JP2008281961A - Negative photosensitive resin composition, method for producing pattern, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition which imparts adequate heat resistance and mechanical characteristics even when heat-treated at a low temperature of ≤220°C, a method for producing a pattern, and electronic components. <P>SOLUTION: The negative photosensitive resin composition comprises; (a) a polybenzoxazole precursor having a repeating unit represented by general formula (I); (b) a compound which generates an acid upon irradiation with actinic rays; and (c) a compound capable of crosslinking or polymerizing with the component (a) under the action of an acid, wherein U or V denotes a divalent organic group and at least one of U and V is a group containing a 1-30C aliphatic chain structure. <P>COPYRIGHT: (C)2009,JPO&INPIT

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, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. However, in recent years, with the progress of higher integration and larger size of semiconductor elements, there has been a demand for thinner and smaller sealing resin packages, and LOC (lead-on-chip) and surface mounting methods such as solder reflow have been adopted. Therefore, a polyimide resin excellent in mechanical properties, heat resistance and the like has been required more than ever.

  Furthermore, a photosensitive polyimide having a photosensitive property imparted to the polyimide resin itself has been used, and when this is used, the pattern production process can be simplified and complicated manufacturing processes can be shortened. A heat-resistant photoresist using a conventional photosensitive polyimide or its precursor and its application are well known. For negative photosensitive polyimide, a method of introducing a methacryloyl group into a polyimide precursor via an ester bond or an ionic bond (for example, see Patent Documents 1 to 4), a soluble polyimide having a photopolymerizable olefin (for example, Patent Document) 5-10), and a self-sensitized polyimide having an benzophenone skeleton and an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded (see, for example, Patent Documents 11 and 12).

  Since the above-mentioned negative photosensitive polyimide requires an organic solvent such as N-methylpyrrolidone at the time of development, recently, a positive photosensitive resin that can be developed with an alkaline aqueous solution has been proposed. For positive photosensitive polyimide, a method of introducing an o-nitrobenzyl group into the polyimide precursor via an ester bond (for example, see Non-Patent Document 1), a naphthoquinone diazide compound mixed with a soluble hydroxylimide or polyoxazole precursor (For example, see Patent Documents 13 and 14), a method for introducing naphthoquinone diazide through an ester bond into a soluble polyimide (for example, see Non-Patent Document 2), a method for mixing naphthoquinone diazide into a polyimide precursor (for example, Patent Document 15).

  However, the above-mentioned negative photosensitive polyimide has problems in terms of function and resolution, and in some applications, yields are reduced in production. Moreover, in the above-mentioned thing, since the structure of the polymer to be used is limited, the physical property of the film finally obtained is limited and it is unsuitable for a multipurpose use. On the other hand, the positive photosensitive polyimide also has the same problems because the sensitivity and resolution are low and the structure is limited due to the problem with the absorption wavelength of the photosensitive agent as described above.

  Also, carboxylic acids such as polybenzoxazole precursor mixed with a diazonaphthoquinone compound (see, for example, Patent Document 16), or polyamic acid having a phenol moiety introduced via an ester bond (for example, see Patent Document 17). Instead of these, phenolic hydroxyl groups have been introduced, but these have insufficient developability, resulting in film loss at unexposed areas and peeling of the resin from the substrate. For the purpose of improving developability and adhesion, a mixture of polyamic acids having a siloxane moiety in the polymer skeleton has been proposed (for example, see Patent Documents 18 and 19). Storage stability deteriorates due to use. In addition, for the purpose of improving storage stability and adhesion, those having amine end groups sealed with a polymerizable group (for example, see Patent Documents 20 to 22) have been proposed. Since a diazoquinone compound containing a large number of aromatic rings is used as an agent, there is a problem that the mechanical properties after thermosetting are remarkably lowered due to low sensitivity and the need to increase the amount of diazoquinone compound added. Is.

JP-A-49-115541 Japanese Patent Laid-Open No. 51-40922 JP 54-145794 A JP 56-38038 A JP 59-108031 A JP 59-220730 A JP 59-232122 A Japanese Unexamined Patent Publication No. 60-6729 JP-A-60-72925 JP-A-61-57620 JP 59-219330 A JP 59-231533 A Japanese Examined Patent Publication No. 64-60630 US Pat. No. 4,395,482 JP 52-13315 A Japanese Patent Publication No. 64-46862 JP-A-10-307393 JP-A-4-31861 Japanese Patent Laid-Open No. 4-46345 JP-A-5-197153 JP-A-9-183846 JP 2001-183835 A Japanese Patent Laid-Open No. 3-763 JP 7-219228 A Japanese Patent Laid-Open No. 10-186664 Japanese Patent Laid-Open No. 11-202489 JP 2001-56559 A JP 2001-194791 A JP 2002-526793 A US Pat. No. 6,143,467 JP 2001-125267 A JP-A-3-58048 JP-A-3-259148 Japanese Patent Laid-Open No. 10-195294 JP-A-11-202488 JP 2000-250209 A JP 2001-249454 A JP 2004-94118 A J. Macromol. Sci. Chem., A24, 12, 1407, 1987 Macromolecules, 23,4796,1990 Macromolecules, 29,6427,1996

