JP2012203359A - Negative photosensitive resin composition, pattern forming method and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition that exhibits good sensitivity and resolution and imparts sufficient chemical resistance, heat resistance and mechanical characteristics even when heat-treated at a low temperature of 220°C or lower.SOLUTION: There is provided a negative photosensitive resin composition comprising: (a) a polybenzoxazole precursor having a repeating unit represented by general formula (I); (b) a compound that generates an acid by irradiation with actinic rays in a wavelength region from 365 to 700 nm; (c) a compound that can crosslink or polymerize with the component (a) by an action of an acid; and (d) a compound that has no absorption in a wavelength region from 365 to 700 nm and generates an acid by heat. In formula (I), U and V each independently represent a divalent organic group; and V represents a group including an aliphatic structure having 1 to 30 carbon atoms, or U represents a group including an aliphatic structure having 2 to 30 carbon atoms that constitute the main chain.

Description

  The present invention relates to a negative photosensitive resin composition, a method for producing a pattern, and an electronic component. More specifically, the present invention relates to a heat-resistant negative photosensitive resin composition containing a heat-resistant polymer having photosensitivity. The present invention relates to a pattern manufacturing method and an electronic component.

  Conventionally, resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used for surface protection films, interlayer insulating films, and the like of semiconductor elements. Among them, polyimide is excellent in heat resistance and mechanical properties. In recent years, a photosensitive polyimide having a photosensitive property imparted to the polyimide itself has been used. When this is used, the pattern production process can be simplified, and a complicated production process can be shortened.

  The photosensitive polyimide has required an organic solvent such as N-methylpyrrolidone at the time of development. Recently, a positive photosensitive polyimide that can be developed with an alkaline aqueous solution has been proposed. As a positive photosensitive polyimide, a method of mixing a naphthoquinonediazide compound as a photosensitive agent with polyimide or a polyimide precursor (for example, see Patent Documents 1 and 2) has been proposed.

  Recently, a polybenzoxazole or a polybenzoxazole precursor has been proposed as a positive photosensitive resin that can be developed with an alkaline aqueous solution. Since polybenzoxazole or polybenzoxazole precursor has a larger contrast between the dissolution rate of the exposed portion and the unexposed portion than polyimide or polyimide precursor, it is possible to form a more precise pattern (for example, patent Reference 3).

  However, the positive photosensitive polybenzoxazole has low sensitivity and resolution because a residue remains when the film becomes thick due to the system specific to the positive photosensitive resin in which the exposed portion is dissolved in the developer. In view of this, negative photosensitive polybenzoxazole that can be developed with an alkaline aqueous solution and exhibits good sensitivity and resolution even with a thick film has been proposed (for example, Patent Document 4). However, with the recent development of a wide variety of semiconductor devices, photosensitive resins exhibiting superior sensitivity and resolution are required.

  In addition, recently, devices such as MRAM (Magnet Resistive RAM) that are vulnerable to high-temperature heating processes have also been proposed. Therefore, negative-type photosensitive that provides sufficient heat resistance and mechanical properties even at low-temperature heat treatment. A functional resin composition has also been proposed (for example, Patent Document 5).

JP-A 64-60630 US Pat. No. 4,395,482 JP 2009-265520 A JP 2008-281961 A JP 2008-281961 A

  However, when the photosensitive resin composition of Patent Document 5 is thermally cured at around 200 ° C., there is a problem that the chemical resistance of the cured film is not sufficient. Therefore, the present invention provides a negative photosensitive resin composition that exhibits good sensitivity and resolution, and provides sufficient chemical resistance, heat resistance, and mechanical properties even when heat-treated at a low temperature of 220 ° C. or lower. .

  The present invention also provides a method for producing a pattern that can be developed with an alkaline aqueous solution and that has a good shape pattern excellent in heat resistance and mechanical properties by using the negative photosensitive resin composition. . Another object of the present invention is to provide a highly reliable electronic component by having a pattern having a good shape and characteristics.

（式中、Ｕ及びＶは、各々独立に二価の有機基を示す。Ｖが炭素数１〜３０の脂肪族構造を含む基であるか、又はＵが、主鎖を構成する炭素数が２〜３０の脂肪族構造を含む基である。） According to the present invention, the following negative photosensitive resin composition and the like are provided.
That is, the negative photosensitive resin composition according to the present invention comprises (a) a polybenzoxazole precursor having a repeating unit represented by the general formula (I), and (b) irradiation with actinic rays in a wavelength region of 365 to 700 nm. A compound capable of generating an acid, (c) a compound that can be crosslinked or polymerized with the component (a) by the action of the acid, and (d) a compound that does not absorb at 365 to 700 nm and generates an acid by heat. It is characterized by comprising.

(In the formula, U and V each independently represent a divalent organic group. V is a group containing an aliphatic structure having 1 to 30 carbon atoms, or U has a carbon number constituting the main chain. It is a group containing 2 to 30 aliphatic structures.)

  Moreover, in the negative photosensitive resin composition by this invention, it is preferable when V contains a C1-C30 aliphatic chain structure.

（式中、Ｒ^１、Ｒ^２は各々独立に水素、フッ素又は炭素数１〜６のアルキレン基又は炭素数１〜６のフッ化アルキレン基であり、Ｕが（ＵＶ１）の構造を含む場合、ａは２〜３０の整数であり、Ｖが（ＵＶ１）の構造を含む場合、ａは１〜３０の整数である。）

（式中、Ｒ^３〜Ｒ^８は各々独立に水素、フッ素、炭素数１〜６のアルキレン基又は炭素数１〜６のフッ化アルキレン基であり、ｂ〜ｄは各々独立に１〜６の整数を表し、ｅは０〜３の整数である。Ａは、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、−Ｃ≡Ｃ−、又は−Ｒ^９Ｃ＝ＣＲ^１０−であり、Ｒ^９及びＲ^１０は各々独立に水素、フッ素又は炭素数１〜６のアルキル基である。） In the negative photosensitive resin composition according to the present invention, at least one of U or V in the general formula (I) of the component (a) is represented by the following general formula (UV1) or (UV2). It is characterized by including the structure represented.

(Wherein R ¹ and R ² are each independently hydrogen, fluorine, an alkylene group having 1 to 6 carbon atoms, or a fluorinated alkylene group having 1 to 6 carbon atoms, and U includes a structure of (UV1), a is an integer of 2 to 30, and when V includes a structure of (UV1), a is an integer of 1 to 30.)

Wherein R ^{3 to} R ⁸ are each independently hydrogen, fluorine, an alkylene group having 1 to 6 carbon atoms or a fluorinated alkylene group having 1 to 6 carbon atoms, and b to d are each independently 1 to 6 Represents an integer, and e is an integer of 0 to _3. A is —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, —C≡. C— or —R ⁹ C═CR ¹⁰ —, wherein R ⁹ and R ¹⁰ are each independently hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms.)

  Moreover, in the negative photosensitive resin composition by this invention, it is preferable that the said (a) component is soluble in alkaline aqueous solution.

  Moreover, in the negative photosensitive resin composition by this invention, it is preferable that the polymer terminal structure in the said (a) component has a functional group which can raise | generate a crosslinking reaction with the said (c) component.

  Moreover, in the negative photosensitive resin composition by this invention, it is preferable that the said (d) component is a sulfonate or a sulfonic acid derivative.

  Moreover, in the negative photosensitive resin composition by this invention, it is preferable that the said (d) component is a sulfonate of a pyridinium derivative.

  Moreover, in the negative photosensitive resin composition by this invention, the said (b) component 0.01-15 weight part and (c) component 0.1 with respect to said (a) component 100 weight part. It is preferable to contain -50 weight part and 0.01-15 weight part of said (d) component.

  In the method for producing a pattern according to the present invention, the negative photosensitive resin composition is applied to a support substrate and dried to form a photosensitive resin film, and the coating and drying steps are used. A step of exposing the exposed photosensitive resin film, a step of developing the exposed photosensitive resin film using an alkaline aqueous solution, and a step of heat-treating the photosensitive resin film after the development. And

  In the pattern manufacturing method according to the present invention, the heat treatment temperature is 220 ° C. or lower in the step of heat-treating the photosensitive resin film after development.

