JP2003248309A - Photosensitive resin composition, method for producing pattern using the same and electronic parts - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition capable of forming a thick film, excellent in photosensitive characteristics, having high sensitivity, giving a pattern of a good shape even with small light exposure and ensuring a high residual film rate after development, excellent properties of a cured film and a low shrinkage percentage of a coating film after heat curing, to provide a method for producing a pattern capable of shortening a production process and capable of decreasing production cost and to provide electronic parts using the pattern. <P>SOLUTION: The photosensitive resin composition comprises (A) a polyimide precursor having a repeating unit represented by formula (I) (where X is a tetravalent aromatic ring-containing group; Y is a divalent aromatic ring- containing group; R<SP>1</SP>and R<SP>2</SP>are each H or a monovalent organic group; and at least one of X and Y has three or more aromatic ring), (B) an addition- polymerizable compound having ≥100°C boiling point under atmospheric pressure and (C) a photoinitiator. The method for producing a pattern uses the composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a high transparency, a high adhesiveness, a small shrinkage rate of a coating film after heat curing, and is particularly suitable for forming a thick film. A photosensitive resin composition suitable for an interlayer insulating film and the like, a method for producing a pattern using this composition, and an electronic component, in particular, a negative photosensitive resin composition and pattern which become a heat-resistant polyimide polymer by heat treatment Manufacturing method and electronic component.

Further, the present invention has high transparency and high adhesion, has a small coating film shrinkage rate after heat curing and is suitable for forming a thick film, and is suitable for cover coat materials for semiconductor devices, core materials for rewiring, solders and the like. The present invention relates to a photosensitive resin composition suitable for so-called packaging, such as a ball color material and an underfill material used in flip chips, a method for producing a pattern using this composition, and an electronic component.

[0003]

2. Description of the Related Art A polyimide or its precursor, which also has a photo-patterning property by itself, is called a photosensitive polyimide and is used for a surface protective film of a semiconductor. Several methods of imparting photosensitivity are known for photosensitive polyimide. A representative one is Japanese Examined Japanese Patent Publication No.55-4
A mixture of a polyamic acid as an ester of hydroxyacrylate as proposed in Japanese Patent No. 1422 and a polyamic acid as proposed in JP-A No. 54-145794 and an amino acrylate. It is known to introduce a photosensitive group by a salt bond.

Since polyamic acid itself is rigid in these materials, there is a drawback that the film state prepared by spin coating or the like has lower sensitivity than conventional ultraviolet curable paints and dry film resists. To improve this, sensitivity can be increased by adding an oxime ester compound, an arylglycine compound, or the like. On the other hand, however, when a thick film is formed, there are drawbacks such as insufficient sensitivity and reduced adhesion. Further, there is a problem that the shrinkage rate of the coating film after heat curing is large, it is difficult to form a thicker film, and the shape of the polyimide pattern and the dimensions of the opening pattern are significantly changed.

In addition, in a new package application developed in recent years, it is required to have a property of relaxing a stress caused by a thermal shock or the like, and depending on the film property of a coating film after heat curing, sufficient relaxation cannot be obtained and a crack is generated. May peel off. Further, in such a package application, peeling may occur unless the adhesion with the under bumping metal layer or the molding material is sufficient.

[0006]

SUMMARY OF THE INVENTION A first object of the present invention is to form a thick film, have excellent photosensitivity, have high sensitivity, and obtain a pattern with a good shape even at a low exposure dose, and leave a pattern after development. It is an object of the present invention to provide a photosensitive resin composition having a high film rate, a cured film excellent in cured film characteristics, and a small coating film shrinkage ratio after heat curing. Particularly, it is to provide a photosensitive resin composition suitable for various uses of a new package.

A second object of the present invention is to form a thick film,
It has excellent photosensitivity, high sensitivity, good shape pattern even at low exposure, high residual film rate after development, small shrinkage rate of coating film after heat curing, and excellent curing film property. It is an object of the present invention to provide a method for producing a pattern, which can obtain a film, has excellent adhesiveness to various members, can shorten the production process, and can reduce the production cost. In addition to the above objects, a third object of the present invention is to provide a highly reliable electronic component, especially a novel package having excellent reliability.

[0008]

The present invention provides (A) general formula (I)

[Chemical 2] (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 are each independently a hydrogen atom or a monovalent organic group, and X and Y At least one has 3 or more aromatic rings), a polyimide precursor having a repeating unit represented by (B) an addition-polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure, and (C) a photoinitiator. And a photosensitive resin composition.

In the present invention, the polyimide precursor is an aromatic ring in which at least one of X and Y in the above-mentioned general formula (I) has a bond between the aromatic rings on both sides at the 1,3 position. It relates to a photosensitive resin composition having at least one. In the present invention, the polyimide precursor is R
¹ and R ² are polyamic acid unsaturated esters having a (meth) acryloxyalkyloxy group and having an esterification rate of 60 to 80 mol%, and diamine polysiloxane is used as a diamine. 1
-30 mol% is used and it is related with the photosensitive resin composition which is obtained.