  In order to improve the problems of the diazoquinone compound, those using various chemical amplification systems have been proposed. Chemically amplified polyimides (for example, see Patent Document 23), chemically amplified polyimides or polybenzoxazole precursors (for example, see Patent Documents 24 to 30), among these, those with high sensitivity are low. The deterioration of the film characteristics caused by the molecular weight is excellent in the film characteristics, and the sensitivity is lowered due to the insufficient solubility caused by the high molecular weight. In addition, a method using a negative chemical amplification system using a crosslinking reaction that proceeds in the presence of an acid catalyst has been proposed (see, for example, the above-mentioned Patent Documents 17 and 31). A hydroxyl group serves as a cross-linking point. Actually, the cross-linking reaction efficiency is low and the sensitivity is not high.

  In addition, recently, devices such as MRAM (Magnet Resistive RAM) that are vulnerable to high-temperature heating processes have also been proposed, and thus there is a demand for lowering the temperature at which the polyimide or polybenzoxazole precursor is cyclized. Is also growing. Although the thing which sensitized the organic solvent soluble polyimide itself which does not require the cyclization process itself is also proposed (for example, refer patent documents 32-38 and nonpatent literature 3), these are photosensitive characteristics, alkaline aqueous solution developability, There is a disadvantage inferior to either heat resistance. Accordingly, there has been a problem that none of them are practically sufficient yet.

  The present invention has been made to solve the conventional problems as described above, and provides a negative photosensitive resin composition that provides sufficient heat resistance and mechanical properties even under heat treatment at a low temperature of 220 ° C. or lower. It is to provide.

  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.

  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), (b) a compound that generates an acid upon irradiation with actinic rays, And (c) a compound which can be crosslinked or polymerized with the component (a) by the action of an acid.

（式中、Ｕ又はＶは二価の有機基を示し、Ｕ又はＶの少なくとも一方は炭素数１〜３０の脂肪族鎖状構造を含む基である。）

(In the formula, U or V represents a divalent organic group, and at least one of U or V is a group containing an aliphatic chain structure having 1 to 30 carbon atoms.)

  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 being expressed.

（式中、Ｒ¹、Ｒ²は各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、ａは１〜３０の整数を示す。）で表される構造を含む基、

(Wherein R ¹ and R ² are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, and a represents an integer of 1 to 30),

（式中、Ｒ³〜Ｒ⁸は各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、ｂから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−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ₃）₂、−Ｃ≡Ｃ−、又は−Ｒ⁹Ｃ＝ＣＲ¹⁰−であり、Ｒ⁹〜Ｒ¹⁰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。）で表される構造を含む基。

Wherein R ^{3 to} R ⁸ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, b to d are each independently an integer of 1 to 6, 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 —. And R ^{9 to} R ¹⁰ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms.)

  In the negative photosensitive resin composition according to the present invention, the component (a) is soluble in an alkaline aqueous solution.

  Moreover, in the negative photosensitive resin composition by this invention, 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, It is characterized by the above-mentioned.

  In the negative photosensitive resin composition according to the present invention, the component (a) is selected from the group consisting of primary or secondary alcohols, phenols, carboxyl groups, amino groups, thiols and aromatic rings. And the component (c) is a cyclic group containing a methylol, alkoxyalkyl group, tertiary alcohol, cycloalkyl group, olefin, triple bond, halogenated alkyl or epoxy group. It contains at least one functional group or bond selected from the group consisting of ether, ester bond, carbonate and isocyanate.

  In the negative photosensitive resin composition according to the present invention, the component (a) is a methylol, alkoxyalkyl group, tertiary alcohol, cycloalkyl group, olefin, triple bond, alkyl halide, or epoxy. Containing at least one functional group or bond selected from the group consisting of a cyclic ether containing a group, an ester bond, a carbonate and an isocyanate, and the component (c) is a primary or secondary alcohol, phenol, It includes at least one functional group or bond selected from the group consisting of a carboxyl group, an amino group, a thiol and an aromatic ring.

  Moreover, in the negative photosensitive resin composition by this invention, the said (b) component 0.01-50 weight part and the said (c) component 0. It contains 1 to 50 parts by weight.

  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

  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.

  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.

  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.

