JP5762706B2 - Photosensitive resin composition and method for producing cured relief pattern - Google Patents

Description

  The present invention relates to a photosensitive resin composition useful as a surface protective film and an interlayer insulating film of a semiconductor device, a method for producing a heat-resistant cured relief pattern using the photosensitive resin composition, and the cured relief pattern. The present invention relates to a semiconductor device.

  Polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like are widely used for surface protection films and interlayer insulating films of semiconductor devices. This polyimide resin is generally often provided in the form of a photosensitive polyimide precursor composition. In the process of manufacturing a semiconductor device, the precursor composition is applied to a substrate such as a silicon wafer, patterned with actinic rays, developed, and subjected to a thermal imidization treatment to become a part of the semiconductor device. A surface protective film, an interlayer insulating film, or the like can be easily formed.

  By the way, in this photosensitive polyimide precursor composition, it is necessary to use an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the developing step. Therefore, countermeasures for removing organic solvents have been demanded due to the recent increase in environmental problems. In response to this demand, recently, it has been proposed to use a heat-resistant photosensitive resin material that can be developed with an alkaline aqueous solution, like a photoresist.

  Among heat-resistant photosensitive resin materials, an alkaline aqueous solution-soluble polyhydroxyamide that becomes a heat-resistant resin after curing, such as polybenzoxazole (hereinafter also referred to as “PBO”) precursor, is converted into a photoacid such as a photosensitive diazoquinone compound. For example, Patent Document 1 discloses a method of mixing a generator with a PBO precursor composition and using the PBO precursor composition as a photosensitive resin composition.

  The development mechanism of this photosensitive resin composition is that the photosensitive diazoquinone compound and the PBO precursor in the unexposed area have a low dissolution rate in an alkaline aqueous solution, whereas the photosensitive diazoquinone compound is converted into an indenecarboxylic acid compound by exposure. This utilizes the fact that the dissolution rate of the exposed portion in the alkaline aqueous solution increases due to chemical change. By utilizing the difference in the dissolution rate with respect to the developer between the exposed portion and the unexposed portion, a relief pattern composed of the unexposed portion can be produced.

  Usually, a relief pattern is produced by applying a photosensitive resin composition on a silicon wafer by spin coating or the like, exposing and developing. In recent years, the wafer diameter has been increased, and the uniformity of the film thickness at the time of coating has been regarded as important. As a study for improving the film thickness uniformity, for example, studies as shown in Patent Documents 2 and 3 are performed.

JP 63-096162 A JP 2005-157327 A JP 2003-261822 A

  However, if the photosensitive resin composition is stored in a varnish state, the viscosity changes with the passage of storage time, and if the short storage time and the long storage time are applied under the same conditions, the film thickness changes. The problem remained.

  The present invention relates to a photosensitive resin composition excellent in film thickness uniformity during coating and film thickness stability (film thickness stability before and after storage), a method for producing a cured relief pattern using the composition, and An object of the present invention is to provide a semiconductor device having a cured relief pattern.

  The present inventor has found that a photosensitive resin composition that solves the above-mentioned problems can be obtained by setting the water content in the photosensitive resin composition to a specific range, and has reached the present invention. That is, the present invention is as follows.

  [1] A photosensitive resin composition containing (b) 1 to 50 parts by mass of a photoacid generator and (c) 30 to 1500 parts by mass of γ-butyrolactone as a solvent with respect to 100 parts by mass of (a) an alkali-soluble resin. A photosensitive resin composition having a moisture content of 0.6 to 18% by mass in the photosensitive resin composition.

  [2] The photosensitive resin composition according to [1], wherein the water content is 1.0 to 12% by mass.

  [3] The photosensitive resin composition according to [1] or [2], further comprising (d) 1 to 50 parts by mass of a crosslinking agent with respect to 100 parts by mass of the (a) alkali-soluble resin.

｛式中、Ｘ_１は、少なくとも２個の炭素原子を有する４価の有機基であり、Ｙ_１は、少なくとも２個の炭素原子を有する２価の有機基であり、そしてｍは、１〜１０００の整数である。｝
で表される繰り返し単位を有するポリヒドロキシアミドであるか、又はフェノール樹脂である、［１］〜［３］のいずれか１項に記載の感光性樹脂組成物。 [4] The (a) alkali-soluble resin is represented by the following general formula (1):

{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, Y ₁ is a divalent organic group having at least 2 carbon atoms, and m is 1 to An integer of 1000. }
The photosensitive resin composition according to any one of [1] to [3], which is a polyhydroxyamide having a repeating unit represented by: or a phenol resin.

  [5] The photosensitive resin composition according to any one of [1] to [4], wherein the (b) photoacid generator is a compound having a naphthoquinonediazide structure.

[6] (1) A step of forming a photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of [1] to [5] on the substrate;
(2) a step of exposing the photosensitive resin layer;
(3) A cured relief comprising a step of forming a relief pattern by developing the photosensitive resin layer after the exposure, and (4) a step of forming a cured relief pattern by heat-treating the obtained relief pattern. Pattern manufacturing method.

  [7] A cured relief pattern produced by the method according to [6].

  [8] A semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element, wherein the cured film is the cured relief pattern according to [7]. .

  According to the present invention, a photosensitive resin composition excellent in film thickness uniformity during coating and film thickness stability can be obtained, and further a step of forming a resin pattern using the photosensitive resin composition. The manufacturing method of the hardening relief pattern containing can be provided, and a semiconductor device.

<Photosensitive resin composition>
Each component which comprises the photosensitive resin composition of this invention is demonstrated concretely below. The photosensitive resin composition of the present invention contains (a) 100 parts by mass of an alkali-soluble resin, (b) a photoacid generator, (c) γ-butyrolactone as a solvent, and optionally (d) a crosslinking agent. The water content in the photosensitive resin composition is 0.6 to 18% by mass.

(A) Alkali-soluble resin (a) Alkali-soluble resin used as the base polymer of the photosensitive resin composition of the present invention has a hydroxyl group and is soluble in an alkaline solution. For example, a polyimide structure, a polybenzoxazole structure , A resin having at least one structure selected from the group consisting of a polyimide precursor structure and a polybenzoxazole precursor structure. Further, the resin may have a plurality of structures described above. Among these structures, it is preferable to have a polyimide precursor structure (for example, polyamic acid (polyamic acid) or the like) or a polybenzoxazole precursor structure from the viewpoint of solubility in a solvent. A resin having a polybenzoxazole precursor structure (hereinafter also referred to as “PBO precursor” or “polyhydroxyamide”) will be described later.

