JP2005099661A - Heat-resistant photosensitive polyimide precursor composition, method for manufacturing pattern using same, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive polyimide precursor composition which can be formed into a thick film, which has excellent photosensitive characteristics and high sensitivity, which gives a pattern of a favorable figure even with low exposure light quantity, and which has a high film remaining rate after development, excellent characteristics of a hardened film, little shrinkage after thermosetting, excellent stress relaxation, high adhesiveness and excellent copper migration resistance, to provide a method for manufacturing a pattern by which the manufacturing process can be decreased and the manufacturing cost can be reduced, and to provide an electronic component obtained by the method. <P>SOLUTION: The heat-resistant photosensitive polyimide precursor composition contains: (A) a polyimide precursor in which both of or one of a diamine component and an acid anhydride component has ≥3 aromatic rings; (B) an addition polymerizable compound having ≥100°C boiling point at normal pressure; (C) a photoinitiator; and (D) a metal harm inhibitor. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is a heat-resistant photosensitive polyimide precursor having high transparency, high adhesion, low film shrinkage after heat curing, suitable for thick film formation, and excellent adhesion to copper wiring and copper migration resistance. For body compositions, heat-resistant photosensitive polyimide precursors suitable for so-called package applications, such as cover coating materials for semiconductor devices, core materials for rewiring, color materials for balls such as solder, underfill materials used in flip chips, etc. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition, a pattern manufacturing method 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 hydroxy acrylate 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.

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

Since these materials are rigid in the polyamic acid itself, there is a drawback that the film state produced 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. On the other hand, however, when a thick film is formed, there are drawbacks such as insufficient sensitivity and reduced adhesion. In addition, there is a problem that the shrinkage ratio 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 size of the opening pattern are significantly changed.
Moreover, in the package use, the characteristic which relieve | moderates the stress produced by the thermal shock etc. is requested | required, and sufficient relaxation may not be obtained depending on the film | membrane characteristic of the coating film after heat-hardening, and a crack and peeling may arise. Furthermore, in package applications, peeling may occur if the adhesiveness to the underbumping metal layer or the mold material is not sufficient. In addition, copper wiring is often used for rewiring, and often directly contacts polyimide. Copper is easily oxidized and causes migration between polyimides, which may cause peeling and a decrease in insulation resistance.
The present invention has been made to solve the above-mentioned problems, and is a heat-resistant photosensitive polyimide precursor that is a useful composition capable of forming a heat-resistant photosensitive resin cured body that satisfies the above-mentioned required characteristics. An object is to provide a body composition, a pattern manufacturing method using the same, and an electronic component.
The invention of claim 1 is capable of forming a thick film, has excellent photosensitivity, has high sensitivity, has a good shape pattern even at low exposure, has a high residual film ratio after development, and has excellent cured film characteristics. It is to provide a heat-resistant photosensitive polyimide precursor composition having a cured film obtained, excellent in copper migration resistance, and having a small coating film shrinkage after heat curing.
The invention of claim 2 is to provide a heat-resistant photosensitive polyimide precursor composition that further enhances the effect of the invention of claim 1.
The invention of claim 3 is capable of forming a thick film, has excellent photosensitivity, high sensitivity, a pattern having a good shape even at a low exposure amount, a high residual film ratio after development, and after heat curing. It is an object of the present invention to provide a pattern production method 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.
The invention of claim 4 provides an electronic component that is further excellent in reliability in addition to the above object.
The invention of claim 5 provides an electronic component useful as a cover coat material, a core material for rewiring, a color material for balls such as solder, and an underfill material for stress relaxation in addition to the above-mentioned object. Is.

