JP2010039214A - Photosensitive resin composition and photosensitive element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in photosensitivity, image contrast, adhesion and pattern formation, which has sufficiently excellent resolution, developability and dimensional accuracy at the same time. <P>SOLUTION: The photosensitive resin composition includes (A) a phenolic resin obtained by a copolymerization reaction including a compound represented by general formula (1) and an aldehyde compound and/or a ketone compound as starting compounds and (B) a 1, 2-quinonediazide compound. In the formula (1), X denotes C(-R<SP>1</SP>)(-R<SP>2</SP>), S, O or S(=O)<SB>2</SB>; and R<SP>1</SP>and R<SP>2</SP>each independently denote H, trifluoromethyl, substituted or unsubstituted 1-6C saturated alkyl, substituted or unsubstituted 1-6C unsaturated alkyl or substituted or unsubstituted phenyl. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition and a photosensitive element using the same.

  As an image forming method used for patterning of semiconductor integrated circuits, liquid crystal display elements, printed wiring boards and the like, a positive type using a photosensitive resin composition containing a novolac type phenolic resin and a 1,2-quinonediazide compound as a raw material A method using a photoresist is known. When a positive photoresist is formed through application of the photosensitive resin composition, the application thickness is generally 0.5 to several μm. When this positive photoresist is used, an image pattern over a wide size range is formed. The size range is wide, for example, from a sub-half micron region of about 0.3 μm to a considerably large size width of about several tens to several hundreds of μm. This makes it possible to finely process a wide variety of substrate surfaces.

  The positive photoresist can be developed with an aqueous alkaline solution and is more widely used than a photoresist that requires development with a solvent, for example, a rubber-based negative photoresist. This is because positive photoresists have better resolution than conventional rubber-based negative photoresists, and the positive photoresists have better acid / etching resistance and are suitable for development. This is because, since no solvent is used, the problem of waste liquid treatment is smaller than when a solvent is used. And, the biggest factor is that the above-mentioned positive photoresist has a very small change in image size due to swelling during development, and the size controllability is relatively easy. Is mentioned.

  Examples of conventional positive photoresist materials include those having phenol novolak resin as a main component and 1,2-quinonediazide sulfonate ester as a photosensitive component (see, for example, Patent Documents 1 and 2). Yes.

JP-A-6-27657 JP 2000-105466 A

  However, it has been difficult to achieve sufficiently excellent resolution, developability, and dimensional accuracy at the same time with a photosensitive resin composition containing a conventional phenol novolac resin as a main component. In order for the photosensitive resin composition to have excellent dimensional accuracy, the resin needs to have a high softening point, and in conventional resins, it is necessary to increase the weight average molecular weight (Mw) in order to improve the softening point. is there. However, increasing the molecular weight of the resin decreases developability and resolution.

  The present invention has been made in view of the above-mentioned problems, and is characterized by having sufficiently excellent resolution, developability, and dimensional accuracy at the same time, and is excellent in photosensitivity, image contrast, adhesion, and pattern formation. It aims at providing a resin composition.

  In order to solve the above-mentioned problems, the inventors have conducted intensive studies. As a result, a phenol resin obtained by copolymerizing a compound having a specific structure and an aldehyde compound and / or a ketone compound, and a 1,2-quinonediazide compound are obtained. It has been found that the photosensitive resin composition contained can achieve excellent resolution, developability and dimensional accuracy at the same time, and the present invention has been completed.

  That is, the photosensitive resin composition of the present invention comprises (A) a phenol resin obtained by a copolymerization reaction (hereinafter referred to as (1)), a compound represented by the following general formula (1), and an aldehyde compound and / or a ketone compound as a raw material compound. A) and (B) 1,2-quinonediazide compound (hereinafter referred to as component (B)).

In the above formula (1), X represents C (—R ¹ ) (— R ² ), S, O, or S (═O) ₂ , and R ¹ and R ² are each independently a hydrogen atom. , A trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted phenyl group. R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C 1-6 saturated alkyl group, a substituted or unsubstituted C 1-6 unsaturated alkyl group, or a substituted or unsubstituted Represents a phenyl group;

  The said photosensitive resin composition is equipped with the said (A) component and the said (B) component, and is equipped with the resolution, developability, and dimensional accuracy which were fully excellent simultaneously. Furthermore, the said photosensitive resin composition is excellent also in photosensitivity, image contrast, adhesiveness, and pattern formation.

  The component (A) preferably includes bisphenol A and / or bisphenol F as the compound represented by the general formula (1).

  When the component (A) contains bisphenol A and / or bisphenol F, a photosensitive resin composition that is further excellent in resolution, developability, and dimensional accuracy can be obtained.

