TW201615696A - Resin and photosensitive resin composition - Google Patents

Abstract

The purpose of the present invention is to provide a resin that is capable of producing a photosensitive resin composition having high sensitivity and high film retention ratio. The present invention provides a resin which has a polyamide structure, a polyimide precursor structure or a polyimide structure wherein an acid having an alicyclic structure with 6-40 carbon atoms or a semi-alicyclic structure with 6-40 carbon atoms or an anhydride of the acid is contained in an amount of 5-95% by mole if the total amount of acids or anhydrides thereof is taken as 100% by mole.

Description

Resin and photosensitive resin composition

The present invention relates to a resin containing a specific structure, and more particularly to a resin suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, or the like; and a use thereof A photosensitive resin composition.

Since the polyimide resin has excellent heat resistance, electrical insulating properties, and mechanical properties, it can be widely used for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent device, and the like.

In the case where polyimide is used as the surface protective film or the interlayer insulating film, one type of formation method of via holes or the like is etched using a positive photoresist. However, in this method, the step of coating or peeling off the photoresist is troublesome, and therefore, research into a photosensitive heat-resistant material for the purpose of rationalizing the work step has been carried out.

In addition, in recent years, the demand for interlayer insulating films that can be applied to multilayer wiring has been increasing due to the miniaturization of components, the increase in density of packages, and the increase in capacity and speed. Therefore, it is desired to perform thick film processing more than ever. A photosensitive resin composition having high sensitivity and high residual film ratio.

For example, a positive photosensitive heat resistant composition which can be developed with an aqueous alkaline solution has been reported to contain a composition containing a phenolic hydroxyl group-containing polyphthalate and an o-quinonediazide compound (Patent Document 1) or a composition comprising a ring-closed polyimine and a naphthoquinonediazide compound soluble in a solvent, and a polyphenylene-containing compound A composition of an azole precursor and a naphthoquinone diazide compound (Patent Document 2). However, in the case where a polyimide having a low transparency is used, there is a problem that the photoreaction efficiency of the photosensitive agent in the exposed portion is deteriorated or the sensitivity of the thick film is particularly deteriorated. .

In order to satisfy such a demand, a photosensitive resin composition which achieves high sensitivity by using a highly transparent polyimine of a tetracarboxylic acid anhydride having an alicyclic structure has been proposed (for example, see Patent Document 3~ 4).

Further, a polyimide resin having a tetracarboxylic acid anhydride having a hexafluoropropyl group and an alicyclic structure has been proposed (for example, see Patent Document 5).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 4-204945

[Patent Document 2] Japanese Patent Laid-Open No. 1-468686

[Patent Document 3] International Publication No. 00/73853

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-196041

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2007-183388

However, the use of four with an alicyclic structure so far Since the polyimine resin of a carboxylic anhydride is too high in solubility in an alkali developing solution, it is difficult to form a thick film structure. Further, the use of a polyimine resin having a hexafluoropropyl group and a tetracarboxylic acid anhydride having an alicyclic structure has a very poor residual film ratio, and it is difficult to achieve a high-sensitivity thick film structure.

In view of the above-described problems of the prior art, the present invention has an object of providing a resin having high sensitivity and residual film ratio when used in a photosensitive resin composition.

In order to solve the above problems, efforts have been devoted to research, and as a result, the present invention has been found.

That is, the present invention has the following constitution.

(1) A resin having a polyamine structure, a polyimine precursor structure or a polyimine structure, which contains 5 to 95 mol% when the total amount of the acid or its anhydride is 100 mol% An acid having an alicyclic structure having a carbon number of 6 to 40 or an alicyclic structure having a carbon number of 6 to 40 and a semi-alicyclic structure of an aromatic ring or an anhydride thereof.

(2) A resin having a structure represented by the general formula (1).

(In the formula (1), R ¹ each independently contains an alicyclic structure selected from a monocyclic or condensed polycyclic ring when the total amount of R ¹ is 100 mol% and is 5 to 95 mol%. a tetravalent organic group having 6 to 40 carbon atoms, an organic group having a monocyclic alicyclic structure, or a tetravalent organic group having 6 to 40 carbon atoms directly or through a crosslinked structure, and having an alicyclic ring at the same time carbon atoms in a ring structure of semi-aliphatic structure and an aromatic ring, a tetravalent organic group having 6 to 40 in the one or more organic groups; R & lt ^two lines each independently represent a carbon number of the divalent organic group having 2 to 40; R ³ lines It represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms; m and n each represent a range of 0 to 100,000 and m+n>2.

(3) The resin according to (2), which is characterized in that the structure represented by the formula (1) has a fluorine component.

(4) The resin according to (2) or (3), wherein the structure represented by the formula (1) has a phenolic hydroxyl group.

(5) (2) to (4) according to one of the resin, characterized in that the general formula ^(1), R ¹ contains one or more selected from the following general formulas (2) to (7) of a Organic base.

(In the general formulae (2) to (7), R ₄ to R ₈₁ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms; and in the formula (3), X ₁ is oxygen. An atom, a sulfur atom, a sulfonyl group or a divalent organic group having 1 to 3 carbon atoms or a divalent crosslinked structure in which two or more of these are bonded; in the formula (6), X ₂ is a direct bond, An oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms, or a divalent crosslinked structure in which two or more organic groups selected from the aryl group are bonded to each other.

(6) The resin according to any one of (2) to (5), wherein, in the general formula (1), when the total amount of R ¹ and R ² is 100 mol%, it has 30 mol. An organic group of a fluorine atom or more above the ear.

(7) The resin according to any one of (2) to (6), wherein, in the formula (1), each of R ¹ is independently contained in an amount of 25 mol% when the total amount of R ¹ is 100%. 80 mol% of a tetravalent organic group having a carbon number of 6 to 40 having a monocyclic or condensed polycyclic alicyclic structure, and an organic group having a monocyclic alicyclic structure directly or crosslinked by a crosslinked structure The tetravalent organic group having 6 to 40 carbon atoms and one or more organic groups having 4 to 40 carbon atoms having a half-alicyclic structure having an alicyclic structure and an aromatic ring.

(8) The resin according to any one of (2) to (6), wherein, in the formula (1), R ¹ each independently contains 40% when the total amount of R ¹ is 100 mol%. 70 mol% of a tetravalent organic group having a carbon number of 6 to 40 having a monocyclic or condensed polycyclic alicyclic structure, and an organic group having a monocyclic alicyclic structure directly or crosslinked by a crosslinked structure The tetravalent organic group having 6 to 40 carbon atoms and one or more organic groups having 4 to 40 carbon atoms having a half-alicyclic structure having an alicyclic structure and an aromatic ring.

(9) A photosensitive resin composition containing any of (1) to (8) A recorded resin.

(10) A photosensitive resin composition comprising (a) a resin having a structure represented by the formula (8) as a main component, (b) a photoacid generator, and (c) a solvent, and having a positive type Photosensitive.

(In the formula (8), R ¹ each independently contains an alicyclic structure selected from a monocyclic or condensed polycyclic ring when the total amount of R ¹ is 100% by mole to 5 to 95 mol%. a tetravalent organic group having 6 to 40 carbon atoms, an organic group having a monocyclic alicyclic structure, or a tetravalent organic group having 6 to 40 carbon atoms directly or through a crosslinked structure, and having an alicyclic ring at the same time carbon atoms in a ring structure of semi-aliphatic structure and an aromatic ring, a tetravalent organic group having 6 to 40 in the one or more organic groups; R & lt ^two lines each independently represent a carbon number of the divalent organic group having 2 to 40; R ³ lines It represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms; m and n each represent a range of 0 to 100,000 and m+n>2, wherein the structure represented by the formula (8) must have a fluorine component and a phenolic hydroxyl group. .)

(11) The photosensitive resin composition according to (9) or (10), wherein R ² in the formula (1) or (8) further contains an aliphatic organic group.

(12) The photosensitive resin composition according to (11), wherein the aliphatic organic group is an organic group containing an aliphatic alkyl group.

(13) A method for producing a heat-resistant resin film, which uses the heat resistance tree of the photosensitive resin composition according to any one of (9) to (12) A method for producing a lipid film comprising: a step of applying the photosensitive resin composition onto a support substrate and drying to obtain a photosensitive resin film, a step of exposing the photosensitive resin film obtained in the step, and using an alkaline aqueous solution The step of developing the exposed photosensitive resin film and the step of heat-treating the developed photosensitive resin film.

(14) An interlayer insulating film obtained by the method for producing a heat resistant resin film according to (13).

(15) An interlayer insulating film for a multilayer wiring structure, which is an interlayer insulating film for a multilayer wiring structure having a total film thickness of 10 μm or more and 50 μm or less obtained by the method for producing a heat resistant resin film according to (13).

(16) A surface protective film obtained by the method for producing a heat resistant resin film according to (13).

(17) An electronic component comprising the interlayer insulating film according to (14) or the surface protective film according to (16).

(18) An insulating layer of an organic electroluminescence device obtained by the method for producing a heat resistant resin film according to (13).

According to the present invention, a resin having high sensitivity and residual film ratio can be obtained when used in a photosensitive resin composition.

1‧‧‧矽 wafer

2‧‧‧Al pads

3‧‧‧passivation film

4‧‧‧Insulation film

5‧‧‧Metal (Cr, Ti, etc.) film

6‧‧‧Wiring (Al, Cu, etc.)

7‧‧‧Insulation film

8‧‧‧ barrier metal

9‧‧‧ cutting road

10‧‧‧ solder bumps

[Fig. 1] A cross-sectional view showing a pad portion of a semiconductor device according to an embodiment of the present invention.

[Fig. 2] A cross-sectional view showing a manufacturing step of a semiconductor device according to an embodiment of the present invention.

