KR101109871B1 - Polyamic acid resin composition, cured film produced using the resin composition, and semiconductor device - Google Patents

Abstract

The polyamic acid resin composition of this invention is a resin composition containing the polyamic acid which has a C5-C20 alkylene chain in a principal chain, and hardens the resin composition of 20 micrometers in thickness which was heat-hardened at the temperature whose imidation ratio becomes 80% or more. The film has a tensile modulus of at least 100 and less than 1500 MPa. According to the present invention, while using a polyimide resin precursor (polyamic acid), it is possible to form a thick film (˜200 μm) by one coating (spin coat), and has low temperature workability (˜200 ° C.), The semiconductor device which has a suitable polyamic-acid resin composition and the cured film obtained from this resin composition can be provided using the protective coating agent of a semiconductor substrate which can obtain the cured film excellent in low curvature, heat resistance, insulation, and low water absorption.

Description

Polyamic acid resin composition, cured film and semiconductor device using the resin composition {POLYAMIC ACID RESIN COMPOSITION, CURED FILM PRODUCED USING THE RESIN COMPOSITION, AND SEMICONDUCTOR DEVICE}

The present invention relates to a polyamic acid resin composition suitable for use in a protective coat layer formed on a semiconductor substrate, a cured film using the same, and a semiconductor device.

In recent years, with the demand for miniaturization of electronic devices, miniaturization of semiconductor devices has been achieved, and CSPs (Chip Size Packages) having almost the same dimensions as semiconductor devices have been mass-produced and commercialized. Moreover, in order to reduce the manufacturing cost of a semiconductor device, WL-CSP (Wafer Level CSP) which forms a semiconductor device in the state of a wafer, and cuts a wafer after that into individual semiconductor devices is also proposed. Further, thinning of wafers is also progressing due to package requirements of laminated structures such as SiP (System in Package).

With the downsizing in such semiconductor devices, the necessity of protecting the chip from the impact during the polishing process, the pattern forming process, the dicing process, and the bonding process becomes remarkable. Polyimide resin excellent in heat resistance and insulation is used.

However, conventional polyimide resins have high modulus of elasticity and mechanical strength, but are soft. When applied to an electronic component as it is, there is a possibility that defects such as warpage of the substrate after curing and generation of resin cracks in the thermal shock test may occur. (1) Since the solubility of resins in various solvents is low, there are many volatile matters, and workability is bad for thick film formation, such as spin coating twice, and (2) if the film thickness is too thick, the substrate is warped, ( 3) There is a problem in that low temperature workability is insufficient because hardening at high temperature is required, and a load is applied to the semiconductor device. Therefore, a sufficient shock absorption effect is not acquired with the conventional polyimide resin, but it became a problem in the mounting process of a semiconductor device.

On the other hand, in order to improve the shock absorption effect of a polyimide resin, the method of copolymerizing the monomer component which has rubber elasticity in resin is proposed (for example, patent document 1).

Patent Document 1: Japanese Patent Application Laid-open No. Hei 1-123824

DISCLOSURE OF INVENTION

Problems to be Solved by the Invention

However, in the method described in Patent Literature 1, the impact absorption property is improved by the addition of a monomer component having rubber elasticity, but a new problem that the heat resistance of the resin itself is deteriorated by this copolymerization monomer component occurs.

This invention is made | formed in view of the said conventional situation, The subject is thick film formation (~ 200 micrometers) by one application | coating (spin coat), using a polyimide resin precursor (polyamic acid), Moreover, it is providing the polyamic-acid resin composition suitable for the protective coating agent of a semiconductor substrate which has a low temperature workability (-200 micrometers) and can obtain the cured film excellent in low curvature, heat resistance, insulation, and low water absorption.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the polyamic-acid resin composition which concerns on this invention is a resin composition containing the polyamic acid which has a C5-C20 alkylene chain in a principal chain, and heat-hardens to the temperature which an imidation ratio becomes 80% or more. The tensile modulus of the resin composition cured film having a thickness of 20 μm is 100 or more and less than 1500 MPa.

In order to have said suitable physical property, it is preferable that the polyamic acid used for this invention includes the structure represented by following General formula (1). Thereby, it can harden | cure at low temperature (-200 degreeC), and the cured film obtained is excellent in low curvature, heat resistance (5% weight loss temperature), insulation, and low water absorption.

However,

(In formula (In 1), to the Ar ¹ is a divalent organic group represented by the formula (2) Formula (3), tetravalent to an organic group, and / or Ar ² is represented by, l is 1 or more Is an integer.)

