JP2001100409A - Alkali negative development type photosensitive resin composition, production method of pattern and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an alkali negative development type photosensitive resin composition less liable to swell in alkali development and excellent in properties of a pattern, adhesiveness to a substrate, crosslinking efficiency, reactivity and compatibility after development, to produce a pattern by polyimide patterning by development with an inexpensive aqueous alkali solution and to provide electronic parts each having the pattern and excellent in reliability. SOLUTION: The photosensitive resin composition contains (a) a photosensitive polyimide precursor having a reactive unsaturated functional group in its molecular chain and soluble in an aqueous alkali solution, (b) an addition polymerizable compound containing a reactive unsaturated functional group and not containing an atom having a non-shared electron pair in its principal skeleton except the reactive unsaturated functional group and (c) a sensitizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali negative development type photosensitive resin composition, a method for producing a pattern using the same, and an electronic component.

[0002]

2. Description of the Related Art In recent years, in the semiconductor industry, an organic material having excellent heat resistance, such as a polyimide resin, has been used as an interlayer insulating material, which has conventionally been formed using an inorganic material, taking advantage of its characteristics. Have been. However, formation of a circuit pattern on a semiconductor integrated circuit or a printed circuit board is complicated and diversified, such as forming a resist material on the base material surface, removing unnecessary portions by exposing and etching predetermined portions, and cleaning the substrate surface. Therefore, development of a heat-resistant photosensitive material that can use a necessary portion of a resist as an insulating material as it is even after pattern formation by exposure and development is desired.

As these materials, for example, heat-resistant photosensitive materials using photosensitive polyimide, cyclized polybutadiene or the like as a base polymer have been proposed. Particularly, photosensitive polyimide has excellent heat resistance and elimination of impurities. Has attracted particular attention because of its ease of use. As such a photosensitive polyimide, a system comprising a polyimide precursor and a dichromate (Japanese Patent Publication No. 49-17374) was first proposed, but this material has practical photosensitivity. In addition, it has advantages such as high film-forming ability, but has disadvantages such as lack of storage stability and chromium ions remaining in polyimide, and thus has not been put to practical use.

[0004] In order to avoid such a problem, for example, a method of adding or mixing a compound having a photosensitive group to a polyimide precursor (Japanese Patent Application Laid-Open No. 54-109828) or the like creates a negative by producing a contrast by a photocrosslinking reaction. It has been proposed as a type of photosensitive polyimide.

However, these negative photosensitive polyimides are basically designed for organic solvent development, and in recent years, alkaline aqueous solution development type is considered to have few problems in waste liquid treatment due to environmental considerations. For example, when alkali development is performed using an aqueous solution of tetramethylammonium hydroxide, which is widely used as a developing solution for photoresist, the solubility is poor or the contrast is difficult to be formed. Have difficulty.

On the other hand, a photosensitive polyimide of an alkali negative development type basically needs to contain a water-soluble group as a material. For example, a method of partially introducing a photoreactive group into a polyimide precursor (Japanese Unexamined Patent Publication No. The negative-working photosensitive polyimide precursor according to JP-A-220558) has high polarity, so that swelling due to water absorption is unavoidable, and there have been problems such as peeling of a developed pattern from a substrate and a reduction in resolution.

However, it is needless to say that this largely depends on the water absorption of each component of the resin composition contained therein. Therefore, the photosensitive polyimide of the alkali negative development type should minimize swelling due to water absorption. It is considered necessary to design the material including the composition components in consideration of the balance between hydrophilicity and hydrophobicity.

[0008]

SUMMARY OF THE INVENTION The present invention provides an alkali-negative development type photosensitive resin composition which has less swelling during alkali development than conventional products and has excellent patternability after development. In addition, the present invention provides an alkali-negative development type photosensitive resin composition that provides higher base adhesion in addition to the above-mentioned problems.

The present invention also provides an alkali-negative development type photosensitive resin composition which provides a higher crosslinking efficiency in addition to the above-mentioned problems. The present invention also provides an alkali-negative development type photosensitive resin composition having excellent reactivity and compatibility, in addition to the above-mentioned problems.

Further, the present invention provides a polyimide pattern processing such as an α-ray shielding film and a buffer coat film for an electronic component such as an interlayer insulating film for a multilayer wiring board or a semiconductor memory device, which is not a conventional organic solvent development, but is inexpensive. The present invention relates to a method for producing a pattern which can be performed by developing with an aqueous alkali solution. Furthermore, the present invention
An object of the present invention is to provide an electronic component having excellent reliability by having the pattern.

[0011]

The present invention provides (a) a photosensitive polyimide precursor having a reactive unsaturated functional group in a molecular chain and being soluble in an aqueous alkali solution, and (b) a reactive polyimide precursor. An alkali-negative developing photosensitive composition containing a saturated functional group, an addition-polymerizable compound not containing an atom having an unshared electron pair in a main skeleton other than the reactive unsaturated functional group, and (c) a sensitizing agent The present invention relates to a water-soluble resin composition.

In the present invention, the component (a) may be a compound represented by the general formula (1):

Embedded image (X is a tetravalent organic group containing no atom having a lone pair in the skeleton connecting two amide groups bonded to X, and Y is non-valent in the skeleton connecting the two amide groups bonded to Y. A divalent organic group that does not contain an atom having a shared electron pair), and
The present invention relates to an alkali-negative development type photosensitive resin composition which is a photosensitive polyimide precursor having an acid functional group and a photosensitive group in a molecule.

In the present invention, the component (a) may have, as a repeating unit, only the repeating unit represented by the general formula (1), or a compound represented by the general formula (1): 3. An alkali-negative development type photosensitive resin composition according to claim 2, which comprises, in place of Y in the formula (1), a repeating unit having a silicon atom-containing divalent organic group Y ″.

The present invention also relates to an alkali negative development type wherein the component (b) has a vinyl, acryloxy or methacryloxy group as a reactive unsaturated functional group, and the number of the functional groups is 1 to 4. The present invention relates to a photosensitive resin composition. Further, in the present invention, the component (b) has two or more reactive unsaturated functional groups and does not contain a ring structure in a molecular chain connecting the functional groups, and the number of carbon atoms in the molecular chain Is 4 to 12 and relates to an alkali negative development type photosensitive resin composition.

Further, in the present invention, the component (b) has two reactive unsaturated functional groups, the molecular chain connecting the functional groups is a straight chain, and the molecular chain has 4 to 4 carbon atoms. 12 relates to an alkali negative development type photosensitive resin composition. Further, the present invention relates to an alkali-negative development type photosensitive resin composition wherein the component (b) is a linear diol diacrylate or dimethacrylate.

The present invention also relates to any one of the above-mentioned compositions, wherein the component (b) is contained in an amount of 5 to 100 parts by weight and the component (c) is contained in an amount of 0.01 to 40 parts by weight based on 100 parts by weight of the component (a). And an alkali-negative development type photosensitive resin composition. Further, the present invention provides a step of applying the photosensitive resin composition according to any of the above, a step of irradiating an actinic ray from a mask on which a pattern is drawn on a coating film obtained by the step, using an alkali developer. And a heat treatment process.

The present invention also relates to a method for producing a pattern in which the actinic rays are i-rays. Furthermore, the present invention relates to an electronic component having a layer of a pattern obtained by the above-mentioned manufacturing method.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Since the photosensitive resin composition of the present invention is developed with an aqueous alkaline solution, the (a) photosensitive polyimide precursor used must be soluble in an aqueous alkaline solution. The solubility in an aqueous alkali solution is usually achieved by providing the precursor structure with an acid functional group. Examples of the acid functional group include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group, and those having a carboxyl group are preferable because they can impart good solubility.

Further, (a) the photosensitive polyimide precursor comprises:
It is necessary to have photosensitivity. Here, the photosensitive group in the present invention refers to a group that is dimerized or polymerized by light, and among them, a group having a carbon-carbon unsaturated double bond is preferable. In the photosensitive resin composition of the present invention, the component (a) in an exposed portion is crosslinked by dimerization or polymerization of a photosensitive group, and is not or hardly dissolved in an aqueous alkali solution. a) It is dissolved by the presence of an acid functional group in the component (a so-called negative photosensitive composition).