[Formation of the Invention]

The present invention is a resin having a polyamine structure, a polyimine precursor structure or a polyimine structure, which contains 5 to 95 mol% when the total amount of the acid or its anhydride is 100 mol%. An acid having an alicyclic structure having a carbon number of 6 to 40 or an alicyclic structure having a carbon number of 6 to 40 and a semi-alicyclic structure of an aromatic ring or an anhydride thereof.

Further, the resin of the present invention has a structure represented by the following formula (1). The resin having the structure represented by the formula (1) is a polyimine precursor of a polyimine which is closed by heating and which is excellent in heat resistance and solvent resistance, and is obtained by ring closure by heating. The imine, or a portion of the resin, is subjected to a ring closure and a ruthenium imidized polyimide precursor.

Moreover, the present invention is a photosensitive resin composition containing a resin having a structure represented by the general formula (1).

(In the formula (1), R ¹ each independently contains an alicyclic structure selected from a monocyclic or condensed polycyclic ring when the total amount of R ¹ is 100 mol% and is 5 to 95 mol%. a tetravalent organic group having 6 to 40 carbon atoms, an organic group having a monocyclic alicyclic structure, or a tetravalent organic group having 6 to 40 carbon atoms directly or through a crosslinked structure, and having an alicyclic ring at the same time carbon atoms in a ring structure of semi-aliphatic structure and an aromatic ring, a tetravalent organic group having 6 to 40 in the one or more organic groups; R & lt ^two lines each independently represent a carbon number of the divalent organic group having 2 to 40; R ³ lines It represents hydrogen or an organic group having 1 to 20 carbon atoms; m and n each represent a range of 0 to 100,000 and m+n>2.

The structure represented by the formula (1) represents a polyimine at m = 0 and a polyimine precursor at n = 0. Further, when m > 0 and n > 0, it means a part of a polyimine precursor which is subjected to ring closure by heating and which has been imidized.

In addition, the resin having a structure represented by the formula (1) of the present invention may be a copolymer of a resin having a structure represented by the above formula (1) and a structure other than the structure represented by the formula (1).

In the formula (1), R ¹ each independently has an alicyclic structure selected from a monocyclic or condensed polycyclic ring in an amount of 5 to 95 mol % when the total amount of R ¹ is 100 mol%. a tetravalent organic group having 6 to 40 carbon atoms, an organic group having a monocyclic alicyclic structure, or a tetravalent organic group having 6 to 40 carbon atoms bonded directly or through a crosslinked structure, and having an alicyclic structure at the same time One or more organic groups of a tetravalent organic group having 6 to 40 carbon atoms in a half-alicyclic structure of an aromatic ring; R ² each independently represents a divalent organic group having 2 to 40 carbon atoms; and R ³ represents Hydrogen or an organic group having 1 to 20 carbon atoms; m and n each represent a range of 0 to 100,000 and m+n>2. By containing a monocyclic, condensed polycyclic or semi-alicyclic structure, the resin has low absorbance, so that even a thick film can obtain a highly sensitive photosensitive resin composition.

However, all the polyimine-based resins in which the R ^{1 is an} alicyclic structure are too soluble in the alkali developing solution, so that the developing film is eluted and the residual film ratio is deteriorated, or the alkali developing solution is easily caught. Sticky or residue. Further, the polyimine resin having an alicyclic structure of less than 6 carbon atoms or an alicyclic structure having a carbon number of 41 or more is insufficient in solubility in an alkali developing solution, so that the sensitivity is insufficient, and the pattern during development has a residue. The problem that arises.

In addition, when the fluorine-containing component is contained in the structure represented by the general formula (1), hydrophobicity is imparted to the resin, and penetration into the surface of the film can be suppressed during alkali development, and a tack or a processed pattern in the unexposed portion can be suppressed. It is preferable to have no developing residue and to obtain a resin film having a high residual film ratio.

Further, when the phenolic hydroxyl group is contained in the structure represented by the formula (1), the solubility in the alkali developing solution can be obtained, and the interaction with the sensitizer can be facilitated. Therefore, the residual film ratio can be improved and the hydroxy group can be obtained. A photosensitive resin film is preferred. Further, since the phenolic hydroxyl group also contributes to the reaction with the crosslinking agent, it is also preferable from the viewpoint of obtaining high mechanical properties and chemical resistance.

In addition, R ¹ in the general formula (1) is preferably one or more selected from the following general formulae (2) to (7).

In the general formula (2) ~ (7), R 4 ~ R 81 each independently represent a line a hydrogen atom, a halogen atom or a monovalent organic group having a carbon number of 1 to 3; monovalent organic group having a carbon number of 1 to 3, The hydrogen atom contained in the organic group may be substituted with a halogen atom. In the formula (3), X ₁ is an oxygen atom, a sulfur atom, a sulfonyl group or a divalent organic group having 1 to 3 carbon atoms or a divalent crosslinked structure in which two or more of these are bonded; carbon number 1 The divalent organic group of ~3 may have a hydrogen atom contained in the organic group substituted by a halogen atom. In the formula (6), X ₂ is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms, or a combination of two or more selected from an extended aryl group. A divalent crosslinked structure; a divalent organic group having a carbon number of 1 to 3 and an extended aryl group, wherein a hydrogen atom contained in the organic group may be substituted with a halogen atom.

In the formula (1), R ¹ is a structure derived from an acid dianhydride. The organic group having a monocyclic alicyclic structure having a monocyclic or condensed polycyclic alicyclic structure and having a monocyclic alicyclic structure is directly or through a crosslinked structure. a tetravalent organic group having a carbon number of 6 to 40, and an acid dianhydride having a carbon number of 6 to 40 and having a half-alicyclic structure having an alicyclic structure and an aromatic ring, specifically For example, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid Anhydride, 5-(2,5-di-oxo-tetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentane Alkane dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,5, An alicyclic tetracarboxylic dianhydride of 6-tricarboxy-2-norbornaneacetic acid dianhydride or a compound obtained by substituting such an aromatic ring with an alkyl group or a halogen atom; for example, 1, 3, 3a, 4,5,9b-hexahydro-5(tetrahydro-2,5-di-oxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione The semi-alicyclic tetracarboxylic dianhydride or a compound in which a hydrogen atom of such an aromatic ring is substituted with an alkyl group or a halogen atom.

These acid dianhydrides contain 5 mol% to 95 mol% when R ¹ in the structure represented by the general formula (1) is 100 mol%, and the resin has low absorbance, so even a thick film A photosensitive resin composition having high sensitivity can be obtained.

Further, in the present invention, the pattern obtained from the photosensitive resin composition is preferably high in resolution. The resolution refers to the minimum size obtained when a pattern is formed using a photosensitive resin composition, and a finer pattern can be formed, and the resolution is higher.

When the photosensitive resin composition of the resin having a very low absorbance is used, the light collection ratio is too high, and it is easy to become a pattern width of a target size or more, and the resolution of the obtained pattern is lowered. Therefore, the content of the acid dianhydride at a ^ratio of R ¹ of 100 mol % in the structure represented by the general formula (1) is 25 mol % in terms of the pattern width at which the target size can be obtained during the pattern processing. The above is more preferable, and it is further preferable to be 40 mol% or more.

Further, when the content of the alicyclic structure is small, the concentration of the light is low, and the opening of the small pattern cannot be obtained, so that the resolution of the obtained pattern is lowered. Therefore, the content of the acid dianhydride when the R ¹ in the structure represented by the general formula (1) is 100 mol% is 80 mols in terms of the improvement of the light collection ratio and the opening of the small pattern. % or less is more preferable, and it is further preferable to be 70 mol% or less.

By setting the content of the acid dianhydride within the above range, A high resolution pattern is obtained.

The resin having a structure represented by the general formula (1) preferably has a fluorine component. In the formula (1), at least one of R ¹ and R ² is preferably an organic group having a fluorine atom. By containing a fluorine atom, hydrophobicity is imparted to the surface of the film during alkali development, and penetration from the surface or the like can be suppressed. Therefore, there is no development residue in the adhesive or processed pattern of the unexposed portion, and a high residual film ratio can be obtained. Photosensitive resin film. In the general formula (1), in order to obtain an anti-seepage effect at the interface and an appropriate dissolution rate, the organic group having a fluorine atom is 30 mol% or more when the total amount of R ¹ and R ² is 100 mol%. good. Such a structure can be introduced by using a monomer having a fluorine atom of 30 mol% or more among the monomer components into which R ¹ and R ² are introduced. Further, in order to obtain adhesion to the substrate, the fluorine atom-containing monomer is preferably 90 mol% or less.

Specific examples of the compound having a fluorine atom include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or an aromatic ring of these or the like. Aromatic dianhydride such as a compound substituted with an atom and an acid dianhydride having a guanamine group, or bis(3-amino-4-hydroxyphenyl)hexafluoropropane or 2,2'-bis(trifluoro An aromatic diamine such as methyl)-4,4'-diaminobiphenyl or a part of a hydrogen atom of such an aromatic ring is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like. Substituted compounds, etc. The resin having a structure represented by the general formula (1) is preferably a resin containing a structure derived from these compounds.

Further, the resin having the structure represented by the general formula (1) is preferably a phenolic hydroxyl group. In the formula (1), at least one of R ¹ and R ² is preferably an organic group having a phenolic hydroxyl group. The phenolic hydroxyl group can have a moderate solubility to the alkali developing solution, and interacts with the sensitizer to suppress the solubility of the unexposed portion, so that the residual film ratio can be improved and the sensitivity can be improved. Further, since the phenolic hydroxyl group also contributes to the reaction with the crosslinking agent, it is also preferable from the viewpoint of obtaining high mechanical properties and chemical resistance.

