JP2019085431A - Photopolymerizable monomer, and photosensitive resin composition and cured film of photosensitive resin composition using the same - Google Patents

Abstract

To provide a negative type photosensitive resin composition which prevents an exposure part from foaming in high output laser irradiation, has high residual film ratio after development, and exhibits good film characteristics after heat curing, and a new photopolymerizable monomer.SOLUTION: A photosensitive resin composition contains a photopolymerizable monomer having a structure of a general formula (1). In the general formula (1), R, R, R, and Reach may be the same or different, and represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. L represents a divalent aromatic group having one benzene ring, or represents a divalent organic group having a structure in which 2 to 5 benzene rings are bonded with a single bond, an ether bond, a (trifluoro)isopropylidene group, a carbonyl group, an amide group, and a sulfonyl group, and mark "*" represents a bonding part.SELECTED DRAWING: None

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 of a semiconductor element, an insulating film for rewiring, an interlayer insulating film of a thin film inductor, an insulating film of organic electroluminescence (hereinafter referred to as EL) element, driving of a display device using an organic EL element For thin film transistor (Thin Film Transistor: hereinafter referred to as TFT) substrate planarization film, circuit board wiring protection insulation film, solid-state imaging device on-chip micro lens, various displays, planarization film for solid-state imaging device, etc. 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 surface protection films such as semiconductor elements, insulating films for rewiring, interlayer insulation of thin film inductors due to their excellent mechanical properties, heat resistance, electrical insulation and chemical resistance. It is used as a film, an insulating layer of an organic EL element, a planarization film of a TFT substrate, and the like. Furthermore, photosensitive polyimides to which photosensitivity is imparted for improving productivity, and photosensitive polybenzoxazoles have been put to practical use.

  In recent years, pattern exposure technology by laser direct imaging (LDI) has attracted attention. Unlike the conventional i-line stepper, aligner, and other exposure machines, the LDI method is a process-saving process that does not require a photomask, and can achieve high throughput and low cost. Further, since alignment can be performed for each substrate, it is suitable for patterning that requires high positional accuracy. Therefore, also in the application of the surface protective film of a semiconductor element and the insulating film for rewiring, application of the LDI method by high resolution and high power laser to photosensitive polyimide and photosensitive polybenzoxazole is considered.

JP, 2009-9107, A International Publication No. 2014/054455 JP, 2015-187750, A JP, 2016-122178, A

  However, patterning of photosensitive resin by high resolution and high power laser has a problem of patterning difficulty due to irradiation with laser of very high power as compared with the conventional i-line stepper and aligner. .

  For example, in the case of a positive photosensitive resin composition, a new problem derived from a high power laser is that the naphthoquinone diazide compound, which is a photosensitizer, decomposes upon high power laser irradiation, and the exposed portion is decomposed by nitrogen gas generated by the decomposition. There is a problem that it is easily foamed and patterning becomes difficult. On the other hand, in the negative photosensitive resin composition, since it contains not the naphthoquinone diazide type compound but the photopolymerizable monomer and the photopolymerization initiator, the foaming at the time of high power laser irradiation can not be seen. However, there are problems such as a decrease in film properties of the cured film presumably due to the decomposition of the photopolymerizable monomer, a decrease in in-plane uniformity due to a significant increase in developed film reduction, and difficulty in forming a thick film. Therefore, the negative photosensitive resin composition which expresses an excellent film characteristic after heat curing without developing the foamed part of the exposed part at the time of high power laser irradiation and has a high residual film ratio after heat curing, and further expresses those characteristics. New photopolymerizable monomers are needed.

  As a negative photosensitive resin composition, a photosensitive resin composition containing a polyimide resin, a photopolymerizable monomer, a photopolymerization initiator, and a thermal crosslinking agent (Patent Document 1), and N-alkoxymethyl (meth) acrylamide And a copolymer of a monomer having an alkali soluble group, a photopolymerizable monomer, a photopolymerization initiator, a polymer having a hydroxy group, a photosensitive resin composition containing a solvent (Patent Document 2), an ethylenically unsaturated group The photopolymerizable monomer having a photopolymerization resin, a photosensitive resin composition containing a photopolymerization initiator (Patent Document 3), a polyimide resin, and a resin composition containing a photopolymerizable monomer (Patent Document 4) can be mentioned. There is also a problem in the film characteristics of the cured film and the decrease in the development film.

