JP6724363B2 - Resin and photosensitive resin composition - Google Patents

Description

The present invention relates to a resin containing a specific structure. More specifically, the present invention relates to a resin suitable for a surface protective film of a semiconductor device, an interlayer insulating film, an insulating layer of an organic electroluminescent device, and the like, and a photosensitive resin composition using the same.

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

When using polyimide as a surface protective film or an interlayer insulating film, one of the methods for forming through holes and the like is etching using a positive photoresist. However, this method has a problem that the steps include coating and peeling of the photoresist, which is complicated. Therefore, heat-resistant materials having photosensitivity have been studied for the purpose of streamlining the work process.

Further, in recent years, due to the miniaturization of elements, the higher density of packages, and the higher speed and larger capacity, the demand for interlayer insulating films that can be applied to multilayer wiring has increased. There is a demand for a photosensitive resin composition having a high residual film rate.

For example, regarding a positive photosensitive heat-resistant composition that can be developed with an aqueous alkaline solution, a composition containing a polyamic acid ester containing a phenolic hydroxyl group and an o-quinonediazide compound (Patent Document 1) or a solvent-soluble closed-ring polyimide And a naphthoquinonediazide compound, and a composition containing a polybenzoxazole precursor and a naphthoquinonediazide compound (Patent Document 2). However, when polyimide having low transparency is used in these compositions, there is a problem that the photoreaction efficiency of the photosensitizer in the exposed area is deteriorated and the sensitivity is particularly low in a thick film.

In order to meet such a requirement, a photosensitive resin composition that achieves high sensitivity has been proposed so far by a highly transparent polyimide using a tetracarboxylic acid anhydride having an alicyclic structure (for example, , Patent Documents 3 to 4).

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

JP-A-4-204945 JP-A-1-46862 International Publication No. 00/73853 JP, 2010-196041, A JP, 2007-183388, A

However, it has been difficult to achieve the formation of a thick film structure because conventional polyimide resins using a tetracarboxylic acid anhydride having an alicyclic structure have too high solubility in an alkali developing solution. Further, the polyimide resin using a tetracarboxylic acid anhydride having a hexafluoropropyl group and an alicyclic structure has a very poor residual film rate, and it has been difficult to achieve a highly sensitive thick film structure. ..

Therefore, in view of the above problems of the prior art, it is an object of the present invention to provide a resin having a high sensitivity and a residual film rate when used in a photosensitive resin composition.

As a result of intensive studies to solve the above problems, the present invention has been found.
That is, the present invention has the following configurations.
(1) An acid having an alicyclic structure having 6 to 40 carbon atoms or a semi-alicyclic structure having both an alicyclic structure having 6 to 40 carbon atoms and an aromatic ring, or an anhydride thereof has a total amount of the acid or an anhydride of 100. A resin having a polyamide structure, a polyimide precursor structure, or a polyimide structure, which is contained in an amount of 5 to 95 mol% in terms of mol %.
(2) A resin having a structure represented by the general formula (1).

（一般式（２）〜（７）中、Ｒ_４〜Ｒ_４８、Ｒ_５０、Ｒ_５１、および、Ｒ_５３〜Ｒ_８１は各々独立に水素原子、ハロゲン原子または炭素数１〜３の１価の有機基を示す。一般式（３）中、Ｘ_１は、酸素原子、硫黄原子、スルホニル基もしくは炭素数１〜３の２価の有機基またはそれらが２以上連結してなる２価の架橋構造である。一般式（６）中、Ｘ_２は直接結合、酸素原子、硫黄原子、スルホニル基、炭素数１〜３の２価の有機基もしくはアリーレン基から選ばれた２以上の有機基が連結してなる２価の架橋構造である。）
(In the general formula (1), R ¹ contains 40 to 70 mol% of one or more organic groups selected from the following general formulas (2) to (7) when the total amount of R ¹ is 100 mol %. R ² each independently represents a divalent organic group having 2 to 40 carbon atoms.When the total amount of R ¹ and R ² is 100 mol %, R ¹ containing a fluorine atom and a fluorine atom are The total amount of R ² contained is 30 mol% or more, 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, provided that the structure represented by the general formula (1) has a phenolic hydroxyl group.)

(In the general formulas (2) to (7), R _{4 to} R ₄₈ , R ₅₀ , R ₅₁ , and R _{53 to} R ₈₁ are each independently a hydrogen atom, a halogen atom, or a monovalent group having 1 to 3 carbon atoms. In general formula (3), X ₁ represents an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms, or a divalent crosslinked structure formed by linking two or more of them. In the general formula (6), X ₂ is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, two or more organic groups selected from a divalent organic group having 1 to 3 carbon atoms or an arylene group. It is a divalent crosslinked structure formed by

( 2 ) A photosensitive resin composition containing the resin according to (1 ) .
( 3 ) (a) A resin containing a structure represented by the general formula (8) as a main component, (b) a photoacid generator, and (c) a solvent, and having positive photosensitivity. And a photosensitive resin composition.

（一般式（２）〜（７）中、Ｒ_４〜Ｒ_４８、Ｒ_５０、Ｒ_５１、および、Ｒ_５３〜Ｒ_８１は各々独立に水素原子、ハロゲン原子または炭素数１〜３の１価の有機基を示す。一般式（３）中、Ｘ_１は、酸素原子、硫黄原子、スルホニル基もしくは炭素数１〜３の２価の有機基またはそれらが２以上連結してなる２価の架橋構造である。一般式（６）中、Ｘ_２は直接結合、酸素原子、硫黄原子、スルホニル基、炭素数１〜３の２価の有機基もしくはアリーレン基から選ばれた２以上の有機基が連結してなる２価の架橋構造である。）
（４） 一般式（１）または（８）中のＲ^２が、さらに、脂肪族の有機基を含有する（２）または（３）に記載の感光性樹脂組成物。
（５） 前記脂肪族の有機基が、脂肪族のアルキル基を含有する有機基である（４）に記載の感光性樹脂組成物。
（６） （２）〜（５）のいずれかに記載の感光性樹脂組成物を用いる耐熱性樹脂被膜の製造方法であって、前記感光性樹脂組成物を支持基板上に塗布、乾燥し、感光性樹脂膜を得る工程、該工程により得られた感光性樹脂膜を露光する工程、該露光後の感光性樹脂膜をアルカリ水溶液を用いて現像する工程、および該現像後の感光性樹脂膜を加熱処理する工程を含む耐熱性樹脂被膜の製造方法。 (In the general formula (8), R ¹ contains one or more organic groups selected from the following general formulas (2) to (7) in an amount of 40 to 70 mol% when the total amount of R ¹ is 100 mol %. R ² each independently represents a divalent organic group having 2 to 40 carbon atoms.When the total amount of R ¹ and R ² is 100 mol %, R ¹ containing a fluorine atom and a fluorine atom are The total amount of R ² contained is 30 mol% or more, 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. However, the structure represented by the general formula (8) must have a fluorine component and a phenolic hydroxyl group.)

(In the general formulas (2) to (7), R _{4 to} R ₄₈ , R ₅₀ , R ₅₁ , and R _{53 to} R ₈₁ are each independently a hydrogen atom, a halogen atom, or a monovalent group having 1 to 3 carbon atoms. In general formula (3), X ₁ represents an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms, or a divalent crosslinked structure formed by linking two or more of them. In the general formula (6), X ₂ is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, two or more organic groups selected from a divalent organic group having 1 to 3 carbon atoms or an arylene group. It is a divalent crosslinked structure formed by
(4) The photosensitive resin composition according to (2) or (3), wherein R ² in the general formula (1) or (8) further contains an aliphatic organic group.
(5) The photosensitive resin composition according to (4), wherein the aliphatic organic group is an organic group containing an aliphatic alkyl group.
(6) A method for producing a heat-resistant resin coating using the photosensitive resin composition according to any one of (2) to (5), wherein the photosensitive resin composition is applied onto a supporting substrate and dried, A step of obtaining a photosensitive resin film, a step of exposing the photosensitive resin film obtained by the step, a step of developing the exposed photosensitive resin film with an alkaline aqueous solution, and a photosensitive resin film after the development A method for producing a heat-resistant resin coating, the method including the step of heat-treating.