  The electronic component according to the present invention is an electronic component having an electronic device having a pattern layer obtained by the pattern manufacturing method, wherein the pattern layer is interlayer-insulated in the electronic device. It is provided as a film layer or a surface protective film layer.

  By using the negative photosensitive resin composition of the present invention, it is possible to form a pattern with excellent sensitivity and resolution. Moreover, the film | membrane which pattern-formed and heat-hardened the negative photosensitive resin composition of this invention is excellent in heat resistance and a mechanical characteristic. Furthermore, it becomes possible to pattern a thick film of 10 μm or more with high sensitivity, and in addition, it has excellent cured film characteristics and chemical resistance even by curing at a low temperature of 220 ° C. or less.

  Moreover, according to the pattern manufacturing method of the present invention, by using the negative photosensitive resin composition, a pattern having a good shape and excellent sensitivity, resolution and heat resistance can be obtained. Furthermore, the electronic component of the present invention has an effect of high reliability by having a pattern with a good shape and characteristics.

It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure in embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure in embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure in embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure in embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure in embodiment of this invention.

  DESCRIPTION OF EMBODIMENTS Embodiments of a negative photosensitive resin composition, a pattern production method, and an electronic component according to the present invention will be described below in detail with reference to the drawings. In addition, this invention is not limited by this embodiment.

（式中、Ｕ及びＶは、各々独立に二価の有機基を示す。Ｖが炭素数１〜３０の脂肪族構造を含む基であるか、又はＵが、主鎖を構成する炭素数が２〜３０の脂肪族構造を含む基である。）
尚、主鎖を構成する炭素とは、２つのベンゼン環をつなぐ直鎖（分岐は含まない）を構成する炭素を意味する。例えば、本合成例１９のポリマーＸＩＸは、主鎖を構成する炭素数は１である。
以下、各成分について説明する。 [Negative photosensitive resin composition]
First, the negative photosensitive resin composition according to the present invention will be described.
The negative photosensitive resin composition according to the present invention comprises (a) a polybenzoxazole precursor (hereinafter referred to as “component (a)”) having a repeating unit represented by the following general formula (I), and (b) A compound that generates an acid upon irradiation with actinic rays in the wavelength region of 365 to 700 nm (hereinafter referred to as “component (b)”), and (c) is crosslinked or polymerized with the terminal group of component (a) by the action of the acid. A compound to be obtained (hereinafter referred to as “component (c)”) and (d) a compound that has no absorption longer than 365 to 700 nm and generates an acid by heat (hereinafter referred to as “component (d)”) It contains.

(In the formula, U and V each independently represent a divalent organic group. V is a group containing an aliphatic structure having 1 to 30 carbon atoms, or U has a carbon number constituting the main chain. It is a group containing 2 to 30 aliphatic structures.)
The carbon constituting the main chain means carbon constituting a straight chain (not including a branch) connecting two benzene rings. For example, the polymer XIX of Synthesis Example 19 has 1 carbon atom constituting the main chain.
Hereinafter, each component will be described.

[(A) component]
The component (a) in the present invention is not particularly limited as long as it has a repeating unit represented by the above general formula (I) and can undergo a crosslinking reaction with the component (c) in the presence of an acid. . The cross-linking reaction referred to here includes those accompanied by heating.

  The component (a) is preferably soluble in an alkaline aqueous solution from the viewpoint of reducing the environmental load of the developer. The alkaline aqueous solution here is an alkaline aqueous solution such as a tetramethylammonium hydroxide aqueous solution, a metal hydroxide aqueous solution, or an organic amine aqueous solution. In general, since an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by weight is used, the component (a) is more preferably soluble in this aqueous solution.

  In addition, one reference | standard that (a) component of this invention is soluble in alkaline aqueous solution is demonstrated below. (A) Component alone or a resin solution obtained by dissolving it in an arbitrary solvent together with component (b) and component (c), which will be described in order below, is spin-coated on a substrate such as a silicon wafer to form a film thickness A coating film of about 5 μm is formed. This is immersed in any one of tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution at 20-25 ° C. As a result, when it can be dissolved as a uniform solution, it is determined that the component (a) used is soluble in an alkaline aqueous solution.

  Since the solubility of polyhydroxyamide in an aqueous alkaline solution is derived from a phenolic hydroxyl group, it is preferable that a repeating unit containing a hydroxy group is contained in a certain proportion or more.

The component (a) of the present invention has a functional group that crosslinks with the component (c). In particular, when the component (a) has a functional group that crosslinks with the component (c) at the terminal, crosslinking of the exposed portion proceeds, and the difference in dissolution rate between the exposed portion and the unexposed portion increases. It becomes possible to form a pattern.
The combination of the functional groups of component (a) and component (c) is not particularly limited, but is shared between the functional group of component (a) and the functional group of component (c) by heat in the presence of an acid. It is preferable that any one of a bond, an ionic bond, and a hydrogen bond occurs.

Among these, it is preferable that the component (a) has a functional group selected from the group A, and the component (c) has a functional group selected from the group B from the viewpoint of the sensitivity at the time of pattern formation and the mechanical properties of the film. Alternatively, it is also preferable that the component (a) has a functional group selected from Group B, and the component (c) has a functional group selected from Group A.
[Group A] group derived from primary or secondary alcohol (or primary or secondary alcoholic hydroxyl group), group derived from phenol (or phenolic hydroxyl group), carboxyl group, amino group, thiol group Group derived from an aromatic ring [Group B] methylol, alkoxyalkyl group, group derived from tertiary alcohol (or tertiary alcoholic hydroxyl group), cycloalkyl group, group derived from olefin (or olefin double bond) ), A group having a triple bond, a halogenated alkyl group, a group derived from a cyclic ether such as an epoxy group, a group having an ester bond (—COO—), a group having a carbonate bond (—OCOO—), an isocyanate group

  In addition to the above-mentioned combinations of the functional groups of the component (a) and the component (c), a group having a carboxyl group or an ester bond (—COO—) and an amino group, a carboxyl group or an ester bond (— COO-) group and primary or secondary alcohol-derived group (or primary or secondary alcoholic hydroxyl group), cycloalkyl groups, carboxyl groups, alcohol-derived group (hydroxyl group) It can be cited as a preferable combination having high reactivity, such as a group, an epoxy group, a group derived from an olefin (or an olefin double bond) or a group having a triple bond, and methylol.

Since the functional group is easily introduced, it is preferable to have the above functional group at the terminal of the component (a).
Further preferred combinations are shown below:
(A) a group having a carboxyl group or an ester bond (—COO—) as the functional group of the component, and (c) a group derived from a primary or secondary alcohol (or primary or secondary) as the functional group of the component A secondary alcohol group), an epoxy group, a vinyl ether group or an isocyanate group; or (a) an isocyanate group as a functional group of the component, and a group derived from a primary or secondary alcohol as a functional group of the component (c) ( Or primary or secondary alcoholic hydroxyl group), a group derived from phenol (or phenolic hydroxyl group), a carboxyl group or a group having an ester bond (—COO—).

In addition, as a functional group of the component (a) and the component (c), groups derived from olefins or groups having a triple bond are preferable in terms of a combination capable of obtaining good cured film strength even under low temperature curing conditions. .
Furthermore, it is derived from a phenol skeleton or aromatic ring as the structure of the component (a) and a methylol, alkoxyalkyl group, or tertiary alcohol as the functional group of the component (c) in terms of a combination that can improve the cured film strength and obtain good sensitivity. Particularly preferred are the groups or vinyl ether groups.