As the photosensitive polyimide precursor (a), for example, the following general formula (2) obtained by forming an amide bond between tetracarboxylic acid or its derivative and diamine

Embedded image Wherein X ′ is a tetravalent organic group, Y ′ is a divalent organic group, and R and R ′ are each independently OH or a monovalent organic group. And in the molecule,
Those having an acid functional group and a photosensitive group are included.

As the component (a), the following general formula (1)

Embedded image (X is a tetravalent organic group containing no atom having a lone pair in the skeleton connecting two amide groups bonded to X, and Y is non-valent in the skeleton connecting the two amide groups bonded to Y. A divalent organic group containing no atom having a shared electron pair, R and R ′ each independently represent OH or a monovalent organic group), and have a repeating unit represented by the following formula: A photosensitive polyimide precursor having an acid functional group and a photosensitive group is preferred.

Here, “X” in the general formula (1)
A tetravalent organic group containing no atom having a lone pair in the skeleton linking the two amide groups bonded to
The divalent organic group which does not contain an atom having an unshared electron pair in the skeleton linking two amide groups bonded to is described.

In the definition of X and Y, the "skeleton connecting two amide groups" refers to a skeleton consisting of only atoms constituting a chain of a bond connecting two amide bonds. Accordingly, atoms that do not form a bond chain connecting two amide bonds, such as a hydrogen atom and a fluorine atom, are not included in the skeleton. However, when the skeleton includes atoms constituting a ring (aromatic ring or alicyclic ring), all the atoms constituting the ring are also included in the above “skeleton”. For example, when containing a benzene ring or a cyclohexyl ring, the six carbon atoms constituting the benzene ring or the cyclohexyl ring itself are:
It shall be included in the "skeleton". Note that a substituent or a hydrogen atom bonded on a benzene ring or a cyclohexyl ring is
It is not included in the “skeleton” here.

Therefore, when a carbonyl bond is present on the skeleton, only the carbon atom in the carbonyl group constitutes the chain connecting the two amide groups, and the oxygen atom in the carbonyl group is the same as the above-mentioned “ It does not constitute a "skeleton." In addition, the 2,2-propylidene bond and the hexafluoro-2,2-propylidene bond have a central (2
Only the carbon atoms present at the (position) constitute the skeleton, and the carbon atoms at both ends (the first or third position) do not constitute the above-mentioned "skeleton". In the present invention, examples of the "atom having an unshared electron pair" include an oxygen atom, a nitrogen atom, a sulfur atom and the like, while the "atom having no unshared electron pair" includes a carbon atom, silicon Atoms and the like.

In the photosensitive polyimide precursor (a) used in the present invention, when X does not contain an atom having an unshared electron pair in the skeleton as described above, it is preferable because swelling during alkali development is small. It is preferable that Y does not contain an atom having an unshared electron pair in the skeleton for the same reason.

In the photosensitive polyimide precursor (a) used in the present invention, instead of Y in the repeating unit,
Having Y ″ containing a silicon atom as a part thereof,
For example, a material containing a siloxane bond is preferable because higher substrate adhesion can be imparted. In this case, the ratio is preferably 1 to 20 mol% of all the diamine residues forming the photosensitive polyimide precursor.

In the general formula (1), X and Y represent an alkyl chain having 4 to 20 carbon atoms, a cycloalkyl ring such as a cyclohexyl ring, a benzene ring or a naphthalene ring having 6 to 20 carbon atoms. And those in which 2 to 10 of these aromatic rings are bonded via a single bond, an alkylene group, a fluorinated alkylene group, a carbonyl group, or the like. These may have a substituent such as a hydrocarbon group, a halogenated hydrocarbon group, or a halogen atom on the aromatic ring. Among these Xs and Ys, it is preferable that the atom directly bonded to the atom constituting the skeleton is also an “atom having no lone pair” because of its high effect (in this definition, Excluded are those in which an oxygen atom is directly bonded to a carbon atom constituting the skeleton, such as a carbonyl group, and those in which a fluorine atom is bonded to a carbon atom constituting the skeleton.) Further, it is preferable that X and Y do not contain a fluorine atom because the effect of the present invention is high.

The acid functional group contained in the molecule of the component (a) includes a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and the like, and among them, a carboxyl group is preferable. Further, as the photosensitive group, containing a carbon-carbon unsaturated double bond, vinyl group, allyl group, acryloyl group, methacryloyl group, acryloxy group, methacryloxy group and the like are preferable, among which acryloyl group, methacryloyl group,
An acryloxy group and a methacryloxy group are preferred.

In the component (a), the acid functional group is selected from the group consisting of R and R 'in the repeating unit of the general formula (1) or (2).
Is OH (ie, forms a carboxyl group)
Or in a diamine residue represented by Y or Y ′. Also, the photosensitive group is
In the side chain represented by R or R 'or the diamine residue represented by Y or Y' in the above-mentioned formula, it is preferably present, for example, as a group bonded to an aromatic ring of a diamine residue having an aromatic ring.

In R and R 'of the repeating unit of the general formula (1) or (2), the monovalent organic group includes a photosensitive group.

Embedded image (Wherein, R ¹ and R ² are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁴ is a hydrogen atom or a methyl group. And having no photosensitive group: having 1 to 15 carbon atoms
And an alkylamino group having 1 to 15 carbon atoms. As the component (a) having a repeating unit represented by the general formula (1), the repeating unit represented by the general formula (1) is 5
It is preferably one having 0 to 100 mol%, and among them, a repeating unit having only the repeating unit represented by the general formula (1) or a repeating unit represented by the general formula (1), It is preferable that Y in the formula (1) has a repeating unit that is a divalent organic group containing a silicon atom.

The photosensitive polyimide precursor of the above (a) is
Its molecular weight is 80,000 to 5,
000 is preferable. The weight average molecular weight can be measured by gel permeation chromatography and converted to standard polystyrene.

The photosensitive polyimide precursor of the above-mentioned component (a) can be obtained from tetracarboxylic dianhydride, diamine and, if necessary, a compound having a photosensitive group as a material. Applicable. For example, as described in Japanese Patent Publication No. 4-62306, N, N'-dihydrocarbyl-substituted carbodiimide, trifluoroacetic anhydride and polyamic acid which are condensation polymers of tetracarboxylic dianhydride and diamine are used. It can be synthesized by a synthesis method using an isoimidating agent selected from the group consisting of a compound and a mixture thereof.

The tetracarboxylic dianhydride used as a material may be, for example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride to give the above-mentioned X. 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-
Naphthalenetetracarboxylic dianhydride, 1,4,5,8
-Naphthalenetetracarboxylic dianhydride, 3,4,9,
10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3', 4,4'-tetracarboxylic dianhydride, 4,4′-hexafluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and the like, which may be used alone or in combination of two or more. Used. Among them, pyromellitic dianhydride, 3,3 ',
4,4'-biphenyltetracarboxylic dianhydride is preferred.

Examples of the diamine that give Y include, for example, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2 ', 6,6'-tetramethyl-4,
4'-diaminobiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4,-
(Or 3,4,-, 3,3,-, 2,4,-, 2,2
-) Diaminodiphenylmethane, p-xylylenediamine, m-xylylenediamine, 4,4, -methylene-bis- (2,6-diethylaniline), 4,4, -methylene-bis- (2,6-diisopropyl) Aniline), 1,
5, -diaminonaphthalene, 3,3, -dimethyl-4,
4, -diaminodiphenylmethane, 3,3,5,5,-
Tetramethyl-4,4, -diaminodiphenylmethane,
2,2-bis (4-aminophenyl) propane, 2,
2'-hexafluorodimethyl-4,4'-diaminobiphenyl, 3,3'-hexafluorodimethyl-4,4 '
-Diaminobiphenyl, 4,4'-hexafluoroisopropylidene dianiline, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 2,3,5 6-tetramethyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4,6-trimethyl-1,3 -Phenylenediamine, 2,7-diaminofluorene, 4,4
-Diaminooctafluorobiphenyl, 2,2-hexafluorodimethyl-4,4'-diaminobiphenyl and the like are mentioned as preferable examples, and these are used alone or in combination of two or more.