  In addition, examples of the (a) alkali-soluble resin include a phenol resin and derivatives thereof. Specifically, examples of the phenol resin and derivatives thereof include novolak resins and polyhydroxystyrene resins.

  As the novolac resin, those widely used in the technical field of resists can be used. This novolac resin can be obtained, for example, by reacting phenols with aldehydes or ketones in the presence of an acidic catalyst.

  Among the novolak resins, a novolak resin obtained by concomitant use of metacresol and paracresol and a condensation reaction of these with formaldehyde, formalin or paraformaldehyde is particularly preferable from the viewpoint of sensitivity controllability. The charged mass ratio of metacresol: paracresol is usually 20:80 to 80:20, preferably 50:50 to 70:30.

  The molecular weight of the novolak resin is a weight average molecular weight, and is usually 1,000 to 20,000, preferably 1,000 to 15,000, and more preferably 1,000 to 10,000. The weight average molecular weight of the resin can be controlled within a desired range by adjusting the synthesis conditions. In addition, the narrower the molecular weight distribution, the higher the photosensitivity, so the resin obtained by synthesis is solid-liquid extracted with an organic solvent having an appropriate solubility, or the resin is dissolved in a good solvent and dropped into the poor solvent. Alternatively, the molecular weight distribution may be controlled by dropping a poor solvent into the resin and performing solid-liquid or liquid-liquid extraction. Specific examples of this novolak resin include EP4000B (Asahi Organic Materials Industry: trade name), EP4020G (Asahi Organic Materials Industry: trade name), EP4050G (Asahi Organic Materials Industry: trade name), EP4080G (Asahi Organic Materials Industry: product). Name).

  Next, the polyhydroxystyrene resin and derivatives thereof will be described in detail. Specific examples of the polyhydroxystyrene resin and derivatives thereof include, for example, poly-o-hydroxystyrene, poly-m-hydroxystyrene, poly-p-hydroxystyrene, poly-α-methyl-o-hydroxystyrene, poly-α. -Methyl-m-hydroxystyrene, poly-α-methyl-p-hydroxystyrene, or a partially acetylated product and a silylated product thereof. The weight average molecular weight of these polyhydroxystyrene resins or derivatives thereof is usually in the range of 3,000 to 100,000, particularly preferably 4,000 to 20,000.

｛式中、Ｘ_１は、少なくとも２個の炭素原子を有する４価の有機基であり、Ｙ_１は、少なくとも２個の炭素原子を有する２価の有機基であり、そしてｍは、１〜１０００の整数である。｝
で表される繰り返し単位の構造を含む。 (A) The use of polyhydroxyamide as the alkali-soluble resin is a preferred embodiment of the present invention. The polyhydroxyamide has the following general formula (1):

{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, Y ₁ is a divalent organic group having at least 2 carbon atoms, and m is 1 to An integer of 1000. }
The structure of the repeating unit represented by these is included.

The repeating unit represented by the general formula (1) has a structure obtained by polycondensation of a dicarboxylic acid having a Y ₁ (COOH) ₂ structure and a bisaminophenol having a X ₁ (NH ₂ ) ₂ (OH) ₂ structure. Have The two amino and hydroxy groups of the bisaminophenol are each in the ortho position. When the polyhydroxyamide is heated to about 280 to 400 ° C., the ring is closed, and the polyhydroxyamide is changed to polybenzoxazole which is a heat resistant resin. m is preferably in the range of 2 to 1000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 30.

｛式中、Ｘ_１は、少なくとも２個の炭素原子を有する４価の有機基であり、Ｘ_２、Ｙ_１及びＹ_２は、それぞれ独立に、少なくとも２個の炭素原子を有する２価の有機基であり、ｍは、１〜１０００の整数であり、ｎは、１〜５００の整数であり、そしてｍ／（ｍ＋ｎ）＞０．５である。なお、Ｘ_１及びＹ_１を含むｍ個の単位並びにＸ_２及びＹ_２を含むｎ個の単位の配列順序は問わない。｝
のように、原料のＸ_１（ＮＨ_２）_２（ＯＨ）_２の構造を有するジアミノジヒドロキシ化合物に由来する構造の一部が、Ｘ_２（ＮＨ_２）_２の構造を有するジアミン（ヒドロキシ基を有していない）に由来する構造に置き換わっている重合体を用いてもよい。 In order to control alkali solubility, the polyhydroxyamide may have a structure in which a part of the structure of the repeating unit represented by the general formula (1) is replaced with another structure. Specifically, the following general formula (2):

{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, and X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having at least 2 carbon atoms. M is an integer from 1 to 1000, n is an integer from 1 to 500, and m / (m + n)> 0.5. The arrangement order of m units including X ₁ and Y ₁ and n units including X ₂ and Y ₂ is not limited. }
As described above, a part of the structure derived from the diaminodihydroxy compound having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ as a raw material has a diamine (having a hydroxy group) having the structure of X ₂ (NH ₂ ) _2. A polymer that is replaced with a structure derived from (not) may be used.

  The higher the proportion of the above-mentioned dihydroxydiamide units in the polyhydroxyamide, the better the solubility in an alkaline aqueous solution used as a developer. Therefore, m / (m + n)> 0.5 is preferable, and 0.7 or more More preferably, it is 0.8 or more.

X ₁ is preferably a tetravalent organic group having 2 to 30 carbon atoms in view of good solubility in an alkali developer and heat resistance of the resulting resin film. X ₂ is preferably a divalent organic group having 2 to 30 carbon atoms in view of good solubility in an alkali developer and heat resistance of the resulting resin film. Y ₁ and Y ₂ are preferably divalent organic groups having 2 or more and 30 or less carbon atoms in that the solubility in an alkali developer and the heat resistance of the resulting resin film are good. .

