JP4684314B2 - Photosensitive polymer composition, pattern manufacturing method and electronic component - Google Patents

Description

  The present invention relates to a photosensitive polymer composition, a method for producing a pattern using the composition, and an electronic component. More specifically, the present invention is applied as a surface protective film, an interlayer insulating film, etc. of an electronic component such as a semiconductor element by heat treatment. The present invention relates to a positive heat-resistant photosensitive polymer composition that is a possible polyimide heat-resistant polymer, a pattern production method using the composition, and an electronic component.

  Polyimide is widely used as a surface protective film, an interlayer insulating film, and the like of semiconductor elements because it has excellent heat resistance and mechanical properties, is easy to form a film, and can flatten the surface.

  When polyimide is used as a surface protective film or an interlayer insulating film, a process for forming a through hole or the like is mainly performed by an etching process using a positive type photoresist. However, there is a problem that the process includes application and peeling of photoresist and is complicated. Thus, heat-resistant materials having photosensitivity have been studied for the purpose of rationalizing work processes.

  Regarding the photosensitive polyimide composition: 1. A polyimide precursor composition in which a photosensitive group is introduced by an ester bond (Patent Document 1, etc.); A composition in which a compound containing a carbon-carbon double bond that can be dimerized or polymerized by actinic radiation and an amino group and an aromatic bisazide is added to polyamic acid (Patent Document 2, etc.) is known.

  When using the photosensitive polyimide composition, it is usually applied to a substrate in a solution state and then dried, irradiated with actinic rays through a mask, and unexposed portions are removed with a developer to form a pattern. However, the above compositions 1 and 2 are negative, and an organic solvent is used for development. Therefore, in order to switch from an etching process using a positive photoresist to a negative photosensitive polyimide, it is necessary to change the mask of the exposure apparatus and the development equipment.

  On the other hand, for positive photosensitive polyimide, 3. 3. A polyimide precursor in which an o-nitrobenzyl group is introduced by an ester bond (Patent Document 3). A composition containing a polyamic acid ester containing a phenolic hydroxyl group and an o-quinonediazide compound (Patent Document 4) is known.

  However, the above-mentioned precursor 3 has a problem that the wavelength to be sensitized is mainly 300 nm or less, so that the sensitivity is low, and it is difficult to use especially with the recently used i-line stepper (365 nm single wavelength light). is there. The composition of 4 is more sensitive than the precursor of 3 but has a problem that it is not sufficient. On the other hand, a composition (Patent Document 5) to which a phenol dinuclear body or the like is added in order to improve sensitivity is known. However, when phenol dinuclear or the like is added, the relief pattern is likely to be deformed by heat in the heat treatment process after development, and the resolution is lowered. Thus, the present situation is that a positive photosensitive polyimide having sufficient sensitivity and no problem in practical use has not been obtained.

Japanese Patent Publication No.52-30207 Japanese Patent Publication No. 3-36861 JP 60-37550 A JP-A-4-204945 JP-A-9-302221

  The present invention overcomes the problems of the prior art described above. That is, the present invention provides a positive-type, heat-resistant photosensitive polymer composition having high sensitivity and small deformation of a pattern caused by heat treatment after development. The present invention also relates to a photosensitive polymer composition that further gives any of a higher sensitivity, resolution, shorter development time, a better shaped pattern and the like in addition to the above-mentioned problems.

  In addition, the present invention provides a method for producing a pattern with a high resolution and a good shape pattern by using the above-described highly sensitive composition. In addition, the present invention provides a highly reliable electronic component by having a pattern with a good shape.

The present invention includes (a) a polyamic acid ester or polyimide which is a polyimide precursor soluble in an alkaline aqueous solution having a carboxyl group or a phenolic hydroxyl group, (b) an o-quinonediazide compound that generates an acid by light, and (c) a phenolic hydroxyl group. And (d) a photosensitive polymer composition comprising a compound that causes a crosslinking reaction with the component (a) by heat,
The component (c) is represented by the general formula (II)

（式中、Ｘは単結合又は２価の基を示し、個々のＲ ⁴ 及びＲ ⁵ は各々独立にアルキル基を示し、ｍ及びｎは各々独立に０から３の整数を示す）で表される化合物を含むことを特徴とする感光性重合体組成物に関する。

(Wherein, X represents a single bond or a divalent group, each R ⁴ and R ⁵ each independently represents an alkyl group, and m and n each independently represents an integer of 0 to 3) The present invention relates to a photosensitive polymer composition comprising:

In the present invention , the component (a) is a compound represented by the general formula (I).

（式中、Ｒ¹は４価の有機基を示し、Ｒ²はカルボキシル基又はフェノール性水酸基を有する２価の有機基を示し、２つのＲ³は各々独立に１価の有機基を示す）で表される繰り返し単位を有するポリアミド酸エステルである感光性重合体組成物に関する。

(Wherein R ¹ represents a tetravalent organic group, R ² represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group, and two R ^{3 s} each independently represent a monovalent organic group) It is related with the photosensitive polymer composition which is a polyamic acid ester which has a repeating unit represented by these.

  The present invention also relates to a photosensitive polymer composition in which the component (d) is a compound having two or more epoxy groups. The present invention also relates to a photosensitive polymer composition in which the component (d) is a compound having two or more methylol groups.