[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 having a repeating unit represented by the general formula (I) (hereinafter referred to as “component (a)”), and (b). A compound capable of generating an acid upon irradiation with actinic rays (hereinafter referred to as “component (b)”), and (c) a compound capable of crosslinking or polymerizing with at least the terminal group of component (a) by the action of the acid (hereinafter referred to as “component (b)”). (Referred to as “component (c)”). Hereinafter, each component will be described.

[(A) component]
The component (a) in the present invention is particularly limited as long as it has a repeating unit represented by the above general formula (I) and can bridge and react with the component (c) in the presence of an acid. There is no. The bridge 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 of (a) component of this invention being soluble in alkaline aqueous solution is demonstrated below. The component (a) alone or the varnish obtained by dissolving it in any solvent together with the components (b) and (c) described below in order is spin-coated on a substrate such as a silicon wafer, and the film thickness is 5 μm. A coating film of a degree 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.

  In the present invention, the crosslinking reaction between the component (a) and the component (c) described later is combined with the functional group in the main chain of the component (a) and the crosslinking reaction of the component (c), and the terminal of the component (a) is crosslinked. It can also be a point. That is, the polymer terminal structure in the component (a) may have a functional group capable of causing a crosslinking reaction with the component (c). In the present invention, since there is a crosslinking point at the end of the component (a), there is no crosslinking, that is, the difference in dissolution rate between the exposed part and the unexposed part becomes large, which is effective for good pattern formation. As a combination of the functional group serving as a crosslinking point of the component (a) and the functional group of the component (c), both in the form of a covalent bond, an ionic bond, or a hydrogen bond by heat in the presence of an acid. There is no particular limitation as long as a bond is formed between them.

Among them, from the viewpoints of reactivity, that is, sensitivity at the time of patterning and mechanical properties of the finally obtained film, the functional groups and bonds of the component (a) and the component (c) are one more than the following groups A and B, respectively. Combinations that are selected one by one are preferred. In this case, the component (a) and the component (c) may be selected from either group, but in principle, the component (a) and the component (c) need to be at least one combination selected from different groups. is there.
[Group A] Primary or secondary alcohol, phenol, carboxyl group, amino group, thiol, aromatic ring.
[Group B] Cyclic ethers such as methylol, alkoxyalkyl groups, tertiary alcohols, cycloalkyl groups, olefins, triple bonds, alkyl halides, epoxy groups, ester bonds, carbonates, isocyanates.

  However, even in combinations not corresponding to the above, carboxyl groups or esters and amino groups, carboxyl groups or esters and primary or secondary alcohols, cycloalkyl groups, carboxyl groups, alcohols, epoxy groups, olefins or triples Bonds, methylols and the like can also be mentioned as preferable combinations having high reactivity.

  From the viewpoint of ease of functional group introduction, those in which these preferred functional groups are introduced at the terminal of the component (a) are desirable. Furthermore, from the viewpoint of ease of introduction into the polymer, a particularly preferred combination includes (a) a carboxyl group or ester as the component, and (c) a primary or secondary alcohol, epoxy group, vinyl ether or isocyanate as the component. A combination of (a) component as amino group, (c) component as epoxy group or ester, (a) component as isocyanate, (c) component as primary or secondary alcohol, phenol And a combination with a carboxyl group or an ester.

  In addition, (a) component and (c) component are olefins or triple bonds with each other in terms of a combination that can provide good cured film strength even under low temperature curing conditions. In particular, a combination of phenol and an aromatic ring as the component (a) and a methylol, alkoxyalkyl group, tertiary alcohol or vinyl ether as the component (c) can be mentioned as a particularly preferable one.

  The combination of the terminal group of the component (a) and the functional group of the component (c) is basically a combination that does not cause bonding (crosslinking) when the photosensitive resin composition is applied. That is, the temperature at which crosslinking occurs in the combination is preferably 150 ° C. or higher in the presence of an acid. Therefore, each functional group listed as an example of the combination so far is made latent by a method such as a protective group or a derivative, etc., and desired by a photochemical reaction due to exposure or a chemical change due to heat in a subsequent post-exposure heating step. A technique such as conversion to a functional group can also be taken. For example, since isocyanate reacts even at a low temperature of 150 ° C. or lower, it is introduced into the terminal group of component (a) or component (c) in the state of a precursor in which an amino group is blocked with an alkoxycarbonyl group or the like. Can do.

  In the component (a) used in the present invention, the ratio of the terminal group to the repeating unit is a molar ratio of 1 to 100 repeating units (repeating units consisting of acid residues and amine residues) with respect to the terminal group 2. It is preferable, and it is more preferable that it is 2-50. If the end group ratio is less than 1, the effect of the crosslinking reaction may be diminished or the photosensitive characteristics may be deteriorated. On the contrary, when the terminal group ratio is larger than 100, there is a possibility that sufficient film properties cannot be obtained even if the crosslinking reaction proceeds sufficiently due to the decrease in molecular weight.