Examples of the bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 4,4 ′. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis -(4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis -(4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino- 3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and Examples include 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

から選ばれる芳香族基の場合である。 Among these bisaminophenols having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , X ₁ is preferably the following:

In the case of an aromatic group selected from

｛式中、Ｘ_３は、少なくとも２個以上の炭素原子を有する４価の有機基であり、そして前述した好ましいＸ_１の芳香族基から成る群から選択される少なくとも１つの有機基であることが好ましい。｝
で表されるジアミンが挙げられる。 In addition, as a compound having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , two pairs of diamines having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other (hereinafter referred to as “PBO precursor in the molecule”). It is also possible to use a "diamine having a structure"). For example, the following general formula, which is obtained by reacting bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ with two molecules of nitrobenzoic acid and reducing it,

{Wherein X ₃ is a tetravalent organic group having at least two carbon atoms, and is at least one organic group selected from the group consisting of the preferred aromatic groups of X ₁ described above. Is preferred. }
The diamine represented by these is mentioned.

｛式中、Ｙ_３は、少なくとも２個以上の炭素原子を有する２価の有機基であり、そして後述するＹ_１として示される好ましい有機基から成る群から選択される少なくとも１つの有機基であることが好ましい。｝
で表されるジアミンを得る方法が挙げられる。 As another method for obtaining a diamine having a PBO precursor structure in the molecule, the dicarboxylic acid dichloride having the structure of Y ₃ (COCl) ₂ is reacted with two molecules of nitroaminophenol for reduction, and the following general formula:

{Wherein Y ₃ is a divalent organic group having at least 2 carbon atoms, and is at least one organic group selected from the group consisting of preferable organic groups shown as Y ₁ described later. It is preferable. }
The method of obtaining diamine represented by these is mentioned.

Examples of the diamine having the structure of X ₂ (NH ₂ ) ₂ include aromatic diamine and silicon diamine.

  Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-a Nophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2 , 4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-amino) Benzyl) benzene, imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6)- Amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene 4,4′-diaminodiphenylurea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 4,4′- Bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4 ′ -Diaminobiphenyl, 4,4'-diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobipheny 3,3′-dimethyl-4,4′-diaminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4- Aminophenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′- Di- (3-aminophenoxy) diphenylsulfone, 4,4′-diaminobenzanilide and the like, and the hydrogen atom of the aromatic nucleus of these aromatic diamines are a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, Substituted by at least one group or atom selected from the group consisting of a cyano group and a phenyl group Compounds, and the like.

Moreover, in order to improve adhesiveness with a base material, silicon diamine can be selected as a part or all of the diamine having the structure of X ₂ (NH ₂ ) ₂ , and examples thereof include bis (4-amino Phenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyl) Dimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, and the like.

｛式中、Ａ_１は、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、及び−Ｃ（ＣＦ_３）_２−から成る群から選択される２価の基又は単結合であり、ｍ_５は、１〜３０の整数であり、Ｌ_１は、水素原子、アルキル基、不飽和基、及びハロゲン原子から成る群から選択される基であり、ｊは、０〜４の整数であり、そしてＬ_２は、水素原子、メチル基又は水酸基である。｝
から選ばれた、芳香族基、脂環式基又は脂肪族基であるジカルボン酸が挙げられる。 Y ₁ The dicarboxylic acid having a _{(COOH) 2} and _Y 2 _{(COOH) 2} structure, _{Y 1} and _{Y 2} are each the following group of compounds:

{Wherein A ₁ is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —. A divalent group or a single bond, m ₅ is an integer of 1 to 30, L ₁ is a group selected from the group consisting of a hydrogen atom, an alkyl group, an unsaturated group, and a halogen atom; j is an integer of 0 to 4, and L ₂ is a hydrogen atom, a methyl group or a hydroxyl group. }
The dicarboxylic acid which is an aromatic group, an alicyclic group, or an aliphatic group selected from

In addition, a derivative of 5-aminoisophthalic acid can be used for a part or all of the dicarboxylic acid having the Y ₁ (COOH) ₂ and Y ₂ (COOH) ₂ structures.

  Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivative include 5-norbornene-2,3-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3, 6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1 -Cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, allyl succinic anhydride , Isocyanate ethyl methacrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate 3-cyclohexene-1-carboxylic acid chloride, 2-furancarboxylic acid chloride, crotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propiolic acid chloride, tetrolic acid chloride, thiophene-2-acetyl chloride P-styrene sulfonyl chloride, glycidyl methacrylate, allyl glycidyl ether, chloroformate methyl ester, chloroformate ethyl ester, chloroformate n-propyl ester, chloroformate isopropyl ester, chloroformate isobutyl ester, chloroformate 2 -Ethoxy ester, chloroformate-sec-butyl ester, chloroformate benzyl ester, chloroformate 2-ethylhexyl ester, chloroformate allyl ester, chloroformate phenyl ester, chloride Formic acid 2,2,2-trichloroethyl ester, chloroformic acid-2-butoxyethyl ester, chloroformic acid-p-nitrobenzyl ester, chloroformic acid-p-methoxybenzyl ester, isobornyl benzyl chloroformate , Chloroformic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxycarbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-t-butyl- Dicarbonate, N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosilane, hexamethyldisi Zan, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, isocyanic acid And phenyl, n-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, and cis-1,2-cyclohexanedicarboxylic anhydride, and glutaric anhydride. .

（式中、Ｂは、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、及び−Ｃ（ＣＦ_３）_２−から成る群から選択される２価の基を表す。）
で表される化合物が挙げられる。 Furthermore, as a dicarboxylic acid having a Y ₁ (COOH) _{2 or} Y ₂ (COOH) ₂ structure, a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol or a monoamine can also be used. Here, examples of monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol and the like. Examples of monoamines include butylamine and aniline. Examples of the tetracarboxylic dianhydride include the following chemical formula:

Wherein B is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —. Represents a valent group.)
The compound represented by these is mentioned.

  Alternatively, tetracarboxylic dianhydride can be reacted with bisaminophenol or diamine, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.

（式中、Ｘ_４は、Ｘ_１（ＯＨ）_２（ＮＨ−）_２で表される２価の有機基を表す。Ｘ_１は、式（１）中のＸ_１と同義である。）
で表される化学物が挙げられる。 Also, trimellitic acid chloride is reacted with bisaminophenol to produce tetracarboxylic dianhydride, and ring-opened in the same manner as the above tetracarboxylic dianhydride and used as dicarboxylic acid You can also. The tetracarboxylic dianhydride obtained here has the following chemical formula:

(Wherein, _{X 4 is} .X ₁ representing a divalent organic group represented by X ₁ (OH) 2 _{(NH-) 2} has the same meaning as _{X 1} in the formula (1).)
A chemical represented by

  As a method of polycondensation of the dicarboxylic acid and bisaminophenol (diamine) for synthesizing polyhydroxyamide, bisaminophenol (diamine) is allowed to act after dicarboxylic acid and thionyl chloride are used to form diacid chloride. And a method of polycondensation of dicarboxylic acid and bisaminophenol (diamine) with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.