  In the photosensitive resin composition, when the total amount of the component (A) and the component (B) is 100 parts by mass, the amount of the component (A) is 50 to 95 parts by mass, and the component (B) It is preferable that the compounding quantity of a component is 5-50 mass parts.

  By blending the component (A) and the component (B) as described above, a photosensitive resin composition having good properties can be obtained when used as a photosensitive element.

  The present invention also relates to a photosensitive element comprising a support and a photosensitive resin composition layer comprising the photosensitive resin composition formed on the support.

  According to the present invention, it is possible to provide a photosensitive resin composition excellent in photosensitivity, image contrast, adhesion and pattern formation, characterized by having sufficiently excellent resolution, developability and dimensional accuracy at the same time. .

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted.

  The photosensitive resin composition of the present invention comprises (A) a phenol resin (hereinafter referred to as (A) obtained by a copolymerization reaction containing a compound represented by the following general formula (1) and an aldehyde compound and / or a ketone compound as raw material compounds. And (B) 1,2-quinonediazide compound (hereinafter referred to as (B) component).

In the above formula (1), X represents C (—R ¹ ) (— R ² ), S, O, or S (═O) ₂ , and R ¹ and R ² are each independently a hydrogen atom. , A trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted phenyl group. R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C 1-6 saturated alkyl group, a substituted or unsubstituted C 1-6 unsaturated alkyl group, or a substituted or unsubstituted Represents a phenyl group;

  Hereinafter, the component (A), the component (B), and the photosensitive resin composition will be described in detail.

((A) component)
The component (A) is a phenol resin obtained by a copolymerization reaction containing the compound represented by the formula (1) and an aldehyde compound and / or a ketone compound as raw material compounds.

  Examples of the compound represented by the above formula (1) include bisphenol A, bisphenol F, bisphenol C, bisphenol E, bisphenol Z, bisphenol S, bisphenol AF, bisphenol AP, di-sec-butyl-bisphenol A, di- Isopropyl-bisphenol A, 1,1-ethylidene-bisphenol, methyl-ethyl-methylene-bisphenol A, methylisobutyl-methylene-bisphenol, methyl-hexyl-methylene-bisphenol, methyl-phenyl-methylene-bisphenol, 4,4'- Examples thereof include thiodiphenol, and these can be used alone or in combination of two or more.

  As the compound represented by the above formula (1), bisphenol A and / or bisphenol F can be preferably used. When these compounds are used, a photosensitive resin composition that is further excellent in resolution, developability, and dimensional accuracy can be obtained.

  Examples of the aldehyde compound and the ketone compound include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, and acetone.

  Examples of the aldehyde compound and / or the ketone compound include 2,2-dimethyl-3-hydroxypropionaldehyde, glyceraldehyde, glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, formyl Using methyl acetate, 2-formylpropionic acid, methyl 2-formylpropionate, pyruvic acid, repric acid, 4-acetylbutyric acid, acetone dicarboxylic acid, 3,3′-4,4′-benzophenone tetracarboxylic acid, etc. Also good.

  These can be used individually by 1 type or in combination of 2 or more types. In addition, as said aldehyde compound and / or said ketone compound, you may use an aldehyde compound precursor and a ketone compound precursor, for example, p-formaldehyde, a trioxane etc. which are the precursors of formaldehyde can be used.

  The copolymerization reaction may include phenols as a raw material compound. Here, the phenol means a compound having a phenolic hydroxyl group. Specifically, for example, alkylphenols such as phenol, cresol, xylenol, ethylphenol and butylphenol, methoxyphenol and 2-methoxy-4-methylphenol, etc. Alkenylphenols such as trimethylphenol, vinylphenol and allylphenol, arylphenols such as phenylphenol, aralkylphenols such as benzylphenol, alkoxycarbonylphenols such as methoxycarbonylphenol, arylcarbonylphenols such as benzoyloxyphenol, chloro Halogenated phenols such as phenol, or polyhydroxybenzenes such as catechol and resorcinol, etc. And the like.

  As said phenols, naphthol compounds, such as (alpha)-or (beta) -naphthol, may be used, and these methylolated products, for example, bishydroxymethyl-p-cresol, etc. can also be used.

  Examples of the phenols include hydroxyalkylphenols such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol and p-hydroxyphenyl-4-butanol, hydroxyalkylcresols such as hydroxyethylcresol, and bisphenol compounds. Alcoholic hydroxyl group-containing phenolic compounds such as monoethylene oxide adducts and bisphenol compound monopropylene oxide adducts can be used.

  Further, the phenols include p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid, and diphenol. A carboxyl group-containing phenol compound such as an acid can be used.

  As said phenols, 1 type chosen from the compound group mentioned above can be used individually or in combination of 2 or more types.

