JP6984322B2 - Photopolymerizable monomer, photosensitive resin composition using it, and cured film of photosensitive resin composition - Google Patents

Description

The present invention relates to a novel photopolymerizable monomer, a photosensitive resin composition using the same, and a cured film of the photosensitive resin composition. More specifically, a surface protective film for a semiconductor element, an insulating film for rewiring, an interlayer insulating film for a thin film transistor, an insulating film for an organic electroluminescence (hereinafter referred to as EL) element, and a display device drive using an organic EL element. Suitable for applications such as thin film transistor (hereinafter referred to as TFT) substrate flattening film, circuit board wiring protection insulating film, on-chip microlenses of solid-state imaging devices, and flattening films for various displays and solid-state imaging devices. The present invention relates to a photosensitive resin composition and a cured film of the photosensitive resin composition.

Resins typified by polyimide and polybenzoxazole have excellent mechanical properties, heat resistance, electrical insulation, chemical resistance, etc., and thus surface protective films for semiconductor devices, insulating films for rewiring, and interlayer insulation of thin film transistors. It is used as a film, an insulating layer of an organic EL element, a flattening film of a TFT substrate, and the like. Further, photosensitive polyimides imparted with photosensitivity and photosensitive polybenzoxazoles have been put into practical use in order to improve productivity.

In recent years, a pattern exposure technique based on a laser direct imaging (LDI) method has attracted attention. Unlike conventional exposure machines such as i-line steppers and aligners, the LDI method is a process-saving process that does not require a photomask, and can achieve high throughput and low cost. Further, since it is possible to align each substrate one by one, it is also suitable for patterning that requires high position accuracy. Therefore, the application of the LDI method using a high-resolution, high-power laser to photosensitive polyimide and photosensitive polybenzoxazole is also being studied for applications such as surface protective films for semiconductor devices and insulating films for rewiring.

Japanese Unexamined Patent Publication No. 2009-9107 International Publication No. 2014/0544555 Japanese Unexamined Patent Publication No. 2015-187750 Japanese Unexamined Patent Publication No. 2016-122178

However, patterning of photosensitive resin with a high-resolution, high-power laser has a problem of difficulty in patterning due to irradiation with a very high-power laser as compared with conventional i-line steppers and aligners. ..

A new problem derived from a high-power laser is, for example, in a positive photosensitive resin composition, a naphthoquinone diazide-based compound, which is a photosensitive agent, is decomposed during irradiation with a high-power laser, and the nitrogen gas generated by the decomposition decomposes the exposed portion. There is a problem that it easily foams and patterning becomes difficult. On the other hand, since the negative photosensitive resin composition contains a photopolymerizable monomer and a photopolymerization initiator instead of a naphthoquinone diazide-based compound, foaming during high-power laser irradiation is not observed. However, there are problems such as deterioration of the film characteristics of the cured film presumed to be caused by decomposition of the photopolymerizable monomer, deterioration of in-plane uniformity due to a significant increase in the reduction of the developing film, and difficulty in forming a thick film. Therefore, a negative photosensitive resin composition that does not foam during high-power laser irradiation, has a high residual film ratio after development, and exhibits good film characteristics after thermosetting, and further exhibits those characteristics. A novel photopolymerizable monomer for this is needed.

Examples of the negative photosensitive resin composition include a photosensitive resin composition containing a polyimide resin, a photopolymerizable monomer, a photopolymerization initiator, and a thermal cross-linking agent (Patent Document 1), and N-alkoxymethyl (meth) acrylamide. , A copolymer of a monomer having an alkali-soluble group, a photopolymerizable monomer, a photopolymerization initiator, a polymer containing a hydroxy group, a photosensitive resin composition containing a solvent (Patent Document 2), an ethylenically unsaturated group. Examples thereof include a photopolymerizable monomer having a photopolymerizable monomer, a photosensitive resin composition containing a photopolymerization initiator (Patent Document 3), a polyimide-based resin, and a resin composition containing a photopolymerizable monomer (Patent Document 4). However, there were problems with the decrease in the amount of the developed film and the film characteristics of the cured film.

The present invention is a negative photosensitive resin composition in which the exposed portion does not foam when irradiated with a high-power laser, the residual film ratio after development is high, and good film characteristics are exhibited after thermosetting, and further, those characteristics. It is an object of the present invention to provide a novel photopolymerizable monomer for expressing the above.

In order to solve the above problems, the photopolymerizable monomer and the photosensitive resin composition of the present invention have the following constitutions.
[1] A photopolymerizable monomer having a structure represented by the general formula (1).

(In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ may be the same or different, respectively, and L represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. A divalent aromatic group having one benzene ring, or a single bond, an ether bond, an isopropylidene group, a trifluoroisopropyridene group, a carbonyl group, an amide group, or a sulfonyl group having 2 to 5 benzene rings. Represents a divalent organic group having a structure bonded with. * Mark indicates a bonded portion.)
[2] The photopolymerizable monomer having the structure represented by the general formula (1) is the photopolymerizable monomer having the structure represented by the general formula (2).

(In the general formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may be the same or different, respectively, and may have the same or different hydrogen atoms or 1 to 10 carbon atoms. L and M may be the same or different, respectively. A divalent aromatic group having one benzene ring, or a single bond of 2 to 5 benzene rings. Represents a divalent organic group having a structure bonded by any of an ether bond, an isopropylidene group, a trifluoroisopropyridene group, a carbonyl group, an amide group, and a sulfonyl group. X represents a single bond, an ether bond, and an isopropylidene. Represents an organic group having one or more selected from the group consisting of a group, a trifluoroisopropylidene group, a carbonyl group, an amide group, and a sulfonyl group.)
[3] The photopolymerizable monomer having the structure represented by the general formula (2) is the photopolymerizable monomer having the structure represented by the general formula (3).

(In the general formula (3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ may be the same or different, respectively, and may have the same or different hydrogen atoms or 1 to 10 carbon atoms. X, Y, Z may be the same or different, respectively, from a single bond, an ether bond, an isopropylidene group, a trifluoroisopropyridene group, a carbonyl group, an amide group, and a sulfonyl group. Represents an organic group having one or more selected from the group consisting of.)
[4] A photosensitive resin composition containing a photopolymerizable monomer (A) having a structure represented by the general formula (1), an alkali-soluble resin (B), and a photopolymerization initiator (C).

The present invention is a negative photosensitive resin composition in which the exposed portion does not foam when irradiated with a high-power laser, the residual film ratio after development is high, and good film characteristics are exhibited after thermosetting, and further, those characteristics. A novel photopolymerizable monomer for expressing the above can be obtained.

It is a figure which showed the enlarged cross section of the pad part of the semiconductor device which has a bump. It is a figure which showed the detailed manufacturing method of the semiconductor device which has a bump. It is sectional drawing of the coil part of the thin film inductor of an electronic component.

The present invention is a photopolymerizable monomer having a structure represented by the general formula (1). Further, a photosensitive resin composition containing the same as a component and a cured film of the photosensitive resin composition. This makes it possible to provide a negative photosensitive resin composition having a high residual film ratio after development after exposure with a high-power laser and exhibiting good film characteristics after heat curing. The reason why such an effect can be obtained as compared with the conventional photopolymerizable monomer is presumed as follows.

In the conventional photopolymerizable monomer, the photocrosslinking reaction proceeds in the presence of active species such as radicals generated in the exposure process to polymerize and insolubilize in a developing solution. However, in high-power laser exposure, high-energy irradiation of the exposed part and high heat are generated, so that the decomposition of the photopolymerizable monomer and the resulting lack of photocrosslinking cause a significant increase in the reduction of the developed film and thermosetting. It is probable that the later film characteristics deteriorated.

On the other hand, the photopolymerizable monomer having the structure represented by the general formula (1) of the present invention has an aromatic ring and an imide ring precursor structure, so that it does not decompose even when exposed to a high-power laser, and further, the laser It is presumed that an imide ring is formed by the action of energy and high heat. As described above, the formation of the imide ring in the laser exposed portion and the photocrosslinking of the photopolymerizable group efficiently promote the insolubilization of the exposed portion in the developing solution, improving the residual film ratio after development, and further, the imide ring even after thermal curing. It is considered that good membrane properties derived from the above can be obtained.
<Photopolymerizable monomer having a structure represented by the general formula (1)>
The photopolymerizable monomer is a monomer having an unsaturated double bond in the molecule, and examples thereof include compounds having a carbon-carbon unsaturated bond such as a (meth) acryloyl group, a vinyl group, a styryl group, and a maleimide group. Be done.

The photopolymerizable monomer of the present invention has a structure represented by the general formula (1). A photopolymerizable monomer having a structure represented by the general formula (2) is preferable, and a photopolymerizable monomer having a structure represented by the general formula (3) is more preferable. Having the above structure is preferable in terms of improving the residual film ratio after development and improving the mechanical properties after exposure with a high-power laser.