Here, the group derived from the phenol or aromatic ring of the terminal group of the component (a) of the present invention is preferably not a phenol group or aromatic ring derived from bisaminophenol or dicarboxylic acid constituting the repeating unit. When the functional group of component (a) is a bisaminophenol, a phenol group derived from dicarboxylic acid, or an aromatic ring, the above-described crosslinking reaction with the functional group of component (c) is not considered to occur sufficiently. It is done.
Then, when introducing the phenol terminal suitable for this invention into (a) component, the method of introduce | transducing into the resin terminal using hydroxy substituted aniline, its derivative (s), or hydroxybenzoic acid and its derivative (s) is mentioned. Moreover, when introduce | transducing an aromatic ring terminal into (a) component, the method of introduce | transducing into a resin terminal using aniline and its derivative (s), benzoic acid and its derivative (s), dicarboxylic acid anhydride, etc. is mentioned.

The combination of the functional group of the component (a) and the functional group of the component (c) is preferably a combination that does not cause chemical bonding (crosslinking) when the photosensitive resin composition is applied. Moreover, it is preferable to perform crosslinking at a temperature of 150 ° C. or higher in the presence of an acid.
Therefore, it is preferable to make each functional group shown so far latent as a derivative protected with a protecting group. In that case, these derivatives are converted into a desired functional group by a photochemical reaction by exposure or a chemical change by heat in a subsequent post-exposure heating step. For example, when the terminal group is an isocyanate, the isocyanate reacts even at a low temperature of 150 ° C. or lower, and therefore it is preferable to use a block isocyanate. Block isocyanate is an isocyanate precursor obtained by blocking isocyanate with an alkoxycarbonyl group or the like, and is introduced into the terminal group of component (a) or component (c).

In the component (a) used in the present invention, the ratio of the terminal group to the repeating unit is a molar ratio, preferably 1 to 100 repeating units with respect to the terminal group 2, and more preferably 2 to 50. .
Here, the repeating unit represents a structural unit composed of a dicarboxylic acid residue and a diamine residue, which can be written in parentheses in the general formula (I).
If the ratio of the repeating units is less than 1, the crosslinking reaction does not proceed so much and the photosensitive characteristics may be deteriorated. Conversely, if the repeating unit is larger than 100, there is a possibility that sufficient film properties cannot be obtained. The ratio between the repeating unit and the end group can be measured by ¹ H-NMR.

When the terminal group of the component (a) is a carboxyl group or an amino group, the terminal group may be derived from a dicarboxylic acid or a diamine used during the synthesis of the component (a).
A compound in which the terminal carboxyl group has a molar ratio of 5 times or more than the amino group is referred to as “carboxyl terminal (a) component”, and the terminal amino group has a molar ratio of 5 times or more than the carboxyl group in the “amino group” The component (a) is the terminal.
Component (a) which is a carboxyl group terminal is obtained by increasing the ratio (molar ratio) of dicarboxylic acid / diamine (bisaminophenol) during synthesis to more than 50/49, and component (a) which is an amino group terminal Is obtained by making the ratio (molar ratio) of diamine (bisaminophenol) / dicarboxylic acid during synthesis greater than 50/49.

When (a) is synthesized using an equivalent amount of dicarboxylic acid and diamine, the (a) component that is the carboxyl group end and the (a) component that is the amino group end are synthesized and the end groups react with each other. , The stability tends to decrease, and the chemical resistance, heat resistance and mechanical properties tend to decrease. The presence of an amino group in the component (a) can be easily quantified by an integral value of ¹ H-NMR.

In the case where the terminal group of the component (a) is a phenol terminal derived from a hydroxy group-substituted aniline and a derivative thereof, the dicarboxylic acid residue is one more than the diamine residue, and the dicarboxylic acid residue: diamine residue = 100: 99 to A range of 2: 1 is preferable, and a range of 50:49 to 3: 2 is more preferable.
When the terminal group is a phenol terminal derived from hydroxybenzoic acid and its derivatives, the dicarboxylic acid residue is one less than the diamine residue, and the dicarboxylic acid residue: diamine residue = 99: 100 to 1: 2 range. It is preferable to be in the range of 49:50 to 2: 3. The quantitative method can be performed by measuring ¹ H-NMR.

The polyhydroxyamide having a repeating unit represented by the general formula (I) that can be used in the present invention may have the repeating unit, but a copolymer represented by the following general formula (II): Can also be used.
Since the solubility of polyhydroxyamide in an aqueous alkaline solution is derived from a phenolic hydroxyl group, it is preferable that a repeating unit containing a hydroxy group is contained in a certain proportion or more.

式中、Ｕ，Ｖ，Ｗ，Ｘは各々独立に二価の有機基を示し、Ｖが炭素数１〜３０の脂肪族構造を含む基であるか、又はＵが主鎖を構成する炭素数が２〜３０の脂肪族構造を含む基であり、ｊ及びｋはＡ構造単位とＢ構造単位のモル分率を示し、ｊ及びｋの和は１００モル％である。
即ち、一般式（II）において、式中のｊとｋのモル分率は、ｊ＝５〜８５モル％、ｋ＝１５〜９５モル％であることが感度、解像度、機械特性、耐熱性及び耐薬品性の点でより好ましい。

In the formula, U, V, W and X each independently represent a divalent organic group, V is a group containing an aliphatic structure having 1 to 30 carbon atoms, or U is the number of carbon atoms constituting the main chain. Is a group containing an aliphatic structure of 2 to 30, j and k represent the mole fraction of the A structural unit and the B structural unit, and the sum of j and k is 100 mol%.
That is, in the general formula (II), the molar fraction of j and k in the formula is such that j = 5 to 85 mol%, k = 15 to 95 mol%, sensitivity, resolution, mechanical properties, heat resistance and More preferable in terms of chemical resistance.

  In the present invention, the polyamide having a repeating unit represented by the general formula (I) can be generally synthesized from a dicarboxylic acid derivative and a hydroxy group-containing diamine. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the diamine. As the dihalide derivative, a dichloride derivative is preferable.

  The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorideation reaction of carboxylic acid can be used.

  As a method of synthesizing the dichloride derivative, it can be synthesized by reacting the dicarboxylic acid derivative and the halogenating agent in a solvent or reacting in an excess halogenating agent and then distilling off the excess. As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

  The amount of these halogenating agents to be used in a solvent is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol relative to the dicarboxylic acid derivative. When making it react in an agent, 4.0-50 mol is preferable and 5.0-20 mol is more preferable. The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

  The reaction between the dichloride derivative and the diamine is preferably performed in an organic solvent in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used. As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used. The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

Next, preferable groups as U and V in the general formulas (I) and (II) will be described.
In formulas (I) and (II), U and V are each a divalent organic group, but at least V is a group containing an aliphatic structure having 1 to 30 carbon atoms, or U constitutes the main chain. And a group containing an aliphatic structure having 2 to 30 carbon atoms.
When V is a group containing an aliphatic structure having 1 to 30 carbon atoms, U may be any divalent organic group. When U is a group containing an aliphatic structure having 2 to 30 carbon atoms constituting the main chain, V may be any divalent organic group. Further, V may be a group including an aliphatic structure having 1 to 30 carbon atoms, and U may be a group including an aliphatic structure having 2 to 30 carbon atoms constituting the main chain.

  In addition, when at least one of U and V is a structure represented by (UV1) or (UV2), or a structure containing a structure represented by (UV1) or (UV2), the dehydration ring closure rate at 280 ° C. or lower Is desirable in terms of high. Further, a group containing an aliphatic structure having 7 to 30 carbon atoms is more preferable because the elastic modulus is low and the elongation at break is high.

（式中、Ｒ^１、Ｒ^２は各々独立に水素、フッ素又は炭素数１〜６のアルキレン基又は炭素数１〜６のフッ化アルキレン基であり、Ｕが（ＵＶ１）の構造を含む場合、ａは２〜３０の整数であり、Ｖが（ＵＶ１）の構造を含む場合、ａは１〜３０の整数である。）

(Wherein R ¹ and R ² are each independently hydrogen, fluorine, an alkylene group having 1 to 6 carbon atoms, or a fluorinated alkylene group having 1 to 6 carbon atoms, and U includes a structure of (UV1), a is an integer of 2 to 30, and when V includes a structure of (UV1), a is an integer of 1 to 30.)