The invention also relates to the (d) photosensitive polymer composition component is a compound having two or more alkoxymethyl group.

  The present invention also relates to a method for producing a pattern including a step of applying and drying any one of the above-mentioned photosensitive polymer compositions onto a support substrate, a step of exposing, a step of developing, and a step of heat treatment. The present invention also relates to a method for producing a pattern in which the light used in the exposure step is i-line. The present invention also relates to an electronic component having a pattern obtained by the above manufacturing method as a surface protective film or an interlayer insulating film.

  The photosensitive polymer composition of the present invention is positive and developable with an alkaline aqueous solution, has high sensitivity, has little pattern deformation due to heat treatment after development, and has a high resolution and good shape polyimide pattern. It is. Moreover, according to the pattern manufacturing method of the present invention, a pattern having a high resolution and a good shape can be obtained by using the above-described highly sensitive composition. In addition, the electronic component of the present invention has high reliability by having a polyimide pattern having a good shape as a surface protective film or an interlayer insulating film.

Since the component (a) in the present invention needs to be soluble in an alkaline aqueous solution used as a developer, a heavy selected from a polyimide precursor or a polyimide soluble in an alkaline aqueous solution having a carboxyl group or a phenolic hydroxyl group. It is a coalescence. The type of polymer in the present invention is excellent in heat resistance and exhibits excellent properties as an interlayer insulating film and surface protective film for semiconductor devices and multilayer wiring boards, so polyimide, polyamic acid, polyamic acid ester, polyamic acid amide The polyimide precursors such as are listed as candidates, and as described later, polyimide and the polyamic acid ester of the polyimide precursor are preferable .

  The component (a) has a carboxyl group or a phenolic hydroxyl group and is soluble in an alkaline aqueous solution used as a developer. However, after exposure, the dissolution rate of the exposed area increases due to changes in the component (b). Since a difference in dissolution rate from the unexposed area occurs, a relief pattern can be formed.

  The alkaline aqueous solution is an aqueous solution exhibiting alkalinity in which tetramethylammonium hydroxide, metal hydroxide, amine, and the like are dissolved in water.

  Among the polyimide precursor and polyimide of component (a) having a carboxyl group or a phenolic hydroxyl group, polyamic acid ester or polyimide is preferable because it has good lithography properties, and among them, it has a repeating unit represented by the general formula (I). The polyamic acid ester is more preferable because it has excellent adhesion to the substrate.

In the general formula (I), the tetravalent organic group represented by R ¹ reacts with diamine to form a structure of a polyimide precursor, which is a tetracarboxylic acid, a dianhydride thereof, or a derivative thereof. It is a residue, preferably a tetravalent aromatic group or an aliphatic group, more preferably a group having 4 to 40 carbon atoms, and further preferably a tetravalent aromatic group having 4 to 40 carbon atoms. An aromatic group refers to a group containing an aromatic ring (such as a benzene ring or a naphthalene ring). As the tetravalent aromatic group, it is preferable that all four bonding sites are present on the aromatic ring. These binding sites are divided into two sets of two binding sites, and those two binding sites are preferably located at the ortho or peri position of the aromatic ring. The two sets may be present in the same aromatic ring, or may be present in separate aromatic rings bonded through various bonds.

In the general formula (I), the divalent organic group having a carboxyl group or a phenolic hydroxyl group represented by R ² reacts with a tetracarboxylic acid, its dianhydride or a derivative thereof to form a structure of a polyimide precursor. Is a residue excluding an amino group of a diamine having a carboxyl group or a phenolic hydroxyl group, preferably an aromatic group or an aliphatic group, and having 2 to 40 carbon atoms excluding the carboxyl group More preferred is an aromatic group. Here, as the aromatic group, those in which the two binding sites are directly present on the aromatic ring are preferable. In this case, the two binding sites are present in the same aromatic ring but in different aromatic rings. May be. Moreover, it is preferable to have 1-8 carboxyl groups or phenolic hydroxyl groups, and those which are directly bonded to an aromatic ring are also preferable.

In the general formula (I), the monovalent organic group represented by R ³ is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably one having 1 to 20 carbon atoms.

  The polyimide precursor having a repeating unit represented by the general formula (I) may have a repeating unit other than the repeating unit represented by the general formula (I). For example, the following general formula (IV)

（式中、Ｒ⁸は４価の有機基を示し、Ｒ⁹はカルボキシル基及びフェノール性水酸基を有しない２価の有機基を示し、Ｒ¹⁰は１価の有機基を示す）で表される繰り返し単位を有してもよい。

(Wherein R ⁸ represents a tetravalent organic group, R ⁹ represents a divalent organic group having no carboxyl group or phenolic hydroxyl group, and R ¹⁰ represents a monovalent organic group). You may have a repeating unit.

In the general formula (IV), the description of the tetravalent organic group represented by R ⁸ is the same as the description of R ¹ . Further, in the general formula (IV), the explanation of the divalent organic group having no carboxyl group and phenolic hydroxyl group represented by R ⁹ has neither carboxyl group nor phenolic hydroxyl group in the explanation of R ^2. Is the same as R ² except. Further, in the general formula (IV), the description of the monovalent organic group among the groups represented by R ¹⁰ is the same as the description of R ³ described above. In general formula (I) and general formula (IV), there are two groups represented by R ³ and R ¹⁰ in each repeating unit, but these may be the same or different. In the plurality of repeating units, the groups represented by R ¹ , R ² , R ³ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different.