The molar ratio of the acid residue to the amine residue in the component (a) is not particularly limited, but when the terminal group is derived from aminophenol, the acid residue is one more than the amine residue, and 100: 99-2 Is preferably in the range of 1: 1, and more preferably in the range of 50:49 to 3: 2. When the terminal group is a hydroxybenzoic acid derivative, the acid residue is less than the amine residue, preferably in the range of 99: 100 to 1: 2, and in the range of 49:50 to 2: 3. Is more preferable. The quantitative method can be performed by ¹ H NMR measurement.

  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 an amide unit containing a hydroxy group is contained in a certain proportion or more.

（式中、Ｕ, Ｖ, Ｗ, Ｘは二価の有機基を示し、Ｕ又はＶの少なくとも一方は炭素数１〜３０の脂肪族鎖状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。）

(In the formula, U, V, W and X represent a divalent organic group, at least one of U or V is a group containing an aliphatic chain structure having 1 to 30 carbon atoms, and j and k are A structures. The mole fraction of the unit and the B structural unit is shown, and the sum of j and k is 100 mol%.)

  That is, in the general formula (II), the mole fraction of j and k in the formula is such that j = 5 to 85 mol%, k = 15 to 95 mol%, patternability, mechanical properties, heat resistance, chemical resistance It is more preferable in terms of sex.

  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, a preferable group as U in the general formulas (I) and (II) will be described. The group containing an aliphatic chain structure having 1 to 30 carbon atoms may be present as U or V in the general formulas (I) and (II). As a group containing an aliphatic chain structure, it is desirable that at least one of U and V is a structure represented by (UV1) or (UV2) in that the dehydration ring closure rate at 280 ° C. or less is high. Furthermore, an aliphatic straight chain structure having 7 to 30 carbon atoms is more preferable because it has a low elastic modulus and a high elongation at break.

（式中、Ｒ¹、Ｒ²は各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、ａは１〜３０の整数を示す。）

(Wherein R ¹ and R ² are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, and a represents an integer of 1 to 30.)

（式中、Ｒ³〜Ｒ⁸は各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、ｂから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−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ₃）₂、−Ｃ≡Ｃ−、又は−Ｒ⁹Ｃ＝ＣＲ¹⁰−であり、Ｒ⁹〜Ｒ¹⁰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 or an alkyl group having 1 to 6 carbon atoms, b to d are each independently an integer of 1 to 6, 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 —. R ^{9 to} 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。）が挙げられる。 Examples of the diamines include compounds represented by the following general formula (III)

(Wherein n is an integer of 1 to 6).

  In addition, U (when V contains a fatty chain) or W diamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 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, 4,4′-diaminodiphenyl ether, 4, 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylene Amine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- ( 4-aminophenoxy) phenyl] ether, aromatic diamine compounds such as 1,4-bis (4-aminophenoxy) benzene, and other diamines containing a silicone group such as LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C and X-22-161E (all manufactured by Shin-Etsu Chemical Co., Ltd., trade names) and the like may be mentioned, but are not limited thereto. These compounds are used alone or in combination of two or more.

  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.

  In the present invention, the group containing an aliphatic chain structure having 1 to 30 carbon atoms may be present as U or V in the general formulas (I) and (II). As the group containing an aliphatic chain structure, the structure represented by the above (UV1) or (UV2) has high heat resistance, high transparency in the ultraviolet and visible light range, and below 280 ° C. Is excellent in that it has a high dehydration ring closure rate. Furthermore, when the aliphatic linear structure has 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 storage stability is also improved. high. 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, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid , Suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluoroseba Acid, 1,9-nonanedioic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanedioic acid, nonadecanoic acid, eicosannic acid, heneicosanoic acid, docosannic acid, tricosanoic acid , Tetracosannic acid, pentacosannic acid, hexacosannic acid, heptacosannic acid, octacosannic acid, nonacosannic acid, triacontaninic acid, hentriacontaninic acid, dotriacontaninic acid, diglycolic acid and the like. Furthermore, the compound shown by the following general formula (IV) is also included.

（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。）

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

  Other V in the general formulas (I) and (II) (when U contains a fatty chain), dicarboxylic acids of X 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-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, etc. Aromatic dicarboxylic acids can be used in combination. 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.

[Component (b)]
In the negative photosensitive resin composition of the present invention, together with the polybenzoxazole precursor used as the component (a), a compound (hereinafter referred to as an acid generator) that generates an acid upon irradiation with actinic rays as the component (b). Use. The content of the acid generator is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of component (a) in order to improve the sensitivity and resolution during exposure. It is more preferably 20 parts by weight, and further preferably 0.5 to 20 parts by weight.