(In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ may be the same or different, respectively, and L represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. A divalent aromatic group having one benzene ring, or a single bond, an ether bond, an isopropylidene group, a trifluoroisopropyridene group, a carbonyl group, an amide group, or a sulfonyl group having 2 to 5 benzene rings. Represents a divalent organic group having a structure bonded with. * Mark indicates a bonded portion.)

(In the general formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may be the same or different, respectively, and may have the same or different hydrogen atoms or 1 to 10 carbon atoms. L and M may be the same or different, respectively. A divalent aromatic group having one benzene ring, or a single bond of 2 to 5 benzene rings. Represents a divalent organic group having a structure bonded by any of an ether bond, an isopropylidene group, a trifluoroisopropyridene group, a carbonyl group, an amide group, and a sulfonyl group. X represents a single bond, an ether bond, and an isopropylidene. Represents an organic group having one or more selected from the group consisting of a group, a carbonyl group, an amide group, and a sulfonyl group.)

(In the general formula (3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ may be the same or different, respectively, and may have the same or different hydrogen atoms or 1 to 10 carbon atoms. X, Y, Z may be the same or different, respectively, from a single bond, an ether bond, an isopropylidene group, a trifluoroisopropyridene group, a carbonyl group, an amide group, and a sulfonyl group. Represents an organic group having one or more selected from the group consisting of.)
<Method for producing a photopolymerizable monomer having a structure represented by the general formula (1)>
The method for producing the photopolymerizable monomer having the structure represented by the general formula (1) is not particularly limited, but the following method can be adopted.

As a first step, first, an acid anhydride represented by the following general formula (4) is added to a solution in which an aromatic diamine compound is dissolved in the presence of a hydroquinone compound, and the mixture is stirred.

(In the formula, * marks indicate the joint.)
Preferred examples of aromatic diamine compounds used in the production of photopolymerizable monomers are m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diamino. Diphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (4-amino) Phenyl) hexafluoropropane, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 2 , 2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl -4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl , 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) ) Sulphonate, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) Examples thereof include hydroxy) biphenyl, 2,2-bis (4-aminophenyl) hexafluoropropane and the like. Of these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'- Diaminodiphenyl sulfone and 2,2-bis (4-aminophenyl) hexafluoropropane are more preferable in terms of improving mechanical properties.

Preferred examples of the acid anhydride used for producing the photopolymerizable monomer include phthalic acid anhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 3. , 3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride Anhydrous, 4,4'-(hexafluoroisopropyridene) diphthalic acid anhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride and the like can be mentioned. Of these, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'- Benzophenone tetracarboxylic acid dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic acid anhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride is used in terms of improving mechanical properties. More preferred.

As the second step, a compound having a carbon-carbon unsaturated bond having the following structure is added and stirred.

(In the general formula (5), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ may be the same or different, respectively, and may be the same or different, and may be a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Shows.)
Preferred examples of compounds having a carbon-carbon unsaturated bond used in the production of photopolymerizable monomers include diacrylic acid anhydride, methacrylic acid anhydride, acrylate methacrylic acid anhydride, tiglic acid anhydride, angelic acid anhydride, and the like. Examples thereof include bis (3-methyl-2-butenoic acid) anhydride and crotonic acid anhydride. Of these, diacrylic acid anhydride and methacrylic acid anhydride are more preferable in terms of improving the residual film ratio after development after exposure with a high-power laser.

As a third step, the reaction solution is put into a poor solvent such as water, the precipitated solid is filtered off, washed with water and dried to obtain a photopolymerizable monomer represented by the above general formula (1).

Examples of the reaction solvent include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and 1,3-dimethyl-. Examples thereof include 2-imidazolidinone, N, N-dimethylpropylene urea, 3-methoxy-N, N-dimethylpropionamide, and deltavalerolactone. These can be contained alone or in two or more kinds.
The photopolymerizable monomer in the present invention can be identified by using infrared absorption spectroscopy (IR) or a nuclear magnetic resonance apparatus (NMR).

IR is an analytical method that can obtain information on the structure and functional groups of molecules by measuring the absorption spectrum obtained by irradiating a sample with infrared rays, and the most commonly used is Fourier transform infrared spectrophotometric intensity. It is a total (FT-IR). When having an amide group, the absorption spectrum of IR has an absorption band derived from C = O stretching motion near ^{1650 cm -1} and an absorption band derived from NH variable angular vibration near ^{1540 cm -1.} If having a benzene ring, the absorption band and from vibration of a benzene ring skeleton around 1505cm ^-1, an absorption band derived from C-H in-plane bending vibration of the benzene ring in the vicinity of 1015cm ^-1, 900-800cm ^-1 It has an absorption band in the vicinity due to the CH out-of-plane oscillation of the benzene ring. When it has an unsaturated double bond group, it has an absorption band derived from C = C stretching vibration near ^{1620 cm -1} and an absorption band derived from CH stretching vibration at ^{3100-3000 cm -1.} When it has an ether bond, it has an absorption band derived from C- ^{OC expansion and contraction vibration near 1235 cm-1.} If a carboxyl group, the absorption band derived from the O-H stretching vibration in 3500-2500cm-1 and an absorption band derived from C = O stretching vibration in the vicinity of 1720 cm ^-1, around 1410cm ^-1 C-O-H It has an absorption band derived from variable-angle vibration.

NMR is generated when a sample is placed in a strong magnetic field, a molecule with the same direction of nuclear spin is irradiated with a pulsed radio wave, and nuclear magnetic resonance is performed, and then the molecule returns to its original stable state. This is an analysis method that detects a signal and analyzes the molecular structure and the like. ^{The 1} H-NMR spectrum is most often used in NMR analysis, from the chemical shift of the peak to the environment in which the hydrogen atom is located, from the integrated value to the number of hydrogen atoms, and from the splitting of the peak to the adjacent protons. Information on the molecular structure, such as effects, can be obtained. As an example showing a characteristic chemical shift, the chemical shift of hydrogen bound to the allyl carbon is 1.5-2 ppm, the chemical shift of the hydrogen atom bound to the alkene is 4.5-6 ppm, and the chemical shift to the aromatic ring is hydrogen. The chemical shift of the atom peaks at 6-9 ppm, and the chemical shift of the hydrogen bonded to the amide group peaks at 5-11 ppm.

The photosensitive resin composition using the photopolymerizable monomer (A) of the present invention will be described.

The photosensitive resin composition is a resin composition that undergoes a chemical or structural change by irradiation with light, and the solubility in a developing solution such as an organic solvent or an alkaline aqueous solution changes. When it has positive photosensitivity, the solubility of the light-irradiated portion in the developing solution is increased, and the light-irradiated portion is dissolved to obtain a positive-type relief pattern. When the photosensitivity is negative, the light-irradiated portion is insoluble in the developing solution, and a negative relief pattern can be obtained.

The photosensitive resin composition of the present invention contains a photopolymerizable monomer (A) having a structure represented by the above general formula (1), an alkali-soluble resin (B), and a photopolymerization initiator (C). do.

In the photosensitive resin composition of the present invention, the photopolymerizable monomer (A) having the structure represented by the general formula (1) is preferably the photopolymerizable monomer having the structure represented by the general formula (2). It is a photopolymerizable monomer having a structure represented by the general formula (3). Having the above structure is preferable in terms of improving the residual film ratio after development and improving the mechanical properties after exposure with a high-power laser.

In the photosensitive resin composition of the present invention, the content of the photopolymerizable monomer (A) having the structure represented by the general formula (1) is 10 parts by mass with respect to 100 parts by mass of the total amount of the alkali-soluble resin (B). It is preferably parts to 70 parts by mass. When it is 10 parts by mass or more, it is preferable in terms of improving the residual film ratio after development at the time of high-power laser exposure, and more preferably 15 parts by mass or more. When it is 70 parts by mass or less, it is preferable in that excellent film characteristics such as mechanical properties can be obtained, and more preferably 60 parts by mass or less.

The photosensitive resin composition of the present invention has two ethylenically unsaturated bonds as the photopolymerizable monomer (D) other than the photopolymerizable monomer (A) having the structure represented by the general formula (1). The monomer having the above may be contained. Examples of the monomer having two or more ethylenically unsaturated bonds include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate tetraethylene glycol diacrylate, and tetraethylene. Glycoldimethacrylate, trimethylolpropanediacrylate, trimethylolpropanetriacrylate, trimethylolpropanedimethacrylate, trimethylolpropanetrimethacrylate, 1,3-butanediol diacrylate, 1,3-butanedioldimethacrylate, neopentyl glycol di. Acrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10 -Decandiol dimethacrylate, dimethylol-tricyclodecanediacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,3- Diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy-2-hydroxypropane, N, N-methylenebisacrylamide, "Blemmer" (registered trademark) PDBE-250 (trade name, manufactured by Nichiyu Co., Ltd.) , BP-6EM (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), AH-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), AT-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), UA-306H (product name) Name, Kyoeisha Chemical Co., Ltd.), UA-306T (trade name, Kyoeisha Chemical Co., Ltd.), Light Acrylate DCP-A (trade name, Eisha Chemical Co., Ltd.), Ethylene oxide-modified bisphenol A diacrylate, Examples thereof include ethylene oxide-modified bisphenol A dimethacrylate. These can be contained alone or in combination of two or more.