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

FIG. 6 is a cross-sectional view of a pad portion of a semiconductor device showing an embodiment of the present invention. FIG. 6 is a sectional view of a semiconductor device manufacturing process showing the embodiment of the present invention.

In the present invention, an acid having an alicyclic structure having 6 to 40 carbon atoms or a semi-alicyclic structure having both an alicyclic structure having 6 to 40 carbon atoms and an aromatic ring or an anhydride thereof is the total amount of the acid or an anhydride thereof. Is a resin having a polyamide structure, a polyimide precursor structure, or a polyimide structure, which is contained in an amount of 5 to 95 mol %.
Further, the resin of the present invention has a structure represented by the following general formula (1). The resin having a structure represented by the general formula (1) is a polyimide precursor which becomes a polyimide having excellent heat resistance and solvent resistance when closed by heating, or a polyimide which is closed by heating. This is a polyimide precursor in which a ring is closed by heating to be imidized.

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

(In the general formula (1), R ¹ is independently a tetravalent organic group having a carbon number of 6 to 40 and having a monocyclic or condensed polycyclic alicyclic structure, or an organic compound having a monocyclic alicyclic structure. A tetravalent organic group having 6 to 40 carbon atoms in which the groups are directly linked to each other or via a crosslinked structure, and 4 to 6 carbon atoms having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring It contains 5 to 95 mol% of one or more organic groups selected from valent organic groups, where R ¹ is 100 mol %.R ² is independently a divalent organic group having 2 to 40 carbon atoms. 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.)
The structure represented by the general formula (1) shows a polyimide when m=0 and a polyimide precursor when n=0. When m>0 and n>0, a part of the polyimide precursor is ring-closed and imidized by heating.

The resin having a structure represented by the general formula (1) of the present invention is a resin having a structure other than the structure represented by the general formula (1) and the structure represented by the general formula (1). It may be a copolymer of

In the general formula (1), R ¹ is independently a tetravalent organic group having 6 to 40 carbon atoms and a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure. Is a tetravalent organic group having 6 to 40 carbon atoms, which is directly or through a crosslinked structure, and a tetravalent group having 6 to 40 carbon atoms, which has a semi-alicyclic structure having both an alicyclic structure and an aromatic ring. It has 5 to 95 mol% of one or more kinds of organic groups selected from the above organic groups when the total amount of R ¹ is 100 mol %. R ^2's each independently represent a divalent organic group having 2 to 40 carbon atoms. 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 a low absorbance, so that a highly sensitive photosensitive resin composition can be obtained even with a thick film.

However, a polyimide resin in which all of R ¹ is an alicyclic structure has too high solubility in an alkali developing solution, so that the developing film is eluted and the residual film rate is deteriorated, or the alkali developing solution is easily taken in, and thus tackiness is high. Properties and residues are generated. In addition, a polyimide resin containing an alicyclic structure having less than 6 carbon atoms or an alicyclic structure having at least 41 carbon atoms has insufficient solubility in an alkali developing solution, and thus has insufficient sensitivity and is less sensitive during development. There was a problem that residues were generated in the pattern.

Further, when the structure represented by the general formula (1) contains a fluorine component, the resin is rendered water repellent, and it is possible to suppress the penetration of the surface of the film during alkali development, so that the tack of the unexposed area can be suppressed. It is preferable because a resin film having a high residual film ratio and having no development residue in the processing pattern can be obtained.

In addition, when the structure represented by the general formula (1) contains a phenolic hydroxyl group, appropriate solubility in an alkali developing solution is obtained and it contributes to the interaction with the photosensitizer, thus improving the residual film rate, It is preferable because a resin film capable of high sensitivity can be obtained. Further, the phenolic hydroxyl group also contributes to the reaction with the cross-linking agent, and is therefore preferable in that high mechanical properties and chemical resistance can be obtained.

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

In formulas (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 monovalent organic group having 1 to 3 carbon atoms, the hydrogen atom contained in the organic group may be substituted with a halogen atom. In the general formula (3), X ₁ is 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 of them are linked. In the divalent organic group having 1 to 3 carbon atoms, the hydrogen atom contained in the organic group may be replaced with a halogen atom. In the general 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 divalent organic group which is an arylene group. It is a cross-linked structure. In the divalent organic group having 1 to 3 carbon atoms and the arylene group, the hydrogen atom contained in the organic group may be substituted with a halogen atom.

In general formula (1), R ¹ is a structure derived from an acid dianhydride. The monovalent or condensed polycyclic alicyclic structure-containing tetravalent organic group having 6 to 40 carbon atoms and the organic group having a monocyclic alicyclic structure used in the present invention are directly or through a crosslinked structure. Acid group containing a tetravalent organic group having 6 to 40 carbon atoms and a tetravalent organic group having 6 to 40 carbon atoms having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring. As the anhydride, specifically, 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-cyclohexane tetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride , 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, Bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,5,6 Alicyclic tetracarboxylic dianhydrides such as tricarboxy-2-norbornaneacetic acid dianhydride or compounds in which these aromatic rings are substituted with alkyl groups or halogen atoms, 1,3,3a,4,5, Semi-alicyclic tetracarboxylic dianhydrides such as 9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione or their fragrances The compound which substituted the hydrogen atom of the group ring by the alkyl group and the halogen atom can be mentioned.

When R ¹ in the structure represented by the general formula (1) is 100 mol %, these acid dianhydrides contain 5 mol% to 95 mol %, whereby the resin has low absorbance, Even with a thick film, a highly sensitive photosensitive resin composition can be obtained.

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

A photosensitive resin composition using a resin having a very low absorbance has a too high light-collecting rate and tends to have a pattern width larger than a target dimension. The resolution of the resulting pattern is reduced. Therefore, when R ¹ in the structure represented by the general formula (1) is 100 mol %, the content of the acid dianhydride is 25 mol% in that a pattern width of a target dimension can be obtained at the time of pattern processing. The above content is more preferable, and the content is more preferably 40 mol% or more.

Further, when the content of the alicyclic structure is small, the light collection rate is low, and it is not possible to obtain a small pattern of apertures, so the resolution of the obtained pattern decreases. Therefore, the content of the acid dianhydride when R ¹ in the structure represented by the general formula (1) is 100 mol% is 80 in that the light collection efficiency is increased and a small pattern of openings can be obtained. It is more preferably at most mol%, further preferably at most 70 mol%.

By setting the content of the acid dianhydride in the above range, a high resolution pattern can be obtained.

The resin having the structure represented by the general formula (1) preferably has a fluorine component. In general 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, water repellency is imparted to the surface of the film during alkali development, and it is possible to suppress bleeding from the surface, so there is no development residue on the tack or processing pattern of the unexposed area, and high A photosensitive resin film having a residual film ratio is obtained. In the general formula (1), the organic group having a fluorine atom is preferably 30 mol% or more when the total amount of R ¹ and R ² is 100 mol% in order to obtain the effect of preventing the penetration of an interface and an appropriate dissolution rate. .. Such a structure is introduced by using 30 mol% or more of a monomer containing a fluorine atom in the monomer components introducing R ¹ and R ² . Further, in order to obtain adhesion to the substrate, it is preferable that the content of the fluorine atom-containing monomer is 90 mol% or less.

Specific examples of the compound having a fluorine atom include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or a compound in which these aromatic rings are substituted with an alkyl group or a halogen atom, And aromatic acid dianhydrides such as acid dianhydrides having an amide group, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2′-bis(trifluoromethyl)-4,4′ -Aromatic diamines such as diaminobiphenyl, and compounds in which a part of hydrogen atoms of these aromatic rings are 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.

The resin having the structure represented by the general formula (1) preferably has a phenolic hydroxyl group component. In the general 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 has an appropriate solubility in an alkali developing solution, and interacts with the photosensitizer to suppress the solubility of the unexposed area, so that the residual film rate can be improved and the sensitivity can be increased. Further, the phenolic hydroxyl group also contributes to the reaction with the cross-linking agent, and is therefore preferable in that high mechanical properties and chemical resistance can be obtained.