  The acid generator (b) used in the present invention exhibits acidity upon irradiation with actinic rays such as ultraviolet rays, and crosslinks the component (c) with the functional group of the component (a) by its action, or (C) It has the effect | action which superposes components. Specific examples of the component (b) compound include diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acids. Esters, nitrobenzyl esters, oxime sulfonates, aromatic N-oxyimide sulfonates, aromatic sulfamides, haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, naphthoquinone diazide-4-sulfonate esters, etc. Used. Two or more kinds of such compounds can be used in combination as needed, or can be used in combination with other sensitizers. Of these, aromatic oxime sulfonic acid esters and aromatic N-oxyimide sulfonates are preferred because the effect can be expected in terms of high sensitivity.

[Component (c)]
The component (c) used in the present invention, that is, a compound that can be cross-linked or polymerized by the action of an acid and that can cross-link with at least the terminal group of the component (a) Although there is no limitation, it is preferably a compound having at least one, preferably two or more reactive functional groups in the molecule. The temperature at which component (c) can be crosslinked is preferably 150 ° C. or higher so that crosslinking does not proceed in each step of coating, drying, exposure, and development of the photosensitive resin composition. The component (c) is cross-linked with the terminal group of the component (a), and in combination therewith, a compound that polymerizes between the molecules of the component (c) may be used.

  Preferred as such compounds are 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. Examples thereof include compounds having functional groups corresponding to those preferable for combination with the component (a) exemplified above, such as a group, an amino group and an isocyanate group.

  Particularly preferred are compounds in which these substituents are substituted on the aromatic ring, namely phenols, bisphenols, polyphenols, novolac resins, resole resins, and melamine, benzoguanamine, glycoluril, urea compounds in which the N-position is substituted with these substituents. preferable. 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、Ｒ¹¹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、ｑは各々独立に０〜４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 0 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、Ｒ¹²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良い。）

(In the formula, each Z independently represents a functional group that reacts with the component (a), each R ¹² independently represents a hydrogen atom or a monovalent organic group, and is bonded to each other to form a ring structure. Is also 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、Ｒ¹³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. Are selected from a group in which part or all of them are 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 And 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良く、Ｚは各々独立に（ａ）成分と反応する官能基を示し、Ｒ¹⁴〜Ｒ¹⁵は各々独立に水素原子又は一価の有機基を示し、ｐ、ｑ、ｒ及びｓは各々独立に０〜４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 reacts independently with component (a)) R ^{14 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent organic group, and p, q, r and s are each independently an integer of 0 to 4.)

  These (c) components which are these crosslinking agents may be used independently, and may be used in combination of 2 or more types.

  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.

[Other components: (1) Acid generating compound]
In addition to the components (a) to (c), the negative photosensitive resin composition according to the present invention includes (1) an acid generating compound, (2) adhesion imparting, (3) a surfactant or a leveling agent. (4) You may contain a solvent etc.

  First, in order to promote the crosslinking reaction of component (c), an acid generating compound that generates an acid by an acid catalyst or heat may be used in combination. The acid used as the catalyst is preferably a strong acid. Specifically, arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, perfluorosulfonic acid such as camphorsulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid. Alkyl sulfonic acids such as alkyl sulfonic acids, methane sulfonic acids, ethane sulfonic acids, butane sulfonic acids are desirable. The compound which generates the acid by heat is added to the negative photosensitive resin composition of the present invention in the form of a salt or a covalent bond such as imide sulfonate as an onium salt.

  Among them, those having a thermal decomposition starting temperature of 50 ° C. to 270 ° C. are desirable. Specifically, it is desirable that the 1% weight loss temperature measured by thermogravimetric analysis (Tg) is 50 ° C. to 270 ° C., or the 5% weight loss temperature is 60 ° C. to 300 ° C. Furthermore, those having a thermal decomposition starting temperature of 140 ° C. to 250 ° C. are more preferable because no acid is generated during pre-baking and there is no possibility of adversely affecting the photosensitive characteristics and the like. Specifically, it is desirable that the 1% weight loss temperature measured by thermogravimetric analysis (Tg) is 140 ° C. to 250 ° C., or the 5% weight loss temperature is 170 ° C. to 265 ° C.

  When using these acid catalysts or compounds that generate an acid by heat, it is preferably added in an amount of 10 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of component (a). If the amount added exceeds 10 parts by weight, the influence of thermal decomposition during pre-baking may not be negligible.