  In the polyamic acid ester having a repeating unit represented by the general formula (I), the ratio of the repeating unit of the general formula (I) to the general formula (IV) is as follows: the former number is a and the latter number is b. It is preferable that it is 0.2-1 in a / (a + b), and it is more preferable that it is 0.4-1. If this value is less than 0.2, the solubility in an alkaline aqueous solution tends to be poor.

In the polyamic acid ester having the repeating unit represented by the general formula (I), as another repeating unit, one of two R ³ or two R ^{10 in} the general formula (I) or the general formula (IV). Alternatively, both may have a repeating unit changed to a hydrogen atom.

  In the polyamic acid ester, the total number of repeating units of the general formula (I) and the general formula (IV), that is, the total number of repeating units in which the carboxyl group in the tetracarboxylic acid residue is completely esterified is The total number of repeating units is preferably 50% to 100%, more preferably 80% to 100%, and particularly preferably 90 to 100%. In addition, the repeating unit here is one unit composed of one acid residue and one amine residue.

  The molecular weight of the polyimide precursor or polyimide of the component (a) in the present invention is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, in terms of weight average molecular weight. The molecular weight can be measured by gel permeation chromatography and converted using a standard polystyrene calibration curve to obtain a value.

  In the present invention, when the component (a) is a polyamic acid ester, for example, a tetracarboxylic acid diester dihalide (chloride, bromide, etc.), a diamine having a carboxyl group or a phenolic hydroxyl group, and, if necessary, a carboxyl group or It can be obtained by reacting with a diamine having no phenolic hydroxyl group. In this case, the reaction is preferably performed in an organic solvent in the presence of a dehalogenating agent.

  The tetracarboxylic acid diester dihalide is preferably tetracarboxylic acid diester dichloride. Tetracarboxylic acid diester dichloride can be obtained by reacting a tetracarboxylic acid diester obtained by reacting a tetracarboxylic dianhydride and an alcohol compound with thionyl chloride.

  Examples of the tetracarboxylic 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, 3,3 ′, 4,4′- Biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5 , 6-Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6 -Pyridine tetra Rubonic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Aromatic tetracarboxylic dianhydrides such as tetraphenylsilanetetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride are preferred, and these are used alone. Or it can use in combination of 2 or more types.

  In the polyamic acid ester, an alcohol compound is used as a raw material that becomes an ester moiety in the side chain. Examples of the alcohol compound include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, 1-pentanol, 2-pentanol, 3- Preference is given to alkyl alcohols such as pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol and 3-hexanol, phenol, benzyl alcohol and the like, and these can be used alone or in combination of two or more.

  Furthermore, diamine is used as a raw material for the polyamic acid ester. A diamine having an acidic group such as a carboxyl group or a phenolic hydroxyl group can be used in an aqueous alkaline solution when the carboxyl group of the tetracarboxylic acid does not remain, such as the polyamic acid ester, polyamic acid amide, and polyimide. Always used to melt. Examples of such diamines include 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, and bis (4-amino-3-carboxyl). Phenyl) methylene, bis (4-amino-3-carboxyphenyl) ether, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-5,5′-dicarboxy-2, 2'-dimethylbiphenyl, 1,3-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino- 3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) pro Bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxy) Aromatic diamines such as phenyl) ether, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane are preferred, and these are used alone or in combination of two or more. Used in combination.

  Examples of the diamine having no carboxyl group and no phenolic hydroxyl group include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl sulfide. , Benzidine, 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, 4,4'-diamino-2,2'-dimethylbiphenyl Group diamine compounds are preferred, which It can be used alone or in combination of two or more.

  In addition, in order to improve heat resistance, 4,4′-diaminodiphenyl ether-3-sulfonamide, 3,4′-diaminodiphenyl ether-4-sulfonamide, 3,4′-diaminodiphenyl ether-3′-sulfonamide, 3 , 3'-diaminodiphenyl ether-4-sulfonamide, 4,4'-diaminodiphenyl ether-3-carboxamide, 3,4'-diaminodiphenyl ether-4-carboxamide, 3,4'-diaminodiphenyl ether-3'-carboxamide, 3, , 3′-diaminodiphenyl ether-4-carboxamide and other diamines having a sulfonamide group or a carboxamide group can be used alone or in combination of two or more. When used in combination, these are 15 mol% or less in the total amount of the diamine compound. Can be used in Preferred, it is more preferably in the range of 10 mol% or less.

  In the synthesis of the polyamic acid ester, a method for synthesizing the tetracarboxylic acid diester compound can be obtained, for example, by mixing the tetracarboxylic dianhydride and the alcohol compound in an organic solvent in the presence of a base. The ratio (molar ratio) between the tetracarboxylic dianhydride and the alcohol compound is preferably in the range of 1/2 to 1 / 2.5, and most preferably 1/2, in the former / the latter. Further, the ratio (molar ratio) of the tetracarboxylic dianhydride and the base is preferably in the range of 1 / 0.001 to 1/3 in the former / the latter, and is set to 1 / 0.005 to 1/2. It is more preferable. The reaction temperature is preferably 10 to 60 ° C., and the reaction time is preferably 3 to 24 hours.