As the compound having a phenolic hydroxyl group, specifically, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or a compound obtained by substituting the aromatic ring thereof with an alkyl group or a halogen atom , And an aromatic acid dianhydride such as an acid dianhydride having an amide group, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis( 3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis Substitute a hydroxyl group-containing diamine such as (3-amino-4-hydroxyphenyl)fluorene or a part of hydrogen atoms of these aromatic rings with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like. The compounds mentioned above can be mentioned. 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 containing an alicyclic structure having 6 to 40 carbon atoms or a semi-alicyclic structure, a compound having a phenolic hydroxyl group and a compound having a fluorine atom, A high-residual film-rate and high-sensitivity photosensitive resin composition having no tack or development residue can be obtained.

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

Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3′,4′-biphenyltetracarboxylic acid. Dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'- Benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1- Bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane 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, 2,3,3 Aromatic tetracarboxylic dianhydrides such as 5,6-pyridinetetracarboxylic dianhydride and 3,4,9,10-perylenetetracarboxylic dianhydride, and bis(3,4-dicarboxyphenyl) sulfone The dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or the aromatic ring of these compounds is substituted with an alkyl group. And compounds substituted with halogen atoms, and aromatic acid dianhydrides such as acid dianhydrides having an amide group. These can be used in combination of two or more kinds with an acid dianhydride containing an alicyclic structure having 6 to 40 carbon atoms or a semi-alicyclic structure.

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

The aliphatic diamine means a diamine having no aromatic ring, a polyalkyl group, an aliphatic alkyldiamine containing an alkylene ether group such as a polyethylene ether group, a polyoxypropylene group, or a tetramethylene ether group, an alicyclic group. Examples thereof include diamines and aliphatic diamines having a siloxane structure.
Specifically, as the aliphatic alkyldiamine, polyalkyldiamine tetramethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, diamine Jeffamine KH-511 containing a diamine containing a polyethylene ether group, 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, RT-1000 of diamine containing tetramethylene ether group, HT-1100, HT-1000 of alkyl ether diamine containing amino group, HE-1000 (trade name, manufactured by HUNTSMAN Corporation) ) And the like. Examples of the alicyclic diamine include cyclohexyldiamine and methylenebiscyclohexylamine. Examples of the aliphatic diamine having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane and bis(p -Aminophenyl)octamethylpentasiloxane and the like. Of these, the use of an aliphatic alkyldiamine is preferable because flexibility is imparted to it, the elongation at break is improved, and the elastic modulus is lowered, so that warpage of the wafer is suppressed. These characteristics are effective in a multilayer or thick film. At the time of introduction, the residue derived from the aliphatic alkyldiamine in all the diamine residues is preferably 10 mol% or more, and from the viewpoint of heat resistance, it is preferably 50 mol% or less.

Further, when an aliphatic group having a siloxane structure is copolymerized within a range that does not lower the heat resistance, the adhesiveness with the substrate can be improved. The thing copolymerized by 1 to 15 mol% is preferable.

Also, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4). -Hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, hydroxyl group-containing diamines such as bis(3-amino-4-hydroxyphenyl)fluorene, 3-sulfonic acid-4,4'-diaminodiphenyl ether and other sulfonic acid-containing diamines, dimercaptophenylenediamine and other thiol group-containing diamines, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4' -Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1, 4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl) sulfone, bis(3 -Aminophenoxyphenyl)sulfone, 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'- Aromatic diamines such as bis(trifluoromethyl)-4,4′-diaminobiphenyl, and some of the hydrogen atoms of these aromatic rings are substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, etc. And the like. These diamines can be used as they are or as a corresponding diisocyanate compound or trimethylsilylated diamine. Moreover, you may use combining these 2 or more types of diamine components. In applications where heat resistance is required, it is preferable to use aromatic diamine in an amount of 50 mol% or more based on the whole diamine.

Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4, 4'-diaminodiphenyl sulfide, bis(4-aminophenoxyphenyl) sulfone, bis(3-aminophenoxyphenyl) sulfone, 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 or a compound in which an aromatic ring thereof is substituted with an alkyl group or a halogen atom, And diamines having an amide group shown below are preferable. These are used alone or in combination of two or more.

Further, the resin having a structure represented by the general formula (1) of the present invention may contain a sulfonic acid group, a thiol group, or the like. By using a resin having an appropriate sulfonic acid group and thiol group, a positive type photosensitive resin composition having an appropriate alkali solubility is obtained.

In the general formula (1), m and n represent the number of repeating structural units of the resin and represent the range of 0 to 100,000, and m+n>2. From the viewpoint of improving 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 the solubility of the photosensitive resin composition containing the obtained resin in an alkaline developer.

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

In addition, the resin having the structure represented by the general formula (1) may be capped with a terminal capping agent such as monoamine, acid anhydride, acid chloride, or monocarboxylic acid. By sealing the terminal of the resin with an end-capping 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 in an alkaline aqueous solution can be easily adjusted to a preferable range. Can be adjusted. The terminal blocking agent is preferably used in an amount of 0.1 to 60 mol%, more preferably 5 to 50 mol%, based on all amine components of the resin.

The resin having the structure represented by the general formula (1) can be produced according to a known method for producing a polyimide precursor. For example, (I) a method in which a tetracarboxylic dianhydride having an R ¹ group, a diamine compound having an R ² group, and a monoamino compound that is an end capping agent are reacted under low temperature conditions, and (II) an R ¹ group is added. A dicarboxylic acid compound having a tetracarboxylic acid dianhydride and an alcohol, which is then reacted with a diamine compound having an R ² group, a monoamino compound serving as a terminal blocking agent, and a condensing agent, (III) R ¹ group A method of obtaining a diester by using the tetracarboxylic dianhydride and an alcohol, and then converting the remaining two carboxyl groups into acid chlorides and reacting with a diamine compound having an R ² group and a monoamino compound that is an end-capping agent is exemplified. be able to. It is desirable that the resin polymerized by the above method is poured into a large amount of water or a mixed solution of methanol/water, precipitated, filtered, dried and isolated. By this precipitation operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and the film characteristics after heat curing are improved. In addition, a polyimide which has been subjected to imidization of a polyimide precursor and closed a ring can be synthesized by using a known imidization reaction method after obtaining the above polyimide precursor.

Hereinafter, as a preferable example of (I), an example of a method for producing a polyimide precursor will be described. First, a diamine compound having an R ² group is dissolved in a polymerization solvent. To this solution, a tetracarboxylic acid dianhydride having an R ¹ group is gradually added in a substantially equimolar amount to the diamine compound. Using a mechanical stirrer, the mixture is stirred at -20 to 100°C, preferably 10 to 50°C for 0.5 to 100 hours, more preferably 2 to 24 hours. When using an end-capping agent, after addition of tetracarboxylic dianhydride, after stirring at the required temperature and time, the end-capping agent may be gradually added, or added once and reacted. You may let me.

The polymerization solvent is not particularly limited as long as it can dissolve the tetracarboxylic dianhydrides and the diamines that are the raw material monomers. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone amides, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α -Cyclic esters such as methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl- 2-imidazolidinone, sulfolane, dimethyl sulfoxide, etc. can be mentioned. The polymerization solvent is preferably used in an amount of 100 to 1900 parts by weight, more preferably 150 to 950 parts by weight, based on 100 parts by weight of the resin obtained.

