KR101494577B1 - Photosensitive resin material and resin film - Google Patents

Abstract

The present invention aims to provide a resin film which is formed with a photosensitive resin material, maintains performance as a permanent film, and has excellent processability. The photosensitive resin material is used to form a permanent film and has an iron content of 0.005-80 ppm, measured by frameless atomic absorption analysis, with respect to a non-volatile ingredient.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin material,

The present invention relates to a photosensitive resin material and a resin film, for example, a photosensitive resin material used for forming a permanent film.

A photosensitive resin material may be used as a material for forming a permanent film constituting an electronic device such as an insulating layer constituting a re-wiring layer. Such techniques include those described in, for example, Patent Documents 1 and 2.

The technique described in Patent Document 1 relates to a photosensitive resin composition for forming a permanent resist. Patent Document 2 discloses a photosensitive resin composition solution containing imidized tetracarboxylic acid having a specific structure, a diamine and / or isocyanate compound, a photosensitive resin, and a photopolymerization initiator and having a viscosity of 100 mPa · s or less at 25 ° C .

Japanese Laid-Open Patent Publication No. 2008-180992 Japanese Laid-Open Patent Publication No. 2010-006864

For a resin film formed using a photosensitive resin material, patterning is performed using, for example, lithography. However, due to the dissolving solution used for development, a whitish layer, which is resistant to the dissolving solution, may be formed on the surface of the resin film. In this case, it is feared that it becomes difficult to realize excellent processability at the time of patterning. Therefore, it is required to realize a good processability while maintaining the performance as a permanent film for a resin film formed using a photosensitive resin material.

According to the present invention,

As a photosensitive resin material used for forming a permanent film,

The content of iron is not less than 0.005 ppm and not more than 80 ppm based on the entire non-volatile component measured by the frame-less atomic absorption spectrometry.

According to the present invention, there is provided a resin film obtained by curing the above-described photosensitive resin material.

According to the present invention,

A resin film constituting a permanent film and having an iron content of not less than 0.005 ppm and not more than 80 ppm measured by frame-less atomic absorption spectrometry is provided.

According to the present invention, excellent workability can be realized while maintaining the performance as a permanent film for a resin film formed using a photosensitive resin material.

1 is a cross-sectional view showing an example of an electronic apparatus according to this embodiment.

Hereinafter, embodiments will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and a description thereof will be omitted.

(First Embodiment)

1 is a sectional view showing an example of an electronic device 100 according to the present embodiment.

The photosensitive resin material according to the present embodiment is a photosensitive resin material used for forming a permanent film, and the content of iron is 0.005 ppm or more and 80 ppm or less with respect to the whole non-volatile component measured by frame-less atomic absorption spectrometry.

The inventor of the present invention has found that by setting the content of iron to the entire non-volatile component of the photosensitive resin material within the above-described range, the resin film formed using the photosensitive resin material can exhibit a whiteness at the time of lithography Layer formation can be suppressed. The performance as a permanent film is, for example, durability evaluated by a tensile elongation. For this reason, according to the present embodiment, excellent workability can be realized while maintaining the performance as a permanent film for a resin film formed using a photosensitive resin material.

Hereinafter, the structure of the electronic device 100 including the photosensitive resin material and the permanent film formed by the photosensitive resin material according to the present embodiment will be described in detail.

First, the photosensitive resin material according to the present embodiment will be described.

The photosensitive resin material is used for forming a permanent film. By curing the photosensitive resin material, a resin film constituting the permanent film is obtained. In the present embodiment, a permanent film is formed by, for example, patterning a coating film composed of a photosensitive resin material into a desired shape by exposure and development, and then curing the coating film by heat treatment or the like.

Examples of the permanent film formed by using the photosensitive resin material include an interlayer film, a surface protective film, and a dam material. The use of the permanent film is not limited to this, but does not include a use as a film having high light shielding property against visible light such as a color filter or a black matrix.

The interlayer film refers to an insulating film formed in the multilayer structure, and the kind thereof is not particularly limited. Examples of the interlayer film include those used in semiconductor device applications such as an interlayer insulating film constituting a multilayer interconnection structure of a semiconductor element, a build-up layer constituting a circuit board, or a core layer. As the interlayer film, for example, a flattening film covering a thin film transistor (TFT (Thin Film Transistor)) in a display device, a liquid crystal alignment film, a color filter substrate of a MVA (Multi Domain Vertical Alignment) For example, a projection formed on a substrate, or a barrier rib for forming a cathode of an organic EL element.

The surface protective film refers to an insulating film formed on the surface of an electronic component or an electronic device to protect the surface, and the kind thereof is not particularly limited. Examples of such a surface protective film include a passivation film or a buffer coat layer formed on a semiconductor element, or a cover coat formed on a flexible substrate. The dam member is a spacer used for forming a hollow portion for disposing an optical element or the like on a substrate.

The photosensitive resin material contains iron. The content of iron in the non-volatile component of the photosensitive resin material, as measured by the frame-less atomic absorption spectrometry, is 0.005 ppm or more and 80 ppm or less. By setting the content of iron to the lower limit or higher, it is possible to suppress the occurrence of a whitish layer which is hard to develop with the developing solution when the resin film formed using the photosensitive resin material is exposed and developed. Therefore, the workability in patterning can be improved. By setting the content of iron to the upper limit or lower, it is possible to realize a permanent film having excellent durability by setting a good tensile elongation percentage in a resin film formed by using a photosensitive resin material. It is also possible to suppress the occurrence of pattern defects during patterning. Furthermore, by setting the content of iron to the entire non-volatile component of the photosensitive resin material within the above-described range, it is possible to suppress the occurrence of deviation in the lithography characteristics due to the deviation of the exposure time from the resin film formation step to the exposure and development step It is possible.

In the present embodiment, the content of iron relative to the total non-volatile component of the photosensitive resin material is preferably 0.01 ppm or more and 50 ppm or less, more preferably 0.01 ppm or more, More preferably 0.03 ppm or more and 30 ppm or less.