[Other components: (2) Adhesiveness imparting agent]
The negative photosensitive resin composition of the present invention can contain (2) an adhesion-imparting agent such as an organic silane compound and 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, ureapropyltriethoxysilane, 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 (2) 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: (3) Surfactant or leveling agent]
In addition, the negative photosensitive resin composition of the present invention can be applied with an appropriate (3) surfactant or leveling agent in order to prevent coatability, for example, striation (film thickness unevenness) or improve developability. Can be added. Examples of such surfactants or leveling agents 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 and 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: (4) Solvent]
In the present invention, the above-described components are dissolved in (4) 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, 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. May be.

[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 (for example, 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 novolak-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). This 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.
(Examples 1-18)
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 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-hydroxy (Phenyl) hexafluoropropane (13.92 g) and aniline (0.37 g) were added and dissolved by stirring. Then, while maintaining the temperature at 0 to 5 ° C., 5.64 g of malonic acid dichloride was added dropwise over 10 minutes, followed by stirring for 60 minutes. Continued. 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 polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as polymer I and To do). 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 Example 2)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that malonic acid dichloride used in Synthesis Example 1 was replaced with succinic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer II) had a weight average molecular weight of 20,400 and a dispersity of 1.8 determined by standard polystyrene conversion.

(Synthesis Example 3)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that malonic acid dichloride used in Synthesis Example 1 was replaced with glutaric acid dichloride and aniline was removed. The obtained polyhydroxyamide (hereinafter referred to as polymer III) had a weight average molecular weight of 12,800 and a dispersity of 1.7 determined by standard polystyrene conversion.

(Synthesis Example 4)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that the malonic acid dichloride used in Synthesis Example 1 was replaced with adipic acid dichloride and aniline was removed. The obtained polyhydroxyamide (hereinafter referred to as polymer IV) had a weight average molecular weight of 29,300 and a dispersity of 1.9 determined by standard polystyrene conversion.

(Synthesis Example 5)
Synthesis was performed under the same conditions as in Synthesis Example 1 except that malonic acid dichloride used in Synthesis Example 1 was replaced with suberic acid dichloride and aniline was replaced with m-aminoanisole. The obtained polyhydroxyamide (hereinafter referred to as polymer V) had a weight average molecular weight of 36,900 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 6)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that the malonic acid dichloride used in Synthesis Example 1 was replaced with sebacic acid dichloride and aniline was replaced with m-aminoanisole. The obtained polyhydroxyamide (hereinafter referred to as polymer VI) had a weight average molecular weight of 33,100 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 7)
Synthesis was performed under the same conditions as in Synthesis Example 1 except that malonic acid dichloride used in Synthesis Example 1 was replaced with dodecanoic acid dichloride and aniline was replaced with m-aminophenol. The obtained polyhydroxyamide (hereinafter referred to as polymer VII) had a weight average molecular weight of 31,600 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 8)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that the malonic acid dichloride used in Synthesis Example 1 was replaced with dimethylmalonic acid dichloride and aniline was replaced with m-aminophenol. The obtained polyhydroxyamide (hereinafter referred to as polymer VIII) had a weight average molecular weight of 22,200 and a dispersity of 1.8 determined by standard polystyrene conversion.

(Synthesis Example 9)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that the malonic acid dichloride used in Synthesis Example 1 was replaced with hexafluoroglutaric acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer IX) had a weight average molecular weight of 10,700 and a dispersity of 1.6 determined by standard polystyrene conversion.

(Synthesis Example 10)
The malonic acid dichloride used in Synthesis Example 1 was changed to glutaric acid dichloride, and 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was changed to 2,2′-bis (3-amino-4-hydroxyphenyl). ) Synthesis was performed under the same conditions as in Synthesis Example 1 except that propane was used. The obtained polyhydroxyamide (hereinafter referred to as “polymer X”) had a weight average molecular weight of 16,400 and a dispersity of 1.6 determined by standard polystyrene conversion.

(Synthesis Example 11)
Malonic acid dichloride used in Synthesis Example 1 was converted to suberic acid dichloride, and 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was converted to 2,2′-bis (3-amino-4-hydroxyphenyl). ) Synthesis was carried out under the same conditions as in Synthesis Example 1 except that propane was replaced and aniline was removed. The resulting polyhydroxyamide (hereinafter referred to as polymer XI) had a weight average molecular weight of 33,400 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 12)
Malonic acid dichloride used in Synthesis Example 1 was changed to sebacic acid dichloride, and 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was changed to 2,2'-bis (3-amino-4-hydroxyphenyl). ) Synthesis was carried out under the same conditions as in Synthesis Example 1 except that propane was replaced and aniline was removed. The obtained polyhydroxyamide (hereinafter referred to as polymer XII) had a weight average molecular weight of 28,800 and a dispersity of 1.9, as determined by standard polystyrene conversion.