（式中、Ｒ^３〜Ｒ^８は各々独立に水素、フッ素、炭素数１〜６のアルキレン基又は炭素数１〜６のフッ化アルキレン基であり、ｂ〜ｄは各々独立に１〜６の整数を表し、ｅは０〜３の整数である。Ａは、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、−Ｃ≡Ｃ−、又は−Ｒ^９Ｃ＝ＣＲ^１０−であり、Ｒ^９及びＲ^１０は各々独立に水素、フッ素又は炭素数１〜６のアルキル基である。）

Wherein R ^{3 to} R ⁸ are each independently hydrogen, fluorine, an alkylene group having 1 to 6 carbon atoms or a fluorinated alkylene group having 1 to 6 carbon atoms, and b to d are each independently 1 to 6 Represents an integer, and e is an integer of 0 to _3. A is —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, —C≡. C— or —R ⁹ C═CR ¹⁰ —, wherein R ⁹ and R ¹⁰ are each independently hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms.)

式中、ｎは１〜６の整数である。 Examples of the diamines include compounds represented by the following general formula (III).

In formula, n is an integer of 1-6.

  In addition, diamines having an organic group represented by U (when V is a group including an aliphatic structure having 1 to 30 carbon atoms) or W include bis (3-amino-4-hydroxyphenyl) sulfone, Bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis ( 4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, and the like. Not intended to be.

  These compounds are used alone or in combination of two or more. Among these, diamines are bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (2, from the viewpoints of exposure light transmittance and developability. 3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3 It is preferable to use 3,3-hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, or 2,2-bis (4-amino-3-hydroxyphenyl) propane.

  Next, a preferable group as V in the general formulas (I) and (II) will be described. The divalent organic group represented by V in the general formulas (I) and (II) is generally a dicarboxylic acid residue that reacts with a diamine to form a polyamide structure.

When V is a structure represented by the above (UV1) or (UV2) as a group containing an aliphatic structure having 1 to 30 carbon atoms, it has high heat resistance, high transparency in the ultraviolet and visible light range. It is excellent in that the dehydration ring closure rate at 280 ° C. or lower is high.
Furthermore, when the group contains an aliphatic structure having 7 to 30 carbon atoms, the polymer is easily soluble in solvents such as γ-butyrolactone and propylene glycol monomethyl ether acetate in addition to N-methyl-2-pyrrolidone, and is stable in storage. Is also expensive. Furthermore, the elastic modulus is low and the elongation at break is high, which is more preferable.

  Examples of the dicarboxylic acids as described above include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, and 2,2-dimethyl. Succinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3 -Dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodeca Fluorosberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid Dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanedioic acid, nonadecanoic acid, eicosanic acid, heneicosanoic acid, docosanic acid, tricosannic acid, tetracosannic acid, pentacosannic acid, hexacosanic acid, heptasanic acid, heptasanic acid Examples include acids, octacosannic acid, nonacosannic acid, triacontaninic acid, hentriacontaninic acid, dotriacontaninic acid, and diglycolic acid.

式中、Ｔは炭素数１〜６の炭化水素基、ｎは１〜６の整数である。 Furthermore, a compound represented by the following general formula (IV) is also preferable.

In the formula, T is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.

Among these, as the dicarboxylic acids, those having 6 or more carbon atoms excluding the carboxyl group are preferably used from the viewpoint of mechanical properties, those having 6 to 20 carbon atoms are more preferable, and those having 8 to 14 carbon atoms are more preferable. The following are preferably used.
When the number of carbon atoms is less than 6, sufficient mechanical properties may not be obtained. When the number of carbon atoms is larger than 20, compatibility with other components and deterioration of photosensitive properties may occur.

  Other V in the general formulas (I) and (II) (when U is a group including an aliphatic structure having 2 to 30 carbon atoms constituting the main chain) or an organic group represented by X Dicarboxylic acids include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4′-dicarboxybiphenyl, 4,4 '-Dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5-bromo Aromatic dicarboxylic acids such as isophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid and 2,6-naphthalenedicarboxylic acid can be used in combination. Kill. These compounds can be used alone or in combination of two or more.

  The molecular weight of the component (a) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000 in terms of weight average molecular weight. If the weight average molecular weight is less than 3,000, the cured film becomes brittle and the mechanical properties may be remarkably deteriorated. On the other hand, if it exceeds 200,000, the solubility in the developing solution and the resolution may be lowered. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

  Further, as the component (a), in addition to aminophenols having organic groups represented by U and W, the following diamines can also be used as long as the effects of the present invention are not impaired. Such diamines include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 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- Aromatic diamine compounds such as (4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene can be mentioned.

As other diamines having a silicone group, LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C and X-22-161E (all Shin-Etsu Chemical Co., Ltd.) (Trade name, manufactured by Co., Ltd.).
Such diamines are used in a molar ratio with aminophenols having organic groups represented by U and W, and at most, these diamines are used as 25% or less of the total aminophenols. It is preferable in order not to deteriorate the photosensitive properties of the polymer represented by II). More preferably, it is 15% or less.

[Component (b)]
In the negative photosensitive resin composition of the present invention, together with the polybenzoxazole precursor used as the component (a), a compound capable of generating an acid upon irradiation with actinic rays in the wavelength region of 365 to 700 nm as the component (b) , Referred to as an acid generator).
The content of the acid generator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of component (a) in order to improve the sensitivity and resolution during exposure. 10 parts by weight is more preferable, and 0.5 to 5 parts by weight is even more preferable. When the amount of the component (b) exceeds 15 parts by weight, the exposed light does not reach the bottom due to the absorption band derived from the component (b), and undercut or the like occurs, so that the pattern shape may be deteriorated. On the other hand, if the amount of component (b) is less than 0.01 parts by mass, the sensitivity may be significantly reduced.

  The acid generator (b) used in the present invention exhibits acidity upon irradiation with actinic rays in the wavelength region of 365 to 700 nm, and crosslinks the functional groups of the component (c) and the component (a) by its action. Or (c) has an effect of polymerizing the components. Examples of such component (b) include diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, oxime sulfones. Examples include acid esters, aromatic N-oxyimide sulfonates, aromatic sulfamides, haloalkyl group-containing hydrocarbon compounds, and haloalkyl group-containing heterocyclic compounds. These can be used individually by 1 type or in combination of 2 or more types.

ｎは２〜３の整数、ｍは０〜１の整数で、ｎ＋ｍ＝３である。Ｒは１価のアルキル基である。Ｚは芳香環である。Ｘ⁻は発生する酸の共役塩基である。 As the diarylsulfonium salt, triarylsulfonium salt and dialkylphenacylsulfonium salt, compounds represented by the following general formula (BI) are preferred.

n is an integer of 2 to 3, m is an integer of 0 to 1, and n + m = 3. R is a monovalent alkyl group. Z is an aromatic ring. X ^- is the conjugate base of the acid generated.

ｎは０又は１である。Ｒ_１及びＲ_３は各々独立に１価のアルキル基、Ｒ_２は各々独立に一価のアリール基である。 Moreover, as a diaryl iodonium salt, the compound represented with the following general formula (BII) or (BIII) is preferable.

n is 0 or 1. R ₁ and R ₃ are each independently a monovalent alkyl group, and R ₂ are each independently a monovalent aryl group.

Ｒ_１は１価の炭素数６〜１０のアリール基、炭素数１〜１０のアルキル基又はこれらを組み合わせた基である。Ｒ_２は１価のアリール基又はアルキル基で、これらの基はヘテロ原子を介してベンゼン環に置換していてもよい。Ｒ_３はアルキル基又はシアノ基である。 The aromatic sulfonic acid ester is preferably a nitrobenzyl ester compound or a compound represented by the following general formula (BIV) or (BV).

R ₁ is a monovalent aryl group having 6 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a group obtained by combining these. R ₂ is a monovalent aryl group or alkyl group, and these groups may be substituted on the benzene ring via a hetero atom. R ₃ is an alkyl group or a cyano group.

Ｒは１価のアリール基又はアルキル基である。 As the aromatic N-oxyimide sulfonate, a compound represented by the following general formula (BVI) or (BVII) is preferable.

R is a monovalent aryl group or alkyl group.