In the present embodiment, the content of iron in the entire non-volatile component of the photosensitive resin material can be calculated from the content of iron in the vanadium-based photosensitive resin material measured by, for example, frame-less atomic absorption analysis. Further, in the frame-less atomic absorption analysis, for example, a varnish-phase photosensitive resin material diluted with NMP (N-methylpyrrolidone) or the like may be used.

The ratio (mass%) of the nonvolatile component in the photosensitive resin material can be measured, for example, as follows. First, 1.0 g of the photosensitive resin material is weighed as a sample in an aluminum cup in which the mass (m ₀ ) is measured. At this time, the total mass of the sample and the aluminum cup is m ₁ . Then, the aluminum cup was kept at atmospheric pressure for 1 hour in a hot air dryer adjusted to 210 DEG C, taken out from the hot air dryer, and cooled to room temperature. Next, the total mass (m ₂ ) of the cooled sample and the aluminum cup is measured. Then, the ratio (mass%) of the nonvolatile component in the photosensitive resin material is calculated from the following equation.

Nonvolatile matter (mass%) = (m ₂ - m ₀ ) / (m ₁ - m ₀ ) × 100

The iron furnace present in the photosensitive resin material contains, for example, nonionic iron. Thereby, when the resin film formed by using the photosensitive resin material is exposed and developed, generation of the whitened layer can be effectively suppressed and the workability can be improved. Examples of the nonionic iron rail include iron-containing particles such as iron and particles made of the compound or particles made of an alloy of iron and another metal. The iron compound includes, for example, iron oxide. As another metal, for example, nickel can be mentioned. In the present embodiment, such a structure can be obtained by mixing iron-containing particles such as iron particles, iron oxide particles, or iron alloy particles into a photosensitive resin material. Examples of the iron-containing particles include nanoparticles manufactured by Sigma-Aldrich, manufactured by Atotech Co., Ltd. and Nippon Quantum Design Co., Ltd., which are commercially available.

When non-ionic iron is contained in the photosensitive resin material, the content of nonionic iron in the non-volatile component of the photosensitive resin material is preferably 0.005 ppm or more and 80 ppm or less, more preferably 0.01 ppm or more and 50 ppm or less And more preferably 0.03 ppm or more and 30 ppm or less. This makes it possible to improve the workability in patterning more effectively while maintaining the performance as a permanent film such as durability for a resin film formed using a photosensitive resin material.

The iron furnace present in the photosensitive resin material may contain iron ions. In this case, from the viewpoint of suppressing the whitening layer, it is preferable that both the non-ionic iron and the iron ion are contained in the photosensitive resin material.

The photosensitive resin material does not contain, for example, iron particles having a particle diameter of 0.2 m or more. In this case, iron present in the photosensitive resin material is present as fine particles having a particle diameter of less than 0.2 탆 or dissolved iron ions in the photosensitive resin material. At this time, when the photosensitive resin material is filtered using a filter having a pore diameter of 0.2 mu m, no residue remains in the filter. This makes it possible to effectively suppress the occurrence of whitening layer while reliably suppressing pattern defects in the lithography process. Such a constitution can be realized by, for example, filtering a photosensitive resin material obtained by blending each component with a filter having a pore diameter of 0.2 mu m.

The photosensitive resin material contains, for example, an alkali-soluble resin (A) and a photosensitizer (B). As a result, a photosensitive resin film capable of patterning by lithography can be formed using a photosensitive resin material.

((A) an alkali-soluble resin)

Examples of the alkali-soluble resin (A) include those having a hydroxyl group and / or a carboxyl group such as a phenolic hydroxyl group in the main chain or side chain, and examples thereof include phenol resin, hydroxystyrene resin, methacrylic acid resin, , A cyclic olefin resin, a precursor having an amide bond such as a polybenzoxazole precursor and a polyimide precursor, and a resin obtained by dehydration ring closure of the precursor. Among them, it is preferable to contain a phenol resin, a hydroxystyrene resin, or a precursor having an amide bond, and it is particularly preferable to contain a precursor having an amide bond from the viewpoint of improving heat resistance and film toughness. The alkali-soluble resin (A) may contain one or more of these.

As the precursor having an amide bond in the alkali-soluble resin (A), for example, those having a repeating unit represented by the following general formula (1) can be used.

[Chemical Formula 1]

In the formula (1), X and Y are organic groups. R ₁ is a hydroxyl group, -OR ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group, and when they have plural groups, they may be the same or different. R ₂ is a hydroxyl group, a carboxyl group, -OR ₃ , or -COO-R ₃ , and when they have plural groups, they may be the same or different. R ₁ and R ₂ of R ₃ in, is an organic group having a carbon number of 1-15. When there is no hydroxyl group as R ₁ , at least one of R ₂ is a carboxyl group. When R ₂ does not have a carboxyl group, at least one of R ₁ is a hydroxyl group. m is an integer of 0 to 8, and n is an integer of 0 to 8.

In the amide resin represented by the general formula (1), X, Y, R ₁ to R ₃ , m and n may be the same or different for each repeating unit.

In the precursor having an amide bond having the structure represented by the general formula (1), a polyimide resin or a polybenzoxazole resin, or an imide bond and an oxazole ring are contained in the precursor by heating dehydration or dehydration reaction using a catalyst ≪ / RTI > When a precursor having an amide bond is used as the alkali-soluble resin (A), the alkali-soluble resin (A) may further contain one or both of a polyimide resin and a polybenzoxazole resin.

When the precursor having an amide bond represented by the general formula (1) is a polybenzoxazole precursor, at least one of R ₁ is a hydroxyl group. In this case, dehydration ring closure occurs between R ₁ and the amide structure by heat dehydration or dehydration reaction using a catalyst to produce a polybenzoxazole resin having an oxazole ring. At this time, at least one of the polybenzoxazole precursor or the polybenzoxazole resin is contained in the alkali-soluble resin (A).