According to the present invention, in 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 on the surface protective film layer, the photosensitive material for the cover coat layer is used. Resin composition. Further, the present invention is for the core material in 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 rewiring core formed thereon is formed. It relates to a photosensitive resin composition.

Further, according to the present invention, a surface protective film layer is formed on a wiring layer of a semiconductor device, a rewiring layer and a cover coat layer are formed on the surface protection film layer, and an external connection terminal is formed on the rewiring layer. The present invention relates to the above-mentioned photosensitive resin composition for a color material for holding the formed balls, in a semiconductor device having a structure for holding the conductive balls.
The present invention also relates to the above-mentioned photosensitive resin composition for use as an underfill material for semiconductor devices.

The present invention also provides a step of forming a polyimide precursor film by applying the photosensitive resin composition as described above on a supporting substrate,
After exposure by irradiation with an actinic ray through a photomask of a predetermined pattern, the unexposed portion is dissolved and removed with an organic solvent or a basic aqueous solution to obtain a desired relief pattern. Regarding manufacturing method.

The present invention also relates to an electronic component having a polyimide film obtained by imidizing the pattern obtained by the above manufacturing method as a surface protective film or an interlayer insulating film. The present invention also relates to an electronic component having as a cover coat layer a polyimide film obtained by imidizing the pattern obtained by the above production method. Further, the present invention is
The present invention relates to an electronic component having a polyimide film obtained by imidizing a pattern obtained by the above-mentioned manufacturing method as a core for a rewiring layer.

Further, the present invention is an electronic component having a polyimide film obtained by imidizing the pattern obtained by the above-mentioned manufacturing method as a collar for holding a conductive ball formed as an external connection terminal. Regarding The present invention also relates to an electronic component having a polyimide film obtained by imidizing the pattern obtained by the above manufacturing method as an underfill.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Polyimide acid, polyamic acid ester, polyamic acid amide and the like are available as types of the polyimide precursor having the repeating unit represented by the general formula (I) used in the present invention. Although not particularly limited, it is preferable that R ¹ and R ² in the general formula (I) are polyimide precursors each of which is a monovalent organic group having a carbon-carbon unsaturated double bond capable of photopolymerization.

Examples of such a polyimide precursor include a polyamic acid unsaturated ester and a polyamic acid unsaturated amide having a structure in which a photopolymerizable compound having a carbon-carbon unsaturated double bond is covalently bonded to a polyamic acid as a side chain. ,
Examples thereof include those obtained by mixing a polyamic acid with an amine compound having a carbon-carbon double bond and introducing the carbon-carbon double bond by an ionic bond between a carboxyl group and an amino group. From the viewpoint of reactivity, the carbon-carbon unsaturated double bond is preferably contained in the form of an acryloyl group or a methacryloyl group. Therefore, for example, in the case of a polyamic acid unsaturated ester, as R ¹ and R ² in the general formula (I),

[Chemical 3] (In the formula, R ³ represents a divalent alkylene group having 1 to 10 carbon atoms, R ^3
4 is a hydrogen atom or a methyl group) (meta)
Those having a structure of an acryloxyalkyloxy group are preferred.

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

In the polyimide precursor, the introduced amount of the compound having a carbon-carbon double bond (referred to as the esterification rate in the polyamic acid unsaturated ester) depends on the solubility in the developing solution, photocurability, heat resistance and the like. From the viewpoint, it is preferably 20 to 100 mol%, more preferably 30 to 90 mol%, and further preferably 60 to 80 mol% based on the carboxyl group of the polyamic acid.

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 methacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, caprolactone 2- (methacryloxy) ethyl Examples thereof include esters and dicaprolactone 2- (methacryloyloxy) ethyl ester.

The weight average molecular weight of the polyimide precursor is preferably 3,000 to 200,000, and more preferably 5,000 to 100,000. The molecular weight can be measured by a gel permeation chromatography method. In the present invention, the above (A) polyimide precursor has an aromatic ring in either or both of Y (generally a residue of a diamine component) and X (generally a residue of an acid anhydride component) of the general formula (I). Those having three or more are used. Among them, it is preferable that at least one of X and Y has at least one aromatic ring having a bond between the adjacent aromatic rings at the 1,3 position.

Examples of the diamine component include 1,3
-Bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, bis (4-aminophenoxyphenyl) biphenyl, 2,2- Screw {4-
(4-Aminophenoxy) phenyl} hexafluoropropane, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4 ′-{1,3-phenylenebis (1-methylethylidene)} bisaniline, bis-p −
Aminophenylaniline, bis- (4-aminophenoxyphenyl) sulfide, bis- (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, 9,9-bis (4-aminophenyl) fluorene, 9 , 9-bis (4-aminophenyl)
Examples include, but are not limited to, aromatic diamines such as anthracene. Among them, those having at least one aromatic ring having a 1,3-position bond between the aromatic rings on both sides are preferable. Specific compounds include 1,3-bis (3-aminophenoxy) benzene, 1,3
3-bis (4-aminophenoxy) benzene is preferred. These are used alone or in combination of two or more.