[Figure 2]

(In formula (2), X represents a C5-C20 alkylene group, R <^1> and R <^2> respectively independently represents a hydrogen atom, a C1-C6 alkyl group, or a C1-C3 alkoxy group, m and n Are each independently an integer of 1 to 3.)

[Tue 3]

(In Formula (3), Z represents a single bond or a divalent organic group, and each of Y ¹ and Y ² independently represents an alkylene group having 5 to 20 carbon atoms.)

In addition, in said General formula (3), Z is further low temperature (-200 degreeC) by using the polyamic acid represented by either of following General formula (4), General formula (5), and General formula (6). The cured film in the film is improved, and the cured film obtained is excellent in low warpage, heat resistance (5% weight loss temperature), insulation and low water absorption.

[Figure 4]

(In formula (4), R <^3> represents a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkenyl group, or a C1-C3 alkoxy group, m shows the integer of 1-4. In the case of two or more, a plurality of R ^{3 's} may be the same or different.)

[Figure 5]

(In formula (5), R <^4> represents a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkenyl group, or a C1-C3 alkoxy group, and nx represents the integer of 1-4. Nx In the case of two or more, two or more R <^4> may be same or different.)

[6]

(In formula (6), R <^5> represents a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkenyl group, or a C1-C3 alkoxy group, and p represents the integer of 1-4. Is 2 or more, a plurality of R ⁵ may be the same or different.)

Moreover, even if heating temperature is 200 degrees C or less, the said polyamic acid can harden | cure, More specifically, even if it is a heating temperature of 200 degrees C or less, the imidation ratio can be made into 80% or more. If the heating temperature required for hardening is 200 degrees C or less, it is preferable from a viewpoint of the load reduction with respect to a semiconductor device, and the curvature reduction of a semiconductor device.

Moreover, the cured film which concerns on this invention is formed by heat-hardening the polyamic-acid composition of the said invention, It is characterized by the above-mentioned. And the semiconductor device which concerns on this invention is provided with the hardened layer formed using the polyamic-acid resin composition of the said invention.

Effects of the Invention

The polyamic acid resin composition of the present invention is excellent in low temperature curability, and the resulting cured film is excellent in low warpage, heat resistance, insulation and low water absorption, and can be suitably used as a protective coating agent for semiconductor substrates. Moreover, by the said outstanding characteristic of the polyamic-acid resin composition of this invention, the semiconductor device of the outstanding characteristic can be provided by forming the cured film of a semiconductor device using the polyamic-acid resin composition of this invention.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail.

The resin composition of this invention contains the polyamic acid which has a C5-C20 alkylene chain in a principal chain.

As a method of obtaining the polyamic acid of this invention, it can obtain by making (A) tetracarboxylic dianhydride component and (B) diamine component react.

Here, by including an alkylene chain of 5 to 20 carbon atoms in one or both main chains of the (A) tetracarboxylic dianhydride component and the (B) diamine component, low-temperature curing property is realized and low glass transition temperature, A cured film having good flexibility, low water absorption and low warpage can be formed.

Moreover, the heat resistance of the cured film obtained can be improved by including an aromatic group in either or both main chains of (A) tetracarboxylic dianhydride component and (B) diamine component.

Moreover, it is preferable that the polyamic acid of this invention does not contain ether bonds, such as a polyalkyleneoxy group. The ether bond is a factor that the bond is easily broken at high temperature, and the heat resistance (5% weight loss temperature) of the resin is lowered. Moreover, when the ether bond is obtained, the resulting resin becomes easy to absorb and may be a factor that adversely affects the insulating properties (HAST) of the resin and the like.

As (A) tetracarboxylic dianhydride component which has a C5-C20 alkylene chain in the said main chain, the compound represented by following General formula (7) is mentioned.

[Tue 7]

(In formula (7), X represents a C5-C20 alkylene group.)

As a compound represented by the said General formula (7), a pentamethylene bistrimer dianhydride, a hexamethylene bistrimeric dianhydride, a heptamethylene bistrimeric dianhydride, an octamethylene bistrimeric dianhydride, a nonnamethylene bistrimer dianhydride, for example , Decamethylene bistrimerate dianhydride, dodecamethylene bistrimerate dianhydride, and the like.

These are used individually or in combination of 2 types.

As (B) diamine component which has a C5-C20 alkylene chain in the said main chain, For example, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,11- diamino degree, Decane, 1,12-diaminooctadecane, 2,5-dimethylhexamethylenediamine, 3-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylene Aliphatic diamines, such as diamine and 3-methoxyhexamethylene diamine, the compound represented by following General formula (8), (9), (10), etc. are mentioned.