The alkali-soluble resin (B) is a resin having an acidic group, and examples thereof include a resin having an acidic group such as a hydroxyl group, a carboxyl group, and a sulfonic acid group. The alkali-soluble resin (B) preferably contains one or more resins selected from the group consisting of a polyimide precursor, a polyamide-imide, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. These resins can be heated or catalyzed to become polymers with an imide ring, an oxazole ring, or other cyclic structure. More preferably, a polyimide having a closed ring, a polyamic acid or polyamic acid ester of a polyimide precursor, and a polyhydroxyamide of a polybenzoxazole precursor can be mentioned. The annular structure dramatically improves heat resistance and chemical resistance. Examples of the resin other than the polyimide precursor, polyamideimide, polyimide, polybenzoxazole precursor, and polybenzoxazole include radical polymerizable resins having acrylic acid, phenol-novolak resin, polyhydroxystyrene, polysiloxane, and the like. .. Further, the acidic groups of these resins may be protected to adjust the alkali solubility. Such an alkali-soluble resin is dissolved in an alkaline aqueous solution such as choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, and sodium carbonate, in addition to tetramethylammonium hydroxide. Two or more of these alkali-soluble resins may be contained, but the proportion of the total alkali-soluble resin other than the polyimide precursor, polyamideimide, polyimide, polybenzoxazole precursor, and polybenzoxazole is 70% by mass or less. It is preferable that a resin film having excellent film properties can be obtained after heat curing.

The polyimide can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, a tetracarboxylic acid diester dichloride, etc. with a diamine, a corresponding diisocyanate compound, a trimethylsilylated diamine, etc., and a tetracarboxylic acid residue. And has a diamine residue. For example, it can be obtained by dehydrating and closing the ring of polyamic acid, which is one of the polyimide precursors obtained by reacting tetracarboxylic dianhydride with diamine, by heat treatment. During this heat treatment, a solvent that azeotropes with water such as m-xylene can also be added. Alternatively, it can also be obtained by adding a dehydration condensing agent such as carboxylic acid anhydride or dicyclohexylcarbodiimide or a base such as triethylamine as a ring-closing catalyst and dehydrating and ring-closing by chemical heat treatment. Alternatively, it can also be obtained by adding a weakly acidic carboxylic acid compound and dehydrating and ring-closing by heat treatment at a low temperature of 100 ° C. or lower.

Polybenzoxazole can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester, or the like, and has a dicarboxylic acid residue and a bisaminophenol residue. For example, it can be obtained by dehydrating and closing the ring of polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting a bisaminophenol compound with a dicarboxylic acid, by heat treatment. Alternatively, it can be obtained by adding anhydrous phosphoric acid, a base, a carbodiimide compound, or the like and dehydrating and closing the ring by chemical treatment.

In the photosensitive resin composition of the present invention, the polyimide is added to the tetracarboxylic acid residue and / or the diamine residue as OR ²⁷ , SO ₃ R ²⁷ , CONR ²⁷ R ²⁸ , COOR ²⁷ , from the viewpoint of solubility in an alkaline aqueous solution. It is preferable to have an acidic group or an acidic group derivative represented by SO ₂ NR ²⁷ R ^{28 or the like, and it is more preferable to have a hydroxyl group.} Here, R ²⁷ and R ²⁸ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The acidic group ^{indicates a case where R 27} and R ²⁸ are all hydrogen atoms, and the acidic group derivative indicates a case where R ²⁷ and R ²⁸ contain a monovalent organic group having 1 to 20 carbon atoms. Examples of the organic group include an alkyl group, an alkoxyl group and an ester group.

In addition, polybenzoxazole is an acidic group or acidic group represented ^{by OR 29} , SO ₃ R ²⁹ , CONR ²⁹ R ³⁰ , COOR ²⁹ , SO ₂ NR ²⁹ R ^{30 and the} like on dicarboxylic acid residues and / or bisaminophenol residues. It is preferable to have a group derivative, and more preferably to have a hydroxyl group. Here, R ²⁹ and R ³⁰ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The acidic group ^{indicates a case where all of R 29} and R ³⁰ are hydrogen atoms, and the acidic group derivative indicates a case where R ²⁹ or R ³⁰ contains a monovalent organic group having 1 to 20 carbon atoms. Examples of the organic group include an alkyl group, an alkoxyl group and an ester group.

In the photosensitive resin composition of the present invention, the preferred structures of the tetracarboxylic acid residue of polyimide and the dicarboxylic acid residue of polybenzoxazole (hereinafter, these are collectively referred to as acid residue) are the structures shown below and these. In the structure of, a part of the hydrogen atom is replaced with an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group, a cyano group, a fluorine atom, or a chlorine atom. Can be mentioned.

Wherein, J is a direct _{bond, -COO -, - CONH -,} - CH 2 -, - C 2 H 4 -, - O -, - C 3 H 6 -, - C 3 F 6 -, - SO 2 - _{, -S -, - Si (CH} 3) 2 -, - OSi (CH 3) 2 -O -, - C 6 H 4 -, - C 6 H 4 -O-C 6 H 4 -, - C 6 H _{4 -C 3 H 6 -C 6 H} 4 -, or _{-C 6 H 4 -C 3 F 6} -C 6 H 4 - represents any.

In the photosensitive resin composition of the present invention, the preferred structures of the diamine residue of polyimide and the bisaminophenol residue of polybenzoxazole (hereinafter, these are collectively referred to as diamine residue) are the structures shown below and these. Examples of the structure include a structure in which a part of hydrogen atoms in the structure is substituted with 1 to 4 alkyl groups having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group, a cyano group, a fluorine atom, or a chlorine atom. Be done.

Wherein, J is a direct _{bond, -COO -, - CONH -,} - CH 2 -, - C 2 H 4 -, - O -, - C 3 H 6 -, - C 3 F 6 -, - SO 2 - _{, -S -, - Si (CH} 3) 2 -, - O-Si (CH 3) 2 -O -, - C 6 H 4 -, - C 6 H 4 -O-C 6 H 4 -, - C _{6 H 4 -C 3 H 6 -C} 6 H 4 -, or _{-C 6 H 4 -C 3 F 6} -C 6 H 4 - indicating either.

In the photosensitive resin composition of the present invention, the polyimide precursor and the polybenzoxazole precursor are resins having an amide bond in the main chain, and are dehydrated and closed by heat treatment or chemical treatment to form the above-mentioned polyimide and polybenzoxazole. Become. The number of repetitions of the structural unit is preferably 10 to 100,000. Examples of the polyimide precursor include polyamic acid, polyamic acid ester, polyamic acid amide, polyisoimide and the like, and polyamic acid and polyamic acid ester are preferable. Examples of the polybenzoxazole precursor include polyhydroxyamide, polyaminoamide, polyamide, polyamideimide and the like, and polyhydroxyamide is preferable.

From the viewpoint of solubility in alkaline aqueous solutions, polyimide precursors and polybenzoxazole precursors have OR ³¹ , SO ₃ R ³¹ , CONR ³¹ R ³² , COOR ³¹ , SO ₂ NR ³¹ R ^{31 in acid residues or diamine residues.} It is preferable to have an acidic group or an acidic group derivative represented by such as, and it is more preferable to have a hydroxyl group. Here, R ³¹ and R ³² each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Here, the acidic group ^{indicates a case where R 31} and R ³² are all hydrogen atoms, and the acidic group derivative indicates a case where R ³¹ or R ³² contains a monovalent organic group having 1 to 20 carbon atoms. .. Examples of the organic group include an alkyl group, an alkoxyl group and an ester group.

Examples of the acid component constituting the acid residue of the polyimide precursor and the polybenzoxazole precursor include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyldicarboxylic acid, and benzophenone. Examples of tricarboxylic acids such as dicarboxylic acid and triphenyldicarboxylic acid include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyltricarboxylic acid and the like, and examples of tetracarboxylic acid include pyromellitic acid, 3,3', 4,4'. -Biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid , 2,2', 3,3'-benzophenone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoro Propane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2, 3-Dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6 , 7-Naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid and other aromatic tetracarboxylic acids, butanetetracarboxylic acid, cyclobutanetetracarboxylic acid Acid, 1,2,3,4-cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo [2.2.1. ] Heptanetetracarboxylic acid, bicyclo [3.3.1. ] Tetracarboxylic acid, bicyclo [3.1.1. ] Hept-2-enetetracarboxylic acid, bicyclo [2.2.2. ] Aliphatic tetracarboxylic acids such as octanetetracarboxylic acid and adamatanetetracarboxylic acid can be mentioned. In addition, some of the hydrogen atoms of the dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid exemplified above are acidic represented by OR ³³ , SO ₃ R ³³ , CONR ³³ R ³⁴ , COOR ³³ , SO ₂ NR ³³ R ^{34, and the} like. It is preferably substituted with a group or an acidic group derivative, and more preferably 1 to 4 with a hydroxyl group, a sulfonic acid group, a sulfonic acid amide group, a sulfonic acid ester group or the like. Here, R ³³ and R ³⁴ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

These acids can be used as is or as acid anhydrides or active esters. Moreover, you may use 2 or more kinds of these.

