JP2005099353A - Photosensitive resin composition, method for manufacturing pattern using the same, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a pattern for obtaining a hardened film which can be hardened at a low temperature and has excellent photosensitive characteristics and high sensitivity, which results in a pattern with a favorable profile even with low exposure, which shows a high residual film rate after development, little shrinkage of a coating film after heating and hardening and which has excellent hardened film characteristics, and for decreasing the manufacturing processes and the manufacturing cost. <P>SOLUTION: The photosensitive resin composition contains: (A) a polyimide precursor having a repeating unit expressed by general formula (I); (B) an addition polymerizable compound having ≤350 molecular weight; and (C) a photoinitiator. In general formula (I), X represents a group containing a tetravalent aromatic ring; Y represents a group containing a divalent aromatic ring; each of R1 and R2 independently represents a hydrogen atom or a monovalent organic group; and at least either X or Y in a plurality of repeating units has two or more kinds of structures with different numbers of aromatic rings. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention has high transparency, high adhesion, low coating film shrinkage after heat curing, particularly suitable for thick film formation, and photosensitivity suitable for a surface protective film of a semiconductor element, an interlayer insulating film of a multilayer wiring board, etc. The present invention relates to a resin composition, a method for producing a pattern using the composition, and an electronic component, and more particularly, to a negative photosensitive resin composition that becomes a polyimide heat-resistant polymer by heat treatment, a method for producing a pattern, and an electronic component.

  In addition, the present invention is highly transparent and highly adhesive, and has a small shrinkage ratio of the coating film after heat curing and is suitable for thick film formation. For semiconductor device cover coat materials, core materials for rewiring, color balls for solder, etc. The present invention relates to a photosensitive resin composition suitable for so-called packaging applications, such as an underfill material used in a material, flip chip, and the like, a method for producing a pattern using the composition, and an electronic component.

  A polyimide or a precursor thereof, which itself has photo-patterning properties, is called photosensitive polyimide, and is used for a semiconductor surface protective film or the like. Several methods for imparting photosensitivity are known for photosensitive polyimide. Typical examples include those prepared by converting polyamic acid into an ester with hydroxyacrylate as proposed in JP-B-55-41422, and polyamides as proposed in JP-A-54-145794. An acid compound such as amino acrylate is known and a photosensitive group is introduced by a salt bond.

  Since these materials are rigid in polyamic acid itself, there is a disadvantage that the film state formed by spin coating or the like is less sensitive than conventional ultraviolet curable paints and dry film resists. To improve this, it is possible to increase the sensitivity by adding an oxime ester compound, an aryl glycine compound or the like. However, on the other hand, when it is cured at low temperature, there are drawbacks such as insufficient cured film properties and reduced adhesion. In addition, there is a problem that the shape of the polyimide pattern after heat curing changes significantly.

Japanese Patent Publication No.55-41422 JP 54-145794 A

  The present invention has been made to solve the above-described problems, and is useful for forming a cured heat-resistant photosensitive resin that satisfies the required characteristics, and a pattern forming method using the same. Is the purpose.

  The first object of the present invention is that it can be cured at low temperature, has excellent photosensitivity, is highly sensitive, has a good shape pattern even at low exposure, has a high residual film ratio after development, and has excellent cured film characteristics. An excellent cured film is obtained, and further a photosensitive resin composition having a small coating film shrinkage ratio after heat curing is provided.

The second object of the present invention is that it can be cured at low temperature, has excellent photosensitivity, is highly sensitive, has a good shape pattern even at low exposure, has a high residual film ratio after development, and has a high film thickness after heat curing. It is an object of the present invention to provide a method for producing a pattern in which a cured film having a small coating film shrinkage ratio and excellent cured film characteristics can be obtained, the production process can be shortened, and the production cost can be reduced.

  A third object of the present invention is to provide an electronic component having further excellent reliability in addition to the above object.

The present invention relates to the following.
(1) (A) General formula (I)

（式中、Ｘは４価の芳香環を含む基、Ｙは２価の芳香環を含む基、Ｒ１及びＲ２は各々独立に水素原子又は１価の有機基を示し、複数の繰り返し単位中のＸ及びＹの少なくとも一方が芳香環数の異なる２種類以上の構造を有する）で示される繰り返し単位を有するポリイミド前駆体、（Ｂ）３５０以下の分子量を有する付加重合性化合物及び（Ｃ）光開始剤を含有してなる感光性樹脂組成物。

(In the formula, X is a group containing a tetravalent aromatic ring, Y is a group containing a divalent aromatic ring, R 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group, A polyimide precursor having a repeating unit represented by (at least one of X and Y having two or more structures having different aromatic ring numbers), (B) an addition-polymerizable compound having a molecular weight of 350 or less, and (C) photoinitiation Photosensitive resin composition comprising an agent.

(2) (A) The polyimide precursor has at least one aromatic ring in which at least one of X and Y in the general formula (I) is bonded to the adjacent aromatic ring or amide group at the 1,3-position. The photosensitive resin composition according to (1), which is a product.
(3) (A) The polyimide precursor is in the general formula (I), and X is the following structure

を全酸無水物成分の５０モル％以上含有するものである前記（１）又は（２）記載の感光性樹脂組成物。

The photosensitive resin composition according to the above (1) or (2), which contains 50 mol% or more of the total acid anhydride component.

  (4) The polyimide precursor is a polyamic acid unsaturated ester having a (meth) acryloxyalkyloxy group as R1 and R2, the esterification rate is 50 to 80 mol%, and as a diamine The photosensitive resin composition according to the above (1), (2) or (3), which is obtained by using diaminopolysiloxane in an amount of 1 to 30 mol% of the total diamine.

  (5) In the semiconductor device having a structure in which a surface protective film layer is formed on a wiring layer of a semiconductor element and a cover coat layer is formed thereon, the above (1), ( The photosensitive resin composition according to 2), (3) or (4).