  A method for synthesizing tetracarboxylic acid diester dichloride is known. For example, it can be obtained by reacting a tetracarboxylic acid diester dissolved in an organic solvent by dropwise addition of thionyl chloride. The ratio (molar ratio) of tetracarboxylic acid diester to thionyl chloride is preferably in the range of 1 / 1.1-1 / 2. The range is more preferable. The reaction temperature is preferably -20 to 40 ° C, and the reaction time is preferably 1 to 10 hours.

  The polyamic acid ester is prepared by, for example, dissolving a dehalogenating agent such as the diamine and pyridine in an organic solvent, dropping and reacting a tetracarboxylic acid diester dihalide dissolved in the organic solvent, and then in a poor solvent such as water. It is obtained by throwing it in, filtering the precipitate and drying it. The ratio of the total amount of diamine and the tetracarboxylic acid diester dihalide (molar ratio) is preferably in the range of 0.6 / 1 to 1 / 0.6 in the former / the latter, 0.7 / 1 to 1 / 0.7. A range is more preferred. The reaction temperature is preferably -20 to 40 ° C, and the reaction time is preferably 1 to 10 hours. The ratio of the dehalogenating agent and the tetracarboxylic acid diester dihalide is preferably in the range of 1.8 / 1 to 2.2 / 1, the former / the latter (molar ratio) being 1.9 / 1 to 2.1 /. A range of 1 is more preferred.

  In the synthesis of the polyamic acid ester, when a diamine compound having no acidic group such as a carboxyl group or a phenolic hydroxyl group is used in combination, the ratio of the diamine having an acidic group and the diamine having no acidic group is 20 to 100 mol%. The latter 80 to 0 mol% is preferably used so that the whole is 100 mol%, the former 40 to 100 mol%, and the latter 60 to 0 mol% is used so that the whole is 100 mol%. Is more preferable. The former diamine is used to impart solubility to an aqueous alkaline solution to the polyamic acid ester, but if it is less than 20 mol%, the sensitivity tends to decrease or the development time tends to be long.

  The polyamic acid ester having an acidic group has been described in detail. However, when a polyamic acid is used as the component (a), a carboxyl group as a residue of a tetracarboxylic acid is present. It is not necessary to use a diamine having an acidic group such as a hydroxyl group. The polyamic acid can be obtained by directly reacting the tetracarboxylic dianhydride and diamine in an organic solvent.

  Moreover, what a part of ester is a carboxyl group can also be used as a polyamic acid ester which does not have an acidic group in a diamine residue. This is obtained by reacting the tetracarboxylic dianhydride, tetracarboxylic acid diester dihalide and diamine.

  In addition, in the case of polyamic acid amide or polyimide, in order to make it soluble in an alkaline aqueous solution, a diamine having an acidic group such as a carboxyl group or a phenolic hydroxyl group is generally used as the diamine. The preferred ratio of the diamine not used is the same as that in the synthesis of the polyamic acid ester.

  The polyamic acid amide is a monoamine compound such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutyl in the synthesis of the polyamic acid ester instead of the alcohol compound. It can be synthesized by using amine, 1-pentylamine, 2-pentylamine, 3-pentylamine, isoamylamine, 1-hexylamine, 2-hexylamine, 3-hexylamine, morpholine, aniline, benzylamine, etc. it can. A polyimide is obtained by once synthesizing a polyamic acid and dehydrating and ring-closing it.

  The o-quinonediazide compound that generates an acid by light, which is the component (b) used in the present invention, is a photosensitizer and has a function of generating an acid and increasing the solubility of the light irradiated portion in an alkaline aqueous solution. Is.

  The o-quinonediazide compound has a site that changes to carboxylic acid by light. This compound can be obtained, for example, by subjecting o-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent. Examples of the o-quinonediazide sulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. Etc. can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,3,4-trihydroxybenzophenone. 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4, 3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro -1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2, -a] indene, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane can be used.

  Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl sulfide. , O-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3- Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis ( 3-amino-4-hydroxyphenyl) hexafluo Propane, and bis (4-amino-3-hydroxyphenyl) hexafluoropropane can be used.

  The o-quinonediazide sulfonyl chloride and the hydroxy compound and / or amino compound may be blended so that the total of hydroxy group and amino group is 0.5 to 1 equivalent with respect to 1 mol of o-quinonediazide sulfonyl chloride. preferable. A preferred ratio of the dehydrochlorinating agent and o-quinonediazidesulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95. A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 10 hours.

  As the reaction solvent, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used. Examples of the dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

  In the photosensitive polymer composition of the present invention, the blending amount of component (b) is based on 100 parts by weight of component (a) in terms of the difference in dissolution rate between the exposed and unexposed areas and the allowable sensitivity range. 5-100 weight part is preferable and 8-40 weight part is more preferable.

  The component (c) used in the present invention is a compound having a phenolic hydroxyl group. By using this component (c), the dissolution rate of the exposed area when developing with an alkaline aqueous solution is increased, and the sensitivity can be increased. In addition, the polyimide or polyimide precursor as said (a) component is excluded from (c) component of this invention. The component (c) is preferably a compound having a molecular weight of 1,500 or less because the effect of promoting the dissolution of the exposed portion decreases as the molecular weight increases.