Specific examples of the compound having a phenolic hydroxyl group include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or such an aromatic ring as an alkyl group or A compound substituted with a halogen atom, an aromatic acid dianhydride such as an acid dianhydride having a guanamine group, or a bis(3-amino-4-hydroxyphenyl)hexafluoropropane or a bis(3-amino-4) -hydroxyphenyl)anthracene, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene (bis(3-amino-4-hydroxyphenyl)methylene) , bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)anthracene, etc. The amine or a compound in which a part of the hydrogen atom of the aromatic ring is substituted with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom or the like. The resin having a structure represented by the general formula (1) is preferably a resin containing a structure derived from these compounds.

By using an appropriate amount of the above-mentioned acid dianhydride having an alicyclic structure or a semi-alicyclic structure having a carbon number of 6 to 40, a compound having a phenolic hydroxyl group, and a compound having a fluorine atom, no adhesive or development can be obtained at the time of development. A high residual film ratio of the residue and a high sensitivity photosensitive resin composition.

R ¹ in the above formula (1) may have a structure derived from another acid dianhydride in addition to the acid dianhydride.

As the acid dianhydride, specifically, pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-linked Pyromellitic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketone Tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-double (2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)B Alkane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2 , 3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-fluorene tetracarboxylic dianhydride, etc. Anhydride; bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-dual ( 3,4-dicarboxyphenyl)hexafluoropropane dianhydride or a compound obtained by substituting an aromatic ring of such a compound with an alkyl group or a halogen atom, and an aromatic acid such as an acid dianhydride having a guanamine group anhydride. These can be used in combination of two or more kinds of acid dianhydrides having an alicyclic structure or a semi-alicyclic structure having 6 to 40 carbon atoms.

Further, R ² in the formula (1) of the present invention may have a structure derived from another diamine in addition to the diamine.

In the case of an aliphatic diamine, it means a diamine having no aromatic ring, and examples thereof include a polyalkyl group, or a polyethylene ether group, a polyoxypropylene group, a tetramethylene ether group or the like. An aliphatic alkyl diamine of an alkylene ether group, an alicyclic diamine, or an aliphatic diamine having a decane structure.

Specifically, as the aliphatic alkylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, and 12-methylenediamine of polyalkylenediamine may be mentioned. Amine, polyethylene ether-containing diamine JEFFAMINE KH-511, JEFFAMINE ED-600, JEFFAMINE ED-900, JEFFAMINE ED-2003, JEFFAMINE EDR-148, JEFFAMINE EDR-176, polyoxypropylene diamine D-200, D-400, D-2000, D-4000, RP-409, RP-2009, tetramethyl ether group-containing diamine RT-1000, HT- 1100, HT-1000 containing an amino group-containing alkyl ether diamine, HE-1000 (above, trade name, manufactured by HUNTSMAN), and the like; Methylene dicyclohexylamine or the like; in the case of an aliphatic diamine having a decane structure, bis(3-aminopropyl)tetramethyldioxane, bis(p-aminophenyl) VIII Methyl pentaoxanes and the like. Among them, in the case of using an aliphatic alkylenediamine, it is preferable to control the warpage of the wafer by increasing the elongation at break and increasing the modulus of elasticity in order to impart flexibility. These properties are effective properties in multilayer or thick films. At the time of introduction, the residue derived from the aliphatic alkanediamine in all the diamine residues is preferably 10 mol% or more, and more preferably 50 mol% or less from the viewpoint of heat resistance.

Moreover, in the case where the aliphatic group having a siloxane structure is copolymerized in a range where the heat resistance is not lowered, the adhesion to the substrate can be improved. It is preferred to copolymerize 1 to 15 mol%.

Further, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)fluorene, bis(3-amino-4-hydroxyphenyl) can be mentioned. Propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis( a hydroxyl group-containing diamine such as 3-amino-4-hydroxyphenyl)anthracene; a sulfonic acid-containing diamine such as 3-sulfonic acid-4,4'-diaminodiphenyl ether; dimercaptophenylenediamine; a thiol-containing diamine; 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylmethane, 3,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, petroleum ether, M-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)fluorene, bis(3-aminophenoxybenzene) , bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene , 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'- Diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-di An aromatic diamine such as an aminobiphenyl group; or a compound obtained by substituting a part of a hydrogen atom of the aromatic ring with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom or the like. These diamines can be used as they are, or can be used as a corresponding diisocyanate compound or trimethylsulfonium alkylated diamine. Further, these two or more kinds of diamine components may be used in combination. In applications requiring heat resistance, it is preferred to use 50 mol% or more of an aromatic diamine of the entire diamine.

Among these, preferred are 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl. Anthracene, 4,4'-diaminodiphenylanthracene, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, bis(4-aminobenzene) Oxyphenyl)anthracene, bis(3-aminophenoxyphenyl)anthracene, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl} Ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane Further, a compound obtained by substituting such an aromatic ring with an alkyl group or a halogen atom, and a diamine having a guanamine group shown below. These may be used singly or in combination of two or more.

In addition, the resin having the structure represented by the formula (1) of the present invention may contain a sulfonic acid group, a thiol group or the like, and has a moderate alkali solubility by using a resin having a moderately sulfonic acid group or a thiol group. A positive photosensitive resin composition.

In the general formula (1), m and n represent the number of repetitions of the resin structural unit, and represent a range of 0 to 100,000, and m+n>2. From the viewpoint of the elongation of the obtained resin, m+n is preferably 10 or more. On the other hand, m+n is 200,000 or less, preferably 1,000 or less, and more preferably 100 or less from the viewpoint of solubility of the photosensitive resin composition containing the obtained resin to the alkali developer.

The weight average molecular weight of the resin having the structure represented by the general formula (1) is preferably from 3,000 to 80,000, more preferably from 8,000 to 50,000, in terms of polystyrene using gel permeation chromatography. If it is within this range, a thick film can be formed easily.

Further, the resin having the structure represented by the general formula (1) can also be blocked by a terminal blocking agent such as a monoamine, an acid anhydride, an acid chloride or a monocarboxylic acid. By dissolving the end of the resin through a blocking agent having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group or an allyl group, the dissolution rate of the resin to the alkaline aqueous solution can be easily adjusted. To the best range. The blocking agent is preferably used in an amount of 0.1 to 60 mol%, more preferably 5 to 50 mol%, based on the total amine component of the resin.

The resin having the structure represented by the general formula (1) can be produced in accordance with a known method for producing a polyimide precursor. Examples thereof include: (I) a tetracarboxylic dianhydride having R ¹ group with a compound having the R ² group is a diamine, an amine compound as a single method of capping agent under low temperature conditions of the reaction; (II) having a through a method of reacting a diamine compound having an R ² group with a monoamine compound as a blocking agent in the presence of a condensing agent after obtaining a diester of an R ¹ -based tetracarboxylic dianhydride with an alcohol; (III) A method in which a dicarboxylic acid having an R ¹ group and an alcohol are used to obtain a diester, and then the remaining two carboxyl groups are chlorinated to react a diamine compound having an R ² group with a monoamine compound as a blocking agent. Wait. The resin obtained by the above-mentioned method is preferably added to a large amount of water or a mixed liquid of methanol or water, precipitated, and dried by filtration, and is preferably isolated. By removing the oligomer component such as an unreacted monomer or a dimer or a trimer by this precipitation operation, the film characteristics after heat curing are improved. Further, the polyimine which is obtained by subjecting the ruthenium imide of the polyimine precursor to ring closure can be synthesized by a known ruthenium imidization reaction after the obtained polyimide precursor is obtained. .

Hereinafter, an example of the method for producing a polyimide precursor will be described with reference to a preferred example of (I). First, a diamine compound having an R ² group is dissolved in a polymerization solvent. A tetracarboxylic dianhydride having an R ¹ group substantially equivalent to the diamine compound is slowly added to the solution. The mixture is stirred at -20 to 100 ° C, preferably 10 to 50 ° C for 0.5 to 100 hours, more preferably for 2 to 24 hours using a mechanical stirrer. In the case of using a blocking agent, after adding tetracarboxylic dianhydride, after stirring at a desired temperature and a required time, a terminal blocking agent can be added slowly, and it can also add it in one time.

The polymerization solvent is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride and the diamine as the raw material monomers. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone amides; γ-butyrolactone, γ-pentyl Lactone, δ-pentyl Cyclic esters such as lactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone; carbonates such as ethyl carbonate and propyl carbonate; triethylene glycol, etc. Glycols; phenols such as m-cresol and p-cresol; acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclobutane, methyl sulfoxide, and the like. The polymerization solvent is preferably used in an amount of from 100 to 1900 parts by weight, more preferably from 150 to 950 parts by weight, per 100 parts by weight of the obtained resin.

The photosensitive resin composition of the present invention may contain an alkali-soluble resin other than the resin having the structure represented by the formula (1). Specifically, an alkali-soluble polybenzoate is exemplified. Oxazole, polybenzo An azole precursor, a polyamine, an acrylic polymer obtained by copolymerizing acrylic acid, a novolac resin, a resol resin, a decyl olefin resin, a polyhydroxystyrene resin, and a methylol or an alkane introduced therein a resin of a crosslinking group such as an oxymethyl group or an epoxy group, or a copolymer thereof. Such a resin is an aqueous solution dissolved in a base such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide or sodium carbonate. By. By containing such an alkali-soluble resin, the properties of each alkali-soluble resin can be imparted while maintaining the adhesion of the heat-resistant resin film or the excellent sensitivity. Among the resins contained in the photosensitive resin composition of the present invention, the resin containing the structure represented by the general formula (1) is preferably 30% by weight or more.

Next, the photosensitive resin composition having positive photosensitive properties of the present invention will be described, but the scope of the present invention is not limited thereto. When a photosensitive resin composition having a negative photosensitive property which is reacted by the exposure portion during development is used, when a polyimide having a low transparency is used, the photoreaction efficiency of the photosensitive agent in the exposed portion is deteriorated to leave a film. The rate becomes lower and becomes It is difficult to obtain a thick film structure. Therefore, it is necessary to develop a polyimide having high transparency similar to the positive type for the photosensitive resin composition having high sensitivity.