  The present invention is a negative photosensitive resin composition which does not foam at the time of high power laser irradiation, has a high residual film ratio after development, and exhibits good film characteristics after heat curing, and further, those characteristics It is an object of the present invention to provide a novel photopolymerizable monomer for expressing

In order to solve the said subject, the photopolymerizable monomer and photosensitive resin composition of this invention have the following structures.
[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 and each represents a hydrogen atom or a C 1-10 monovalent organic group. L is Any of a divalent aromatic group having one benzene ring, or 2 to 5 benzene rings each having a single bond, an ether bond, an isopropylidene group, a trifluoroisopropylidene group, a carbonyl group, an amido group or a sulfonyl group Represents a divalent organic group having a structure bonded via a heel (the mark * indicates a bond)
[2] A photopolymerizable monomer having a structure represented by General Formula (1) is a photopolymerizable monomer having a structure represented by 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 and each represents a hydrogen atom or a carbon number of 1 to 10) L and M, which may be the same or different, each represents a divalent aromatic group having one benzene ring, or a single bond of 2 to 5 benzene rings, It represents a divalent organic group having a structure bonded by an ether bond, an isopropylidene group, a trifluoroisopropylidene group, a carbonyl group, an amido group or a sulfonyl group, and X represents a single bond, an ether bond, isopropylidene And R 1 represents an organic group having one or more selected from the group consisting of a group, a trifluoroisopropylidene group, a carbonyl group, an amido group and a sulfonyl group.)
[3] A photopolymerizable monomer having a structure represented by General Formula (2) is a photopolymerizable monomer having a structure represented by 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, and each represents a hydrogen atom or a carbon number of 1 to 10 X, Y and Z, which may be the same or different, each represents a single bond, an ether bond, an isopropylidene group, a trifluoroisopropylidene group, a carbonyl group, an amido group or a sulfonyl group Represents an organic group having one or more selected from the group consisting of
[4] A photosensitive resin composition comprising 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 which does not foam at the time of high power laser irradiation, has a high residual film rate after development, and exhibits good film properties after heat curing, and further, those properties It is possible to obtain a novel photopolymerizable monomer for expressing.

It is the figure which showed the expanded cross section of the pad part of the semiconductor device which has a bump. FIG. 7 is a diagram illustrating a detailed method of manufacturing a semiconductor device having 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). They are a photosensitive resin composition containing it as a component, and a cured film of the photosensitive resin composition. As a result, it is possible to provide a negative photosensitive resin composition which has a high residual film ratio after development after exposure with a high-power laser and which exhibits excellent film properties after heat curing. The reason why such an effect can be obtained as compared with conventional photopolymerizable monomers is presumed as follows.

  Conventional photopolymerizable monomers undergo photocrosslinking reaction in the presence of active species such as radicals generated in the exposure step to polymerize and become insoluble in a developer. However, in high power laser exposure, high energy irradiation to the exposed area and associated high heat are generated, so the decomposition of the photopolymerizable monomer and the lack of photocrosslinking caused by it significantly increase the reduction of the developed film and the thermal curing. It is considered that the later deterioration of the membrane characteristics occurred.

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 by high-power laser exposure, and 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 area and the photocrosslinking of the photopolymerizable group efficiently insolubilize the exposed area in the developer to improve the residual film ratio after development, and also the imide ring after heat curing. It is believed that good film properties derived from can be obtained.
<Photopolymerizable Monomer Having a Structure Represented by 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 (meth) acryloyl group, vinyl group, styryl group, maleimide group and the like. Be

  The photopolymerizable monomer of the present invention has a structure represented by the general formula (1). Preferably, it is a photopolymerizable monomer which has a structure represented by General formula (2), More preferably, it is a photopolymerizable monomer which has a structure represented by General formula (3). It is preferable to have the above-described structure from the viewpoint of improving the residual film ratio after development after exposure with a high power laser and improving the mechanical characteristics.

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or a C 1-10 monovalent organic group. L is Any of a divalent aromatic group having one benzene ring, or 2 to 5 benzene rings each having a single bond, an ether bond, an isopropylidene group, a trifluoroisopropylidene group, a carbonyl group, an amido group or a sulfonyl group Represents a divalent organic group having a structure bonded via a heel (the mark * indicates a bond)

(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 and each represents a hydrogen atom or a carbon number of 1 to 10) L and M, which may be the same or different, each represents a divalent aromatic group having one benzene ring, or a single bond of 2 to 5 benzene rings, It represents a divalent organic group having a structure bonded by an ether bond, an isopropylidene group, a trifluoroisopropylidene group, a carbonyl group, an amido group or a sulfonyl group, and X represents a single bond, an ether bond, isopropylidene Represents an organic group having one or more selected from the group consisting of a group, a carbonyl group, an amido 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, and each represents a hydrogen atom or a carbon number of 1 to 10 X, Y and Z, which may be the same or different, each represents a single bond, an ether bond, an isopropylidene group, a trifluoroisopropylidene group, a carbonyl group, an amido group or a sulfonyl group Represents an organic group having one or more selected from the group consisting of
<Production Method of Photopolymerizable Monomer Having a Structure Represented by 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 employed.

  As a first step, first, an acid anhydride represented by the following general formula (4) is charged into 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, * mark shows a joint.)
Preferred examples of the aromatic diamine compound used for producing the photopolymerizable monomer include m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diamino Diphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 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) sulfone, bis (3-amino-4-hydroxy) Phenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, 2,2-biphenyl (4-aminophenyl) hexafluoropropane and the like. Among 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 mechanical property improvement.