Further, by using a silicon atom-containing tetracarboxylic acid such as dimethylsilanediphthalic acid or 1,3-bis (phthalic acid) tetramethyldisiloxane, adhesion to a substrate, oxygen plasma used for cleaning, UV ozone, etc. are used. The resistance to processing can be increased. It is preferable to use 1 to 30 mol% of these silicon atom-containing tetracarboxylic dians as the total acid component, and 1 mol% or more is preferable in terms of substrate adhesion and effect on plasma treatment. When it is 30 mol% or less, it is preferable in terms of the solubility of the obtained resin in an alkaline aqueous solution.

Examples of the diamine components constituting the diamine residues of the polyimide precursor and the polybenzoxazole precursor include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and bis (3-amino-4-4). Hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino- Hydroxyl group-containing diamines such as 4-hydroxy) biphenyl and bis (3-amino-4-hydroxyphenyl) fluorene, carboxyl group-containing diamines such as 3,5-diaminobenzoic acid and 3-carboxy-4,4'-diaminodiphenyl ether. , 3-sulfonic acid-4,4'-diaminodiphenyl ether and other sulfonic acid-containing diamines, dithiohydroxyphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4 , 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-Aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) Sulfur, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2, 2', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) ) -4,4'-Diaminobiphenyl, compounds in which some of the hydrogen atoms of these aromatic rings are replaced with alkyl groups or halogen atoms such as F, Cl, Br, I, cyclohexyldiamine, methylenebiscyclohexylamine, etc. Fat family biphenyl And so on. Further, in these diamines, a part of the hydrogen atom is an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group, a fluoroalkyl group having 1 to 10 carbon atoms such as a trifluoromethyl group, F, Cl, Br, and the like. It may be replaced with a halogen atom such as I. Further, the diamine exemplified above preferably has an acidic group or an acidic group derivative ^{represented by OR 35} , SO ₃ R ³⁵ , CONR ³⁵ R ³⁶ , COOR ³⁵ , SO ₂ NR ³⁵ R ^{36, and has a hydroxyl group.} Is more preferable. Here, R ³⁵ and R ³⁶ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

These diamines can be used as is or as the corresponding diisocyanate compound, trimethylsilylated diamine. Moreover, you may use 2 or more kinds of these. For applications where heat resistance is required, it is preferable to use 50 mol% or more of the total amount of aromatic diamine.

Further, by using a silicon atom-containing diamine such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane or 1,3-bis (4-anilino) tetramethyldisiloxane as the diamine component, adhesion to the substrate is performed. It is possible to improve the properties and resistance to oxygen plasma and UV ozone treatment used for cleaning and the like. These silicon atom-containing diamines are preferably used in an amount of 1 to 30 mol% of the total diamine component, and more than 1 mol% is preferable in that the adhesiveness can be improved and the resistance to plasma treatment can be enhanced. When it is 30 mol% or less, it is preferable in terms of the solubility of the obtained resin in an alkaline aqueous solution.

Further, it is preferable to seal the ends of polyimide, polybenzoxazole, and their precursors with a monoamine having a hydroxyl group, a carboxyl group, a sulfonic acid group or a thiol group, an acid anhydride, a monocarboxylic acid, and an acid chloride. Two or more of these may be used. By having the above-mentioned group at the resin terminal, the dissolution rate of the resin in an alkaline aqueous solution can be easily adjusted within a preferable range.

Preferred examples of monoamines are 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-amino. Naphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy -6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3- Aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino- 4,6-Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-amino-4-tert-butylphenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Can be mentioned.

Preferred examples of acid anhydrides, monocarboxylic acids and acid chlorides include phthalic acid anhydrides, maleic anhydrides, nadic acid anhydrides, cyclohexanedicarboxylic acid anhydrides, acid anhydrides such as 3-hydroxyphthalic acid anhydrides, 3-. Carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto Monocarboxylic acids such as -7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and their carboxyl groups are acid chlorides. Monoic acid chloride compound, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxylene Reaction of monoacid chloride compounds, monoacid chloride compounds, in which only one carboxyl group of dicarboxylic acids such as naphthalene is acid chloride, with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide. The active ester compound obtained by the above can be mentioned.

The content of monoamine, acid anhydride, monocarboxylic acid, and acid chloride used as the above-mentioned terminal encapsulant is preferably in the range of 0.1 to 60 mol% of the number of moles of the acid component monomer or diamine component monomer charged. , 5-50 mol% is more preferred. Within such a range, it is possible to obtain a photosensitive resin composition having an appropriate viscosity of the solution when the photosensitive resin composition is applied and having excellent film physical characteristics.

The terminal sealant introduced into the alkali-soluble resin (B) can be easily detected by the following method. For example, the resin into which the terminal encapsulant has been introduced is dissolved in an acidic solution, decomposed into a diamine component and an acid component, which are the constituent units of the resin, and this is measured by gas chromatography (GC) or NMR. The encapsulant can be easily detected. Apart from this, it is also possible to directly detect the resin into which the terminal encapsulant has been introduced by directly ^{measuring the pyrolysis gas chromatograph (PGC), the infrared spectrum and the 13} C-NMR spectrum.

In the present invention, the content of the alkali-soluble resin (B) is preferably 40 parts by mass to 80 parts by mass, where 100 parts by mass is the total amount of the photosensitive resin composition excluding the solvent. When it is 40 parts by mass or more, it is preferable in that excellent film characteristics such as mechanical properties derived from the alkali-soluble resin (B) can be obtained, and more preferably 45 parts by mass or more. When it is 80 parts by mass or less, it is preferable from the viewpoint of improving the sensitivity at the time of high-power laser exposure, and more preferably 75 parts by mass or less.

The photosensitive resin composition of the present invention contains a photopolymerization initiator (C).

The photopolymerization initiator is a compound that generates active species such as radicals when irradiated with light. By containing the photopolymerization initiator (C) and the photopolymerizable monomer (A), the active radicals generated in the light-irradiated portion promote the radical polymerization of the photopolymerizable monomer (A), and the light-irradiated portion becomes insoluble. A negative relief pattern can be obtained.

Examples of the photopolymerization initiator (C) include the following.

Benzophenones such as benzophenone, Michler's ketone, 4,4, -bis (diethylamino) benzophenone, 3,3,4,4,-tetra (t-butylperoxycarbonyl) benzophenone.

Benzylidenes such as 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidin and 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidin.

7-diethylamino-3-tenonylcoumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1-methylbenzoimidazolyl) coumarin, 3 -(2-Benzothiozolyl) -7-coumarins such as diethylaminocoumarin.

Anthraquinones such as 2-t-butyl anthraquinone, 2-ethyl anthraquinone, and 1,2-benz anthraquinone.

Benzoins such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

Mercaptos such as ethylene glycol di (3-mercaptopropionate), 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole.

Glycines such as N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- (p-chlorophenyl) glycine, N- (4-cyanophenyl) glycine.

1-Phenyl-1,2-butandion-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o (methoxycarbonyl) oxime, 1-phenyl-1,2-propane Dione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, bis (A-isonitrosopropiophenone oxime) isophthal, "IRGACURE" (registered) Trademark) OXE-01 (trade name, manufactured by BASF Japan Co., Ltd.), "IRGACURE" (registered trademark) OXE-02 (trade name, manufactured by BASF Japan Co., Ltd.), NCI-831 (trade name, manufactured by ADEKA Co., Ltd.) ) And other oximes.

2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-2-methyl-1 [4- (methylthio) phenyl] -2-moriphorinopropane-1-one, "IRGACURE" ”(Registered Trademark) 907 (trade name, manufactured by BASF Japan Ltd.), α-aminoalkylphenones, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl Biimidazole etc.

Of these, those having the above-mentioned oxime-type structure are preferable in terms of improving the residual film ratio after development, and more preferable ones are 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime. 1-Phenyl-1,2-propanedione-2- (o-benzoyl) oxime, bis (A-isonitrosopropiophenone oxime) isophthal, "IRGACURE" (registered trademark) OXE-01 (trade name, BASF Japan) (Manufactured by Co., Ltd.), "IRGACURE" (registered trademark) OXE-02 (trade name, manufactured by BASF Japan Co., Ltd.), NCI-831 (trade name, manufactured by ADEKA Co., Ltd.). These can be contained alone or in combination of two or more.

The content of the photopolymerization initiator (C) is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the total amount of the alkali-soluble resin (B). When it is 2 parts by mass or more, sufficient radicals are generated by light irradiation at the time of exposure and the photocrosslinking reaction proceeds, and the residual film ratio after development is improved. When it is 10 parts by mass or less, it is preferable at the time of exposure. The irradiated light is transmitted from the surface to the bottom of the coating film, the photocrosslinking reaction proceeds in the entire coating film, and the residual film ratio after development is improved.