The photosensitive resin composition having a positive photosensitive property of the present invention contains (a) a resin having a structure represented by the formula (8) as a main component, (b) a photoacid generator, and (c) a solvent. Here, the main component means that the structure represented by the formula (8) in the resin having the structure represented by the formula (8) exhibits 50 mol% or more, preferably 70 mol% or more, more preferably 90. More than Mole.

(In the formula (8), R ¹ each independently contains an alicyclic structure selected from a monocyclic or condensed polycyclic ring when the total amount of R ¹ is 100% by mole to 5 to 95 mol%. a tetravalent organic group having 6 to 40 carbon atoms, an organic group having a monocyclic alicyclic structure, or a tetravalent organic group having 6 to 40 carbon atoms directly or through a crosslinked structure, and having an alicyclic ring at the same time carbon atoms in a ring structure of semi-aliphatic structure and an aromatic ring, a tetravalent organic group having 6 to 40 in the one or more organic groups; R & lt ^two lines each independently represent a carbon number of the divalent organic group having 2 to 40; R ³ lines It represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms; m and n each represent a range of 0 to 100,000 and m+n>2, wherein the structure represented by the formula (8) must have a fluorine component and a phenolic hydroxyl group. .)

The photosensitive resin composition having a positive photosensitive property of the present invention is preferably a resin to which the photosensitive resin composition of the present invention described above is applied, and may contain two or more of these.

The photosensitive resin composition having a positive photosensitive property of the present invention may contain other alkali-soluble resins in addition to the resin having a structure represented by the general formula (8) as a main component. Specifically, an alkali-soluble polybenzoate is exemplified. Oxazole, polybenzo An azole precursor, a polyamine, an acrylic polymer obtained by copolymerizing acrylic acid, a novolac resin, a resol resin, a decyl olefin resin, a polyhydroxystyrene resin, and a methylol or an alkane introduced therein a resin of a crosslinking group such as an oxymethyl group or an epoxy group, or a copolymer thereof. Such a resin is an aqueous solution dissolved in a base such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide or sodium carbonate. By. By containing such an alkali-soluble resin, the properties of each alkali-soluble resin can be imparted while maintaining the adhesion of the heat-resistant resin film or the excellent sensitivity.

The photoacid generator of the component (b) of the present invention is a compound which imparts an acid to light irradiation to increase the solubility of the light-irradiating portion in the alkaline aqueous solution, and has a quinonediazide compound, a phosphonium salt, a phosphonium salt, Diazonium salt, barium salt, and the like.

The quinonediazide compound may be one in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound by an ester, and a sulfonic acid of a quinonediazide is bonded to a polyamine compound by a sulfonamide. The quinonediazide sulfonic acid is ester-bonded and/or sulfonamide bonded to a polyhydroxypolyamine compound. All of the functional groups of these polyhydroxy compounds or polyamine-based compounds may be substituted without quinonediazide, but it is preferred to substitute 50 mol% or more of the entire functional group with quinonediazide. If it is less than 50% by mole, the solubility in the alkali developing solution may become too high, and comparison with the unexposed portion may not be obtained, and a desired pattern may not be obtained. By using such a quinonediazide compound, an i-line which is a mercury lamp as a general ultraviolet ray can be obtained. (365 nm), h-line (405 nm), g-line (436 nm) photosensitive positive photosensitive resin composition. Such a compound can be used singly or in combination of two or more kinds. Moreover, by using two kinds of photoacid generators, the ratio of the dissolution rate of the large exposed portion to the unexposed portion can be obtained, and thus a highly sensitive photosensitive resin composition can be obtained.

Examples of the polyhydroxy compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-B P, TML-HQ , TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above is the trade name, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A46DMOC, 46DMOEP, TM-BIP-A (above, trade name, Asahi Organic Industry Co., Ltd.), 2,6-Dimethoxymethyl-4-tributylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethyloxymethyl-p-cresol, naphthol , tetrahydroxydiphenyl ketone, methyl gallate, bisphenol A, bisphenol E methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc., but not limited to such .

Examples of the polyamine-based compound include 1,4-phenylenediamine and 1,3-benzene. Amine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylanthracene, 4,4'-diaminodiyl Phenyl sulfide, etc., but is not limited to this.

Further, examples of the polyhydroxy polyamine-based compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto.

In the present invention, the quinonediazide system may preferably be any one of a 5-naphthoquinonediazidesulfonyl group and a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonate compound has absorption in the i-line region of the mercury lamp and is suitable for i-line exposure. The 5-naphthoquinonediazide sulfonate compound absorbs and elongates until it reaches the g-line region of the mercury lamp, and is suitable for g-line exposure. In the present invention, a 4-naphthoquinonediazide sulfonate compound or a 5-naphthoquinonediazide sulfonate compound is preferably selected depending on the wavelength of exposure. Further, a naphthoquinonediazide sulfonate compound in which 4-naphthoquinonediazidesulfonyl group and 5-naphthoquinonediazidesulfonyl group are used together in the same molecule can be obtained, or 4-naphthoquinone II can also be mixed. The azidosulfonate compound is used with a 5-naphthoquinonediazide sulfonate compound.

Further, when the molecular weight of the quinonediazide compound is larger than 5,000, the quinonediazide compound is incompletely thermally decomposed in the subsequent heat treatment, and the obtained film has low heat resistance, low mechanical properties, and low adhesiveness. The possibility of waiting for the problem. From such a viewpoint, the preferred quinonediazide compound has a molecular weight of from 300 to 3,000, more preferably from 350 to 1,500.

The quinonediazide compound used in the present invention can be synthesized from a specific phenol compound by the following method. Can be cited For example, a method of reacting 5-naphthoquinonediazidesulfonium chloride with a phenol compound in the presence of triethylamine. The method for synthesizing the phenol compound is, for example, a method of reacting an α-(hydroxyphenyl)styrene derivative with a polyhydric phenol compound under an acid catalyst.

Among the photoacid generators used as the component (b) of the present invention, the photoacid generator which moderately stabilizes the acid component generated by the exposure is an antimony salt, a phosphonium salt or a diazonium salt. good. In order to use the resin composition obtained from the photosensitive resin composition of the present invention as a permanent film, the residual of phosphorus or the like is not preferable in the environment, and the color tone of the film must also be considered. Therefore, it is preferable to use 鋶 among them. salt. As a particularly preferred one, a triarylsulfonium salt can be cited.

When the photosensitive resin composition of the present invention contains (b) a photoacid generator, an acid is generated in the light-irradiating portion, and the solubility of the light-irradiating portion in the alkaline aqueous solution is increased, whereby the light-irradiating portion can be dissolved. Positive pattern.

In the present invention, the content of the photoacid generator used as the component (b) is preferably 0.01% by weight based on 100 parts by weight of the resin (a) having the structure represented by the formula (8) as a main component. 50 parts by weight. Among them, the quinonediazide compound is preferably in the range of 3 to 40 parts by weight. Further, the compound selected from the group consisting of a phosphonium salt, a phosphonium salt, and a diazonium salt is preferably in the range of 0.05 to 40 parts by weight, and more preferably in the range of 0.1 to 30 parts by weight. By making the content of the (b) photoacid generator within this range, higher sensitivity can be obtained. Further, a sensitizer or the like may be optionally contained.

Moreover, in order to improve the sensitivity of the photosensitive resin composition, it is possible to reduce the shrinkage ratio after curing as needed. Contains a compound having a phenolic hydroxyl group.

The compound having a phenolic hydroxyl group may, for example, be Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP- EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (TetrakisP-DO-BPA), TrisP-HAP, TrisP -PA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP , Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP, (above, trade name, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (above, trade name, Asahi Organic Industry Co., Ltd.).

Among these, preferred compounds having a phenolic hydroxyl group used in the present invention are, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP- MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR- PTBP, BIR-BIPC-F, etc. Among these, particularly preferred compounds having a phenolic hydroxyl group are, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F. By containing the compound having a phenolic hydroxyl group, the obtained resin composition is exposed It is hardly dissolved in the alkali developing solution before the light, and can be easily dissolved in the alkali developing solution upon exposure, so that the film loss due to development is reduced and development is easy in a short time.

The content of the phenolic hydroxyl group-containing compound is preferably from 1 to 50 parts by weight, more preferably from 3 to 50 parts by weight based on 100 parts by weight of the resin represented by the formula (8). ~40 parts by weight range.

The photosensitive resin composition having a positive photosensitive property of the present invention contains (c) a solvent, and examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, and N,N-dimethyl a polar aprotic solvent such as carbamide, N,N-dimethylacetamide or dimethyl hydrazine; tetrahydrofuran, Ethers such as alkane and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone and diacetone; ethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy An ester such as methyl propionate, 3-ethoxyethyl propionate, ethyl acetate or ethyl lactate; an aromatic hydrocarbon such as toluene or xylene; and the like. Two or more such compounds may also be contained. (c) The content of the solvent is preferably 100 parts by weight or more and 1500 parts by weight or less based on 100 parts by weight of the resin having the structure represented by the formula (8) as a main component.

The photosensitive resin composition having a positive photosensitive property of the present invention may contain a component other than the above (a) to (c), and preferably contains a compound having an alkoxymethyl group, a methylol group or an epoxy group. Since the methylol group and the alkoxymethyl group generate a crosslinking reaction in a temperature range of 100 ° C or higher, crosslinking can be carried out by heat treatment, whereby a heat resistant resin film having excellent mechanical properties can be obtained.

In the case of an alkoxymethyl group or a hydroxymethyl group, For example: DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC , DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL , TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP , HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, trade name, Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (above, trade name, Sanwa Chemical Co., Ltd.). Among them, in the case where HMOM-TPHAP or MW-100LM containing a plurality of alkoxymethyl groups is added, crosslinking efficiency is good, which is preferable.