As the diamine component of the polyimide precursor, when it is used in combination with the diamine or when an acid anhydride component having three or more aromatic rings is used,
It may contain other aromatic diamines. For example, 2,4
-Diaminobenzoic acid, 3,4-diaminobenzoic acid, 4,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether-3-sulfonamide, 3,4 '
-Diaminodiphenyl ether-4-sulfonamide,
3,4'-diaminodiphenyl ether-3'-sulfonamide, 3,3'-diaminodiphenyl ether-4
-Sulfonamide, 3,4'-diaminodiphenyl ether-3'-carboxide, 3,3'-diaminodiphenyl ether-4-carboxide, 4,4'-dihydroxy-3,3'-diaminobiphenyl, 3,3 ' −
Examples thereof include, but are not limited to, dihydroxy-4,4′-diaminobiphenyl. When using these, it is preferable to use 1 to 50 mol% with respect to the total amine component. These diamines are used alone or in combination of two or more.

In addition, as the diamine, the following general formula (II) is used in order to improve adhesiveness and other photosensitive characteristics.

[Chemical 4] (In the formula, R ⁵ and R ⁶ each independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁷ and R ⁸ each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms. , T is an integer of 1 to 100), and diamines such as diaminopolysiloxane are preferably used.

Examples of the R ⁵ and R ^6, a methylene group, an ethylene group, alkylene groups such as propylene group, such as an arylene group these linking groups such as a phenylene group and the like, R ⁷
Examples of R ⁸ include alkyl groups such as methyl group and ethyl group, aryl groups such as phenyl group, and the like. When these are used, the amount is 1 to 30 mol% based on all amine components.
It is preferable to use. These diamines are used alone or in combination of two or more.

The acid anhydride used for producing the (A) polyimide precursor is, for example, 5,5 '-[(1-
Methylethylidene) bis (4,1-phenyleneoxy)] bis-1,3-isobenzofurandione, 5,
5 '-[1,3-phenylenebis (oxy)] bis-
1,3-isobenzofurandione, perylene-2,3
8,9-tetracarboxylic dianhydride, perylene-3,
4,9,10-tetracarboxylic dianhydride, perylene-
4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene -1,2,6,7-Tetracarboxylic acid dianhydride, phenanthrene-1,2,9,1
Examples thereof include, but are not limited to, 0-tetracarboxylic dianhydride. These alone or 2
Used in combination of two or more species.

As the acid anhydride component of the (A) polyimide precursor, when a diamine component having three or more aromatic rings is used or when it is used in combination with the acid anhydride, other acid is used. Anhydrous may be used. For example, oxydiphthalic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride , 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3', 4
4'-biphenyltetracarboxylic dianhydride, 1,2,
5,6-naphthalenetetracarboxylic dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride,
1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2, 3,5,6-pyridinetetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,4,5-tetracarboxylic dianhydride, thiophene Examples thereof include, but are not limited to, -2,3,4,5-tetracarboxylic dianhydride. Among them, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and oxydiphthalic dianhydride are preferable, and oxydiphthalic dianhydride is more preferable. Moreover, in using these, they are used individually or in combination of 2 or more types. When using these, it is preferable to use 1 to 100 mol% with respect to the total acid anhydride component, and when using one having 3 or more aromatic rings as the acid anhydride component, use 1 to 30 mol%. It is preferable.

(B) The addition-polymerizable compound having a boiling point of 100 ° C. or higher under normal pressure is a compound obtained by condensing a polyhydric alcohol and an α, β-unsaturated carboxylic acid, for example, ethylene glycol diacrylate ( Or methacrylate), triethylene glycol diacrylate (or methacrylate), tetraethylene glycol diacrylate (or methacrylate), trimethylolpropane diacrylate (or methacrylate), trimethylolpropane triacrylate (or methacrylate), 1,2-propylene glycol Diacrylate (or methacrylate), di (1,2-propylene glycol) diacrylate (or methacrylate), tri (1,2-propylene glycol) diacrylate (or methacrylate), Tetra (1,2-propylene glycol) diacrylate (or methacrylate),
Dimethylaminoethyl acrylate (or methacrylate), diethylaminoethyl acrylate (or methacrylate), dimethylaminopropyl acrylate (or methacrylate), diethylaminopropyl acrylate (or methacrylate), 1,4-butanediol diacrylate (or methacrylate), 1,6 -Hexanediol diacrylate (or methacrylate),
Pentaerythritol triacrylate (or methacrylate), 2-hydroxyethyl acrylate (or methacrylate), 1,3-acryloyl (or methacryloyl) oxy-2-hydroxypropane, neopentyl glycol diacrylate (or methacrylate),
Examples thereof include pentaerythritol diacrylate (or methacrylate), dipentaerythritol hexaacrylate (or methacrylate), tetramethylolpropane tetraacrylate (or methacrylate), and the like, which may be used alone or in combination of two or more kinds. Of these, tetraethylene glycol diacrylate (or methacrylate) is preferable.

The content of the component (B) is preferably 1 to 200 parts by weight, more preferably 5 to 50 parts by weight, based on 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 developing solution tend to be poor, and if it exceeds 200 parts by weight, the mechanical properties of the film tend to be poor.

