JP5488752B1 - Photosensitive resin material and resin film - Google Patents

Abstract

A resin film formed using a photosensitive resin material achieves excellent processability while maintaining performance as a permanent film.
A photosensitive resin material is a photosensitive resin material used for forming a permanent film, and the content of iron with respect to the whole nonvolatile components measured by flameless atomic absorption spectrometry is 0.005 ppm or more. 80 ppm or less.
[Selection] Figure 1

Description

  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 rewiring layer. Examples of such a technique include those described in 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 includes a photosensitivity having an imidized tetracarboxylic acid having a specific structure, a diamine and / or an isocyanate compound, a photosensitive resin, and a photopolymerization initiator and having a viscosity of 100 mPa · s or less at 25 ° C. A functional resin composition solution is described.

JP 2008-180992 A JP 2010-006864 A

  The resin film formed using the photosensitive resin material is patterned using lithography, for example. However, due to the solution used for development, a whitening layer that is hardly soluble in the solution may occur on the surface of the resin film. In this case, there is a concern that it becomes difficult to realize excellent workability during patterning. Therefore, a resin film formed using a photosensitive resin material is required to achieve excellent processability while maintaining the performance as a permanent film.

According to the present invention,
A photosensitive resin material used to form a permanent film,
There is provided a photosensitive resin material having an iron content of 0.005 ppm or more and 80 ppm or less based on the whole non-volatile component as measured by flameless atomic absorption spectrometry.

  According to this invention, the resin film obtained by hardening the above-mentioned photosensitive resin material is provided.

According to the present invention,
There is provided a resin film constituting a permanent film and having an iron content of 0.005 ppm or more and 80 ppm or less as measured by flameless atomic absorption spectrometry.

  ADVANTAGE OF THE INVENTION According to this invention, the outstanding workability can be implement | achieved, maintaining the performance as a permanent film about the resin film formed using the photosensitive resin material.

It is sectional drawing which shows an example of the electronic device which concerns on this embodiment.

  Hereinafter, embodiments will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

(First embodiment)
FIG. 1 is a cross-sectional view illustrating 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 iron content with respect to the entire nonvolatile components measured by frameless atomic absorption spectrometry is 0.005 ppm or more. 80 ppm or less.

  The inventor makes the content of iron with respect to the entire nonvolatile component of the photosensitive resin material within the above range, thereby maintaining the performance as a permanent film for the resin film formed using the photosensitive resin material, It was newly discovered that the generation of a whitening layer during lithography can be suppressed. The performance as a permanent film includes, for example, durability evaluated by tensile elongation. For this reason, according to this embodiment, it is possible to achieve excellent processability while maintaining the performance as a permanent film for a resin film formed using a photosensitive resin material.

  Hereinafter, the configuration of the electronic device 100 including the photosensitive resin material according to the present embodiment and a permanent film formed of the photosensitive resin material 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 a permanent film can be obtained. In this embodiment, for example, after a coating film made of a photosensitive resin material is patterned into a desired shape by exposure and development, the coating film is cured by heat treatment or the like to form a permanent film.
Examples of the permanent film formed 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 use as a film having a high light-shielding property against visible light such as a color filter and a black matrix.

  The interlayer film refers to an insulating film provided in a 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 wiring structure of a semiconductor element, a buildup layer or a core layer constituting a circuit board. Further, as the interlayer film, for example, a flattening film that covers a thin film transistor (TFT) in the display device, a liquid crystal alignment film, and a protrusion provided on a color filter substrate of an MVA (Multi Domain Vertical Alignment) type liquid crystal display device Or what is used in display apparatus uses, such as a partition for forming the cathode of an organic EL element, is also mentioned.

  The surface protective film refers to an insulating film that is formed on the surface of an electronic component or an electronic device and protects the surface, and the type thereof is not particularly limited. Examples of such a surface protective film include a passivation film or a buffer coat layer provided on a semiconductor element, or a cover coat provided on a flexible substrate. The dam material is a spacer used to form a hollow portion for arranging an optical element or the like on the substrate.

The photosensitive resin material contains iron. The iron content with respect to the entire nonvolatile components of the photosensitive resin material, measured by flameless atomic absorption spectrometry, is 0.005 ppm or more and 80 ppm or less. Suppressing the occurrence of a whitening layer that is hardly soluble in the developer when exposing and developing a resin film formed using a photosensitive resin material by setting the iron content to the above lower limit or more. it can. For this reason, the workability in patterning can be improved. Further, by making the iron content not more than the above upper limit value, the tensile elongation rate in the resin film formed using the photosensitive resin material is made a good value, and a permanent film having excellent durability is realized. Can do. It is also possible to suppress the occurrence of pattern defects during patterning. Furthermore, by setting the iron content with respect to the entire non-volatile components of the photosensitive resin material within the above range, the lithography characteristics may vary due to variations in the holding time from the resin film formation process to the exposure and development processes. It can also be suppressed.
In the present embodiment, the iron content relative to the entire nonvolatile components of the photosensitive resin material is 0.01 ppm or more and 50 ppm from the viewpoint of improving workability in patterning while maintaining the performance as a permanent film such as durability. More preferably, it is 0.03 ppm or more and 30 ppm or less.