Further, the photosensitive resin composition of the present invention may contain a thermal cross-linking agent (E). For example, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC (hereinafter, trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as having one thermally crosslinkable group. , PA type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (trade name, Asahi Organic Materials Industry Co., Ltd. DMLMBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, Dimethyrol-Bis-C, Dimethyrol-BisOC -P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (above, trade name, Honshu Kagaku) Industrial Co., Ltd.), "Nicarac" (registered trademark) MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), BA type benzoxazine, Bm type benzoxazine (above, trade name, Shikoku) (Manufactured by Kasei Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. TM-BIP-A (trade name, Asahi Organic Materials Industry Co., Ltd.) as having four such as TriML-P, TriML-35XL, TriML-TrisCR-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) , TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (hereinafter, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), "Nicarac" (registered trademark) MX-280, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, product) as having six such as "Nicarac" (registered trademark) MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.) Names include (manufactured by Honshu Chemical Industry Co., Ltd.), “Nicarac” (registered trademark) MW-390, and “Nicarac” (registered trademark) MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).

The structure of the heat-crosslinking agent (E) particularly preferably used in the photosensitive resin composition of the present invention is shown below.

These thermal cross-linking agents (E) can be contained alone or in combination of two or more.

The content of the heat-crosslinking agent (E) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 3 parts by mass or more, based on 100 parts by mass of the total amount of the alkali-soluble resin (B). It is particularly preferably 5 parts by mass or more, preferably 150 parts by mass or less, and more preferably 130 parts by mass or less. By setting the content of the heat-crosslinking agent (E) to 150 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (B), the thermal decomposition temperature of the cured film obtained by thermally curing the resin composition coating can be improved. can. On the other hand, when the content is 0.5 parts by mass or more, the heat resistance of the resin composition coating is improved due to the effect of increasing the molecular weight by crosslinking.

In addition, for the purpose of adjusting the alkali developability of the photosensitive resin composition of the present invention, a compound having a phenolic hydroxyl group can be contained.

Examples of the compound having a phenolic hydroxyl group that can be used in the photosensitive resin composition of the present invention include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, and BisOCHP. -Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakiss P-DO-BPA), TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP -OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR- Examples thereof include PTBP, BIRC-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, and TEP-BIP-A (hereinafter, trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.).

Among these, compounds having a preferable phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-. BIPC-F. By containing this compound having a phenolic hydroxyl group, the obtained negative photosensitive resin composition has improved solubility in an alkaline developer in an unexposed area, and the development contrast due to the difference in solubility with the exposed area. It is preferable in terms of improvement.

The content of the compound having a phenolic hydroxyl group is preferably 1 to 60 parts by mass, and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the total amount of the alkali-soluble resin (B).

The photosensitive resin composition of the present invention may contain an adhesion improver. Examples of the adhesion improver include an alkoxysilane-containing compound and the like. Two or more of these may be contained. By containing these compounds, the adhesiveness between the cured film and the substrate can be improved.

Specific examples of the alkoxysilane-containing compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, and N-phenylamino. Butyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane , 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxy Examples thereof include silane, 3-aminopropyltriethoxysilane, vinyltricrolsilane, and vinyltris (β-methoxyethoxy) silane.

The total content of the adhesion improver is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (B). The amount of 0.01 parts by mass or more is preferable in that the adhesiveness between the cured film and the substrate can be improved. When the amount is 15 parts by mass or less, the adhesiveness is improved without deteriorating the alkali developability due to excessive adhesion, which is preferable.

The photosensitive resin composition of the present invention may contain a surfactant, whereby the wettability with the substrate can be improved.

As surfactants, "FLOURAD" (registered trademark) (manufactured by 3M Japan Co., Ltd.), "Megafuck" (registered trademark) (manufactured by DIC Co., Ltd.), "Surflon" (registered trademark) (Asahi Glass Co., Ltd.) Fluorosurfactants such as KP341 (trade name, manufactured by Shinetsu Chemical Industry Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.), Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), " Organic siloxane surfactants such as "BYK" (registered trademark) (manufactured by BIC Chemie Co., Ltd.), acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), etc. are mentioned. Available from.

In the photosensitive resin composition of the present invention, each component (A) to (C), (D) other photopolymerizable monomers, a heat-crosslinking agent (E), a compound having a phenolic hydroxyl group, an adhesion improver and a surfactant. The activator is preferably contained in a state of being dissolved or dispersed in an organic solvent. The organic solvent preferably contains a solvent having a boiling point of 80 ° C. to 250 ° C. under atmospheric pressure.

Specific examples of the organic solvent that can be preferably contained in the photosensitive resin composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ale, propylene glycol monoethyl ether, and ethylene glycol dimethyl ether. Ethers such as ethylene glycol diethyl ether and ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Acetates such as acetate, methyl lactate, ethyl lactate, butyl lactate, ketones such as acetylacetone, methylpropylketone, methylbutylketone, methylisobutylketone, cyclopentanone, 2-heptanone, butyl alcohol, isobutylalcohol, pentanol, Alcohols such as 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, N-methyl-2 -Pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylpropylene Examples include urea, 3-methoxy-N, N-dimethylpropionamide, deltavalerolactone and the like. These can be contained alone or in two or more kinds.

Among these, the photopolymerizable monomer (A) having the structure represented by the general formula (1), the alkali-soluble resin (B), and the photopolymerization initiator (C) are dissolved, and the boiling point under atmospheric pressure is high. Those having a temperature of 100 ° C to 210 ° C are particularly preferable. When the boiling point is within this range, excessive volatilization of the organic solvent is suppressed when the photosensitive resin composition is applied, the coatability is improved, and the drying temperature of the photosensitive resin composition does not have to be raised. There are no restrictions on the material of the substrate. Further, by using a photopolymerizable monomer (A) having a structure represented by the general formula (1), an alkali-soluble resin (B), and an organic solvent that dissolves the photopolymerization initiator (C), a base substrate is used. It is possible to form a coating film having good uniformity.

Specific preferred organic solvents having such a boiling point include cyclopentanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, methyl lactate, ethyl lactate, diacetone alcohol, and 3-methyl. Examples thereof include -3-methoxybutanol, gamma butyrolactone and N-methyl-2-pyrrolidone.

The organic solvent that can be contained in the photosensitive resin composition of the present invention is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, based on 100 parts by mass of the total amount of the alkali-soluble resin (B). Yes, preferably 800 parts by mass or less, more preferably 500 parts by mass or less.

Next, a method for producing the photosensitive resin composition of the present invention will be described. For example, a photopolymerizable monomer (A) having a structure represented by the general formula (1), an alkali-soluble resin (B), a photopolymerization initiator (C), and if necessary, a component (D) and (E). A photosensitive resin composition can be obtained by dissolving the components and the like. Examples of the melting method include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, and is usually 20 ° C to 80 ° C. Further, the dissolution order of each component is not particularly limited, and for example, there is a method of sequentially dissolving compounds having low solubility. In addition, for components that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, by dissolving other components and then adding them last, the other components are poorly dissolved due to the generation of bubbles. Can be prevented.

It is preferable that the obtained photosensitive resin composition is filtered using a filtration filter to remove dust and particles. The filter hole diameter is, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.03 μm, 0.02 μm, 0.01 μm, 0.005 μm, and the like, but is not limited thereto. The material of the filtration filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE) and the like, but PE and NY are preferable.

Next, a method for producing a cured film using the photosensitive resin composition of the present invention will be described with reference to an example.

First, the photosensitive resin composition is applied onto the substrate. As the substrate, silicon wafers, ceramics, gallium arsenide and the like are used, but the substrate is not limited thereto. The substrate may be pretreated with a chemical solution such as a silane coupling agent or a titanium chelating agent. For example, a solution obtained by dissolving the above-mentioned coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate in an amount of 0.5 to 20% by mass. Surface treatment by spin coating, dipping, spray coating, steam treatment, etc. In some cases, the reaction between the substrate and the coupling agent can be allowed to proceed by subsequently applying a temperature of 50 ° C to 300 ° C.

As a method for applying the photosensitive resin composition, there are methods such as rotary coating using a spinner, spray coating, and roll coating. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but it is usually preferable to apply the film so that the film thickness after drying is 1 to 50 μm.

Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive coating film. This process is also called prebaking. Drying is preferably carried out in the range of 70 to 140 ° C. for 1 minute to several hours using an oven, a hot plate, infrared rays or the like. When a hot plate is used, the coating film can be held and heated directly on the plate or on a jig such as a proxy pin installed on the plate. As the material of the proxy pin, there is a metal material such as aluminum or stainless steel, or a synthetic resin such as polyimide resin or "Teflon" (registered trademark), and any material of the proxy pin may be used as long as it has heat resistance. .. The height of the proxy pin varies depending on the size of the substrate, the type of the coating film, the purpose of heating, and the like, but is preferably 0.1 to 10 mm.