  In addition, the copolymerization reaction may partially contain compounds other than phenols such as m-xylene as raw material compounds.

  The above copolymerization reaction can be performed under known conditions when synthesizing a phenol resin. For example, copolymerization is performed using an acidic catalyst such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, oxalic acid, and the like. The reaction can be performed.

  In the said copolymerization reaction, it is preferable to use an aldehyde compound and / or a ketone compound in the ratio of 0.7-1 mol with respect to 1 mol of compounds represented by the said Formula (1).

  The phenol resin used as the component (A) preferably has a polystyrene-reduced weight average molecular weight of 300 to 100,000 by gel permeation chromatography, more preferably 1,000 to 30,000, and particularly preferably 5,000 to 20,000. When the weight average molecular weight is less than 300, the image contrast tends to be inferior, and when it is more than 100,000, the developability tends to be inferior.

  The phenol resin used as the component (A) preferably has a softening point of 130 to 200 ° C, more preferably 140 to 190 ° C, and even more preferably 150 to 180 ° C. When the softening point is less than 130 ° C., the dimensional accuracy tends to be inferior, and when the softening point is 200 ° C. or more, the flexibility tends to be inferior.

  The component (A) can be reacted with a drying oil and then mixed with the component (B) to form a photosensitive resin composition. Examples of the drying oil include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, and the like, and these can be used alone or in combination of two or more.

  Reaction of the said (A) component and dry oil is normally performed at 50-130 degreeC, and the said dry oil can be made to react 1-50 mass% with respect to the said (A) component 100 mass%. At this time, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be added as a catalyst.

  In addition, the component (A) is mixed with the component (B) after photopolymerization of a phenol resin using a chain extender to increase the molecular weight, if necessary. It can be a thing.

  As the chain extender, a diepoxy compound, a dioxazoline compound, a diisocyanate compound, or the like can be used.

  As said (A) component, the phenol resin obtained by the copolymerization reaction which contains the compound represented with the said General formula (1), an aldehyde compound, and / or a ketone compound as a raw material compound is used individually by 1 type or 2 A combination of more than one species can be used. Examples of the combination of two or more include two or more phenol resins composed of different copolymer components, two or more phenol resins having different mass average molecular weights, and two or more phenol resins having different dispersities. Can be mentioned.

((B) component)
Examples of the 1,2-quinonediazide compound used as the component (B) include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, and orthoanthraquinonediazidesulfonic acid. Examples thereof include complete ester compounds, partial ester compounds, amidated products, partially amidated products and the like of quinonediazide group-containing sulfonic acids and the like and a compound having a hydroxyl group or an amino group.

  Examples of the compound having a hydroxyl group or amino group include (I) 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3 , 6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, , 3 ′, 4,4 ′, 6-pentahydroxybenzophenone, 2,2 ′, 3,4,4′-pentahydroxybenzophenone, 2,2 ′, 3,4,5-pentahydroxybenzophenone, 2,3 ′ , 4,4 ′, 5 ′, 6-hexahydroxybenzophenone, 2,3,3 ′, 4,4 ′, 5′-hexahydroxybenzo Polyhydroxybenzophenones such as enone, (II) bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4 ′ -Hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2' , 3 ′, 4′-trihydroxyphenyl) propane, 4,4 ′-{1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol, 3,3′-dimethyl -[1- [4- [2- (3-Methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol and other bis [(poly Hydroxyphenyl] alkanes, (III) tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) ) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis ( Tris (hydroxyphenyl) methanes such as 4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane and bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane Or a methyl-substituted product thereof, (IV) bis (3-cyclohexyl) 4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, Bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl- 4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl)- 4-hydroxy Phenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3- Cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2- Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes such as hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane, or methyl-substituted products thereof, (V) phenol P-methoxyphenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, 4,4′-diaminobenzophenone, etc. Examples thereof include a compound having a hydroxyl group or an amino group, (VI) novolak, pyrogallol-acetone resin, a homopolymer of p-hydroxystyrene or a copolymer with a monomer copolymerizable therewith.

  Among the compounds having a hydroxyl group or an amino group, compounds represented by the following general formula (2), (3) or (4) are preferable.

In the above formulas (2) to (4), R ^{1 to} R ¹¹ each independently represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or an alkoxy group. X represents a single bond, —O—, or a divalent phenyl group.

  Of the compounds represented by the formulas (2) to (4), compounds represented by the following formulas (5) to (7) are more preferable.

