JPH11130858A - Polyimide, its precursor, their production and photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyimide having low temperature hardenability, excellent heat resistance, moisture resistance, adhesiveness, etc., by using a specific repeating unit having an organic group containing an aromatic ring, a specific repeating unit having an organic group not containing any aromatic ring and a polyimide precursor having a specific terminal structure. SOLUTION: This polyimide is obtained by subjecting a polyimide precursor having a repeating unit of formula I (R<1> is a four functional organic group; R<2> is a bifunctional organic group containing an aromatic ring; X is OH or the like), a repeating unit of formula II (R<3> is a bifunctional organic group not containing any aromatic ring) and further having one or both chain ends of formula III R<4> is a halogen or the like; (n) is 0-4} of a part or whole of molecules to imido-ring closure. The polyimide precursor is obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing an aromatic ring, a diamine not containing any aromatic ring and a compound of formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyimide, a precursor thereof, a method for producing them, and a photosensitive resin composition.

[0002]

2. Description of the Related Art In recent years, in response to the miniaturization, weight reduction, multifunctionality, high reliability, and low price of electronic devices, printed circuit boards have been required to use conductive patterns without using component holes called surface mounting methods. A component mounting method for electrically connecting a component to a substrate on the surface of a semiconductor device is rapidly expanding. In the manufacture of printed wiring boards, photosensitive solder resist has been used for the purpose of limiting the soldering position and protecting the wiring, but the photosensitive solder resist used for printed wiring boards using the surface mounting method has been used. Is required to have better heat resistance, moisture resistance and adhesiveness. In the case of a conventional photosensitive solder resist containing an epoxy resin as a main component, when a pressure cooker test (hereinafter abbreviated as PCT) is performed, the resist becomes There is a problem that blistering or peeling occurs and heat resistance, moisture resistance and adhesion are insufficient.

On the other hand, in the field of semiconductors, photosensitive polyimide resins having excellent heat resistance, moisture resistance and adhesion are used for protecting wiring. However, photosensitive polyimide is used in the form of a polyamic acid as a polyimide precursor at the time of image formation, and since a high-boiling nitrogen-containing polar solvent is used as a solvent, a cured film having the above excellent characteristics is obtained. Requires high-temperature curing, usually at 300 ° C. or higher. Therefore, there is a problem that it cannot be used for a printed wiring board from the viewpoint of heat resistance of a substrate or the like.

[0004]

SUMMARY OF THE INVENTION The first and second aspects of the present invention provide a polyimide precursor which is curable at a low temperature and gives a polyimide having excellent heat resistance, moisture resistance, adhesion and the like. . The invention according to claims 3 to 7 is
An object of the present invention is to provide a method for producing a polyimide precursor which can be easily produced to give a polyimide which is low-temperature curable and has excellent heat resistance, moisture resistance, adhesion and the like.

The invention according to claim 8 provides a polyimide having excellent heat resistance, moisture resistance, adhesion and the like. The invention according to claim 9 has excellent heat resistance,
An object of the present invention is to provide a production method capable of easily producing a polyimide having moisture resistance and adhesion. Further, the invention according to claim 10 provides a photosensitive resin composition which is curable at a low temperature, provides a polyimide film having excellent heat resistance, moisture resistance, adhesion and the like, and is excellent in developability and storage stability. Things.

[0006]

The present invention provides a compound represented by the general formula (I):

Embedded image (Wherein, R ¹ represents a tetravalent organic group, and R ² has at least 1
X represents a divalent organic group containing two aromatic rings, and each X independently represents OH or a monovalent organic group), a repeating unit represented by the general formula (II):

Embedded image (Wherein, R ¹ represents a tetravalent organic group, R ³ represents a divalent organic group not containing an aromatic ring, and X each independently represents OH or a monovalent organic group). Having a repeating unit,
Further, some or all of the molecules have the general formula (III)

Embedded image (Wherein, R4 represents a halogen, a nitro group or an alkyl group having 1 to 9 carbon atoms, and n is an integer of 0 to 4). .

Further, the present invention provides a divalent organic group represented by R ³ in the repeating unit represented by the general formula (II):

Embedded image (Wherein, R ⁵ is _{^{-CHR 8 -CH 2 -, - CH}} 2 -CH 2 -
Or -CH ₂ -CHR ⁸ - shows a, a, b and c denotes the number of repeating units in the formula, a and b are 0 or a positive integer, c is a positive integer, R ^6, R ⁷ and R ⁸ are an alkyl group having 1 to 3 carbon atoms).

The present invention also relates to (A) tetracarboxylic dianhydride or a derivative thereof, (B) a diamine containing at least one aromatic ring, (C) a diamine containing no aromatic ring, and (D) a diamine containing an aromatic ring. IV)

Embedded image Wherein n is an integer of 0 to 4 and R ⁴ represents a halogen, a nitro group or an alkyl group having 1 to 9 carbon atoms, wherein the aminobenzimidazole represented by the following formula is reacted: It relates to the method of manufacturing the body.

The present invention also relates to a method for producing the polyimide precursor, which is reacted in a non-nitrogen-containing polar solvent. The present invention also relates to the method for producing the polyimide precursor, wherein (C) the diamine containing no aromatic ring is used in an amount of 1 to 90 mol% of the total amine used. Further, the present invention relates to the method for producing the polyimide precursor, wherein (D) the aminobenzimidazole represented by the general formula (IV) is used in an amount of 0.1 to 10 mol% of the total amine used. The present invention also relates to the method for producing the polyimide precursor, wherein the non-nitrogen-containing polar solvent is γ-butyrolactone.