The present invention includes (A) a polyimide precursor in which either or both of the diamine component and the acid anhydride component have three or more aromatic rings, (B) an addition polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure, The present invention relates to a heat-resistant photosensitive polyimide precursor composition containing (C) a photoinitiator and (D) a metal harm preventing agent.
Further, the present invention provides the polyimide precursor having at least one aromatic ring in which the bond between the adjacent aromatic rings in the diamine component and the acid anhydride component or both of them is located at the 1,3-position. It is related with the heat-resistant photosensitive polyimide precursor composition containing.
Moreover, this invention relates to the pattern manufacturing method including the process of apply | coating and drying the said heat resistant photosensitive polyimide precursor composition on a support substrate, the process of exposing, the process of developing, and the process of heat-processing. Preferably, a step of forming a thick film using the heat-resistant photosensitive polyimide precursor composition, a step of irradiating the film with light through a mask having a predetermined pattern, and a film after the light irradiation It is a pattern manufacturing method including the process developed using an organic solvent or basic aqueous solution.
The present invention also relates to an electronic component having a pattern layer obtained by the pattern manufacturing method.
The present invention also relates to an electronic component comprising a surface protective film or an interlayer insulating film, comprising a step of forming the heat-resistant photosensitive polyimide precursor composition on an adherend and a step of heat treatment.

The heat-resistant photosensitive polyimide precursor composition of the present invention is capable of forming a thick film, has excellent photosensitivity, a high-sensitivity pattern with a good shape even at low exposure, and a high residual film ratio after development. It also has excellent cured film properties, small shrinkage after heat curing, excellent stress relaxation, high adhesion to metal layers and mold materials, and excellent copper migration resistance.
In addition, the pattern manufacturing method of the present invention can form a thick film, has excellent photosensitivity, is highly sensitive, has a good pattern even at low exposure, has a high residual film ratio after development, and has a cured film characteristic. An excellent cured film can be obtained, the shrinkage rate during thermosetting can be suppressed to a minimum, the manufacturing process can be shortened, and the manufacturing cost can be reduced.

(A) A diamine component and / or an acid anhydride component used in the present invention include a polyamic acid, a polyamic acid ester, a polyamic acid amide, etc. as a polyimide precursor having at least three aromatic rings, and is not particularly limited. Is preferably a polyimide precursor having a photopolymerizable carbon-carbon unsaturated double bond.
Polyamic acid unsaturated ester, polyamic acid unsaturated amide having a structure in which a photopolymerizable compound having a carbon-carbon unsaturated double bond is covalently bonded to the polyamic acid as a side chain, an amine having a carbon-carbon double bond in the polyamic acid Examples thereof include a compound in which a carbon-carbon double bond is introduced by an ionic bond between a carboxyl group and an amino group. The carbon-carbon unsaturated double bond is preferably contained in the form of an acryloyl group or a methacryloyl group.

The polyamic acid 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, followed by acid chloride with thionyl chloride, and then a diamine. Or a tetracarboxylic acid half ester can be synthesized by an acid chloride method in which a carbodiimide is used as a condensing agent and a diamine, 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 developing solution, photocurability, heat resistance, and the like. It is preferable to set it as 20 to 100% with respect to the carboxyl group to have, and it is more preferable to set it as 30 to 90%.

  Examples of the compound having a carbon-carbon unsaturated double bond include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 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 3000 to 200000 in terms of weight average molecular weight, and more preferably 5000 to 100000. As the polyimide precursor of the component (A), it is necessary that both or either of the diamine component and the acid anhydride component have at least three aromatic rings. 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-bis [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-aminophen Noxyphenyl) sulfone, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) anthracene, and the like, but are not limited thereto. You may use these individually or in combination of 2 or more types.

Moreover, as a diamine component of the said polyimide precursor, you may contain another diamine. 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-sulfone Amides, 3,4'-diaminodiphenyl ether-3'-sulfonamide, 3,3'-diaminodiphenyl ether-4-sulfonamide, 3,4'-diaminodiphenyl ether-3'-carboxide, 3,3'-diaminodiphenyl ether Examples include, but are not limited to, -4-carboxide, 4,4′-dihydroxy-3,3′-diaminobiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, and the like. When using these, it is preferable to use 1-50 mol% with respect to all the amine components. These diamines are used alone or in combination of two or more.
In addition, as the diamine, a diamine such as diaminopolysiloxane represented by the following general formula (1) may be used for improving the adhesion. Examples of R ¹ and R ² include alkylene groups such as methylene group, ethylene group and propylene group, arylene groups such as phenylene group, and bonding groups thereof. R ³ and R ⁴ include methyl group and ethyl group. And alkyl groups such as phenyl groups and aryl groups such as phenyl groups. When using these, it is preferable to use 1-30 mol% with respect to all the amine components. These diamines may be used alone or in combination of two or more.