Next, the photosensitive coating film is irradiated with chemical rays through a mask having a desired pattern and exposed. Chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, YAG laser (355 nm), mercury lamp i-line (365 nm), h-line (405 nm), g-ray (g-ray). It is preferable to use 436 nm), and more preferably a YAG laser (355 nm). When it has a negative photosensitive property, the exposed portion is cured and insolubilized in a developing solution.

Next, if necessary, a post-exposure baking process is performed. The temperature is preferably in the range of 50 to 150 ° C, and more preferably in the range of 60 to 140 ° C. The time is not particularly limited, but 10 seconds to several hours is preferable from the viewpoint of subsequent developability.

After exposure, in order to form a pattern of the resin film, an unexposed portion is removed using a developing solution. The developing solution is tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl. An aqueous solution of an alkaline compound such as methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine is preferable. In some cases, these alkaline aqueous solutions include polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide, methanol, ethanol, and isopropanol. Alcohols such as, ethyl lactate, esters such as propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added in one or more kinds.

After development, it is common to rinse with water. For the rinsing treatment, one or more kinds of alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate, propylene glycol monomethyl ether acetate and 3-methoxymethyl propanol may be added to water.

After development, the obtained coating film pattern is heated in a temperature range of 160 to 500 ° C. to convert the resin film into a cured film. It is preferable that this heat treatment is carried out for 5 minutes to 5 hours while selecting a temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. Examples include a method of heat-treating at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each, and a method of linearly raising the temperature from room temperature to 220 ° C. over 2 hours.

Next, a method for producing a photosensitive resin sheet using the photosensitive resin composition of the present invention and a method for producing a cured film using the photosensitive resin sheet will be exemplified.

In order to obtain the photosensitive resin composition of the present invention into a photosensitive resin sheet, it is preferable that the photosensitive resin composition is formed on a support and used. As a method of applying the photosensitive resin composition of the present invention to a support film, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure Examples include coaters, screen coaters, and slit die coaters. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but it is usually preferable that the film thickness after drying is 0.5 μm or more and 100 μm or less.

The support is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. The joint surface between the support and the resin sheet may be surface-treated with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like in order to improve adhesion and peelability. The thickness of the support is not particularly limited, but is preferably in the range of 10 to 100 μm from the viewpoint of workability. A photosensitive resin sheet can be obtained by subjecting the photosensitive resin composition applied on the support to a drying step. The drying temperature is preferably 50 ° C. or higher from the viewpoint of drying property, and preferably 150 ° C. or lower from the viewpoint of not impairing the photosensitivity. At this time, the film thickness of the photosensitive resin sheet is preferably 5 μm or more from the viewpoint of step embedding property at the time of laminating, and preferably 150 μm or less from the viewpoint of film thickness uniformity.

Further, the photosensitive resin sheet of the present invention may have a protective film on the film in order to protect the surface. This makes it possible to protect the surface of the photosensitive resin sheet from contaminants such as dust and dust in the atmosphere.

Examples of the protective film include a polyolefin film and a polyester film. The protective film preferably has a low adhesive force with the photosensitive resin sheet.

Next, a method for producing a cured film using a photosensitive resin sheet will be described with reference to an example.

When using a photosensitive resin sheet, the photosensitive resin sheet is attached to the substrate. Examples of the substrate include, but are not limited to, glass substrates, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and those on which circuit constituent materials are arranged. .. Examples of organic circuit boards include glass substrate copper-clad laminates such as glass cloth and epoxy copper-clad laminates, composite copper-clad laminates such as glass non-woven fabrics and epoxy copper-clad laminates, polyetherimide resin substrates, and polyether. Examples thereof include heat-resistant and thermoplastic substrates such as ketone resin substrates and polysulfone-based resin substrates, flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates. Examples of the inorganic circuit board include a ceramic substrate such as an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate, and a metal-based substrate such as an aluminum base substrate and an iron base substrate. Examples of circuit constituent materials are conductors containing metals such as silver, gold and copper, resistors containing inorganic oxides, low dielectrics containing glass materials and / or resins, resins and highs. Dielectric constants Examples include high dielectrics containing inorganic particles and insulators containing glass-based materials.

If the photosensitive resin sheet has a protective film, it is peeled off, the photosensitive resin sheet and the substrate are opposed to each other, and the photosensitive resin sheet is bonded by thermocompression bonding to obtain a resin film. The thermocompression bonding can be performed by a hot press treatment, a hot laminating treatment, a hot vacuum laminating treatment, or the like. The bonding temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of adhesion to the substrate and embedding property. Further, in order to prevent the resolution of pattern formation in the exposure / development process from deteriorating, the bonding temperature is preferably 150 ° C. or lower. Further, at the time of thermocompression bonding, it may be performed under reduced pressure for the purpose of removing air bubbles.

A cured film can be obtained by exposing, baking, developing, and thermosetting the resin film obtained from the photosensitive resin sheet by exposure, post-exposure baking, development, and thermosetting as in the above-mentioned photosensitive resin composition.

The cured film obtained from the photosensitive resin composition of the present invention or the photosensitive resin sheet is an interlayer insulation of a surface protective film of a semiconductor component, an insulating film for rewiring, an electronic component such as a thin film inductor, and a multilayer wiring for high-density mounting. It is suitably used for applications such as a film and an insulating layer of an organic electroluminescent element. Next, an application example of the photosensitive resin composition of the present invention to a semiconductor device having bumps will be described with reference to the drawings (Application Example 1). FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having a bump of the present invention. As shown in FIG. 1, in the silicon wafer 1, a passivation film 3 is formed on an aluminum (hereinafter, Al) pad 2 for input / output, and a via hole is formed in the passivation film 3. Further, an insulating film 4 is formed on this as a pattern by the cured film of the photosensitive resin composition of the present invention, and further, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2. Metal wiring (Al, Cu, etc.) 6 is formed by electrolytic plating or the like. A pattern formed by the cured film of the photosensitive resin composition of the present invention is formed on the metal wiring 6 as an insulating layer 7, and a barrier metal 8 and a solder bump 9 are formed at the openings. Further, the opening of the insulating film 4 and the insulating film 7 forms a scribe line 10 for dicing and separating each chip. Since the cured film of the photosensitive resin composition of the present invention is also excellent in high elongation, the cured film itself can be deformed to relieve the stress from the sealing resin even during mounting, so that bumps, wiring, and the like can be used. It is possible to prevent damage to the low-k layer and provide a highly reliable semiconductor device.

Next, FIG. 2 shows a detailed manufacturing method of the semiconductor device. As shown in 2a of FIG. 2, an Al pad 2 for input / output and a passivation film 3 are formed on the silicon wafer 1, and an insulating film 4 is formed as a pattern by a cured film of the photosensitive resin composition of the present invention. Subsequently, as shown in 2b of FIG. 2, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and as shown in 2c of FIG. 2, metal wiring (Al, Cu, etc.) is formed. ) 6 is formed by a plating method. Next, as shown in 2d'of FIG. 2, the photosensitive resin composition of the present invention is applied, and a cured film is formed through a photolithography step, and an insulating film 7 is formed as a pattern as shown in 2d of FIG. Wiring (so-called rewiring) can be further formed on the insulating film 7. When forming a multilayer wiring structure having two or more layers, by repeating the above steps, the rewiring of the two layers or more is carried out by an interlayer insulating film which is a cured film obtained from the photosensitive resin composition of the present invention. It is possible to form a separated multilayer wiring structure. There is no upper limit to the number of layers in the multi-layer wiring structure, but 2 to 10 layers are preferable. Next, as shown in 2e and 2f of FIG. 2, the barrier metal 8 and the solder bump 9 are formed. Then, dicing along the last scribe line 10 is performed to cut each chip.

Next, an application example 2 of an electronic component to a thin film inductor using the photosensitive resin composition of the present invention will be described with reference to the drawings. FIG. 3 is a cross-sectional view of a coil portion of a thin film inductor having an insulating film of the present invention. As shown in FIG. 3, the insulating film 12 is formed on the substrate 11, and the insulating film 13 is formed as a pattern on the insulating film 12. Ferrite or the like is used as the substrate 11. The resin composition of the present invention may be used for the insulating film 12 and / or the insulating film 13. A metal (Cr, Ti, etc.) film 14 is formed at the opening of this pattern, and a metal wiring (Ag, Cu, etc.) 15 is plated and formed on the metal (Cr, Ti, etc.) film 14. The metal wiring 15 (Ag, Cu, etc.) is formed on a spiral. By repeating the steps of forming the insulating film 12 to the metal wiring 15 a plurality of times and laminating them, the function as a coil can be obtained. Finally, the metal wiring 15 (Ag, Cu, etc.) is connected to the electrode 17 by the metal wiring 16 (Ag, Cu, etc.) and is sealed by the sealing resin 18. There is no upper limit to the number of insulating layers, but 2 to 10 layers are preferable.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The photosensitive resin composition and the cured film in the examples were evaluated by the following methods.