  In the polyhydroxyamide having the repeating unit represented by the above general formula (1), it is also preferable to use the terminal group by sealing the end group with an organic group (hereinafter referred to as “sealing group”). In the polycondensation of hydroxypolyamide, when the dicarboxylic acid component is used in an excess number of moles compared to the sum of the bisaminophenol component and the diamine component, an amino group or a compound having a hydroxyl group is used as the sealing group. Is preferred. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, and hydroxyethyl acrylate.

  On the other hand, when both components of the bisaminophenol component and the diamine component are used in an excess number of moles compared to the dicarboxylic acid component, as the sealing group, acid anhydride, carboxylic acid, acid chloride, isocyanate group, etc. It is preferable to use a compound having Examples of the compound include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methylcyclohexane dicarboxylic anhydride Products, cyclohexenedicarboxylic anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, and tosyl chloride.

(B) Photoacid generator As the photoacid generator (b) contained in the photosensitive resin composition of the present invention, the photosensitive resin composition can be applied as a positive type or a negative type depending on the intended use. Can be used. When the photosensitive resin composition is used as a positive type, as the photoacid generator (b), a photosensitive diazoquinone compound, an onium salt, a halogen-containing compound and the like can be used, and a photosensitive diazoquinone compound is preferable. .

  Examples of the onium salts include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, and diazonium salts. Among these, onium salts selected from the group consisting of diaryl iodonium salts, triaryl sulfonium salts, and trialkyl sulfonium salts are preferable.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferable.

｛式中、Ｑは、水素原子またはナフトキノンジアジドスルホン酸エステル基であり、そして全てのＱが同時に水素原子であることはない。｝
を有する化合物が挙げられる。 The photosensitive diazoquinone compound is a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure. US Pat. No. 2,772,972, US Pat. No. 2,797,213 And known substances described in U.S. Pat. No. 3,669,658. Compounds having a naphthoquinone diazide structure are preferred, examples include the following naphthoquinone diazide structure:

{In the formula, Q is a hydrogen atom or a naphthoquinone diazide sulfonate group, and all Qs are not hydrogen atoms at the same time. }
The compound which has is mentioned.

が挙げられる。 Preferred naphthoquinone diazide sulfonate groups are the following groups:

Is mentioned.

  When used as a positive photosensitive composition, the blending amount of (b) the photoacid generator with respect to (a) the alkali-soluble resin is from 1 to 50 masses per 100 parts by mass of (a) the alkali-soluble resin. Part and preferably 5 to 30 parts by mass. (B) When the blending amount of the photoacid generator is 1 part by mass or more, the patterning property of the resin is good, and when it is 50 parts by mass or less, the tensile elongation of the cured film is good and the development residue (scum in the exposed part) )Less is.

  In addition, when using the photosensitive resin composition of this invention by a negative type, the compound which generate | occur | produces an acid by irradiation of actinic rays is used as (b) photo-acid generator, This is mentioned later (d) Crosslinking agent It can be used as a negative type by combining with. Examples of compounds that generate an acid upon irradiation with actinic rays include the following compounds a) to k).

A) Trichloromethyl-s-triazines Tris (2,4,6-trichloromethyl) -s-triazine, 2-phenyl-bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -Bis (4,6-trichloromethyl) -s-triazine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4 6-trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl) ) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) Bis (4,6-trichloromethyl-s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6 -Trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (3,4,5-trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis (4 , 6-Trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthio-β Styryl) - bis (4,6-trichloromethyl) -s-triazine.

A) Diaryl iodonium compounds diphenyl iodonium tetrafluoroborate, diphenyl iodonium tetrafluorophosphate, diphenyl iodonium tetrafluoroarsenate, diphenyl iodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenyl Phenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4- Meto Xiphenylphenyliodonium-p-toluenesulfonate, bis (4-ter-butylphenyl) iodonium tetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter-butylphenyl) iodonium Trifluoromethanesulfonate, bis (4-ter-butylphenyl) iodonium trifluoroacetate, bis (4-ter-butylphenyl) iodonium-p-toluenesulfonate, and the like.

C) Triarylsulfoniums Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfo NATO, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium tri Fluoroacetate, 4-methyl Toxiphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethane Sulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, 4-phenylthiophenyl diphenyl-p-toluene sulfonate and the like.

  Among the compounds (a) to (c), trichloromethyl-s-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4- Chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -Bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine and the like are used as diaryliodonium as diphenyliodonium tri Fluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium tri Fluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, etc., and triarylsulfonium compounds include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4 -Methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate and the like can be mentioned as suitable ones.

D) Diazoketone compound Examples of the diazoketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound, and the like, and specific examples include 1,2-naphthoquinonediazide-4 of phenols. -A sulfonic acid ester compound can be mentioned.

E) Sulfone compounds Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphenacyl. Examples include sulfone and bis (phenacylsulfonyl) methane.

F) Sulfonic acid compound Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred examples include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl p-toluene sulfonate, and the like.

G) Sulfonimide compound Specific examples of the sulfonimide compound include, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N -(Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like can be mentioned.

C) Oxime ester compound 2- [2- (4-Methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals, trade name) “Irgacure PAG121”), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals, trade name “Irgacure PAG103”) , [2- (n-octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals, trade name “Irgacure PAG108”), α- (N-octanesulfo Ruokishiimino) -4-methoxybenzyl cyanide (Ciba Specialty Chemicals, can be mentioned trade name "CGI725") or the like.

I) Diazomethane compounds Specific examples of the diazomethane compounds include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and the like.

  In particular, from the viewpoint of sensitivity, the above) oxime ester compound group is particularly preferable.

  When using as a negative photosensitive composition, the compounding quantity of (b) photo-acid generator is 1-50 mass parts with respect to 100 mass parts of (a) alkali-soluble resin. If the blending amount is 1 part by mass or more, the effect of improving the sensitivity can be sufficiently obtained, and if the blending amount is 50 parts by mass or less, the mechanical properties after curing are good. The blending amount is preferably 1 to 30 parts by mass.