In the present embodiment, the iron content relative to the entire nonvolatile components of the photosensitive resin material can be calculated from the iron content in the varnish-like photosensitive resin material measured by, for example, flameless atomic absorption analysis. In the flameless atomic absorption analysis, for example, a varnish-like photosensitive resin material diluted with NMP (N-methylpyrrolidone) or the like may be used.
Moreover, the ratio (mass%) of the non-volatile component in the photosensitive resin material can be measured as follows, for example. First, 1.0 g of a photosensitive resin material is weighed out as a sample in an aluminum cup whose mass (m ₀ ) has been measured. At this time, let m _{1 be} the total mass of the sample and the aluminum cup. Next, the aluminum cup is kept in a hot air dryer adjusted to 210 ° C. under normal pressure for 1 hour, and then taken out of 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. And the ratio (mass%) of the non-volatile component in the photosensitive resin material is computed from the following formula | equation.
Nonvolatile content (mass%) = (m ₂ −m ₀ ) / (m ₁ −m ₀ ) × 100

  Examples of the iron present in the photosensitive resin material include nonionic iron. Thereby, when exposing and developing the resin film formed using the photosensitive resin material, it is possible to effectively suppress the generation of the whitened layer and improve the workability. Examples of nonionic iron include iron-containing particles such as particles made of iron or a compound thereof, or particles made of an alloy of iron and another metal. Examples of the iron compound include iron oxide. Another example of the metal is nickel. In the present embodiment, for example, such a configuration can be obtained by mixing iron-containing particles such as iron particles, iron oxide particles, or iron alloy particles in the photosensitive resin material. Examples of such iron-containing particles include commercially available nanoparticles manufactured by Sigma-Aldrich, manufactured by Atotech, and manufactured by Nippon Quantum Design.

  When nonionic iron is contained in the photosensitive resin material, the content of nonionic iron with respect to the entire nonvolatile components of the photosensitive resin material is preferably, for example, 0.005 ppm or more and 80 ppm or less. It is more preferably from 01 ppm to 50 ppm, and particularly preferably from 0.03 ppm to 30 ppm. Thereby, it becomes possible to improve the workability in patterning more effectively while maintaining the performance as a permanent film such as durability for the resin film formed using the photosensitive resin material.

  The iron 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 nonionic iron and iron ions are contained in the photosensitive resin material.

  The photosensitive resin material does not contain particles having a particle diameter of 0.2 μm or more, for example, as iron. In this case, the iron present in the photosensitive resin material exists as fine particles having a particle diameter of less than 0.2 μm or iron ions dissolved 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 μm, no residue remains on the filter. Thereby, generation | occurrence | production of a whitening layer can be suppressed effectively, suppressing the pattern defect in a lithography process reliably. Such a configuration can be realized, for example, by filtering a photosensitive resin material obtained by blending each component using a filter having a pore diameter of 0.2 μm.

  The photosensitive resin material contains, for example, an alkali-soluble resin (A) and a photosensitive agent (B). Thus, a photosensitive resin film that can be patterned by lithography can be formed using the photosensitive resin material.

((A) alkali-soluble resin)
The alkali-soluble resin (A) has a hydroxyl group such as a phenolic hydroxyl group and / or a carboxyl group in the main chain or side chain. For example, a phenol resin, a hydroxystyrene resin, a methacrylic acid resin, a methacrylic ester resin, etc. A precursor having an amide bond such as an acrylic resin, a cyclic olefin resin, a polybenzoxazole precursor and a polyimide precursor, and a resin obtained by dehydrating and ring-closing the precursor. Among these, it is preferable to include a phenol resin, a hydroxystyrene resin, or a precursor having an amide bond, and it is particularly preferable to include a precursor having an amide bond from the viewpoint of improving heat resistance and film toughness. Alkali-soluble resin (A) can contain the 1 type (s) or 2 or more types of these.

  As a precursor which has an amide bond in alkali-soluble resin (A), what has a repeating unit shown, for example by following General formula (1) can be used.

In formula (1), X and Y are organic groups. R ₁ is a hydroxyl group, —O—R ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group, and when there are a plurality of R _{1 s} , they may be the same or different. R ₂ is a hydroxyl group, a carboxyl group, —O—R ₃ , or —COO—R ₃ , and when there are a plurality of R _{2 s} , they may be the same or different. R ₃ in R ₁ and R ₂ is an organic group having 1 to 15 carbon atoms. When R ₁ has no hydroxyl group, at least one of R ₂ is a carboxyl group. If there is no carboxyl group as R _2, 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 for each repeating unit, or may be different from each other.

  In a precursor having an amide bond having a structure represented by the general formula (1), a polyimide resin or a polybenzoxazole resin, or an imide bond and an oxazole ring are formed by causing a heat dehydration or a dehydration reaction using a catalyst. A copolymer containing is produced. When using the precursor which has an amide bond as alkali-soluble resin (A), alkali-soluble resin (A) may further contain one or both of polyimide resin and 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, a dehydration ring closure occurs between R ₁ and the amide structure by heat dehydration or a dehydration reaction using a catalyst, and a polybenzoxazole resin having an oxazole ring is generated. At this time, the alkali-soluble resin (A) contains at least one of a polybenzoxazole precursor or a polybenzoxazole resin.
Also, if 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 heat dehydration or a dehydration reaction using a catalyst, and a polyimide resin is generated. At this time, the alkali-soluble resin (A) includes at least one of a polyimide precursor or a polyimide resin.

In the precursor having an amide bond having a repeating unit represented by the general formula (1), R ₁ and R ₂ are a hydroxyl group or a carboxyl group for adjusting the solubility of the precursor having an amide bond in an alkaline aqueous solution. The group can include a group protected with a protecting group R ₃ . As such R ₁ , —O—R ₃ can be used, and as R ₂ , —O—R ₃ or —COO—R ₃ can be used. Examples of the organic group having 1 to 15 carbon atoms as R ₃ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group and tetrahydrofuranyl group. Groups, and tetrahydropyranyl groups.

  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. For example, an aromatic group having a structure such as a benzene ring, a naphthalene ring or a bisphenol structure. A heterocyclic organic group having a structure such as a group, a pyrrole ring or a furan ring, and a siloxane group. More specifically, those shown below are preferable. These can be used alone or in combination of two or more.