(6) In the semiconductor device having the structure in which the surface protective film layer is formed on the wiring layer of the semiconductor element and the cover coat layer is formed thereon, the above (1), (2) for the cover coat layer ), (3) or (4).

  (7) In the semiconductor device having the structure in which the surface protective film layer is formed on the wiring layer of the semiconductor element and the core for rewiring is formed thereon, (1), ( The photosensitive resin composition according to 2), (3) or (4).

  (8) A surface protective film layer is formed on the wiring layer of the semiconductor element, a rewiring layer and an overcoat layer are formed on the surface protective film layer, and a conductive material formed as an external connection terminal on the rewiring layer. The photosensitive resin composition according to (1), (2), (3) or (4), which is for a color material for holding the ball in a semiconductor device having a structure for holding the ball.

  (9) The photosensitive resin composition according to (1), (2), (3) or (4), which is used for an underfill material of a semiconductor device.

  (10) A step of applying a photosensitive resin composition according to any one of (1) to (9) on a support substrate to form a polyimide precursor film, the polyimide precursor film having a predetermined A method for producing a pattern comprising a step of obtaining a desired relief pattern by irradiating an actinic ray through a photomask of a pattern and exposing to light, and then dissolving and removing an unexposed portion with an organic solvent or a basic aqueous solution. .

  (11) An electronic component having a polyimide film obtained by imidizing a pattern obtained by the production method according to (10) as a surface protective film or an interlayer insulating film.

  (12) An electronic component comprising, as a cover coat layer, a polyimide film obtained by imidizing a pattern obtained by the production method according to (10).

  (13) An electronic component having a polyimide film obtained by imidizing a pattern obtained by the production method according to (10) as a core for a rewiring layer.

  (14) An electronic component having a polyimide film obtained by imidizing a pattern obtained by the production method according to (10) as a collar for holding conductive balls formed as external connection terminals.

  (15) An electronic component having, as an underfill, a polyimide film obtained by imidizing a pattern obtained by the production method according to (10).

  The photosensitive resin composition of the present invention can form a thick film, has excellent photosensitivity, has a highly sensitive pattern with a good shape even at low exposure, has a high residual film ratio after development, and has a cured film characteristic. In addition, the shrinkage rate after thermosetting is small.

  Moreover, since the photosensitive resin composition of the present invention is excellent in stress relaxation and has high adhesion to a metal layer and a molding material, it is excellent for various packages.

  The pattern production method of the present invention is capable of forming a thick film, has excellent photosensitivity, can provide a good pattern even with high sensitivity and low exposure, has a high residual film ratio after development, and has excellent cured film characteristics. Thus, the shrinkage rate at the time of thermosetting can be suppressed to a minimum, the manufacturing process can be shortened, and the manufacturing cost can be reduced.

Therefore, the electronic component of the present invention is extremely excellent in reliability without cracks or peeling.

  (A) The type of polyimide precursor having a repeating unit represented by the general formula (I) used in the present invention includes polyamic acid, polyamic acid ester, polyamic acid amide, etc., and is not particularly limited. R1 and R2 in the formula (I) are preferably polyimide precursors that are monovalent organic groups having a photopolymerizable carbon-carbon unsaturated double bond.

  Examples of such polyimide precursors include polyamic acid unsaturated esters, polyamic acid unsaturated amides, polyamic acids having a structure in which a compound having a carbon-carbon unsaturated double bond capable of photopolymerization is covalently bonded to polyamic acid as a side chain. A compound having a structure in which an amine compound having a carbon-carbon double bond is mixed and a carbon-carbon double bond is introduced by an ionic bond between a carboxyl group and an amino group is preferable.

  The polyamic acid unsaturated ester is prepared by mixing and reacting a tetracarboxylic dianhydride and a hydroxy group-containing compound having an unsaturated group to produce a tetracarboxylic acid half ester, and then acidifying with thionyl chloride, The tetracarboxylic acid half ester can be synthesized by a method of reacting with a diamine using a carbodiimide as a condensing agent, a method using a carbodiimide condensing agent, an isoimide method, or the like.

  In addition, when the carbon-carbon unsaturated double bond is introduced by the ester bond, the amount of the compound having the carbon-carbon double bond introduced is that of the polyamic acid from the viewpoint of solubility in a developer, photocurability, heat resistance, and the like. It is preferable to set it as 20 to 100% with respect to the carboxyl group to have, It is more preferable to set it as 30 to 90%, It is further more preferable to set it as 50 to 80%.

  Examples of the compound having a carbon-carbon unsaturated double bond include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl. Examples include methacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, caprolactone 2- (methacryloxy) ethyl ester, dicaprolactone 2- (methacryloyloxy) ethyl ester, and the like.

  The molecular weight of the polyimide precursor is preferably 3,000 to 200,000 in terms of weight average molecular weight, and more preferably 5,000 to 100,000. The molecular weight can be measured by gel permeation chromatography.

  In the present invention, the polyimide precursor (A) has a plurality of Y (generally residues of diamine components) and / or X (generally residues of acid anhydride components) of the general formula (I). Among repeating units, those having two or more types of structures having different aromatic ring numbers are used.

  Thereby, the excellent effect of the present invention, that is, high transparency, high adhesiveness, a small shrinkage of the coating film after heat curing, and a composition particularly suitable for thick film formation can be obtained.

  Examples of the diamine component having one aromatic ring include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,4-diaminobenzoic acid, 3,4-diaminobenzoic acid, and 3,5-diaminobenzoic acid. Acid, 3,5-diaminochlorobenzene, 5-nitro-m-phenylenediamine, 4-chloro-m-phenylenediamine, 4,6-dimethyl-m-phenylenediamine, 2,4-diaminomesitylene, 3,5-diaminoacetanilide , 3,5-diaminobenzonitrile, 2,4-diaminopyridine, p-xylylenediamine, m-xylylenediamine, o-xylylenediamine and the like, but are not limited thereto. Absent. Of these, m-phenylenediamine, 5-nitro-m-phenylenediamine, and 4,6-dimethyl-m-phenylenediamine are preferable. These are used alone or in combination of two or more. These are preferably used in an amount of 1 to 90 mol% based on the total amine component.