  The component (B) is a compound represented by the above formulas (2) to (7) and naphthoquinone-1,2-diazido-5-sulfonic acid or naphthoquinone-1,2-diazide-4-sulfonic acid. An ester compound is preferable. If it is such an ester compound, it is well dissolved in a solvent that is usually used when the photosensitive resin composition is used as a solution, has good compatibility with the component (A), and the resulting photosensitive resin composition The product is excellent in light sensitivity, image contrast and heat resistance. Moreover, generation | occurrence | production of the foreign material at the time of using the photosensitive resin composition as a solution can be suppressed.

  The ester compound of the compound represented by the above formula (2) and quinonediazide sulfonic acid is, for example, tri (4-hydroxyphenyl) methane and naphthoquinone-1,2-diazide-sulfonyl chloride in the presence of an alkali in a polar solvent. It can be prepared by condensing under and complete esterification or partial esterification.

  The ester compound of the compound represented by the above formula (3) and quinonediazidesulfonic acid is, for example, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl]. Ethylidene] bisphenol and naphthoquinone-1,2-diazide-sulfonyl chloride can be produced by condensation in a polar solvent in the presence of an alkali and complete esterification or partial esterification.

  The ester compound of the compound represented by the above formula (4) and quinonediazidesulfonic acid is, for example, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, naphthoquinone-1,2-diazide-sulfonyl chloride, Can be produced by condensation in a polar solvent in the presence of an alkali and complete esterification or partial esterification.

  Here, as the polar solvent, dioxane, THF or the like can be preferably used. Further, as the alkali, triethylamine, triethanolamine, alkali carbonate, alkali hydrogen carbonate, or the like can be used. As the naphthoquinone-1,2-diazide-sulfonyl chloride, naphthoquinone-1,2-diazide-4-sulfonyl chloride and naphthoquinone-1,2-diazide-5-sulfonyl chloride can be preferably used.

(Photosensitive resin composition)
The said photosensitive resin composition contains the said (A) component and the said (B) component as an essential component, Comprising: As for the compounding quantity, the total amount of (A) component and (B) component is 100 mass parts. The component (A) is preferably 50 to 95 parts by mass, more preferably 55 to 90 parts by mass, and still more preferably 60 to 85 parts by mass. When the blending amount of the component (A) is less than 50 parts by mass, the coating film of the photosensitive resin composition tends to be brittle, and when used as a photosensitive element, the coating property tends to be inferior. Moreover, when the compounding quantity of (A) component exceeds 95 mass parts, there exists a tendency for photosensitivity to become inadequate.

  The said photosensitive resin composition may contain the phenol resin which does not contain the compound represented by the said Formula (1) as a raw material compound other than the said (A) component and the said (B) component. As such a phenol resin, known ones can be used, for example, a novolac type phenol resin, a resol type phenol resin, a polyphenol compound obtained by a reaction of a phenol compound and a diolefin compound (divinylbenzene, dicyclopentadiene, etc.). And a polyphenol compound obtained by a reaction between a phenol compound and an aralkyl halide (or a derivative thereof), a polyphenol compound obtained by a reaction between a phenol compound and an aralkyl alcohol (or a derivative thereof), and a triazine phenol novolac resin. These can be used individually by 1 type or in combination of 2 or more types.

  The said photosensitive resin composition may contain surfactant for the purpose of improving applicability | paintability, a defoaming property, leveling property, etc. as needed.

  Examples of the surfactant include BM-1000 or BM-1100 (manufactured by BM Chemie), Megafuck F142D, Megafuck F172, Megafuck F173, Megafuck F183, Megafuck R-08, Megafuck R-30. , MegaFac R-90PM-20 or MegaFac BL-20 (manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 or Florard FC-4430 (Sumitomo 3M Co., Ltd.), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141 or Surflon S-145 (Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH -193, SZ-6032 or SF-8428 Toray Silicone Co., Ltd.), a fluorine-based surfactant commercially available can be used etc., these can be used alone or in admixture. The blending amount of these surfactants is preferably 5 parts by mass or less when the total amount of the component (A) and the component (B) is 100 parts by mass.

  Moreover, the said photosensitive resin composition may contain an adhesion assistant for the purpose of improving the adhesiveness with a base material as needed.

  A functional silane coupling agent is effective as the adhesion aid. Here, the functional silane coupling agent means a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group or an epoxy group. Specifically, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane and the like. These can be used individually by 1 type or in combination of 2 or more types. The compounding amount of the adhesion assistant is preferably 20 parts by mass or less when the total amount of the component (A) and the component (B) is 100 parts by mass.

  Furthermore, the photosensitive resin composition may be monocarboxylic acid, hydroxymonocarboxylic acid, polyvalent carboxylic acid, acid anhydride, high-boiling solvent, etc. for the purpose of adjusting the solubility in an alkaline developer, if necessary. You may contain a solubility regulator.

  Examples of the monocarboxylic acid include acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso-valeric acid, benzoic acid, cinnamic acid and the like.