When the precursor having an amide bond represented by the general formula (1) is a polyimide precursor, at least one of R ₂ is a carboxyl group. In this case, dehydration ring closure (imidization) occurs between R ₂ and the amide structure by thermal dehydration or dehydration reaction using a catalyst, and a polyimide resin is produced. At this time, at least one of the polyimide precursor and the polyimide resin is contained in the alkali-soluble resin (A).

In the precursor having an amide bond having a repeating unit represented by the general formula (1), as the R ₁ and R ₂ , in controlling the solubility of a precursor having an amide bond in an alkali aqueous solution, the hydroxyl group or the carboxyl group is preferably a protecting group R ₃ < / RTI > protected group. Such -OR ₃ roneun R _1, R ₂ roneun can use the -OR ₃ or -COO-R _3, respectively. Examples of the organic group having 1 to 15 carbon atoms as R _{3 include} a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, a tertiary butoxycarbonyl group, a phenyl group, a benzyl group, a tetrahydrofuranyl group, And tetrahydropyranyl group.

The organic group as X of the precursor having an amide bond having the structure represented by the general formula (1) is not particularly limited. Examples thereof include an aromatic group having a benzene ring, a naphthalene ring or a bisphenol structure, a pyrrole ring or a furan ring , And a siloxane group can be given. More specifically, the following is preferable. These may be used singly or in combination of two or more.

(2)

A represents an alkylene group, a substituted alkylene group, -OC ₆ H ₄ -O-, -O-, -S-, -SO ₂ -, - (CH ₂₎ R ₄ represents one selected from the group consisting of an alkyl group, an alkyl ester group and a halogen atom, and may be the same or different from one another in each repeating unit, R ₅ is a group selected from the group consisting of C (= O) -, -NHC Represents an alkyl group, an alkyl ester group, and a halogen atom, s represents an integer of 0 to 4. R ₆ to R ₉ each represent an organic group. The substituent R ₁ of X is omitted)

Among these, particularly preferred ones include, for example, those shown below (including those in which R ₁ shown in the general formula (1) is shown).

(3)

(* Denotes that bound to NH in formula (1) wherein A is an alkylene group, a substituted alkylene _{group, -O-, -S-, -SO 2 -} , -C (= O) - , -NHC (= O) -, -CH 3 -, -C (CH 3) H-, -C (CH 3) 2 -, -C (CF 3) 2 -., or a single bond R ₁₀ is an alkyl group , an alkoxy group, and one selected from the group consisting of an acyloxy group and a cycloalkyl group, when R ₁₀ is plural, each R ₁₀ is the same to or different from each other. c represents an integer of 0 to 3)

As specific examples of the alkylene group and the substituted alkylene group as the group A,

. Among them, -CH ₂ -, -CH (CH ₃ ) -, and -C (CH ₃ ) ₂ - are preferred not only in an aqueous alkaline solution but also in a solvent and have a sufficient solubility and a precursor having an amide bond It is preferable from the viewpoint that it can be obtained.

Y in the precursor having an amide bond having the structure represented by the general formula (1) is an organic group. Examples of such an organic group include the same as X. Examples of Y in the general formula (1) include heterocyclic organic groups having a structure such as an aromatic group having a structure such as a benzene ring, a naphthalene ring or a bisphenol structure, a pyrrole ring, a pyridine ring or a furan ring, And a siloxane group. More concretely, it is preferable to be shown below. These may be used singly or in combination of two or more.

[Chemical Formula 4]

(* Represents a bond to the C = O group in the general formula (1), J represents -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, -S-, -SO ₂ - (= O) -, -NHC (= O) -, -C (CF ₃ ) ₂ - or a single bond, R ₁₃ is an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group and a halogen atom R ₁₄ represents one selected from the group consisting of a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom, and t is an integer of 0 or more and 2 or less. And R ₁₅ to R ₁₈ are organic groups. Here, the substituent R ₂ of Y in the general formula (1) is omitted here)

Among these, particularly preferred ones include the following ones (including those in which R ₂ is represented by the general formula (1)).

The structure derived from the tetracarboxylic acid dianhydride among the structures shown below is such that the position bonding to the C = O group in the general formula (1) Position and para position, respectively.

[Chemical Formula 5]

(* Represents a bond to the C = O group in the general formula (1), R ₁₉ represents one selected from the group consisting of an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group and a halogen atom, R ₂₀ represents a hydrogen atom or an organic group having 1 to 15 carbon atoms and may be partially substituted, and u is an integer of 0 or more and 2 or less)

 In the case of a precursor having an amide bond represented by the general formula (1), the amino group at the end of the precursor may be substituted with an organic group selected from an alkenyl group, an alkynyl group, and a hydroxyl group, to a degree that does not affect the mechanical properties and heat resistance of the cured product cured at a low temperature An aliphatic group having at least one group, or an acid anhydride or a monocarboxylic acid containing a cyclic compound group, may be end-sealed as an amide.

Examples of the acid anhydride or monocarboxylic acid containing an aliphatic group or cyclic compound group having at least one organic group selected from an alkenyl group, an alkynyl group and a hydroxyl group include maleic anhydride, citraconic anhydride, 2,3 -Cyclohexene-1,2-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene- 3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, itaconic anhydride, heptanoic anhydride, Phthalic anhydride, 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, 4-hydroxybenzoic acid, and 3-hydroxybenzoic acid. These may be used alone, or two or more of them may be used in combination, or a part of the end-sealed amide portion may be subjected to dehydration ring closure.

In the case of a precursor having an amide bond represented by the general formula (1), the carboxylic acid residue at the terminal of the precursor may be replaced with an aliphatic or cyclic compound group having at least one organic group selected from an alkenyl group, an alkynyl group and a hydroxyl group May be end-sealed as an amide by using an amine derivative containing an amine.