[0010] The present invention also relates to a polyimide obtained by subjecting the polyimide precursor to imide ring closure. The present invention also relates to a method for producing a polyimide, wherein the polyimide precursor is subjected to imide ring closure. Furthermore, the present invention relates to a photosensitive resin composition containing the polyimide precursor and a photosensitive agent.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polyimide precursor of the present invention has the repeating units represented by the general formulas (I) and (II), and some or all of the molecules have the general formula (III) Has one or both of the terminal structures represented by
R ¹ in each general formula is a tetravalent organic group, and is generally a residue of a tetracarboxylic acid or a derivative thereof (an acid anhydride or the like) that can react with a diamine to form a polyimide precursor. The total carbon number of the tetravalent organic group is preferably 4 to 40. As the tetravalent organic group, a group containing an aromatic ring, a group containing an aliphatic ring without containing an aromatic ring, and the like are preferable.
Groups containing an aromatic ring are more preferred. Aromatic ring (benzene ring,
The group containing a naphthalene ring, a pyridine ring, etc.), R ¹
Are preferably present directly on the aromatic ring. These binding sites are divided into two sets of two, and two binding sites in each set are preferably located at the ortho or peri position of the aromatic ring. Said 2
The sets may be on the same aromatic ring or on separate aromatic rings linked through various bonds. In a plurality of repeating units present in the polyimide precursor of the present invention, R ¹ may be the same or different.

Examples of the tetracarboxylic acid or a derivative thereof that provides the residue represented by R ¹ include oxydiphthalic acid, pyromellitic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, and 3,3 ′ 2,4,4'-biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, Sulfonyl diphthalic acid, m-terphenyl-3,
3 ′, 4,4′-tetracarboxylic acid, p-terphenyl-3,3 ′, 4,4′-tetracarboxylic acid, 1,1,
1,3,3,3-hexafluoro-2,2-bis (2
3- or 3,4-dicarboxyphenyl) propane,
2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis [4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl] propane, 1, 1,1,3,3,3-hexafluoro-2,2
Aromatic tetracarboxylic acids such as -bis [4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl] propane, dianhydrides thereof, and the following general formula (V)

Embedded image (In the formula, R ⁹ and R ¹⁰ each independently represent a monovalent hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms. When a plurality of carbon atoms are present, they may be the same or different. 1 or more, preferably an integer of 1 to 10), such as aromatic tetracarboxylic dianhydrides, cyclobutenetetracarboxylic acids and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid; And these may be used alone or in combination of two or more.

In the general formula (I), the divalent organic group containing an aromatic ring represented by R ² is generally an aromatic diamine compound capable of forming a polyimide precursor by reacting with tetracarboxylic acid or a derivative thereof. Residue. The divalent organic group preferably has 4 to 40 carbon atoms. Here, examples of the aromatic ring include a benzene ring, a naphthalene ring, and a pyridine ring. The number of aromatic rings is preferably from 1 to 4. Preferably, the two binding sites present on R ² are present directly on the aromatic ring, in which case the two binding sites may be present on the same aromatic ring but on different aromatic rings. Is also good.

Examples of the diamine providing the residue represented by R ² as a residue include, for example, 4,4 ′-(or 3,4 ′)
-, -3,3'-, 2,4'-, 2,2'-) diaminodiphenyl ether), 4,4'- (or 3,4'-,
-3,3 '-, 2,4'-, 2,2 '-) diaminodiphenylmethane, 4,4'- (or 3,4'-, -3,
3'-, 2,4'-, 2,2'-) diaminodiphenyl sulfone, 4,4'- (or 3,4'-, -3,3 '
-, 2,4 '-, 2,2'-) diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidinesulfone, 4,4 '-
Methylene-bis (2,6-diethylaniline), 4,
4'-methylene-bis- (2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis [4- (4'-aminophenoxy) phenyl Sulfone, 1,1,1,3,3,3-hexafluoro-2,2
-Bis (4-aminophenyl) propane, 2,2-bis [4- (4'-aminophenoxy) phenyl] propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5 , 5'-Tetramethyl-4,
4'-diaminodiphenylmethane, bis [4- (3'-
[Aminophenoxy) phenyl] sulfone, 2,2-bis (4-aminophenyl) propane and the like, and these can be used alone or in combination of two or more.

In the general formula (II), the divalent organic group not containing an aromatic ring represented by R ³ is generally other than an aromatic group which can react with tetracarboxylic acid or a derivative thereof to form a polyimide precursor. Is the residue of the diamine compound. Here, as the divalent organic group containing no aromatic ring, a linear or branched hydrocarbon group having 2 to 750 carbon atoms, or a carbon atom having 6 to 14 carbon atoms including an alicyclic hydrocarbon group is used. A group in which the hydrocarbon group is linked via one or more ether bonds, a group in which the hydrocarbon group is linked via a (poly) siloxane bond, and the like.

Examples of the diamine providing the group represented by R ³ include ethylene diamine, propylene diamine,
Tetramethylene diamine, hexamethylene diamine,
1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, the following general formula (VI)

Embedded image (Wherein, R ¹¹ and R ^{12 each} represent a divalent hydrocarbon group (preferably having 1 to 10 carbon atoms), which may be the same or different, and R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group ( Preferably represents 1 to 10 carbon atoms, and may be the same or different, and m is 1 or more, preferably an integer of 1 to 10), such as an aliphatic diamine such as diaminopolysiloxane, Alkylenediamine, for example, the following general formula (VII)

Embedded image (Wherein, R ⁵ is _{^{-CHR 8 -CH 2 -, - CH}} 2 -CH 2 -
Or -CH ₂ -CHR ⁸ - shows a, a, b and c denotes the number of repeating units in the formula, a and b are 0 or a positive integer, c is a positive integer, R ^6, R ⁷ and R ⁸ are an alkyl group having 1 to 3 carbon atoms).