(C) Solvent (c) The solvent used in the present invention will be described. The photosensitive resin composition of the present invention comprises (a) an alkali-soluble resin, (b) a photoacid generator, and (d) a cross-linking agent or (e) other additive which is used as necessary ( c) It is provided as a photosensitive resin composition dissolved in γ-butyrolactone used as a solvent to form a varnish. γ-Butyrolactone is a good solvent for (a) an alkali-soluble resin and (b) a photoacid generator, and is an essential component in the present invention. (C) The solvent contains γ-butyrolactone as an essential component and may contain other solvents. For example, the above solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, 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-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate Etc. can be used alone or in admixture of two or more. Among these solvents, non-amide solvents are preferable because they have little influence on photoresists, and specific more preferable examples include GBL, dimethyl sulfoxide (DMSO), cyclopentanone, cyclohexanone, isophorone, and the like. Can do. (C) The addition amount of a solvent is the range of 30-1500 mass parts with respect to 100 mass parts of (a) alkali-soluble resin according to the desired coating film thickness and viscosity of a photosensitive resin composition, Preferably it is 50. It is the range of -1000 mass parts, Most preferably, it is the range of 100-300 mass parts. (C) About the addition amount of a solvent, it is preferable to adjust so that it can set to the viscosity suitable for a coating device and coating thickness within said range, in order to make manufacture of a cured relief pattern easy. (C) The content of γ-butyrolactone in the solvent is preferably 60% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass.

(D) Crosslinking agent When the photosensitive resin composition of the present invention is used in a positive type, it is used in a negative type for the purpose of improving the chemical resistance of the film after heat curing (photosensitive resin layer). It is preferable to further include (d) a crosslinking agent for the purpose of increasing the chemical resistance of the film after thermosetting and for the purpose of pattern formation.

  (D) As a crosslinking agent, an aromatic compound having a methylol group and / or an alkoxymethyl group, a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, an epoxy compound, an oxetane compound, an allyl compound, and ( At least one compound selected from the group consisting of (meth) acrylate compounds can be used.

  Among these (d) crosslinking agents, at least one selected from the group consisting of an aromatic compound having a methylol group and / or an alkoxymethyl group and a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group Is preferable from the viewpoint of chemical resistance after thermosetting.

｛式中、Ｒ_３１は、水酸基であり、ｍ_３１は、０〜３の整数であり、Ｒ_３２は、炭素数１〜３０の有機基であり、ｍ_３２は、０〜３の整数であり、Ｒ_３３は、水素原子又は炭素数１〜８のアルキル基であり、そしてｍ_３３は、１〜６の整数である。｝
で表される構造を有するものが好ましい。 As an aromatic compound having a methylol group and / or an alkoxymethyl group, the following general formula (3):

{In the formula, R ₃₁ is a hydroxyl group, m ₃₁ is an integer of 0 to 3, R ₃₂ is an organic group of 1 to 30 carbon atoms, and m ₃₂ is an integer of 0 to 3] , R ₃₃ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and m ₃₃ is an integer of 1 to 6. }
What has the structure represented by these is preferable.

の化合物が挙げられる。 More specifically, as an aromatic compound having a methylol group and / or an alkoxymethyl group, the following:

The compound of this is mentioned.

｛式中、Ｒ_３４及びＲ_３５は、それぞれ独立に、水素原子又は炭素数１〜８のアルキル基であり、そしてＲ_３６は、炭素数１〜３０の有機基である。｝
で表される構造を有するものが好ましい。 As a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, the following general formula (4):

{In the formula, R ₃₄ and R ₃₅ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₃₆ is an organic group having 1 to 30 carbon atoms. }
What has the structure represented by these is preferable.

  More specifically, as a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, more specifically, melamine resin, benzoguanamine resin, glycoluril resin, hydroxyethylene urea resin, urea resin, glycol urea resin, alkoxymethylated melamine Mention may be made of resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, and alkoxymethylated urea resins.

  Among these, alkoxymethylated melamine resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, and alkoxymethylated urea resins are known methylolated melamine resins, methylolated benzoguanamine resins, or methylols of methylolated urea resins. It can be obtained by converting the group into an alkoxymethyl group. Examples of the kind of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.

  Specific examples of compounds in which the N-position is substituted with a methylol group and / or an alkoxymethyl group include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170 and 1174, UFR65 and 300 (manufactured by Mitsui Cytec Co., Ltd.), Nicarax MX-270, -280 and -290, and Nicarak MS-11, Nicarac MW-30, -100, -300,- 390 and -750 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

並びにヘキサメトキシメチルメラミン、及びジメトキシメチル尿素等を挙げることができる。 In addition, a monomer of a resin described as an example of a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group can also be used as (d) a crosslinking agent. For example, the following compound:

And hexamethoxymethylmelamine and dimethoxymethylurea.

  The epoxy compound is a compound having a three-membered cyclic ether structure, and specific examples thereof include bisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, glycidylamine type epoxy resin, polysulfide type epoxy resin. However, it is not limited to these.

  An oxetane compound is a compound having a 4-membered cyclic ether structure, and is capable of a cationic ring-opening polymerization reaction or an addition reaction with carboxylic acid, thiol, or phenol. Specific examples of the oxetane compound include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 4,4′-bis. [(3-Ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3 -Oxetanylmethyl) ether, poly [ 3-[(3-ethyl-3-oxetanyl) methoxy] propyl] silasesquioxane] derivatives, oxetanyl silicate, phenol novolac oxetane, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, Examples include, but are not limited to, OXT121 (Toagosei: trade name), OXT221 (Toagosei: trade name), and the like.

  From the viewpoint of heat resistance, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, and OXT121 (Toagosei Co., Ltd.) : Product name) is preferable.

  Specific examples of allyl compounds include allyl alcohol, allyl anisole, benzoic acid allyl ester, cinnamic acid allyl ester, N-allyloxyphthalimide, allyl phenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate , Diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimelliate (TRIAM705 manufactured by Wako Pure Chemical Industries, Ltd.), pyromerit Examples include triallyl acid (TRIAM805 manufactured by Wako Pure Chemical Industries, Ltd.), triallyl oxydiphthalate, triallyl phosphate, triallyl phosphite, and triallyl citrate. However, it is not limited to these. From the viewpoint of sensitivity, triallyl trimellitic acid (TRIAM705 manufactured by Wako Pure Chemical Industries, Ltd.) and triallyl pyromellitic acid (TRIAM805 manufactured by Wako Pure Chemical Industries, Ltd.) are preferable.