Further, since the epoxy group is thermally crosslinked with the polymer at 200 ° C or lower, since the dehydration reaction due to crosslinking does not occur, the film shrinkage is less likely to occur, so that in addition to mechanical properties, low temperature hardening and low warpage are caused. It is also quite effective. Examples of the compound having an epoxy group include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a propylene glycol diepoxypropyl ether, a polypropylene glycol diepoxypropyl ether, and a polymethyl group. An epoxy group-containing polyfluorene or the like such as (glycidoxypropyl) azide or the like, but the present invention is not limited to these. Specifically, EPICLON850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLONHP-820 , EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-859CRP, EPICLONEXA-1514, EPICLON EXA-4880, EPICLON EXA-4850-150, EPICLON EXA-4850-1000, EPICLON EXA-4816, EPICLON EXA-4822 (above is the trade name, Dainippon Ink Chemical Industry Co., Ltd.), RIKARESIN BEO-60E (trade name below, New Japan Physical and Chemical Co., Ltd.), EP-4003S, EP-4000S (ADEKA (share)) Wait.

Two or more of these compounds having an alkoxymethyl group, a methylol group or an epoxy group may also be contained.

The content of the compound having an alkoxymethyl group, a methylol group or an epoxy group is 10 to 50 parts by weight, preferably 10 parts by weight based on 100 parts by weight of the resin containing the structure represented by the above formula (8) as a main component. ~40 parts by weight.

The photosensitive resin composition of the present invention may further contain a decane compound. The adhesion of the heat resistant resin film is improved by containing a decane compound. Specific examples of the decane compound include N-phenylaminoethyltrimethoxydecane, N-phenylaminoethyltriethoxydecane, and N-phenylaminopropyltrimethoxy. Decane, N-phenylaminopropyltriethoxydecane, N-phenylaminobutyltrimethoxydecane, N-phenylaminobutyltriethoxydecane, vinyltrimethoxydecane, Vinyl triethoxy decane, vinyl trichloro decane, vinyl ginseng (β-methoxyethoxy) decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-propenyl methoxy group Propyltrimethoxydecane, p-styryltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxy Decane and so on. Containing decane compounds The amount is preferably 0.01 parts by weight or more and 15 parts by weight or less based on 100 parts by weight of the resin containing (a) the structure represented by the formula (8) as a main component.

Further, the photosensitive resin composition having a positive photosensitive property of the present invention may optionally contain a surfactant, ethyl lactate or propylene glycol monomethyl ether for the purpose of improving the coating property with the substrate. Esters such as esters; alcohols such as ethanol; ketones such as cyclohexanone and methyl isobutyl ketone; tetrahydrofuran, An ether such as an alkane. In addition, inorganic particles such as cerium oxide or titanium dioxide or powders of polyimine may be contained for the purpose of suppressing the thermal expansion coefficient, high capacitance, and low capacitance.

Next, a method of producing the photosensitive resin composition of the present invention will be exemplified. The method of adding the components of the above (a) to (c) and other components added as needed to a glass flask or a stainless steel vessel and stirring and dissolving it by a mechanical stirrer or the like A method of dissolving a sound wave, a method of stirring and dissolving by a planetary stirring defoaming device, and the like. The viscosity of the positive photosensitive resin composition is preferably from 1 to 10,000 mPa. s. Further, in order to remove foreign matter, the photosensitive resin composition may be filtered through a filter having a pore size of 0.1 μm to 5 μm.

Next, a method of forming a pattern of a heat resistant resin film using the photosensitive resin composition of the present invention will be described.

The photosensitive resin body composition of the present invention can be formed into a pattern of polyimine by a step of coating on a support substrate and drying, a step of exposure, a step of developing, and a step of heat treatment.

First, a photosensitive resin composition is coated on a substrate. As the substrate, a germanium wafer, a ceramic, a gallium arsenide, a metal, a glass, a metal oxide insulating film, tantalum nitride, ITO, or the like can be used, but is not limited thereto. Coating The method may be a method of spin coating, spray coating, roll coating, slit die coating, or the like using a spinner. The coating film thickness varies depending on the coating method, the solid content concentration of the positive photosensitive resin composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 μm.

Next, the substrate on which the photosensitive resin composition is applied is dried to obtain a photosensitive resin film. The drying system uses an oven, a hot plate, infrared rays, etc., and is preferably carried out in the range of 50 ° C to 150 ° C for 1 minute to several hours.

Next, an actinic ray is irradiated onto the photosensitive resin film by a mask having a desired pattern. Examples of the actinic rays used for the exposure include ultraviolet rays, visible rays, electron rays, X-rays, and the like. However, in the present invention, i-line (365 nm), h-line (405 nm), and g-line (436 nm) using a mercury lamp are used. ) is better.

In order to form a pattern from the photosensitive resin film, it is only necessary to remove the exposed portion using a developing solution after exposure. The developing solution is preferably tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine or acetic acid. Methylaminoethyl ester, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, etc. An aqueous solution of the compound. Depending on the case, one or more N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide may be added to the alkaline aqueous solution. , polar solvent such as dimethyl hydrazine, γ-butyrolactone, dimethyl acrylamide; alcohols such as methanol, ethanol, isopropanol; ethyl lactate, propylene glycol monomethyl ether acetate And other esters; ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone. After development, it is usually rinsed with water. In the rinsing treatment, one or more of an alcohol such as ethanol or isopropyl alcohol, an ester such as ethyl lactate, propylene glycol monomethyl ether acetate or 3-methoxymethyl propionate may be added to the water.

After the development, a temperature of 150 ° C to 500 ° C is applied to convert into a heat resistant resin film. This heat treatment is carried out by stepwise temperature rise at a selected temperature or 5 minutes to 5 hours while continuously increasing the temperature in a certain temperature range. As an example, a method of heat-treating for 30 minutes at 130 ° C, 200 ° C, and 350 ° C is used, and a method of linearly raising the temperature from room temperature to 320 ° C for 2 hours is used. Further, with the heating at a high temperature or the repetition thereof, there is a possibility that the electrical characteristics of the element may change or the warpage of the substrate may become large. Therefore, it is preferable to carry out the heat treatment at 250 ° C or lower.

The heat resistant resin film formed of the photosensitive resin composition of the present invention can be used for an electronic component such as a semiconductor device or a multilayer wiring board. Specifically, it is applied to a passivation film of a semiconductor, a surface protective film of a semiconductor element, an interlayer insulating film, an interlayer insulating film of a multilayer wiring for high-density packaging, an insulating layer of an organic electroluminescent device, or the like, but is not limited thereto. , can use a variety of structures.

Next, an application example of a semiconductor device having bumps using the photosensitive resin composition of the present invention will be described using a drawing. Fig. 1 is an enlarged cross-sectional view showing a pad portion of a semiconductor device having bumps of the present invention. As shown in FIG. 1, in the wafer 1, a passivation film 3 is formed on the Al pad 2 for input and output, and a via hole is formed in the passivation film 3. Further, a pattern (insulating film) 4 using the photosensitive resin composition of the present invention is formed thereon, and a metal (Cr, Ti, etc.) film 5 is formed to be connected to the Al pad 2, and the metal film 5 is etched. The periphery of the bump 10 is used to insulate between the pads. The barrier metal 8 and the solder bumps 10 are formed in the insulated pads. When the soft component is introduced into the photosensitive resin composition, the warpage of the wafer is small, so that exposure or wafer conveyance can be performed with high precision. Further, since the polyimide resin has excellent mechanical properties, the stress from the sealing resin can be alleviated during packaging, so that damage of the low-k layer can be prevented, and a highly reliable semiconductor device can be provided.

Next, a detailed method of manufacturing the semiconductor device will be described. As shown by 2c in Fig. 2, the metal wiring 6 is formed by a plating method. Next, as shown in 2d' of Fig. 2, the photosensitive resin composition of the present invention is applied, and a pattern (insulating film 7) of 2d as shown in Fig. 2 is formed through a photolithography step. At this time, the photosensitive resin composition of the insulating film 7 is subjected to thick film processing on the scribe line 9. In the case of forming a multilayer wiring structure of three or more layers, the above steps can be repeated to form each layer. Since the multilayer wiring structure has a repeating insulating film formation, the total thickness of the interlayer insulating film is 10 μm or more, and is preferably 50 μm or less from the influence of warpage on the wafer or the like. The more the multilayer wiring structure is formed, the thicker the dicing process is required. Therefore, the photosensitive resin composition is preferably a heat-resistant resin film which can be patterned to have a film thickness of 10 μm or more. Moreover, in order to form a high-density multilayer wiring structure, it is preferable to obtain a high-resistance heat-resistant resin film. Next, as shown in 2e and 2f of FIG. 2, the barrier metal 8 and the bump bump 10 are formed. Moreover, cutting is performed along the last scribe line 9 and cut into each wafer. Insulation When the film 7 is not patterned or the residue remains, the film 7 is cracked during the cutting, which affects the reliability evaluation of the wafer. Therefore, in order to obtain high reliability of the semiconductor device, it is very good to provide excellent pattern processing for thick film processing as in the present invention.

[Examples]

The present invention will be described by way of examples and the like, but the invention is not limited thereto. Further, the evaluation of the resin and the photosensitive resin composition in the examples was carried out according to the following method.

(Method for measuring film thickness)

Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. was used to measure the film thickness after prebaking, after development, and after hardening at a refractive index of 1.629.