（＊は、一般式（１）におけるＮＨ基に結合することを示す。Ａは、アルキレン基、置換アルキレン基、−Ｏ−Ｃ_６Ｈ_４−Ｏ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−または単結合である。Ｒ_４は、アルキル基、アルキルエステル基およびハロゲン原子からなる群から選ばれた１つを示し、繰り返し単位毎に同一であっても異なっていてもよい。Ｒ_５は、水素原子、アルキル基、アルキルエステル基およびハロゲン原子からなる群から選ばれた１つを示す。ｓは０〜４の整数である。Ｒ_６〜Ｒ_９はそれぞれ有機基である。ここでは、一般式（１）に示すＸの置換基Ｒ_１は省略している）

(* Indicates bonding to the NH group in the general formula (1). A represents an alkylene group, a substituted alkylene group, —O—C ₆ H ₄ —O—, —O—, —S—, —SO. _2- , -C (= O)-, -NHC (= O)-or a single bond, R ₄ represents one selected from the group consisting of an alkyl group, an alkyl ester group and a halogen atom, and Each unit may be the same or different, and R ₅ represents one selected from the group consisting of a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom, and s is an integer of 0 to 4. R _{6 to} R ₉ are each an organic group (here, the substituent R _{1 of} X shown in the general formula (1) is omitted)

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

（＊は一般式（１）におけるＮＨ基に結合することを示す。式中Ａは、アルキレン基、置換アルキレン基、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、−ＣＨ_３−、−Ｃ（ＣＨ_３）Ｈ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、または単結合である。Ｒ_１０は、アルキル基、アルコキシ基、アシルオキシ基およびシクロアルキル基からなる群から選ばれた１つであり、Ｒ_１０が複数ある場合、各Ｒ_１０はそれぞれ同じでも異なってもよい。ｃは０以上３以下の整数である）

(* Indicates bonding to the NH group in the general formula (1). In the formula, A represents 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 , alkyl group, alkoxy group is one selected from acyloxy group and the group consisting of cycloalkyl group, if there are a plurality of R ₁₀ s, respective R ₁₀ is optionally the same or different .c 0 to 3 Integer)

Specific examples of the alkylene group and substituted alkylene group as A include —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CH (CH ₂ CH ₃ ) —, _{-C (CH 3) (CH 2} CH 3) -, - C (CH 2 CH 3) (CH 2 CH 3) -, - CH (CH 2 CH 2 CH 3) -, - C (CH 3) (CH _{2 CH 2 CH 3) -,} - CH (CH (CH 3) 2) -, - C (CH 3) (CH (CH 3) 2) -, - CH (CH 2 CH 2 CH 2 CH 3) -, _{-C (CH 3) (CH 2} CH 2 CH 2 CH 3) -, - CH (CH 2 CH (CH 3) 2) -, - C (CH 3) (CH 2 CH (CH 3) 2) -, _{-CH (CH 2 CH 2 CH 2} CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 2 _{CH 2 CH 3) -, -} CH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) -, and _{-C (CH 3) (CH 2} CH 2 CH 2 CH 2 CH 2 CH 3) - include . Among these, —CH ₂ —, —CH (CH ₃ ) —, and —C (CH ₃ ) ₂ — have sufficient solubility not only in an aqueous alkali solution but also in a solvent, and are excellent in balance. It is preferable because a precursor having an amide bond can be obtained.

  Y in the precursor having an amide bond having a structure represented by the general formula (1) is an organic group, and examples of such an organic group include the same as X. Y in the general formula (1) is, for example, an aromatic group having a structure such as a benzene ring, a naphthalene ring or a bisphenol structure, a heterocyclic organic group having a structure such as a pyrrole ring, a pyridine ring or a furan ring, and a siloxane group. Etc. More specifically, those shown below are preferable. These can be used alone or in combination of two or more.

（＊は、一般式（１）におけるＣ＝Ｏ基に結合することを示す。Ｊは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、−Ｃ（ＣＦ_３）_２−または単結合である。Ｒ_１３は、アルキル基、アルキルエステル基、アルキルエーテル基、ベンジルエーテル基およびハロゲン原子からなる群から選ばれた１つを示し、繰り返し単位毎に同じでも異なってもよい。Ｒ_１４は、水素原子、アルキル基、アルキルエステル基およびハロゲン原子からなる群から選ばれた１つを示す。ｔは０以上２以下の整数である。Ｒ_１５〜Ｒ_１８は、有機基である。ここでは、一般式（１）に示すＹの置換基Ｒ_２は省略している）

(* Indicates bonding to the C═O group in the general formula (1). J represents —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —. , —C (═O) —, —NHC (═O) —, —C (CF ₃ ) ₂ — or a single bond, R ₁₃ represents an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and 1 is selected from the group consisting of halogen atoms, and may be the same or different for each repeating unit, and R ₁₄ is one selected from the group consisting of a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom. T is an integer of 0 to 2. R _{15 to} R ₁₈ are organic groups.Here, the substituent R _{2 of} Y shown in the general formula (1) is omitted).

Among these, particularly preferable ones include those shown below (including those shown by R ₂ shown in the general formula (1)).
Of the structures shown below, the structures derived from tetracarboxylic dianhydrides include those in which the positions bonded to the C═O group in the general formula (1) are both in the meta position and those in both the para positions. However, it may have a structure including a meta position and a para position.

（＊は一般式（１）におけるＣ＝Ｏ基に結合することを示す。Ｒ_１９は、アルキル基、アルキルエステル基、アルキルエーテル基、ベンジルエーテル基およびハロゲン原子からなる群から選ばれた１つを表し、繰り返し単位毎に同じでも異なっていてもよい。Ｒ_２０は、水素原子または炭素数１以上１５以下の有機基から選ばれた１つを示し、一部が置換されていてもよい。ｕは０以上２以下の整数である）

(* Indicates bonding to the C═O group in the general formula (1). R ₁₉ is 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 is one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms, and may be partially substituted. 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 terminal amino group of the precursor is alkenyl group to the extent that it does not affect the mechanical properties and heat resistance of the cured product cured at low temperature. In addition, an acid anhydride or monocarboxylic acid containing an aliphatic group or a cyclic compound group having at least one organic group selected from alkynyl group and hydroxyl group can be used to end-cleave as an amide.
Examples of acid anhydrides or monocarboxylic acids containing an aliphatic group or cyclic compound group having at least one organic group selected from alkenyl groups, alkynyl groups, and hydroxyl groups include maleic anhydride, citraconic anhydride, and the like. , 2,3-dimethylmaleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene -2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, itaconic acid anhydride, het acid anhydride, 5-norbornene-2-carboxylic acid, 4-ethynylphthalic acid anhydride , 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, 4-hydroxybenzoic acid, and 3-hydroxybenzoic acid It can be mentioned. These may be used alone or in combination of two or more, and a part of the end-capped amide moiety may be dehydrated and closed.