The photosensitive resin composition of the present invention may contain an alkali-soluble resin other than the resin having the structure represented by the general formula (1). Specifically, alkali-soluble polybenzoxazole, polybenzoxazole precursor, polyamide, acrylic polymer copolymerized with acrylic acid, novolac resin, resole resin, siloxane resin, polyhydroxystyrene resin, and methylol group, alkoxymethyl Examples thereof include resins in which a cross-linking group such as a group or an epoxy group is introduced, and copolymers thereof. Such a resin is soluble in an aqueous solution of an alkali such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide and sodium carbonate. By containing these alkali-soluble resins, the characteristics of each alkali-soluble resin can be imparted while maintaining the adhesiveness and excellent sensitivity of the heat resistant resin coating. 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 positive photosensitive resin composition of the present invention will be described, but the scope of the present invention is not limited thereto. Regarding a negative photosensitive resin composition having a negative type photosensitivity in which an exposed portion reacts by development, when a polyimide having low transparency is used, the photoreaction efficiency of the photosensitizer in the exposed portion is deteriorated and the residual film is left. The rate becomes low and it becomes difficult to obtain a thick film structure. Therefore, as for the photosensitive resin composition having high sensitivity, it is necessary to develop a highly transparent polyimide as in the positive type.

The photosensitive resin composition having a positive photosensitivity of the present invention comprises (a) a resin containing a structure represented by the general formula (8) as a main component, (b) a photoacid generator and (c) a solvent. contains. Here, the main component means that in the resin having the structure represented by the general formula (8), the structure represented by the general formula (8) is 50 mol% or more, preferably 70 mol% or more. , And more preferably 90 mol% or more.

(In the general formula (8), R ¹ is independently a tetravalent organic group having 6 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure. A tetravalent organic group having 6 to 40 carbon atoms in which groups are directly connected to each other or via a crosslinked structure, and a tetravalent organic group having 6 to 40 carbon atoms having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring 5 to 95 mol% when the total amount of R ¹ is 100 mol %. R ² is independently a divalent organic group having 2 to 40 carbon atoms. 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, provided that the general formula (8) is satisfied. The structure represented by must have a fluorine component and a phenolic hydroxyl group.)
The photosensitive resin composition having a positive photosensitivity of the present invention preferably contains the resin preferably used in the photosensitive resin composition of the present invention described above, and contains two or more kinds of these. Good.

The photosensitive resin composition having a positive photosensitivity of the present invention may contain other alkali-soluble resin in addition to the resin containing the structure represented by the general formula (8) as a main component. Specifically, alkali-soluble polybenzoxazole, polybenzoxazole precursor, polyamide, acrylic polymer copolymerized with acrylic acid, novolac resin, resole resin, siloxane resin, polyhydroxystyrene resin, and methylol group, alkoxymethyl Examples thereof include resins in which a cross-linking group such as a group or an epoxy group is introduced, and copolymers thereof. Such a resin is soluble in an aqueous solution of an alkali such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide and sodium carbonate. By containing these alkali-soluble resins, the characteristics of each alkali-soluble resin can be imparted while maintaining the adhesiveness and excellent sensitivity of the heat resistant resin coating.

The photo-acid generator which is the component (b) of the present invention is a compound which gives the property of generating an acid upon irradiation with light and increasing the solubility of the light-irradiated portion in an aqueous alkaline solution, such as a quinonediazide compound and a sulfonium salt. , Phosphonium salts, diazonium salts, iodonium salts and the like.

The quinonediazide compound is a polyhydroxy compound in which a sulfonic acid of a quinonediazide is bound with an ester, a polyamino compound in which a sulfonic acid of a quinonediazide is bound in a sulfonamide, and a polyhydroxypolyamino compound is an ester bond of a quinonicdiazide sulfonic acid and/or a sulfonamide. Examples include those that are combined. It is not necessary that all the functional groups of these polyhydroxy compounds and polyamino compounds be substituted with quinonediazide, but it is preferable that 50 mol% or more of all the functional groups be substituted with quinonediazide. If it is less than 50 mol %, the solubility in an alkali developing solution becomes too high, and the contrast with the unexposed area may not be obtained, and the desired pattern may not be obtained. By using such a quinonediazide compound, it is possible to obtain a positive-type photosensitive resin composition that is sensitive to general ultraviolet rays i line (365 nm), h line (405 nm), and g line (436 nm) of a mercury lamp. it can. Such compounds may be used alone or in combination of two or more. Further, by using two kinds of photoacid generators, the ratio of the dissolution rate of the exposed area to the unexposed area can be made larger, and as a result, a highly sensitive photosensitive resin composition can be obtained.

The polyhydroxy compound is 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, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ. , TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by 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, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.) ), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and the like can be mentioned, but not limited to these.

The polyamino compound is 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Examples thereof include, but are not limited to, sulfoxide and the like.

Examples of the polyhydroxy polyamino compound include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

In the present invention, the quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinonediazide sulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of light to be exposed. It is also possible to obtain a naphthoquinone diazide sulfonyl ester compound in which a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in the same molecule, and a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound It is also possible to mix and use.

When the molecular weight of the quinonediazide compound is more than 5000, the quinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the obtained film is deteriorated, the mechanical properties are deteriorated, and the adhesiveness is deteriorated. Problems can occur. From such a viewpoint, the molecular weight of the preferable quinonediazide compound is 300 to 3000. More preferably, it is 350-1500.

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

Among the photo-acid generators used as the component (b) of the present invention, the photo-acid generator that appropriately stabilizes the acid component generated by exposure is preferably a sulfonium salt, a phosphonium salt or a diazonium salt. Since the resin composition obtained from the photosensitive resin composition of the present invention is used as a permanent film, it is environmentally unfavorable that phosphorus or the like remains, and it is necessary to consider the color tone of the film. Then, a sulfonium salt is preferably used. Particularly preferred are triarylsulfonium salts.

When the photosensitive resin composition of the present invention contains (b) a photo-acid generator, an acid is generated in the light-irradiated part and the solubility of the light-irradiated part in an alkaline aqueous solution is increased, so that the light-irradiated part is dissolved. A positive pattern can be obtained.

The content of the photo-acid generator used as the component (b) in the present invention is preferably 0. 0 with respect to 100 parts by weight of the resin (a) having the structure represented by the general formula (8) as a main component. It is from 01 to 50 parts by weight. Of these, the quinonediazide compound is preferably in the range of 3 to 40 parts by weight. The compound selected from the sulfonium salt, the phosphonium salt and the diazonium salt is 0. The range of 05 to 40 parts by weight is preferable, and the range of 0.1 to 30 parts by weight is more preferable. (B) By setting the content of the photo-acid generator within this range, higher sensitivity can be achieved. Further, a sensitizer and the like may be contained if necessary.

In addition, for the purpose of improving the sensitivity of the photosensitive resin composition, a compound having a phenolic hydroxyl group may be contained, if necessary, within a range not reducing the shrinkage rate after curing.

Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, and BisP-EZ. , Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakis P-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, (trade names, manufactured by 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 (these are trade names, manufactured by Asahi Organic Materials Co., Ltd.).

Of these, compounds having a preferred phenolic hydroxyl group used in the present invention include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, and 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. are mentioned. Of 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 this compound having a phenolic hydroxyl group, the resin composition obtained is hardly dissolved in an alkali developing solution before exposure and easily dissolved in an alkali developing solution after exposure, so that film loss due to development is reduced. Development is facilitated in a short time in a small amount.

The content of such a compound having a phenolic hydroxyl group is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the resin (a) having the structure represented by the general formula (8) as a main component, More preferably, it is in the range of 3 to 40 parts by weight.

The positive-type photosensitive resin composition having a positive photosensitivity of the present invention contains (c) a solvent. As the solvent, polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide and dimethylsulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, etc. Ethers, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxymethyl propanate, 3-ethoxyethyl propanate, ethyl acetate, ethyl lactate And aromatic hydrocarbons such as toluene and xylene. You may contain 2 or more types of these. The content of the solvent (c) is preferably 100 parts by weight or more and 1500 parts by weight or less with respect to 100 parts by weight of the resin containing (a) the structure represented by the general formula (8) as a main component.

The photosensitive resin composition having a positive photosensitivity of the present invention may contain components other than the above (a) to (c), and contains a compound having an alkoxymethyl group, a methylol group, or an epoxy group. Preferably. Since the methylol group and the alkoxymethyl group cause a crosslinking reaction in the temperature range of 100° C. or higher, they can be crosslinked by heat treatment to obtain a heat resistant resin film having excellent mechanical properties.