  As the compound having a phenolic hydroxyl group as the component (c), the following general formula (II)

（式中、Ｘは単結合又は２価の基を示し、Ｒ⁴及びＲ⁵は各々独立にアルキル基を示し、ｍ及びｎは各々独立に０から３の整数を示す）で示される化合物が、好ましいものとして使用される。一般式（II）で表される化合物は、フェノール性水酸基を有する化合物の中でも、感度において、優れるものである。

(Wherein X represents a single bond or a divalent group, R ⁴ and R ⁵ each independently represents an alkyl group, and m and n each independently represents an integer of 0 to 3) Used as preferred. The compound represented by the general formula (II) is excellent in sensitivity among compounds having a phenolic hydroxyl group.

  Specific examples of the compound represented by the general formula (II) include 2,2′-biphenol, 5,5′-dimethyl-[(1,1′-biphenyl) -2,2′-diol], 2, 2'dihydroxydiphenylmethane, 2,2'-methylenebis (4-methylphenol), 2,2'-ethylidenebis (4-methylphenol), 2,2'-methylenebis (4,6-dimethylphenol), 2,6 -Bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol and the like. Of these, 2,2'-methylenebis (4-methylphenol) is most preferable in terms of sensitivity.

  As phenol compounds other than the compound represented by the general formula (II), biphenol, bisphenol A, bisphenol F, 4,4′-dihydroxybenzophenone, tris (4-hydroxyphenyl) methane, 2,4 ′, 4 ″ -methyl Redentrisphenol, tris (4-hydroxyphenyl) ethane, tris (4-hydroxy-2-methylphenyl) ethane, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4 ′, 4 ″, 4 ′ ″-(1,2-ethanedylidene) tetrakisphenol, 2,2′-methylenebis [6-[(2-hydroxy-5-methylphenyl) methyl] -4-methyl Phenol can also be used.

  In the photosensitive polymer composition of the present invention, the blending amount of the component (c) is 1 to 30 with respect to 100 parts by weight of the component (a) from the viewpoint of the development time and the allowable width of the unexposed part remaining film ratio. Part by weight is preferable, and 5 to 20 parts by weight is more preferable.

  In the present invention, a compound that causes a crosslinking reaction with the component (a) by heat is used as the component (d). Here, as temperature which raise | generates the crosslinking reaction of (d) component, 120-350 degreeC is preferable. The crosslinking reaction occurs during the heat treatment after pattern formation by development. The crosslinking reaction generally occurs between a phenolic hydroxyl group, a carboxyl group, an amino group, etc. present in the component (a) and a functional group capable of reacting with these groups in the component (d).

  The component (d) is preferably a compound having two or more epoxy groups, a compound having a methylol group, or a compound having two or more alkoxymethyl groups. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, glycidylamine type epoxy resin, polysulfide type epoxy resin, dimethylol urea, tri Examples include methylol melamine, hexamethylol melamine, dimethylol ethylene urea, dimethylol propylene urea, 1,4-bis (methoxyphenoxy) benzene, trimethoxymethyl melamine, and hexamethoxymethyl melamine. Of these, bisphenol A type epoxy resin, dimethylolurea, and 1,4-bis (methoxyphenoxy) benzene are most preferable from the viewpoint of reducing deformation caused by heat.

  In the photosensitive polymer composition of the present invention, the blending amount of the component (d) is 100 parts by weight of the component (a) from the viewpoint of the deformation of the pattern in the heat treatment after development and the allowable width of the residue generated during development. The amount is preferably 0.5 to 20 parts by weight, and more preferably 5 to 10 parts by weight.

In this invention, you may use the compound (e) which has the effect which inhibits melt | dissolution of (a) component with respect to alkaline aqueous solution as another arbitrary component . By using such a compound (e) , the dissolution rate of the unexposed area when developing with an alkaline aqueous solution is decreased, and the solubility difference between the exposed area and the unexposed area is increased in combination with the effect of the component (c). Pattern can be formed.

As said compound (e), an onium salt, a diaryl compound, and a tetraalkylammonium salt are preferable. Examples of the onium salt include iodonium salts such as diaryliodonium salts, sulfonium salts such as triarylsulfonium salts, diazonium salts such as phosphonium salts, aryldiazonium salts, and the like. Examples of the diaryl compound include those in which two aryl groups such as diaryl sulfone, diaryl ketone, diaryl ether, diarylpropane, diarylhexafluoropropane and the like are bonded via a bonding group. Examples of the tetraalkylammonium salt include tetraalkylammonium halides in which the alkyl group is a methyl group or an ethyl group.

  Among these, examples showing good dissolution inhibiting effects include diaryliodonium salts, diarylsulfone compounds, tetramethylammonium halide compounds, and the like. Examples of the diaryl iodonium salt include diphenyl iodonium salt, examples of the diaryl urea compound include diphenyl urea and dimethyl diphenyl urea, examples of the diaryl sulfone compound include diphenyl sulfone and dimethyl diphenyl sulfone, and examples of the tetramethylammonium halide compound. Examples thereof include tetramethylammonium chloride, tetramethylammonium bromide, and tetramethylammonium iodide.