  The compounds represented by the above general formula can be used in combination of two or more as required, or in combination with other sensitizers. Among the compounds described above, those having no salt structure are preferred from the viewpoint of suppressing the stability of the photosensitive resin composition and ion migration. Furthermore, from the viewpoint of using the aromatic oxime sulfonate ester or aromatic N-oxyimide sulfonate represented by the general formula (BIV), (BV), (BVI) or (BVII), the sensitivity can be increased. Particularly preferred.

[Component (c)]
The component (c) used in the present invention, that is, a compound that can be crosslinked or polymerized with the component (a) by the action of an acid (hereinafter also referred to as “crosslinking agent”) is not particularly limited as long as it satisfies the above-mentioned conditions. However, it is preferably a compound having at least one functional group that reacts with the component (a) in the molecule, and the temperature at which the crosslinking reaction with the component (a) of the component (c) is 150 ° C. or more. Preferably there is.
When the temperature is lower than 150 ° C., the photosensitive resin composition may cause a crosslinking reaction in each step of coating, drying, exposure and development. Although the component (c) undergoes a crosslinking reaction with the component (a), it may be a compound that polymerizes between molecules of the component (c).

  As such component (c), two or more methylol groups, alkoxymethyl groups, epoxy groups, oxetanes, vinyl ether groups, olefins, alkynyl groups, cyano groups, hydroxy groups, carboxyl groups, ester bonds, cycloalkyls in the molecule It preferably has a group, an amino group, an isocyanate group or the like.

  Particularly preferably, a compound in which these substituents are substituted on an aromatic ring, that is, a compound in which the above substituent is substituted on an aromatic ring such as phenol, bisphenol, polyphenol, novolac resin, and resole resin, or N in these substituents. Particularly preferred are melamine, benzoguanamine, glycoluril, urea compounds and the like substituted in position. Examples of these preferable compound groups are given as the following general formulas (V) and (VI), but the present invention is not limited thereto.

式中、Ｘは単結合又は一価〜四価の有機基を示し、Ｚは（ａ）成分と反応する官能基を示し、Ｒ^１１は水素原子、水酸基又は一価の有機基を示し、ｆは１〜４の整数であり、ｐ及びｑは各々独立に１〜４の整数である。

In the formula, X represents a single bond or a monovalent to tetravalent organic group, Z represents a functional group that reacts with the component (a), R ¹¹ represents a hydrogen atom, a hydroxyl group, or a monovalent organic group, f Is an integer of 1 to 4, and p and q are each independently an integer of 1 to 4.

式中、Ｚは各々独立に（ａ）成分と反応する官能基を示し、Ｒ^１２は各々独立に水素原子又は一価の有機基を示し、互いが結合することで環構造となっていてもよい。

In the formula, each Z independently represents a functional group that reacts with the component (a), and each R ¹² independently represents a hydrogen atom or a monovalent organic group, and may be bonded to each other to form a ring structure. Good.

  In the general formula (V), as the organic group represented by X, an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group or a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, Arylene groups having 6 to 30 carbon atoms such as phenylene groups, groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms, sulfone groups, carbonyl groups, ether bonds, thioether bonds, An amide bond etc. are mentioned, Moreover, the bivalent organic group shown by the following general formula (VII) is mentioned as a preferable thing.

式中、個々のＸ’は、各々独立に、単結合、アルキレン基（例えば炭素原子数が１〜１０のもの）、アルキリデン基（例えば炭素数が２〜１０のもの）、それらの水素原子の一部又は全部をハロゲン原子で置換した基、スルホン基、カルボニル基、エーテル結合、チオエーテル結合、アミド結合等から選択されるものであり、Ｒ^１３は水素原子、ヒドロキシ基、アルキル基又はハロアルキル基であり、複数存在する場合は互いに同一でも異なっていてもよく、ｇは１〜１０の整数である。

In the formula, each X ′ is independently a single bond, an alkylene group (for example, having 1 to 10 carbon atoms), an alkylidene group (for example having 2 to 10 carbon atoms), or a hydrogen atom thereof. A group partially or entirely substituted with a halogen atom, a sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond, etc., and R ¹³ is a hydrogen atom, a hydroxy group, an alkyl group or a haloalkyl group Yes, when there are a plurality, they may be the same or different, and g is an integer of 1 to 10.

  Furthermore, those listed in the following general formula (VIII) are particularly preferable because they are excellent in sensitivity and resolution.

式中、２つのＹは各々独立に水素原子又は炭素原子数１〜１０のアルキル基であり酸素原子又はフッ素原子を含んでいてもよく、Ｚは各々独立に（ａ）成分と反応する官能基を示し、Ｒ^１４〜Ｒ^１５は各々独立に水素原子又は一価の有機基を示し、ｐ及びｑは各々独立に０〜４の整数、ｒ及びｓは各々独立に１〜４の整数である。

In the formula, two Y's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and may contain an oxygen atom or a fluorine atom, and Z is a functional group that independently reacts with the component (a). R ^{14 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent organic group, p and q are each independently an integer of 0 to 4, and r and s are each independently an integer of 1 to 4. .

Ｚは炭素数１〜１０の一価のアルキル基を表し、Ｒは炭素数１〜２０のアルキル基を表す。 As such a component (c), those having the following structure are particularly preferred from the viewpoint of chemical resistance. These may be used alone or in combination of two or more.

Z represents a monovalent alkyl group having 1 to 10 carbon atoms, and R represents an alkyl group having 1 to 20 carbon atoms.

  The content of the component (c) used in the present invention is 0.1 to 50 with respect to 100 parts by weight of the component (a) in order to suppress the sensitivity and resolution at the time of light exposure and the melting of the pattern at the time of curing. It is preferable to set it as a weight part, It is more preferable to set it as 0.1-20 weight part, It is further more preferable to set it as 0.5-20 weight part.

[D component]
In the negative photosensitive resin composition of the present invention, in order to promote the cyclization of the component (a) during thermosetting and to promote the crosslinking reaction of the component (c), an acid is generated by the heat during curing. Use compounds. Here, the component (d) needs to be a compound having no absorption in the wavelength region of 365 to 700 nm so as not to prevent the photoreaction of the acid generator used as the component (b) at the time of exposure.
Here, it defines about having no absorption in a wavelength range of 365-700 nm. Absorbance was measured with a spectrophotometer as a 1.5 × 10 ⁻² M solution using a quartz cell with a cell length (optical path length) of 1 cm, and the absorbance in the wavelength range of 365 to 700 nm was 0.015 or less. In some cases, this compound has no absorption in the 365-700 nm wavelength region.

  As such component (d), the acid generated by heat is preferably a strong acid. Among them, the use of a sulfonate or a sulfonic acid derivative that generates sulfonic acid by heat is more preferable because it does not deteriorate the photosensitive characteristics on the copper substrate and is excellent in ion migration resistance. Specific examples of strong acids generated by heat include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid. Alkyl sulfonic acids such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid are desirable.

  As the component (d) that generates such an acid, it is preferable to use a compound having a covalent bond such as an onium salt or a pyridinium derivative as a salt form, imide sulfonate, or sulfonate. . For example, diaryliodonium salts such as diphenyliodonium salts, di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salts, trialkylsulfonium salts such as trimethylsulfonium salts, and dialkylmonoaryls such as dimethylphenylsulfonium salts Examples thereof include diarylmonoalkyliodonium salts such as sulfonium salts and diphenylmethylsulfonium salts, and triarylsulfonium salts.

上記一般式（ＤＩ）中、Ｒ^１、Ｒ^２及びＲ^３は各々独立にアルキル基又はアリール基を表し、Ｘ⁻は発生する酸の共役塩基を表す。
前記Ｒ^１、Ｒ^２及びＲ^３として用いるアルキル基としては、メチル基が好ましく、アリール基としては、フェニル基又は置換基を有するフェニル基が好ましい。Ｘ⁻で表される酸の共役塩基としては、メタンスルホニル又はトリフルオロメタンスルホニルが好ましい。これらの中では、薬液耐性、機械特性向上の観点からメタンスルホン酸のトリアルキルスルホニウム塩がより好ましく、特にメタンスルホン酸のトリメチルスルホニウム塩が好ましい。 The sulfonium salt is preferably a compound represented by the following general formula (DI).