In the case of a precursor having an amide bond represented by the general formula (1), a group end-capped with a nitrogen-containing cyclic compound is present in at least one of the terminals so as not to affect the mechanical properties and heat resistance of the cured product cured at a low temperature . This makes it possible to improve adhesion with metal wiring (particularly, copper wiring) and the like. Examples of the nitrogen-containing cyclic compound include 1- (5-1H-triazoyl) methylamino group, 3- (1H-pyrazolyl) amino group, 4- (3-1H-pyrazolyl) methylamino group, 1- (4-1H-pyrazolyl) methylamino group, 1- (1 H-tetrazol-5-yl) methyl-amino group, and 3- (1H-tetrazol-5-yl) benz-amino group.

The precursor having an amide bond having the structure represented by the general formula (1) is a precursor having an amide bond represented by the general formula (1), for example, a diamine, bis (aminophenol) or 2,4-diaminophenol containing X in the general formula And a compound selected from tetracarboxylic acid dianhydride, trimellitic acid anhydride, dicarboxylic acid, dicarboxylic acid dichloride or dicarboxylic acid derivative containing Y, and the like. In the case of using a dicarboxylic acid, in order to increase the reaction yield and the like of a precursor having an amide bond, an active ester type Of the dicarboxylic acid derivative may be used.

Examples of the precursor having an amide bond contained in the alkali-soluble resin (A) in the present embodiment include those having a repeating unit shown below, for example. The precursor having an amide bond in the present embodiment is not limited to this.

In the formula, R ₂₁ represents a hydrogen atom or -CH ₃ .

[Chemical Formula 6]

Examples of the phenol resin in the alkali-soluble resin (A) include a reaction product of a phenol compound and an aldehyde compound represented by a novolak type phenol resin, a reaction product of a phenol compound represented by a phenol aralkyl resin and a dimethanol compound Can be used. Among them, it is particularly preferable to use a phenol resin obtained by reacting a phenol compound and an aldehyde compound from the viewpoint of suppressing film reduction in the developing step and from the viewpoint of production cost.

Examples of the phenol compound include, but are not limited to, cresols such as phenol, o-cresol, m-cresol or p-cresol, 2,3-xylenol, 2,4- Xylenol such as xylenol, 2,6-xylenol, 3,4-xylenol or 3,5-xylenol, ethyl such as o-ethylphenol, m-ethylphenol or p- Alkylphenols such as phenol, isopropylphenol, butylphenol or p-tert-butylphenol, or polyhydric phenols such as resorcin, catechol, hydroquinone, pyrogallol or phloroglucine. These phenol compounds may be used alone or in combination of two or more.

The aldehyde compound is not particularly limited as long as it is an organic compound having an aldehyde group. For example, formalin, paraformaldehyde, acetaldehyde, benzaldehyde, or salicylaldehyde can be used. The benzaldehyde may be substituted with at least one of an alkyl group, an alkoxy group, and a hydroxyl group, or an unsubstituted benzaldehyde. These aldehyde compounds may be used alone or in combination of two or more.

In the present embodiment, for example, a phenol resin which is an alkali-soluble resin (A) is obtained by synthesizing the phenol compound and the aldehyde compound by reacting them under an acid catalyst. The acid catalyst is not particularly limited, but oxalic acid, nitric acid, sulfuric acid, diethyl sulfate, acetic acid, p-toluenesulfonic acid, phenolsulfonic acid, or benzenesulfonic acid can be used.

Examples of the dimethanol compound include, but are not limited to, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-biphenyldimethanol, 3,4'-biphenyldimethanol, 3 , Dimethanol compounds such as 3'-biphenyl dimethanol or 2,6-naphthalene dimethanol, 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) (Methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 3,3'-bis (methoxymethyl) biphenyl or 2,6-naphthalenedicarboxylate Bis (bromomethyl) benzene, 1,3-bis (chloromethyl) benzene, 1,3-bis (chloromethyl) benzene, Bis (chloromethyl) biphenyl, 4,4'-bis (chloromethyl) biphenyl, 3,3'-bis Bis (bromomethyl) biphenyl, 3,4'-bis (bromomethyl) biphenyl or 3,3'-bis (bromomethyl) The. These dimethanol compounds may be used alone or in combination of two or more.

As the hydroxystyrene resin in the alkali-soluble resin (A), a polymerization reaction product or copolymerization reaction product obtained by radical polymerization, cation polymerization or anion polymerization of hydroxystyrene, styrene or a derivative thereof can be used.

In the present embodiment, the content of the alkali-soluble resin (A) is preferably 30% by weight or more and 95% by weight or less, more preferably 50% by weight or more and 90% by weight or less with respect to the total amount of the nonvolatile component of the photosensitive resin composition Do.

((B) photosensitive agent)

The photosensitive resin composition contains a photosensitizer (B). As the photosensitizer (B), a compound capable of generating an acid by light can be used. Examples of the photosensitizer (B) include onium salts such as photosensitive diazoquinone compounds, diaryliodonium salts, triarylsulfonium salts and sulfonium borate salts, 2- A nitrobenzyl ester compound, an N-iminosulfonate compound, an imidosulfonate compound, a 2,6-bis (trichloromethyl) -1,3,5-triazine compound, or a dihydropyridine compound. Among them, it is particularly preferable to use photosensitive diazoquinone compounds having excellent sensitivity and solvent solubility.

As the photosensitive diazoquinone compound, for example, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide- .

When the photosensitive resin composition is a positive type, it is considered that the photosensitive agent remaining in the relief pattern of the unexposed portion is decomposed by heat at the time of curing to generate an acid, and the photosensitive agent also plays an important role as a reaction promoter. As the photosensitive diazoquinone compound having such a role, it is particularly preferable to use an ester of 1,2-naphthoquinone-2-diazide-4-sulfonic acid which is more easily decomposed by heat.