  In the case of the precursor having an amide bond represented by the general formula (1), the carboxylic acid residue at the terminal of the precursor is at least an organic group selected from an alkenyl group, an alkynyl group, and a hydroxyl group. An amine derivative containing one aliphatic group or cyclic compound group can be used to end-cleave as an amide.

  In the case of the precursor having an amide bond represented by the general formula (1), at least one of the terminals is terminated with a nitrogen-containing cyclic compound so as not to affect the mechanical properties and heat resistance of the cured product cured at a low temperature. You may have the group sealed. Thereby, adhesiveness with a metal wiring (especially copper wiring) etc. can be improved. Examples of the nitrogen-containing cyclic compound include 1- (5-1H-triazoyl) methylamino group, 3- (1H-pyrazoyl) amino group, 4- (1H-pyrazoyl) amino group, and 5- (1H-pyrazoyl) amino group. 1- (3-1H-pyrazolyl) methylamino group, 1- (4-1H-pyrazoyl) methylamino group, 1- (5-1H-pyrazoyl) methylamino group, (1H-tetrazol-5-yl) amino Groups, 1- (1H-tetrazol-5-yl) methyl-amino group, and 3- (1H-tetrazol-5-yl) benz-amino group.

  The precursor having an amide bond having a structure represented by the general formula (1) is, for example, a compound selected from diamine containing X in the general formula (1), bis (aminophenol), 2,4-diaminophenol, and the like. , Y-containing tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic acid, dicarboxylic acid dichloride or dicarboxylic acid derivative and the like can be reacted to synthesize. In the case of using a dicarboxylic acid, an active ester type dicarboxylic acid obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like with dicarboxylic acid in advance in order to increase the reaction yield of the precursor having an amide bond. Derivatives may be used.

As an example of the precursor which has an amide bond contained in alkali-soluble resin (A) in this embodiment, what has the repeating unit shown below is mentioned, for example. In addition, the precursor which has an amide bond in this embodiment is not limited to this.
In the following formulae, R ₂₁ represents a hydrogen atom or —CH ₃ .

  Examples of the phenol resin in the alkali-soluble resin (A) include a reaction product of a phenol compound and an aldehyde compound typified by a novolak type phenol resin, or a reaction product of a phenol compound and dimethanol compounds typified by a phenol aralkyl resin. Can be used. Among these, 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 loss in the development process and from the viewpoint of production cost.

  Although it does not specifically limit as a phenol compound, For example, cresols, such as phenol, o-cresol, m-cresol, or p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6 -Xylenols such as xylenol, 3,4-xylenol or 3,5-xylenol, ethylphenols such as o-ethylphenol, m-ethylphenol or p-ethylphenol, isopropylphenol, butylphenol or p-tert-butylphenol Or polyphenols such as resorcin, catechol, hydroquinone, pyrogallol or phloroglucin can be used. These phenol compounds can be used alone or in combination of two or more.

The aldehyde compound is not particularly limited as long as it is an organic group having an aldehyde group. For example, formalin, paraformaldehyde, acetaldehyde, benzaldehyde, or salicylaldehyde can be used. As the benzaldehyde, one substituted with at least one of an alkyl group, an alkoxy group or a hydroxy group, or an unsubstituted one can be used. These aldehyde compounds can be used alone or in combination of two or more.
In this embodiment, the phenol resin which is alkali-soluble resin (A) is obtained by, for example, reacting and synthesizing the phenol compound and the aldehyde compound under an acid catalyst. The acid catalyst is not particularly limited, and for example, oxalic acid, nitric acid, sulfuric acid, diethyl sulfate, acetic acid, p-toluenesulfonic acid, phenolsulfonic acid, or benzenesulfonic acid can be used.

  The dimethanol compound is not particularly limited. For example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4′-biphenyldimethanol, 3,4′-biphenyldimethanol, 3,3 ′ -Dimethanol compounds such as biphenyldimethanol or 2,6-naphthalenediethanol, 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 4,4'-bis (methoxymethyl) Bis (alkoxymethyl) compounds such as biphenyl, 3,4′-bis (methoxymethyl) biphenyl, 3,3′-bis (methoxymethyl) biphenyl or methyl 2,6-naphthalenedicarboxylate, or 1,4-bis ( Chloromethyl) benzene, 1,3-bis (chloromethyl) benzene, 1,4-bis (bromome L) benzene, 1,3-bis (bromomethyl) benzene, 4,4'-bis (chloromethyl) biphenyl, 3,4'-bis (chloromethyl) biphenyl, 3,3'-bis (chloromethyl) biphenyl, Bis (hargenoalkyl) compounds such as 4,4′-bis (bromomethyl) biphenyl, 3,4′-bis (bromomethyl) biphenyl, or 3,3′-bis (bromomethyl) biphenyl can be used. These dimethanol compounds can 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 a 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, and preferably 50% by weight or more and 90% by weight with respect to the entire nonvolatile components of the photosensitive resin composition. The following is more preferable.

((B) Photosensitizer)
The photosensitive resin composition contains a photosensitive agent (B). As the photosensitizer (B), a compound capable of generating an acid by light can be used. For example, a photosensitive diazoquinone compound, an onium salt such as a diaryl iodonium salt, a triaryl sulfonium salt or a sulfonium borate salt, 2-nitrobenzyl ester A compound, an N-iminosulfonate compound, an imidosulfonate compound, a 2,6-bis (trichloromethyl) -1,3,5-triazine compound, or a dihydropyridine compound can be used. Among these, it is particularly preferable to use a photosensitive diazoquinone compound having excellent sensitivity and solvent solubility.