As examples having an alkoxymethyl group or a methylol 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 (trade names, manufactured by 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, manufactured by Sanwa Chemical Co., Ltd.). Among these, it is preferable to add HMOM-TPHAP or MW-100LM containing a large number of alkoxymethyl groups because the crosslinking efficiency is good.

Further, the epoxy group is thermally cross-linked with the polymer at 200° C. or lower, and the dehydration reaction due to the cross-linking does not occur, so that the film shrinkage hardly occurs. Therefore, in addition to the mechanical properties, it is effective for low temperature curing and low warpage. Examples of the compound having an epoxy group include epoxy group-containing epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl(glycidyloxypropyl) siloxane, and silicone. However, the present invention is not limited to these. Specifically, Epicron 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron EXA-4710, Epicron HP-4770, Epicron EXA-859CRP, Epicron EXA-1514, Epicron EXA-4880, Epiclon EXA-4850-150, Epiclon EXA-4850-1000, Epicron EXA-4816, Epicron EXA-4822 (these trade names are manufactured by Dainippon Ink and Chemicals, Inc.), Rikaresin BEO-60E (the following). Trade name, Shin-Nippon Rika Co., Ltd., EP-4003S, EP-4000S (Adeka Corporation), and the like.

Two or more kinds of these compounds having an alkoxymethyl group, a methylol group, or an epoxy group may 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 with respect to 100 parts by weight of the resin containing the structure represented by the general formula (8) as a main component. It is preferably ˜40 parts by weight.

The photosensitive resin composition of the present invention may further contain a silane compound. The inclusion of the silane compound improves the adhesion of the heat resistant resin coating. Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, and N-phenylaminobutyltrisilane. Methoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltri Examples thereof include methoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. The content of the silane compound is preferably 0.01 part by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the resin containing (a) the structure represented by the general formula (8) as a main component.

Further, the photosensitive resin composition having a positive photosensitivity of the present invention, if necessary, a surfactant, an ester such as ethyl lactate or propylene glycol monomethyl ether acetate for the purpose of improving the wettability with a substrate. , Alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane. Further, for the purpose of suppressing the coefficient of thermal expansion, increasing the dielectric constant, and decreasing the dielectric constant, inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder may be contained.

Next, a method for producing the photosensitive resin composition of the present invention will be exemplified. Each of the above components (a) to (c), and optionally other components are placed in a glass flask or a stainless steel container and dissolved by stirring with a mechanical stirrer, a method of dissolving by ultrasonic waves, planetary stirring Examples include a method of stirring and dissolving with a defoaming device. The viscosity of the positive photosensitive resin composition is preferably 1 to 10,000 mPa·s. Further, the photosensitive resin composition may be filtered with a filter having a pore size of 0.1 μm to 5 μm to remove foreign matters.

Next, a method for 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 polyimide pattern through the steps of coating and drying on a supporting substrate, exposing, developing and heat-treating.

First, the photosensitive resin composition is applied onto the substrate. The substrate may be, but is not limited to, a silicon wafer, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, ITO or the like. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and slit die coating. The coating film thickness varies depending on the coating method, the solid content concentration of the positive photosensitive resin composition, the viscosity, etc., but it is generally applied so that the film thickness after drying will be 0.1 to 150 μm.

Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin film. Drying is preferably performed using an oven, a hot plate, infrared rays or the like at a temperature of 50° C. to 150° C. for 1 minute to several hours.

Then, the photosensitive resin film is irradiated with actinic rays through a mask having a desired pattern. Examples of actinic rays used for exposure include ultraviolet rays, visible rays, electron rays, and X-rays. In the present invention, i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp are used. preferable.

In order to form a pattern from the photosensitive resin film, the exposed portion may be removed using a developing solution after the exposure. The developing solution is tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate. Aqueous solutions of compounds showing alkalinity, such as cyclohexylamine, ethylenediamine, and hexamethylenediamine are preferred. In some cases, a polar solvent such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone or dimethylacrylamide, methanol, ethanol or isopropanol may be added to these alkaline aqueous solutions. One or more of alcohols such as, ethyl lactate, esters such as propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added. After development, it is common to perform a rinse treatment with water. In the rinse treatment, one or more kinds of alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate and 3-methoxymethyl propanate may be added to water.

After development, a temperature of 150° C. to 500° C. is applied to convert the film into a heat resistant resin film. It is preferable that this heat treatment is carried out for 5 minutes to 5 hours while selecting the temperature and gradually increasing the temperature or selecting a certain temperature range and continuously increasing the temperature. Examples include a method of performing heat treatment at 130° C., 200° C., and 350° C. for 30 minutes each, and a method of linearly heating from room temperature to 320° C. over 2 hours. Further, the heating treatment is preferably performed at 250° C. or lower because the electrical characteristics of the element may be changed and the substrate may be warped by heating at high temperature or repetition thereof.

The heat-resistant resin film formed from the photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards. Specifically, it is preferably used for applications such as a semiconductor passivation film, a surface protective film for semiconductor elements, an interlayer insulating film, an interlayer insulating film for multi-layer wiring for high-density packaging, and an insulating layer for organic electroluminescent elements. The structure is not limited to, and various structures can be adopted.

Next, application examples of the photosensitive resin composition of the present invention to a semiconductor device having bumps will be described with reference to the drawings. FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having bumps according to the present invention. As shown in FIG. 1, a silicon wafer 1 has a passivation film 3 formed on an Al pad 2 for input/output, and a via hole is formed in the passivation film 3. Further, a pattern (insulating film) 4 made of the photosensitive resin composition of the present invention is further formed thereon, and a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and the metal The film 5 etches the periphery of the solder bump 10 to insulate each pad. A barrier metal 8 and a solder bump 10 are formed on the insulated pad. When the soft component is introduced into the photosensitive resin composition, since the warp of the wafer is small, the exposure and the transportation of the wafer can be performed with high accuracy. In addition, since the polyimide resin has excellent mechanical properties, stress from the sealing resin can be relieved even during mounting, so that damage to the low-k layer can be prevented and a highly reliable semiconductor device can be provided.

Next, a detailed method of manufacturing a semiconductor device will be described. As shown in 2c of FIG. 2, the metal wiring 6 is formed by a plating method. Next, as shown in FIG. 22d', the photosensitive resin composition of the present invention is applied, and a pattern (insulating film 7) as shown in FIG. 22d is formed through a photolithography process. At this time, the photosensitive resin composition of the insulating film 7 is subjected to thick film processing in the scribe line 9. When forming a multi-layer wiring structure having three or more layers, each layer can be formed by repeating the above steps. In this way, in the multilayer wiring structure, the formation of the insulating film is repeated, so that the total film thickness of the interlayer insulating film becomes 10 μm or more, and it is preferably 50 μm or less from the influence on the warp of the chip. Since a scribe line thick film processing is required for a multi-layer wiring structure, it is preferable that the photosensitive resin composition be capable of forming a patternable heat-resistant resin film having a film thickness of 10 μm or more. Further, in order to form a high-density multilayer wiring structure, it is also preferable to obtain a high-resolution heat-resistant resin film. Next, as shown in FIGS. 22e and 2f, the barrier metal 8 and the solder bump 10 are formed. Then, dicing is performed along the last scribe line 9 to divide into chips. When the insulating film 7 has no pattern formed on the scribe line 9 or when a residue remains, cracks or the like occur during dicing, which affects the reliability evaluation of the chip. Therefore, as in the present invention, providing pattern processing excellent in thick film processing is very preferable in order to obtain high reliability of the semiconductor device.

Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. The resins and photosensitive resin compositions in the examples were evaluated by the following methods.

(Method of measuring film thickness)
Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the film thickness after prebaking, development, and curing was measured with a refractive index of 1.629.