It should be noted that, in the general formula (VII), the number of repetitions of a, b and c only means the number of each repetition unit, and the repetition units in a block-like order in this order. Is not meant to be present, but also includes compounds in which each repeating unit is bonded in a random order. a is 0
20, b is preferably an integer of 0 to 70, and c is preferably an integer of 1 to 90.

Examples of the diamine represented by the general formula (VII) include Jeffamine D-230, D-400, D-2000, and D-400 manufactured by San Techno Chemical Co., Ltd.
0, ED-600, ED-900, ED2001, ED
A commercially available product such as R-148 can be used. These are used alone or in combination of two or more. Among them, the diamine represented by the general formula (VII) is preferable because it has excellent low-temperature curability.

In the polyimide precursor of the present invention, the terminal represented by the general formula (III) is formed by using the aminobenzimidazole represented by the general formula (IV) as an amine. It may be present in some or all of the molecules of the polyimide precursor of the invention.
In the polyimide precursor, the terminal represented by the general formula (III) may be present on one side or both sides. As the aminobenzimidazole represented by the general formula (IV), for example, 2-aminobenzimidazole, 2-amino-6-methylbenzimidazole, 2-amino-6-
Ethyl benzimidazole, 2-amino-6-butylbenzimidazole, 2-amino-6-nitrobenzimidazole and the like can be mentioned. These are used alone or in combination of two or more.

In the method for producing a polyimide precursor of the present invention, the proportion of the repeating units of the general formulas (I) and (II) and the frequency of the terminal represented by the general formula (III) in the entire polyimide precursor are as follows: Can be prepared by the mixing ratio of the amine giving the general formula of According to the production method of the present invention, in the obtained polyimide precursor, one having a structure having no terminal represented by the general formula (III) at both ends may be formed, In the case where there is a repeating unit of the general formulas (I) and (II) and a molecule having a terminal represented by the general formula (III),
It is within the scope of the present invention.

The amount of the diamine used to give the repeating unit represented by the general formula (II) is preferably in the range of 1 to 90 mol%, more preferably in the range of 2 to 85 mol% of the total amount of the amine used. Is more preferred. If the amount is less than 1 mol%, the curability at low temperatures and the adhesiveness tend to decrease.
If it exceeds 0 mol%, the heat resistance tends to decrease. The amount of the aminobenzimidazole that gives a terminal represented by the general formula (III) is preferably in the range of 0.1 to 10 mol%, more preferably in the range of 0.2 to 8 mol% of the total amount of the amine used. More preferably, it is more preferably in the range of 0.5 to 5 mol%. When the amount is less than 0.1 mol%, the adhesiveness and wet heat resistance tend to decrease, and when it exceeds 10 mol%, the heat resistance tends to decrease. The amount of the diamine used to give the repeating unit represented by the general formula (I) may be the balance of each diamine. It is preferable that the polyimide precursor of the present invention has each repeating unit or terminal at the same ratio as the amount of each amine as a whole as a whole.

The polyimide precursor of the present invention may optionally have units other than the repeating units of the general formulas (I) and (II). Examples of such a repeating unit include those in which each of the repeating units of the general formulas (I) and (II) is partially imidized. In this case, the total amount of the repeating units of the general formulas (I) and (II) is preferably at least 50 mol% based on all the repeating units (including imidized units and the like) constituting the polyimide precursor.

X in the repeating units of the general formulas (I) and (II) is each independently OH or a monovalent organic group. Examples of the monovalent organic group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, a vinyl group, and an allyl group. Hydrocarbon group such as alkenyl group such as acryloyl group, methacryloyl group, methacryloyloxyalkyl group, acryloyloxyalkyl group, vinyl ether group, group having a polymerizable unsaturated double bond such as cinnamyl group, glycidyl group, hydroxyphenyl Groups and the like are bonded via -O-, -NH- or the like, and a monovalent organic group having a total carbon number of 1 to 20 is preferable, and those having 1 to 10 carbon atoms are preferable. More preferred.

A part or all of X is a photosensitive group such as a group having a polymerizable unsaturated double bond (for example, a group capable of leaving upon irradiation with light, a group capable of dimerizing or copolymerizing upon irradiation with light, etc.) ) Is preferable for use as a photosensitive material because it can impart photosensitivity to the polyimide precursor itself, and among these, a group having a polymerizable unsaturated double bond easily provides good photosensitivity. It is preferable because it can be provided. When a part of X is a photosensitive group, it is preferable that 10 mol% or more of the total X is a photosensitive group.

As the group having a polymerizable unsaturated double bond, for example, the following general formula:

Embedded image (However, R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently selected from hydrogen, an alkyl group, a phenyl group, a vinyl group and a propenyl group, and R ¹⁸ represents a divalent organic group.) The organic group to be used is preferable because it can impart high-sensitivity photosensitivity. The alkyl group preferably has 1 to 4 carbon atoms. The divalent organic group represented by R ¹⁸ is preferably an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, and a propylene group. In particular, a methacryloyloxyalkyl group and an acryloyloxyalkyl group (having an alkyl having 1 to 4 carbon atoms) not only realize high sensitivity but also are easy to synthesize and are suitable for the photosensitive resin composition of the present invention. is there.