  Examples of the (meth) acrylate compound include compounds selected from the group consisting of acrylic acid esters, methacrylic acid esters, acrylamides, and methacrylamides.

  Specific examples of preferred (meth) acrylate compounds include NK-ester series M-20G, M-40G, M-90G, M-230G, CB-1, SA, S, AMP-10G, manufactured by Shin-Nakamura Chemical Co., Ltd. AMP-20G, AMP-60G, AM-90G, A-SA, LA, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, 9PG, 701, BPE-100, BPE-200, BPE-500, BPE-1300, A-200, A-400, A-600, A-HD, A-NPG, APG-200, APG-400, APG-700, A-BPE-4, 701A, TMPT, A-TMPT, A-TMM-3, A-TMM-3L, A-TMMT and 1- (acryloyloxy) -3- (methacryloyloxy) -2-propano Le, 1,3-bis (acryloyloxy) -2-but propanol, without limitation. The number of carbon atoms in the (meth) acrylate compound is preferably 9 or more from the viewpoint of developability, and preferably 30 or less from the viewpoint of solubility in a solvent.

  From the viewpoint of alkali solubility, the (meth) acrylate compound preferably contains a polar group such as a hydroxyl group, a carbonyl group, an amino group, and a thiol group. Further, from the viewpoint of adhesion, the polar group is a hydroxyl group. It is preferable that Specifically, as such (meth) acrylate compounds, NK-701, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, 1,3-bis (acryloyloxy) -2- Examples include propanol. The term “(meth) acrylate” refers to acrylate or methacrylate.

  (D) A crosslinking agent can be used individually or in mixture of 2 or more types. (A) The blending amount of the (d) crosslinking agent relative to the alkali-soluble resin is preferably 1 to 50 parts by mass, and 3 to 40 parts by mass with respect to 100 parts by mass of the (a) alkali-soluble resin. More preferred. When the blending amount is 1 part by mass or more, crosslinking proceeds well and the patterning property becomes good. When the blending amount is 100 parts by mass or less, the mechanical properties after curing are kept good.

(E) Other additives In the photosensitive resin composition of the present invention, if necessary, phenol compounds, dyes, surfactants, stabilizers, and / or additives known as additives for photosensitive resin compositions Or it is also possible to add additives, such as an adhesion aid for improving the adhesiveness with a silicon wafer.

  More specifically, the above-mentioned additives include, as the phenol compound, a ballast agent used in the photosensitive diazoquinone compound, paracumylphenol, bisphenols, resorcinol, or MtrisPC, MtetraPC (manufactured by Honshu Chemical Industry Co., Ltd.). : Non-linear phenolic compounds such as Triphenol P-HAP, TrisP-PHBA, TrisP-PA (trade name) manufactured by Honshu Chemical Industry Co., Ltd., and the hydrogen atom 2 of the phenyl group of diphenylmethane And a compound in which 1 to 5 hydrogen atoms of a phenyl group of 2,2-diphenylpropane are substituted with a hydroxyl group. By adding the phenol compound, the adhesion of the relief pattern during development can be improved and the generation of residues can be suppressed. In addition, a ballast agent means the phenol compound currently used as a raw material for the above-mentioned photosensitive diazoquinone compound which is a phenol compound in which a part of the phenolic hydrogen atom is converted to naphthoquinonediazide sulfonic acid ester.

  0.01-50 mass parts is preferable with respect to 100 mass parts of (a) alkali-soluble resin, and, as for the addition amount in the case of adding a phenol compound, 1-30 mass parts is more preferable. If the addition amount is 50 parts by mass or less, the heat resistance of the film after thermosetting is good.

  Examples of the surfactant include polypropylene glycol, polyglycols such as polyoxyethylene lauryl ether, and nonionic surfactants made of derivatives thereof. Further, fluorine-based surfactants such as Fluorard (manufactured by Sumitomo 3M: trade name), MegaFac (manufactured by Dainippon Ink & Chemicals, Inc .: trade name), or Lumiflon (trade name, manufactured by Asahi Glass Co., Ltd.) can be used. Furthermore, organosiloxane surfactants such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), DBE (manufactured by Chisso Corporation: trade name), or granol (manufactured by Kyoeisha Chemical Co., Ltd .: trade name) are listed. By adding the surfactant, it is possible to make it more difficult for the coating film to be repelled at the wafer edge during coating.

  0.001-10 mass parts is preferable with respect to 100 mass parts of (a) alkali-soluble resin, and, as for the addition amount in the case of adding surfactant, 0.01-1 mass part is more preferable. When the addition amount is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.

  Examples of the adhesion assistant include t-butyl novolak, aluminum compounds, titanium coupling agents, epoxy polymers, and various silane coupling agents such as epoxy silane.

  Specific preferred examples of the silane coupling agent include 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxy. Reaction of alkylsilane, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane with acid anhydride or acid dianhydride, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane What converted the amino group into the urethane group or the urea group is mentioned. In this case, the alkyl group includes a methyl group, an ethyl group, a butyl group, the acid anhydride includes maleic anhydride, phthalic anhydride, the acid dianhydride includes pyromellitic dianhydride, 3, 3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, etc., urethane group is t-butoxycarbonylamino group, urea group is phenylaminocarbonylamino Group and the like.

  The addition amount in the case of adding an adhesion assistant is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the (a) alkali-soluble resin. If the addition amount is 30 parts by mass or less, the heat resistance of the film after thermosetting is good.

  As the dye and stabilizer, known ones can be used as long as they are suitable for the use of the present invention.

<Moisture in photosensitive resin composition>
Furthermore, in the present invention, in order to improve the sensitivity and storage stability of the photosensitive resin composition, a specific range of water is contained in the photosensitive resin composition. (A) The alkali-soluble resin has a hydroxyl group in the molecular skeleton. These polar groups are considered to form a three-dimensional network between (a) alkali-soluble resins via hydrogen bonds as the distance approaches. In the present invention, the presence of sufficient moisture in the photosensitive resin composition (a) suppresses the formation of hydrogen bonds between alkali-soluble resins and improves the dispersion state. It is thought that thickness stability can be improved. Further, it is considered that the storage stability of the entire photosensitive resin composition reaches a stable region that is less susceptible to external factors due to a sufficient amount of water.