In the general formula (DI), R ¹ , R ² and R ³ each independently represents an alkyl group or an aryl group, and X ⁻ represents a conjugate base of the generated acid.
The alkyl group used as R ¹ , R ² and R ³ is preferably a methyl group, and the aryl group is preferably a phenyl group or a phenyl group having a substituent. X ^- is the acid conjugate base of which is represented by, methanesulfonyl or trifluoromethanesulfonyl are preferred. Among these, a trialkylsulfonium salt of methanesulfonic acid is more preferable from the viewpoint of chemical resistance and improvement of mechanical properties, and a trimethylsulfonium salt of methanesulfonic acid is particularly preferable.

式中、ｎは１〜３の整数、ｍは０〜２の整数であり、ｎ＋ｍ＝３である。Ｒは１価のアルキル基である。Ｚは水素、１価の飽和アルキル基又はアルコキシ基である。Ｘ⁻は発生する酸の共役塩基である。 Furthermore, the compound represented by the following general formula (DII) is preferable.

In the formula, n is an integer of 1 to 3, m is an integer of 0 to 2, and n + m = 3. R is a monovalent alkyl group. Z is hydrogen, a monovalent saturated alkyl group or an alkoxy group. X ^- is the conjugate base of the acid generated.

ｎ及びｍはそれぞれ０〜２の整数で、ｎ＋ｍ＝２である。Ｒは１価のアルキル基である。Ｚは水素、１価の飽和アルキル基又はアルコキシ基である。Ｘ⁻は発生する酸の共役塩基である。 As said iodonium salt, the compound represented by the following general formula (DIII) is preferable.

n and m are each an integer of 0 to 2, and n + m = 2. R is a monovalent alkyl group. Z is hydrogen, a monovalent saturated alkyl group or an alkoxy group. X ^- is the conjugate base of the acid generated.

ｎは０〜５の整数である。Ｒは１価のアルキル基、Ｘ⁻は発生する酸の共役塩基である。 As said pyridinium derivative, the compound represented by the following general formula (DIV) is preferable.

n is an integer of 0-5. R is a monovalent alkyl group, X ^- is the conjugate base of the acid generated.

ｎは１又は２である。Ｒ_１は炭素数１〜５の一価のアルキル基、炭素数６〜１０のアリール基、又はこれらを組み合わせた基であり、Ｒ_２は水素又は１価のアルキル基である。 The imide sulfonate is preferably any of compounds represented by the following general formulas (DV), (DVI), and (DVII).

n is 1 or 2. R ₁ is a monovalent alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a combination thereof, and R ₂ is hydrogen or a monovalent alkyl group.

The sulfonic acid ester is preferably a compound represented by the following general formula (DVIII).
R ₁ —SO ₃ —R ₂ (DVIII)
In the formula, R ₁ and R ₂ are each independently a monovalent aryl group or an alkyl group.

  Of the above compounds, a pyridinium derivative as represented by the general formula (DIV) is preferable because it greatly improves the cyclization efficiency of the component (a) to the oxazole ring during thermosetting. Furthermore, a sulfonate salt of a pyridinium derivative is particularly preferable because it is excellent in terms of the balance of storage stability, sensitivity, and resolution of the resin.

  Among these components (d), those having a thermal decomposition starting temperature of 50 ° C. to 260 ° C. are desirable. Specifically, it is desirable that the 1% weight loss temperature measured by thermogravimetric analysis (Tg) is 50 ° C. to 260 ° C., or the 5% weight loss temperature is 60 ° C. to 280 ° C. Furthermore, those having a 1% weight loss temperature of 140 ° C. to 245 ° C. are more preferable because no acid is generated during pre-baking and there is no possibility of adversely affecting the photosensitive properties and the like. Specifically, it is desirable that the 1% weight loss temperature measured by thermogravimetric analysis (Tg) is 140 ° C. to 245 ° C., or the 5% weight loss temperature is 170 ° C. to 250 ° C.

  Component (d) is preferably added in an amount of 15 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of component (a). When the addition amount exceeds 15 parts by weight, the influence of thermal decomposition during pre-baking may not be negligible.

  In the composition of the present invention, for example, 90% by weight or more, 95% by weight or more, 98% by weight or more, and 100% by weight may comprise the components (A) to (D).

[Other ingredients]
In addition to the components (a), (b), (c) and (d), the negative photosensitive resin composition according to the present invention comprises (1) adhesion imparting, (2) a surfactant or leveling agent. (3) You may contain a solvent etc.

[Other components: (1) Adhesiveness imparting agent]
The negative photosensitive resin composition of the present invention may contain (1) an adhesion-imparting agent such as an organic silane compound or an aluminum chelate compound in order to enhance the adhesion of the cured film to the substrate.

Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n- Propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol Ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis ( Ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldihi Loxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) ) Benzene and the like.
Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate, and the like.

  When using these (1) adhesion-imparting agents, it is preferable to contain 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight based on 100 parts by weight of component (a). preferable.

[Other components: (2) Surfactant or leveling agent]
In addition, the negative photosensitive resin composition of the present invention has an appropriate (2) surfactant or leveling agent in order to prevent coatability, for example, striation (film thickness unevenness) or improve developability. It may be added.
Examples of such a surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like.

  Commercially available products include Megafax F171, F173, R-08 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC430, FC431 (trade name, manufactured by Sumitomo 3M), organosiloxane polymers KP341, KBM303, KBM403, KBM803 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

[Other components: (3) Solvent]
In the present invention, the above-described components are dissolved in (3) a solvent and generally used in the form of a varnish. As the solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, 2-methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, There are propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol acetate, cyclohexanone, cyclopentanone, tetrahydrofuran, etc. You may mix and use.

[Pattern manufacturing method]
Next, a pattern manufacturing method according to the present invention will be described. The method for producing a pattern according to the present invention includes a step of applying the above-described negative photosensitive resin composition on a support substrate and drying to form a photosensitive resin film, and a photosensitive resin obtained by the coating and drying steps. Through a step of exposing the film, a step of developing the photosensitive resin film after the exposure using an alkaline aqueous solution, and a step of heat-treating the photosensitive resin film after the development, a desired high heat resistance is obtained. Molecular patterns can be produced. Hereinafter, each step will be described.

[Coating / drying (film formation) process]
In the step of applying and drying the negative photosensitive resin composition on the support substrate, the above-described process is performed on the support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO ₂ ), or silicon nitride. The photosensitive resin composition is spin-coated using a spinner or the like. Then, the photosensitive resin film which is a film of a negative photosensitive resin composition is formed on a support substrate by drying using a hotplate, oven, etc.

[Exposure process]
Next, in the exposure step, the photosensitive resin composition (photosensitive resin film) formed as a film on the support substrate is irradiated with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask. In addition, you may further include the process of heating the photosensitive resin film after exposure if desired.

[Development process]
Subsequently, in the development process, a pattern is obtained by removing the unexposed portions with a developer. Preferred examples of the developer include aqueous alkali 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.

[Heat treatment process]
Next, in the heat treatment step, for example, by using various heat diffusion furnaces, heating furnaces and curing furnaces, the obtained pattern is preferably subjected to heat treatment at 150 to 450 ° C., thereby forming a heat resistant polymer pattern. Become. In the present invention, sufficient film properties can be obtained even if the heat treatment is performed at 220 ° C. or lower, preferably 150 to 220 ° C.

[Microwave curing]
The heat treatment is not limited to a thermal diffusion furnace or the like, and microwaves can also be used. When microwaves are irradiated in a pulsed manner while changing the frequency, standing waves can be prevented and the substrate surface can be heated uniformly. In addition, when metal wiring is included as an electronic component as a substrate, it is possible to prevent the occurrence of electric discharge from the metal and to protect the electronic component from destruction by irradiating microwaves in pulses while changing the frequency. It is preferable at the point which can do.

  In the negative photosensitive resin composition of the present invention, the microwave frequency to be irradiated is in the range of 0.5 to 20 GHz, but is practically preferably in the range of 1 to 10 GHz, and more preferably in the range of 2 to 9 GHz. preferable.