  Examples of the diamine component having two or more aromatic rings include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylpropane, 4 , 4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether-3-sulfonamide, 3,3'-dimethyl-4,4'- Examples include, but are not limited to, diaminobiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, diaminoterphenyl, and the like. Among these, it is preferable to use one having two aromatic rings. These are used alone or in combination of two or more. These are preferably used in an amount of 1 to 90 mol% based on the total amine component.

  In addition, as a diamine, in order to improve adhesiveness, the following general formula (II)

（式中Ｒ３及びＲ４は２価の炭化水素基を示し、それぞれ同一でも異なっていてもよく、Ｒ５及びＲ６は１価の炭化水素基を示し、それぞれ同一でも異なっていてもよく、ｔは１以上の整数である）で表されるジアミノポリシロキサン等のジアミンを使用することもできる。

(Wherein R3 and R4 represent a divalent hydrocarbon group, which may be the same or different, and R5 and R6 represent a monovalent hydrocarbon group, which may be the same or different, and t is 1 It is also possible to use a diamine such as diaminopolysiloxane represented by the above integer).

  Examples of R3 and R4 include alkylene groups such as methylene group, ethylene group and propylene group, arylene groups such as phenylene group, and bonding groups thereof. R5 and R6 include alkyl groups such as methyl group and ethyl group, An aryl group such as a phenyl group, and a bonding group thereof. When using these, it is preferable to use 1-30 mol% with respect to all the amine components. These diamines are used alone or in combination of two or more.

  Although there is no restriction | limiting in particular as an acid anhydride which has one aromatic ring used for manufacture of said (A) polyimide precursor, For example, pyromellitic dianhydride, benzene 1,2,3,4- Tetracarboxylic dianhydride, 1,4-dimethoxy-2,3,5,6-benzenetetracarboxylic dianhydride, 1,4-trimethylsilyl-2,3,5,6-benzenetetracarboxylic dianhydride 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, , 4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, etc. But these The present invention is not limited. Moreover, in using these, it uses individually or in combination of 2 or more types.

  Moreover, there is no restriction | limiting in particular as an acid anhydride which has two or more aromatic rings used for manufacture of the said (A) polyimide precursor, For example, oxydiphthalic dianhydride, 3,3 ', 4 , 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3, Examples thereof include, but are not limited to, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, terphenyltetracarboxylic dianhydride, and the like. Among these, it is preferable to use one having two aromatic rings. In using these, it is used individually or in combination of 2 or more types. Of these, oxydiphthalic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are preferred.

  As the acid anhydride component of the polyimide precursor (A), it is preferable to use 50 mol% or more of oxydiphthalic dianhydride with respect to the total acid anhydride component because of excellent properties such as high transparency. It is more preferable to use at least mol%, and it is even more preferable to use 70 to 100 mol%.

  In addition, (A) the polyimide precursor has an aromatic ring in which at least one of X and Y in the general formula (I) is in the 1,3-position (that is, the meta position) with the adjacent aromatic ring or amide group. It is preferable to have at least one because it is excellent in high transparency, high adhesion, shrinkage of the coating film after heat curing, and the like. In the present invention, each diamine residue and acid residue derived from the aromatic acid or diamine of the polyimide precursor preferably has one or two aromatic rings.

  Further, the polyimide precursor is a polyamic acid unsaturated ester having a (meth) acryloxyalkyloxy group as R1 and R2, and having an esterification rate of 50 to 80 mol%, and diamino as a diamine. A polysiloxane obtained by using 1 to 30 mol% of the total diamine is preferable because of excellent adhesion and the like.

  (B) As the addition polymerizable compound, one having a molecular weight of 350 or less is used. If the molecular weight exceeds this, the effect film characteristics after heat treatment are poor.

  Examples of such addition polymerizable compounds include compounds obtained by condensing polyhydric alcohol and α, β-unsaturated carboxylic acid, such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene. Glycol dimethacrylate, neopentyl glycol dimethacrylate, butylethylpropanediol methacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate Examples include, but are not limited to, acrylate, butylethylpropanediol diacrylate, 1,6-hexanediol diacrylate, etc. is not. Moreover, you may use these individually or in combination of 2 or more types.

  The content of the component (B) is preferably 1 to 200 parts by weight and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the polyimide precursor. If the amount used is less than 1 part by weight, the photosensitive properties including solubility in the developer tend to be inferior. If it exceeds 200 parts by weight, the mechanical properties of the film tend to be inferior.

  (C) Although there is no restriction | limiting in particular as a photoinitiator, For example, Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4-bis (diethylamino) Benzophenone, acetophenone, benzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzyl, diphenyl Disulfide, phenanthrenequinone, 2-isopropylthioxanthone, riboflavin tetrabutyrate, 2,6-bis (p-diethylaminobenzal) -4-methyl-4-azacyclohexano N-ethyl-N- (p-chlorophenyl) glycine, N-phenyldiethanolamine, 2- (o-ethoxycarbonyl) oxyiminopropan-1-one, 3,3,4,4-tetra (t-butylperoxy) Carbonyl) benzophenone, 3,3-carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl) -bis- [2,6-difluoro-3- (py-1-yl) phenyl] titanium, hexaarylbi Examples include, but are not limited to, imidazole compounds. Moreover, you may use these individually or in combination of 2 or more types.

  The content of the component (C) is preferably 1 to 30 parts by weight and more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the polyimide precursor.