<Preparation of resin film>
A photosensitive resin composition is applied onto an 8-inch silicon wafer so that the film thickness after prebaking is 13 μm, and then using a hot plate (ACT-8 manufactured by Tokyo Electron Limited) at 120 ° C. for 3 minutes. By prebaking, a photosensitive coating film was obtained.

<Measurement method of film thickness>
Using Lambda Ace STM-602J manufactured by Dainippon Screen Mfg. Co., Ltd., the film thickness was measured with a refractive index of 1.63 for the photosensitive coating film.

<Evaluation of residual film ratio after development by LDI method>
^{The photosensitive coating film formed on an 8-inch silicon wafer is exposed to an exposure amount of 50 mJ / cm 2} at a laser output of 0.5 W using a laser direct drawing exposure device DW-3000 (manufactured by SCREEN Co., Ltd.). rice field.

After exposure, heat treatment was performed at 120 ° C. for 1 minute using a hot plate (ACT-8 manufactured by Tokyo Electron Limited), and then hydroxylated at 50 rpm using a developing device of ACT-8 manufactured by Tokyo Electron Limited. A 2.38% aqueous solution of tetramethylammonium was discharged for 10 seconds. Then, the mixture was allowed to stand at 0 rpm for 30 seconds, rinsed with pure water at 500 rpm, shaken off at 3000 rpm for 10 seconds, and dried to obtain a film after development.

When the film thickness after prebaking was T1 (μm) and the film thickness after development was T2 (μm), the residual film ratio after development was defined as T2 / T1 × 100 (%). Very good after-development residual film ratio of 90% or more (A), good of 80% or more and less than 90% (B), acceptable of 70% or more and less than 80% (C), less than 70% Was insufficient (D).

<Thermosetting (cure)>
After development, the film was coated using an Inert Oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.) in an oven atmosphere with an oxygen concentration of 20 ppm or less from 50 ° C to a temperature rise rate of 3.5 ° C / min 220. The temperature was raised to ° C., and heat treatment was performed at 220 ° C. for 1 hour. Then, it was slowly cooled until the temperature in the oven became 50 ° C. or less to obtain a cured film.

<Mechanical characteristic evaluation (high elongation)>
The cured film of the photosensitive resin composition formed on the 8-inch silicon wafer was immersed in 45% by mass of hydrofluoric acid for 3 minutes to peel off the cured film from the wafer. This film is cut into strips having a width of 1 cm and a length of 9 cm, and using Tensilon RTM-100 (manufactured by Orientec Co., Ltd.), a tensile speed of 50 mm / at a room temperature of 23.0 ° C. and a humidity of 45.0% RH. It was pulled in minutes and the break point elongation was measured. The measurement was performed on 10 strips per sample, and the average value of the top 5 points was obtained from the results. A breaking point elongation value of 50% or more is very good (A), a breaking point elongation value of 30% or more and less than 50% is good (B), and a breaking point elongation value of 10% or more and less than 30% is acceptable (C), 10 Those less than% were regarded as insufficient (D).

<Synthesis Example 1 Polyimide Synthesis>
Under a dry nitrogen stream, 32.9 g (0.09 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF, manufactured by AZ Electronic Materials Co., Ltd.) was dissolved in 500 g of NMP. To this, 31.0 g (0.1 mol) of ODPA was added together with 50 g of NMP, and the mixture was stirred at 30 ° C. for 2 hours. Then, 2.18 g (0.02 mol) of 3-aminophenol (manufactured by Tokyo Kasei Co., Ltd.) was added, and the mixture was stirred at 40 ° C. for 2 hours. Further, 5 g of pyridine (manufactured by Tokyo Kasei Co., Ltd.) is diluted with toluene (30 g manufactured by Tokyo Kasei Co., Ltd.), added to the solution, a cooling tube is attached, and water is azeotropically removed together with toluene to remove the solution. The reaction was carried out at a temperature of 120 ° C. for 2 hours and further at 180 ° C. for 2 hours. The temperature of this solution was lowered to room temperature, and the solution was poured into 3 L of water to obtain a white powder. This powder was collected by filtration and further washed with water three times. After washing, the white powder was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain polyimide.

<Synthesis Example 2 Synthesis of Hydroxy Group-Containing Diamine Compound (HFHA)>
2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF) 18.3 g (0.05 mol), 100 mL of acetone, propylene oxide (manufactured by Tokyo Kasei Co., Ltd.) ) Was dissolved in 17.4 g (0.3 mol) and cooled to −15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Kasei Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of the dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

30 g of the obtained white solid was placed in a 300 mL stainless autoclave, dispersed in 250 mL of methyl cell solve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated after confirming that the balloon did not deflate any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (HFHA) represented by the following formula.

<Synthesis Example 3 Synthesis of Polyimide Precursor>
51.3 g (0.085 mol) of HFHA obtained in Synthesis Example 2 and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (SiDA, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.24 g under a dry nitrogen stream. (0.005 mol), 3-aminophenol (manufactured by Tokyo Kasei Co., Ltd.) 2.18 g (0.02 mol) was dissolved in 200 g of N-methyl-2-pyrrolidone (NMP). To this, 31.0 g (0.1 mol) of ODPA was added, and the mixture was stirred at 40 ° C. for 2 hours. Then, a solution of 7.14 g (0.06 mol) of dimethylformamide dimethylacetal (DFA manufactured by Mitsubishi Rayon Co., Ltd.) diluted with 5 g of NMP was added dropwise over 10 minutes. After the dropping, stirring was continued at 40 ° C. for 2 hours. After the stirring was completed, the solution was poured into 2 L of water and the precipitate of the polymer solid was collected by filtration. Further, the mixture was washed 3 times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide precursor.

<Synthesis Example 4 Synthesis of Polybenzoxazole Precursor>
Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was cooled to −15 ° C. Here, 7.4 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Agricultural Chemicals Co., Ltd.) and 5.1 g (0.025 mol) of isophthalic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) are added to 25 g of γ-butyrolactone. The dissolved solution was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropping, stirring was continued at −15 ° C. for 6 hours. After completion of the reaction, the solution was poured into 3 L of water containing 10% by mass of methanol to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polybenzoxazole precursor.

[Example 1]
Under a dry nitrogen stream, 10.01 g (0.05 mol) of 4,4'-diaminodiphenyl ether (manufactured by Wakayama Seika Kogyo Co., Ltd., DAE) and 4-methoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd., MEHQ) 0. 15 g was dissolved in 40 g of NMP. To this, 7.76 g (0.025 mol) of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA, manufactured by Shanghai Synthetic Resin Research Institute) was added together with 10 g of NMP, and the temperature was 30 ° C. overnight. Stirred. Then, 7.71 g (0.05 mol) of methacrylic acid anhydride (manufactured by Sigma-Aldrich) was added, and the mixture was stirred and reacted for 2 hours. This solution was poured into 3 L of water to obtain a white powder. This powder was collected by filtration and further washed with water three times. After washing, the white powder was dried in a dryer at 50 ° C. for 72 hours to obtain a photopolymerizable monomer RA1 represented by the following formula.
The results of FT-IR and NMR used to identify the structure of the photopolymerizable monomer are shown below.
FT-IR / cm-1: 3500-2500, 3100-3000, 1720, 1650, 1620, 1540, 1505, 1410, 1235, 1010, 930, 830.
^{1 1} H-NMR (DMSO): 10.3 (s, 2H), 9.7 (s, 2H), 8.0 (d, 2H), 7.6-7.8 (m, 12H), 6. 9-7.1 (m, 8H), 5.8 (s, 2H), 5.5 (s, 2H), 1.9 (s, 6H).