The content of the photosensitizer (B) in the photosensitive resin composition is not particularly limited, but is preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A), more preferably 5 parts by mass or more and 20 parts by mass Or less. This makes it possible to realize a photosensitive resin composition having good patterning performance.

The photosensitive resin composition may contain, if necessary, one or more additives such as a surfactant, a crosslinking agent, a coupling agent, a dissolution accelerator, an antioxidant, a filler, or a sensitizer.

(solvent)

The photosensitive resin composition can be used by dissolving the above-described components in a solvent and using it as a varnish phase. Examples of the solvent include N-methyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Propylene 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 and methyl-3-methoxy propionate. These may be used alone or in combination of two or more.

The resin film obtained by curing the photosensitive resin material preferably has, for example, a tensile modulus at 23 캜 of 0.5 ㎬ or more, more preferably 1.0 ㎬ or more. Thereby, the mechanical strength of the resin film formed by the photosensitive resin material can be improved, and the reliability of the electronic device provided with the resin film as a permanent film can be improved.

The tensile modulus of the resin film obtained by curing the photosensitive resin material can be measured by measuring the tensile modulus at 23 deg. C of the resin film obtained by curing the photosensitive resin material under a nitrogen atmosphere at 300 deg. C for 30 minutes, (Elongation speed: 5 mm / min), and can be calculated from the initial gradient of the obtained stress-strain curve.

The resin film obtained by curing the photosensitive resin material preferably has a tensile elongation percentage at 23 캜 of 20% or more, more preferably 30% or more, for example. As a result, excellent durability can be realized for a resin film formed using a photosensitive resin material, and cracks, cracks, and the like can be reliably suppressed.

The tensile elongation at 23 deg. C of the resin film obtained by curing the photosensitive resin material can be measured by measuring the tensile elongation at 23 deg. C of the resin film obtained by curing the photosensitive resin material under a nitrogen atmosphere at 300 deg. C for 30 minutes, (Elongation speed: 5 mm / min) is carried out, and it can be calculated from the fracture distance and the initial distance using the following formula.

Tensile elongation (%) = (breaking distance - initial distance) / initial distance x 100

As described above, the resin film obtained by curing the photosensitive resin material can constitute a permanent film such as an interlayer film, a surface protective film, or a dam member. As a result, durability and the like can be improved for an electronic apparatus having the resin film as a permanent film.

The content of iron with respect to the entirety of the resin film, which is measured by frame-less atomic absorption analysis, is, for example, 0.005 ppm or more and 80 ppm or less. As a result, durability and connection reliability can be improved, and reliability of the electronic device can be improved. From the viewpoint of improving the reliability of the electronic device, the content of iron with respect to the whole resin film is more preferably 0.01 ppm or more and 50 ppm or less, and particularly preferably 0.03 ppm or more and 30 ppm or less. In addition, iron present in the resin film contains at least one of nonionic iron or iron ion. From the viewpoint of improving the reliability of the electronic device, it is preferable that both of the non-ionic iron and the iron ion are contained in the resin film.

Such a resin film can be realized, for example, by setting the content of iron to the entire non-volatile component of the photosensitive resin material measured by frame-less atomic absorption analysis to the above-described numerical range in the present embodiment.

Next, an example of the electronic device 100 will be described.

The electronic device 100 shown in Fig. 1 is, for example, a semiconductor chip. In this case, for example, the electronic device 100 is mounted on the wiring board via the bumps 52 to obtain a semiconductor package. The electronic device 100 includes a semiconductor substrate on which semiconductor elements such as transistors are formed, and a multilayer wiring layer formed on the semiconductor substrate (not shown). An interlayer insulating film 30 and an uppermost wiring 34 formed on the interlayer insulating film 30 are formed on the uppermost layer of the multilayer wiring layers. The uppermost wiring 34 is made of, for example, Al. In addition, a passivation film 32 is formed on the interlayer insulating film 30 and the uppermost wiring 34. In the part of the passivation film 32, an opening through which the uppermost layer wiring 34 is exposed is formed.

On the passivation film 32, a re-wiring layer 40 is formed. The redistribution layer 40 includes an insulation layer 42 formed on the passivation film 32, a redistribution line 46 formed on the insulation layer 42, and a redistribution line 46 formed on the insulation layer 42 and the redistribution line 46 And an insulating layer 44 formed on the substrate. The insulating layer 42 is formed with an opening to be connected to the uppermost layer wiring 34. The rewiring lines 46 are formed in the openings formed in the insulating layer 42 and the insulating layer 42 and are connected to the uppermost wiring 34. In the insulating layer 44, an opening for connecting to the redistribution line 46 is formed.

In the present embodiment, at least one of the passivation film 32, the insulating layer 42, and the insulating layer 44 can be constituted by, for example, a resin film formed by curing the above-described photosensitive resin material . In this case, the passivation film 32, the insulating layer 42, or the insulating layer (not shown) may be formed by patterning, for example, a coating film formed of a photosensitive resin material by exposure to ultraviolet light, 44 are formed.

In the opening formed in the insulating layer 44, the bump 52 is formed, for example, with a UBM (Under Bump Metallurgy) layer 50 interposed therebetween. The electronic device 100 is connected to a wiring board or the like via, for example, a bump 52. [

Example

Next, an embodiment of the present invention will be described.

(Synthesis of alkali-soluble resin (A-1)

21.43 g (0.083 mol) of diphenyl ether-4,4'-dicarboxylic acid and 1 g of 1-hydroxy-1, 3'-dicarboxylic acid were added to four separable glass flasks equipped with a thermometer, stirrer, (0.083 mol) of a mixture of the dicarboxylic acid derivative obtained by reacting 22.43 g (0.166 mol) of 2,3-benzotriazole monohydrate with 10.0 g (0.083 mol) of hexafluoro-2,2- 36.62 g (0.100 mol) of N-methyl-2-pyrrolidone and 296.96 g of N-methyl-2-pyrrolidone were added and dissolved. Thereafter, the reaction was carried out at 75 DEG C for 15 hours using an oil bath. Next, 6.98 g (0.0425 mol) of 3,6-endmethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in 34.88 g of N-methyl-2-pyrrolidone was added and the mixture was further stirred for 3 hours The reaction was terminated by stirring.