Among them, 2,2'-dimethyl-4,4'-
Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 ', 6,6'-tetramethyl-
4,4'-diaminobiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl, paraphenylenediamine, metaphenylenediamine, 2,4-diaminomesitylene, 2,3,5 6-tetramethyl-
1,4-phenylenediamine, 2,5-dimethyl-1,
4-phenylenediamine, 2,4-diaminotoluene,
2,6-diaminotoluene, 2,4,6-trimethyl-
Preferred are 1,3-phenylenediamine and the like.

If Y is a bifunctional amine that does not contain an atom having an unshared electron pair in the skeleton connecting the amino group, it has at least one phenolic hydroxyl group and / or carboxyl group as an acid functional group. Is also good. For example,
2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, bis (4-amino-3-carboxyphenyl) methylene, 4,4′- Diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-5,5'-dicarboxy-2,2'-dimethylbiphenyl, 1,3-
Diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 3,3′-diamino-4,
4'-dihydroxybiphenyl, 4,4'-diamino-
3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) hexafluoropropane,
Bis (4-amino-3-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-carboxyphenyl) methane, 4,4′-diamino-2,2′-dicarboxybiphenyl, and the like are preferred. . These are used alone or in combination of two or more with the diamine. Among them, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, 4,4′-diamino-3,3′-dicarboxybiphenyl, and 4,4′-diamino- 5,5'-
Dicarboxy-2,2'-dimethylbiphenyl is preferred.

Further, the following general formula (3) is given as a material giving Y ″ containing a silicon atom.

Embedded image (M and n are each independently an integer of 1 to 10, and S is 1 to
And an aliphatic diamine such as diaminopolysiloxane. When this is used, its compounding amount is 20 mol% of all diamines.
The following is preferred from the viewpoints of less swelling during development and heat resistance in the physical properties of the formed film. In addition,
In addition, a tetracarboxylic dianhydride or a diamine that provides a residue other than those represented by X and Y may be used to the extent that the effects of the present invention are not impaired.

In order to obtain a polyimide precursor having a photosensitive group, for example, a compound having a carbon-carbon unsaturated double bond and an amino group or a quaternized salt thereof is prepared by converting a compound having a carboxyl group of a polyamic acid and an amino group A method of preparing a polyimide precursor having a form ionically bonded to a group or a quaternized salt thereof, introducing a carbon-carbon unsaturated double bond into a side chain via a covalent bond such as an ester bond or an amide bond. There are ways to do that.

Among them, carbon-
A photosensitive polyimide precursor (polyamic acid ester) in which a carbon unsaturated double bond is introduced is suitable for alkali development. When a carbon-carbon unsaturated double bond is introduced by an ester bond, the amount of the compound having a carbon-carbon unsaturated double bond to be introduced is determined by the solubility in alkali, photocurability, heat resistance, and reactivity. From the viewpoint of compatibility, it is preferable that the amount is 85 to 25 mol% with respect to the total amount of the carboxyl groups of the polyamic acid, and the remainder is the carboxyl group (i.e., the polyamic acid partial ester).

Here, examples of the compound for introducing a carbon-carbon unsaturated double bond through an ester bond include the following compounds. 2-hydroxyethyl acrylate, 3-
Hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, caprolactone 2- ( (Methacryloyloxy) ethyl ester, dicaprolactone 2- (methacryloyloxy) ethyl ester, caprolactone 2- (acryloyloxy) ethyl ester, dicaprolactone 2- (acryloyloxy) ethyl ester, and the like.

Next, the component (b) of the present invention will be described. In the present invention, as the component (b), an addition polymerizable compound containing a reactive unsaturated functional group and not containing an atom having an unshared electron pair in a main skeleton other than the reactive unsaturated functional group may be used. is important. Since this component has a hydrophobic skeleton, it has little swelling at the time of alkali development, thereby giving good patternability after development.

Here, the above-mentioned reactive unsaturated functional group includes a reactive carbon-carbon unsaturated double bond, a carbon-carbon unsaturated triple bond, etc., which are usually treated as one substituent. Examples thereof include a vinyl group, an isopropenyl group, an allyl group, an acryloxy group, a methacryloxy group, an acroyl group, a methacryloyl group, a vinylidene group, a vinylene group, an ethynyl group, and a propargyl group. Among these, a vinyl group, an acryloxy group, and a methacryloxy group are preferable in terms of reactivity.

The number of reactive unsaturated functional groups contained in the component (b) is preferably from 1 to 4 from the viewpoint of stability, and each may not be the same.
In the definition of the component (b), the “main skeleton” other than the reactive unsaturated functional group refers to a skeleton composed of only atoms constituting a chain of a molecular bond, and does not include a terminal atom. Therefore, atoms that do not form a bond chain, such as a hydrogen atom and a fluorine atom, are not included. When the terminal has a substituent as a functional group (for example, a carboxyl group, a hydroxyl group, an amino group, or the like), the substituent is not included.
Therefore, an oxygen atom in a hydroxyl group and a nitrogen atom in an amino group constitute a bonding chain of a molecule, but are not included in the “main skeleton”.

When the atoms constituting the ring structure are contained in the main skeleton, all the atoms constituting the ring itself are also included in the aforementioned "main skeleton". For example, when a benzene ring or a cyclohexyl ring is contained, six carbon atoms constituting the benzene ring or the cyclohexyl ring are included in the “main skeleton”. Therefore, an oxygen atom (ether bond) connecting carbon atoms, a sulfur atom (thioether bond), a nitrogen atom (imino bond), or an amide bond or an ester bond connecting carbon atoms is referred to as the “main skeleton” (that is, Those included in (other than the reactive functional group) are excluded. Among them, the structure excluding the reactive unsaturated functional group is preferably composed of only carbon atoms and hydrogen atoms.

Examples of the addition polymerizable compound as the component (b) include styrene, α-methylstyrene, 1,2-
Dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, isobornyl acrylate, cyclohexyl methacrylate 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-
Butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol Examples include triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, and pentaerythritol tetramethacrylate. These are used alone or in combination of two or more.

The component (b) has two or more reactive unsaturated functional groups from the viewpoint of reactivity and does not contain a ring structure in a molecular chain connecting the functional groups. The number of carbon atoms is more preferably 4 or more from the viewpoint of reactivity and 12 or less from the viewpoint of compatibility.

As such, for example, 1,4
-Butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol diacrylate, 1,9-
Nonanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate,
Pentaerythritol tetramethacrylate and the like. These are used alone or in combination of two or more.

Further, from the viewpoint of reactivity, those having two reactive unsaturated functional groups, and having a linear molecular chain connecting the functional groups and having 4 to 12 molecules are preferred. ,
Particularly, diacrylate or methacrylate of a linear diol is preferable. Such things include, for example,
1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol diacrylate,
9-nonanediol dimethacrylate.

The amount of the compound (b) used in the present invention is preferably 5 to 100 parts by weight based on 100 parts by weight of the photosensitive polyimide precursor resin (a). More preferably, the content is 5 to 40 parts by weight in terms of solubility. If this amount is less than 5 parts by weight,
The exposed part is eluted at the time of development, so that the film after development tends to not remain. is there.

The photosensitive resin composition of the present invention further contains (c) a photosensitive agent. Examples of the photosensitive agent include
Benzophenone, Michler's ketone, 4,4, -bis (diethylamino) benzophenone, 3,3,4,4
Benzophenones such as -tetra (t-butylperoxycarbonyl) benzophenone and 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone;
Benzylidenes such as 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 7-diethylamino-3-thenonylcoumarin, 4,6-dimethyl-
Coumarins such as 3-ethylaminocoumarin, 3,3, -carbonylbis (7-diethylaminocoumarin), 7-diethylamino3- (1-methylmethylbenzimidazolyl) coumarin, and 3- (2-benzothiazolyl) -7-diethylaminocoumarin. , 2-t-butylanthraquinone, 2-ethylanthraquinone, anthraquinones such as 1,2-benzanthraquinone, benzoins such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, 2,4-dimethylthioxanthone, 2,4 -Diethylthioxanthone, 2,
Thioxanthones such as 4-diisopropylthioxanthone and 2-isopropylthioxanthone, mercaptos such as ethylene glycol di (3-mercaptopropionate), 2-mercaptobenzthiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole; N Glycines such as -phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- (p-chlorophenyl) glycine, N- (4-cyanophenyl) glycine, and 1-phenyl-1,2-butanedione- 2-
(O-methoxycarbonyl) oxime, 1-phenyl-
1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2 Oximes such as-(o-benzoyl) oxime; and photopolymerization initiators or sensitizers such as 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole. Can be These are used alone or in combination of two or more.