  Examples of the hydroxy monocarboxylic acid include lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4- Examples thereof include hydroxycinnamic acid, 5-hydroxyisophthalic acid, and syringic acid.

  Examples of the polyvalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, Examples include 1,2,4-cyclohexanetricarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid.

  Examples of the acid anhydride include itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1 , 2,3,4-butanetetracarboxylic acid, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic anhydride, glycerin tris anhydride Trimellitate and the like.

  The high boiling point solvent represents a solvent having a boiling point of 150 ° C. or higher under normal pressure, specifically, for example, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid Examples include ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

  These solubility regulators can be used alone or in combination of two or more. Further, the blending amount of the solubility modifier can be appropriately adjusted according to the application and application method, and is not particularly limited as long as the blending amount allows the photosensitive resin composition to be uniformly mixed. The content is preferably 60% by mass or less, more preferably 40% by mass or less, based on the total amount of the conductive resin composition.

  The photosensitive resin composition may be a sensitizer, a light-absorbing agent (dye), a cross-linking agent, a plasticizer, a pigment, a filler, a flame retardant, a stabilizer, an adhesion-imparting agent, a release accelerator, or an oxidation, if necessary. You may contain an inhibitor, a fragrance | flavor, an imaging agent, a thermal crosslinking agent, etc. These can be used individually by 1 type or in combination of 2 or more types. Although these compounding quantities will not be restrict | limited especially if it is a range which does not impair the characteristic of the said photosensitive resin composition, It is preferable that it is 50 mass% or less with respect to the said photosensitive resin composition whole quantity.

  The photosensitive resin composition may be prepared by mixing and stirring by a usual method. When a filler or pigment is added, the photosensitive resin composition may be dispersed and mixed using a disperser such as a dissolver, a homogenizer, or a three roll mill. That's fine. Moreover, you may further filter using a mesh, a membrane filter, etc. as needed.

  Next, the photosensitive element of the present invention will be described.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 has a structure in which a photosensitive resin composition layer 14 is laminated on a support 10. The photosensitive resin composition layer 14 is a layer made of the photosensitive resin composition.

  As the support 10, for example, a metal plate such as copper, a copper-based alloy, iron, or an iron-based alloy, or a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. The thickness of the support 10 is preferably 1 to 150 μm, more preferably 5 to 50 μm, and particularly preferably 10 to 30 μm. When the thickness is less than 1 μm, the mechanical strength decreases, and in the step of applying the photosensitive resin composition or the step of peeling the support film before development, the support film tends to be easily broken, while 150 μm is reduced. If it exceeds, the resolution of the resist pattern tends to decrease.

  The photosensitive resin composition layer 14 can be formed by applying the photosensitive resin composition on the support 10 as a liquid resist.

  When the photosensitive resin composition is applied onto the support 10, if necessary, the photosensitive resin composition is dissolved in a predetermined solvent to form a solution having a solid content of 30 to 60% by mass. It can be used as a coating solution. Examples of the solvent include methanol, ethanol, propanol, ethylene glycol, propylene glycol, octane, decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, toluene, and xylene. , Tetramethylbenzene, N, N-dimethylformamide, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene Glycol monoe Ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate , Organic solvents such as dipropylene glycol monomethyl ether acetate, or a mixed solvent thereof.

  Examples of the coating method include a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater. Moreover, the removal of the said solvent can be performed by heating, for example, the heating temperature in that case is preferable in it being 70-150 degreeC, and heating time is preferable in it being 5-30 minutes.

  The amount of the remaining organic solvent in the photosensitive resin composition layer 14 formed by the above method is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

  Moreover, although the thickness of the said photosensitive resin composition layer 14 changes with uses, it is preferable that the thickness after removing a solvent is about 0.5-100 micrometers.

  The photosensitive element 1 may cover the surface F1 opposite to the support side of the photosensitive resin composition layer 14 with a protective film (not shown) as necessary.

  Examples of the protective film include polymer films such as polyethylene and polypropylene. The protective film is preferably a low fisheye film, and the adhesive force between the protective film and the photosensitive resin composition layer 14 is such that the protective film is easily peeled off from the photosensitive resin composition layer 14. Therefore, it is preferable that the adhesive strength between the photosensitive resin composition layer 14 and the support 10 is smaller.

  The photosensitive element 1 includes a cushion layer, an adhesive layer, and a light absorption layer between the support 10 and the photosensitive resin composition layer 14 and / or between the photosensitive resin composition layer 14 and the protective film. Further, an intermediate layer such as a gas barrier layer or a protective layer may be further provided.