[Figure 8]

(In formula (8), Y <^1> and Y <^2> respectively independently show a C5-C20 alkylene group, R <^6> represents a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkenyl group, or C1-C1-C 3 represents an alkoxy group, q represents an integer of 1 to 4. In addition, when q is 2 or more, a plurality of R ^{6 's} may be the same or different.)

[Figure 9]

(In formula (9), Y <^1> and Y <^2> respectively independently represent a C5-C20 alkylene group, R <^7> represents a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkenyl group, or C1-C1-C An alkoxy group of 3, r represents an integer of 1 to 4. In addition, when r is 2 or more, a plurality of R ^{7 's} may be the same or different.)

[10]

(In formula (10), Y <^1> and Y <^2> respectively independently represent a C5-C20 alkylene group, R <^8> represents a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkenyl group, or C1-C1-C An alkoxy group of 3, s represents an integer of 1 to 4. In addition, when s is 2 or more, two or more R <^8> may be same or different.)

As a compound represented by General formula (9), [3, 4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene (brand name "Versamine551", Cognis Japan (Note) ) Company is available as a commercial item. These are used individually or in combination of 2 types.

As tetracarboxylic dianhydride components other than the (A) tetracarboxylic dianhydride component which has a C5-C20 alkylene chain in the said main chain, a pyromellitic dianhydride, 1,2,3,4- benzene tetra Carboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid anhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid anhydride, 3,3', 4,4'-biphenyltetracar Acid anhydrides, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'- Benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyl ether tetracarboxylic anhydride (4,4'- Oxydiphthalic dianhydride), 2,3 ', 4,4'-diphenylethertetracar Acid dianhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 2,3,3', 4'-diphenylsulfontetracarboxylic dianhydride, 2,3,6,7- Naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic acid Anhydrides, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyl Oxy) phenyl] nonane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] decane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) Phenyl] tridecane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] tetradecane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) Phenyl] pentadecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2-methyldecane dianhydride, 1,1-bis [4- (3,4- Carboxybenzoyloxy) phenyl] -2-methyloctane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2-ethylpentadecane dianhydride, 2,2-bis [3 , 5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] dodecane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] Decane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] tridecane dianhydride, 2,2-bis [3,5-diethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] pentadecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] cyclohexane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] propylcyclohexane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] heptylcyclohexane dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 4,4-bis (2,3-dicarboxyphenoxy) diphenylmethane dianhydride, and the like. It can be used.

As (B) diamine component other than the (B) diamine component which has a C5-C20 alkylene chain in the said main chain, For example, 4,4'- diamino diphenylmethane, 3,3'- dimethyl-4, 4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraethyl-4,4 ' -Diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-tilylenebis (cyclohexylamine), 3,3 ' -Dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'-diethoxy-4,4'-diaminodi Phenylmethane, bis (3-aminophenyl) ether, bis (4-aminophenyl) ether, 3,4'-diaminodiphenyl ether, 3,3'-diethyl-4,4'-diaminodiphenyl ether , 3,3'-dimethoxy-4,4'-diaminodiphenylether, bis [4- (4-aminophenoxy) phenyl] ether, 3,3'-dimethyl-4,4'-diaminodi Phenylsulfone, 3,3'-diethyl-4,4'-diaminodiphenylsulfone, 3,3'-dimethoxy-4,4'-di Minodiphenylsulfone, 3,3'-diethoxy-4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diethyl- 4,4'-diaminodiphenylpropane, 3,3'-dimethoxy-4,4'-diaminodiphenylpropane, 3,3'-diethoxy-4,4'-diaminodiphenylpropane, 2 , 2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 4,4'-dia Minodiphenylsulfide, 3,3'-dimethyl-4,4'-diaminodiphenylsulfide, 3,3'-diethyl-4,4'-diaminodiphenylsulfide, 3,3'- Dimethoxy-4,4'-diaminodiphenylsulfide, 3,3'-diethoxy-4,4'-diaminodiphenylsulfide, 2,2'-diaminodiethylsulfide, 2,4 '-Diaminodiphenylsulfide, m-phenylenediamine, p-phenylenediamine, 1,3-bis (4-aminophenoxy) benzene, 1,2-bis (4-aminophenyl) ethane, 1, 2-bis (4-aminophenyl) ethane, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, o-toluidinesulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-diaminodibenzylsulfoxide, bis (4-aminophenyl) diethyl Silane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) ethylphosphine oxide, bis (4-aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) -N-phenylamine, Bis (4-aminophenyl) -N-methylamine, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-dia Minonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 1,4-diamino-2-methylnaphthalene, 1,5-diamino-2-methylnaphthalene , 1,3-diamino-2-phenylnaphthalene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,3 '-Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4'-D Tyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 2,4- Diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminotoluene, 1-methoxy-2,4-diaminobenzene, 1,3-diamino-4, 6-dimethylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2-methoxy-5-methylbenzene, 1,4-diamino-2,3,5,6 -Tetramethylbenzene, 1,4-bis (2-methoxy-4-aminopentyl) benzene, 1,4-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,4-bis (4- Aminophenoxy) benzene, o-xylenediamine, m-xylenediamine, p-xylenediamine, 9,10-bis (4-aminophenyl) anthracene, 3,3'-diaminobenzophenone, 4,4'-dia Minobenzophenone, 4-aminophenyl-3-aminobenzoate, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2- ( 3-aminophenyl) -2- (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4- Minophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis (4-aminophenyl) -1-phenyl-2,2, 2-trifluoroethane, 1,1-bis [4- (4-aminophenoxy) phenyl] -1-phenyl-2,2,2-trifluoroethane, 1,3-bis (3-aminophenyl ) Hexafluoropropane, 1,3-bis (3-aminophenyl) decafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3 -Amino-4-methylphenyl) hexafluoropropane, 2,2-bis (5-amino-4-methylphenyl) hexafluoropropane, 1,4-bis (3-aminophenyl) buta-1-ene 3-phosphate These etc. can be mentioned, It can use it, mixing with an essential component.