  Although it is desirable to continuously change the frequency of the microwave to be irradiated, the irradiation is actually performed by changing the frequency stepwise. At that time, the shorter the time for irradiating a single-frequency microwave, the less likely it is that standing waves or metal discharges occur, and the time is preferably 1 millisecond or less, particularly preferably 100 microseconds or less.

  The output of the microwave to be irradiated varies depending on the size of the apparatus and the amount of the object to be heated, but is generally in the range of 10 to 2000 W, practically preferably 100 to 1000 W, more preferably 100 to 700 W, further preferably 100 to 700 W. 500 W is most preferred. If the output is 10 W or less, it is difficult to heat the object to be heated in a short time, and if it is 2000 W or more, a rapid temperature rise is likely to occur.

  In the negative photosensitive resin composition of the present invention, the microwave to be irradiated is preferably turned on / off in pulses. By irradiating the microwaves in a pulsed manner, the set heating temperature can be maintained, and damage to the polyimide thin film and the substrate can be avoided. Although the time for irradiating the pulsed microwave at one time varies depending on the conditions, it is approximately 10 seconds or less.

  In the negative photosensitive resin composition of the present invention, the time for heat curing is the time until the remaining solvent and volatile components are sufficiently scattered, but is approximately 5 hours or less in view of work efficiency. Moreover, the atmosphere of heat processing can also select any in air | atmosphere or inert atmosphere, such as nitrogen.

[Semiconductor device manufacturing process]
Next, as an example of a pattern manufacturing method using the negative photosensitive resin composition according to the present invention, an example of a manufacturing process of a semiconductor device (electronic component) will be described with reference to the drawings. 1 to 5 are schematic cross-sectional views for explaining a manufacturing process of a semiconductor device having a multilayer wiring structure. 1 to 5, a semiconductor substrate 1 such as a Si substrate having a circuit element (not shown) is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and is exposed. A first conductor layer 3 is formed thereon. On this semiconductor substrate 1, an interlayer insulating film layer 4 of a negative photosensitive resin composition as an interlayer insulating film is formed by spin coating or the like (FIG. 1).

  Next, a chlorinated rubber-based or phenol novolac-based photosensitive resin layer 5 is formed on the interlayer insulating film layer 4 by spin coating, and a predetermined portion of the interlayer insulating film layer 4 is exposed by a known photolithography technique. A window 6A is provided as shown in FIG. The interlayer insulating film layer 4 exposed by the window 6A is selectively etched by a 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 (FIG. 3).

  Further, the second conductor layer 7 is formed by using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (FIG. 4). 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 layer 8 is formed. In the example of FIGS. 1 to 5, the surface protective film layer 8 is coated with the photosensitive resin composition by a spin coat method and dried, and light is applied from above a mask on which a pattern for forming a window 6 </ b> C is formed at a predetermined portion. Then, development is performed with an alkaline aqueous solution to form a pattern, which is then heated to obtain a heat resistant polymer film (FIG. 5). The heat-resistant polymer film as the surface protective film layer 8 protects the conductor layer from external stress, alpha rays, etc., and the obtained semiconductor device is excellent in reliability. In the above example, not only the surface protective film layer 8 but also the interlayer insulating film layer 4 can be formed using the negative photosensitive resin composition of the present invention.

[Electronic parts]
Next, the electronic component according to the present invention will be described. The negative photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards. Specifically, the surface protective film, interlayer insulating film of semiconductor devices, and interlayers of multilayer wiring boards are used. It can be used for forming an insulating 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 negative photosensitive resin composition, and can have various structures. The electronic component by this invention contains the pattern formed by the manufacturing method of the said pattern using the negative photosensitive resin composition of this invention. Moreover, as an electronic component, a semiconductor device, a multilayer wiring board, various electronic devices, etc. are included.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.
In Examples and Comparative Examples described later, the weight average molecular weight of the synthesized polymer was determined by gel permeation chromatography (GPC, apparatus manufactured by Hitachi, Ltd., column manufactured by Hitachi Chemical Co., Ltd. Gel Pack), It calculated | required by standard polystyrene conversion.

Synthesis example 1
Synthesis of Polybenzoxazole Precursor (Polymer I) In a 0.2 liter flask equipped with a stirrer and a thermometer, 60 g of N-methylpyrrolidone was charged and 2,2′-bis (3-amino-4-hydroxyphenyl) ) After adding 13.92 g (38 mmol) of hexafluoropropane (amine component) and 0.37 g (4 mmol) of aniline (terminal group-introducing compound), stirring and dissolving, malonic acid dichloride while maintaining the temperature at 0 to 5 ° C. (Acid component) After 5.64 g (40 mmol) was added dropwise over 10 minutes, stirring was continued for 60 minutes. The obtained solution was poured into 3 liters of water, the precipitate was collected, washed with pure water three times, and then decompressed to obtain a polyhydroxyamide having a terminal aromatic ring (polybenzoxazole precursor). (Hereinafter referred to as polymer I). The polymer I had a weight average molecular weight of 11,500 and a dispersity of 1.7 determined by GPC standard polystyrene conversion.

Synthesis Examples 2-19
Synthesis of Polybenzoxazole Precursors (Polymers II to XIX) Polymers II to XIX were synthesized in the same manner as in Synthesis Example 1, except that the polymer raw materials and blending amounts were changed as shown in Tables 1 and 2. Each component shown in Tables 1 and 2 is as follows.

Amine 1: 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropanamine 2: 2,2′-bis (3-amino-4-hydroxyphenyl) propanoic acid 1: malonic acid dichloride acid 2 : Succinic acid dichloride acid 3: Glutaric acid dichloride acid 4: Adipic acid dichloride acid 5: Suberic acid dichloride acid 6: Sebacic acid dichloride acid 7: Dodecanoic acid dichloride acid 8: Dimethylmalonic acid dichloride acid 9: Hexafluoroglutaric acid dichloride acid 10: 4,4'-diphenyl ether dicarboxylic acid dichloride end group introduction compound 1: aniline end group introduction compound 2: m-aminoanisole end group introduction compound 3: m-aminophenol end group introduction compound 4: p-aminophenol

(Measurement conditions of weight average molecular weight by GPC method)
Measuring device: Detector L4000 UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 × 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow rate: 1.0 ml / min, detector: UV 270 nm
The measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.

Examples 1-22 and Comparative Examples 1-6
Preparation of negative photosensitive resin composition (a) component or component (b) to (d) or components corresponding to these with respect to 100 parts by weight of each of the above polymers I to XIX as components corresponding to component (a) Were blended in predetermined amounts shown in Tables 3 to 5 to prepare negative photosensitive resin compositions. However, Comparative Example 6 is a positive photosensitive resin composition.
As the organic solvent as the solvent, γ-butyrolactone (BLO) or N-methylpyrrolidone (NMP) was used in a predetermined amount shown in Tables 3 to 5.

Ｄ１：ピリジニウム−ｐ−トルエンスルホネート（みどり化学社製）
Ｄ２：２，４，６−トリメチルピリジニウム−ｐ−トルエンスルホネート（東京化成社製）
Ｄ３：トリメチルスルホニウムメチルスルフェート（フルオロケム社製）
Ｄ４：トリメチルスルホニウムトリフルオロメタンスルホネート（日立化成社製）

Ｄ１〜Ｄ５をそれぞれアセトニトリル溶液として１．５×１０^−２Ｍの溶液を作成し、日立製作所製分光光度計Ｕ−３３１０により３６５〜７００ｎｍの波長領域のＵＶ吸収スペクトルを測定した。セル長（光路長）は１ｃｍとした。結果、いずれも吸光度は０．０１５以下であることを確認した。
Ｄ６は、３６５ｎｍにおける吸光度が０．０１５を大きく上回った。また１．５×１０^−２Ｍでは吸光度＞２となり測定精度に問題があるため、１０倍に希釈して測定をした。その結果、３６５ｎｍにおける吸光度は０．９であった。 B1-B4, C1-C7, D1-D6 are shown below.
B1 to 3 are the component (b), but B4 is not the component (b).
C1-7 are (c) components.
D1 to 5 are the component (d), but D6 is not the component (d).