After filtration of the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, sufficiently washed with water and then dried under vacuum to obtain the desired alkali- ). The weight average molecular weight of the obtained compound was 13,040.

(Synthesis of alkali-soluble resin (A-2)

30.0 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added to four separable glass flasks equipped with a thermometer, stirrer, feed inlet and dry nitrogen gas inlet tube , And dissolved in 400 ml of acetone. Subsequently, 12.4 g (0.18 mol) of para-nitrobenzoyl chloride dissolved in 100 ml of acetone was added dropwise over 30 minutes while cooling to a temperature of less than 20 캜 to obtain a mixture. After the dropwise addition, the temperature of the mixture was heated to 40 占 폚 and stirred for 2 hours. Then, 30.0 g (0.218 mol) of potassium carbonate was slowly added thereto and further stirred for 2 hours. Heating was stopped, and the mixture was further stirred at room temperature for 18 hours. Then, while vigorously stirring the mixture, an aqueous solution of sodium hydroxide was gradually added, and the mixture was heated to 55 캜 and further stirred for 30 minutes. After the completion of the stirring, the mixture was cooled to room temperature, and 37% by weight hydrochloric acid aqueous solution and 500 ml water were added to adjust the solution pH to 6.0-7.0. Subsequently, the resulting precipitate was separated by filtration, the filtrate was washed with water, and dried at 60 to 70 ° C to obtain bis (N, N '- (para-nitrobenzoyl) hexafluoro-2,2-bis -Hydroxyphenyl) propane. ≪ / RTI >

316 g of acetone and 158 g of methanol were added to 51.0 g of the obtained solid, and the mixture was heated to 50 캜 to dissolve completely. There, 300 ml of pure water at 50 占 폚 was added over 30 minutes and heated to 65 占 폚. The precipitated crystals were filtered and the crystals were purified by drying at 70 ° C to give bis-N, N '- (para-nitrobenzoyl) hexafluoro-2,2-bis (4 -Hydroxyphenyl) propane.

20 g of bis-N, N '- (para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane obtained above was placed in a 1 L flask, and 5% palladium- 1.0 g and ethyl acetate 180.4 g were added to make a suspension state. The hydrogen gas was purged therefrom, and the mixture was shaken for 35 minutes while being heated to 50 to 55 占 폚 to carry out a reduction reaction. After completion of the reaction, the reaction mixture was cooled to 35 DEG C and nitrogen was purged from the suspension. After the catalyst was removed by filtration separation, the filtrate was added to this separator to evaporate the solvent. The obtained product was dried at 90 占 폚 to obtain bis-N, N '- (para-aminobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane.

N, N '- (para-aminobenzoyl) hexafluoro-2,2-bis (4 (meth) acrylate) obtained in the above was added to four glass separable flasks equipped with a stirrer, a thermometer, a stirrer, -Hydroxyphenyl) propane (14.5 g, 0.024 mol) was added, and 40 g of? -Butyrolactone was added to dissolve and the solution was cooled to 15 占 폚 with stirring. 6.8 parts by mass (0.022 mol) of 4,4'-oxydiphthalic anhydride and 12.0 parts by mass of? -Butyrolactone were added thereto, followed by stirring at 20 ° C for 1.5 hours. Thereafter, the mixture was heated to 50 占 폚 and stirred for 3 hours. Then, 5.2 g (0.044 mol) of N, N-dimethylformamide dimethyl acetal and 10.0 g of? -Butyrolactone were added and stirred at 50 占 폚 for further 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain the desired alkali-soluble resin (A-2). The weight average molecular weight of the obtained compound was 13,200.

(Synthesis of alkali-soluble resin (A-3)) [

(0.60 mole) of m-cresol, 43.3 g (0.40 mole) of p-cresol, and 30.0 g of p-cresol were placed in a four-neck round bottom glass round bottom flask equipped with a stirrer, a thermometer, 65.1 g of formaldehyde in water (0.65 mol of formaldehyde) and 0.63 g (0.005 mol) of oxalic acid dihydrate were poured into an oil bath, and the reaction solution was refluxed for 4 hours at 100 DEG C to carry out a polycondensation reaction . Subsequently, the temperature of the oil bath was raised to 200 DEG C over 3 hours, and the pressure in the flask was reduced to 50 mmHg or lower to remove moisture and volatile components. Thereafter, the resin was cooled to room temperature to obtain an alkali-soluble resin (A-3) having a weight average molecular weight of 3200.

(Synthesis of photosensitizer)

11.04 g (0.026 mol) of phenol represented by the formula (C-1) and 0.04 g (0.026 mol) of 1,2-naphthoquinone-2-diamine were placed in a four-necked separable flask equipped with a thermometer, a stirrer, (0.070 mol) of bis (trimethylsilyl) azide-4-sulfonyl chloride and 170 g of acetone were added and dissolved by stirring.

Subsequently, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise while cooling the flask in a water bath so that the temperature of the reaction solution did not exceed 35 캜. After the reaction was allowed to proceed at room temperature for 3 hours, 1.05 g (0.017 mol) of acetic acid was added, followed by further reaction for 30 minutes. Then, after the reaction mixture was filtered, the filtrate was poured into a mixed solution of water / acetic acid (990 ml / 10 ml). Subsequently, the precipitate was collected by filtration, sufficiently washed with water, and then dried under vacuum. Thus, a photosensitive agent (B) represented by the formula (Q-1) was obtained.