The photopolymerizable monomer RA1 and the following substances were added to 10.20 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition.
As the photopolymerizable monomer (A), 1.50 g of RA1 of the photopolymerizable monomer was used.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 2]
The following substances were added to 11.28 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 3.00 g of RA1 of the photopolymerizable monomer was used.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 3]
The following substances were added to 12.37 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 4.50 g of RA1 of the photopolymerizable monomer was used.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 4]
The following substance was added to 13.45 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 6.00 g of the photopolymerizable monomer RA1 was added.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 5]
The following substances were added to 9.47 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 0.50 g of RA1 of the photopolymerizable monomer was used.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 6]
The following substances were added to 9.83 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 1.00 g of RA1 of the photopolymerizable monomer was used.
As the alkali-soluble resin (B), 10.00 g of the polyimide precursor of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 7]
The following substances were added to 14.18 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 7.00 g of the photopolymerizable monomer RA1 was added.
As the alkali-soluble resin (B), 10.00 g of the polybenzoxazole precursor of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 8]
The following substance was added to 16.71 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 7.50 g of the photopolymerizable monomer RA1 was added.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 9]
The following substance was added to 13.29 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 3.00 g of RA1 of the photopolymerizable monomer was used.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
0.20 g of NCI-831 as the photopolymerization initiator (C),
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 10]
The following substance was added to 13.87 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 3.00 g of RA1 of the photopolymerizable monomer was used.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 1.00 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 11]
The following substance was added to 13.22 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 3.00 g of RA1 of the photopolymerizable monomer was used.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
0.10 g of NCI-831 as the photopolymerization initiator (C),
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 12]
The following substances were added to 13.94 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 3.00 g of RA1 of the photopolymerizable monomer was used.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
1.10 g of NCI-831 as the photopolymerization initiator (C),
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 13]
The following substance was added to 13.45 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 3.00 g of RA1 of the photopolymerizable monomer was used.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of "IRGACURE" 907,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 14]
The following substances were added to 11.28 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 3.00 g of RA1 of the photopolymerizable monomer was used.
As the alkali-soluble resin (B), 10.00 g of the polyimide precursor of Synthesis Example 3 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 15]
The following substances were added to 11.28 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As the photopolymerizable monomer (A), 3.00 g of RA1 of the photopolymerizable monomer was used.
As the alkali-soluble resin (B), 10.00 g of the PBO precursor of Synthesis Example 4 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 16]
Under a dry nitrogen stream, NMP 40 g of 1,4-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.41 (0.05 mol) g and 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd., MEHQ) 0.15 g. Dissolved in. To this, 7.76 g (0.025 mol) of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA, manufactured by Shanghai Synthetic Resin Research Institute) was added together with 10 g of NMP, and the temperature was 30 ° C. overnight. Stirred. Then, 7.71 g (0.05 mol) of methacrylic acid anhydride (manufactured by Sigma-Aldrich) was added, and the mixture was stirred and reacted for 2 hours. This solution was poured into 3 L of water to obtain a white powder. This powder was collected by filtration and further washed with water three times. After washing, the white powder was dried in a dryer at 50 ° C. for 72 hours to obtain a photopolymerizable monomer RA2 represented by the following formula.
The results of FT-IR and NMR used to identify the structure of the photopolymerizable monomer are shown below.
FT-IR / cm-1: 3500-2500, 3100-3000, 1720, 1650, 1620, 1540, 1505, 1410, 1235, 1010, 930, 830.
^{1 1} H-NMR (DMSO): 10.3 (s, 2H), 9.7 (s, 2H), 7.9 (d, 2H), 7.6-7.8 (m, 8H), 6. 9-7.1 (m, 4H), 5.8 (s, 2H), 5.5 (s, 2H), 1.9 (s, 6H).

The photopolymerizable monomer RA2 and the following substances were added to 11.28 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition.
As the photopolymerizable monomer (A), 3.00 g of the photopolymerizable monomer RA2,
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Example 17]
Under a dry nitrogen stream, NMP 40 g of 1,4-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.41 (0.05 mol) g and 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd., MEHQ) 0.15 g. Dissolved in. To this, 5.45 g (0.025 mol) of pyromellitic anhydride (manufactured by Daicel Corporation) was added together with 10 g of NMP, and the mixture was stirred overnight at 30 ° C. Then, 7.71 g (0.05 mol) of methacrylic acid anhydride (manufactured by Sigma-Aldrich) was added, and the mixture was stirred and reacted for 2 hours. This solution was poured into 3 L of water to obtain a white powder. This powder was collected by filtration and further washed with water three times. After washing, the white powder was dried in a dryer at 50 ° C. for 72 hours to obtain a photopolymerizable monomer RA3 represented by the following formula.
The results of FT-IR and NMR used to identify the structure of the photopolymerizable monomer are shown below.
FT-IR / cm-1: 3500-2500, 3100-3000, 1720, 1650, 1620, 1540, 1505, 1410, 1010, 930, 830.
^{1 1} H-NMR (DMSO): 10.3 (s, 2H), 9.7 (s, 2H), 8.6 (d, 2H), 7.6-7.8 (m, 8H), 5. 8 (s, 2H), 5.5 (s, 2H), 1.9 (s, 6H).

The photopolymerizable monomer RA3 and the following substances were added to 11.28 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition.
As the photopolymerizable monomer (A), 3.00 g of the photopolymerizable monomer RA3,
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
It does not contain any other photopolymerizable monomer (D) and does not contain.
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Comparative Example 1]
The following substance was added to 9.11 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
It does not contain the photopolymerizable monomer (A) and does not contain.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
As another photopolymerizable monomer (D) having no amide bond, 3.00 g of PDBE-250,
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

[Comparative Example 2]
The following substances were added to 11.28 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
It does not contain the photopolymerizable monomer (A) and does not contain.
As the alkali-soluble resin (B), 10.00 g of the polyimide of Synthesis Example 1 was added.
As the photopolymerization initiator (C), 0.43 g of NCI-831,
As another photopolymerizable monomer (D) having no amide bond, 3.00 g of DCP-A,
1.43 g of Nicarac MX-270 as a heat-crosslinking agent (E)
0.71 g of KBM-403 as an adhesion improver,
As a surfactant, Polyflow No. 0.01 g of 77.
Using the obtained photosensitive resin composition, the post-development residual film ratio evaluation and the mechanical property evaluation were carried out by the above method.

Table 1 shows Examples 1 to 17 and Comparative Examples 1 and 2 with respect to the above composition and evaluation results. If the results of the post-development residual film ratio evaluation and the mechanical property evaluation by the LDI method are both C or higher, there is no problem.

The names shown in Table 1 have the following meanings.
RA1: Photopolymerizable monomer RA1
RA2: Photopolymerizable monomer RA2
RA3: Photopolymerizable monomer RA3
Polyimide: Polyimide polyimide precursor of Synthesis Example 1: Polyimide precursor of Synthesis Example 3 PBO precursor: Polybenzoxazole precursor of Synthesis Example 4 NCI-831: ADEKA ARCULDS NCI-831 (trade name, manufactured by ADEKA Corporation)
IRGACURE 907: "IRGACURE" (registered trademark) 907 (trade name, manufactured by BASF Japan Ltd.),
PDBE-250: "Blemmer" (registered trademark)
PDBE-250 (trade name, manufactured by NOF CORPORATION)
DCP-A: Light acrylate DCP-A (trade name, manufactured by Kyoei Kagaku Co., Ltd.)
MX-270: Nicarax MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.)
KBM-403: Silane coupling agent KBM-403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
PF77: Polyflow No. 77 (Product name, manufactured by Kyoei Kagaku Co., Ltd.)
GBL: γ-Butyrolactone

1 Silicon wafer 2 Al pad 3 Passivation film 4 Insulation film 5 Metal (Cr, Ti, etc.) film 6 Metal wiring (Al, Cu, etc.)
7 Insulation film 8 Barrier metal 9 Handa bump 10 Scribline 11 Substrate 12 Insulation film 13 Insulation film 14 Metal (Cr, Ti, etc.) film 15 Metal wiring (Ag, Cu, etc.)
16 Metal wiring (Ag, Cu, etc.)
17 Electrode 18 Encapsulating resin

Claims (9)

A photosensitive resin composition containing a photopolymerizable monomer (A) having a structure represented by the general formula (2), an alkali-soluble resin (B), and a photopolymerization initiator (C).

(In general formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² May be the same or different, respectively, and indicate a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. L and M may be the same or different, respectively, and may be a divalent aromatic group having one benzene ring, or a single bond, an ether bond, an isopropylidene group, or a trifluoro having 2 to 5 benzene rings. Represents a divalent organic group having a structure bonded by any of an isopropyridene group, a carbonyl group, an amide group, and a sulfonyl group. X represents an organic group having one or more selected from the group consisting of a single bond, an ether bond, an isopropyridene group, a trifluoroisopropyridene group, a carbonyl group, an amide group and a sulfonyl group. ) The photosensitive resin composition according to claim 1 , wherein the photopolymerizable monomer (A) having the structure represented by the general formula (2) has the structure represented by the general formula (3).

(In the general formula (3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ may be the same or different, respectively, and may have the same or different hydrogen atoms or 1 to 10 carbon atoms. X, Y, Z may be the same or different, respectively, from a single bond, an ether bond, an isopropylidene group, a trifluoroisopropyridene group, a carbonyl group, an amide group, and a sulfonyl group. Represents an organic group having one or more selected from the group consisting of.) The photosensitive resin according to claim 1 or 2 , wherein the photopolymerizable monomer (A) is contained in an amount of 10 parts by mass to 70 parts by mass with respect to 100 parts by mass of the total amount of the alkali-soluble resin (B). Composition. 13 . The photosensitive resin composition according to any one. A photosensitive resin sheet formed from the photosensitive resin composition according to any one of claims 1 to 4. The photosensitive resin composition according to any one of claims 1 to 4 , or a cured film obtained by curing the photosensitive resin sheet according to claim 5. An electronic component or a semiconductor component in which the cured film according to claim 6 is arranged as an interlayer insulating film or a surface protective film. An electronic component or a semiconductor component in which the cured film according to claim 6 is arranged as an interlayer insulating film between rewiring. An electronic component or semiconductor device in which the cured film according to claim 6 is repeatedly arranged in 2 to 10 layers as an interlayer insulating film between rewiring.

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