(production of developing film A)

A varnish was spin-coated on an 8-inch wafer, and then baked at a heating plate of 120 ° C (using a coating and developing device Act-8 manufactured by TOKYO ELECTRON Co., Ltd.) for 3 minutes to prepare a pre-baked film having a thickness of 10 μm. . I-line stepper (NIKON NSR i9), at the exposure amount of 0 ~ 1000mJ / cm ² to 10mJ / cm ² step from this film is exposed. After the exposure, development was carried out with a 2.38 wt% aqueous solution of tetramethylammonium (TMAH) (manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM-D) for 90 seconds, followed by rinsing with pure water to obtain an isolated pattern having 10 μm. Developing film A.

(1) Sensitivity evaluation

The exposure amount (referred to as the minimum exposure amount Eth) in which the exposed portion of the developing film A is completely eluted and disappeared after exposure and development is determined as the sensitivity. When Eth is 400 mJ/cm ² or less, it can be judged to be high sensitivity, and more preferably 300 mJ/cm ² or less.

(2) Evaluation of residual film rate

The ratio of the film thickness of the developing film to the pre-baked film was the residual film ratio (residual film ratio = (film thickness of developing film) / (film thickness of pre-baked film) × 100), and 80% or more was determined to be acceptable.

(3) Pattern evaluation of the developing film

The surface of the photosensitive resin composition film formed by the development was visually observed for the viscosity of the unexposed portion and the residue of the exposed portion. When the pattern of the developing film was not problematic, it was judged to be good (○), and it was judged to be defective (×) in the case where the unexposed portion was sticky or the residue was generated in the exposed portion.

(Production of heat-resistant resin film B)

The varnish was spin-coated on an 8-inch wafer, and then baked on a hot plate at 120 ° C (using a coating and developing device Act-8 manufactured by TOKYO ELECTRON Co., Ltd.) for 3 minutes to prepare pre-baked films having different film thicknesses. This film was exposed at an exposure amount of 1000 mJ/cm ² using an i-line stepper (Nikon NSR i9). After the exposure, it was developed with a 2.38 wt% aqueous solution of tetramethylammonium (TMAH) (manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM-D) for 90 seconds, followed by rinsing with pure water to obtain a developing film. The developed film was heated to 250 ° C at 5 ° C / min under an oxygen concentration of 20 ppm or less using Inert Oven CLH-21 CD-S (manufactured by KOYO THERMO SYSTEMS Co., Ltd.), and heat-treated at 250 ° C for 1 hour. After the temperature reached 50 ° C or lower, the ruthenium wafer was taken out, and the film thickness of the heat resistant resin film on the ruthenium wafer was measured.

(4) Thick film formation evaluation

For the heat-resistant resin film, the exposed portion is completely dissolved and disappears The maximum film thickness at the time of forming a pattern (referred to as a processable pattern) was evaluated. The film-formed heat-resistant resin film having a film thickness of 15 μm or more is determined to be good (?), and a heat-resistant resin film having a pattern of 10 μm or more and less than 15 μm is obtained to be slightly good (○). The film-processed heat-resistant resin film of less than 10 μm was determined to be defective (×).

(5) Resolution evaluation

The minimum opening pattern size was measured for a heat-resistant resin film having a film thickness of 10 μm, and the resolution was determined. When the resolution is less than 3 μm, it is excellent (?), 3 μm or more and less than 7 μm is good (○), 7 μm or more and less than 10 μm is set to be slightly good (Δ), and 10 μm or more is not available. The heat resistant resin film having a film thickness of 10 μm was determined to be defective (×).

The names of the abbreviations of acid dianhydride and diamine in the examples and comparative examples are as follows.

PMDA-HH: 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride

TDA100: 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-di-oxo-3-furanyl)naphtho[1,2-c]furan-1,3- Diketone

CBDA: cyclobutane tetracarboxylic dianhydride

6FDA: 4,4'-hexafluoroisopropylidene dicarboxylate dianhydride

ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride

SiDA: 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)dioxane

BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

APBS: bis(3-amino-4-hydroxyphenyl)indole

DAE: 4,4'-diaminodiphenyl ether

NMP: N-methyl-2-pyrrolidone

ED-600: JEFFAMINE ED-600 (trade name, HUNTSMAN (share) system)

KBM-403: 3-glycidoxypropyltrimethoxydecane.

The thermally crosslinkable compound used in each of the examples and the comparative examples is shown below.

Synthesis Example 1 Synthesis of Hydroxyl-Containing Diamine Compound (a)

18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone, 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 °C. Here, a solution obtained by dissolving 20.4 g (0.11 mol) of 3-nitrobenzhydryl chloride in 100 mL of acetone was added dropwise. After the completion of the dropwise addition, the mixture was allowed to react at -15 ° C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered and dried under vacuum at 50 °C.

30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl sarcolo, and 2 g of 5% palladium-carbon was added. Here, hydrogen is introduced into a balloon, and a reduction reaction is carried out at room temperature. After about 2 hours, it was confirmed that the balloon was no longer deflated and the reaction was terminated. After completion of the reaction, filtration was carried out to remove the palladium compound as a catalyst, and the mixture was concentrated by a rotary evaporator to obtain a hydroxyl group-containing diamine compound (a) represented by the following formula. The obtained solid was directly used for the reaction.

Synthesis Example 2 Synthesis of Bismuth Azide Compound (b)

21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.86 g (0.10 mol) of 5-naphthoquinonediazide sulfonium chloride under a stream of dry nitrogen gas 13.43 g (0.05 mol) of 4-naphthoquinonediazidesulfonium chloride dissolved in 50 g of 1,4-di In the alkane, it is made to room temperature. In the system, it does not become 35 ° C or more, and drops 50 g of 1,4-two here. 15.18 g of alkane mixed triethylamine. After dripping, it was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the precipitate precipitated was collected by filtration, and the precipitate was dried in a vacuum dryer to obtain a quinonediazide compound (b) represented by the following formula.

Synthesis Example 3 Synthesis of Bismuth Azide Compound (c)

Dissolve 15.31 g (0.05 mol) of TrisP-HAP (trade name, manufactured by Honshu Chemical Co., Ltd.) and 5-naphthoquinonediazide sulfonium chloride 40.28 g (0.15 mol) under a stream of dry nitrogen gas. 450g of 1,4-two In the alkane, it is made to room temperature. Use with 1,4-two of 50g 15.18 g of an alkane-mixed triethylamine was obtained in the same manner as in Synthesis Example 2 to obtain a quinonediazide compound (c) represented by the following formula.

Synthesis Example 4 Synthesis of Bismuth Azide Compound (d)

In a dry nitrogen gas stream, 28.83 g (0.05 mol) of TekP-4HBPA (trade name, manufactured by Honshu Chemical Co., Ltd.) and 13.43 g (0.125 mol) of 5-naphthoquinonediazidesulfonium chloride were dissolved in 450g of 1,4-two In the alkane, it is made to room temperature. Use with 1,4-two of 50g 20.24 g of a triethylamine mixed with an alkane was carried out in the same manner as in Synthesis Example 2 to obtain a quinonediazide compound (d) represented by the following formula.

Synthesis Example 5 Synthesis of Acrylic Resin (e)

A 500 ml flask was charged with 5 g of 2,2'-azobis(isobutyronitrile), 5 g of tertiary dodecanethiol, and 150 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA). Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, 35 g of tricyclo [5.2.1.0 ^2,6 ] 癸-8-ester of methacrylate were charged, and stirred at room temperature for a while in the flask. After nitrogen substitution, the mixture was heated and stirred at 70 ° C for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the obtained solution, and the mixture was heated and stirred at 90 ° C for 4 hours to obtain an alkali-soluble acrylic acid. Resin (e) solution. The solid content concentration of the acrylic resin solution (e) was 43% by weight.

Synthesis Example 6 Synthesis of Novolak Resin (f)

Under a dry nitrogen gas stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 75.5 g (formaldehyde 0.93 mol) of 37 wt% formaldehyde solution, 0.63 g of oxalic acid dihydrate were charged. After 264 g of (0.005 mol) and methyl isobutyl ketone, the mixture was immersed in an oil bath, and a polycondensation reaction was carried out for 4 hours while refluxing the reaction liquid. After that, it takes 3 hours to warm the oil bath. After the temperature was raised, the pressure in the flask was reduced to 40 to 67 hPa, the volatile matter was removed, and the dissolved resin was cooled to room temperature to obtain a polymer solid of the alkali-soluble novolak resin (f). The Mw obtained by GPC was 3,500. Γ-butyrolactone (GBL) was added to the obtained novolac resin (f) to obtain a novolak resin (f) solution having a solid content concentration of 43% by weight.

Synthesis Example 7 Polybenzoic Acid Synthesis of azole precursor (g)

Under a dry stream of nitrogen, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP, 26.4 g (0.3 mol) of propylene glycol methyl ether, and the temperature of the solution was cooled to -15 °C. A solution obtained by dissolving 14.7 g of diphenylether dicarboxymethyl chloride (manufactured by Nippon Pesticide Co., Ltd., 0.050 mol) in 25 g of GBL was dropped thereto so that the internal temperature did not exceed 0 °C. After the completion of the dropwise addition, stirring was continued at -15 ° C for 6 hours. After completion of the reaction, the solution was poured into 3 L of water containing 10% by weight of methanol to precipitate a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain an alkali-soluble polybenzobenzene. Azole precursor (g). The obtained polybenzoic acid GBL was added to the azole precursor (g) to obtain a polybenzoic acid having a solid content concentration of 43% by weight. Azole precursor (g) solution.

Synthesis Example 8 Synthesis of Polyhydroxystyrene (h)

Into a mixed solution of 500 ml of tetrahydrofuran as a starter, a total of 20 g of p-tert-butoxystyrene and styrene were added in a molar ratio of 3:1. Hour, and make it aggregate. 0.1 mol of methanol was added to the reaction solution, and polymerization was terminated to terminate the reaction. Next, in order to purify the polymer, the reaction mixture was poured into methanol, and the precipitated polymer was dried to obtain a white polymer. Further dissolved in 400 ml of acetone, a small amount of concentrated hydrochloric acid was added at 60 ° C After stirring for 7 hours, it is poured into water to precipitate a polymer, and the tertiary styrene styrene is deprotected and converted into hydroxystyrene, which is washed and dried to obtain purified p-hydroxystyrene and styrene. Copolymer (h).