D1: Pyridinium-p-toluenesulfonate (manufactured by Midori Chemical Co., Ltd.)
D2: 2,4,6-trimethylpyridinium-p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.)
D3: Trimethylsulfonium methyl sulfate (manufactured by Fluorochem)
D4: Trimethylsulfonium trifluoromethanesulfonate (manufactured by Hitachi Chemical Co., Ltd.)

A 1.5 × 10 ⁻² M solution was prepared using D1 to D5 as acetonitrile solutions, respectively, and a UV absorption spectrum in a wavelength region of 365 to 700 nm was measured with a spectrophotometer U-3310 manufactured by Hitachi, Ltd. The cell length (optical path length) was 1 cm. As a result, it was confirmed that the absorbance was 0.015 or less.
For D6, the absorbance at 365 nm greatly exceeded 0.015. Further, at 1.5 × 10 ⁻² M, the absorbance was> 2, and there was a problem in measurement accuracy. As a result, the absorbance at 365 nm was 0.9.

(Creation of cured film)
The negative photosensitive resin composition solution obtained as described above is spin-coated on a silicon wafer to form a coating film having a dry film thickness of 11 to 13 μm, and then an ultrahigh pressure mercury lamp through an interference filter. Was used for i-line exposure at 30 to 1000 mJ / cm ² . After exposure, the film is heated at 120 ° C. for 3 minutes, developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide until the exposed silicon wafer is exposed, rinsed with water, and the remaining film ratio (before and after development) The minimum exposure amount (sensitivity) and resolution required for pattern formation that can obtain a film thickness ratio of 90% or more were determined. The results are shown in Tables 3-5.

(Measurement of film properties)
Next, the negative photosensitive resin composition solution was spin-coated on a silicon wafer and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of 15 μm. Thereafter, the coating film was heated in an inert gas oven manufactured by Koyo Thermo Systems Co., Ltd. in a nitrogen atmosphere at 150 ° C. for 30 minutes, and then heated at 320 ° C. or 200 ° C. for 1 hour to obtain a cured film. Next, this cured film was peeled off using a 4.9% hydrofluoric acid aqueous solution, washed with water, dried, and then examined for film properties such as glass transition point (Tg) and elongation at break.
Tg was determined from the inflection point of thermal expansion using a TMA / SS6000 manufactured by Seiko Instruments Inc. at a heating rate of 5 ° C./min.
The elongation at break was determined from a tensile test using an autograph AGS-100NH manufactured by Shimadzu Corporation.
The results are shown in Tables 3-5.

(Chemical chemical resistance)
The chemical resistance of the 200 ° C. cured film was examined. A cured film was formed by a method similar to the method for forming a cured film in the measurement of the film properties, and the presence or absence of a swelling of the film was examined in addition to the presence or absence of cracks when immersed in each solvent. The results are shown in Tables 3-5. In the table, regarding cracks, C indicates that a crack that can be visually observed occurs, B indicates that a fine crack that can be confirmed with a metal microscope is observed, and A indicates that no crack occurs.
Regarding swelling, C indicates that the film thickness has increased by 1 μm or more, B indicates that the film thickness has increased within 0.5 to 1 μm, and A indicates that the film thickness change has remained within 0.5 μm. did.

When the photosensitive resin compositions of Examples 1 to 22 were used, all exhibited good sensitivity, resolution, mechanical properties, and chemical resistance. (D) In Comparative Example 1 containing no component and in Comparative Example 3 using D6 having absorption at 365 nm, the sensitivity decreased. It was found that by using both the component (b) and the component (d), the sensitivity is improved by a synergistic effect.
In Comparative Example 2 in which the component (b) was not used, no cross-linking reaction or insolubilization due to polymerization occurred in the exposed area, and no pattern was obtained.
The comparative examples 4 and 5 which do not have a group containing an aliphatic structure in the component (a) have low sensitivity. This is presumably because the transparency in the exposure wavelength region was improved by having a group containing an aliphatic structure in the component (a), and as a result, the sensitivity was improved.
Furthermore, the wholly aromatic polybenzoxazole precursors used in Comparative Examples 4 and 5 tended to have a large elongation at break when cured at 200 ° C. In Comparative Example 6, a negative image was not obtained and a positive image was given.

  As described above, according to the negative photosensitive resin composition of the present invention, it is possible to form a pattern with excellent sensitivity and resolution. Moreover, the film | membrane which pattern-formed and heat-hardened the negative photosensitive resin composition of this invention is excellent in heat resistance and a mechanical characteristic. Moreover, according to the pattern manufacturing method of the present invention, by using the negative photosensitive resin composition, a pattern having a good shape and excellent sensitivity, resolution and heat resistance can be obtained. Furthermore, the electronic component of the present invention has high reliability by having a pattern with a good shape and characteristics. Therefore, the present invention is useful for electronic components such as electronic devices.

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 (11)

(A) a polybenzoxazole precursor having a repeating unit represented by the general formula (I), (b) a compound that generates an acid upon irradiation with actinic rays in a wavelength region of 365 to 700 nm, and (c) the above ( a negative photosensitive resin composition comprising: a) a compound capable of crosslinking or polymerizing with the component; and (d) a compound which does not absorb in the wavelength region of 365 to 700 nm and generates an acid by heat.

(In the formula, U and V each independently represent a divalent organic group. V is a group containing an aliphatic structure having 1 to 30 carbon atoms, or U has 2 to 30 carbon atoms constituting the main chain. A group containing an aliphatic structure of   The negative photosensitive resin composition according to claim 1, wherein V is a group containing an aliphatic chain structure having 1 to 30 carbon atoms. The negative photosensitive resin composition according to claim 1, wherein at least one of U and V in the formula (I) includes a structure represented by the general formula (UV1) or (UV2).

(Wherein R ¹ and R ² are each independently hydrogen, fluorine, an alkylene group having 1 to 6 carbon atoms, or a fluorinated alkylene group having 1 to 6 carbon atoms, and U includes a structure of (UV1), a is an integer of 2 to 30, and when V includes a structure of (UV1), a represents an integer of 1 to 30.)

Wherein R ^{3 to} R ⁸ are each independently hydrogen, fluorine, an alkylene group having 1 to 6 carbon atoms or a fluorinated alkylene group having 1 to 6 carbon atoms, and b to d are each independently 1 to 6 Represents an integer, and e is an integer of 0 to _3. A is —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, —C≡. C— or —R ⁹ C═CR ¹⁰ —, wherein R ⁹ and R ¹⁰ are each independently hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms.)   The negative photosensitive resin composition according to claim 1, wherein the component (a) is soluble in an alkaline aqueous solution.   The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the polymer terminal structure in the component (a) has a functional group capable of causing a crosslinking reaction with the component (c).   The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the component (d) is a sulfonate or a sulfonic acid derivative.   The negative photosensitive resin composition according to claim 1, wherein the component (d) is a sulfonate salt of a pyridinium derivative.   The component (b) 0.01 to 15 parts by weight, the component (c) 0.1 to 50 parts by weight, and the component (d) 0.01 to 15 parts by weight with respect to 100 parts by weight of the component (a). The negative photosensitive resin composition in any one of Claims 1 thru | or 7 containing a part.   A process for forming a photosensitive resin film by applying and drying the negative photosensitive resin composition according to claim 1 on a support substrate, and the photosensitive resin film obtained by the coating and drying process. The pattern manufacturing method including the process of exposing the photosensitive resin film after exposure, the process of developing the photosensitive resin film after exposure using alkaline aqueous solution, and the process of heat-processing the photosensitive resin film after the said development.   The pattern manufacturing method according to claim 9, wherein the heat treatment temperature is 220 ° C. or lower in the step of heat-treating the photosensitive resin film after development.   11. An electronic component having an electronic device having a pattern layer obtained by the pattern manufacturing method according to claim 9, wherein the pattern layer is an interlayer insulating film layer or a surface protection layer in the electronic device. Electronic component provided as a film layer.

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