(7)

(Example 1)

100 parts by weight of the alkali-soluble resin (A-1), 15 parts by weight of the photosensitizer (B), 5 parts by weight of 1,4-benzene dimethanol as a crosslinking agent and 3 parts by weight of 3-methacryloxypropyltrimethoxysilane 5 And 0.000013 parts by weight of iron oxide (III) (manufactured by Sigma-Aldrich Co., average particle diameter <50 nm) were mixed and dissolved in? -Butyrolactone as a solvent and then filtered with a PTFE membrane filter having a pore diameter of 0.2 占 퐉 Thereby obtaining a photosensitive resin material on the varnish.

The content of iron in the obtained non-volatile component in the photosensitive resin material was 0.10 ppm. The content of iron in the entire nonvolatile component of the photosensitive resin material was calculated from the content of iron in the varnish-receiving photosensitive resin material measured by a frame-less atomic absorption spectrometry (ZEEnit 60, manufactured by Rigaku Corporation). The same is true for the respective examples and comparative examples below.

(Example 2)

100 parts by weight of the alkali-soluble resin (A-1), 15 parts by weight of the photosensitizer (B), 5 parts by weight of 1,4-benzene dimethanol as a crosslinking agent and 3 parts by weight of 3-methacryloxypropyltrimethoxysilane 5 And 0.00013 part by weight of iron oxide (III) (manufactured by Sigma-Aldrich Co., average particle diameter <50 nm) were mixed and dissolved in? -Butyrolactone as a solvent and then filtered through a PTFE membrane filter having a pore diameter of 0.2 占 퐉 Thereby obtaining a photosensitive resin material on the varnish. The content of iron in the obtained non-volatile component in the photosensitive resin material was 1.04 ppm.

(Example 3)

100 parts by weight of the alkali-soluble resin (A-1), 15 parts by weight of the photosensitizer (B), 5 parts by weight of 1,4-benzene dimethanol as a crosslinking agent and 3 parts by weight of 3-methacryloxypropyltrimethoxysilane 5 And 0.0013 part by weight of iron oxide (III) (manufactured by Sigma-Aldrich Co., average particle diameter <50 nm) were mixed and dissolved in? -Butyrolactone as a solvent and then filtered with a PTFE membrane filter having a pore diameter of 0.2 占 퐉 Thereby obtaining a photosensitive resin material on the varnish. The content of iron in the obtained non-volatile component in the photosensitive resin material was 10.4 ppm.

(Example 4)

100 parts by weight of the alkali-soluble resin (A-2), 15 parts by weight of the photosensitizer (B), 5 parts by weight of 1,4-benzene dimethanol as a cross-linking agent and 3 parts by weight of 3-methacryloxypropyltrimethoxysilane 5 And 0.00013 part by weight of iron oxide (III) (manufactured by Sigma-Aldrich Co., average particle diameter <50 nm) were mixed and dissolved in? -Butyrolactone as a solvent and then filtered through a PTFE membrane filter having a pore diameter of 0.2 占 퐉 Thereby obtaining a photosensitive resin material on the varnish. The content of iron in the obtained non-volatile component in the photosensitive resin material was 1.04 ppm.

(Example 5)

20 parts by weight of the alkali-soluble resin (A-3), 15 parts by weight of the photosensitizer (B), 5 parts by weight of 1,4-benzene dimethanol as a crosslinking agent, 5 parts by weight of 3-methacryloxypropyltrimethoxysilane as a ring agent and 0.00013 parts by weight of iron oxide (III) (manufactured by Sigma-Aldrich Co., average particle diameter <50 nm) were mixed and dissolved in? -Butyrolactone as a solvent And filtered through a PTFE membrane filter having a pore diameter of 0.2 mu m to obtain a photosensitive resin material on a varnish. The content of iron in the obtained non-volatile component in the photosensitive resin material was 1.04 ppm.

(Comparative Example 1)

100 parts by weight of the alkali-soluble resin (A-1), 15 parts by weight of the photosensitizer (B), 5 parts by weight of 1,4-benzene dimethanol as a crosslinking agent and 3 parts by weight of 3-methacryloxypropyltrimethoxysilane 5 Were mixed and dissolved in? -Butyrolactone as a solvent, and the mixture was filtered through a fluororesin filter having a pore diameter of 0.2 占 퐉 to obtain a varnish-type photosensitive resin material. The obtained photosensitive resin material had an iron content of 0.002 ppm with respect to the total non-volatile component.

(Comparative Example 2)

100 parts by weight of the alkali-soluble resin (A-1), 15 parts by weight of the photosensitizer (B), 5 parts by weight of 1,4-benzene dimethanol as a crosslinking agent and 3 parts by weight of 3-methacryloxypropyltrimethoxysilane 5 And 0.13 part by weight of iron oxide (III) (manufactured by Sigma-Aldrich Co., average particle diameter <50 nm) were mixed and dissolved in? -Butyrolactone as a solvent and then filtered with a PTFE membrane filter having a pore diameter of 0.2 占 퐉 Thereby obtaining a photosensitive resin material on the varnish. The content of iron in the obtained non-volatile component in the photosensitive resin material was 1040 ppm.

(Appearance evaluation)

For each of the Examples and Comparative Examples, the obtained photosensitive resin material was applied on an 8-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 120 캜 for 3 minutes to obtain a resin film having a film thickness of about 7.5 탆 . Subsequently, a part of the surface of the resin film was dissolved by treatment with a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 DEG C for 20 seconds. At this time, the presence or absence of whitened portions on the surface of the resin film was observed.

For each example and each comparative example, this measurement was performed five times. A white circle was observed in all of the resin films, and a white circle was observed in at least one of the resin films. The results are shown in Table 1.