(式中Ｒ^１及びＲ^２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、Ｒ^３及びＲ^４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、ｎは１以上の整数である)

(Wherein R ¹ and R ² represent a divalent hydrocarbon group, which may be the same or different, and R ³ and R ⁴ represent a monovalent hydrocarbon group, which may be the same or different, respectively. , N is an integer greater than or equal to 1)

  Examples of the acid anhydride of the polyimide precursor (A) include 5,5 ′-[(1-methylethylidene) bis (4,1-phenyleneoxy)] bis-1,3-isobenzofurandion, 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, Examples include 8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, and phenanthrene-1,2,9,10-tetracarboxylic dianhydride. It is not limited. You may use these individually or in combination of 2 or more types.

  Moreover, as an acid anhydride component of the said (A) polyimide precursor, you may contain another acid anhydride. For example, oxydiphthalic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride Anhydride, 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-tetraca Examples include, but are not limited to, rubonic acid dianhydride and thiophene-2,3,4,5-tetracarboxylic acid dianhydride. Moreover, in using these, you may use individually or in combination of 2 or more types. When using these, it is preferable to use 1-30 mol% with respect to the total acid anhydride component.

  (B) Examples of the addition polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure include compounds obtained by condensing polyhydric alcohol and α, β-unsaturated carboxylic acid, such as ethylene glycol diacrylate (ethylene glycol diacrylate). Methacrylate), triethylene glycol diacrylate (triethylene glycol dimethacrylate), tetraethylene glycol diacrylate (tetraethylene glycol dimethacrylate), trimethylolpropane diacrylate (trimethylolpropane dimethacrylate), trimethylolpropane triacrylate (trimethylol) Propane trimethacrylate), 1,2-propylene glycol diacrylate (1,2-propylene glycol dimethacrylate), di (1,2-propylene glycol) diacryle (Di (1,2-propylene glycol) dimethacrylate), tri (1,2-propyleneglycol) diacrylate (tri (1,2-propyleneglycol) dimethacrylate), tetra (1,2-propyleneglycol) di Acrylate (tetra (1,2-propylene glycol) dimethacrylate), dimethylaminoethyl acrylate (dimethylaminoethyl methacrylate), diethylaminoethyl acrylate (diethylaminoethyl methacrylate), dimethylaminopropyl acrylate (dimethylaminopropyl methacrylate), diethylaminopropyl acrylate ( Diethylaminopropyl methacrylate), 1,4-butanediol diacrylate (1,4-butanediol dimethacrylate), 1,6-hexanediol diacrylate (1,6-hexene) Sundiol dimethacrylate), pentaerythritol triacrylate (pentaerythritol trimethacrylate), 2-hydroxyethyl acrylate (2-hydroxyethyl methacrylate), 1,3-acryloyloxy-2-hydroxypropane (1,3-methacryloyloxy-2) -Hydroxypropane), neopentyl glycol diacrylate (neopentyl glycol dimethacrylate), pentaerythritol diacrylate (pentaerythritol dimethacrylate), dipentaerythritol hexaacrylate (dipentaerythritol hexamethacrylate), tetramethylolpropane tetraacrylate (tetramethylol) Propanetetramethacrylate) and the like, and these may be used alone or in combination of two or more. There.

  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 (A). 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.

The (C) photoinitiator used in the present invention is not particularly limited. 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-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- (pyridin-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 with respect to 100 parts by weight of the polyimide precursor of the component (A).

  The heat-resistant photosensitive polyimide precursor composition of the present invention may contain a sensitizer as necessary. 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 Examples include acetophenone, dimethylaminobenzophenone, diethylaminobenzophenone, 4,4′-bis (N-ethyl, N-methyl) benzophenone.These contents are preferably 0.05 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyimide precursor of component (A).

There are no particular restrictions on the component (D) used in the present invention, but there are no particular restrictions, but examples include triazoles such as triazole and benzotriazole, tetrazoles such as tetrazole and benzotetrazole, 4,4′-butylidenebis- ( Bisphenols such as 6-tert-butyl-3-methylphenol), hindered phenols such as pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], salicylic acid-derived System, hydrazide derivative system and the like.
The content of the component (D) is preferably 0.1 to 30 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polyimide precursor of the component (A).