  The photosensitive element 1 is, for example, in the form of a flat plate as it is, or by laminating a protective film on one side of the photosensitive resin composition layer (on a surface that is not protected and exposed), to form a cylindrical shape, etc. Can be wound around a core and stored in a roll form. The core is not particularly limited as long as it is conventionally used. For example, plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), etc. Etc. At the time of storage, it is preferable that the support is wound up so as to be the outermost side. Moreover, it is preferable to install an end face separator from the viewpoint of protecting the end face on the end face of the photosensitive element (photosensitive element roll) wound up in a roll shape, and in addition, a moisture-proof end face separator is installed from the viewpoint of edge fusion resistance. It is preferable to do. Moreover, when packaging the photosensitive element 1, it is preferable to wrap it in a black sheet with low moisture permeability.

  Next, a resist pattern forming method will be described.

  The resist pattern is formed by laminating the photosensitive element 1 on a base material so that the photosensitive resin composition layer 14 is in close contact, and irradiating actinic rays in the form of an image to remove the exposed portion by development. To do. The portion not irradiated with actinic rays does not dissolve in alkali because the 1,2-quinonediazide compound interacts with the phenol resin and acts as a dissolution inhibitor, but in the portion irradiated with actinic rays, The 2-quinonediazide compound is photolyzed and loses the dissolution inhibiting effect, so that the exposed portion becomes alkali-soluble.

As a method for laminating the photosensitive resin composition layer 14 on the base material, when the photosensitive element includes a protective film, the protective resin film is removed, and then the photosensitive resin composition layer 14 is heated to about 70 to 130 ° C. The method etc. which are crimped | bonded by pressure of about 0.1-1 MPa (about 1-10 kgf / cm < ² >) to a base material while heating are mentioned. Such a lamination process may be performed under reduced pressure. The surface of the base material on which the photosensitive resin composition layer 14 is laminated is not particularly limited.

  The photosensitive resin composition layer 14 thus laminated on the substrate is irradiated with an actinic ray in an image form through a negative or positive mask pattern to form an exposed portion. At this time, when the support 10 present on the photosensitive resin composition layer 14 is transparent to the actinic ray, the support 10 can be irradiated with an actinic ray, and the support 10 becomes an actinic ray. On the other hand, when the light shielding property is exhibited, the photosensitive resin composition layer 14 is irradiated with actinic rays after the support 10 is removed.

  As the active light source, a conventionally known light source, for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp is used. Further, a laser direct drawing exposure method or the like can also be used.

  After formation of the exposed portion, the resist pattern is formed by removing the photosensitive resin composition layer in the exposed portion by development. As a method for removing the exposed portion, when the support 10 is present on the photosensitive resin composition layer 14, the support 10 is removed with an auto peeler or the like, and development with an alkaline aqueous solution, an aqueous developer, an organic solvent or the like is performed. Examples include a method in which an exposed portion is removed and developed by wet development using a liquid or dry development.

  Examples of the alkali used in the wet development include weak alkali inorganic compounds such as sodium carbonate, potassium carbonate, and ammonia; alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide; monomethyl Weak alkaline organic compounds such as amine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, polyethyleneimine; Tetramethylammonium hydroxide, tetraethylammonium hydroxide; and the like. It can be used as an aqueous solution in or in combination of two or more. The pH of the alkaline aqueous solution containing these alkalis is preferably in the range of 9 to 13, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent, or the like may be mixed in the alkaline aqueous solution.

  Examples of the development method include a dip method, a spray method, brushing, and slapping. In addition, as a process after image development, you may harden a resist pattern by performing a heating etc. of about 60-250 degreeC as needed.

  In this way, a resist pattern can be obtained. By using the photosensitive element 1 of the present invention in which the exposed part of the coating film is easily dissolved in alkali and peeled off from the substrate and the alkali developability is extremely good, the contrast is improved. It is possible to obtain a fine resist pattern excellent in the above.

  In addition, although the example which has only one photosensitive resin composition layer was shown in the said embodiment, the photosensitive resin composition layer of the photosensitive element of this invention may have a multilayer structure.

  For example, when the photosensitive resin composition layer has a two-layer structure, a photosensitive resin composition layer (high sensitivity layer) with high photosensitivity and a photosensitive resin composition layer (low sensitivity layer) with low photosensitivity are used. Can do. If such a two-layer type photosensitive element is used, a complicated resist pattern can be easily obtained in a single process. The high sensitivity layer and the low sensitivity layer can be prepared by changing the contents of the resin and the 1,2-quinonediazide compound in the photosensitive resin composition.