The photoinitiator (C) is not particularly limited, but examples thereof include Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone and 4,4-bis. (Diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl 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-azacyclohexanone, N-ethyl-N-
(P-chlorophenyl) glycine, N-phenyldiethanolamine, 2- (o-ethoxycarbonyl) oxyiminopropan-1-one, 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone,
3,3-carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl) -bis- [2,6
-Difluoro-3- (pyrid-1-yl) phenyl] titanium, hexaarylbiimidazole compounds and the like. 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, based on 100 parts by weight of the polyimide precursor.

The heat-resistant photosensitive resin composition of the present invention may contain a sensitizer, if necessary. Examples of the sensitizer include 7-N, N-diethylaminocoumarin, 7-diethylamino-3-thenonylcoumarin, 3,3′-carbonylbis (7-N, N-diethylamino) coumarin, 3,
3'-carbonylbis (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-Methoxyacetophenone, dimethylaminobenzophenone, diethylaminobenzophenone, 4,4'-bis (N-ethyl, N-methyl) benzophenone and the like can be mentioned. The content of these is preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the polyimide precursor, and is preferably 0.
More preferably, it is 1 to 10 parts by weight.

The photosensitive resin composition of the present invention may further contain other additives such as a plasticizer and an adhesion promoter. The method for producing a pattern of the present invention is to use the photosensitive resin composition of the present invention to form a polyimide film composed of a cured product of the composition by a photolithography technique. In the method for producing a pattern of the present invention, first, a coating film composed mainly of a polyimide precursor using the photosensitive resin composition of the present invention is formed on the surface of a supporting substrate.

In the pattern manufacturing method of the present invention, the surface of the supporting substrate may be previously treated with an adhesion aid in order to improve the adhesiveness between the film or the polyimide coating after heat curing and the supporting substrate. The coating film made of a polyimide precursor is formed, for example, by forming a varnish film of a photosensitive polyimide precursor composition and then drying the film. The method for producing a pattern of the present invention is particularly preferable for forming a thick film, for example, suitable for forming a dry film thickness of 15 μm or more, further 20 μm or more, particularly 50 μm.
It is suitable for application to the above film thickness.

The film of the varnish is formed by means appropriately selected from means such as spin coating using a spinner, dipping, spray printing and screen printing depending on the viscosity of the varnish. The film thickness of the coating film can be adjusted by the coating conditions, the solid content concentration of the composition, and the like. Alternatively, the coating film may be formed by peeling the coating film formed on the supporting substrate in advance from the supporting body and attaching a sheet of the polyimide precursor composition to the surface of the supporting substrate.

Next, this coating is irradiated with light (such as ultraviolet rays) 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,
Obtain the 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 acetate Glycol mono-n-butyl ether, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfo Sid, sulfolane, cyclohexanol, cyclohexanone, cyclohexane oxime,
Cyclohexane, 1,4-cyclohexanedimethanol, cyclohexyl acetate, cyclopentanol,
Examples thereof include cyclopentanone, cyclopentanone oxime, cyclopentane and the like. 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 because of the influence on the supporting substrate and the like. In order to improve the solubility of the polyimide precursor, methanol, ethanol, propanol, isopropanol, butanol, N-methyl-2-pyrrolidone,
It may further contain a water-soluble organic solvent such as N, N-dimethylformamide or N, N-dimethylacetamide.

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 and highly heat-resistant polyimide pattern can be obtained. The heating temperature at this time is 13
The temperature is preferably 0 to 500 ° C., and 150 to 400 ° C.
Is more preferable. This heating temperature is 130 ℃
When it is less than 500 ° C, the mechanical properties and thermal properties of the polyimide film tend to deteriorate, and when it exceeds 500 ° C, the mechanical properties and thermal properties of the polyimide film tend to deteriorate.

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

As described above, the photosensitive resin composition of the present invention is
It can be used as a surface protective film for electronic parts such as semiconductor devices and an interlayer insulating film of a multilayer wiring board. Surface protective film (buffer coat film) using the photosensitive resin composition of the present invention
Has excellent adhesiveness to SiN, a sealing agent, etc., so that the semiconductor element using the interlayer insulating film or the surface protective film obtained from the photosensitive resin composition of the present invention has extremely excellent reliability. .

Further, the photosensitive resin composition of the present invention is very excellent in stress relaxation property, adhesiveness and the like, and therefore, it is suitable as various structural materials in packages of various structures 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 on the Al wiring layer 2, and a surface protective film layer 4 of the device 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 or gold which is an external connection terminal. Further, a cover coat layer 9 is formed on the surface protective film layer 4. The redistribution layer 6 includes conductive balls 7 with a barrier metal 10 interposed therebetween.
A collar 11 is provided to hold the conductive ball 7, which is connected to the collar 11. When mounting a package having such a structure, an underfill 12 may be used to further relax the stress. In this figure, the photosensitive resin composition of the present invention is very suitable not only as an interlayer insulating layer or a surface protective film layer but also as a material for a cover coat layer, a core, a color, an underfill, etc. due to its excellent characteristics. There is. The heat-resistant photosensitive resin cured product using the photosensitive resin composition of the present invention is excellent in adhesiveness with a metal layer, a sealing agent and the like and has a high stress relaxation effect. A semiconductor device using the obtained heat-resistant photosensitive resin cured product for a cover coat layer, a core, a color, an underfill, etc. will have extremely excellent reliability.
The semiconductor device of the present invention as shown in FIG. 1 has a cover coat formed using the composition, a redistribution core, a collar for balls such as solder, and an underfill used for flip chips and the like. Is not particularly limited and can have various structures.