Examples of the photosensitive diazoquinone compound include esters of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid.
When the photosensitive resin composition is a positive type, the photosensitive agent remaining in the relief pattern in the unexposed area is considered to decompose by heat during curing to generate an acid, and the photosensitive agent is also important as a reaction accelerator. Play an important role. As the photosensitive diazoquinone compound having such a role, it is particularly preferable to use an ester of 1,2-naphthoquinone-2-diazido-4-sulfonic acid which is easily decomposed by heat.

  Although content of the photosensitive agent (B) in the photosensitive resin composition is not specifically limited, For example, it 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). It is particularly preferable that the amount is not less than 20 parts by mass. Thereby, it becomes possible to realize a photosensitive resin composition having good patterning performance.

  The photosensitive resin composition contains one or more of additives such as a surfactant, a crosslinking agent, a coupling agent, a dissolution accelerator, an antioxidant, a filler, or a sensitizer, as necessary. May be included.

(solvent)
The photosensitive resin composition can be used by dissolving the above-described components in a solvent and forming a varnish. Examples of such a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether. , Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, and ethyl pyruvate and methyl-3 -Methoxypropionate etc. are mentioned. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

For example, the resin film obtained by curing the photosensitive resin material preferably has a tensile elastic modulus at 23 ° C. of 0.5 GPa or more, and more preferably 1.0 GPa or more. As a result, the mechanical strength of the resin film formed of the photosensitive resin material can be improved, and the reliability of the electronic device including the resin film as a permanent film can be improved.
The tensile elastic modulus at 23 ° C. of the resin film obtained by curing the photosensitive resin material is, for example, that for a resin film obtained by curing the photosensitive resin material in a nitrogen atmosphere at 300 ° C. for 30 minutes. Then, a tensile test (stretching speed: 5 mm / min) is carried out in an atmosphere at 23 ° C., and it can be calculated from the initial gradient of the obtained stress-strain curve.

The resin film obtained by curing the photosensitive resin material, for example, preferably has a tensile elongation at 23 ° C. of 20% or more, more preferably 30% or more. Thereby, about the resin film formed using a photosensitive resin material, the outstanding durability is implement | achieved and a crack, a crack, etc. can be suppressed reliably.
The tensile elongation at 23 ° C. of the resin film obtained by curing the photosensitive resin material is, for example, that for a resin film obtained by curing the photosensitive resin material under a nitrogen atmosphere at 300 ° C. for 30 minutes. Then, a tensile test (stretching speed: 5 mm / min) is performed in an atmosphere at 23 ° C., and the distance can be calculated from the fracture distance and the initial distance using the following formula.
Tensile elongation (%) = (breaking distance−initial distance) / initial distance × 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 material. Thereby, durability etc. can be improved about an electronic device provided with the said resin film as a permanent film.
The iron content with respect to the entire resin film as measured by flameless atomic absorption spectrometry is, for example, 0.005 ppm or more and 80 ppm or less. Thereby, durability and connection reliability can be improved, and the reliability in an electronic device can be improved. From the viewpoint of improving the reliability of the electronic device, the iron content relative to the entire resin film is more preferably 0.01 ppm to 50 ppm, and particularly preferably 0.03 ppm to 30 ppm. Note that the iron present in the resin film contains at least one of nonionic iron or iron ions. From the viewpoint of improving the reliability of the electronic device, it is preferable that both nonionic iron and iron ions are contained in the resin film.
Such a resin film can be realized, for example, by setting the iron content with respect to the entire nonvolatile components of the photosensitive resin material measured by flameless atomic absorption spectrometry within the numerical range described above in the present embodiment.

Next, an example of the electronic device 100 will be described.
An electronic device 100 shown in FIG. 1 is, for example, a semiconductor chip. In this case, for example, a semiconductor package can be obtained by mounting the electronic device 100 on the wiring board via the bumps 52. The electronic device 100 includes a semiconductor substrate provided with a semiconductor element such as a transistor, and a multilayer wiring layer provided on the semiconductor substrate (not shown). An interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer of the multilayer wiring layer. The uppermost layer wiring 34 is made of, for example, Al. Further, a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34. An opening through which the uppermost layer wiring 34 is exposed is provided in a part of the passivation film 32.

A rewiring layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, an insulating layer 44 provided on the insulating layer 42 and the rewiring 46, Have An opening connected to the uppermost layer wiring 34 is formed in the insulating layer 42. The rewiring 46 is formed on the insulating layer 42 and in an opening provided in the insulating layer 42, and is connected to the uppermost layer wiring 34. The insulating layer 44 is provided with an opening connected to the rewiring 46.
In the present embodiment, one or more 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, for example, the passivation film 32, the insulating layer 42, or the insulating layer 44 is formed by patterning by exposing the coating film formed of the photosensitive resin material to ultraviolet rays and performing development, followed by patterning by heating. It is formed.

  Bumps 52 are formed in the openings provided in the insulating layer 44 via, for example, an UBM (Under Bump Metallurgy) layer 50. The electronic device 100 is connected to a wiring board or the like via bumps 52, for example.

  Next, examples of the present invention will be described.

(Synthesis of alkali-soluble resin (A-1))
In a four-necked glass separable flask equipped with a thermometer, stirrer, raw material inlet and dry nitrogen gas inlet tube, 21.43 g (0.083 mol) of diphenyl ether-4,4′-dicarboxylic acid and 1-hydroxy -40,87 g (0.083 mol) of a mixture of dicarboxylic acid derivatives obtained by reacting 22.43 g (0.166 mol) of 1,2,3-benzotriazole monohydrate with hexafluoro- 36.62 g (0.100 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) propane was added, and 296.96 g of N-methyl-2-pyrrolidone was added and dissolved. Then, it was made to react at 75 degreeC for 15 hours using the oil bath. Next, 6.98 g (0.0425 mol) of 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in 34.88 g of N-methyl-2-pyrrolidone was added. The reaction was terminated by stirring for 3 hours.