The said polyamic acid is obtained by carrying out addition polymerization reaction of the said sugar (A) acid component and (B) diamine component in the organic solvent at the reaction temperature of 80 degrees C or less, Preferably it is 50 degrees C or less.

As a solvent at the time of making said (A) tetracarboxylic dianhydride and said (B) diamine component react, for example, nitrogen-containing solvents (N, N'-dimethylsulfoxide, N, N'-dimethyl) Formamide, N, N'-diethylformamide, N, N'-dimethylacetamide, N, N'-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide N-methyl Pyrrolidone, etc.), lactones (γ-butyrolactone, γ-valerolactone, γ-caprolactone, ε-caprolactone, α-acetyl-γ-butyrolactone, etc.) and alicyclic ketones (cyclohexanone , 4-methylcyclohexanone, etc.), ethers (3-methyl-3-methoxybutyl acetate, diethylene glycol dimethyl ether acetate, etc.) etc. are mentioned. Among these, nitrogen-containing solvents, alicyclic ketones, and the like are more preferable, and N-methyl-2-pyrrolidone and cyclohexanone are particularly preferable. These can be used individually or in mixture of 2 or more types.

Although the polyamic acid used for this invention has a C5-C20 alkylene chain in the principal chain obtained by reaction of (A) tetracarboxylic dianhydride component and (B) diamine component, C6-C16 It is preferable that it is an alkylene chain, and it is more preferable that it is a C7-14 alkylene chain. In the alkylene group having less than 5 carbon atoms, the water absorption rate and elastic modulus of the resin tend to increase, and in the alkylene group having 20 carbon atoms or more, the water absorption rate and elastic modulus of the resin tends to decrease.

The combination of the (A) tetracarboxylic dianhydride component and the (B) diamine component is preferably selected in consideration of the heat resistance, mechanical properties, and electrical properties of the polyimide resin film after final curing.

As for the hardening temperature which the imidation ratio of the polyamic acid in this invention becomes 80% or more, 200 degrees C or less is preferable from a viewpoint of the load reduction with respect to a semiconductor device, and the curvature reduction of a semiconductor device. Moreover, it is preferable that the imidation ratio of a polyamic acid is 90% or more from a viewpoint of heat resistance and a low water absorption, and it is more preferable that it is 95% or more. Moreover, as for hardening temperature, 100 degreeC or more and 200 degrees C or less are more preferable from a practical viewpoint, and 150 degreeC or more and 200 degrees C or less are especially preferable.

The polyamic acid in the present invention is preferably subjected to preheating before curing in order to suppress the generation of voids in the film due to removal of the solvent and moisture generated by the imide ring closure of the polyamic acid.

This preheating is performed for 1 to 2 hours, for example, while raising the temperature step by step. It is preferable to perform preheating at 80-150 degreeC.

In addition, the measurement of this imidation ratio can be calculated | required by measuring an infrared absorption spectrum by a transmission method.