The polyimide precursor of the present invention can be obtained by various known production methods. As the material, derivatives such as the above-mentioned tetracarboxylic acid or its anhydride, the above-mentioned various diamines, and, if necessary, alcohols and amines as raw materials constituting side chains are used. When X is OH in the general formulas (I) and (II), it can be obtained by reacting a tetracarboxylic anhydride and a diamine in an organic solvent used as required. Further, when X contains a monovalent organic group and is via -O-,
A method in which tetracarboxylic dianhydride and a hydroxy group-containing compound are mixed and reacted to produce a half ester of tetracarboxylic acid, and then acid chloride with thionyl chloride, followed by reaction with a diamine, It can be synthesized by a method of reacting an ester with a diamine using a carbodiimide as a condensing agent. In the case where X is a monovalent organic group, and in the case of via -NH-, by reacting tetracarboxylic anhydride and a diamine in an organic solvent used as required, and then reacting with an isocyanate compound, Can be manufactured.

The organic solvent used for producing the polyimide precursor of the present invention is preferably a non-nitrogen-containing polar solvent from the viewpoint of low-temperature curability. As the non-nitrogen-containing polar solvent, for example, cyclohexanone, dimethyl sulfoxide, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, γ-butyrolactone, sulfolane, and the like are preferably used. Butyrolactone is most preferred.
The amount of the organic solvent used is 1 to 1 of the generated polyimide precursor.
Preferably, it is 10 times (weight ratio). If it is less than 1 time, the viscosity at the time of synthesis tends to be too high and the synthesis tends to be difficult due to inability to stir. If it exceeds 10 times, the reaction rate tends to decrease.

The polyimide precursor of the present invention preferably has a weight-average molecular weight of 5,000 to 200,000 because of excellent low-temperature curability and excellent heat resistance, mechanical properties, workability and the like. The molecular weight is measured by a gel permeation chromatography method and is obtained by conversion using a standard polystyrene calibration curve.

The polyimide of the present invention can be produced by imide ring-closure of the polyimide precursor. The imide ring closure can be usually performed by heating. The heating condition is not particularly limited, and the heating temperature can be 80 to 450 ° C. However, the heating temperature is preferably 80 to 250 ° C in order to make use of the low-temperature curability which is one of the features of the present invention. If the heating temperature is lower than 80 ° C., the ring closure reaction tends to be slow, and if it exceeds 450 ° C., the generated polyimide tends to deteriorate. The heating time is 10 to
Preferably, it is 100 minutes. The heating time is 10
If the time is less than 1 minute, the ring-closure reaction does not tend to proceed sufficiently.
If the time exceeds 00 minutes, the produced polyimide tends to deteriorate, and the workability tends to decrease.

The photosensitive resin composition of the present invention contains the above-mentioned polyimide precursor and a photosensitive agent. When the polyimide precursor does not have a photosensitive group, photosensitivity can be imparted as needed. Examples of the method of imparting the photosensitivity include a method of introducing an acrylic compound having an amino group to a carboxyl group of a polyimide precursor by an ionic bond, a polyimide precursor and a reactive monomer, a photoacid generator and a photobase generator. And a known method such as mixing a photosensitizer.

Examples of the acrylic compound having an amino group include N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate,
N, N-diethylaminopropyl methacrylate, N,
N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, N, N-diethylaminopropyl acrylate, N, N-dimethylaminoethyl acrylamide, N, N-dimethylaminoethyl acrylamide, etc. Is mentioned. These can be used alone or in combination of two or more. The amount of the acrylic compound having an amino group to be used is preferably 1 to 200% by weight based on the resin content of the polyimide precursor, and is preferably 5% by weight.
More preferably, the content is set to 150% by weight. If the amount is less than 1% by weight, the light sensitivity tends to be poor,
If it exceeds 200% by weight, heat resistance and mechanical properties of the film tend to be inferior.

In the photosensitive resin composition of the present invention, an addition polymerizable compound can be used if necessary. Examples of the addition polymerizable compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, pentenyl acrylate, and pentenyl methacrylate. , Tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, tri Methylolpropane triacrylate, trimethylolpropa Dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6
-Hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl Acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, tris ( β-hydroxyethyl) isocyanurate triacrylate, tris (β-hydroxyethyl)
Triacrylate of isocyanurate, the following general formula (X)

Embedded image (Wherein R ¹⁹ represents hydrogen or a methyl group, and q and r are 1
Or a reaction product of tolylene diisocyanate with 2-hydroxyethyl (meth) acrylate or trimethylhexamethylene diisocyanate, cyclohexanedimethanol and 2-hydroxyethyl (meth) acrylate. Urethane (meth) acrylate such as a reaction product with These can be used alone or in combination of two or more.

The amount of the addition polymerizable compound used is preferably 1 to 200% by weight based on the resin content of the polyimide precursor. When the amount is less than 1% by weight, the photosensitive characteristics including solubility in a developing solution tend to be inferior.
If the amount exceeds the weight percentage, the mechanical properties of the film tend to be inferior.

The photosensitive resin composition of the present invention contains a photosensitive agent. Here, the term "photosensitizer" refers to a change in the photosensitive resin composition of the present invention due to light irradiation such as a photoinitiator, a photoacid generator, a photobase generator, a sensitizer, etc. Negative type), improvement of solubility by generation of acid or base (positive type))
A material that shows or helps to initiate or help. The amount of the photosensitizer varies depending on the type thereof, but is generally 0.001 to 30% by weight based on the resin content of the polyimide precursor.