[0042]

EXAMPLES The present invention will be described below with reference to examples. A method using N, N′-dihydrocarbyl-substituted carbodiimide as an isoimidizing agent is shown in the following synthesis examples, but trifluoroacetic anhydride may be used instead.

[Synthesis Example 1] 50 equipped with a dry nitrogen introducing tube
Into a 0 ml four-necked flask, 21.72 g (0.070 mol) of 4,4′-oxydiphthalic dianhydride and 100 ml of dried N-methylpyrrolidone were added and stirred, and 2-hydroxyethyl methacrylate 1. Thirty
g (0.010 mol) was added. The solution was stirred at room temperature for 1 hour, further heated to 35 ° C. and stirred for 1 hour, then cooled to room temperature, 14.3-bis (4-aminophenoxybenzene) 14.03 g (0.048 mol), 1,3 -Bis (3-aminopropyl) tetramethyldisiloxane 0.
25 g (0.001 mol) and 100 ml of dry N-methylpyrrolidone were added dropwise with stirring at room temperature over 1 hour and stirred overnight. Then, 26.82 g (0.130 mo) of N, N-dicyclohexylcarbodiimide
l) and 100 ml of dry N-methylpyrrolidone were added dropwise with stirring at room temperature over 30 minutes. Furthermore, 45.55 g of 2-hydroxyethyl methacrylate (0.35
mol) was added, and the mixture was stirred at 50 ° C. for 5 hours, cooled to room temperature, and stirred overnight. This reaction mixture was diluted with 50 ml of acetone, and the filtrate obtained by removing unnecessary substances by suction filtration was 2.
It was slowly added to 0 L of ion-exchanged water with vigorous stirring to obtain a precipitate. The deposited precipitate was further washed with ion-exchanged water, washed with methanol, and filtered by suction filtration to obtain a solid substance. The obtained solid is dried in a vacuum dryer until the water content at room temperature is 1.0% by weight or less,
A powdery solid was obtained.

[Synthesis Example 2] 4,4'-oxydiphthalic acid dianhydride 2 was placed in a four-neck flask containing 500 ml of dry nitrogen.
After adding 1.72 g (0.070 mol) and 120 ml of dried N-methylpyrrolidone, the mixture was stirred, and 2-
2.34 g of hydroxyethyl methacrylate (0.01
8 mol) was added. The solution was stirred at room temperature for 1 hour, then at 35 ° C. for 1 hour, then cooled to room temperature and 14.03 g (0.02) of 1,3-bis (3-aminophenoxy) benzene.
048 mol), 1,3-bis (3-aminopropyl)
Tetramethyldisiloxane 0.25g (0.001mo
1) and 80 ml of dried N-methylpyrrolidone were added dropwise with stirring at room temperature over 1 hour and stirred overnight. Then N, N-dicyclohexylcarbodiimide 2
7.9 g (0.135 mol) and 100 ml of dried N-methylpyrrolidone were added dropwise over 30 minutes while stirring at room temperature. Further, 39.04 g (0.30 mol) of 2-hydroxyethyl methacrylate was added, and the temperature was 50 ° C.
After stirring for 5 hours, the mixture was cooled to room temperature and stirred overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was slowly added to 2.0 L of ion-exchanged water with vigorous stirring to obtain a precipitate. The deposited precipitate was further washed with deionized water, washed with methanol, and filtered by suction filtration to obtain a solid. The obtained solid substance was dried under reduced pressure until the water content at room temperature became 1.0% by weight or less, and a powdery solid substance was obtained.

[Synthesis Example 3] 50 equipped with a dry nitrogen introducing tube
Into a 0 ml four-necked flask, 23.27 g (0.075 mol) of 4,4′-oxydiphthalic dianhydride and 125 ml of dried N-methylpyrrolidone were added and stirred, and 2-hydroxyethyl methacrylate 2. 60
g (0.020 mol) was added. The solution was stirred at room temperature for 1 hour, then at 35 ° C. for 1 hour, then cooled to room temperature and bis (4-aminophenoxy) biphenyl 20.63 g.
(0.056 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 0.25 g (0.00
1 mol) and dried N-methylpyrrolidone 75 ml
Was added dropwise with stirring at room temperature over 1 hour and stirred overnight. Then, 28.89 g (0.140 mol) of N, N-dicyclohexylcarbodiimide and dried N were used.
-Methylpyrrolidone 100 ml with stirring at room temperature 3
It was added dropwise over 0 minutes. Further, 45.55 g (0.35 mol) of 2-hydroxyethyl methacrylate was added, and the mixture was stirred at 50 ° C for 5 hours, cooled to room temperature, and stirred overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was washed with 2.0 L of ion-exchanged water, 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 was 1.0% by weight or less, to obtain a powdery solid.