The value of the imidation ratio can be computed by the following formula, making the cured film (resin film thickness: 5 micrometers) hardened | cured at 300 degreeC for 1 hour theoretically 100% (reference).

Imidization ratio = ｛(K / L)-(M / N)｝ / ｛(O / P)-(M / N)｝

(In the formula, K is, the resin composition after curing (an absorbance at the maximum peak in the vicinity of 1375cm ^-1 of any temperature), L is, the resin composition after curing (absorbance at the maximum peak in the vicinity of 1500cm ^-1 of any temperature) and, M is an absorbance at the maximum peak in the vicinity of 1375cm ^-1 before the resin composition is cured, N is a resin composition in the vicinity of 1500cm ^-1 and the absorption maximum peak of before curing, is O, 1 hour to cure the resin composition at 300 ℃ after 1375cm ^-1 and the absorbance of the vicinity of the maximum peak, P is an absorbance at the maximum peak in the vicinity of the resin composition at 300 ℃ after 1 hours curing 1500cm ^-1.)

The tensile modulus of the cured product film using the polyamic acid resin composition in the present invention is 50 to 1500 MPa, preferably 100 to 1200 MPa, more preferably 100 to 500 MPa from the viewpoint of warpage.

Moreover, the water absorption after 24 hours of water immersion at 23 degreeC of the said cured film is 0 or more and less than 2%, more preferably 0 or more and less than 1.5% from a viewpoint of insulation characteristic improvement, More than 0 and less than 0.5% This is particularly preferred.

The semiconductor substrate targeted by the present invention is not particularly limited as long as an electronic circuit or a semiconductor element is formed, and can be used in any kind of semiconductor substrate. Specifically, the silicon wafer in which a memory circuit was formed, the silicon wafer in which a logic circuit was formed, etc. are mentioned, for example.

The method of forming a resin layer using the polyamic acid resin composition of the present invention is, for example, a method of forming a resin layer by spin coating on a semiconductor substrate, or laminating resin formed in a film form on a semiconductor substrate to form a resin layer. The method etc. are mentioned.

Although the polyimide resin composition of this invention makes the above-mentioned polyamic acid resin an essential component, as long as it is not contrary to the objective of this invention, as needed, other components, a silica, a calcium carbonate, magnesium carbonate, sodium carbonate And inorganic fillers such as talc and bentonite, colorants such as thixotropic agents and phthalocyanine green, antifoaming agents, coupling agents, leveling agents and the like can be added and blended to produce them.

The polyamic acid resin composition of this invention is used as an insulating material of insulating films, such as a protective film of a semiconductor chip and the interlayer insulation film of a multilayer wiring, or a flexible circuit board, and is especially suitable for the semiconductor field which needs heat resistance and insulation. Moreover, since the polyamic-acid resin composition of this invention is hardenable at the temperature of 200 degrees C or less, it is used for the field | parts which could not be hardened at the temperature of 200 degrees C or more in the process so far, for example, the field of junction coatings, such as a transistor. It is possible to.

Next, although an Example demonstrates this invention, this invention is not limited by these Examples. In addition, in the following synthesis examples, the number average molecular weight of polyamic acid was measured by gel permeation chromatography (GPC), and it calculated | required in conversion by the analytical curve using standard polystyrene. The conditions of GPC are as follows.

Pump: Hitachi @ L-6000 type [product made by Hitachi, Ltd., brand name]

Detector: Hitachi @ L-3300 type RI [Hitachi Corporation make, brand name]

Column: Gelpack @ GL-S300MDT-5 (two in total) (product made by Hitachi Kasei Kogyo Co., Ltd., brand name)

Eluent: DMF / tetrahydrofuran (weight ratio 1/1)

Flow rate: 1mL / minute

(Reference Example 1)

In a 500 mL four-neck separable flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 30.78 g of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (BAPP) as a (B) diamine component ( 0.075 mol) and 298.2 g of N-methyl-2-pyrrolidone were added as a solvent, and it stirred at 40 degreeC for 15 minutes. Next, 39.19 g (0.075 mol) of decamethylene bistrimer dianhydride (DBTA) was added over 30 minutes as (A) tetracarboxylic dianhydride component, stirring. After the addition was completed, the temperature was raised to 50 ° C., followed by stirring for 3 hours to obtain an N-methyl-2-pyrrolidone solution of polyamic acid. Solid content in the obtained solution was 19% by weight, the number average molecular weight of the polyamic acid was 17800, and the dispersion degree was 2.6.