  The heat-resistant photosensitive polyimide precursor 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 a photolithographic technique using the heat resistant photosensitive polyimide precursor composition of this invention.
In the pattern manufacturing method of the present invention, first, a film is formed from the step of applying and drying the heat-resistant photosensitive polyimide precursor composition of the present invention on a 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 heat-resistant photosensitive polyimide precursor composition is formed by forming a film of the heat-resistant photosensitive polyimide precursor composition varnish and then drying it. 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. The film thickness of the coating can be adjusted by application conditions, the solid content concentration of the composition, and the like. 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 exposed by irradiating light (active light) 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 and developed to obtain a desired relief. Get a pattern. Examples of actinic rays include ultraviolet rays, visible rays, and radiation, and commonly used ultraviolet rays are preferred.

  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, and 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, sulfolane, cyclohexane SANOL, cyclohexanone, cyclohexane oxime, cyclohexane, 1,4-cyclohexane dimethanol, cyclohexyl acetate, cyclopentanol, 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 from the viewpoint of influence on the support substrate and the like. In order to improve the solubility of the polyimide precursor, water-soluble organic solvents such as methanol, ethanol, propanol, isopropanol, butanol, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, etc. May further be contained.
Examples of the basic compound include alkali metal, alkaline earth metal or ammonium ion hydroxides or carbonates, amine compounds, and the like.

In the pattern obtained above, a part of the polyimide precursor of the present invention is usually imidized. By heat-treating this pattern, a stable high heat resistant polyimide pattern can be obtained. The heating temperature at this time is preferably 130 to 500 ° C, more preferably 150 to 400 ° 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. In addition, 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.
The heat-resistant photosensitive polyimide precursor composition of the present invention has excellent photosensitivity, high sensitivity, a pattern having a good shape even at low exposure, high residual film ratio after development, and cured film characteristics. An excellent cured film is obtained, excellent copper migration resistance, coating film shrinkage after heat curing is small, and thick film formation is possible, so an electronic component having a pattern layer obtained by the above pattern production method is The above effects can be sufficiently exhibited.