(Preparation of Development Film A)
A varnish was spin-coated on an 8-inch silicon wafer, and then baked on a 120° C. hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Ltd.) for 3 minutes to form a pre-baked film having a thickness of 10 μm. .. The membrane was exposed at 10 mJ / cm ² steps by the exposure amount of 0~1000mJ / cm ² using an i-line stepper (NIKON NSR i9). After the exposure, it is developed with a 2.38 wt% tetramethylammonium (TMAH) aqueous solution (Mitsubishi Gas Chemical Co., Ltd. ELM-D) for 90 seconds, and then rinsed with pure water to develop an isolated pattern of 10 μm. A film A was obtained.

(1) Sensitivity Evaluation After exposure and development in the developed film A, the exposure amount (hereinafter referred to as the minimum exposure amount Eth) at which the exposed portion was completely dissolved and disappeared was defined as the sensitivity. If Eth is 400 mJ/cm ² or less, it can be determined that the sensitivity is high. It is more preferably 300 mJ/cm ² or less.

(2) Evaluation of residual film ratio The ratio of the film thickness of the developing film to the prebaked film is defined as the residual film ratio (residual film ratio=(developing film thickness)/(prebaking film thickness)×100), and 80% or more I passed.

(3) Evaluation of Pattern of Developed Film The surface of the photosensitive resin composition film formed by development was visually observed for tackiness of unexposed areas and residues of exposed areas. The case where the pattern of the developed film had no problem was judged as good (◯), and the case where the tackiness in the unexposed area and the residue generated in the exposed area were judged as poor (x).

(Preparation of heat resistant resin coating B)
A varnish was spin-coated on an 8-inch silicon wafer, and then baked for 3 minutes on a hot plate at 120° C. (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Ltd.) to prepare pre-baked films having different film thicknesses. .. This film was exposed using an i-line stepper (Nikon NSR i9) at an exposure dose of 1000 mJ/cm ² . After the exposure, the film was developed with a 2.38 wt% tetramethylammonium (TMAH) aqueous solution (Mitsubishi Gas Chemical Co., Ltd. ELM-D) for 90 seconds, and then rinsed with pure water to obtain a developed film. Using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the developed film was heated to 250° C. at 5° C./min at an oxygen concentration of 20 ppm or less, and heat-treated at 250° C. for 1 hour. .. When the temperature reached 50° C. or lower, the silicon wafer was taken out and the film thickness of the heat resistant resin coating on the silicon wafer was measured.

(4) Evaluation of thick film formation With respect to the heat-resistant resin film, the maximum film thickness when the exposed portion was completely eluted and a pattern was formed (that is, pattern processing was possible) was evaluated. Good for obtaining a patterned heat-resistant resin film having a film thickness of 15 μm or more (⊚), somewhat good for obtaining a patterned heat-resistant resin film of 10 μm or more and less than 15 μm (◯), pattern of less than 10 μm The product that yielded the processed heat-resistant resin film was regarded as defective (x).
(5) Resolution evaluation The minimum opening pattern dimension was measured for the heat-resistant resin film having a film thickness of 10 μm and defined as the resolution. A resolution of less than 3 μm is extremely good (⊚), a resolution of 3 μm or more and less than 7 μm is good (◯), a resolution of 7 μm or more and less than 10 μm is slightly good (Δ), a heat resistance of 10 μm or more or a film thickness of 10 μm The case where the resin film was not obtained was regarded as defective (x).

The names of the abbreviations of acid dianhydrides and diamines shown in the following examples and comparative examples are as follows.
PMDA-HH: 1S,2S,4R,5R-Cyclohexanetetracarboxylic dianhydride TDA100: 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl ) Naphtho[1,2-c]furan-1,3-dione CBDA:cyclobutanetetracarboxylic dianhydride 6FDA:4,4'-hexafluoroisopropylidene diphthalic dianhydride ODPA:3,3',4 ,4'-Diphenyl ether tetracarboxylic acid dianhydride SiDA:1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane BAHF:2,2-bis(3-amino-4) -Hydroxyphenyl)hexafluoropropane APBS:bis(3-amino-4-hydroxyphenyl)sulfone DAE:4,4'-diaminodiphenyl ether NMP:N-methyl-2-pyrrolidone ED-600: Jeffamine ED-600 (commodity) Name, manufactured by HUNTSMAN Co., Ltd.)
KBM-403: 3-glycidoxypropyltrimethoxysilane.

The heat-crosslinkable compounds used in each Example and Comparative Example are shown below.

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound (a) BAHF (18.3 g, 0.05 mol) was dissolved in acetone (100 mL), propylene oxide (17.4 g, 0.3 mol), and cooled to -15°C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After the dropping was completed, the reaction was carried out at -15°C for 4 hours, and then the temperature was returned to room temperature. The precipitated white solid was filtered off and dried in vacuum at 50°C.

30 g of the obtained white solid was put into a 300 mL stainless autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here by a balloon to carry out the reduction reaction at room temperature. After about 2 hours, the reaction was terminated after confirming that the balloon did not deflate any more. After the completion of the reaction, the palladium compound as a catalyst was removed by filtration, 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 used for the reaction as it was.

Synthesis Example 2 Synthesis of quinonediazide compound (b) Tris P-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.22 g (0.05 mol) and 5-naphthoquinone diazide sulfonyl acid chloride 26.86 g under a dry nitrogen stream. (0.10 mol) and 13.43 g (0.05 mol) of 4-naphthoquinonediazide sulfonyl chloride were dissolved in 50 g of 1,4-dioxane, and the mixture was brought to room temperature. To this, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not rise to 35°C or higher. After dropping, the mixture was stirred at 30° C. for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Then, the deposited precipitate was collected by filtration. The precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (b) represented by the following formula.

Synthesis Example 3 Synthesis of quinonediazide compound (c) 15.31 g (0.05 mol) of TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 40.28 g of 5-naphthoquinonediazide sulfonyl chloride under a dry nitrogen stream. (0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Using 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane, a quinonediazide compound (c) represented by the following formula was obtained in the same manner as in Synthesis Example 2.

Synthesis example 4 Synthesis of quinonediazide compound (d) 28.83 g (0.05 mol) of TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 13.43 g of 5-naphthoquinonediazide sulfonyl acid chloride under a dry nitrogen stream. (0.125 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Using 20.24 g of triethylamine mixed with 50 g of 1,4-dioxane, a quinonediazide compound (d) represented by the following formula was obtained in the same manner as in Synthesis Example 2.

Synthesis Example 5 Synthesis of Acrylic Resin (e) In a 500 ml flask, 5 g of 2,2′-azobis(isobutyronitrile), 5 g of t-dodecanethiol, and propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) were added. I prepared 150g. Then, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo[5.2.1.0 ^2,6 ]decan-8-yl methacrylate were charged, and the mixture was stirred at room temperature for a while, and the inside of the flask was replaced with nitrogen, then 70 The mixture was heated and stirred at 5°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 resulting solution, and the mixture was heated with stirring at 90° C. for 4 hours to obtain an alkali-soluble acrylic resin (e) solution. Obtained. The solid content concentration of the acrylic resin solution (e) was 43% by weight.

Synthesis Example 6 Synthesis of novolak resin (f) m-cresol 70.2 g (0.65 mol), p-cresol 37.8 g (0.35 mol), 37 wt% formaldehyde aqueous solution 75.5 g ( Formaldehyde (0.93 mol), oxalic acid dihydrate (0.63 g (0.005 mol)) and methyl isobutyl ketone (264 g) were charged, and then immersed in an oil bath to carry out polycondensation reaction for 4 hours while refluxing the reaction solution. went. After that, the temperature of the oil bath is raised over 3 hours, then the pressure in the flask is reduced to 40 to 67 hPa, volatile matter is removed, and the dissolved resin is cooled to room temperature to dissolve the alkali-soluble substance. A polymer solid of novolak resin (f) was obtained. From GPC, Mw was 3,500. Γ-Butyrolactone (GBL) was added to the obtained novolak resin (f) to obtain a novolac resin (f) solution having a solid content concentration of 43% by weight.