(Synthesis Example 13)
The malonic acid dichloride used in Synthesis Example 1 was changed to dodecanoic acid dichloride, and 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was changed to 2,2′-bis (3-amino-4-hydroxyphenyl). ) Synthesis was performed under the same conditions as in Synthesis Example 1 except that propane was replaced and aniline was replaced with p-aminophenol. The obtained polyhydroxyamide (hereinafter referred to as polymer XIII) had a weight average molecular weight of 24,300 and a dispersity of 1.9, as determined by standard polystyrene conversion.

(Synthesis Example 14)
The malonic acid dichloride used in Synthesis Example 1 was changed to dimethylmalonic acid dichloride, and 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was changed to 2,2′-bis (3-amino-4-hydroxy). Synthesis was carried out under the same conditions as in Synthesis Example 1 except that it was replaced with (phenyl) propane and aniline was replaced with p-aminophenol. The obtained polyhydroxyamide (hereinafter referred to as polymer XIV) had a weight average molecular weight of 29,100 and a dispersity of 1.9, as determined by standard polystyrene conversion.

(Synthesis Example 15)
The synthesis was carried out under the same conditions as in Synthesis Example 3 except that 50 mol% of glutaric acid dichloride used in Synthesis Example 3 was replaced with 4,4′-diphenyl ether dicarboxylic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer XV) had a weight average molecular weight of 34,800 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 16)
The synthesis was performed under the same conditions as in Synthesis Example 8 except that 50 mol% of dimethylmalonic acid dichloride used in Synthesis Example 8 was replaced with 4,4′-diphenyl ether dicarboxylic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer XVI) had a weight average molecular weight of 36,200 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 17)
The synthesis was performed under the same conditions as in Synthesis Example 6 except that 40 mol% of sebacic acid dichloride used in Synthesis Example 6 was replaced with 4,4′-diphenyl ether dicarboxylic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer XVII) had a weight average molecular weight of 45,100 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 18)
The synthesis was performed under the same conditions as in Synthesis Example 7 except that 40 mol% of dodecanoic acid dichloride used in Synthesis Example 7 was replaced with 4,4′-diphenyl ether dicarboxylic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer XVIII) had a weight average molecular weight of 41,800 and a dispersity of 2.0 determined by standard polystyrene conversion.

(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 x 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.

(Photosensitive characteristic evaluation)
The component (b) and the component (c) were blended in predetermined amounts shown in Table 1 with respect to 100 parts by weight of each of the polymers I to XVIII as the component (a). As an organic solvent as a solvent, γ-butyrolactone (BLO) or N-methylpyrrolidone (NMP) as shown in Table 1 was used.

  In Table 1, the amount in parentheses indicates the amount added relative to 100 parts by weight of the polymer in parts by weight. In Table 1, B1 and B2 used as the component (b), and C1 to C8 used as the component (c) are compounds represented by the following chemical formulas (IX) and (X). In formula (X), C2 is a mixture of oligomers with h = 1-3. When B1 was used as the component (b), 3 parts by weight of DMEA represented by the chemical formula (IX) was added as a sensitizer with respect to 100 parts by weight of the polymer.

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 12 to 20 μm, and then an ultrahigh pressure through an interference filter. I-line exposure of 100 to 1000 mJ / cm ² was performed using a mercury lamp. 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 (film before and after development) The minimum exposure amount (sensitivity) and resolution required for pattern formation that can obtain a thickness ratio of 90% or more were determined. The results are summarized in Table 2.

  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 and dried, and then the film physical properties such as glass transition point (Tg), elongation at break and 5% weight reduction temperature were examined. 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 and elastic modulus were obtained from a tensile test using an autograph AGS-100NH manufactured by Shimadzu Corporation. The thermal decomposition temperature was measured using a TG / DTA6300 manufactured by Seiko Instruments Inc. under a flow of nitrogen gas of 200 mL / min under a temperature rising rate of 10 ° C./min. The temperature at which the weight loss reached 5% It was temperature. These results are shown in Table 3.

As described above, in Examples 1 to 18, changes in Tg and elongation at 200 ° C. curing were small compared to 320 ° C. curing, and film properties comparable to those obtained at 320 ° C. were obtained.
Regarding the 5% weight loss temperature, the value when cured at 200 ° C. was lower than when it was cured at 320 ° C., but it was as high as 300 ° C. or higher even when cured at 200 ° C. Further, as the component (a), a polymer having a functional group such as a carboxyl group or an aromatic group at the terminal is used, and the elongation at break depends on the curing temperature due to the interaction with the components (b) and (c). It was found that all of them have mechanical properties that are practically no problem, at 10% or more.