Examples of the photoinitiator include Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone,
4'-bis (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,4-
Diethylthioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzyl, diphenyl disulfide, phenanthrene Quinone,
2-isopropylthioxanthone, riboflavin tetrabutyrate, 2,6-bis (p-diethylaminobenzal) -4-methyl-4-azacyclohexanone, N-ethyl-N- (p-chlorophenyl) glycine, N-phenyldiethanolamine, 2- (o-ethoxycarbonyl) oxyimino-1,3-diphenylpropanedione, 1-phenyl-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- (pyr-1-yl) phenyl] titanium benzanthrone, 3,3'-dimethoxy-
4,4'-diazidobiphenyl, 3,5-bis (4-diethylaminobenzylidene) -1-methyl-4-azacyclohexanone, 4-methyl-7-diethylaminocoumarin, 4,6-dimethyl-7-ethylaminocoumarin ,
7-diethylamino-3-thenonylcoumarin, benzyldimethylketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethyl 4-diethylaminobenzoate, 1,3 -Diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, N- (4-cyanophenyl) glycine,
1,7-bis (9-acridinyl) heptane and the like can be mentioned. These can be used alone or in combination of two or more.

The amount of the photoinitiator used is preferably 0.01 to 30% by weight, more preferably 0.05 to 10% by weight, based on the resin content of the polyimide precursor. If the amount is less than 0.01% by weight, the light sensitivity tends to be poor, and if it exceeds 30% by weight, the mechanical properties of the film tend to be inferior.

The photosensitive resin composition of the present invention may contain an azide compound as a photosensitive agent, if necessary.

As the azide compound, for example,

Embedded image

Embedded image And the like. These can be used alone or in combination of two or more.

The amount of the azide compound used is preferably 0.01 to 30% by weight based on the resin content of the polyimide precursor. If this amount is less than 0.01% by weight,
Photosensitivity tends to be inferior, and when it exceeds 30% by weight, mechanical properties of the film tend to be inferior.

Further, the photosensitive resin composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to enhance the stability during storage. As the radical polymerization inhibitor or the radical polymerization inhibitor, for example,
Hydroquinone, hydroquinone monomethyl ether, benzoquinone, diphenyl-p-benzoquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine , N-phenyl-2-naphthylamine, cuperon, phenothiazine, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like. These can be used alone or in combination of two or more. The amount of the radical polymerization inhibitor or the radical polymerization inhibitor used is based on the resin component of the polyimide precursor.
The content is preferably 0.01 to 30% by weight. If the amount is less than 0.01% by weight, the storage stability tends to be inferior, and if it exceeds 30% by weight, the photosensitivity and the mechanical properties of the film tend to be inferior.

The photosensitive resin composition of the present invention is applied to a substrate such as a silicon wafer, a metal substrate, a ceramic substrate, a copper-clad laminate, by a coating method, a dipping method, a spray method, a screen printing method, and a spin coating method. By heating and drying most of the solvent, a coating film having no tackiness can be obtained. After irradiating an actinic ray or actinic ray on the coating film through a mask on which a desired pattern is drawn, a desired relief pattern can be obtained by dissolving and removing an unirradiated portion or an irradiated portion with an appropriate developer. it can.

As the actinic ray or actinic ray for irradiating the photosensitive resin composition of the present invention, for example, a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, an i-line stepper, a g-line stepper And other ultraviolet rays, visible rays, X-rays, and electron beams. As the developer, for example, a good solvent (N, N
-Dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), a mixed solvent of a good solvent and a poor solvent (lower alcohol, water, aromatic hydrocarbon, etc.), a basic solution (hydroxylation) Aqueous solution of tetramethylammonium, aqueous solution of triethanolamine), aqueous solution of inorganic alkali, aqueous solution of inorganic alkali containing a solvent, and the like. After the development, if necessary, it is preferable to rinse with water or a poor solvent and dry at room temperature to about 100 ° C. to make the pattern stable. Further, after the development, irradiation with ultraviolet light from a high-pressure mercury lamp or heating can be performed for the purpose of improving wet heat resistance, solder heat resistance, chemical resistance, and the like.

By heating this relief pattern, a patterned high heat-resistant polyimide film can be formed. The heating temperature at this time is 80 to 450
C., and more preferably 80C to 250C. The heating temperature is less than 80 ° C. or 45
If the temperature exceeds 0 ° C., the mechanical properties and thermal properties of the polyimide film tend to decrease. The heating time at this time is 0.1 mm.
It is preferable to set it for 05 to 10 hours. If the heating time is less than 0.05 hours or more than 10 hours, the mechanical properties and thermal properties of the polyimide film tend to decrease. Thus, the photosensitive resin composition of the present invention can be used for various protective films, insulating films, and the like.

[0044]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. Example 1 100 equipped with a stirrer, thermometer, nitrogen inlet tube and cooling tube
In a ml flask, 2,2'-bis (4-
(4-aminophenoxy) phenyl) propane 3.65
4 g (0.0089 mol), Jeffamine D-2000 (trade name, manufactured by San Techno Chemical Co., Ltd., polyoxyalkylenediamine, amine value 1.
0 (meq / g), the _{structure; H 2 N-CH (CH} 3) CH 2 - (OCH
_{2 CH (CH 3)) n} -NH 2 (n is an average 33) 2.000 g
(0.001 mol), 0.027 g (0.0002 mol) of 2-aminobenzimidazole as the component (D) and 50.44 g of γ-butyrolactone were charged.
The temperature was raised to 5 ° C., and while maintaining the temperature at 43 to 50 ° C., 3.222 g (0.01 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was added little by little as the component (A). did. After the addition, the reaction was continued at 45 ° C. for about 5 hours, and then cooled to room temperature to obtain a polyimide precursor solution (PI-1) having a nonvolatile content of 15% by weight.

The weight average molecular weight of the obtained polyimide precursor was 70,000. The weight average molecular weight is
It was determined by gel permeation chromatography (GPC, apparatus manufactured by Hitachi, Ltd.) in terms of standard polystyrene. The dried polyimide precursor was subjected to an infrared absorption spectrum (JEOL) by the KBr method.
(Manufactured by JIR-100 Co., Ltd.), the absorption of C = O of the amide group near 1600 cm ^-1 and 3
The absorption of NH was confirmed at around 300 cm ^-1 .