Synthesis Example 7 Synthesis of Polybenzoxazole Precursor (g) BAHF (18.3 g, 0.05 mol) was dissolved in NMP (50 g) and glycidyl methyl ether (26.4 g, 0.3 mol) under a dry nitrogen stream, and the temperature of the solution was adjusted. Cooled to -15°C. A solution prepared by dissolving 14.7 g of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Pesticides Co., Ltd., 0.050 mol) in 25 g of GBL was added dropwise thereto so that the internal temperature did not exceed 0°C. After the dropping was completed, 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 deposit 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 polybenzoxazole precursor (g). GBL was added to the obtained polybenzoxazole precursor (g) to obtain a polybenzoxazole precursor (g) solution having a solid content concentration of 43% by weight.

Synthesis Example 8 Synthesis of polyhydroxystyrene (h) To a mixed solution of 500 ml of tetrahydrofuran and 0.01 mol of sec-butyllithium as an initiator, pt-butoxystyrene and styrene were added at a molar ratio of 3:1 in total. 20 g was added and polymerized while stirring for 3 hours. The polymerization termination reaction was carried out by adding 0.1 mol of methanol to the reaction solution. The reaction mixture was then poured into methanol to purify the polymer and the precipitated polymer was dried to give a white polymer. Furthermore, it was dissolved in 400 ml of acetone, a small amount of concentrated hydrochloric acid was added at 60° C., and the mixture was stirred for 7 hours, then poured into water to precipitate the polymer, deprotection of pt-butoxystyrene and conversion into hydroxystyrene, and washing. When dried, a purified copolymer of p-hydroxystyrene and styrene (h) was obtained.

Reference example 1
Under a dry nitrogen stream, BAHF (15.57 g, 0.04 mol) and SiDA (0.62 g, 0.003 mol) were dissolved in NMP (100 g). PMDA-HH1.12g (0.005mol) and 6FDA19.99g (0.045mol) were added here with NMP10g, it was made to react at 60 degreeC for 1 hour, and then it stirred at 180 degreeC for 4 hours. After completion of 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 already-closed ring polyimide 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, 3.0 g of cross-linking agent MX-270, 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish A of the positive photosensitive resin composition. Using the resulting varnish A, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formability evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Reference example 2
Under a dry nitrogen stream, 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. PMDA-HH 10.09g (0.045mol) and 6FDA 2.22g (0.005mol) were added here with NMP10g, it was made to react at 60 degreeC for 1 hour, and then it stirred at 180 degreeC for 4 hours. After completion of 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 already-closed-ring polyimide 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 novolac resin (f) obtained in Synthesis Example 6, 3.0 g of crosslinking agent MX270 3.0 KBM 4031 0.0 g was added to 50 g of GBL to obtain a varnish B of the positive photosensitive resin composition. Using the resulting varnish B, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Example 3
In a dry nitrogen stream, 25.68 g (0.04 mol) of the compound (a) obtained in Synthesis Example 1 and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP. PMDA-HH 4.48g (0.02mol) and ODPA 9.31g (0.03mol) were added here with NMP10g, and it was made to react at 40 degreeC for 1 hour. Then, a solution prepared by diluting 13.10 g (0.11 mol) of N,N-dimethylformamide dimethyl acetal with 15 g of NMP was added dropwise over 10 minutes. After the dropping, the mixture was stirred at 40° C. for 1 hour. After the reaction was completed, the solution was poured into 2 L of water, and the solid precipitate was collected by filtration. The resin solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor resin (C).

17.5 g of the obtained resin (C), 2.3 g of the quinonediazide compound (d) obtained in Synthetic Example 4, 16 g of the polybenzoxazole resin (g) obtained in Synthetic Example 7, HMOM-TPHAP 3. 0 g and 1.0 g of KBM-403 were added to 50 g of GBL to obtain a varnish C of the positive photosensitive resin composition. Using the resulting varnish C, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Example 4
Under a dry nitrogen stream, 11.91 g (0.04 mol) of APBS and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP. PMDA-HH 4.48g (0.02mol) and 6FDA 13.33g (0.03mol) were added here with NMP10g, it was made to react at 60 degreeC for 1 hour, and then it stirred at 180 degreeC for 4 hours. After completion of 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 already-closed ring polyimide 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, crosslinker MX-270 3. 0 g and 1.0 g of KBM-403 were added to 50 g of GBL to obtain a varnish D of the positive photosensitive resin composition. Using the resulting varnish D, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Example 5
Under a dry nitrogen stream, 11.91 g (0.04 mol) of APBS and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP. TDA-100 6.01g (0.02mol) and 6FDA 13.33g (0.03mol) were added here together with NMP10g, it was made to react at 60 degreeC for 1 hour, and then it stirred at 180 degreeC for 4 hours. After completion of 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 already-closed ring polyimide resin (E).

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, 3.0 g of the crosslinking agent HMOM-TPHAP, 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish E of the positive photosensitive resin composition. Using the obtained varnish E, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Example 6
BAHF 9.16 g (0.03 mol), DAE2.0 (0.01 mol), ED600 4.5 g (0.008 mol), SiDA 0.62 g (0.003 mol) were dissolved in NMP 100 g under a dry nitrogen stream. Let TDA-100 6.01g (0.02mol) and 6FDA 13.33g (0.03mol) were added here with NMP10g, and it was made to react at 40 degreeC for 1 hour. Then, a solution prepared by diluting 13.10 g (0.11 mol) of N,N-dimethylformamide dimethyl acetal with 15 g of NMP was added dropwise over 10 minutes. After the dropping, the mixture was stirred at 40° C. for 1 hour. After the reaction was completed, the solution was poured into 2 L of water, and the solid precipitate was collected by filtration. The resin solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor resin (F).

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 the cross-linking agent HMOM-TPHAP 3 0.0 g and 1.0 g of KBM403 were added to 50 g of GBL to obtain a varnish F of the positive photosensitive resin composition. Using the obtained varnish F, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Example 7
BAHF 9.16 g (0.03 mol), DAE2.0 (0.01 mol), ED600 4.5 g (0.008 mol), SiDA 0.62 g (0.003 mol) were dissolved in NMP 100 g under a dry nitrogen stream. Let To this, 6.01 g (0.02 mol) of TDA-100 and 9.31 g (0.03 mol) of ODPA were added together with 10 g of NMP, reacted at 60°C for 1 hour, and then stirred at 180°C for 4 hours. After completion of 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 already-closed-ring polyimide 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 novolac resin (f) obtained in Synthesis Example 6, 3.0 g of MX-270 crosslinking agent, 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish G of a positive photosensitive resin composition. Using the obtained varnish G, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Example 8
Under a dry nitrogen stream, BAHF (15.57 g, 0.04 mol) and SiDA (0.62 g, 0.003 mol) were dissolved in NMP (100 g). TDA-100 6.01g (0.02mol) and 6FDA13.33g (0.03mol) were added here with NMP10g, it was made to react at 60 degreeC for 1 hour, and then it stirred at 180 degreeC for 4 hours. After completion of 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 already-closed-ring polyimide resin (M).