  The photosensitive resin composition of this invention may contain a sensitizer as needed. Examples of the sensitizer include 7-N, N-diethylaminocoumarin, 7-diethylamino-3-thenonylcoumarin, 3,3′-carbonylbis (7-N, N-diethylamino) coumarin, and 3,3′-carbonyl. Bis (7-N, N-dimethoxy) coumarin, 3-thienylcarbonyl-7-N, N-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-N, N-methoxycoumarin, 3- (4′- Methoxybenzoyl) coumarin, 3,3′-carbonylbis-5,7- (dimethoxy) coumarin, benzalacetophenone, 4′-N, N-dimethylaminobenzalacetophenone, 4′-acetaminobenzal-4-methoxy Acetophenone, dimethylaminobenzophenone, diethylaminobenzophenone, 4,4′-bis (N— Chill, N- methyl) benzophenone, and the like, but is not limited thereto. Moreover, it is preferable to set these content as 0.05-20 weight part with respect to 100 weight part of polyimide precursors, and it is more preferable to set it as 0.1-10 weight part.

  The photosensitive resin composition of the present invention may further contain other additives such as plasticizers and adhesion promoters.

  The pattern manufacturing method of this invention forms the polyimide film which consists of hardened | cured material of this composition with the photolithographic technique using the photosensitive resin composition of this invention.

  In the pattern manufacturing method of the present invention, first, a film made of the photosensitive resin composition of the present invention is formed on the surface of the support substrate. In addition, in the pattern manufacturing method of this invention, in order to improve the adhesiveness of a polyimide film after a film or heat-curing, and a support substrate, you may process the support substrate surface with an adhesion | attachment adjuvant beforehand.

  The film made of the photosensitive resin composition is formed, for example, by forming a varnish film of the photosensitive resin composition and then drying it. The pattern production method of the present invention is particularly preferred when the drying is formed by low-temperature curing, for example, suitable for formation at 300 ° C., and further suitable for formation at 250 ° C. The varnish film is formed by means appropriately selected from means such as spin coating using a spinner, immersion, spray printing, and screen printing in accordance with the viscosity of the varnish. In addition, the film thickness of a film can be adjusted with coating conditions, solid content concentration of this composition, etc. Moreover, the above-mentioned film may be formed by peeling a film previously formed on the support substrate from the support and attaching a sheet made of the polyimide precursor composition to the surface of the support substrate.

  Next, the film is irradiated with light (ultraviolet light or the like) through a photomask having a predetermined pattern, and then the unexposed portion is dissolved and removed with an organic solvent or a basic aqueous solution to obtain a desired relief pattern.

  Examples of the organic solvent include acetone, methyl ethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether. , Xylene, tetrahydrofuran, dioxane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, hexyl acetate, methyl cellosolve, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol mono-acetate n-butyl ether, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfoxide, sulfur Orchid, cyclohexanol, cyclohexanone, cyclohexane oxime, cyclohexane, 1,4-cyclohexanedimethanol, cyclohexyl acetate, cyclopentanol, cyclopentanone, cyclopentanone oxime, cyclopentane, and the like. Absent. Moreover, you may use these individually or in combination of 2 or more types.

  The basic aqueous solution is usually a solution in which a basic compound is dissolved in water. The concentration of the basic compound is preferably 0.1 to 50% by weight, more preferably 0.1 to 30% by weight from the viewpoint of influence on the support substrate and the like. In order to improve the solubility of the polyimide precursor, a water-soluble organic solvent such as methanol, ethanol, propanol, isopropanol, butanol, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide is used. Furthermore, you may contain.

  Examples of the basic compound include alkali metal, alkaline earth metal or ammonium ion hydroxides or carbonates, amine compounds, and the like.

  In the obtained pattern, a part of the polyimide precursor of the present invention is usually imidized. By heating this pattern, a stable high heat resistant polyimide pattern can be obtained. The heating temperature at this time is preferably 130 to 500 ° C, and more preferably 150 to 350 ° C. If this heating temperature is less than 130 ° C., the mechanical properties and thermal properties of the polyimide film tend to deteriorate, and if it exceeds 500 ° C., the mechanical properties and thermal properties of the polyimide film tend to be inferior.

  The heating time at this time is preferably 0.01 to 10 hours, and more preferably 0.05 to 5 hours. If this heating time is less than 0.01 hour, the mechanical properties and thermal properties of the polyimide film tend to be reduced, and if it exceeds 10 hours, the mechanical properties and thermal properties of the polyimide film tend to be inferior.

  Thus, the photosensitive resin composition of this invention can be used for the surface protective film for semiconductors, the interlayer insulation film of a multilayer wiring board, etc. Since the surface protective film using the photosensitive resin composition of the present invention is excellent in adhesiveness with SiN, sealant and the like, a semiconductor element using the surface protective film obtained from the photosensitive resin composition of the present invention Is extremely reliable.

  The semiconductor device of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

  Moreover, since the photosensitive resin composition of the present invention is very excellent in stress relaxation property, adhesiveness, etc., it is suitable as various structural materials in various types of packages developed in recent years.

  FIG. 1 shows a cross-sectional structure of an example of a semiconductor device. This sectional view shows a multilayer wiring structure. An Al wiring layer 2 is formed on the interlayer insulating layer 1, an insulating layer 3 (for example, a P-SiN layer) is further formed thereon, and a surface protective film layer 4 of the element is further formed. A rewiring layer 6 is formed from the pad portion 5 of the wiring layer 2 and extends to an upper portion of the core 8 which is a connection portion with a conductive ball 7 formed of solder, gold or the like as an external connection terminal. Further, a cover coat layer 9 is formed on the surface protective film layer 4. The rewiring layer 6 is connected to the conductive ball 7 through the barrier metal 10, and a collar 11 is provided to hold the conductive ball 7. When a package having such a structure is mounted, an underfill 12 may be interposed in order to further relieve stress.