Example 1

15.57 g (0.04 mol) of BAHF and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP under a stream of dry nitrogen. 1.12 g (0.005 mol) of PMDA-HH and 19.99 g (0.045 mol) of 6FDA were added thereto together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the closed-loop polyimine resin (A).

17.5 g of the obtained resin (A), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the acrylic resin (e) obtained in Synthesis Example 5, and 3.0 g of a crosslinking agent MX-270 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish A of a positive photosensitive resin composition. The obtained varnish A was used and subjected to sensitivity evaluation, residual film rate evaluation, pattern evaluation of a developing film, thick film formability evaluation, and resolution evaluation as described above. The evaluation results are shown in Table 2.

Example 2

11.90 g (0.03 mol) of BAHF, 2.0 g (0.01 mol) of DAE, and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP under a stream of dry nitrogen. 10.09 g (0.045 mol) of PMDA-HH and 2.22 g (0.005 mol) of 6FDA were added thereto together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. Stir After the end, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the closed-loop polyimine resin (B).

17.5 g of the obtained resin (B), 2.3 g of the quinonediazide compound (c) obtained in Synthesis Example 3, 16 g of the novolak resin (f) obtained in Synthesis Example 6, and 3.0 g of a crosslinking agent MX270, 1.0 g of KBM403 was added to 50 g of GBL to obtain a varnish B of a positive photosensitive resin composition. The obtained varnish B was used and subjected to sensitivity evaluation, residual film rate evaluation, pattern evaluation of the developed film, evaluation of thick film formation, and resolution evaluation as described above. The evaluation results are shown in Table 2.

Example 3

Under a dry nitrogen gas stream, 25.68 g (0.04 mol) and 0.62 g (0.003 mol) of SiDA of the compound (a) obtained in Synthesis Example 1 were dissolved in 100 g of NMP. 4.48 g (0.02 mol) of PMDA-HH and 9.31 g (0.03 mol) of ODPA were added thereto together with 10 g of NMP, and allowed to react at 40 ° C for 1 hour. Thereafter, a solution of 13.10 g (0.11 mol) of N,N-dimethylformamide dimethyl acetal diluted with 15 g of NMP was added dropwise over 10 minutes. After dripping, it was stirred at 40 ° C for 1 hour. After the reaction was completed, the solution was poured into 2 L of water, and a precipitate of the solid was collected by filtration. The resin solid was dried in a vacuum dryer at 50 ° C for 72 hours to obtain a resin (C) of a polyimide precursor.

17.5 g of the obtained resin (C), 2.3 g of the quinonediazide compound (d) obtained in Synthesis Example 4, and polyphenylene obtained in Synthesis Example 7. 16 g of the azole resin (g), 3.0 g of the crosslinking agent HMOM-TPHAP, and 1.0 g of KBM-403 were added to 50 g of GBL to obtain a varnish C of a positive photosensitive resin composition. The obtained varnish C was used and subjected to sensitivity evaluation, residual film rate evaluation, pattern evaluation of the developed film, evaluation of thick film formation, and resolution evaluation as described above. The evaluation results are shown in Table 2.

Example 4

11.91 g (0.04 mol) of APBS and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP under a stream of dry nitrogen. 4.48 g (0.02 mol) of PMDA-HH and 13.33 g (0.03 mol) of 6FDA were added thereto together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the closed-loop polyimine resin (D).

17.5 g of the obtained resin (D), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the polyhydroxystyrene resin (h) obtained in Synthesis Example 8, and 3.0 g of a crosslinking agent MX-270 and 1.0 g of KBM-403 were added to 50 g of GBL to obtain a varnish D of a positive photosensitive resin composition. The obtained varnish D was used and subjected to sensitivity evaluation, residual film rate evaluation, pattern evaluation of the developed film, evaluation of thick film formation, and resolution evaluation as described above. The evaluation results are shown in Table 2.

Example 5

11.91 g (0.04 mol) of APBS and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP under a stream of dry nitrogen. 6.01 g (0.02 mol) of TDA-100 and 13.33 g (0.03 mol) of 6FDA were added thereto together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. After the stirring is completed, the solution is put into 2L. A white precipitate was obtained in the water. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the polycyclic imide resin (E) which had been closed.

17.5 g of the obtained resin (E), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the acrylic resin (e) obtained in Synthesis Example 5, and 3.0 g of a crosslinking agent HMOM-TPHAP 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish E of a positive photosensitive resin composition. The obtained varnish E was used and subjected to sensitivity evaluation, residual film rate evaluation, pattern evaluation of the developed film, evaluation of thick film formation, and resolution evaluation as described above. The evaluation results are shown in Table 2.

Example 6

9.16 g (0.03 mol) of BAHF, 2.0 (0.01 mol) of DAE, 4.5 g (0.008 mol) of ED600, 0.62 g (0.003 mol) of SiDA were dissolved in 100 g under a stream of dry nitrogen. In NMP. 6.01 g (0.02 mol) of TDA-100 and 13.33 g (0.03 mol) of 6FDA were added thereto together with 10 g of NMP, and allowed to react at 40 ° C for 1 hour. Thereafter, a solution of 13.10 g (0.11 mol) of N,N-dimethylformamide dimethyl acetal diluted with 15 g of NMP was added dropwise over 10 minutes. After dripping, it was stirred at 40 ° C for 1 hour. After the reaction was completed, the solution was poured into 2 L of water, and a precipitate of the solid was collected by filtration. The resin solid was dried in a vacuum dryer at 50 ° C for 72 hours to obtain a resin (F) of a polyimide precursor.

17.5 g of the obtained resin (F), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the polyhydroxystyrene resin (h) obtained in Synthesis Example 8, and 3.0 g of a crosslinking agent HMOM-TPHAP, 1.0 g of KBM403 was added to 50 g of GBL to obtain a positive photosensitive resin composition. Varnish F of the object. The obtained varnish F was used and subjected to sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation as described above. The evaluation results are shown in Table 2.

Example 7

9.16 g (0.03 mol) of BAHF, 2.0 (0.01 mol) of DAE, 4.5 g (0.008 mol) of ED600, 0.62 g (0.003 mol) of SiDA were dissolved in 100 g under a stream of dry nitrogen. In NMP. 6.01 g (0.02 mol) of TDA-100 and 9.31 g (0.03 mol) of ODPA were added thereto together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water for 3 times, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the closed-loop polyimine resin (G).

17.5 g of the obtained resin (G), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the novolak resin (f) obtained in Synthesis Example 6, and 3.0 g of a crosslinking agent MX- 270 and 1.0 g of KBM-403 were added to 50 g of GBL to obtain a varnish G of a positive photosensitive resin composition. The obtained varnish G was used and subjected to sensitivity evaluation, residual film rate evaluation, pattern evaluation of the developed film, evaluation of thick film formation, and resolution evaluation as described above. The evaluation results are shown in Table 2.

Example 8

15.57 g (0.04 mol) of BAHF and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP under a stream of dry nitrogen. 6.01 g (0.02 mol) of TDA-100 and 13.33 g (0.03 mol) of 6FDA were added together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour. Stir at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the closed-loop polyimine resin (M).

17.5 g of the obtained resin (M), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, and polyphenylene obtained in Synthesis Example 7. 16 g of the azole resin (g), 3.0 g of the crosslinking agent MX-270, and 1.0 g of KBM-403 were added to 50 g of GBL to obtain a varnish M of a positive photosensitive resin composition. Using the obtained varnish M, the sensitivity evaluation, the residual film rate evaluation, the pattern evaluation of the developed film, the thick film formation evaluation, and the resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Example 9

9.16 g (0.03 mol) of BAHF, 2.0 (0.01 mol) of ED600, 9.0 g (0.015 mol) of ED600, and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g under a stream of dry nitrogen. In NMP. 6.01 g (0.02 mol) of TDA-100 and 13.33 g (0.03 mol) of 6FDA were added thereto together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the closed-loop polyimine resin (N).

17.5 g of the obtained resin (N), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the polyhydroxystyrene resin (h) obtained in Synthesis Example 8, and 3.0 g of a crosslinking agent HMOM-TPHAP, 1.0 g of KBM403 was added to 50 g of GBL to obtain a positive photosensitive resin composition. Varnish of the material N. The obtained varnish F was used and subjected to sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation as described above. The evaluation results are shown in Table 2.

Example 10

9.16 g (0.03 mol) of BAHF, 9.0 g (0.015 mol) of ED600, and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP under a stream of dry nitrogen. 8.97 g (0.05 mol) of PMDA-HH and 4.44 g (0.01 mol) of 6FDA were added thereto together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the closed-loop polyimine resin (O).

17.5 g of the obtained resin (O), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the acrylic resin (e) obtained in Synthesis Example 5, and 3.0 g of a crosslinking agent HMOM-TPHAP 1.0 g of KBM403 was added to 50 g of GBL to obtain a varnish O of a positive photosensitive resin composition. The obtained varnish O was used and subjected to sensitivity evaluation, residual film rate evaluation, pattern evaluation of the developed film, evaluation of thick film formation, and resolution evaluation as described above. The evaluation results are shown in Table 2.

Example 11

9.16 g (0.03 mol) of BAHF, 9.0 (0.015 mol) of ED600, and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP under a stream of dry nitrogen. 2.80 g (0.013 mol) of PMDA-HH and 16.66 g (0.037 mol) of 6FDA were added thereto together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. Stir After the end, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water for 3 times, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the closed-loop polyimine resin (P).