(Comparative Examples 1-5)
(Synthesis Example 19)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged, and the flask was cooled to 5 ° C., and then 12.64 g of thionyl chloride. Was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid chloride. Next, 87.5 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 18.31 g of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. After stirring and dissolving, 8.53 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, followed by stirring for 30 minutes. Continued. The solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then decompressed to obtain polyhydroxyamide (hereinafter referred to as polymer XIX). The weight average molecular weight calculated | required by standard polystyrene conversion was 17,900, and dispersion degree was 1.5.

  Next, as the component (a), each polymer shown in the following Table 4 was used, and the components (b) and (c) were blended in predetermined amounts shown in Table 4 with respect to 100 parts by weight of these polymers. .

  In Table 4, the amount in parentheses indicates the amount added relative to 100 parts by weight of the polymer in parts by weight. B1, B2 used as the component (b), and C1, C4, C8 used as the component (c) are the compounds described above. C12 used as the component (c) is a compound represented by the following chemical formula (XI).

  Hereinafter, the minimum exposure amount (sensitivity) and the resolution were obtained and evaluated in the same manner as in the examples. These evaluation results are shown in Table 5.

  In Comparative Examples 1 to 2, and 5, no results were obtained because no cross-linking reaction or insolubilization by polymerization occurred in the exposed area. Here, C12 used as the component (c) is a compound that does not cause a crosslinking reaction in the presence of the component (a) and an acid. In Comparative Examples 3 and 4, a negative image could be obtained, but the sensitivity was lower than in Examples 1-18. From this, it can be said that it is necessary to improve the transparency in the exposure wavelength region by having an aliphatic group in the component (a).

  Next, with respect to Comparative Examples 3 and 4 in which patterns were obtained, the characteristics of the cured film were examined in the same manner as in the Examples. The results are shown in Table 6.

  The wholly aromatic polybenzoxazole precursors used in Comparative Examples 3 and 4 give higher physical properties than those of the present invention when cured at 320 ° C., but the properties tend to be greatly reduced by curing at 200 ° C. Furthermore, although the 200 ° C. cured film has heat resistance, it can be said that the mechanical properties have not reached the practical level.

  As described above, the negative photosensitive resin composition according to the present invention enables pattern formation 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.

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.

Explanation of symbols

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

Claims (9)

(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, and (c) the component (a) by the action of the acid; A negative photosensitive resin composition comprising a compound capable of crosslinking or polymerizing.

(In the formula, U or V represents a divalent organic group, and at least one of U or V is a group containing an aliphatic chain structure having 1 to 30 carbon atoms.) The negative photosensitive resin according to claim 1, wherein 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). Resin composition.

(Wherein R ¹ and R ² are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, and a represents an integer of 1 to 30),

Wherein R ^{3 to} R ⁸ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, b to d are each independently an integer of 1 to 6, 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 —. And R ^{9 to} 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 type according to any one of claims 1 to 3, wherein the polymer terminal structure in the component (a) has a functional group capable of causing a crosslinking reaction with the component (c). Photosensitive resin composition.   The component (a) includes at least one functional group or bond selected from the group consisting of a primary or secondary alcohol, a phenol, a carboxyl group, an amino group, a thiol and an aromatic ring, and the component (c) ) Component is at least selected from the group consisting of methylol, alkoxyalkyl groups, tertiary alcohols, cycloalkyl groups, olefins, triple bonds, halogenated alkyls or cyclic ethers containing epoxy groups, ester bonds, carbonates and isocyanates The negative photosensitive resin composition according to any one of claims 1 to 4, comprising one kind of functional group or bond.   The component (a) is selected from the group consisting of a methyl ether, an alkoxyalkyl group, a tertiary alcohol, a cycloalkyl group, an olefin, a triple bond, an alkyl halide, or a cyclic ether containing an epoxy group, an ester bond, a carbonate, and an isocyanate. At least one functional group or bond selected, and the component (c) is selected from the group consisting of primary or secondary alcohols, phenols, carboxyl groups, amino groups, thiols and aromatic rings The negative photosensitive resin composition according to any one of claims 1 to 4, comprising at least one functional group or bond.   The component (a) contains 0.01 to 50 parts by weight and the component (c) 0.1 to 50 parts by weight with respect to 100 parts by weight of the component (a). The negative photosensitive resin composition of any one of Claims 6.   A negative photosensitive resin composition according to any one of claims 1 to 7 is applied to a support substrate and dried to form a photosensitive resin film, and the coating and drying steps. Including a step of exposing the obtained photosensitive resin 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 method for producing a pattern characterized by the above.   It is an electronic component which has an electronic device which has the layer of the pattern obtained by the manufacturing method of the pattern of Claim 8, Comprising: The layer of the said pattern is an interlayer insulation film layer or a surface protective film layer in the said electronic device An electronic component characterized by being provided as

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