(Reference Example 2)

In a 300 mL four-neck separable flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, (A) 29.00 g (0.09 mol) of 4,4'-oxydiphthalic anhydride (BTDA) as a tetracarboxylic dianhydride component, a solvent As an example, 72.6 g of N-methyl-2-pyrrolidone was added and stirred at 60 ° C for 15 minutes. While stirring, 49.96 g (0.09 mol) of [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene (AHOH) was used as the diamine component (B). It added over 40 minutes at 40 degrees C or less. After the addition was completed, the mixture was stirred at 40 ° C for 5 hours to obtain an N-methyl-2-pyrrolidone solution of polyamic acid. Solid content in the obtained solution was 52% by weight, the number average molecular weight of the polyamic acid was 17260, and the dispersion degree was 1.8.

(Example 3)

In a 300 mL four-neck separable flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, (A) 41.8 g (0.08 mol) of decamethylene bistrimeric dianhydride (DBTA) as a tetracarboxylic dianhydride component, N-methyl as a solvent 127.6 g of 2-pyrrolidone was added and stirred at 60 ° C for 15 minutes. Next, while stirring, 44 g (0.08 mol) of [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene (AHOH) was 40 as the diamine component. It added over 15 minutes at degrees C or less. After the addition was completed, the temperature was raised to 60 ° C., followed by stirring for 1 hour to obtain an N-methyl-2-pyrrolidone solution of polyamic acid. Solid content in the obtained solution was 40% by weight, the number average molecular weight of the polyamic acid was 30600, and the dispersion degree was 1.4.

(Comparative Example 1)

In a 300 mL four-neck separable flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 20.2 g (0.05 mol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (BAPP), triblock 50.6 g (0.05 mol) of polyetherdiamine compounds (made by Sun Techno Chemical, brand name "XTJ-542") and 74 g of N-methyl- 2-pyrrolidone were added, and it stirred for 5 minutes. Next, 31.6 g (0.1 mol) of 4,4'- oxydiphthalic dianhydride (ODPA) was added over 20 minutes, stirring. After the addition was completed, the temperature was raised to 60 ° C., followed by stirring for 1 hour to obtain an N-methyl-2-pyrrolidone solution of polyamic acid. Solid content in the obtained solution was 58% by weight, the number average molecular weight of the polyamic acid was 17800, and the dispersion degree was 2.6.

(Comparative Example 2)

In a 300 mL four-neck separable flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 20.2 g (0.05 mol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (BAPP), N- 164 g of methyl-2-pyrrolidone was added and stirred for 5 minutes. Next, 15.8 g (0.05 mol) of 4,4'- oxydiphthalic dianhydride (ODPA) was added over 20 minutes, stirring. After the addition was completed, the temperature was raised to 60 ° C., followed by stirring for 1 hour to obtain an N-methyl-2-pyrrolidone solution of polyamic acid. Solid content in the obtained solution was 18% by weight, the number average molecular weight of the polyamic acid was 61000, and the dispersion degree was 2.5.

(Comparative Example 3)

10.2 g (0.025 mol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (BAPP) in a 300 mL four-neck separable flask equipped with a stirrer, a thermometer and a nitrogen introduction tube 7.23 g (0.025 mol) of 3-bis (3-aminophenoxy) benzene (APB) and 130.3 g of N-methyl-2-pyrrolidone were added, and it stirred for 5 minutes. Next, 26.0 g (0.05 mol) of 2,2-bis [4- (dicarboxyphenoxy) phenyl] propanoic anhydride (BPADA) was added over 20 minutes, stirring. After the addition was completed, the temperature was raised to 70 ° C and stirred for 3 hours to obtain an N-methyl-2-pyrrolidone solution of polyamic acid. Solid content in the obtained solution was 25% by weight, the number average molecular weight of the polyamic acid was 42000, and the dispersion degree was 2.8.

[Measurement of 5% weight loss temperature]

The polyamic acid resin solution obtained by the said reference example 1-2, Example 3, and the comparative examples 1-3 is microadhered in the polyethylene terephthalate film (PET film) (brand name "Purex", the Teijin Dupont film company make) It apply | coated using the applicator and heat-hardened at the temperature which the imidation ratio becomes 80% or more, respectively. Curing conditions are shown in the following (Table 1). The obtained hardened | cured material (film thickness: 20 micrometers) was peeled from PET film, and the 5 x 5 mm test piece was produced. Regarding this test piece, by using a differential scanning calorimeter (trade name "TG / DTA6300", manufactured by Seiko Instruments Co., Ltd.), a 5% weight reduction temperature was increased by a TG-DTA method at a heating rate of 10 ° C / min and 20 mL / min under a nitrogen atmosphere. Measured.