  Among them, general formula (III)

（式中、個々のＲ⁶及びＲ⁷は各々独立に１価の有機基を示し、ｏ及びｐは各々独立に０から５までの整数を示し、Ｘ-は対陰イオンを示す）で表されるジフェニルヨードニウム塩が好ましい。Ｒ⁶及びＲ⁷で示される１価の有機基としては、アルキル基、アルコキシ基、アリール基などが挙げられ、それらの炭素原子数としては、１〜８が好ましい。

Wherein each R ⁶ and R ⁷ each independently represents a monovalent organic group, o and p each independently represent an integer from 0 to 5, and X − represents a counter anion. The diphenyliodonium salt is preferred. Examples of the monovalent organic group represented by R ⁶ and R ⁷ include an alkyl group, an alkoxy group, and an aryl group, and the number of carbon atoms is preferably 1 to 8.

  Examples of the diphenyliodonium salt include diphenyliodonium nitrate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nanofluorobutanesulfonate, diphenyliodonium toluenesulfonate, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium iodide, diphenyliodonium hexa Fluorophosphate, diphenyliodonium-9,10-dimethoxyanthracene-2-sulfonate, diphenyliodonium-8-anilinonaphthalene-1-sulfonate, 4-methoxydiphenyliodonium nitrate, 4-methoxydiphenyliodonium trifluoromethanesulfonate, 4, 4'-di-t-butyldiphenyl De trifluoromethanesulfonate, and the like.

  In the photosensitive polymer composition of the present invention, when the compound (e) is used, the blending amount thereof is set to 0.000 parts by weight with respect to 100 parts by weight of the component (a) from the viewpoints of sensitivity and allowable width of development time. 01-15 weight part is preferable and 0.05-10 weight part is more preferable.

  The photosensitive polymer composition of the present invention dissolves the component (a), the component (b), the component (c), the component (d) and, if necessary, the optional compound (e) and other components in a solvent. Can be obtained. Examples of the solvent include aprotic polarities such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, and γ-butyrolactone. Solvents are preferred, and these may be used alone or in combination of two or more. In order to improve coating properties, solvents such as diethyl ketone, diisobutyl ketone, methyl amyl ketone, ethyl lactate, propylene glycol monomethyl ether acerate can be used in combination.

  In the photosensitive polymer composition of the present invention, if necessary, an organic silane compound, an aluminum chelate compound or a general formula (V) is used as an adhesion assistant.

（式中、Ｒ¹¹は４価の有機基を示し、Ｒ¹²は２価の有機基を示し、Ｒ¹³は１価の有機基を示し、ｚは１以上の整数を示す）で表される繰り返し単位を有するポリアミド酸を含むことができる。

(Wherein R ¹¹ represents a tetravalent organic group, R ¹² represents a divalent organic group, R ¹³ represents a monovalent organic group, and z represents an integer of 1 or more). Polyamic acid having a repeating unit can be included.

  Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and ureapropyl. Examples include triethoxysilane. Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like.

In the polyamic acid having a siloxane structure having a repeating unit represented by the general formula (V), the tetravalent organic group represented by R ¹¹ is a residue of tetracarboxylic dianhydride that is a raw material for polyimide. A tetravalent aromatic group or an aliphatic group is preferred, those having 4 to 40 carbon atoms are more preferred, and tetravalent aromatic groups having 4 to 40 carbon atoms are more preferred. As for a tetravalent aromatic group, it is preferable that all four bonding sites exist in an aromatic ring. These binding sites are preferably divided into two sets of two binding sites, the two binding sites being located at the ortho or peri position of the aromatic ring. The two sets may be present on the same aromatic ring, or may be present on separate aromatic rings bonded through various bonds.

In the general formula (V), the portion between the two R ¹² is a residue excluding the amino group of the silicone diamine compound, and this portion preferably has 6 to 40 carbon atoms as a whole. As the divalent organic group represented by R ¹² , those having 1 to 10 carbon atoms are preferable, and the above-mentioned alkylene group, phenylene group and the like are preferable, and two R ¹² may be the same. May be different. As the monovalent organic group represented by R ¹³ , an organic group having 1 to 5 carbon atoms is preferable, and an alkyl group or a phenyl group having the above carbon atoms is preferable. When using an adhesion assistant, 0.1 to 20 parts by weight is preferable with respect to 100 parts by weight of component (a), and 0.5 to 10 parts by weight is more preferable.

The photosensitive polymer composition of the present invention can be formed into a polyimide pattern through a step of coating and drying on a support substrate, a step of exposing, a step of developing, and a step of heat treatment. In the step of applying and drying on a support substrate, this photosensitive polymer composition is spinner or the like on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO _2, etc.) or silicon nitride. After spin coating using, dry using a hot plate, oven or the like.

  Next, in the exposure step, the photosensitive polymer composition formed into a film on the support substrate is irradiated with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask. Among these, since a high-resolution pattern can be formed, exposure using i-line (365 nm monochromatic light) is particularly preferable. In the development step, a relief pattern is obtained by removing the exposed portion with a developer. Examples of the developer include alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is preferably 0.1 to 10% by weight.

  Furthermore, alcohols and surfactants can be added to the developer and used. Each of these can be blended in the range of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the developer. Next, in the heat treatment step, the obtained relief pattern is preferably subjected to heat treatment at 150 to 450 ° C., so that a heat-resistant polyimide pattern having an imide ring or other cyclic group is obtained.