In addition, the electronic component of the present invention has the above-described exposure step and development step using the heat-resistant photosensitive polyimide precursor composition of the present invention, that is, the heat-sensitive photosensitive polyimide precursor composition is covered. A surface protective film or an interlayer insulating film is formed by a process of forming on the adherend and a process of heat treatment. The step of forming the adherend and the step of heat treatment can be the same as described above.
The electronic component using the heat-resistant photosensitive polyimide precursor composition of the present invention thus obtained is used for balls such as semiconductor device cover coat materials, rewiring core materials, and solder as shown in FIG. It can be used for so-called package applications such as color materials and underfill materials.
The cured resin using the heat-resistant photosensitive polyimide precursor composition of the present invention is excellent in adhesion to a metal layer, a sealant and the like, and also has excellent copper migration resistance and a high stress relaxation effect. The semiconductor element using the resin cured body obtained from the heat resistant photosensitive polyimide precursor composition is extremely excellent in reliability.
The electronic component of the present invention is not particularly limited except that it has a cover coat formed using the composition, a core for rewiring, a ball collar such as solder, an underfill used in a flip chip, etc. Various structures can be taken.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited by these. 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)
In a four-necked flask with 500 ml of dry nitrogen, 21.72 g (0.070 mol) of 4,4′-oxydiphthalic dianhydride and 120 ml of dry N-methylpyrrolidone were added and stirred, and 2-hydroxyethyl methacrylate was added to this solution. 2.34 g (0.018 mol) was added. The solution was stirred at room temperature (25 ° C.) for 1 hour, then stirred at 35 ° C. for 1 hour, cooled to room temperature (25 ° C.), and 14.03 g (0.048 mol) of 1,3-bis (3-aminophenoxy) benzene. 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.25 g, 0.001 mol) and dry N-methylpyrrolidone (80 ml) were added dropwise with stirring at room temperature over 1 hour and stirred overnight. Thereafter, 27.9 g (0.135 mol) of N, N-dicyclohexylcarbodiimide and 100 ml of dried N-methylpyrrolidone were added dropwise over 30 minutes with stirring at room temperature. Further, 39.04 g (0.30 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 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was slowly added to 2.0 liters of ion-exchanged 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 under reduced pressure 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, 21.72 g (0.070 mol) of 4,4′-oxydiphthalic dianhydride and 100 ml of dry N-methylpyrrolidone were added and stirred. 1.30 g (0.010 mol) of 2-hydroxyethyl methacrylate was added. The solution was stirred at room temperature for 1 hour, further heated to 35 ° C., stirred for 1 hour, cooled to room temperature, and 14.03 g (0.048 mol) of 1,4-bis (4-aminophenoxy) benzene, 1,3 -Bis (3-aminopropyl) tetramethyldisiloxane (0.25 g, 0.001 mol) and dry N-methylpyrrolidone (100 ml) were added dropwise with stirring at room temperature over 1 hour and stirred overnight. Thereafter, 26.82 g (0.130 mol) of N, N-dicyclohexylcarbodiimide and 100 ml of dry N-methylpyrrolidone were added dropwise over 30 minutes with stirring at room temperature. Further, 45.55 g (0.35 mol) of 2-hydroxyethyl methacrylate was added and stirred at 50 ° C. for 5 hours, then 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 liters of ion-exchanged 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, 21.72 g (0.070 mol) of 4,4′-oxydiphthalic dianhydride and 100 ml of dry N-methylpyrrolidone were added and stirred. 1.30 g (0.010 mol) of 2-hydroxyethyl methacrylate was added. The solution was stirred at room temperature (25 ° C.) for 1 hour, further heated to 35 ° C. and stirred for 1 hour, cooled to room temperature, 9.60 g (0.048 mol) of oxydianiline, 1,3-bis (3- Aminopropyl) tetramethyldisiloxane (0.25 g, 0.001 mol) and dry N-methylpyrrolidone (100 ml) were added dropwise with stirring at room temperature over 1 hour and stirred overnight. Thereafter, 26.82 g (0.130 mol) of N, N-dicyclohexylcarbodiimide and 100 ml of dry N-methylpyrrolidone were added dropwise over 30 minutes with stirring at room temperature. Further, 45.55 g (0.35 mol) of 2-hydroxyethyl methacrylate was added and stirred at 50 ° C. for 5 hours, then 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 liters of ion-exchanged 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 stirring blade, a thermometer and a nitrogen introduction tube, 35.0 g of the photosensitive polymer powder obtained in Synthesis Example 1, 38.0 g of N-methylpyrrolidone and 0.1 g of p-methoxyphenol were obtained. After stirring and dissolving, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2.0 g, 2-mercaptobenzoxazole 1.0 g and ethyl Michler's Add 0.2g of a photosensitizer of ketone and 7.0g of tetraethylene glycol diacrylate as an addition polymerizable compound and 1.0g of tetrazole as a metal harm-preventing agent, stir and dissolve overnight at room temperature (25 ° C), filter through a filter and heat resistance. A photo polyimide precursor composition solution was obtained.
This solution is spin-coated on a silicon wafer and then dried to form a 20 μm coating film, which is then exposed with a full-wave exposure machine PLA-600FA (manufactured by Canon Inc.) through a pattern mask, and N-methylpyrrolidone and methanol. And then rinsing with ethanol, a good relief pattern without peeling was obtained at an exposure amount of 100 mJ / cm ² . The residual film ratio was calculated from the ratio of the film thickness after coating to development and was 93%.

(Example 2)
A treatment was performed in the same manner as in Example 1 except that the entire wafer surface was exposed at an exposure amount of 100 mJ / cm 2 without using a pattern mask, and then a heat treatment was performed at 350 ° C. for 1 hour in a nitrogen atmosphere. The obtained cured film had a thermal contraction rate of 37%, which was smaller than the conventional one. The obtained cured film was peeled from the silicon wafer, and the mechanical properties of the film were measured. The film showed a good elongation of 80% or more and an elastic modulus of 2.5 GPa, which was smaller than that of the conventional product.