[Measurement of Absorption Rate]

The polyamic acid resin solution obtained in the above Reference Examples 1 to 2, Example 3 and Comparative Examples 1 to 3 was applied to a polyethylene terephthalate film (PET film) (trade name "Purex", manufactured by Teijin DuPont Film Co., Ltd.). It apply | coated using and heat-hardened at the temperature which the imidation ratio becomes 80% or more, respectively. Curing conditions are shown in (Table 1). This glass plate (resin film thickness: 20 micrometers) was immersed in deionized water at 23 degreeC for 24 hours, and the water absorption was computed by the following formula | equation.

λ (%) = ｛(ww ₀ ) / w｝ × 100

λ: Absorption rate (%)

w ₀ : Weight of the resin composition cured film formation glass substrate before immersion in deionized water

w: Weight of the resin composition cured film formation glass substrate after immersion in deionized water

On the other hand, the weight after immersion lightly wiped off the glass substrate surface of the resin composition cured film surface and the opposite surface in which the resin composition cured film is formed with paper towel, and read the value after 10 second.

[Measurement of Tensile Modulus]

The polyamic acid resin solution obtained by the said Reference Examples 1-2, Example 3, and Comparative Examples 1-3 is a microapplicator to a polyethylene terephthalate film (PET film: brand name "Purex", Teijin Dupont Film Co., Ltd. product). It apply | coated using and heat-hardened at the temperature which the imidation ratio becomes 80% or more, respectively. Curing conditions are shown in (Table 1). The obtained hardened | cured material (film thickness: 20 micrometers) was peeled from PET film, and the test piece of 1 cm width was produced. About this test piece, the tensile modulus was measured using the tensile tester (brand name "Autograph AGF-5KN", Shimadzu Corporation make) on the temperature of 23 degreeC, 20 mm between chucks, and 5 mm / min of tensile speeds. Measured.

[Measurement of Glass Transition Temperature and Linear Expansion Coefficient α]

The polyamic acid resin solution obtained by the said Reference Examples 1-2, Example 3, and Comparative Examples 1-3 is a microapplicator to a polyethylene terephthalate film (PET film: "brand name Purex", Teijin Dupont Film Co., Ltd. product). It apply | coated using and heat-hardened at the temperature which the imidation ratio becomes 80% or more, respectively. Curing conditions are shown in (Table 1). The obtained hardened | cured material (film thickness: 20 micrometers) was peeled from PET film, and the test piece of 4 mm was produced. About this test piece, using a tensile tester (trade name "thermomechanical analyzer TMA-120", manufactured by SAI NANO Technology Co., Ltd.), the glass transition temperature and temperature were increased by a TMA method at a heating rate of 10 ° C / min and a load of 3 g. The coefficient of linear expansion α was measured.

[Unsaturated Pressurized Steam Test]

The polyamic acid resin solution obtained by the said Reference Examples 1-2, Example 3, and Comparative Examples 1-3 was apply | coated to the polyimide flexible board | substrate (30 micrometer pitch, tin plating) which carried out copper wiring, and imidation ratio was respectively It heat-hardened at the temperature used as 80% or more, and produced the test piece. Curing conditions are shown in (Table 1). This test piece was evaluated for 100 hours at 120 ° C / 85% RH / 60V under a condition of ion migration tester (trade name "MIG-8600", manufactured by IMV), and the resistance value was 1.E + 8 or more. The thing made into (circle) and resistance value 1.E + 8 was made into x.

[Test of Warpage]

The polyamic acid resin solution obtained by the said Reference Examples 1-2, Example 3, and Comparative Examples 1-3 was apply | coated to an 8-inch silicon wafer (420 +/- 25 micrometers) by spin coating, and imidation ratio is 80% or more, respectively. It hardened | cured at the temperature to become. Curing conditions are shown in (Table 1). The test piece of 200 micrometers of resin film thicknesses was produced. Evaluation of curvature pressed one side and 1 cm of a wafer, and made (circle) and 1 mm or more x that the floating height of the opposite side is less than 1 mm. The measurement result was written together to (Table 1).

The results of each evaluation of the 5% weight loss temperature, water absorption rate, tensile modulus, glass transition temperature, linear expansion coefficient, migration resistance, and warpage performed as described above are listed in Table 1 together.

Moreover, the imidation ratio in the hardening conditions described in Reference Examples 1-2, Example 3, and Comparative Examples 1-3 was 95% or more.

