 19, Example 18 includes a step of developing by partially eluting or removing the resin film with an alkaline aqueous solution, and the result of wiring uniformity is improved.
Comparing Example 20 and Example 18, Example 20 includes a step of subjecting the cured film to a dry etching treatment, resulting in improved barrier metal adhesion.

1 Silicon Wafer 2 Al Pad 3 Passivation Film 4 Insulating Film 5 Metal (Cr, Ti etc.) Film 6 Metal Wiring (Al, Cu etc.)
7 Insulating film 8 Barrier metal 9 Scribe line 10 Solder bump 11 Sealing resin 12 Substrate 13 Insulating film 14 Insulating film 15 Metal (Cr, Ti, etc.) film 16 Metal wiring (Ag, Cu, etc.)
17 metal wiring (Ag, Cu, etc.)
18 electrode 19 sealing resin 20 support substrate (glass substrate, silicon wafer)
21 electrode pad (Cu)
22 insulating film 23 metal wiring (Cu)
24 Cu post 25 Solder bump 26 Semiconductor chip 27 TFT (thin film transistor)
28 wiring 29 insulating layer 30 planarization layer 31 ITO (transparent electrode)
32 substrate 33 contact hole 34 insulating layer

Claims (15)

A resin composition comprising (a) a resin , (b) a resin , and (c) a solvent,
(a) The resin has structural units represented by general formulas (1), (2) and (3), and the sum of the structural units represented by general formulas (1) to (3) is 100 mol%, and the structural unit represented by the general formula (2) has 5 mol% or more and less than 50 mol% ,
(b) resin has a structural unit represented by the following general formula (4), general formula (5) and general formula (6), and the structural unit represented by general formulas (4) to (6) A resin composition having 60 mol% or more and less than 98 mol% of the structural unit represented by the general formula (5), with the total being 100 mol% .

(In general formulas (1) to (3), Y ¹ to Y ³ each independently represent a divalent organic group, and X ¹ to X ³ each independently represent a tetravalent organic group. R ¹ is carbon Indicates a monovalent organic group of numbers 1 to 20. * indicates a chemical bond.)

(In general formulas (4) to (6), Y ⁴ to Y ⁶ each independently represent a divalent organic group, and X ⁴ to X ⁶ each independently represent a tetravalent organic group. R ² is a carbon Indicates a monovalent organic group of numbers 1 to 20. * indicates a chemical bond.) 2. The resin composition according to claim ¹ , wherein R1 in the general formula (2) is an alkyl group having a molecular weight of 100 or less. 3. The resin composition according to claim 1, wherein the diamine residue having a fluorine atom is 20 mol % or more and 80 mol % or less when the total amount of diamine residues in the resin (a) is 100 mol %. The (a) resin and the (b) resin have alkali water solubility,
The resin composition according to any one of claims 1 to 3, wherein (b) the dissolution rate of the resin in the alkaline aqueous solution is 0.5 to 2 times the dissolution rate of the (a) resin in the alkaline aqueous solution. The resin composition according to any one of claims 1 to 4 , wherein the resin (b) contains 25 parts by weight or more and 75 parts by weight or less relative to the total amount of 100 parts by weight of the resin (a) and the resin (b). . 6. The resin composition according to any one of claims 1 to 5 , further comprising (d) a photosensitive compound and (e) a compound having an alkoxymethyl group. 7. The resin composition according to any one of claims 1 to 6 , further comprising (f) an acrylic polymer surfactant. A step of coating the resin composition according to any one of claims 1 to 7 on a substrate and drying it to form a resin film, and a step of developing by partially eluting or removing the resin film with an alkaline aqueous solution. and a method for producing a cured film, comprising the step of heat-treating the resin film that has undergone the developing step to obtain a cured film. 9. The method for producing a cured film according to claim 8 , further comprising the step of subjecting the cured film obtained by the heat treatment to a dry etching treatment. A cured film obtained by curing the resin composition according to any one of claims 1 to 7 . 11. An organic EL display device, wherein the cured film according to claim 10 is disposed on either a flattening layer on a driving circuit or an insulating layer on an electrode. An electronic component or a semiconductor device, wherein the cured film according to claim 10 is disposed as an interlayer insulating film between rewirings. 13. The electronic component or semiconductor device according to claim 12 , wherein said rewiring is a copper metal wiring, and the width of said copper metal wiring and the distance between adjacent wirings are 5 [mu]m or less. 11. An electronic component or semiconductor device, wherein the cured film according to claim 10 is arranged as an interlayer insulating film between rewirings on a sealing resin substrate on which a silicon chip is arranged. A step of disposing the cured film, the silicon chip, and the sealing resin according to claim 10 as an interlayer insulating film between rewirings on the support substrate on which the temporary attachment material is disposed;
After that, including a step of peeling off the support substrate on which the temporary attachment material is arranged,
Methods of manufacturing electronic components or semiconductor devices.

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