Among these, in the present invention, the above-mentioned benzophenones, glycines, mercaptos, oximes, and 2,2′-bis (o-chlorophenyl) -4,
A combination selected from 4 ′, 5,5′-tetraphenylbiimidazole is preferred from the viewpoint of photoreaction. These photosensitive agents are used alone or in combination of two or more. The amount of the photosensitive agent to be used is preferably 0.01 to 40 parts by weight based on 100 parts by weight of the polyimide precursor as the component (a) from the viewpoint of reactivity and other properties. Usually, it is 0.01 to 15 parts by weight for one kind, and 0.1 to 40 parts by weight in total when combined.

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,
p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-1-naphthylamine, N-phenyl-2- Examples include naphthylamine, cuperon, phenothiazine, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like. These are used alone or in combination of two or more. When a radical polymerization inhibitor or a radical polymerization inhibitor is used, the amount used is usually 0.01 to 30 parts by weight per 100 parts by weight of the polyimide precursor of the component (a).
Parts by weight.

The photosensitive resin composition of the present invention may contain other additives known to be used in the photosensitive resin composition, for example, additives such as a plasticizer and an adhesion promoter. The photosensitive resin composition is generally produced by dissolving in an organic solvent, and as the organic solvent to be used, a polar solvent that completely dissolves the produced polyimide is generally preferable. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide,
Examples include dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, and the like.

Other than the polar solvent, ketones,
Esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate , Diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4
-Dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like can also be used. These organic solvents are used alone or in combination of two or more.

The photosensitive resin composition of the present invention is applied onto a base material such as a silicon wafer, a metal substrate, a ceramic substrate or the like by a dipping method, a spray method, a screen printing method, a spin coating method or the like, and the solvent is heated appropriately. By drying, a coating film having no tackiness can be obtained. On this coating film,
Actinic rays or actinic rays are irradiated through a mask on which a desired pattern is drawn. As a device for irradiating actinic rays or actinic rays, a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, an i-ray stepper, a g-ray stepper, other ultraviolet rays, a visible light source,
An X-ray or electron beam generator can be used. At present, i-line exposure is becoming mainstream, and the composition of the present invention is suitable for pattern formation by this i-line exposure.

After the irradiation, the unirradiated portion is dissolved and removed with a developing solution to obtain a desired negative pattern. As the developing solution, an alkaline aqueous solution such as an aqueous solution of tetramethylammonium hydroxide or an aqueous solution of triethanolamine is used. After the development, rinsing is performed with water or a poor solvent as necessary. By heating the pattern thus obtained, a stable high heat-resistant polyimide pattern from which the photosensitive agent and the solvent have been completely removed is obtained.

The heating temperature at this time is preferably from 150 to 500 ° C., more preferably from 200 to 400 ° C. When the heating temperature is lower than 150 ° C.,
The mechanical and thermal properties of the polyimide film tend to decrease, and when the temperature exceeds 500 ° C., the mechanical and thermal properties of the polyimide film tend to decrease. The heating time at this time is preferably set to 0.05 to 10 hours. If the heating time is less than 0.05 hours, the mechanical and thermal characteristics of the polyimide film tend to decrease, and if it exceeds 10 hours, the mechanical and thermal characteristics of the polyimide film tend to decrease.

The polyimide pattern thus obtained using the photosensitive resin composition of the present invention can be used for a surface protective film for a semiconductor, an interlayer insulating film of a multilayer wiring board, and the like. Since the surface protective film using the photosensitive resin composition of the present invention has excellent adhesion to SiN, a sealing agent, and the like, a semiconductor device using the surface protective film obtained from the photosensitive resin composition of the present invention. Is extremely reliable.

The electronic component of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures. An example of a manufacturing process of a semiconductor device will be described below as an example of the electronic component of the present invention.

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In the figure, a semiconductor substrate such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer is formed on the exposed circuit element. . A film 4 of a polyimide resin or the like as an interlayer insulating film is formed on the semiconductor substrate by a spin coating method or the like (step (a)).

Next, a photosensitive resin layer 5 of a chlorinated rubber type, a phenol novolak type or the like is formed on the interlayer insulating film 4 by spin coating, and a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. A window 6A is provided to perform the process (step (b)).

The interlayer insulating film 4 in the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride, and a window 6B is opened.
Next, the photosensitive resin layer 5 is completely removed by using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (step (c)).

Further, using a known photolithography technique,
The conductor layer 7 is formed, and the electrical connection with the first conductor layer 3 is made completely (step (d)). When a multilayer wiring structure of three or more layers is formed, the above steps are repeated to form each layer.

Next, a surface protection film 8 is formed. In the example of this figure, the surface protective film is coated with the photosensitive polymer composition by a spin coating method, dried, and irradiated with light from a mask on which a pattern for forming a window 6C is drawn on a predetermined portion. A pattern is formed by developing with an aqueous solution, and heated to form a polyimide film. This polyimide film protects the conductor layer from external stress, α-rays and the like, and the resulting semiconductor device has excellent reliability. In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

[0065]

The present invention will be described below in detail with reference to examples. In the following synthesis examples, N,
A method using N'-dihydrocarbyl-substituted carbodiimide will be described, but trifluoroacetic anhydride may be used instead. In that case, trifluoroacetic anhydride may be used in an amount equivalent to the amount of the isoimidating agent used in the synthesis examples.