The polyamic-acid resin composition of this invention of Reference Examples 1-2 and Example 3 can be hardened at 200 degrees C or less by containing a C5-C20 alkylene chain in a principal chain. The cured film obtained by hardening this resin composition has the outstanding flexibility, and its glass transition temperature is low. In the polyamic acid resin composition of this invention of Examples 1-3, the cured film of 80% or more of imidation ratio can be formed at low temperature, and reduction of the hydrophilic group (carboxylic acid residue and / or amine residue) accompanying a ring closure, and alkylene group The hydrophobic group of can realize the low water absorption rate and insulation characteristic of a cured film. In addition, since the cured film obtained from the polyamic resin composition of this invention has a low elasticity modulus, since base material followability is high and it can harden | cure at low temperature, low curvature can be realized from being able to suppress linear expansion of a base material. Moreover, the heat resistance of resin can be improved by containing an aromatic group in a principal chain.

On the other hand, as shown in the comparative example 1, when the ether bond of a polyalkylene oxy group is included, the ether bond in resin is easily broken at high temperature, and it becomes a factor which reduces the heat resistance (5% weight loss temperature) of the obtained cured film. Moreover, the obtained cured film is easy to absorb by having an ether bond, and the bad effect is exerted on insulation characteristic (HAST). In addition, as shown in Comparative Examples 2 and 3, in the case of the polyamic resin composition having no alkylene chain in the main chain, the glass transition temperature is high, and the curing temperature is high. This becomes a factor that the load on a semiconductor device becomes large. In addition, warpage also increases, which causes deterioration of workability and reliability of the semiconductor.

As mentioned above, the polyamic-acid resin composition which concerns on this invention is excellent in low-temperature sclerosis | hardenability, and the obtained cured film is excellent in low curvature, heat resistance, insulation, and low water absorption, and can be used suitably for the protective coating agent of a semiconductor substrate. Moreover, since the cured film is formed using the polyamic-acid resin composition of this invention, the semiconductor device of this invention has the outstanding outstanding mechanical and electrical protection property.

Claims (8)

A resin composition comprising a polyamic acid having an alkylene chain having 5 to 20 carbon atoms in a main chain, wherein the tensile modulus of the resin composition cured film having a thickness of 20 µm heat cured at a temperature at which the imidization ratio becomes 80% or more is 50 or more and less than 1500 MPa , The said polyamic acid has following general formula (1): However,

(In Formula (1), Ar ¹ is a tetravalent organic group represented by the following general formula (2) and Ar ² is a divalent organic group represented by the following general formula (3), and l is an integer of 1 or more) [Figure 2]

(In formula (2), X represents a C5-C20 alkylene group, R <^1> and R <^2> respectively independently represents a hydrogen atom, a C1-C6 alkyl group, or a C1-C3 alkoxy group, m and n Are each independently an integer of 1 to 3.) [Tue 3]

(In formula (3), Y <^1> and Y <^2> show a C5-C20 alkylene group each independently.), Z in the said General formula (3) is following General formula (5) and (6): [Figure 5]

(In formula (5), R <^4> represents a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkenyl group, or a C1-C3 alkoxy group, and nx represents the integer of 1-4. In addition, nx Is 2 or more, a plurality of R ⁴ may be the same or different.) [6]

(In formula (6), R <^5> represents a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkenyl group, or a C1-C3 alkoxy group, and p shows the integer of 1-4. Is 2 or more, a plurality of R ⁵ may be the same or different.) Polyamic acid resin composition, characterized in that any one of. delete delete The polyamic acid resin composition of Claim 1 WHEREIN: The said polyamic acid has low temperature hardening characteristic that an imidation ratio becomes 80% or more by the heating temperature of 200 degrees C or less, The polyamic acid resin composition characterized by the above-mentioned. The polyamic acid resin composition of Claim 1 WHEREIN: The said polyamic acid has low temperature hardening characteristic that an imidation ratio becomes 80% or more by the heating temperature of 200 degrees C or less, The polyamic acid resin composition characterized by the above-mentioned. The polyamic acid resin composition of Claim 1 WHEREIN: The said polyamic acid has low temperature hardening characteristic that an imidation ratio becomes 80% or more by the heating temperature of 200 degrees C or less, The polyamic acid resin composition characterized by the above-mentioned. The cured film formed by heat-hardening the polyamic-acid composition in any one of Claim 1 or 4-6. The semiconductor device provided with the hardened layer formed using the polyamic-acid resin composition in any one of Claim 1 or 4-6.