Example 2 In the same flask as in Example 1, 2 was added as the component (B).
2'-bis (4- (4-aminophenoxy) phenyl)
3.736 g (0.0091 mol) of propane, (C)
1.600 g (0.0008 mol) of Jeffamine D-2000 (trade name, manufactured by San Techno Chemical Co., Ltd., polyoxyalkylenediamine) as a component, and 0.027 g of 2-aminobenzimidazole as a component (D)
(0.0002 mol) and γ-butyrolactone
After charging 65 g, the same operation as in Example 1 was performed to obtain a polyimide precursor solution (PI
-2) was obtained. The weight average molecular weight of the obtained polyimide precursor was 76,000. Further, those obtained by drying the obtained polyimide precursor, by KBr method, infrared absorption spectrum (JEOL Co., JIR-100 type) was measured, both, amide around 1600 cm ^-1 The absorption of C 吸収 O of the group and the absorption of NH at around 3300 cm ⁻¹ were confirmed.

Example 3 In the same flask as in Example 1, 2 was added as the component (B).
2'-bis (4- (4-aminophenoxy) phenyl)
3.243 g (0.0079 mol) of propane, (C)
0.120 g of ethylenediamine (0.00%
2 mol), 0.027 g (0.0002 mol) of 2-aminobenzimidazole and 38.65 g of γ-butyrolactone as the component (D), and the same operation as in Example 1 was carried out to obtain a nonvolatile matter of 15 wt. % Polyimide precursor solution (PI-3). The weight average molecular weight of the obtained polyimide precursor was 45,000. Also,
The obtained polyimide precursor was dried to obtain KBr.
Infrared absorption spectrum (JEOL Ltd., JI
R-100) were measured.
absorption of C = O of amide group near cm ^-1, the absorption of N-H were observed at around 3300 cm ^-1.

Example 4 In Example 3, 0.120 g of ethylenediamine was replaced with 0.232 g (0.02 mol) of hexamethylenediamine.
In the same manner as in Example 3 except that 38.85 g of γ-butyrolactone was changed to 38.10 g, a polyimide precursor solution (PI-4) having a nonvolatile content of 15% was obtained. The weight average molecular weight of the obtained polyimide precursor was 62,000.
It was 0. When the obtained polyimide precursor was dried, an infrared absorption spectrum (JIR-100, manufactured by JEOL Ltd.) was measured by the KBr method.
Both the absorption of C = O of amide group near 1600 cm ^-1, absorption of N-H were observed at around 3300 cm ^-1.

Comparative Example 1 In the same flask as in Example 1, 2,2'-bis (4-
(4-aminophenoxy) phenyl) propane 4.1
06 g (0.01 mol) and γ-butyrolactone
After charging 25 g, the temperature was raised to 45 ° C., and while maintaining the temperature at 43 to 50 ° C., 3.351 g (0.0104 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was added little by little. Was added. After the addition, the reaction was continued at 45 ° C. for about 5 hours, and then cooled to room temperature to obtain a polyimide precursor solution (PI-5) having a nonvolatile content of 15% by weight. The weight average molecular weight of the obtained polyimide precursor was 84,000. The dried polyimide precursor was subjected to an infrared absorption spectrum (JEOL) by the KBr method.
(Manufactured by JIR-100 Co., Ltd.), the absorption of C = O of the amide group near 1600 cm ^-1 and 3
The absorption of NH was confirmed at around 300 cm ^-1 .

Comparative Example 2 In the same flask as in Example 1, 2,2'-bis (4-
(4-aminophenoxy) phenyl) propane 3.6
95 g (0.009 mol), Jeffamine D-20
2.00 g (0.001 mol) (polyoxyalkylenediamine, trade name, manufactured by San Techno Chemical Co., Ltd.)
And 50.53 g of γ-butyrolactone,
Raise the temperature to 45 ° C and keep it at 43-50 ° C,
3.222 g (0.01 mol) of 3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added little by little. After the addition, the reaction was continued at 45 ° C. for about 5 hours, and then cooled to room temperature to obtain a polyimide precursor solution (PI-6) having a nonvolatile content of 15% by weight. The weight average molecular weight of the obtained polyimide precursor was 78,000. The dried polyimide precursor was obtained by the KBr method.
Infrared absorption spectrum (JIR-100, manufactured by JEOL Ltd.)
Of the amide group at around 1600 cm ^-1 and N-H at around 3300 cm ^-1.
Was observed.

Comparative Example 3 In the same flask as in Example 1, 2,2'-bis (4-
(4-aminophenoxy) phenyl) propane 4.0
After charging 64 g (0.0099 mol), 0.027 g (0.0002 mol) of 2-aminobenzimidazole and 41.44 g of γ-butyrolactone, the temperature was raised to 45 ° C, and the temperature was kept at 43 to 50 ° C. , 3 ', 4,4'
-Benzophenonetetracarboxylic dianhydride 3.22
2 g (0.01 mol) were added in small portions. After addition, 4
After continuing the reaction at 5 ° C. for about 5 hours, the mixture was cooled to room temperature to obtain a polyimide precursor solution (PI-7) having a nonvolatile content of 15% by weight. The weight average molecular weight of the obtained polyimide precursor is 8
It was 0000. Further, those obtained by drying the obtained polyimide precursor, by KBr method, infrared absorption spectrum (JEOL Co., JIR-100 type) was measured, both, amide around 1600 cm ^-1 C =
O absorption and N-H absorption were confirmed at around 3300 cm ^-1 .