Synthesis Example 1 15.27 g (0.070 g) in 100 ml of dry N-methylpyrrolidone under dry nitrogen
mol) of a stirred solution of pyromellitic dianhydride
0 g (0.010 mol) of 2-hydroxyethyl methacrylate was added. The solution is left at room temperature for 1 hour and at 35 ° C.
, And then cooled to room temperature. The reaction solution was treated with 8.49 in 100 ml of dry N-methylpyrrolidone.
g (0.040 mol) of 3,3′-dimethyl-4,
4'-diaminobiphenyl and 0.25 g (0.00
(1 mol) of a solution of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was added dropwise over 1 hour and stirred at room temperature overnight. Then 100ml
26.82 g (0.1 in dry N-methylpyrrolidone
(30 mol) of a solution of N, N-dicyclohexylcarbodiimide was added dropwise with stirring to the resulting reaction solution over 30 minutes. 45.55 g of the reaction solution
(0.35 mol) of 2-hydroxyethyl methacrylate was added and stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 liter of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 2 15.70 g (0.072) in 120 ml of dry N-methylpyrrolidone under dry nitrogen
2.3 mol) of a pyromellitic dianhydride in a stirred solution.
4 g (0.018 mol) of 2-hydroxyethyl methacrylate was added. The solution is left at room temperature for 1 hour and at 35 ° C.
, And then cooled to room temperature. 5.09 g of this reaction solution in 80 ml of dry N-methylpyrrolidone
(0.024 mol) of 3,3′-dimethyl-4,4 ′
Diaminobiphenyl and 3.65 g (0.024 m
ol) 3,5-diaminobenzoic acid and 0.25 g
(0.001 mol) of a solution of 1,3-bis (3-aminopropyl) tetramethyldisiloxane in a stirred solution.
Add dropwise over time and stir at room temperature overnight. Then 27.9 g in 100 ml of dry N-methylpyrrolidone
A solution of (0.135 mol) N, N-dicyclohexylcarbodiimide was added dropwise with stirring to the resulting reaction solution over 30 minutes. This reaction solution was applied to 39.
04 g (0.30 mol) of 2-hydroxyethyl methacrylate was added and stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 liter of ion-exchanged water with vigorous stirring.
The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 3 16.36 g (0.075 g) in 125 ml of dry N-methylpyrrolidone under dry nitrogen
2.6 mol) of a stirred solution of pyromellitic dianhydride.
0 g (0.020 mol) of 2-hydroxyethyl methacrylate was added. The solution is left at room temperature for 1 hour and at 35 ° C.
, And then cooled to room temperature. 3.03 g of this reaction solution in 75 ml of dry N-methylpyrrolidone
(0.028 mol) of metaphenylenediamine and 4.26 g (0.028 mol) of 3,5-diaminobenzoic acid and 0.25 g (0.001 mol) of 1,3
To the stirred solution of the solution of -bis (3-aminopropyl) tetramethyldisiloxane was added dropwise over 1 hour and stirred at room temperature overnight. Then 28.89 g (0.140 mol) of N, in 100 ml of dry N-methylpyrrolidone
A solution of N-dicyclohexylcarbodiimide was added dropwise with stirring to the resulting reaction solution over 30 minutes.
To the reaction solution, 45.55 g (0.35 mol) of 2-hydroxyethyl methacrylate was added, and the mixture was stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 liter of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight. Synthesis Example 4 8.72 g (0.040 mol) of pyromellitic dianhydride and 11.77 g (0.040 m) in 140 ml of dry N-methylpyrrolidone under dry nitrogen
ol) of 3,3,4,4, -biphenyltetracarboxylic dianhydride in a stirred solution.
l) 2-Hydroxyethyl methacrylate was added.
After stirring the solution for 1 hour at room temperature and 1 hour at 35 ° C.
Cooled to room temperature. The reaction solution was mixed with 80 ml of dry N-
3.03 g (0.028 mol) in methylpyrrolidone
Of metaphenylenediamine and g (0.028mo
l) 3,5-diaminobenzoic acid and 4.26 g
(0.028 mol) of a solution of 1,3-bis (3-aminopropyl) tetramethyldisiloxane in a stirred solution.
Add dropwise over time and stir at room temperature overnight. Then 28.89 in 100 ml of dry N-methylpyrrolidone.
g (0.140 mol) of a solution of N, N-dicyclohexylcarbodiimide was added dropwise with stirring to the resulting reaction solution over 30 minutes. The reaction solution is 3
9.04 g (0.30 mol) of 2-hydroxyethyl methacrylate was added, and the mixture was stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was subjected to 2.0 mL.
The mixture was treated with 1 liter of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 5 21.18 g (0.072) in 125 ml of dry N-methylpyrrolidone under dry nitrogen
mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride in a stirred solution.
ol) of 2-hydroxyethyl methacrylate. The solution was stirred at room temperature for 1 hour and at 35 ° C. for 1 hour before cooling to room temperature. 11.68 g (0.055 m) of this reaction solution in 75 ml of dry N-methylpyrrolidone
ol) 3,3'-dimethyl-4,4'-diaminobiphenyl and 0.25 g (0.001 mol) of 1,3-
The solution was added dropwise over 1 hour to a stirred solution of bis (3-aminopropyl) tetramethyldisiloxane and stirred overnight at room temperature. Then 28.89 g (0.14 mol) of N, N- in 100 ml of dry N-methylpyrrolidone.
A solution of dicyclohexylcarbodiimide was added dropwise with stirring to the resulting reaction solution over 30 minutes. To this reaction solution, 39.00 g (0.30 mol) of 2-
Hydroxyethyl methacrylate was added and stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture is
The filtrate obtained by diluting with acetone and removing unnecessary substances by suction filtration was treated with 2.0 liters of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 6 22.07 g (0.075 g) in 120 ml of dry N-methylpyrrolidone under dry nitrogen
mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride in a stirred solution.
ol) of 2-hydroxyethyl methacrylate. The solution was stirred at room temperature for 1 hour and at 35 ° C. for 1 hour before cooling to room temperature. The reaction solution was combined with 5.95 g (0.055 mol) in 80 ml of dry N-methylpyrrolidone.
l) paraphenylenediamine and 0.25 g (0.
001 mol) of 1,3-bis (3-aminopropyl)
To the stirred solution of the tetramethyldisiloxane solution was added dropwise over 1 hour and stirred at room temperature overnight. Then 100
26.82 g in ml of dry N-methylpyrrolidone
(0.130 mol) of a solution of N, N-dicyclohexylcarbodiimide was added dropwise over 1 hour to the resulting reaction solution with stirring. This reaction solution was applied to 39.
04 g (0.30 mol) of 2-hydroxyethyl methacrylate was added and stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 liter of ion-exchanged water with vigorous stirring.
The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 7 22.07 g (0.075) in 120 ml of dry N-methylpyrrolidone under dry nitrogen
mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride in a stirred solution.
ol) of 2-hydroxyethyl methacrylate. The solution was stirred at room temperature for 1 hour and at 35 ° C. for 1 hour before cooling to room temperature. The reaction solution was combined with 5.95 g (0.055 mol) in 80 ml of dry N-methylpyrrolidone.
l) metaphenylenediamine and 0.25 g (0.
001 mol) of 1,3-bis (3-aminopropyl)
To the stirred solution of the tetramethyldisiloxane solution was added dropwise over 1 hour and stirred at room temperature overnight. Then 100
26.82 g in ml of dry N-methylpyrrolidone
(0.130 mol) of a solution of N, N-dicyclohexylcarbodiimide was added dropwise over 1 hour to the resulting reaction solution with stirring. This reaction solution was applied to 39.
04 g (0.30 mol) of 2-hydroxyethyl methacrylate was added and stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 liter of ion-exchanged water with vigorous stirring.
The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 8 22.07 g (0.075) in 120 ml of dry N-methylpyrrolidone under dry nitrogen
mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride in a stirred solution.
ol) of 2-hydroxyethyl methacrylate. The solution was stirred at room temperature for 1 hour and at 35 ° C. for 1 hour before cooling to room temperature. This reaction solution was combined with 5.31 g (0.025 mol) in 80 ml of dry N-methylpyrrolidone.
l) 3,3'-dimethyl-4,4'-diaminobiphenyl and 3.80 g (0.025 mol) of 3,5-diaminobenzoic acid and 0.25 g (0.001 mol)
Was added dropwise over 1 hour to a stirred solution of a solution of 1,3-bis (3-aminopropyl) tetramethyldisiloxane in Example 1 and stirred at room temperature overnight. Then 100 ml of dry N-
26.82 g (0.130 mo in methylpyrrolidone)
l) A solution of N, N-dicyclohexylcarbodiimide was added dropwise with stirring to the resulting reaction solution over 1 hour. 39.04 g (0.30 g) of the reaction solution
mol) of 2-hydroxyethyl methacrylate and stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 liter of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 9 21.18 g (0.072) in 120 ml of dry N-methylpyrrolidone under dry nitrogen
mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride in a stirred solution.
ol) of 2-hydroxyethyl methacrylate. The solution was stirred at room temperature for 1 hour and at 35 ° C. for 1 hour before cooling to room temperature. The reaction solution was mixed with 2.70 g (0.025 mol) in 80 ml of dry N-methylpyrrolidone.
l) paraphenylenediamine and 3.80 g (0.
025 mol) of 3,5-diaminobenzoic acid and 0.1.
To the stirred solution of a solution of 25 g (0.001 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was added dropwise over 1 hour and stirred at room temperature overnight.
Then 2 ml in 100 ml of dry N-methylpyrrolidone
A solution of 9.92 g (0.145 mol) of N, N-dicyclohexylcarbodiimide was added dropwise to the resulting reaction solution over 1 hour with stirring. 45.5 g (0.35 mol) of 2-hydroxyethyl methacrylate was added to the reaction solution, and the mixture was stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 liter of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 10 21.18 g (0.07 g) in 120 ml of dry N-methylpyrrolidone under dry nitrogen
2.33 g (0.018 g) in a stirred solution of 2,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.
mol) of 2-hydroxyethyl methacrylate. The solution was stirred at room temperature for 1 hour and at 35 ° C. for 1 hour before cooling to room temperature. The reaction solution was mixed with 2.70 g (0.025 mol) in 80 ml of dry N-methylpyrrolidone.
l) metaphenylenediamine and 3.80 g (0.
025 mol) of 3,5-diaminobenzoic acid and 0.1.
To the stirred solution of a solution of 25 g (0.001 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was added dropwise over 1 hour and stirred at room temperature overnight.
Then 2 ml in 100 ml of dry N-methylpyrrolidone
A solution of 9.92 g (0.145 mol) of N, N-dicyclohexylcarbodiimide was added dropwise to the resulting reaction solution over 1 hour with stirring. To the reaction solution, 45.55 g (0.35 mol) of 2-hydroxyethyl methacrylate was added, and the mixture was stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 liter of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 11 22.34 g (0.07) in 120 ml of dry N-methylpyrrolidone under dry nitrogen
2.34 g (0.018 mol) of 2-hydroxyethyl methacrylate was added to a stirred solution of 2,4'-oxydiphthalic dianhydride. The solution was stirred at room temperature for 1 hour and at 35 ° C. for 1 hour before cooling to room temperature. The reaction solution was combined with 11.68 g (0.055 mol) of 3,3'-in 80 ml of dry N-methylpyrrolidone.
Dimethyl-4,4'-diaminobiphenyl and 0.2
To a stirred solution of a solution of 5 g (0.001 mol.) Of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was added dropwise over 1 hour and stirred at room temperature overnight.
Then 2 ml in 100 ml of dry N-methylpyrrolidone
A solution of 9.92 g (0.145 mol) of N, N-dicyclohexylcarbodiimide was added dropwise to the resulting reaction solution over 1 hour with stirring. 45.5 g (0.35 mol) of 2-hydroxyethyl methacrylate was added to the reaction solution, and the mixture was stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 liter of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 12 22.34 g (0.07) in 120 ml of dry N-methylpyrrolidone under dry nitrogen
2.34 g (0.018 mol) of 2-hydroxyethyl methacrylate was added to a stirred solution of 2,4'-oxydiphthalic dianhydride. The solution was stirred at room temperature for 1 hour and at 35 ° C. for 1 hour before cooling to room temperature. The reaction solution was combined with 11.01 g (0.055 mol) of 4,4'-in 80 ml of dry N-methylpyrrolidone.
Oxydianiline and 0.25 g (0.001 mo.
l) was added dropwise over 1 hour to a stirred solution of a solution of 1,3-bis (3-aminopropyl) tetramethyldisiloxane over 1 hour and stirred at room temperature overnight. Then 29.92 g (0.145 m) in 100 ml of dry N-methylpyrrolidone
ol) of N, N-dicyclohexylcarbodiimide was added dropwise with stirring to the resulting reaction solution over 1 hour. 45.5 g (0.35 g) was added to the reaction solution.
mol) of 2-hydroxyethyl methacrylate and stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 liter of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 13 22.34 g (0.07) in 120 ml of dry N-methylpyrrolidone under dry nitrogen
2.34 g (0.018 mol) of 2-hydroxyethyl methacrylate was added to a stirred solution of 2,4'-oxydiphthalic dianhydride. The solution was stirred at room temperature for 1 hour and at 35 ° C. for 1 hour before cooling to room temperature. The reaction solution was combined with 11.90 g (0.055 mol) of 4,4'-in 80 ml of dry N-methylpyrrolidone.
Thiodianiline and 0.25 g (0.001 mo.
l) was added dropwise over 1 hour to a stirred solution of a solution of 1,3-bis (3-aminopropyl) tetramethyldisiloxane over 1 hour and stirred at room temperature overnight. Then 29.92 g (0.145 m) in 100 ml of dry N-methylpyrrolidone
ol) of N, N-dicyclohexylcarbodiimide was added dropwise with stirring to the resulting reaction solution over 1 hour. 45.5 g (0.35 g) was added to the reaction solution.
mol) of 2-hydroxyethyl methacrylate and stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 liter of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 14 15.27 g (0.07 g) in 120 ml of dry N-methylpyrrolidone under dry nitrogen
(0 mol) of pyromellitic dianhydride in a stirred solution.
82 g (0.014 mol) of 2-hydroxyethyl methacrylate were added. The solution is left at room temperature for 1 hour and 35
After stirring at 1 ° C. for 1 hour, the mixture was cooled to room temperature. The reaction solution was mixed with 11.0 in 80 ml of dry N-methylpyrrolidone.
1 g (0.055 mol) of 4,4′-oxydianiline and 0.25 g (0.001 mol.) Of 1,3-
The solution was added dropwise over 1 hour to a stirred solution of bis (3-aminopropyl) tetramethyldisiloxane and stirred overnight at room temperature. Then 29.92 g (0.145 mol) of N, N in 100 ml of dry N-methylpyrrolidone
A solution of -dicyclohexylcarbodiimide was added dropwise with stirring to the resulting reaction solution over 1 hour. 45.5 g (0.35 mol) of 2-
Hydroxyethyl methacrylate was added and stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture is
The filtrate obtained by diluting with acetone and removing unnecessary substances by suction filtration was treated with 2.0 liters of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 15 15.70 g (0.07 g) in 120 ml of dry N-methylpyrrolidone under dry nitrogen
(2 mol) of pyromellitic dianhydride in a stirred solution.
34 g (0.018 mol) of 2-hydroxyethyl methacrylate were added. The solution is left at room temperature for 1 hour and 35
After stirring at 1 ° C. for 1 hour, the mixture was cooled to room temperature. The reaction solution was combined with 11.6 in 80 ml of dry N-methylpyrrolidone.
Dropwise over one hour a stirred solution of a solution of 8 g (0.054 mol) of 4,4'-thiodianiline and 0.25 g (0.001 mol.) Of 1,3-bis (3-aminopropyl) tetramethyldisiloxane Was added and stirred at room temperature overnight. Then 29.92 g (0.145 mol) of N, N- in 100 ml of dry N-methylpyrrolidone.
A solution of dicyclohexylcarbodiimide was added dropwise with stirring to the resulting reaction solution over 1 hour. 45.5 g (0.35 mol) of 2-hydroxyethyl methacrylate was added to the reaction solution, and the mixture was stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture is
The filtrate obtained by diluting with acetone and removing unnecessary substances by suction filtration was treated with 2.0 liters of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Synthesis Example 16 21.18 g (0.07) in 120 ml of dry N-methylpyrrolidone under dry nitrogen
1.82 g (0.01 mol) in a stirred solution of 2,3 ′, 4,4 ′,-biphenyltetracarboxylic dianhydride.
(4 mol) of 2-hydroxyethyl methacrylate. The solution was stirred at room temperature for 1 hour and at 35 ° C. for 1 hour before cooling to room temperature. 11.68 g (0.054 g) of this reaction solution in 80 ml of dry N-methylpyrrolidone
mol) 4,4'-thiodianiline and 0.25 g
(0.001 mol) of a solution of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was added dropwise over 1 hour and stirred at room temperature overnight. Then 29.9 in 100 ml of dry N-methylpyrrolidone
A solution of 2 g (0.145 mol) of N, N-dicyclohexylcarbodiimide was added dropwise with stirring to the resulting reaction solution over 1 hour. The reaction solution was
5.5 g (0.35 mol) of 2-hydroxyethyl methacrylate was added and stirred at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 liter of ion-exchanged water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water and then with methanol, dried by suction on a filter, and dried at room temperature under reduced pressure until the water content became less than 1.0% by weight.