  In this figure, the photosensitive resin composition of the present invention is not only suitable for interlayer insulating layers and surface protective film layers, but also for its excellent properties, and is therefore very suitable as a material for cover coat layers, cores, collars, underfills and the like. Yes. Since the heat-resistant photosensitive resin cured body using the photosensitive resin composition of the present invention is excellent in adhesiveness with a metal layer, a sealant and the like and has a high stress relaxation effect, the photosensitive resin composition of the present invention A semiconductor element in which the obtained heat-resistant photosensitive resin cured product is used for a cover coat layer, a core, a collar, an underfill, etc. has extremely excellent reliability.

  The semiconductor device of the present invention as shown in FIG. 1 has a cover coat formed using the composition, a core for rewiring, a collar for balls such as solder, an underfill used for flip chips, etc. Is not particularly limited, and can have various structures.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention does not receive a restriction | limiting by these at all. The following synthesis example shows a method using N, N′-dihydrocarbyl-substituted carbodiimide as an isoimidating agent, but trifluoroacetic anhydride may be used instead.
(Synthesis Example 1)
Pyromellitic dianhydride 3.4880 g (0.0160 mol), 4,4'-oxydiphthalic dianhydride 9.8528 g (0.0640 mol) and dried in a 500 ml four-necked flask equipped with a dry nitrogen inlet tube 100 ml of N-methylpyrrolidone was added and stirred, and 2.6000 g (0.0200 mol) of 2-hydroxyethyl methacrylate was added to this solution. The solution was stirred at room temperature for 1 hour, further heated to 40 ° C. and stirred for 1 hour, then cooled to room temperature, m-phenylenediamine 2.3358 g (0.0216 mol), p-phenylenediamine 5.4502 g (0.0504 mol). ) And 120 ml of dry N-methylpyrrolidone was added dropwise over 1 hour with stirring at room temperature and stirred overnight.

  Thereafter, 26.8200 g (0.1300 mol) of N, N-dicyclohexylcarbodiimide and 100 ml of dry N-methylpyrrolidone were added dropwise over 30 minutes with stirring at room temperature. Further, 31.2340 g (0.2400 mol) of 2-hydroxyethyl methacrylate was added, stirred at 50 ° C. for 5 hours, cooled to room temperature and stirred overnight.

The reaction mixture was diluted with 100 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was slowly added to 2.0 L of ion exchange water with vigorous stirring to obtain a precipitate. The deposited precipitate was further washed with ion exchange water, then washed with methanol, and filtered by suction filtration to obtain a solid. The obtained solid was dried with a vacuum dryer until the water content at room temperature became 1.0% by weight or less to obtain a powdery solid.
(Synthesis Example 2)
In a 500 ml four-necked flask equipped with a dry nitrogen inlet tube, 24.8160 g (0.0800 mol) of 4,4′-oxydiphthalic dianhydride and 100 ml of dried N-methylpyrrolidone were added and stirred. 2.6000 g (0.0200 mol) of 2-hydroxyethyl methacrylate was added. The solution was stirred at room temperature for 1 hour, further heated to 40 ° C., stirred for 1 hour, cooled to room temperature, and 3,2862 g (0.0216 mol) of 2,4-diaminobenzoic acid, 4,4′-diaminodiphenyl ether 10 0.0800 g (0.0504 mol) and 120 ml of dry N-methylpyrrolidone were added dropwise over 1 hour with stirring at room temperature and stirred overnight.
Thereafter, 26.8200 g (0.1300 mol) of N, N-dicyclohexylcarbodiimide and 100 ml of dry N-methylpyrrolidone were added dropwise over 30 minutes with stirring at room temperature. Further, 31.2340 g (0.2400 mol) of 2-hydroxyethyl methacrylate was added, stirred at 50 ° C. for 5 hours, cooled to room temperature and stirred overnight.
The reaction mixture was diluted with 100 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was slowly added to 2.0 L of ion exchange water with vigorous stirring to obtain a precipitate. The deposited precipitate was further washed with ion exchange water, then washed with methanol, and filtered by suction filtration to obtain a solid. The obtained solid was dried with a vacuum dryer until the water content at room temperature became 1.0% by weight or less to obtain a powdery solid.
(Synthesis Example 3)
In a 500 ml four-necked flask equipped with a dry nitrogen inlet tube, 24.8160 g (0.0800 mol) of 4,4′-oxydiphthalic dianhydride and 100 ml of dried N-methylpyrrolidone were added and stirred. 2.6000 g (0.0200 mol) of 2-hydroxyethyl methacrylate was added. The solution was stirred at room temperature for 1 hour, further heated to 40 ° C., stirred for 1 hour, cooled to room temperature, and 2.9160 g (0.0216 mol) of 4,6-dimethyl-m-phenylenediamine, 4, 4′- The mixture was changed to 10.0800 g (0.0504 mol) of diaminodiphenyl ether and 120 ml of dry N-methylpyrrolidone was added dropwise over 1 hour with stirring at room temperature, and the mixture was stirred overnight.

Thereafter, 26.8200 g (0.1300 mol) of N, N-dicyclohexylcarbodiimide and 100 ml of dry N-methylpyrrolidone were added dropwise over 30 minutes with stirring at room temperature. Further, 31.2340 g (0.2400 mol) of 2-hydroxyethyl methacrylate was added, stirred at 50 ° C. for 5 hours, cooled to room temperature and stirred overnight.
The reaction mixture was diluted with 100 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was slowly added to 2.0 L of ion exchange water with vigorous stirring to obtain a precipitate. The deposited precipitate was further washed with ion exchange water, then washed with methanol, and filtered by suction filtration to obtain a solid. The obtained solid was dried with a vacuum dryer until the water content at room temperature became 1.0% by weight or less to obtain a powdery solid.
(Synthesis Example 4)
Pyromellitic dianhydride 1.7440 g (0.0080 mol), 4,4′-oxydiphthalic dianhydride 22.3344 g (0.0720 mol) and dried in a 500 ml four-necked flask equipped with a dry nitrogen inlet tube 100 ml of N-methylpyrrolidone was added and stirred, and 2.6000 g (0.0200 mol) of 2-hydroxyethyl methacrylate was added to this solution. The solution was stirred at room temperature for 1 hour, further heated to 40 ° C. and stirred for 1 hour, then cooled to room temperature, m-phenylenediamine 2.3358 g (0.0216 mol), 4,4′-diaminodiphenyl ether 10.0800 g ( 0.0504 mol) and 120 ml of dry N-methylpyrrolidone were added dropwise over 1 hour with stirring at room temperature and stirred overnight.