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

(Synthesis of alkali-soluble resin (A-2))
To a four-necked glass separable flask equipped with a thermometer, stirrer, raw material inlet and dry nitrogen gas inlet tube, 30.0 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane ( 0.082 mol) was added, and 400 ml of acetone was added and dissolved. Next, 12.4 g (0.18 mol) of para-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise over 30 minutes while cooling so that the temperature was less than 20 ° C. to obtain a mixture. After the addition, the temperature of the mixture was heated to 40 ° C. and stirred for 2 hours, and then 30.0 g (0.218 mol) of potassium carbonate was gradually added and further stirred for 2 hours. Heating was stopped and the mixture was further stirred at room temperature for 18 hours. Thereafter, while vigorously stirring the mixture, an aqueous sodium hydroxide solution was gradually added. After the addition, the mixture was heated to 55 ° C. and further stirred for 30 minutes. After completion of the stirring, the mixture was cooled to room temperature, 37% by weight hydrochloric acid aqueous solution and 500 ml of water were added, and the pH of the solution was adjusted to be in the range of 6.0 to 7.0. Next, the obtained precipitate was filtered off, the filtrate was washed with water and dried at 60 to 70 ° C., and bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2 A solid of bis (4-hydroxyphenyl) propane was obtained.

  To 51.0 g of the obtained solid, 316 g of acetone and 158 g of methanol were added and heated to 50 ° C. to be completely dissolved. Thereto, 300 mL of pure water at 50 ° C. was added over 30 minutes and heated to 65 ° C. Thereafter, the crystals which have been slowly cooled to room temperature are filtered, and the crystals are purified by drying at 70 ° C. to obtain bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis. (4-Hydroxyphenyl) propane was obtained.

  Into a 1 L flask, 20 g of the bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane obtained above was placed, and 1.0 g of 5% palladium-carbon catalyst. And 180.4 g of ethyl acetate were added to make a suspension. Hydrogen gas was purged there, and the mixture was shaken for 35 minutes while being heated to 50 to 55 ° C. to carry out a reduction reaction. After completion of the reaction, it was cooled to 35 ° C. and the suspension was purged with nitrogen. After removing the catalyst by filtration, the filtrate was subjected to an evaporator to evaporate the solvent. The obtained product was dried at 90 ° C. to obtain bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane.

  Into a four-necked glass separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, bis-N, N ′-(para-aminobenzoyl) hexafluoro-2, obtained above, 14.5 g (0.024 mol) of 2-bis (4-hydroxyphenyl) propane was added, 40 g of γ-butyrolactone was added and dissolved, and the mixture was cooled to 15 ° C. with stirring. Thereto, 6.8 parts by mass (0.022 mol) of 4,4′-oxydiphthalic anhydride and 12.0 parts by mass of γ-butyrolactone were added and stirred at 20 ° C. for 1.5 hours. Thereafter, the mixture was heated to 50 ° C. and stirred for 3 hours. Then, 5.2 g (0.044 mol) of N, N-dimethylformamide dimethylacetal and 10.0 g of γ-butyrolactone were added, and the mixture was further stirred at 50 ° C. for 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))
In a 4-neck glass round bottom flask equipped with a thermometer, stirrer, raw material inlet and dry nitrogen gas inlet tube, 64.9 g (0.60 mol) of m-cresol, p-cresol 43 under a dry nitrogen stream .3 g (0.40 mol), 30 wt% aqueous formaldehyde solution 65.1 g (formaldehyde 0.65 mol), and oxalic acid dihydrate 0.63 g (0.005 mol) were charged in an oil bath. The polycondensation reaction was carried out at 100 ° C. for 4 hours while immersing and refluxing the reaction solution. Subsequently, after raising the temperature of the oil bath to 200 ° C. over 3 hours, the pressure in the flask was reduced to 50 mmHg or less to remove moisture and volatile matter. 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)
In a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 11.04 g (0.026 mol) of phenol represented by the formula (C-1), 2-Naphthoquinone-2-diazide-4-sulfonyl chloride 18.81 g (0.070 mol) and acetone 170 g were added and stirred for dissolution.
Next, 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 with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After reacting for 3 hours at room temperature, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was further continued for 30 minutes. Subsequently, after filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 ml / 10 ml). Next, the precipitate was collected by filtration, thoroughly washed with water, and then dried under vacuum. This obtained the photosensitive agent (B) represented by the structure of Formula (Q-1).

Example 1
100 parts by weight of an alkali-soluble resin (A-1), 15 parts by weight of a photosensitive agent (B), 5 parts by weight of 1,4-benzenedimethanol as a crosslinking agent, and 3-methacryloxypropyltrimethoxysilane as a coupling agent 5 parts by weight and 0.000013 parts by weight of iron (III) oxide (manufactured by Sigma-Aldrich, average particle size <50 nm) were mixed and dissolved in γ-butyrolactone as a solvent. It filtered with the membrane filter made from PTFE, and obtained the varnish-like photosensitive resin material.

  Iron content with respect to the whole non-volatile component in the obtained photosensitive resin material was 0.10 ppm. In addition, the iron content with respect to the whole non-volatile component of the photosensitive resin material was calculated from the iron content in the varnish-like photosensitive resin material measured by flameless atomic absorption analysis (ZEEnit60, manufactured by Rigaku Corporation). . The same applies to each example and each comparative example.

(Example 2)
100 parts by weight of an alkali-soluble resin (A-1), 15 parts by weight of a photosensitive agent (B), 5 parts by weight of 1,4-benzenedimethanol as a crosslinking agent, and 3-methacryloxypropyltrimethoxysilane as a coupling agent 5 parts by weight and 0.00013 parts by weight of iron (III) oxide (manufactured by Sigma-Aldrich, average particle size <50 nm) were mixed and dissolved in γ-butyrolactone as a solvent, and then the pore size was 0.2 μm. It filtered with the membrane filter made from PTFE, and obtained the varnish-like photosensitive resin material. The iron content with respect to the whole non-volatile component in the obtained photosensitive resin material was 1.04 ppm.