Evaluation Copper-clad laminate of copper foil 18 μm (manufactured by Hitachi Chemical Co., Ltd., MC
LE-679) was polished with Scotch Bright manufactured by Sumitomo 3M Limited, washed with water, and dried at 80 ° C. for 15 minutes.
The polyimide precursor solution (PI-1 to PI-7) was uniformly applied to the test substrate using an applicator. Then, 480 at 90 ° C. using a hot plate.
After heating for 2 seconds to form a coating film of about 20 μm, the coating was cured at a predetermined temperature for 60 minutes using a dryer (in an air atmosphere). The test substrate thus obtained was subjected to a test at 121 ° C. and 2.013 × 1 using a PCT tester manufactured by Hirayama Seisakusho.
0 ⁵ Pa conditions performs PCT treatment up to 300 hours to evaluate PCT resistance by the following methods. The PCT resistance was evaluated by performing a substrate test on the adhesion after the PCT treatment for a predetermined time. In addition, the base grid test was performed by scratching the base grid with a cutter knife so that 100 squares could be formed at 1 mm, peeling it off with cellophane tape in accordance with JIS standard (JIS K5400), and cutting the 100 squares. Is a method of expressing the number of remaining squares. The evaluation results are shown in Tables 1 and 2.

[0053]

[Table 1]

[0054]

[Table 2]

Synthesis Example (Synthesis of Photopolymerizable Monomer) In a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel and a cooling tube, 210 g (1.00 mol) of trimethylhexamethylene diisocyanate and 137 toluene After charging 3 g, the temperature was raised to 70 ° C.
While maintaining the temperature at 70 to 75 ° C, 72 g (0.50 mol) of cyclohexanedimethanol and 130 g (1.00 mol) of 2-hydroxyethyl methacrylate were added dropwise little by little. After dropping, the reaction was continued at 70 ° C for about 5 hours,
After cooling to room temperature, a photopolymerizable monomer solution (M-1) was obtained.

Examples 5 to 8 and Comparative Examples 4 and 6 The polyimide precursor solutions (PI-I) obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were placed in a flask equipped with a stirrer, cooling tube and thermometer. 1 to PI-7), the photopolymerizable monomer solution (M-1) obtained in Synthesis Example 1, benzyl dimethyl ketal (I-651 manufactured by Ciba Geigy) as a photoinitiator, and Victoria Pure Blue (dye). After mixing with stirring at a weight ratio shown in No. 3 and stirring and mixing, the mixture was filtered with a filter to obtain uniform photosensitive resin composition solutions (PPI-1 to PPI-7).

[0057]

[Table 3]

A copper-clad laminate of 18 μm copper foil (Hitachi Chemical Industries, Ltd.)
MCL E-679) manufactured by Sumitomo 3M Limited was polished with Scotch Bright, washed with water, and dried at 80 ° C. for 15 minutes. The photosensitive resin composition solution (PPI-1 to PPI-7) was applied to the test substrate using an applicator.
Was applied uniformly. Then, using a hot plate,
Heating was performed at 90 ° C. for 480 seconds to form a coating film of about 20 μm. The test substrate on which the layer of the photosensitive resin composition thus obtained was formed was evaluated for developability, storage stability, solder heat resistance and PCT resistance by the following methods. The evaluation results are shown in Tables 4 and 5.

(1) Developability The test substrate on which the layer of the photosensitive resin composition obtained above was formed was prepared by using an alkaline aqueous solution containing 5% by weight of heptanoic acid diethanolamide and 0.5% by weight of sodium carbonate. At 45 ° C. for 60 seconds. The developability was evaluated by visual observation of the resin remaining after being magnified 30 times.
The evaluation criteria are as follows. ：: Good developability (no resin left on substrate surface) ×: Poor developability (residual resin left on substrate surface)

(2) Storage stability The photosensitive resin composition obtained above was heated at room temperature (23 ° C.) for 1 hour.
After storing for a week, a test substrate was prepared in the same manner as in (1), and the developability was evaluated. The evaluation criteria are as follows. ：: Good storage stability (no resin remains on the substrate surface and good developability) ×: Poor storage stability (a little resin remains on the substrate surface and developability) Bad one)

(3) Solder heat resistance The above-mentioned copper-clad laminate having a copper thickness of 18 μm (Hitachi Chemical Industry Co., Ltd.)
MCL-E-679) was polished with Scotch Bright manufactured by Sumitomo 3M Limited, washed with water, and dried at 80 ° C. for 15 minutes. The photosensitive resin composition solution (PPI-1 to PPI-7) was uniformly applied to the test substrate using an applicator. Then, using a hot plate, 90
Heating was performed at 480 ° C. for 480 seconds to form a coating film of about 20 μm.
Next, a negative mask was brought into close contact with the photosensitive resin composition layer, and exposed with an exposure amount of 500 mJ / cm ² using an HMW-680 type exposure machine manufactured by Oak Manufacturing Co., Ltd. Next, after the negative mask was removed, spray development was performed at 45 ° C. for 60 seconds using an alkaline aqueous solution containing 5% by weight of heptanoic acid diethanolamide and 0.5% by weight of sodium carbonate as a developer. After development, heat and dry at 80 ° C. for 10 minutes,
Ultraviolet irradiation was performed again at an amount of ³ J / cm ² using an ultraviolet irradiation apparatus manufactured by Toshiba Electric Materials Co., Ltd., and then further heated at 200 ° C. for 60 minutes in a dryer (in an air atmosphere). The rosin-based flux A-226 was applied to the surface of the test substrate thus obtained.
(Manufactured by Tamura Kaken Co., Ltd.), immersed in a solder bath at 260 ° C. for 180 seconds,
The flux was removed by immersion for 2 seconds. After performing such an operation, the appearance of the photosensitive resin composition layer was evaluated. The evaluation criteria are as follows. ：: Good solder heat resistance (no cracks or floating in the photosensitive resin composition layer, no peeling) ×: Poor solder heat resistance (cracks or floating in the photosensitive resin composition layer, What causes peeling)