[Synthesis Example 4] 50 equipped with a dry nitrogen introducing tube
In a 0 ml four-necked flask, 8.72 g (0.040 mol) of pyromellitic dianhydride, 12.41 g (0.040 mol) of 4,4′-oxydiphthalic dianhydride and 140 ml of dried N-methylpyrrolidone. After charging, the mixture was stirred, and 3.12 g (0.024 mol) of 2-hydroxyethyl methacrylate was added to this solution. The solution was stirred at room temperature for 1 hour, then at 35 ° C. for 1 hour, then cooled to room temperature and bis (4-aminophenoxy) biphenyl 2
0.63 g (0.056 mol), 1,3-bis (3-
Aminopropyl) tetramethyldisiloxane 0.25g
(0.001 mol) and 80 ml of dried N-methylpyrrolidone were added dropwise with stirring at room temperature over 1 hour, and the mixture was stirred overnight. Then, 28.89 g (0.140 mol) of N, N-dicyclohexylcarbodiimide and 100 ml of dried N-methylpyrrolidone were added dropwise over 30 minutes while stirring at room temperature. Furthermore, 45.55 g of 2-hydroxymethyl methacrylate (0.35 m
ol) was added, and the mixture was stirred at 50 ° C. for 5 hours, cooled to room temperature, and stirred overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate obtained by removing unnecessary substances by suction filtration was adjusted to 2.0.
After washing with L ion-exchanged water, washing with methanol and filtration by suction filtration were carried out to obtain a solid. The obtained solid substance was dried under reduced pressure until the water content at room temperature became 1.0% by weight or less, and a powdery solid substance was obtained.

[Synthesis Example 5] 50 equipped with a dry nitrogen introducing tube
In a 0 ml four-necked flask, 32.16 g (0.080 mol) of 5,5 ′-[1,3-phenylenebis (oxy)] bis-1,3-isobenzofurandione and 150 ml of dried N-methylpyrrolidone were added. After the addition, the mixture is stirred, and 2-hydroxyethyl methacrylate 3.12 is added to this solution.
g (0.024 mol) was added. The solution was stirred at room temperature for 1 hour, then at 35 ° C. for 1 hour, then cooled to room temperature and 11.20 g of 4,4′-diaminodiphenyl ether.
(0.056 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 0.25 g (0.00
1 mol) and 80 ml of dried N-methylpyrrolidone
Was added dropwise with stirring at room temperature over 1 hour and stirred overnight. Then, 28.89 g (0.14 mol) of N, N-dicyclohexylcarbodiimide and dried N-
30 ml of methylpyrrolidone 100 ml with stirring at room temperature
It was added dropwise over the minutes. Further, 45.55 g (0.35 mol) of 2-hydroxyethyl methacrylate was added, and the mixture was stirred at 50 ° C for 5 hours, cooled to room temperature, and stirred overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was washed with 2.0 L of ion-exchanged water, washed with methanol, and filtered by suction filtration to obtain a solid. The obtained solid is dried under reduced pressure until the water content at room temperature is 1.0% by weight or less,
A powdery solid was obtained. The polyimide precursors obtained in any of the synthesis examples had a carboxyl group esterification ratio (esterification ratio) of about 70 mol%.

Example 1 In a 100 ml four-necked flask equipped with a stirring blade, a thermometer and a nitrogen inlet tube, 35.0 g of the powder of the photosensitive polymer obtained in Synthesis Example 1 and 38.0 g of N-methylpyrrolidone were added. And p-methoxyphenol 0.1g
Was dissolved with stirring, and then 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 2.0 g, 2-mercaptobenzoxazole 1.
0 g and 0.2 g of ethyl Michler's ketone and 7.0 g of tetraethylene glycol diacrylate as an addition-polymerizable compound were added and dissolved by stirring overnight at room temperature, followed by filtration with a filter to obtain a photosensitive resin composition solution. This solution is spin coated on a silicon wafer and then dried to 70 μm.
After forming a coating film of m, it was exposed with a full-wavelength exposure machine PLA-600FA (manufactured by Canon Inc.) through a pattern mask, developed with a mixed solution of N-methylpyrrolidone and methanol, and then with ethanol. As a result of rinsing, a good relief pattern without peeling was obtained at an exposure dose of 200 mJ / cm ² . The residual film rate after development at this exposure amount was 98%. In addition, the shrinkage rate of the coating film after thermosetting to polyimide was 34%.

[Example 2] The same procedure as in Example 1 was carried out except that the photosensitive polymer powder obtained in Synthesis Example 2 was used. As a result, a good relief without peeling was obtained at an exposure dose of 250 mJ / cm ^2. The pattern was obtained. The residual film rate after development at this exposure amount was 97%. The shrinkage rate of the coating film after thermosetting and polyimidization was 35%.

[Example 3] The same procedure as in Example 1 was carried out except that the photosensitive polymer powder obtained in Synthesis Example 3 was used. As a result, a good relief without peeling was obtained at an exposure dose of 230 mJ / cm ^2. The pattern was obtained. The residual film rate after development at this exposure amount was 98%. The shrinkage rate of the coating film after thermosetting was 33%.