Thereafter, 26.8200 g (0.1300 mol) of N, N-dicyclohexylcarbodiimide and 100 ml of dry N-methylpyrrolidone were added dropwise over 30 minutes with stirring at room temperature. Further, 31.2340 g (0.2400 mol) of 2-hydroxyethyl methacrylate was added, stirred at 50 ° C. for 5 hours, cooled to room temperature and stirred overnight.
The reaction mixture was diluted with 100 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was slowly added to 2.0 L of ion exchange water with vigorous stirring to obtain a precipitate. The deposited precipitate was further washed with ion exchange water, then washed with methanol, and filtered by suction filtration to obtain a solid. The obtained solid was dried with a vacuum dryer until the water content at room temperature became 1.0% by weight or less to obtain a powdery solid.
(Synthesis Example 5)
In a 500 ml four-necked flask equipped with a dry nitrogen inlet tube, 9.4080 g (0.0160 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 4,4′-oxydiphthalic dianhydride The product 19.8528 g (0.0640 mol) of dried N-methylpyrrolidone 100 ml was added and stirred, and 2.6000 g (0.0200 mol) of 2-hydroxyethyl methacrylate was added to this solution. The solution was stirred at room temperature for 1 hour, further heated to 40 ° C., stirred for 1 hour, cooled to room temperature, 6.9209 g (0.0640 mol) of m-phenylenediamine, 3.2000 g of 4,4′-diaminodiphenyl ether ( 0.0160 mol) and 120 ml of dry N-methylpyrrolidone were added dropwise over 1 hour with stirring at room temperature and stirred overnight.

Thereafter, 26.8200 g (0.1300 mol) of N, N-dicyclohexylcarbodiimide and 100 ml of dry N-methylpyrrolidone were added dropwise over 30 minutes with stirring at room temperature. Further, 31.2340 g (0.2400 mol) of 2-hydroxyethyl methacrylate was added, stirred at 50 ° C. for 5 hours, cooled to room temperature and stirred overnight.
The reaction mixture was diluted with 100 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was slowly added to 2.0 L of ion exchange water with vigorous stirring to obtain a precipitate. The deposited precipitate was further washed with ion exchange water, then washed with methanol, and filtered by suction filtration to obtain a solid. The obtained solid was dried with a vacuum dryer until the water content at room temperature became 1.0% by weight or less to obtain a powdery solid.

(Example 1)
In a 100 ml four-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 35.0 g of the photosensitive polymer powder obtained in Synthesis Example 1, 38.0 g of dry N-methylpyrrolidone, and P-methoxyphenol 0. After stirring and dissolving 1 g, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2.0 g, 2-mercaptobenzoxazole 1.0 g and ethyl Michler's ketone 0.2 g of a photosensitizer and 7.0 g of triethylene glycol diacrylate as an addition polymerizable compound were added and stirred and dissolved overnight at room temperature, and then filtered to obtain a photosensitive resin composition solution. This solution was spin-coated on a silicon wafer and dried to form a 20 μm coating film, which was then exposed with a full-wavelength exposure machine PLA-600FA (manufactured by Canon Inc.) through a pattern mask, and N-methyl When developing with a mixed solution of pyrrolidone and methanol and rinsing with ethanol, a good relief pattern without peeling was obtained at an exposure amount of 200 mJ / cm 2. The residual film ratio after development at this exposure amount is 90% or more, and when the wafer after development is heated at 250 ° C. for 2 hours, it exhibits excellent cured film characteristics and adhesion, and the shrinkage ratio of the coating film after thermal curing. Was 30% or less. A solution prepared in the same manner except that the amount of N-methylpyrrolidone added in the photosensitive resin composition solution was changed to 26.4 g was spin-coated on a silicon wafer and then dried to form a 70 μm coating film. Then, it exposed with the full wavelength exposure machine MPA600super (made by Canon Inc.) through the pattern mask, spray-developed using the mixed solution of N-methylpyrrolidone and methanol, and rinsed with ethanol, 30 micrometers Patterns up to can be formed. Further, the embedding property at a step having a width of 100 μm and a depth of 60 μm was satisfactory without any problem.

(Example 2)
In a 100 ml four-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 35.0 g of the photosensitive polymer powder obtained in Synthesis Example 2, 38.0 g of dry N-methylpyrrolidone, 0. After stirring and dissolving 1 g, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2.0 g, 2-mercaptobenzoxazole 1.0 g and ethyl Michler's ketone 0.2 g of a photosensitizer and 7.0 g of 1,6-hexanediol diacrylate as an addition polymerizable compound were added, and the mixture was stirred and dissolved overnight at room temperature, and then filtered to obtain a photosensitive resin composition solution. This solution was spin-coated on a silicon wafer and dried to form a 20 μm coating film, which was then exposed with a full-wavelength exposure machine PLA-600FA (manufactured by Canon Inc.) through a pattern mask, and N-methyl When developing with a mixed solution of pyrrolidone and methanol and rinsing with ethanol, a good relief pattern without peeling was obtained at an exposure amount of 250 mJ / cm 2. The residual film ratio after development at this exposure amount is 90% or more, and when the wafer after development is heated at 250 ° C. for 2 hours, it exhibits excellent cured film characteristics and adhesion, and the shrinkage ratio of the coating film after thermal curing. Was 30% or less. A solution prepared in the same manner except that the addition amount of N-methylpyrrolidone in the photosensitive resin composition solution was changed to 26.4 g was spin-coated on a silicon wafer and then dried to form an 80 μm coating film. Then, it exposed with the full wavelength exposure machine MPA600super (made by Canon Inc.) through the pattern mask, spray-developed using the mixed solution of N-methylpyrrolidone and methanol, and rinsed with ethanol, 30 micrometers Patterns up to can be formed. Further, the embedding property at the step having a width of 100 μm and a depth of 60 μm was a good result without causing problems such as voids.