Each of the photosensitive polyimide precursor resins used in Examples of the present invention has a weight average molecular weight of 1
It is a polyamic acid partial ester which is in the range of 0000 to 80000, is esterified to 25 to 85 mol% of all repeating units, and the remainder is a carboxyl group.

Example 1 In a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, 35.0 g of the negative development type photosensitive polyimide precursor resin obtained in Synthesis Example 1 and 50.0 g of N-methylpyrrolidone were added. p-methoxyphenol 0.
After stirring and mixing 1 g (0.08 mmol) to dissolve,
Further, 2,2′-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole 2.0
g (0.03 mmol), 1.0 g (0.66 mmol) of 2-mercaptobenzoxazole and 0.2 g (0.06 mmol) of ethyl Michler's ketone, and 1,6-hexanedioldiamine as an addition polymerizable compound. After adding and dissolving 7.0 g (3.1 mmol) of acrylate at room temperature with stirring for 24 hours, the solution was filtered and a photosensitive resin composition solution was obtained. This solution is spin-coated on a 5-inch silicon wafer and then dried to obtain a solution of 5.0 ± 1.0 μm.
After forming a coating film, a pattern mask was applied using an i-line stepper LD-5010i manufactured by Hitachi, Ltd.
/ Cm ² . After leaving it in a light-shielding box for 1 hour, it was further heated at 120 ° C on a hot plate.
After heating for 60 seconds, paddle development was performed using a 2.38% aqueous solution of tetramethylammonium hydroxide for 1.2 times the development time required to remove unexposed portions, and rinsed with water. The minimum via hole diameter reached 6 μm, and a very good relief pattern was obtained even in a shape without bridging in a 6 μm line pattern portion.