  When the two-layer type photosensitive element is laminated on a base material, the low-sensitivity layer is laminated on the substrate side, and actinic rays are irradiated from the high-sensitivity layer side. At this time, by adjusting the irradiation amount of the actinic ray, the portion where the base material is exposed after development, the portion where the high sensitivity layer is removed and the low sensitivity layer is exposed, and the high sensitivity layer and the low sensitivity layer remain. Part is formed. By etching this, a three-stage resist pattern can be formed.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

[Synthesis of phenol resin A1]
m-cresol, p-cresol and bisphenol F were mixed at a mass ratio of 20:30:50, formalin was added thereto, and condensed by an ordinary method using an oxalic acid catalyst, and the mass average molecular weight was 20000 and the softening point was 170. A phenol resin A1 at 0 ° C. was obtained.

[Synthesis of phenol resin A2]
o-Cresol and bisphenol A are mixed at a mass ratio of 50:50, formalin is added thereto, and condensation is performed by a conventional method using an oxalic acid catalyst to obtain a phenol resin A2 having a mass average molecular weight of 10,000 and a softening point of 150 ° C. Obtained.

[Synthesis of phenol resin A3]
Formalin was added to bisphenol A and condensed by an ordinary method using an oxalic acid catalyst to obtain a phenol resin A3 having a mass average molecular weight of 10,000 and a softening point of 160 ° C.

[Synthesis of Comparative Phenolic Resin B1]
m-cresol and p-cresol are mixed at a mass ratio of 50:50, formalin is added thereto, and condensed by an ordinary method using an oxalic acid catalyst to obtain a phenol resin having a mass average molecular weight of 10,000 and a softening point of 140 ° C. Obtained. This resin is designated as phenol resin B1.

[Synthesis of Comparative Phenolic Resin B2]
m-cresol and p-cresol are mixed in a mass ratio of 40:60, formalin is added thereto, and condensed by an ordinary method using an oxalic acid catalyst to obtain a phenol resin having a weight average molecular weight of 15000 and a softening point of 160 ° C. Obtained. This resin is designated as phenol resin B2.

(Examples 1-3)
The photosensitive resin compositions of Examples 1 to 3 were obtained using the phenol resins A1 to A3 as the component (A) and DNQ as the component (B). Here, DNQ is a compound obtained by reacting 1 mol of the compound represented by the above chemical formula (5) with 3 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride. Table 1 shows the blending amount of each component when the total amount of the component (A) and the component (B) is 100 parts by mass with respect to Examples 1 to 3. In the table, PGMEA represents propylene glycol monomethyl ether acetate, and MEK represents methyl ethyl ketone.

(Comparative Examples 1-2)
The said phenol resin B1, DNQ, PGMEA, and MEK were mixed, and it was set as Comparative Examples 1-2. In Table 1, the compounding quantity of each component when the total amount of phenol resin B1 and DNQ is 100 parts by mass is shown for Comparative Examples 1 and 2.

(Comparative Example 3)
The above phenol resin B2, DNQ, PGMEA and MEK were mixed to obtain Comparative Example 3. Table 1 shows the blending amounts of the components in Comparative Example 3 when the total amount of the phenol resin B2 and DNQ is 100 parts by mass.

[Production of photosensitive element]
The photosensitive element was produced according to the following procedures using the photosensitive resin composition of Examples 1-3 and Comparative Examples 1-3.

  A photosensitive resin composition solution was applied on a polyethylene terephthalate film (hereinafter referred to as “PET film”) having a width of 380 mm and a thickness of 50 μm, and the photosensitive resin was held in a hot air convection dryer set at 100 ° C. A composition layer was formed. At that time, the thickness of the photosensitive resin composition layer after heating was set to 2 μm. And Example 1 with which the photosensitive resin composition layer was coat | covered with the protective film by mounting the 35-micrometer-thick polyethylene film as a protective film on the formed photosensitive resin composition layer, and pressing with a roll. The photosensitive element of -3 and Comparative Examples 1-3 was obtained.

[Production of sample for characteristic evaluation]
On the glass plate, the photosensitive resin composition layers of the photosensitive elements of Examples 1 to 3 and Comparative Examples 1 to 3 were laminated while being heated to 120 ° C., and the characteristics of Examples 1 to 3 and Comparative Examples 1 to 3 were obtained. An evaluation sample was obtained.

  Using the samples for property evaluation of Examples 1 to 3 and Comparative Examples 1 to 3 thus obtained, the alkali resistance evaluation of the unexposed part, the evaluation of the developability of the exposed part, the adhesion, the dimensional change and the baking The subsequent resist shape was evaluated.

[Evaluation of alkali resistance of unexposed areas]
The PET film was removed from the sample for property evaluation, immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at room temperature for 60 seconds, and the state of the coating film after immersion was visually evaluated according to the following criteria. The obtained results are shown in Table 2.
A: Alkali resistance good ... No abnormality in coating film appearance B: Poor alkali resistance ... Part of the coating film is peeled off.