(Example 3)
100 parts by weight of an alkali-soluble resin (A-1), 15 parts by weight of a photosensitive agent (B), 5 parts by weight of 1,4-benzenedimethanol as a crosslinking agent, and 3-methacryloxypropyltrimethoxysilane as a coupling agent After 5 parts by weight and 0.0013 part by weight of iron (III) oxide (manufactured by Sigma-Aldrich, average particle size <50 nm) were mixed and dissolved in γ-butyrolactone as a solvent, the pore diameter was 0.2 μm. It filtered with the membrane filter made from PTFE, and obtained the varnish-like photosensitive resin material. Iron content with respect to the whole non-volatile component in the obtained photosensitive resin material was 10.4 ppm.

(Example 4)
100 parts by weight of alkali-soluble resin (A-2), 15 parts by weight of photosensitizer (B), 5 parts by weight of 1,4-benzenedimethanol as a crosslinking agent, and 3-methacryloxypropyltrimethoxysilane as a coupling agent 5 parts by weight and 0.00013 parts by weight of iron (III) oxide (manufactured by Sigma-Aldrich, average particle size <50 nm) were mixed and dissolved in γ-butyrolactone as a solvent, and then the pore size was 0.2 μm. It filtered with the membrane filter made from PTFE, and obtained the varnish-like photosensitive resin material. The iron content with respect to the whole non-volatile component in the obtained photosensitive resin material was 1.04 ppm.

(Example 5)
80 parts by weight of alkali-soluble resin (A-1), 20 parts by weight of alkali-soluble resin (A-3), 15 parts by weight of photosensitizer (B), and 5 parts by weight of 1,4-benzenedimethanol as a crosslinking agent Γ-butyrolactone as a solvent, 5 parts by weight of 3-methacryloxypropyltrimethoxysilane as a coupling agent and 0.00013 parts by weight of iron (III) oxide (Sigma-Aldrich, average particle size <50 nm) After being mixed and dissolved, it was filtered through a PTFE membrane filter having a pore diameter of 0.2 μm to obtain a varnish-like photosensitive resin material. The iron content with respect to the whole non-volatile component in the obtained photosensitive resin material was 1.04 ppm.

(Comparative Example 1)
100 parts by weight of an alkali-soluble resin (A-1), 15 parts by weight of a photosensitive agent (B), 5 parts by weight of 1,4-benzenedimethanol as a crosslinking agent, and 3-methacryloxypropyltrimethoxysilane as a coupling agent 5 parts by weight were mixed with γ-butyrolactone as a solvent and dissolved, and then filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a varnish-like photosensitive resin material. The iron content with respect to the whole non-volatile component in the obtained photosensitive resin material was 0.002 ppm.

(Comparative Example 2)
100 parts by weight of an alkali-soluble resin (A-1), 15 parts by weight of a photosensitive agent (B), 5 parts by weight of 1,4-benzenedimethanol as a crosslinking agent, and 3-methacryloxypropyltrimethoxysilane as a coupling agent 5 parts by weight and 0.13 part by weight of iron (III) oxide (manufactured by Sigma-Aldrich, average particle size <50 nm) were mixed and dissolved in γ-butyrolactone as a solvent, and then the pore size was 0.2 μm. It filtered with the membrane filter made from PTFE, and obtained the varnish-like photosensitive resin material. Iron content with respect to the whole non-volatile component in the obtained photosensitive resin material was 1040 ppm.

(Appearance evaluation)
About each Example and each comparative example, after apply | coating the obtained photosensitive resin material on an 8-inch silicon wafer using a spin coater, it prebaked at 120 degreeC with a hotplate for 3 minutes, and film thickness of about 7. A 5 μm resin film was obtained. Next, a part of the resin film surface was dissolved by treatment with an aqueous 2.38% tetramethylammonium hydroxide solution at 23 ° C. for 20 seconds. At this time, the presence or absence of a whitened portion on the resin film surface was observed.
This measurement was performed five times for each example and each comparative example. A case where no whitened portion was observed in all of the resin films was marked as ◯, and a case where a whitened portion was observed in one or more resin films was marked as x. The results are shown in Table 1.

(Processability evaluation)
About each Example and each comparative example, after apply | coating the obtained photosensitive resin material on an 8-inch silicon wafer using a spin coater, it prebaked at 120 degreeC with a hotplate for 3 minutes, and film thickness of about 7.5 micrometers A resin film was obtained. Through this resin film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a left pattern and a blank pattern having a width of 0.88 to 50 μm are drawn) is passed through an i-line stepper (Nikon Corporation, NSR-). 4425i) was used for irradiation with varying exposure. Next, a 2.38% tetramethylammonium hydroxide aqueous solution is used as a developing solution, and the developing time is adjusted so that the difference between the film thickness after pre-baking and the film thickness after developing is 1.0 μm, and paddle twice. The exposed portion was dissolved and removed by developing, and then rinsed with pure water for 10 seconds. About the opening part of the pattern formed in the resin film, it observed with the magnification of 200 times of the optical microscope, and confirmed the presence or absence of residue generation. The case where no residue was observed was marked with ◎, the amount where residue was observed but could withstand use was marked with ○, and the case where a residue unbearable was observed was marked with ×. The results are shown in Table 1.

(Tensile modulus)
For each Example and each Comparative Example, a tensile test was performed on a test piece (10 mm × 60 mm × 10 μm thickness) obtained by curing the obtained photosensitive resin material under a nitrogen atmosphere at 300 ° C. for 30 minutes. (Stretching speed: 5 mm / min) was performed in a 23 ° C. atmosphere. The tensile test was performed using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec. Five test pieces were measured, the tensile modulus was calculated from the initial gradient of the obtained stress-strain curve, and the averaged value was taken as the tensile modulus. Table 1 shows the results.