(Example 3)
In a 100 ml four-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 35.0 g of the photosensitive polymer powder obtained in Synthesis Example 3, 38.0 g of dry N-methylpyrrolidone, and P-methoxyphenol 0. After stirring and dissolving 1 g, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2.0 g, 2-mercaptobenzoxazole 1.0 g and ethyl Michler's ketone 0.2 g of a photosensitizer and 7.0 g of triethylene glycol dimethacrylate as an addition polymerizable compound were added and stirred and dissolved overnight at room temperature, and then filtered to obtain a photosensitive resin composition solution. This solution was spin-coated on a silicon wafer and dried to form a 20 μm coating film, which was then exposed with a full-wavelength exposure machine PLA-600FA (manufactured by Canon Inc.) through a pattern mask, and N-methyl When developing with a mixed solution of pyrrolidone and methanol and rinsing with ethanol, a good relief pattern without peeling was obtained at an exposure amount of 300 mJ / cm 2. The residual film ratio after development at this exposure amount is 90% or more, and when the wafer after development is heated at 250 ° C. for 2 hours, it exhibits excellent cured film characteristics and adhesion, and the shrinkage ratio of the coating film after thermal curing. Was 30% or less. A solution prepared in the same manner except that the addition amount of N-methylpyrrolidone in the photosensitive resin composition solution was changed to 26.4 g was spin-coated on a silicon wafer and then dried to form an 80 μm coating film. Then, it exposed with the full-wavelength exposure machine MPA600super (made by Canon Inc.) through a pattern mask, developed using a mixed solution of N-methylpyrrolidone and methanol, and rinsed with ethanol. Pattern could be formed. Further, the embedding property at the step having a width of 100 μm and a depth of 60 μm was a good result without causing problems such as voids.

Example 4
In a 100 ml four-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 35.0 g of the photosensitive polymer powder obtained in Synthesis Example 4, 38.0 g of dry N-methylpyrrolidone and 0. After stirring and dissolving 1 g, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2.0 g, 2-mercaptobenzoxazole 1.0 g and ethyl Michler's ketone 0.2 g of a photosensitizer and 7.0 g of triethylene glycol diacrylate as an addition polymerizable compound were added and stirred and dissolved overnight at room temperature, and then filtered to obtain a photosensitive resin composition solution. This solution was spin-coated on a silicon wafer and dried to form a 20 μm coating film, which was then exposed with a full-wavelength exposure machine PLA-600FA (manufactured by Canon Inc.) through a pattern mask, and N-methyl When developing with a mixed solution of pyrrolidone and methanol and rinsing with ethanol, a good relief pattern without peeling was obtained at an exposure amount of 350 mJ / cm 2. The residual film ratio after development at this exposure amount is 90% or more, and when the wafer after development is heated at 250 ° C. for 2 hours, it exhibits excellent cured film characteristics and adhesion, and the shrinkage ratio of the coating film after thermal curing. Was 30% or less. A solution prepared in the same manner except that the amount of N-methylpyrrolidone added in the photosensitive resin composition solution was changed to 26.4 g was spin-coated on a silicon wafer and then dried to form a 70 μm coating film. After that, it was exposed with a full-wavelength exposure machine MPA600super (manufactured by Canon Inc.) through a pattern mask, developed using a mixed solution of N-methylpyrrolidone and methanol, and rinsed with ethanol. Pattern could be formed. Further, the embedding property at the step having a width of 100 μm and a depth of 60 μm was a good result without causing problems such as voids.

(Example 5)
In a 100 ml four-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 35.0 g of the photosensitive polymer powder obtained in Synthesis Example 5, 38.0 g of dry N-methylpyrrolidone and 0. After stirring and dissolving 1 g, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2.0 g, 2-mercaptobenzoxazole 1.0 g and Michler's ketone 0.2 g After adding 7.0 g of 1,6-hexanediol diacrylate as an addition polymerizable compound and stirring and dissolving at room temperature overnight, the mixture was filtered to obtain a photosensitive resin composition solution. This solution was spin-coated on a silicon wafer and dried to form a 20 μm coating film, which was then exposed with a full-wavelength exposure machine PLA-600FA (manufactured by Canon Inc.) through a pattern mask, and N-methyl When developing with a mixed solution of pyrrolidone and methanol and rinsing with ethanol, a good relief pattern without peeling was obtained at an exposure amount of 250 mJ / cm 2. The residual film ratio after development at this exposure amount is 90% or more, and when the wafer after development is heated at 250 ° C. for 2 hours, it exhibits excellent cured film characteristics and adhesion, and the shrinkage ratio of the coating film after thermal curing. Was 30% or less. A solution prepared in the same manner except that the amount of N-methylpyrrolidone added in the photosensitive resin composition solution was changed to 26.4 g was spin-coated on a silicon wafer and then dried to form a 70 μm coating film. After that, it was exposed with a full-wavelength exposure machine MPA600super (manufactured by Canon Inc.) through a pattern mask, developed using a mixed solution of N-methylpyrrolidone and methanol, and rinsed with ethanol. Pattern could be formed. In addition, the embedding property at the step having a width of 100 μm and a depth of 60 μm showed good results without causing problems such as voids.