[Example 4] The same treatment as in Example 1 was carried out except that the photosensitive polymer powder obtained in Synthesis Example 4 was used. As a result, a good relief without peeling was obtained at an exposure dose of 200 mJ / cm ^2. The pattern was obtained. The residual film rate after development at this exposure amount was 99%. In addition, the shrinkage rate of the coating film after thermosetting to polyimide was 34%.

[Example 5] The same treatment as in Example 1 was carried out except that the photosensitive polymer powder obtained in Synthesis Example 5 was used. As a result, a good relief without peeling was obtained at an exposure dose of 230 mJ / cm ^2. The pattern was obtained. The residual film rate after development at this exposure amount was 98%. In addition, the shrinkage rate of the coating film after thermosetting to polyimide was 34%.

Example 6 The solution used in Example 1 was spin-coated on a silicon wafer and then dried to 20 μm.
m coating film, then full wavelength exposure machine PLA-600F
A (manufactured by Canon Inc.) was exposed to 200 mJ / cm ² . This was oven-baked at 350 ° C. for 1 hour to form a polyimide film. When this film was peeled from the silicon wafer and the cured film characteristics were evaluated, the following favorable values were shown. Tensile strength: 152 Mpa, elongation rate: 13
7%, 5% weight loss temperature: 413 ° C.

[Comparative Example 1] Synthesis Example 1 except that 5.18 g (0.048 mol) of p-phenylenediamine was used in place of 1,4-bis (4-aminophenoxybenzene) used in Synthesis Example 2. When a photosensitive polymer powder obtained in the same manner was used and treated in the same manner as in Example 2, a relief pattern was obtained after development, but the coating shrinkage ratio after thermosetting and polyimidization was 55%. there were.

[Comparative Example 2] 2,5 instead of 1,3-bis (3-aminophenoxy) benzene used in Synthesis Example 2 was used.
The same procedure as in Example 2 was carried out using the powder of the photosensitive polymer obtained in the same manner as in Synthesis Example 2 except that 7.30 g (0.048 mol) of diaminobenzoic acid was used. No pattern was obtained.

[Comparative Example 3] When the same treatment as in Example 1 was carried out without using the addition-polymerizable compound tetraethylene glycol diacrylate used in Example 1, the sensitivity was low and the pattern swelled after development. No good relief pattern was obtained.

Example 7 In a 100 ml four-necked flask equipped with a stirring blade, a thermometer and a nitrogen inlet tube, 35.0 g of the powder of the photosensitive polymer obtained in Synthesis Example 2 and 38.0 g of N-methylpyrrolidone were added. And p-methoxyphenol 0.1g
Was dissolved with stirring, and then 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 2.0 g, 2-mercaptobenzoxazole 1.
0 g and 0.2 g of ethyl Michler's ketone and 7.0 g of tetraethylene glycol diacrylate as an addition-polymerizable compound were added, and the mixture was stirred and dissolved overnight at room temperature and filtered to obtain a photosensitive resin composition solution. This solution was spin-coated on a silicon wafer and then dried to 20 μm.
After forming the coating film of No. 1, it was exposed through a pattern mask with a full-wavelength exposure machine PLA-600FA (manufactured by Canon Inc.), developed using a mixed solution of N-methylpyrrolidone and methanol, and rinsed with ethanol. As a result, a good relief pattern without peeling was obtained at an exposure dose of 100 mJ / cm ² .

[Example 8] The same procedure as in Example 1 was carried out except that the photosensitive polymer powder obtained in Synthesis Example 1 was used. As a result, a good relief without peeling was obtained at an exposure dose of 200 mJ / cm ^2. The pattern was obtained.

Example 9 The solution used in Example 1 was spin-coated on a substrate having a rewiring layer and dried to form a coating film of 20 μm, and then a full-wavelength exposure machine PLA-6 was used.
00FA (Canon Co., Ltd.) at 100 mJ / cm ² for exposure, development using a mixed solution of N-methylpyrrolidone and methanol, and rinsing with ethanol.
A um-square via hole was formed. This was oven-baked at 350 ° C. for 1 hour to form a cover coat polyimide film. After forming an under bumping metal in the hole portion, the solder ball was bumped to manufacture a test part as shown in FIG. Further, test parts were mounted and sealed to obtain a test sample. When the test sample was subjected to a temperature cycle test (-55 to 125 ° C., 1000 cycles), defects such as cracks and peeling were not observed.

Comparative Example 4 Synthesis Example 2 was repeated except that 5.18 g (0.048 mol) of p-phenylenediamine was used in place of 1,3-bis (3-aminophenoxy) benzene used in Synthesis Example 2. When a photosensitive resin composition solution obtained by blending in the same manner as in Example 7 using the photosensitive polymer powder obtained in the same manner was treated as in Example 9,
Peeling was observed at the interface with the solder crack and the under bumping metal.