Example 2 35.0 g of the negative development photosensitive polyimide precursor resin obtained in Synthesis Example 2 was used as the negative development photosensitive polyimide precursor resin.
When the treatment was carried out in exactly the same manner as in Example 1, the minimum via hole diameter reached 5 μm, and a very good relief pattern having a non-bridged shape in the 5 μm line pattern portion was obtained.

Example 3 Instead of adding 1,6-hexanediol diacrylate used in Example 2, 7.0 g (2.6 mmol) of 1,9-nonanediol diacrylate was added as an addition polymerizable compound. Other than that, when the same processing was performed in exactly the same composition, the minimum via hole diameter reached 5 μm, and further 4 μm.
A very good relief pattern was obtained even in a shape without cross-linking in the line pattern portion of m.

Example 4 35.0 g of the negative development type photosensitive polyimide precursor resin obtained in Synthesis Example 3 was used as the negative development type photosensitive polyimide precursor resin.
When the treatment was carried out in exactly the same manner as in Example 1, the minimum via hole diameter reached 6 μm, and a very good relief pattern was obtained in a 6 μm line pattern portion without a bridge.

Example 5 As a negative developing photosensitive polyimide precursor resin, 35.0 g of the negative developing photosensitive polyimide precursor resin obtained in Synthesis Example 4 was used.
When the treatment was carried out in exactly the same manner as in Example 1, the minimum via hole diameter reached 6 μm, and a very good relief pattern was obtained in a 6 μm line pattern portion without a bridge.

Example 6 The negative-developable photosensitive polyimide precursor resin obtained in Synthesis Example 5 was used as a negative-developable photosensitive polyimide precursor resin in an amount of 35.0 g.
When the treatment was carried out in exactly the same manner as in Example 1, the minimum via hole diameter reached 8 μm, and a very good relief pattern having a non-bridged shape in the 6 μm line pattern portion was obtained.

Example 7 Instead of adding 1,6-hexanediol diacrylate used in Example 6, 7.0 g (2.6 mmol) of 1,9-nonanediol diacrylate was added as an addition polymerizable compound. Other than that, when the processing was performed in exactly the same manner with the same composition, the minimum via hole diameter reached 6 μm, and further 6 μm.
A very good relief pattern was obtained even in a shape without cross-linking in the line pattern portion of m.

Example 8 35.0 g of the negative development photosensitive polyimide precursor resin obtained in Synthesis Example 6 was used as the negative development photosensitive polyimide precursor resin.
When the treatment was carried out in exactly the same manner as in Example 1, the minimum via hole diameter reached 8 μm, and a very good relief pattern having a non-bridged shape in the 6 μm line pattern portion was obtained.

Example 9 35.0 g of the negative developing photosensitive polyimide precursor resin obtained in Synthesis Example 7 was used as a negative developing photosensitive polyimide precursor resin.
When the treatment was carried out in exactly the same manner as in Example 1, the minimum via hole diameter reached 6 μm, and a very good relief pattern was obtained in a 6 μm line pattern portion without a bridge.

Example 10 The same procedure as in Example 1 was carried out except that 35.0 g of the negative developing photosensitive polyimide precursor resin obtained in Synthesis Example 8 was used as the negative developing photosensitive polyimide precursor resin. And the minimum via-hole diameter reached 6 μm, and was 6 μm
In the line pattern portion, a very good relief pattern having a shape without cross-linking was obtained.

Example 11 Instead of adding 1,6-hexanediol diacrylate used in Example 10, 7.0 g (2.6 mmol) of 1,9-nonanediol diacrylate was added as an addition polymerizable compound. ,
Except for that, when the processing was performed in exactly the same manner and with exactly the same composition, the minimum via hole diameter reached 5 μm, and the minimum via hole diameter reached 5 μm.
In the μm line pattern portion, a very good relief pattern was obtained even in a shape without cross-linking.

Example 12 The same procedure as in Example 1 was carried out except that 35.0 g of the negative developing photosensitive polyimide precursor resin obtained in Synthesis Example 9 was used as the negative developing photosensitive polyimide precursor resin. And the minimum via hole diameter reached 6 μm and was 6 μm
In the line pattern portion, a very good relief pattern having a shape without cross-linking was obtained.

Example 13 The same procedure as in Example 1 was carried out except that 35.0 g of the negative development type photosensitive polyimide precursor resin obtained in Synthesis Example 10 was used as the negative development type photosensitive polyimide precursor resin. And the minimum via hole diameter reached 5 μm,
In the line pattern portion, a very good relief pattern having a shape without cross-linking was obtained.

Comparative Example 1 As a negative developing photosensitive polyimide precursor resin, 35.0 g of the negative developing photosensitive polyimide precursor resin obtained in Synthesis Example 11 was used.
-The same amount of tetraethylene glycol diacrylate was added in place of hexanediol diacrylate, and the other components were treated exactly in the same manner as in Example 1 and swelled by a developer. Although the diameter reached up to 8 μm, cross-linking partially occurred in the line pattern portion of 8 μm or less, and a good pattern as in the example was not formed.

Comparative Example 2 Instead of tetraethylene glycol diacrylate used in Comparative Example 1, 3-
Hydroxy 2,2-dimethylpropyl 3-hydroxy-
When the same amount of 2,2-dimethylpropionate diacrylate was added, and the other conditions were exactly the same as in Example 1, and the processing was performed in exactly the same manner, swelling with a developing solution occurred.
The minimum via hole diameter reaches only 10 μm, and the shape is not something like a square hole due to the remarkable swelling due to the developing solution.
A good pattern as in the example was not formed.

[Comparative Example 3] As the negative development type photosensitive polyimide precursor resin, 35.0 g of the negative development type photosensitive polyimide precursor resin obtained in Synthesis Example 112 was used.
When the same amount of triethylene glycol diacrylate was added instead of 6-hexanediol diacrylate, and the same treatment was carried out with the same composition as in Example 1 except for the above, swelling due to the developing solution occurred. The via hole diameter reached only 10 μm, and significant cross-linking and development residue occurred in the line pattern portion of 10 μm or less, so that a good pattern as in the example was not formed.

Comparative Example 4 Instead of the triethylene glycol diacrylate used in Comparative Example 3, 3-hydroxy 2,2-dimethylpropyl 3-hydroxy-
When the same amount of 2,2-dimethylpropionate diacrylate was added, and the other conditions were exactly the same as in Example 1, and the processing was performed in exactly the same manner, swelling with a developing solution occurred.
The minimum via hole diameter reaches only 10 μm, and the shape is not something like a square hole due to the remarkable swelling due to the developing solution.
A good pattern as in the example was not formed.

[Comparative Example 5] 35.0 g of the negative developing photosensitive polyimide precursor resin obtained in Synthesis Example 13 was used as the negative developing photosensitive polyimide precursor resin.
-The same amount of triethylene glycol diacrylate was added in place of hexanediol diacrylate, and the same treatment as in Example 1 was performed except for the same amount, and swelling due to the developing solution occurred. Although the diameter reached 10 μm, cross-linking partially occurred in a line pattern portion of 8 μm or less, and a good pattern as in the example was not formed.

Comparative Example 6 Instead of the triethylene glycol diacrylate used in Comparative Example 5, 3-hydroxy-2,2-dimethylpropyl 3-hydroxy-
When the same amount of 2,2-dimethylpropionate diacrylate was added, and the other conditions were exactly the same as in Example 1, and the processing was performed in exactly the same manner, swelling with a developing solution occurred.
The minimum via hole diameter reaches only 10 μm, and the shape is not something like a square hole due to the remarkable swelling due to the developing solution.
A good pattern as in the example was not formed.

[Comparative Example 7] As the negative developing photosensitive polyimide precursor resin, 35.0 g of the negative developing photosensitive polyimide precursor resin obtained in Synthesis Example 14 was used.
-The same amount of tetraethylene glycol dimethacrylate was added in place of hexanediol diacrylate, and the same treatment as in Example 1 was carried out except for the same amount, and swelling due to the developing solution occurred. Although the diameter reached up to 8 μm, cross-linking partially occurred in the line pattern portion of 8 μm or less, and a good pattern as in the example was not formed.