(Processability evaluation)

For each of the Examples and Comparative Examples, the obtained photosensitive resin material was applied on an 8-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 120 캜 for 3 minutes to obtain a resin film having a film thickness of about 7.5 탆 . This resin film was passed through a mask (Test Chart No. 1: a residual pattern having a width of 0.88 to 50 탆 and an extraction pattern is drawn) manufactured by Tohpan Printing Co., Ltd., and an i-line stepper (manufactured by Nikon Corporation, NSR-4425i ) Was used to examine the amount of exposure. Next, by using a 2.38% aqueous solution of tetramethylammonium hydroxide as the developer, the development time was adjusted so that the difference between the film thickness after pre-baking and the film thickness after development was 1.0 占 퐉 to perform padding twice to dissolve the exposed portions And then rinsed with pure water for 10 seconds. The opening of the pattern formed on the resin film was observed at a magnification of 200 times with an optical microscope to confirm whether or not residue was generated. ?, No residue was observed?, The residue was observed but the product was able to withstand use,?, And the product with unacceptable residue was evaluated as?. The results are shown in Table 1.

(Tensile modulus)

For each of the examples and comparative examples, a test piece (10 mm x 60 mm x 10 m thickness) obtained by curing the obtained photosensitive resin material under a nitrogen atmosphere at 300 deg. C for 30 minutes was subjected to a tensile test (stretching speed: 5 mm / min) in an atmosphere of 23 캜. The tensile test was carried out using a tensile tester (Tensilon RTC-1210A) manufactured by Orientech. Five test pieces were measured, and the tensile elastic moduli were calculated from the initial gradients of the obtained stress-strain curves, respectively. Table 1 shows the results.

(Tensile elongation)

For each of the examples and comparative examples, a test piece (10 mm x 60 mm x 10 m thickness) obtained by curing the obtained photosensitive resin material under a nitrogen atmosphere at 300 deg. C for 30 minutes was subjected to a tensile test (stretching speed: 5 mm / min) in an atmosphere of 23 캜. The tensile test was carried out using a tensile tester (Tensilon RTC-1210A) manufactured by Orientech. Five test pieces were measured, and the tensile elongation was calculated from the fracture distance and the initial distance using the following formula, and the tensile elongation was obtained by averaging. Table 1 shows the results.

Tensile elongation (%) = (breaking distance - initial distance) / initial distance x 100

As shown in Table 1, in Examples 1 to 5, no whitening layer was observed in appearance evaluation, and good results were obtained in evaluation of workability. In Examples 1 to 5, the tensile elongation was 20% or more, indicating that sufficient durability was realized. In Examples 1 to 5, the tensile modulus was 0.5 ㎬ or more, which was a sufficient value.

This application claims priority based on Japanese Patent Application No. 2013-182424 filed on September 3, 2013, and hereby accepts all disclosures thereof.

100: Electronic device
30: Interlayer insulating film
32: Passivation film
34: Top layer wiring
40: rewiring layer
42, 44: insulating layer
46: Cultivation line
50: UBM layer
52: Bump

Claims (11)

As a photosensitive resin material used for forming a permanent film,
The iron content in the whole non-volatile component measured by the frame-less atomic absorption analysis is 0.005 ppm or more and 80 ppm or less,
As the iron, a nonionic iron-
A photosensitive composition comprising an alkali-soluble resin (A) and a photosensitive diazoquinone compound,
The alkali-soluble resin (A) contains a precursor having an amide bond having a repeating unit represented by the following formula (1).

R ₁ is a hydroxyl group, -OR ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group, and they may be the same or different when they have plural R ₂ groups, is a hydroxy group, a carboxyl group, -OR _3, or -COO-R _3, and the case has a plurality is also equal to or different from each other. R ₁ and the R ₃ in R ₂ is an organic group having a carbon number of 1 to 15 a. R ₁ when there is no hydroxyl group, at least one of R ₂ is a carboxyl group. in an R ₂ when there is no carboxyl group, and at least one of R ₁ is a hydroxyl group. m is an integer of 0 ~ 8, n is 0 To 8, provided that m and n are both zero.) As a photosensitive resin material used for forming a permanent film,
The iron content in the whole non-volatile component measured by the frame-less atomic absorption analysis is 0.005 ppm or more and 80 ppm or less,
As the iron, a nonionic iron-
A photosensitive composition comprising an alkali-soluble resin (A) and a photosensitive diazoquinone compound,
The alkali-soluble resin (A) contains at least one of a polyimide or a polyimide precursor. The method according to claim 1,
As the iron, a photosensitive resin material not containing particles having a particle diameter of 0.2 탆 or more. The method according to claim 1,
Wherein the resin film obtained by curing the photosensitive resin material has a tensile modulus at 23 占 폚 of 0.5 占 ㎬ or more. The method according to claim 1,
Wherein the permanent film is an interlayer film, a surface protective film, or a dam material. 3. The method of claim 2,
As the iron, a photosensitive resin material not containing particles having a particle diameter of 0.2 탆 or more. 3. The method of claim 2,
Wherein the resin film obtained by curing the photosensitive resin material has a tensile modulus at 23 占 폚 of 0.5 占 ㎬ or more. 3. The method of claim 2,
Wherein the permanent film is an interlayer film, a surface protective film, or a dam material. A resin film obtained by curing the photosensitive resin material according to any one of claims 1 to 8. A permanent film is formed, and the content of iron measured by the flame-less atomic absorption spectrometry is 0.005 ppm or more and 80 ppm or less,
As the iron, a nonionic iron-
An alkali-soluble resin (A) containing a precursor having an amide bond having a repeating unit represented by the following formula (1) and a resin film obtained by curing a photosensitive resin material containing a photosensitive diazoquinone compound.

R ₁ is a hydroxyl group, -OR ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group, and they may be the same or different when they have plural R ₂ groups, is a hydroxy group, a carboxyl group, -OR _3, or -COO-R _3, and the case has a plurality is also equal to or different from each other. R ₁ and the R ₃ in R ₂ is an organic group having a carbon number of 1 to 15 a. R ₁ when there is no hydroxyl group, at least one of R ₂ is a carboxyl group. in an R ₂ when there is no carboxyl group, and at least one of R ₁ is a hydroxyl group. m is an integer of 0 ~ 8, n is 0 To 8, provided that m and n are both zero.) delete

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