(Comparative Example 1)
Instead of m-phenylenediamine and p-phenylenediamine used in Synthesis Example 1, 4,4′-diaminobiphenyl was used, and pyromellitic dianhydride was not used as the acid component. When the obtained photosensitive polymer powder was used in the same manner as in Example 1, a relief pattern was obtained after development, but the sensitivity was low and it was not practical.
(Comparative Example 2)
When the same treatment as in Example 2 was performed except that dipentaerythritol hexaacrylate (having a molecular weight of more than 350) was used instead of 1,6-hexanediol diacrylate of the addition polymerizable compound used in Example 2, Although a relief pattern was obtained after development, the cured film characteristics after heat treatment were inferior.
(Comparative Example 3)
When the same treatment as in Example 3 was carried out without using the addition-polymerizable compound triethylene glycol diacrylate used in Example 3, the sensitivity became low and the pattern swelled after development, and a satisfactory pattern was not obtained.

(Example 6)
The solution used in Examples 1 to 5 was spin-coated on a substrate on which a rewiring layer was formed and then dried to form a 20 um coating film. Then, a full-wave exposure machine PLA-600FA (manufactured by Canon Inc.) ) For 200 mJ / cm 2, developed using a mixed solution of N-methylpyrrolidone and methanol, rinsed with ethanol to form 200 um square via holes. This was oven baked at 250 ° C. for 2 hours to form a cover coat polyimide film. After forming an under bumping metal in the hole portion, a solder ball was bumped to produce a test part as shown in FIG. Furthermore, a test part was mounted and sealed to obtain a test sample.

When the test samples were subjected to a temperature cycle test (-55 to 125 ° C., 1000 cycles), no defects such as cracks and peeling were observed.
(Comparative Example 4)
Photosensitivity obtained in the same manner as in Synthesis Example 2 except that pyromellitic dianhydride was used in place of 4,4′-oxydiphthalic acid dianhydride used in Synthesis Example 2 and that all diamines were p-phenylenediamine. When a photosensitive resin composition solution obtained by blending in the same manner as in Example 2 using a conductive polymer powder was treated in the same manner as in Example 6, peeling was observed at the interface with solder cracks and underbumping metal. It was.

It is sectional drawing which shows the outline | summary of the cross-sectional structure of an example of the semiconductor device of this invention. It is sectional drawing which shows the outline | summary of the cross-sectional structure of the semiconductor device produced in Example 6 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Interlayer insulating layer, 2 ... Al wiring layer, 3 ... Insulating layer, 4 ... Surface protective film layer, 5 ... Pad part of wiring layer, 6 ... Rewiring layer, 7 ... conductive balls, 8 ... core, 9 ... cover coat layer, 10 ... barrier metal, 11 ... collar, 12 ... underfill

Claims (15)

(A) General formula (I)

(In the formula, X is a group containing a tetravalent aromatic ring, Y is a group containing a divalent aromatic ring, R 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group, A polyimide precursor having a repeating unit represented by (at least one of X and Y having two or more structures having different aromatic ring numbers), (B) an addition-polymerizable compound having a molecular weight of 350 or less, and (C) photoinitiation Photosensitive resin composition comprising an agent.   (A) The polyimide precursor has at least one aromatic ring in which at least one of X and Y in the general formula (I) is bonded to the adjacent aromatic ring or amide group at the 1,3-position. The photosensitive resin composition of Claim 1. (A) The polyimide precursor is in the general formula (I), and X is the following structure

The photosensitive resin composition of Claim 1 or 2 which contains 50 mol% or more of all the acid anhydride components.   The polyimide precursor is a polyamic acid unsaturated ester having a (meth) acryloxyalkyloxy group as R1 and R2, having an esterification rate of 50 to 80 mol%, and diaminopolysiloxane as a diamine The photosensitive resin composition according to claim 1, 2 or 3, which is obtained using 1 to 30 mol% of the total diamine.   5. A semiconductor device having a structure in which a surface protective film layer is formed on a wiring layer of a semiconductor element and a cover coat layer is formed thereon, for the surface protective film layer. The photosensitive resin composition as described.   5. The cover coat layer for a semiconductor device having a structure in which a surface protective film layer is formed on a wiring layer of a semiconductor element and a cover coat layer is formed thereon. Photosensitive resin composition.   5. A semiconductor device having a structure in which a surface protective film layer is formed on a wiring layer of a semiconductor element, and a core for rewiring is formed thereon. The photosensitive resin composition as described.   A surface protection film layer is formed on the wiring layer of the semiconductor element, a rewiring layer and an overcoat layer are formed thereon, and a conductive ball formed as an external connection terminal is further formed on the rewiring layer. The photosensitive resin composition according to claim 1, 2, 3, or 4, wherein the photosensitive resin composition is used for a color material for holding the ball in a semiconductor device having a holding structure.   The photosensitive resin composition according to claim 1, 2, 3, or 4, which is used for an underfill material of a semiconductor device.   A process of forming a polyimide precursor film by applying the photosensitive resin composition according to any one of claims 1 to 9 on a support substrate, and a photomask having a predetermined pattern on the polyimide precursor film. A method for producing a pattern, comprising: a step of irradiating an actinic ray and exposing, and then dissolving and removing an unexposed portion with an organic solvent or a basic aqueous solution to obtain a desired relief pattern.   The electronic component which has as a surface protective film or an interlayer insulation film the polyimide film obtained by imidating the pattern obtained by the manufacturing method of Claim 10.   An electronic component comprising a polyimide film obtained by imidizing a pattern obtained by the production method according to claim 10 as a cover coat layer.   The electronic component which has as a core for rewiring layers the polyimide film obtained by imidating the pattern obtained by the manufacturing method of Claim 10.   An electronic component comprising a polyimide film obtained by imidizing a pattern obtained by the production method according to claim 10 as a collar for holding conductive balls formed as external connection terminals. An electronic component comprising, as an underfill, a polyimide film obtained by imidizing a pattern obtained by the production method according to claim 10.

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