17.5 g of the obtained resin (M), 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2, 16 g of the polybenzoxazole resin (g) obtained in Synthesis Example 7, and a cross-linking agent MX-270 3. 0 g and 1.0 g of KBM-403 were added to 50 g of GBL to obtain a varnish M of the positive photosensitive resin composition. Using the obtained varnish M, the sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Example 9
BAHF 9.16 g (0.03 mol), ED600 2.0 (0.01 mol), ED600 9.0 g (0.015 mol), SiDA 0.62 g (0.003 mol) were dissolved in NMP 100 g under a dry nitrogen stream. Let TDA-100 6.01g (0.02mol) and 6FDA 13.33g (0.03mol) were added here together with NMP10g, it was made to react at 60 degreeC for 1 hour, and then it stirred at 180 degreeC for 4 hours. After completion of 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 already-closed ring polyimide 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 the cross-linking agent HMOM-TPHAP 3 0.0 g and 1.0 g of KBM403 were added to 50 g of GBL to obtain a varnish N of positive photosensitive resin composition. Using the obtained varnish F, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Reference example 3
Under a dry nitrogen stream, 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. PMDA-HH 8.97g (0.05mol) and 6FDA 4.44g (0.01mol) were added here with NMP10g, it was made to react at 60 degreeC for 1 hour, and then it stirred at 180 degreeC for 4 hours. After completion of 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 already-closed-ring polyimide 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, 3.0 g of the cross-linking agent HMOM-TPHAP, 1.0 g of KBM403 was added to 50 g of GBL to obtain a varnish O of the positive photosensitive resin composition. Using the obtained varnish O, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Reference example 4
Under a dry nitrogen stream, 9.16 g (0.03 mol) of BAHF, ED6009.0 (0.015 mol) and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP. PMDA-HH 2.80g (0.013mol) and 6FDA 16.66g (0.037mol) were added here with NMP10g, it was made to react at 60 degreeC for 1 hour, and then it stirred at 180 degreeC for 4 hours. After completion of 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 already-closed ring polyimide 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 novolak resin (f) obtained in Synthesis Example 6, and 3.0 g of the cross-linking agent HMOM-TPHAP. , KBM403 (1.0 g) was added to GBL (50 g) to obtain a varnish N of a positive photosensitive resin composition. Using the obtained varnish N, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Comparative Example 1
Under a dry nitrogen stream, BAHF (15.57 g, 0.04 mol) and SiDA (0.62 g, 0.003 mol) were dissolved in NMP (100 g). 22.21 g (0.05 mol) of 6FDA was added thereto together with 10 g of NMP, reacted at 60°C for 1 hour, and then stirred at 180°C for 4 hours. After completion of 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 already-closed ring polyimide 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, 3.0 g of crosslinking agent MX-270, 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish H of positive photosensitive resin composition. Using the obtained varnish H, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Comparative example 2
Under a dry nitrogen stream, BAHF (15.57 g, 0.04 mol) and SiDA (0.62 g, 0.003 mol) were dissolved in NMP (100 g). CBDA (9.81 g, 0.05 mol) was added thereto together with NMP (10 g), and the mixture was reacted at 60°C for 1 hour and then stirred at 180°C for 4 hours. After completion of 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 already-closed-ring polyimide resin (I).

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, 3.0 g of crosslinking agent MX-270, 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish I of positive photosensitive resin composition. Using the obtained varnish I, sensitivity evaluation, residual film rate evaluation, developed film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Comparative Example 3
Under a dry nitrogen stream, DAE 8.5 g (0.04 mol) and SiDA 0.62 g (0.003 mol) were dissolved in NMP 100 g. 11.21 g (0.05 mol) of PMDA-HH was added thereto together with 10 g of NMP, and reacted at 40° C. for 1 hour. Then, a solution prepared by diluting 13.10 g (0.11 mol) of N,N-dimethylformamide dimethyl acetal with 15 g of NMP was added dropwise over 10 minutes. After the dropping, the mixture was stirred at 40° C. for 1 hour. After the reaction was completed, the solution was poured into 2 L of water, and the solid precipitate was collected by filtration. The resin solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor resin (J) 17.5 g of the obtained resin (J), the quinonediazide compound (b) obtained in Synthesis Example 2. 3 g, acrylic resin (e) 16 g obtained in Synthesis Example 5, cross-linking agent MX-270 3.0 g, and KBM-403 1.0 g were added to GBL 50 g to obtain a varnish J of a positive photosensitive resin composition. .. Using the obtained varnish J, sensitivity evaluation, residual film rate evaluation, developed film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

Comparative Example 4
Under a dry nitrogen stream, BAHF (15.57 g, 0.04 mol) and SiDA (0.62 g, 0.003 mol) were dissolved in NMP (100 g). 11.21 g (0.05 mol) of PMDA-HH was added thereto together with 10 g of NMP, reacted at 60° C. for 1 hour, and then stirred at 180° C. for 4 hours. After completion of 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 already-closed ring polyimide 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, 3.0 g of 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. As described above, the obtained varnish K was used for sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation. Pattern evaluation was impossible. The results are shown in Table 2.

Comparative Example 5
Under a dry nitrogen stream, 11.91 g (0.04 mol) of APBS and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP. TDA-100 15.01 g (0.05 mol) was added here together with NMP10g, it was made to react at 60 degreeC for 1 hour, and then it stirred at 180 degreeC for 4 hours. After completion of 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 already-closed ring polyimide 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, 3.0 g of cross-linking agent MX-270, 1.0 g of KBM-403 was added to 50 g of GBL to obtain a varnish L of the 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 the development film was all eluted, sensitivity evaluation/ Pattern evaluation was impossible. The results are shown in Table 2.

According to the present invention, it is possible to obtain a resin having high sensitivity and a residual film ratio when used in a photosensitive resin composition.

1 Silicon Wafer 2 Al Pad 3 Passivation Film 4 Insulating Film 5 Metal (Cr, Ti, etc.) Film 6 Wiring (Al, Cu, etc.)
7 Insulating film 8 Barrier metal 9 Scribe line 10 Solder bump

Claims (6)

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

(In the general formula (1), R ¹ contains 40 to 70 mol% of one or more organic groups selected from the following general formulas (2) to (7) when the total amount of R ¹ is 100 mol %. R ² each independently represents a divalent organic group having 2 to 40 carbon atoms.When the total amount of R ¹ and R ² is 100 mol %, R ¹ containing a fluorine atom and a fluorine atom are The total amount of R ² contained is 30 mol% or more, 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, provided that the structure represented by the general formula (1) has a phenolic hydroxyl group.)

(In the general formulas (2) to (7), R _{4 to} R ₄₈ , R ₅₀ , R ₅₁ , and R _{53 to} R ₈₁ are each independently a hydrogen atom, a halogen atom, or a monovalent group having 1 to 3 carbon atoms. In general formula (3), X ₁ represents an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms, or a divalent crosslinked structure formed by linking two or more of them. In the general formula (6), X ₂ is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, two or more organic groups selected from a divalent organic group having 1 to 3 carbon atoms or an arylene group. It is a divalent crosslinked structure formed by
A photosensitive resin composition containing the resin according to claim 1 . A photosensitive material containing (a) a resin having a structure represented by the general formula (8) as a main component, (b) a photoacid generator, and (c) a solvent, and having a positive photosensitivity. Resin composition.

(In the general formula (8), R ¹ contains one or more organic groups selected from the following general formulas (2) to (7) in an amount of 40 to 70 mol% when the total amount of R ¹ is 100 mol %. R ² each independently represents a divalent organic group having 2 to 40 carbon atoms.When the total amount of R ¹ and R ² is 100 mol %, R ¹ containing a fluorine atom and a fluorine atom are The total amount of R ² contained is 30 mol% or more, 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. However, the structure represented by the general formula (8) must have a fluorine component and a phenolic hydroxyl group.)

(In the general formulas (2) to (7), R _{4 to} R ₄₈ , R ₅₀ , R ₅₁ , and R _{53 to} R ₈₁ are each independently a hydrogen atom, a halogen atom, or a monovalent group having 1 to 3 carbon atoms. In general formula (3), X ₁ represents an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms, or a divalent crosslinked structure formed by linking two or more of them. In the general formula (6), X ₂ is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, two or more organic groups selected from a divalent organic group having 1 to 3 carbon atoms or an arylene group. It is a divalent crosslinked structure formed by
Formula (1) or (8) R ² of in further photosensitive resin composition according to claim 2 or 3 containing an aliphatic organic group. The photosensitive resin composition according to claim 4 , wherein the aliphatic organic group is an organic group containing an aliphatic alkyl group. A method for producing a heat-resistant resin film using the photosensitive resin composition according to claim 2 , wherein the photosensitive resin composition is applied onto a supporting substrate and dried to form a photosensitive resin film. A step of obtaining, a step of exposing the photosensitive resin film obtained by the step, a step of developing the exposed photosensitive resin film with an alkaline aqueous solution, and a step of heat-treating the photosensitive resin film after the developing A method for producing a heat-resistant resin film containing:

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