(4) PCT resistance The above-mentioned copper-clad laminate having a copper thickness of 18 μm (Hitachi Chemical Industry Co., Ltd.)
MCL-E-679) was polished with Scotch Bright manufactured by Sumitomo 3M Limited, washed with water, and dried at 80 ° C. for 15 minutes. The photosensitive resin composition solution (PPI-1 to PPI-7) was uniformly applied to the test substrate using an applicator. Then, using a hot plate, 90 ° C
For 480 seconds to form a coating film of about 20 μm. Next, exposure was performed at an exposure of 500 mJ / cm ² using an HMW-680 type exposure machine manufactured by Oak Manufacturing Co., Ltd., and then re-irradiated at an amount of ³ J / cm ² using an ultraviolet irradiation apparatus manufactured by Toshiba Electric Materials Co., Ltd. Then, it was further heated in a dryer at a predetermined temperature for 60 minutes (in an air atmosphere). The test substrate thus obtained was subjected to a test at 121 ° C. and 2.0 ° C. using a PCT tester manufactured by Hirayama Seisakusho.
PCT treatment was performed for up to 300 hours under the condition of 13 × 10 ⁵ Pa, and the PCT resistance was evaluated by the following method. PCT resistance
The property was evaluated by performing a substrate test on the adhesion after the PCT treatment for a predetermined time. In addition, in the base grid test, the base grid was scratched with a cutter knife so that 100 squares could be formed at 1 mm, and this was cut in accordance with the JIS standard (JIS K54).
This is a method of peeling off with cellophane tape in accordance with (00) and expressing the number of remaining squares for 100 squares.

[0063]

[Table 4]

[0064]

[Table 5]

[0065]

The polyimide precursor according to claims 1 and 2 gives a polyimide which is excellent in low-temperature curability, heat resistance, moisture resistance and adhesion. According to the method for producing a polyimide precursor according to claims 3 to 7, a polyimide precursor which gives a polyimide excellent in low-temperature curability and excellent in heat resistance, moisture resistance, adhesion and the like can be easily produced. The polyimide according to claim 8 has excellent heat resistance, moisture resistance, adhesion, and the like.
According to the method for producing a polyimide according to the ninth aspect, a polyimide having excellent heat resistance, moisture resistance, adhesion, and the like can be easily produced. The photosensitive resin composition according to the tenth aspect provides a polyimide film having excellent low-temperature curability, excellent heat resistance, excellent moisture resistance, good adhesion, and the like, and excellent excellent developability and storage stability.

Claims (10)

[Claims] 1. A compound of the general formula (I) (Wherein, R ¹ represents a tetravalent organic group, and R ² has at least 1
X represents a divalent organic group containing two aromatic rings, and X independently represents OH or a monovalent organic group), and a repeating unit represented by the general formula (II): (Wherein, R ¹ represents a tetravalent organic group, R ³ represents a divalent organic group not containing an aromatic ring, and X each independently represents OH or a monovalent organic group). Having a repeating unit,
Further, some or all of the molecules are represented by the general formula (III): (Wherein, R ⁴ represents a halogen, a nitro group or an alkyl group having 1 to 9 carbon atoms, and n is an integer of 0 to 4). . 2. The divalent organic group represented by R ³ in the repeating unit represented by the general formula (II) is represented by the following formula: (Wherein, R ⁵ is _{^{-CHR 8 -CH 2 -, - CH}} 2 -CH 2 -
Or -CH ₂ -CHR ⁸ - shows a, a, b and c denotes the number of repeating units in the formula, a and b are 0 or a positive integer, c is a positive integer, R ^6, R ⁷ and R ⁸ are an alkyl group having 1 to 3 carbon atoms). 3. A tetracarboxylic dianhydride or a derivative thereof, (B) a diamine containing at least one aromatic ring, (C) a diamine containing no aromatic ring, and (D) a general formula (IV) Formula 5 Wherein n is an integer of 0 to 4 and R ⁴ represents a halogen, a nitro group or an alkyl group having 1 to 9 carbon atoms, wherein the aminobenzimidazole represented by the following formula is reacted: How to make the body. 4. The method for producing a polyimide precursor according to claim 3, wherein the reaction is carried out in a non-nitrogen-containing polar solvent. 5. The use amount of the diamine containing no aromatic ring (C) is 1 to 90 mol% of the total amine use amount.
Or the method for producing a polyimide precursor according to 4. (D) The amount of aminobenzimidazole represented by the general formula (IV) is 0.1% of the total amount of amine used.
The method for producing a polyimide precursor according to claim 1 or 3, wherein the amount is 10 to 10 mol%. 7. The method for producing a polyimide precursor according to claim 4, wherein the non-nitrogen-containing polar solvent is γ-butyrolactone. 8. A polyimide obtained by imide-closing the polyimide precursor according to claim 1 or 2, or the polyimide precursor obtained by the production method according to claim 3, 4, 5, 6, or 7. 9. A method for producing a polyimide, comprising subjecting the polyimide precursor according to claim 1 or 2 or the polyimide precursor obtained by the method according to claim 3, 4, 5, 6, or 7 to imide ring closure. . 10. A photosensitive resin composition comprising the polyimide precursor according to claim 1 or 2, or the polyimide precursor obtained by the production method according to claim 3, 4, 5, 6, or 7, and a photosensitive agent. .