[Evaluation of developability of exposed areas]
The PET film was removed from the sample for characteristic evaluation, and exposed using an exposure machine (trade name: HMW-590, manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp lamp at an exposure amount of 100 mJ / cm ² .

After the exposure, development was performed at 30 ° C. for 60 seconds using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, and the presence of the remaining resin coating film was visually evaluated based on the following criteria. The obtained results are shown in Table 2.
A: Good developability ... no deposit on the glass surface B: poor developability ... The deposit remains on the glass surface.

[Evaluation of adhesion]
An exposure machine (Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp lamp in which a PET film is removed from a sample for characteristic evaluation, a photo tool having a wiring pattern with a line / space of 3/50 to 30/50 (unit: μm) is arranged The product was exposed at an exposure amount of 100 mJ / cm ² using a product name of HMW-590.

  After the exposure, development was carried out by spraying an aqueous 2.38 mass% tetramethylammonium hydroxide solution (30 ° C.). Adhesion was evaluated by measuring the minimum line width (μm) remaining without peeling after development. The obtained results are shown in Table 2. In Table 2, the adhesion is indicated by the minimum line width, and the smaller the minimum line width, the better the adhesion.

[Evaluation of dimensional change]
An exposure machine (trade name, manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp lamp in which a PET film is removed from a sample for characteristic evaluation, a photo tool having a wiring pattern with a line / space of 5/5 (unit: μm) is disposed. : HMW-590) with an exposure amount of 100 mJ / cm ² .

After the exposure, development was carried out by spraying an aqueous 2.38 mass% tetramethylammonium hydroxide solution (30 ° C.). After development, baking was performed at 140 ° C. for 3 minutes. The line width (μm) before and after baking was measured and the dimensional change was evaluated according to the following criteria. The obtained results are shown in Table 2.
A: The dimensional change rate of the resist pattern is 10% or less.
B: The dimensional change rate of the resist pattern is 11% to 19%.
C: The dimensional change rate of the resist pattern is 20% or more.

[Evaluation of resist shape]
An exposure machine (trade name, manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp lamp in which a PET film is removed from a sample for characteristic evaluation, a photo tool having a wiring pattern with a line / space of 5/5 (unit: μm) is disposed. : HMW-590) with an exposure amount of 100 mJ / cm ² .

After the exposure, development was carried out by spraying an aqueous 2.38 mass% tetramethylammonium hydroxide solution (30 ° C.). After development, baking was performed at 140 ° C. for 3 minutes. The line pattern after baking was cut from the vertical direction, observed with an electron microscope from the cross-sectional direction of the pattern, and the resist shape was evaluated according to the following criteria. The obtained results are shown in Table 2.
A: There is no film reduction, and the pattern side wall stands up at an angle of 80 degrees or more with respect to the substrate.
B: There is no film reduction, and the pattern side wall stands up at an angle of 70 degrees or more and less than 80 degrees with respect to the substrate.
C: There is film reduction, and the pattern side wall stands up at an angle of less than 70 degrees with respect to the substrate.

  As is apparent from the results shown in Table 2, according to the photosensitive resin compositions of Examples 1 to 3, compared to the photosensitive resin compositions of Comparative Examples 1 to 3, the alkali resistance of the unexposed part and It was confirmed that the developability of the exposed portion was good, the contrast between the unexposed portion and the exposed portion was excellent, the heat resistance was good, and the dimensional accuracy in forming a fine pattern was excellent.

It is a schematic cross section which shows suitable one Embodiment of the photosensitive element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 14 ... Photosensitive resin composition layer.

Claims (4)

(A) a phenol resin obtained by a copolymerization reaction containing a compound represented by the following general formula (1) and an aldehyde compound and / or a ketone compound as a raw material compound;
(B) a 1,2-quinonediazide compound;
A photosensitive resin composition comprising:

[In the above formula (1), X represents C (—R ¹ ) (— R ² ), S, O, or S (═O) ₂ , and R ¹ and R ² are each independently a hydrogen atom, A trifluoromethyl group, a substituted or unsubstituted saturated alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted phenyl group is shown. R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C 1-6 saturated alkyl group, a substituted or unsubstituted C 1-6 unsaturated alkyl group, or a substituted or unsubstituted Represents a phenyl group; ]   The photosensitive resin composition according to claim 1, wherein the phenol resin includes bisphenol A and / or bisphenol F as a compound represented by the general formula (1).   The blending amount of the phenol resin is 50 to 95 parts by weight and the blending amount of the 1,2-quinonediazide compound is 5 to 50 parts by weight with respect to 100 parts by weight of the total amount of the phenol resin and the 1,2-quinonediazide compound. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a part. A support;
A photosensitive element comprising: a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 3 formed on the support.

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