Comparative Example 8 Instead of the tetraethylene glycol diacrylate used in Comparative Example 7, 3-
Hydroxy 2,2-dimethylpropyl 3-hydroxy-
The same amount of 2,2-dimethylpropionate dimethacrylate was added, and otherwise, with exactly the same formulation as in Example 1,
When treated in exactly the same way, swelling due to the developer occurs, and the minimum via hole diameter reaches only 10 μm,
Further, the shape was not a square hole due to the remarkable swelling due to the developing solution, and a remarkable cross-linking and development residue occurred in a line pattern portion of 10 μm or less, so that a good pattern as in the example was not formed. Was.

[Comparative Example 9] As the negative developing photosensitive polyimide precursor resin, 35.0 g of the negative developing photosensitive polyimide precursor resin obtained in Synthesis Example 15 was used.
-The same amount of diethylene glycol dimethacrylate was added in place of hexanediol diacrylate, and the other conditions were exactly the same as in Example 1, and processing was performed in exactly the same manner. Although it reached 10 μm, cross-linking partially occurred in a line pattern portion of 8 μm or less, and a good pattern as in the example was not formed.

Comparative Example 10 Instead of the diethylene glycol dimethacrylate used in Comparative Example 9, 3-
Hydroxy 2,2-dimethylpropyl 3-hydroxy-
When the same amount of 2,2-dimethylpropionate diacrylate was added, and the other conditions were exactly the same as in Example 1, and the processing was performed in exactly the same manner, swelling with a developing solution occurred.
The minimum via hole diameter reaches only 10 μm, and the shape is not something like a square hole due to the remarkable swelling due to the developing solution.
A good pattern as in the example was not formed.

[Comparative Example 11] As the negative development type photosensitive polyimide precursor resin, 35.0 g of the negative development type photosensitive polyimide precursor resin obtained in Synthesis Example 16 was used.
Except that the same amount of diethylene glycol dimethacrylate was added instead of 6-hexanediol diacrylate, and processing was carried out in exactly the same manner as in Example 1 except that swelling and elution by the developing solution occurred. The via hole diameter reached only 20 μm, and the shape was not like a square hole due to the remarkable swelling due to the developing solution. Further, significant cross-linking and development residue occurred in the line pattern portion of 15 μm or less. Such a good pattern was not formed.

Comparative Example 12 Instead of diethylene glycol dimethacrylate used in Comparative Example 11, the same amount of tripropylene glycol diacrylate was added.
Except for this, when processing was carried out in exactly the same manner as in Example 1, swelling due to the developing solution occurred, the minimum via hole diameter reached only 10 μm, and the shape was sharpened due to significant swelling due to the developing solution. It was not a hole, and remarkable cross-linking and development residue occurred in a line pattern portion of 10 μm or less, so that a good pattern as in the example was not formed.

[0107]

The alkali-negative development type photosensitive resin composition of the present invention is excellent in patternability after development because it has less swelling during alkali development than conventional products. In addition, the alkali-negative development type photosensitive resin composition of the present invention exhibits the above-mentioned effects, and further provides high base adhesion.

Further, the alkali-negative developing type photosensitive resin composition of the present invention exhibits the above-mentioned effects, and gives a higher crosslinking efficiency. Further, the alkali-negative development type photosensitive resin composition of the present invention exhibits the above-mentioned effects, and is further excellent in reactivity and compatibility.

According to the pattern manufacturing method of the present invention,
Α for interlayer insulation film for multilayer wiring board and semiconductor memory device
A pattern having good characteristics can be manufactured by processing a polyimide pattern such as a line shielding film and a buffer coat film by using an inexpensive alkaline aqueous solution instead of the conventional organic solvent development. Further, the electronic component of the present invention has excellent reliability by having the pattern.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Protective film, 3 ... First conductor layer, 4 ... Interlayer insulating film layer, 5 ... Photosensitive resin layer, 6A, 6B, 6C ... Window,
7: second conductor layer, 8: surface protective film layer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/028 G03F 7/028 7/075 511 7/075 511 7/40 501 7/40 501 H01L 21 / 027 H01L 21/30 502R (72) Inventor Yasunori Kojima 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical DuPont Microsystems Co., Ltd. Yamazaki Development Center (72) Inventor Naoki Watanabe Higashicho, Hitachi City, Ibaraki Prefecture 13-1 Hitachi Chemical DuPont Microsystems, Inc. Yamazaki Development Center F-term (reference) 2H025 AA00 AA04 AA14 AB15 AB16 AB17 AC01 AD01 BC14 BC17 BC37 BC43 BC69 BC77 BC82 FA03 FA17 FA29 2H096 AA00 AA25 AA26 AA27 BA05 BA06 BA20 EA02 GA08 HA01 4J011 QA03 QA08 QA09 QA12 QA13 QA17 QA23 QB17 SA22 SA25 SA26 SA28 SA34 SA62 SA63 SA64 SA65 SA78 SA82 SA83 TA01 UA01 UA03 UA04 UA06 VA01 WA01 4J027 AD03 AD04 AD06 BA05 BA07 BA19 BA21 BA25 BA28 CB10 CC03 CC04 CC05 CC06 CC08 CD10 4J043 PA19 PC015 PC035 PC065 PC145 QB15 QB26 RA06 RA35 SA06 SB01 TA22 TB01 UA121 UA121 012121 UB402 WA09 WA16 YB07 YB19 ZA60 ZB22

Claims (11)

[Claims] 1. A photosensitive polyimide precursor which has a reactive unsaturated functional group in a molecular chain and is soluble in an aqueous alkali solution, and (b) a reactive polyimide functional group containing a reactive unsaturated functional group An alkali-negative-developing photosensitive resin composition comprising, in a main skeleton other than an unsaturated functional group, an addition-polymerizable compound containing no atom having a lone pair, and (c) a photosensitizer. 2. The component (a) is represented by the general formula (1): ## STR1 ## (X is a tetravalent organic group containing no atom having a lone pair in the skeleton connecting two amide groups bonded to X, and Y is non-valent in the skeleton connecting the two amide groups bonded to Y. A divalent organic group containing no atom having a shared electron pair, R and R ′ each independently represent OH or a monovalent organic group), and have a repeating unit represented by the following formula: The alkali negative development type photosensitive resin composition according to claim 1, which is a photosensitive polyimide precursor having an acid functional group and a photosensitive group. (3) The component (a) has, as a repeating unit, only a repeating unit represented by the general formula (1);
Or, it comprises a repeating unit represented by the general formula (1) and a repeating unit having a silicon atom-containing divalent organic group Y ″ instead of Y in the general formula (1). 3. The photosensitive composition of claim 2, wherein 4. The component (b) according to claim 1, wherein the reactive unsaturated functional group has a vinyl group, an acryloxy group or a methacryloxy group, and the number of the functional groups is 1 to 4. Alkaline negative development type photosensitive resin composition. 5. The component (b) has two or more reactive unsaturated functional groups, does not contain a ring structure in a molecular chain connecting the functional groups, and has a carbon number of the molecular chain. The alkali negative development type photosensitive resin composition according to claim 1, wherein the composition is 4 to 12. 6. The component (b) having two reactive unsaturated functional groups, wherein the molecular chain connecting the functional groups is linear, and the molecular chain has 4 to 12 carbon atoms. Claim 1, wherein
5. The alkali negative development type photosensitive resin composition according to 2, 3 or 4. 7. The alkali-negative developing photosensitive resin composition according to claim 6, wherein the component (b) is a linear diol diacrylate or dimethacrylate. (8) 100 parts by weight of the component (a) and (b)
5 to 100 parts by weight of component, 0.01 to 40 component (c)
The alkali negative development type photosensitive resin composition according to any one of claims 1 to 7, which is contained by weight. 9. A step of applying the photosensitive resin composition according to any one of claims 1 to 8, a step of irradiating an actinic ray from a mask on which a pattern is drawn on a coating film obtained in the step, an alkali. A method for producing a pattern including a step of removing an unirradiated portion using a developer and a step of performing a heat treatment. 10. The method according to claim 9, wherein the actinic ray is i-ray. 11. An electronic component having a layer of a pattern obtained by the method according to claim 9.