17.5 g of the obtained resin (P), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the novolac resin (f) obtained in Synthesis Example 6, and 3.0 g of a crosslinking agent HMOM- TPHAP and 1.0 g of KBM403 were added to 50 g of GBL to obtain a varnish N of a positive photosensitive resin composition. The obtained varnish N was used and subjected to sensitivity evaluation, residual film rate evaluation, pattern evaluation of the developed film, evaluation of thick film formation, and resolution evaluation as described above. The evaluation results are shown in Table 2.

Comparative example 1

15.57 g (0.04 mol) of BAHF and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP under a stream of dry nitrogen. 22.21 g (0.05 mol) of 6FDA was added thereto together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the closed-loop polyimine resin (H).

17.5 g of the obtained resin (H), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the acrylic resin (e) obtained in Synthesis Example 5, and 3.0 g of a crosslinking agent MX-270 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish H of a positive photosensitive resin composition. The obtained varnish H was used and subjected to sensitivity evaluation, residual film rate evaluation, pattern evaluation of the developed film, evaluation of thick film formation, and resolution evaluation as described above. The evaluation results are shown in Table 2.

Comparative example 2

15.57 g (0.04 mol) of BAHF and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP under a stream of dry nitrogen. 9.81 g (0.05 mol) of CBDA was added thereto together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the polyimine resin (I) which had been closed.

17.5 g of the obtained resin (I), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the acrylic resin (e) obtained in Synthesis Example 5, and 3.0 g of a crosslinking agent MX-270 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish I of a positive photosensitive resin composition. The obtained varnish I was used and subjected to sensitivity evaluation, residual film rate evaluation, pattern evaluation of the developed film, evaluation of thick film formation, and resolution evaluation as described above. The evaluation results are shown in Table 2.

Comparative example 3

Under a stream of dry nitrogen, 8.5 g (0.04 mol) of DAE, 0.62 g (0.003 mol) of SiDA was dissolved in 100 g of NMP. 11.21 g (0.05 mol) of PMDA-HH was added thereto together with 10 g of NMP, and allowed to react at 40 ° C for 1 hour. Thereafter, a solution of 13.10 g (0.11 mol) of N,N-dimethylformamide dimethyl acetal diluted with 15 g of NMP was added dropwise over 10 minutes. After dripping, it was stirred at 40 ° C for 1 hour. After the reaction was completed, the solution was poured into 2 L of water, and a precipitate of the solid was collected by filtration. The resin solid was dried in a vacuum dryer at 50 ° C for 72 hours to obtain a resin of the polyimide precursor (J).

17.5 g of the obtained resin (J), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the acrylic resin (e) obtained in Synthesis Example 5, and 3.0 g of a crosslinking agent MX-270 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish J of a positive photosensitive resin composition. Using the obtained varnish J, the sensitivity evaluation, the residual film rate evaluation, the pattern evaluation of the developed film, the thick film formation evaluation, and the resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Comparative example 4

15.57 g (0.04 mol) of BAHF and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP under a stream of dry nitrogen. 11.21 g (0.05 mol) of PMDA-HH was added thereto together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the closed-loop polyimine resin (K).

17.5 g of the obtained resin (K), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the acrylic resin (e) obtained in Synthesis Example 5, and 3.0 g of a crosslinking agent MX-270 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish K of a positive photosensitive resin composition. Using the obtained varnish K, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above, but since all of the development films were eluted, sensitivity could not be performed. Rating and pattern assessment. The results are shown in Table 2.

Comparative Example 5

11.91 g (0.04 mol) of APBS and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP under a stream of dry nitrogen. 15.01 g (0.05 mol) of TDA-100 was added thereto together with 10 g of NMP, and allowed to react at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of the closed-loop polyimine resin (L).

17.5 g of the obtained resin (L), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the acrylic resin (e) obtained in Synthesis Example 5, and 3.0 g of a crosslinking agent MX-270 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish L of a positive photosensitive resin composition. Using the obtained varnish L, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above, but since all of the development films were eluted, sensitivity could not be performed. Rating and pattern assessment. The results are shown in Table 2.

[Industrial availability]

According to the present invention, when a photosensitive resin composition is used, a resin having high sensitivity and residual film ratio can be obtained.

1‧‧‧矽 wafer

2‧‧‧Al pads

3‧‧‧passivation film

4‧‧‧Insulation film

5‧‧‧Metal (Cr, Ti, etc.) film

6‧‧‧Wiring (Al, Cu, etc.)

7‧‧‧Insulation film

8‧‧‧ barrier metal

9‧‧‧ cutting road

10‧‧‧ solder bumps

Claims (18)

a resin having a polyamine structure, a polyimine precursor structure or a polyimine structure, which contains 5 to 95 mol% when the total amount of the acid or its anhydride is 100 mol% The alicyclic structure having a carbon number of 6 to 40 is an acid having a carbon number of 6 to 40 and an acid of an alicyclic structure of an aromatic ring or an anhydride thereof. a resin having a structure represented by the general formula (1), In the formula (1), R ¹ each independently contains an alicyclic structure having a monocyclic or condensed polycyclic ring type, which is 5 to 95 mol % when the total amount of R ¹ is 100 mol%. a tetravalent organic group having 6 to 40 carbon atoms, an organic group having a monocyclic alicyclic structure, or a tetravalent organic group having 6 to 40 carbon atoms bonded directly or through a crosslinked structure, and having an alicyclic structure at the same time One or more organic groups of a tetravalent organic group having 6 to 40 carbon atoms in a half-alicyclic structure of an aromatic ring; R ² each independently represents a divalent organic group having 2 to 40 carbon atoms; and R ³ represents Hydrogen or a monovalent organic group having 1 to 20 carbon atoms; m and n each represent a range of 0 to 100,000 and m+n>2. The resin of claim 2, wherein the structure represented by the formula (1) has a fluorine component. The resin of claim 2 or 3, wherein the structure represented by the formula (1) has a phenolic hydroxyl group. The resin according to any one of claims 2 to 4, wherein R ¹ in the formula (1) contains one or more organic groups selected from the group consisting of the following general formulae (2) to (7), In the general formulae (2) to (7), R ₄ to R ₈₁ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms; in the formula (3), X ₁ is an oxygen atom. a sulfur atom, a sulfonyl group or a divalent organic group having 1 to 3 carbon atoms or a two-valent crosslinked structure in which two or more of these are bonded; in the formula (6), X ₂ is a direct bond, oxygen A divalent crosslinked structure in which an atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms, or a combination of two or more organic groups selected from an extended aryl group. The resin according to any one of claims 2 to 5, wherein, in the general formula (1), when the total amount of R ¹ and R ² is 100 mol%, the fluorine atom having 30 mol% or more is contained. Organic base. The resin according to any one of claims 2 to 6, wherein, in the formula (1), each of the R ¹ groups independently contains 25 to 80 mol % when the total amount of R ¹ is 100 mol%. A carbon number of 6 to 40 tetravalent organic groups having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly or through a crosslinked structure a tetravalent organic group of ~40 and one or more organic groups having a carbon number of 6 to 40 and a tetravalent organic group having a alicyclic structure and an aromatic ring. The resin according to any one of claims 2 to 6, wherein, in the formula (1), each of the R ¹ groups independently contains 40 to 70 mol % when the total amount of R ¹ is 100 mol%. A carbon number of 6 to 40 tetravalent organic groups having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly or through a crosslinked structure a tetravalent organic group of ~40 and one or more organic groups having a carbon number of 6 to 40 and a tetravalent organic group having a alicyclic structure and an aromatic ring. A photosensitive resin composition containing the resin according to any one of claims 1 to 8. A photosensitive resin composition comprising (a) a resin having a structure represented by the formula (8) as a main component, (b) a photoacid generator, and (c) a solvent, and having a positive photosensitive property; In the formula (8), each of the R ¹ groups independently contains an alicyclic structure having a monocyclic or condensed polycyclic ring type when the total amount of R ¹ is 100 to 95% by mol. a tetravalent organic group having 6 to 40 carbon atoms, an organic group having a monocyclic alicyclic structure, or a tetravalent organic group having 6 to 40 carbon atoms bonded directly or through a crosslinked structure, and having an alicyclic structure at the same time One or more organic groups of a tetravalent organic group having 6 to 40 carbon atoms in a half-alicyclic structure of an aromatic ring; R ² each independently represents a divalent organic group having 2 to 40 carbon atoms; and R ³ represents Hydrogen or a monovalent organic group having 1 to 20 carbon atoms; m and n each represent a range of 0 to 100,000 and m+n>2; and the structure represented by the formula (8) must have a fluorine component and a phenolic hydroxyl group. The photosensitive resin composition of claim 9 or 10, wherein R ² in the formula (1) or (8) further contains an aliphatic organic group. The photosensitive resin composition of claim 11, wherein the aliphatic organic group is an organic group containing an aliphatic alkyl group. A method for producing a heat-resistant resin film, which is a method for producing a heat-resistant resin film according to any one of claims 9 to 12, which comprises coating the photosensitive resin composition a step of obtaining a photosensitive resin film on a support substrate, a step of exposing the photosensitive resin film obtained in the step, a step of developing the exposed photosensitive resin film using an alkaline aqueous solution, and developing the film The subsequent photosensitive resin film is subjected to a heat treatment step. An interlayer insulating film obtained by the method for producing a heat resistant resin film according to claim 13. An interlayer insulating film for a multilayer wiring structure, which is an interlayer insulating film for a multilayer wiring structure having a total film thickness of 10 μm or more and 50 μm or less obtained by the method for producing a heat resistant resin film according to claim 13. A surface protective film obtained by the method for producing a heat resistant resin film according to claim 13. An electronic component having an interlayer insulating film as claimed in claim 14 or a surface protective film as claimed in claim 16. An insulating layer of an organic electric field light-emitting element obtained by the method for producing a heat-resistant resin film according to claim 13.