  The photosensitive polymer composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards, and specifically, surface protection films and interlayer insulating films of semiconductor devices, and interlayer insulation of multilayer wiring boards. It can be used for forming a film or the like. The semiconductor device of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

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

  Next, a chlorinated rubber-based or phenol novolak-based photosensitive resin layer 5 is formed on the interlayer insulating film 4 by spin coating, and a window is formed so that a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. 6A is provided (step (b)). The interlayer insulating film 4 in the window 6A is selectively etched by dry etching means using a gas such as oxygen or carbon tetrafluoride to open the window 6B. Next, the photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (step (c)).

  Furthermore, the second conductor layer 7 is formed using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (step (d)). When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps.

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

Hereinafter, the present invention will be described with reference to examples.
Example 1
In a 0.3 liter flask equipped with a stirrer and a thermometer, 24.82 g (0.08 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 11.86 g of n-butyl alcohol (0.16 mol), 0.4 g (0.004 mol) of triethylamine and 110 g of N-methylpyrrolidone (NMP) were stirred and reacted at room temperature for 8 hours to give 3,3 ′, 4,4′- An NMP solution (α) of diphenyl ether tetracarboxylic acid di-n-butyl ester was obtained.

  Then, after cooling the flask to 0 ° C., 17.13 g (0.144 mol) of thionyl chloride was added dropwise to react for 1 hour, and di-n-butyl 3,3 ′, 4,4′-diphenyl ether tetracarboxylate. A solution (β) of ester dichloride was obtained. Next, 105 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 26.37 g (0.072 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. After adding and dissolving with stirring, 22.78 g (0.288 mol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., di-n-butyl 3,3 ′, 4,4′-diphenyl ether tetracarboxylate After the ester dichloride solution (β) was added dropwise over 20 minutes, the temperature was raised to 30 ° C. and stirring was continued for 1 hour. The solution was poured into 3 liters of water, and the precipitate was collected and washed, and then dried under reduced pressure to obtain a polyamic acid ester (δ).

  10.00 g of polyamic acid ester (δ), 1.40 g of an orthoquinonediazide compound obtained by reacting tris (4-hydroxyphenyl) methane with naphthoquinone-1,2-diazide-5-sulfonyl chloride at a molar ratio of 1/3, 2 , 2′-methylenebis (4-methylphenol) 1.20 g, YL-980 (manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin) 0.50 g, diphenyliodonium nitrate 0.10 g, urea propyltriethoxy 0.60 g of a 50% methanol solution of silane was stirred and dissolved in 17.78 g of N-methylpyrrolidone. This solution was filtered under pressure using a Teflon (registered trademark) filter having a pore size of 3 μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and heat-dried on a hot plate at 110 ° C. for 3 minutes to obtain a 7.5 μm coating film. This coating film was exposed to 100 to 500 mJ / cm ² via a reticle using an i-line stepper (manufactured by Hitachi, Ltd.) as an exposure machine. Subsequently, paddle development was performed for 80 seconds using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide as a developer, and washed with pure water to obtain a relief pattern. The appropriate exposure was determined to be 300 mJ / cm ² by pattern observation. The remaining film ratio in the unexposed area was 77%. When the obtained relief pattern was heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere, a good polyimide film pattern was obtained. The resolution was 3 μm and there was no change from the value immediately after development.

Example 2
Orthoquinonediazide prepared by reacting 10.00 g of the polyamic acid ester (δ) prepared in Example 1, tris (4-hydroxyphenyl) methane and naphthoquinone-1,2-diazide-5-sulfonyl chloride at a molar ratio of 1/3. 1.40 g of compound, 1.20 g of 2,2′-methylenebis (4-methylphenol), 0.50 g of dimethylolurea, 0.10 g of diphenyliodonium nitrate, 0.60 g of 50% methanol solution of ureapropyltriethoxysilane, The mixture was dissolved in 17.78 g of N-methylpyrrolidone with stirring. This solution was filtered under pressure using a Teflon (registered trademark) filter having a pore size of 3 μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner and heat-dried on a hot plate at 110 ° C. for 3 minutes to obtain a 7.6 μm coating film. This coating film was exposed to 100 to 500 mJ / cm ² via a reticle using an i-line stepper (manufactured by Hitachi, Ltd.) as an exposure machine. Subsequently, paddle development was performed for 90 seconds using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide as a developer, and washed with pure water to obtain a relief pattern. The appropriate exposure was determined to be 300 mJ / cm ² by pattern observation. The remaining film ratio in the unexposed area was 79%. The pattern shape was good. When the obtained relief pattern was heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere, a good polyimide film pattern was obtained. The resolution was 3 μm and there was no change from the value immediately after development.