Example 3
The film was processed in the same manner as in Example 1 except that the number of spin coating rotations was adjusted to form an 80 μm coating film. When the exposure amount was 200 mJ / cm ² , the resolution was 10 μm and a good pattern without peeling was obtained. Obtained.

Example 4
Except that the photosensitive polymer powder obtained in Synthesis Example 2 was used, processing was carried out in the same manner as in Example 1. As a result, a good relief pattern without peeling was obtained at an exposure amount of 200 mJ / cm ² .

(Example 5)
A similar process was performed in Example 1 except that a wafer having a copper sputtered film (thickness: 1500 mm) formed on a silicon wafer was used instead of the silicon wafer, and a cured film was prepared at 350 ° C. under nitrogen. . When this cured film was observed, no discoloration of the copper substrate was observed. Further, when a cross-cut test (JIS-5400) was performed, no peeling was observed and good adhesion was exhibited.

(Example 6)
Except that the photosensitive polymer powder obtained in Synthesis Example 2 was used, the same treatment as in Example 5 was performed and the same test was performed. As a result, no peeling was observed and good adhesion was exhibited.

(Comparative Example 1)
A solution was prepared in the same manner as in Example 1 except that the photosensitive polymer powder obtained in Synthesis Example 3 was used, and the solution was processed in the same manner as in Example 3. As a result, the exposure amount of 500 mJ / cm ² was satisfactory. A relief pattern could not be obtained. The pattern was a reverse taper, and peeling from the wafer was observed.

(Comparative Example 2)
A solution in which tetrazole, which is a metal harm prevention agent, was not added in Example 1, a cured film was prepared by the same treatment as in Example 5, and then the same test as in Example 5 was performed. The copper substrate was discolored and peeling was observed in the cross cut test.

(Comparative Example 3)
In Example 6, a solution in which tetrazole, which is a metal harm prevention agent, was not added was prepared. The copper substrate was discolored and peeling was observed in the cross cut test.

As shown in Examples 1 to 6, the polyimide precursor (A) of the present invention in which either or both of the diamine component and the acid anhydride component have three or more aromatic rings (in the diamine component in the examples, (B) An addition polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure, (C) a photoinitiator, (D) a heat-resistant photosensitive polyimide precursor composition containing a metal damage inhibitor The photosensitive polyimide using the product 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. Excellent, shrinkage ratio after thermosetting is small, stress relaxation is excellent, adhesion to metal layer and molding material is high, and copper migration resistance is excellent. On the other hand, in the case of the polyimide precursor of Synthesis Example 3 in which both (A) the diamine component and the acid anhydride component do not have three or more aromatic rings, the exposure amount is as large as 500 mJ / cm ^2. A good pattern cannot be obtained even with an exposure amount, poor adhesion, and when no metal damage inhibitor is blended, the copper substrate is discolored and peeled off in a cross-cut test, resulting in copper migration resistance and adhesion. Inferior.

Explanatory drawing of the electronic component (schematic diagram of a semiconductor device cross section) manufactured using the heat resistant photosensitive polyimide precursor composition of this invention.

Claims (5)

(A) A polyimide precursor in which either or both of a diamine component and an acid anhydride component have three or more aromatic rings, (B) an addition polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure, (C) light A heat-resistant photosensitive polyimide precursor composition comprising an initiator and (D) a metal harm inhibitor. 2. The polyimide precursor according to claim 1, wherein the diamine component and / or the acid anhydride component includes a polyimide precursor having at least one aromatic ring in which the bond between the adjacent aromatic rings is in the 1,3-position. A heat-resistant photosensitive polyimide precursor composition. The pattern manufacturing method including the process of apply | coating and drying the heat-resistant photosensitive polyimide precursor composition of Claim 1 or Claim 2 on a support substrate, the process of exposing, the process of developing, and the process of heat-processing. An electronic component comprising a pattern layer obtained by the manufacturing method according to claim 3. An electronic component formed by forming a surface protective film or an interlayer insulating film by a step of forming the heat-resistant photosensitive polyimide precursor composition according to claim 1 or 2 on an adherend and a step of heat treatment.

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