[0061]

EFFECTS OF THE INVENTION The photosensitive resin composition of the present invention can form a thick film, is excellent in photosensitivity, has high sensitivity, can form a well-shaped pattern even at a low exposure amount, and has a high residual film rate after development. Also, it has excellent cured film characteristics and has a small shrinkage ratio after heat curing. Further, the photosensitive resin composition of the present invention is excellent in stress relaxation and has high adhesiveness to a metal layer and a molding material, and is therefore excellent for various packages. The pattern manufacturing method of the present invention is capable of forming a thick film, has excellent photosensitivity, has high sensitivity, can obtain a good pattern even at a low exposure amount, has a high residual film rate after development, and has excellent cured film properties. A film can be obtained, the shrinkage rate at the time of thermosetting can be suppressed to the minimum, the manufacturing process can be shortened, and the manufacturing cost can be reduced. Therefore, the electronic component of the present invention is extremely reliable without cracks or peeling.

[Brief description of drawings]

FIG. 1 is a sectional view showing an outline of a sectional structure of an example of a semiconductor device of the present invention.

FIG. 2 is a sectional view showing the outline of the sectional structure of a semiconductor device created in Example 9 of the present invention.

[Explanation of symbols]

1 ... Interlayer insulating layer, 2 ... Al wiring layer, 3 ... Insulating layer, 4 ...
..Surface protective film layer, 5 ... Pad portion of wiring layer, 6 ... Rewiring layer, 7 ... Conductive ball, 8 ... Core, 9 ... Cover coat layer, 10.・ Barrier metal, 11 ・ ・ ・ Color, 12 ・ ・ ・
Underfill

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI Theme Coat (reference) H01L 21/312 H01L 21/30 502R 575 (72) Inventor Takeharu Motobu 4-13, Higashimachi, Hitachi City, Ibaraki Prefecture No. 1 Hitachi Chemical DuPont Micro Systems Co., Ltd. Yamazaki Development Center (72) Inventor Naoki Watanabe 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture F Term (Hitachi Kasei DuPont Micro Systems Co., Ltd. Reference) ) 2H025 AA01 AA10 AA14 AB16 AB17 AC01 AD01 BC14 BC42 BC69 CA01 CA27 CA28 FA03 FA15 4J027 AD04 BA13 BA19 BA20 BA23 BA24 BA26 BA27 BA28 CB10 CC05 CD06 4J043UA02 PA19 PC085 QUA15 TB01 RA35 SA06 SB121 TA22 TB01 TB22 UA262 UA332 UA362 UA712 UB011 UB021 UB061 UB122 UB131 UB152 UB301 UB351 UB402 VA051 VA081 ZA60 ZB22 5F046 NA19 5F058 AA02 AA08 AC02 AC07 AF04 AG01 AG09 AH02 AH03

Claims (13)

[Claims] 1. (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 are each independently a hydrogen atom or a monovalent organic group, and X and Y At least one has 3 or more aromatic rings), a polyimide precursor having a repeating unit represented by (B) an addition-polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure, and (C) a photoinitiator. A photosensitive resin composition comprising: 2. The polyimide precursor is a compound of the general formula (I), wherein at least one of X and Y has at least one aromatic ring having a 1,3-position bond between the adjacent aromatic rings. The photosensitive resin composition according to claim 1. 3. The polyimide precursor is a polyamic acid unsaturated ester having a (meth) acryloxyalkyloxy group as R ¹ and R ² and having an esterification rate of 6
The photosensitive resin composition according to claim 1 or 2, which is 0 to 80 mol% and is obtained by using diaminopolysiloxane as a diamine in an amount of 1 to 30 mol% of all diamines. 4. The cover coat layer in 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 on the surface protective film layer. Or the photosensitive resin composition according to item 3. 5. The core material in 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 rewiring core formed on the surface protective film layer is formed. Item 1. The photosensitive resin composition according to item 1, 2 or 3. 6. A surface protective film layer is formed on a wiring layer of a semiconductor device, a rewiring layer and a cover coat layer are formed thereon, and further formed as an external connection terminal on the rewiring layer. The photosensitive resin composition according to claim 1, which is for a color material for holding the ball in a semiconductor device having a structure for holding a conductive ball. 7. The photosensitive resin composition according to claim 1, which is used as an underfill material for a semiconductor device. 8. A step of forming a polyimide precursor film by applying the photosensitive resin composition according to claim 1 on a supporting substrate, and a predetermined pattern on the polyimide precursor film. The method for producing a pattern, which comprises a step of irradiating an actinic ray through a photomask of 1 above to perform exposure, and then dissolving and removing an unexposed portion with an organic solvent or a basic aqueous solution to obtain a desired relief pattern. 9. An electronic component comprising a polyimide film obtained by imidizing the pattern obtained by the production method according to claim 8 as a surface protective film or an interlayer insulating film. 10. An electronic component having a cover coat layer comprising a polyimide film obtained by imidizing the pattern obtained by the production method according to claim 8. 11. An electronic component comprising a polyimide film obtained by imidizing the pattern obtained by the production method according to claim 8 as a core for a rewiring layer. 12. An electronic component having a polyimide film obtained by imidizing the pattern obtained by the manufacturing method according to claim 8 as a collar for holding a conductive ball formed as an external connection terminal. . 13. An electronic component comprising a polyimide film obtained by imidizing the pattern obtained by the manufacturing method according to claim 8 as an underfill.