Example 3
Orthoquinonediazide prepared by reacting 10.00 g of the polyamic acid ester (δ) prepared in Example 1, tris (4-hydroxyphenyl) methane and naphthoquinone-1,2-diazide-5-sulfonyl chloride at a molar ratio of 1/3. 1.40 g of compound, 1.20 g of 2,2′-methylenebis (4-methylphenol), 0.50 g of 1,4-bis (methoxyphenoxy) benzene, 0.10 g of diphenyliodonium nitrate, 50 of urea propyltriethoxysilane A 0.60 g% methanol solution was stirred and dissolved in 17.78 g of N-methylpyrrolidone. This solution was filtered under pressure using a Teflon (registered trademark) filter having a pore size of 3 μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner and heat-dried on a hot plate at 110 ° C. for 3 minutes to obtain a 7.6 μm coating film. This coating film was exposed to 100 to 500 mJ / cm ² via a reticle using an i-line stepper (manufactured by Hitachi, Ltd.) as an exposure machine. Subsequently, paddle development was performed for 80 seconds using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide as a developer, and washed with pure water to obtain a relief pattern. The appropriate exposure was determined to be 350 mJ / cm ² by pattern observation. The remaining film ratio in the unexposed area was 80%. The pattern shape was good. When the obtained relief pattern was heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere, a good polyimide film pattern was obtained. The resolution was 3 μm and there was no change from the value immediately after development.

Comparative Example 1
Ortho obtained by reacting 10.00 g of the polyamic acid ester (δ) obtained in Example 1, tris (4-hydroxyphenyl) methane and naphthoquinone-1,2-diazide-5-sulfonyl chloride at a molar ratio of 1/3. 1.40 g of a quinonediazide compound, 1.20 g of 2,2′-methylenebis (4-methylphenol) and 0.60 g of a 50% methanol solution of urea propyltriethoxysilane were dissolved in 17.78 g of N-methylpyrrolidone with stirring. This solution was filtered under pressure using a Teflon (registered trademark) filter having a pore size of 3 μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner and heat-dried at 105 ° C. for 3 minutes on a hot plate to obtain a 7.4 μm coating film. This coating film was exposed to 100 to 500 mJ / cm ² via a reticle using an i-line stepper (manufactured by Hitachi, Ltd.) as an exposure machine. Next, paddle development was performed for 25 seconds using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide as a developer, and washed with pure water to obtain a relief pattern. The appropriate exposure was determined to be 450 mJ / cm ² by pattern observation. The remaining film ratio in the unexposed area was 80%. When the obtained relief pattern was heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere, a polyimide film pattern was obtained, but the resolution was 10 μm, which was worse than 3 μm immediately after development.

  The photosensitive polymer composition of the present invention is positive and developable with an alkaline aqueous solution, has high sensitivity, has little pattern deformation due to heat treatment after development, and has a high resolution and good shape polyimide pattern. It is.

  Moreover, according to the pattern manufacturing method of the present invention, a pattern having a high resolution and a good shape can be obtained by using the above-described highly sensitive composition. In addition, the electronic component of the present invention has high reliability by having a polyimide pattern having a good shape as a surface protective film or an interlayer insulating film.

It is a manufacturing process figure of the semiconductor device of a multilayer wiring structure.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Protective film 3 1st conductor layer 4 Interlayer insulating film layer 5 Photosensitive resin layer 6A, 6B, 6C Window 7 2nd conductor layer 8 Surface protective film layer

Claims (9)

(A) Polyamic acid ester or polyimide that is a polyimide precursor soluble in an alkaline aqueous solution having a carboxyl group or a phenolic hydroxyl group, (b) an o-quinonediazide compound that generates an acid by light, (c) a compound having a phenolic hydroxyl group, And (d) a photosensitive polymer composition comprising a compound that causes a crosslinking reaction with the component (a) by heat,
The component (c) is represented by the general formula (II)

(Wherein, X represents a single bond or a divalent group, each R ⁴ and R ⁵ each independently represents an alkyl group, and m and n each independently represents an integer of 0 to 3) And a photosensitive polymer composition comprising a compound having a molecular weight of 1500 or less . Component (c) is 2,2′-biphenol, 5,5′-dimethyl-[(1,1′-biphenyl) -2,2′-diol], 2,2′dihydroxydiphenylmethane, 2,2′- Methylenebis (4-methylphenol), 2,2′-ethylidenebis (4-methylphenol), 2,2′-methylenebis (4,6-dimethylphenol) and 2,6-bis [(2-hydroxy-5- The photosensitive polymer composition according to claim 1, which is a kind selected from the group consisting of (methylphenyl) methyl] -4-methylphenol. The component (a) is represented by the general formula (I)

(Wherein R ¹ represents a tetravalent organic group, R ² represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group, and two R ^{3 s} each independently represent a monovalent organic group) photosensitive polymer composition according to claim 1 or 2 is a polyamic acid ester having in represented by repeating units. The photosensitive polymer composition according to any one of claims 1 to 3, wherein the component (d) is a compound having two or more epoxy groups. The photosensitive polymer composition according to any one of claims 1 to 3, wherein the component (d) is a compound having two or more methylol groups. The photosensitive polymer composition according to any one of claims 1 to 3, wherein the component (d) is a compound having two or more alkoxymethyl groups. The manufacturing method of a pattern including the process of apply | coating and drying the photosensitive polymer composition of any one of Claims 1-6 on a support substrate, the process of exposing, the process of developing, and the process of heat-processing. The method for producing a pattern according to claim 7 , wherein the light used in the exposing step is i-line. An electronic component comprising a pattern obtained by the production method according to claim 7 or 8 as a surface protective film or an interlayer insulating film.

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