(Tensile elongation)
For each Example and each Comparative Example, a tensile test was performed on a test piece (10 mm × 60 mm × 10 μm thickness) obtained by curing the obtained photosensitive resin material under a nitrogen atmosphere at 300 ° C. for 30 minutes. (Stretching speed: 5 mm / min) was performed in a 23 ° C. atmosphere. The tensile test was performed using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec. Five test pieces were measured, the tensile elongation was calculated from the fractured distance and the initial distance using the following formulas, and the averaged tensile elongation was determined. Table 1 shows the results.
Tensile elongation (%) = (breaking distance−initial distance) / initial distance × 100

As shown in Table 1, in Examples 1 to 5, no whitening layer was observed in the appearance evaluation, and good results were obtained in the workability evaluation. Moreover, Examples 1-5 have the tensile elongation rate of 20% or more, and it turns out that sufficient durability is implement | achieved. Furthermore, Examples 1-5 were 0.5 GPa or more also about the tensile elasticity modulus, and showed sufficient value.
Hereinafter, examples of the reference form will be added.
1. A photosensitive resin material used to form a permanent film,
The photosensitive resin material whose iron content with respect to the whole non-volatile component measured by flameless atomic absorption spectrometry is 0.005 ppm or more and 80 ppm or less.
2.1. In the photosensitive resin material described in
A photosensitive resin material containing nonionic iron as the iron.
3.1. Or 2. In the photosensitive resin material described in
A photosensitive resin material containing no particles having a particle diameter of 0.2 μm or more as the iron.
4.1. ~ 3. In the photosensitive resin material according to any one of the above,
The photosensitive resin material whose tensile elasticity modulus in 23 degreeC of the resin film obtained by hardening | curing the said photosensitive resin material is 0.5 GPa or more.
5.1. ~ 4. In the photosensitive resin material described in
An alkali-soluble resin (A);
A photosensitive agent (B);
A photosensitive resin material containing.
6.5. In the photosensitive resin material described in
The alkali-soluble resin (A) is a photosensitive resin material containing a precursor having an amide bond having a repeating unit represented by the formula (1).
7.5. In the photosensitive resin material described in
The alkali-soluble resin (A) is a photosensitive resin material containing at least one of polyimide or a polyimide precursor.
8.5. In the photosensitive resin material described in
The alkali-soluble resin (A) is a photosensitive resin material containing a phenol resin obtained by reacting a phenol compound and an aldehyde compound.
9.1. ~ 8. In the photosensitive resin material according to any one of the above,
The permanent film is a photosensitive resin material that is an interlayer film, a surface protective film, or a dam material.
10.1. ~ 9. A resin film obtained by curing the photosensitive resin material according to any one of the items.
11. A resin film constituting a permanent film and having an iron content measured by flameless atomic absorption spectrometry of 0.005 ppm or more and 80 ppm or less.

100 Electronic Device 30 Interlayer Insulating Film 32 Passivation Film 34 Top Layer Wiring 40 Rewiring Layers 42, 44 Insulating Layer 46 Rewiring 50 UBM Layer 52 Bump

Claims (7)

A photosensitive resin material used to form a permanent film,
Measured by flameless atomic absorption spectrometry, the content of iron to total nonvolatiles state, and are more 80ppm or less 0.005 ppm,
As the iron, non-ionic iron is included,
An alkali-soluble resin (A) and a photosensitive diazoquinone compound,
The alkali-soluble resin (A) is a photosensitive resin material containing a precursor having an amide bond having a repeating unit represented by the following formula (1) .

(In the formula (1), X and Y are organic groups. R ₁ is a hydroxyl group, —O—R ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group. good .R ₂ be different even include a hydroxyl group, a carboxyl group, _{-O-R 3} or a _{-COO-R 3,,} respectively may be identical or different if more than having .R ₁ and _{R 3} in _{R 2,} when no hydroxyl group is, if at least one of _{R 2} is not a carboxyl group as the .R ₂ is a carboxyl group as .R ₁ is an organic group having 1 to 15 carbon atoms, R _At least one of 1 is a hydroxyl group, m is an integer of 0 to 8, and n is an integer of 0 to 8) A photosensitive resin material used to form a permanent film,
The content of iron with respect to the entire nonvolatile component, as measured by flameless atomic absorption spectrometry, is 0.005 ppm or more and 80 ppm or less,
As the iron, non-ionic iron is included,
An alkali-soluble resin (A) and a photosensitive diazoquinone compound,
The alkali-soluble resin (A) is a photosensitive resin material containing at least one of polyimide or a polyimide precursor . In the photosensitive resin material of Claim 1 or 2,
A photosensitive resin material containing no particles having a particle diameter of 0.2 μm or more as the iron. In the photosensitive resin material as described in any one of Claims 1-3,
The photosensitive resin material whose tensile elasticity modulus in 23 degreeC of the resin film obtained by hardening | curing the said photosensitive resin material is 0.5 GPa or more. In the photosensitive resin material as described in any one of Claims 1-4 ,
The permanent film is a photosensitive resin material that is an interlayer film, a surface protective film, or a dam material. The resin film obtained by hardening the photosensitive resin material as described in any one of Claims 1-5 . Constitute a permanent film, and the content of iron is measured by flameless atomic absorption spectrometry is Ri 80ppm der less than 0.005 ppm,
As the iron, non-ionic iron is included,
A resin film obtained by curing a photosensitive resin material containing an alkali-soluble resin (A) containing a precursor having an amide bond having a repeating unit represented by the following formula (1) and a photosensitive diazoquinone compound .

(In the formula (1), X and Y are organic groups. R ₁ is a hydroxyl group, —O—R ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group. good .R ₂ be different even include a hydroxyl group, a carboxyl group, _{-O-R 3} or a _{-COO-R 3,,} respectively may be identical or different if more than having .R ₁ and _{R 3} in _{R 2,} when no hydroxyl group is, if at least one of _{R 2} is not a carboxyl group as the .R ₂ is a carboxyl group as .R ₁ is an organic group having 1 to 15 carbon atoms, R _At least one of 1 is a hydroxyl group, m is an integer of 0 to 8, and n is an integer of 0 to 8)

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