  From the above viewpoint, the water content in the photosensitive resin composition is 0.6 to 18% by mass, and preferably 1.0 to 12% by mass. Moisture may be introduced as a secondary component from each component constituting the photosensitive resin composition, or may be intentionally added. When the moisture content is 0.6% by mass or more, the sensitivity and storage stability of the photosensitive resin composition are ensured and the effect of improving the film thickness uniformity and film thickness stability of the varnish is sufficiently obtained. Can do. Moreover, the solubility in (c) solvent of (a) alkali-soluble resin is securable because water content is 18 mass% or less. The water content in the photosensitive resin composition described in the present specification is a value measured by the Karl Fischer coulometric titration method. A measurement method by Karl Fischer coulometric titration will be described later.

<Method for producing cured relief pattern>
Next, the manufacturing method of the cured relief pattern of the present invention will be specifically described below. The manufacturing method of the hardening relief pattern of this invention includes the following process (1)-(4).

(1) A step of forming the photosensitive resin composition on a substrate in the form of a layer or a film;
In step (1), the photosensitive resin composition of the present invention is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spin coater or a coater such as a die coater or roll coater. To do. It is also possible to apply the photosensitive resin composition to a predetermined place on the substrate using an inkjet nozzle or a dispenser. This layer or film is heated to, for example, 50 to 140 ° C., preferably 100 to 140 ° C. using, for example, an oven or a hot plate, and dried to remove the solvent (hereinafter referred to as “soft bake” or “pre-bake”). Also called.) Thus, a photosensitive resin layer or film can be formed on the substrate.

(2) exposing the photosensitive resin layer;
Subsequently, in the step (2), the photosensitive resin layer is exposed with actinic rays. Specifically, exposure with actinic radiation is performed using a contact aligner or a stepper, or light, electron beam, or ion beam is directly irradiated. As the actinic ray, for example, g-line, h-line, i-line, or KrF laser can be used. Here, when using a negative photosensitive resin composition, after exposure, heat treatment (post-exposure baking (PEB)) is performed. This PEB process is a process for sensitizing the sensitivity of the photosensitive resin composition, and is usually necessary for obtaining the effects of the present invention satisfactorily. The PEB temperature is preferably 80 to 160 ° C., more preferably 90 to 150 ° C. in consideration of the sensitivity, the pattern shape to be obtained, and the like.

(3) The process of forming a relief pattern by developing the photosensitive resin layer after exposure;
In the step (3), when a positive photosensitive resin composition is used, the exposed portion (irradiated portion in the case of direct irradiation with actinic rays) is dissolved and removed with a developer, and preferably, rinse with a rinsing solution is continued. To obtain a desired relief pattern. When using a negative photosensitive resin composition, the unexposed portion is dissolved and removed with a developer in the same manner. As a developing method, a spray, paddle, dip, or ultrasonic method can be used. As the rinsing liquid, distilled water, deionized water or the like can be used.

  The developer used for developing the photosensitive resin layer dissolves and removes the alkaline aqueous solution-soluble polymer, and typically needs to be an alkaline aqueous solution in which an alkali compound is dissolved. The alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.

  Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, and potassium silicate. , Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia.

  Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine. -N-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine and the like.

  Furthermore, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, and a resin dissolution inhibitor can be added to the alkaline aqueous solution. .

(4) A step of forming a cured relief pattern by heat-treating the obtained relief pattern;
In step (4), the obtained relief pattern is heat-treated (cured), so that (a) a heat-resistant curing containing a resin having a polybenzoxazole structure when the alkali-soluble resin has a PBO precursor structure When the relief pattern and (a) the alkali-soluble resin have a polyimide precursor structure, a heat-resistant cured relief pattern containing a resin having a polyimide structure is formed. As the heating device, an oven furnace, a hot plate, a vertical furnace, a belt conveyor furnace, a pressure oven, or the like can be used. As a heating method, heating by hot air, infrared rays, or electromagnetic induction is preferable. The heating temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C. The heating time is preferably 15 minutes to 8 hours, and more preferably 1 hour to 4 hours. The atmosphere during the heat treatment is preferably in an inert gas such as nitrogen or argon.

  A cured relief pattern can be produced as described above.

  Moreover, the hardening relief pattern manufactured by the method containing the said process (1)-(4) is also 1 aspect of this invention.

<Semiconductor device>
The semiconductor device of the present invention includes a semiconductor element and a cured film provided on the semiconductor element, and the cured film is a cured relief pattern made of the cured film of the above-described photosensitive resin composition. Features. As the cured film, a passivation film on a semiconductor element, a protective film such as a buffer coat film formed by forming a cured film of the above-described photosensitive resin composition on the passivation film, or a circuit formed on the semiconductor element Examples thereof include an insulating film such as an interlayer insulating film formed by forming a cured film of the above-described photosensitive resin composition, an α-ray blocking film, a planarizing film, a protrusion (resin post), a partition wall, and the like.

  The photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films for display devices, and light-emitting elements. is there.

  The present invention will be described more specifically based on reference examples, examples and comparative examples. However, it should be understood that they are intended to describe the present invention in detail and not to limit the present invention.

<Synthesis of polyhydroxyamide>
[Reference Example 1]
In a separable flask having a volume of 2 liters, 2,7-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (197.8 g, 0.54 mol), pyridine (75.9 g, 0.96 mol), dimethylacetamide ( 692 g of DMAc) was mixed and stirred at room temperature (25 ° C.) to dissolve. Separately, a mixed solution obtained by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride in 88 g of γ-butyrolactone (GBL) was dropped into the obtained mixture with a dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.

After completion of the dropwise addition, the flask was heated to 50 ° C. with a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured, and characteristic absorption of imide groups at 1385 cm ⁻¹ and 1772 cm ⁻¹ appeared. It was confirmed.

Next, the flask was cooled to 8 ° C. with a water bath, and a mixed solution in which 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride was separately dissolved in 398 g of GBL was dropped from a dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of dropping, the reaction solution was dropped into 12 l of water under high-speed stirring to disperse and precipitate the polymer. The purified precipitate was recovered, washed with water as appropriate, dehydrated and then vacuum dried to obtain polyhydroxyamide (P-1). The weight average molecular weight of the thus synthesized polyhydroxyamide (P-1) by gel permeation chromatography (GPC) was 14,000 in terms of polystyrene. The analysis conditions for GPC are described below.
Column: Showa Denko Co., Ltd. Trade name: Shodex 805/804/803 Series separation liquid: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI SE-61

<Preparation of photosensitive resin composition>
[Examples 1-8, Comparative Examples 1-5] (However, Example 1 is Reference Example A.)
(C) 154 parts by mass of γ-butyrolactone (GBL) as a solvent or a mixed solvent of 108 parts by mass of γ-butyrolactone (GBL) and 46 parts by mass of propylene glycol monomethyl ether (PGME) is obtained in Reference Example 1 above. (A) Polyhydroxyamide (P-1) or novolac resin (EP4080G manufactured by Asahi Organic Materials Co., Ltd.) (P-2) as an alkali-soluble resin, 100 parts by mass, and (b) photoacid in parts by mass shown in Table 1 After dissolving the following photosensitive diazoquinone compound (Q-1) as a generator and the following product (D-1) as a (d) cross-linking agent in parts by mass shown in Table 1, the viscosity of the resulting solution is determined. It adjusted to about 10 poise, and it was set as the photosensitive resin composition by adding water further as needed.

The water content in each photosensitive resin composition thus prepared was measured by the Karl Fischer coulometric titration method. For the measurement, Hiranuma trace moisture measuring device AQ-200 (manufactured by Hiranuma Sangyo Co., Ltd.) was used. About 1 ml of a sample was collected using a syringe and precisely weighed to the nearest 0.0001 g to obtain a sample amount of 1, and then injected into the apparatus to measure the amount of water (actual water content). The weight of the syringe after injection was precisely weighed to the order of 0.0001 g to obtain a sample amount of 2. The water content in the photosensitive resin composition was determined by the following formula.
Water content (unit:%) = {measured water content / (sample amount 1−sample amount 2)} × 100
Table 1 shows each composition and water content.

｛式中、Ｑは、下記式（Ｑ−１）’：

又は水素原子を示す｝
で表される化合物である。また、化合物（Ｑ−１）については、Ｑ全体の約８３％が（Ｑ−１）’基であり、かつＱが（Ｑ−１）’基により１〜３置換された化合物でよい。
（Ｑ−２）ＰＡＧ１２１（チバスペシャルティケミカルズ社製）
（Ｄ−１）ＭＸ−２７０（三和ケミカル製） (Q-1) The following formula:

{Wherein Q is the following formula (Q-1) ':

Or represents a hydrogen atom}
It is a compound represented by these. In addition, the compound (Q-1) may be a compound in which about 83% of the total Q is a (Q-1) ′ group and Q is substituted by 1 to 3 by a (Q-1) ′ group.
(Q-2) PAG121 (Ciba Specialty Chemicals)
(D-1) MX-270 (manufactured by Sanwa Chemical)

<Evaluation of photosensitive resin composition>
(1) Solution uniformity Solution uniformity refers to a property indicating whether water in the composition is mixed with the solution. Solution uniformity is evaluated according to the following criteria.
○: When the composition is visually observed and mixed.
X: When the composition is visually observed and not mixed.

(2) Film thickness uniformity The photosensitive resin compositions obtained in the above examples and comparative examples were spun on a 12-inch silicon wafer using a spin coater (Act 12 manufactured by Tokyo Electron Ltd.) at a rotation speed of 1000 rpm for 30 seconds. After coating and prebaking at 120 ° C. for 180 seconds, the wafer diameter was measured at 31 points at intervals of 8 mm, and the film thickness was measured using NanoSpec M6100A (manufactured by NANOMETRICS). Thickness uniformity was calculated.
Film thickness uniformity = {(maximum film thickness [μm] −minimum film thickness [μm]) / average film thickness [μm]} × 100

(3) Film thickness stability The photosensitive resin compositions obtained in the above examples and comparative examples were placed at room temperature for 3 weeks, and then on a 12-inch silicon wafer using a spin coater under the same conditions as in (2). The film thickness was measured at 33 points on the wafer, and the film thickness was compared with (2) and recorded as film thickness stability.
Film thickness stability = {(3) average film thickness [μm] − (2) average film thickness [μm]} / {(2) average film thickness [μm]} × 100
The results of the items (1) to (3) are shown in Table 2.

  As is clear from Table 2, in Examples 1 to 8 in the range of the water content according to the present invention, both film thickness uniformity and film thickness stability are excellent.

  The photosensitive resin composition of the present invention includes a surface protective film for semiconductor devices, an interlayer insulating film, a rewiring insulating film, a protective film for flip chip devices, a protective film for devices having a bump structure, and an interlayer insulating layer for multilayer circuits. It can be suitably used as a film, a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film and the like.

Claims (5)

(A) A photosensitive resin composition containing 1 to 50 parts by mass of a photoacid generator and (c) 30 to 1500 parts by mass of γ-butyrolactone as a solvent with respect to 100 parts by mass of an alkali-soluble resin. The water content in the photosensitive resin composition is 2.3 to 18% by mass, and the (a) alkali-soluble resin is represented by the following general formula (1):

{Wherein X ₁ is a tetravalent organic group having at least 2 carbon atoms, Y ₁ is a divalent organic group having at least 2 carbon atoms, and m is 1 to An integer of 1000. }
The photosensitive resin composition which is polyhydroxyamide which has a repeating unit represented by these, or is a novolak resin or a polyhydroxystyrene resin .   The photosensitive resin composition of Claim 1 whose said water | moisture content is 2.3-12 mass%.   The photosensitive resin composition of Claim 1 or 2 which further contains 1-50 mass parts of (d) crosslinking agents with respect to 100 mass parts of said (a) alkali-soluble resin.   The photosensitive resin composition of any one of Claims 1-3 whose said (b) photo-acid generator is a compound which has a naphthoquinone diazide structure. (1) The process of forming the photosensitive resin layer on this board | substrate by apply | coating the photosensitive resin composition of any one of Claims 1-4 on a board | substrate,
(2) a step of exposing the photosensitive resin layer;
(3) A cured relief comprising a step of forming a relief pattern by developing the photosensitive resin layer after the exposure, and (4) a step of forming a cured relief pattern by heat-treating the obtained relief pattern. Pattern manufacturing method.