  Preferred examples of the acid anhydride used for producing the photopolymerizable monomer include phthalic anhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 3 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid Anhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 3,3', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride etc. can be mentioned. Among these, 3,3 ', 4,4'-diphenylethertetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4'- Benzophenone tetracarboxylic acid dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 3,3', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride is a point of mechanical property improvement. More preferable.

  As a second step, a compound having a carbon-carbon unsaturated bond of the following structure is charged 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, and each represents a hydrogen atom or a C 1-10 monovalent organic group Indicate
Preferred examples of the compound having a carbon-carbon unsaturated bond used for producing a photopolymerizable monomer include diacrylic acid anhydride, methacrylic acid anhydride, acrylic acid methacrylic acid anhydride, tiglic acid anhydride, angelic acid anhydride, Bis (3-methyl-2-butenoic acid) anhydride, crotonic acid anhydride and the like can be mentioned. Among these, diacrylic acid anhydride and methacrylic acid anhydride are more preferable in terms of improvement of the residual film rate after development after exposure with a high power laser.

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

As a reaction solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl- Examples thereof include 2-imidazolidinone, N, N-dimethylpropyleneurea, 3-methoxy-N, N-dimethylpropionamide, delta valerolactone and the like. These can be contained singly or in combination of two or more.
The photopolymerizable monomer in the present invention can be identified using infrared absorption spectroscopy (IR) or nuclear magnetic resonance (NMR).

IR is an analysis method that can obtain information on the molecular structure and functional groups by measuring the absorption spectrum obtained by applying infrared light to a sample, and the most frequently used is Fourier transform infrared spectroscopy It is a total (FT-IR). When it has an amide group, the absorption spectrum of IR has an absorption band derived from C = O stretching motion in the vicinity of 1650 cm ⁻¹ and an absorption band derived from N—H bending vibration in the vicinity of 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 In the vicinity there is an absorption band derived from C—H out-of-plane vibration of the benzene ring. When having an unsaturated double bond group, having absorption band and derived from the C = C stretching vibration in the vicinity of 1620 cm ^-1, an absorption band derived from C-H stretching vibration 3100-3000cm ^-1. When it has an ether bond, it has an absorption band derived from C—O—C stretching vibration in the vicinity of 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 bending vibration.

In NMR, a sample is placed in a strong magnetic field, and a molecule whose nuclear spin direction is aligned is irradiated with pulsed radio waves, subjected to nuclear magnetic resonance, and then generated when the molecule returns to its original stable state. It is an analysis method that detects signals and analyzes molecular structure and the like. The most frequently used in NMR analysis is the ¹ H-NMR spectrum, from the chemical shift of the peak to the environment where the hydrogen atom is located, from the integral value to the number of hydrogen atoms, from the splitting of the peak to the adjacent protons It is possible to obtain information on molecular structure such as influence. As an example showing characteristic chemical shift, the chemical shift of hydrogen bonded to carbon at allyl position is 1.5-2 ppm, the chemical shift of hydrogen atom bonded to alkene is 4.5-6 ppm, hydrogen bonded to aromatic ring The chemical shift of the atom peaks at 6-9 ppm, and the chemical shift of hydrogen bonded to the amide group appears 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 which causes a chemical or structural change by light irradiation and changes the solubility in a developing solution such as an organic solvent or an aqueous alkaline solution. In the case of having positive photosensitivity, the solubility of the light-irradiated portion in the developer is increased, and the light-irradiated portion is dissolved, whereby a positive relief pattern can be obtained. In the case of having negative photosensitivity, the light-irradiated part is insolubilized in the developer, 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 a structure represented by the general formula (1) is preferably a photopolymerizable monomer having a structure represented by the general formula (2) And more preferably a photopolymerizable monomer having a structure represented by the general formula (3). It is preferable to have the above-described structure from the viewpoint of improving the residual film ratio after development after exposure with a high power laser and improving the mechanical characteristics.

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

  The photosensitive resin composition of the present invention has two ethylenically unsaturated bonds as another photopolymerizable monomer (D) other than the photopolymerizable monomer (A) having a structure represented by the general formula (1). You may contain the monomer which has more than. As a monomer having two or more ethylenically unsaturated bonds, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate triethylene glycol dimethacrylate tetraethylene glycol diacrylate, tetraethylene Glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol dimethacrylate Acrylate, 1,4-butanediol diacrylate 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclode Candiacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 3-Dimethacryloyloxy-2-hydroxypropane, N, N-methylenebisacrylamide, "Blenmer" (registered trademark) ) PDBE-250 (trade name, manufactured by NOF Corporation), BP-6EM (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), AH-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), AT-600 (trade name) , Kyoeisha Chemical Co., Ltd., UA-306H (trade name, Kyoeisha Chemical Co., Ltd.), UA-306T (trade name, Kyoeisha Chemical Co., Ltd.), light acrylate DCP-A (trade name, E. Co., Ltd.) Chemical Co., Ltd. product, ethylene oxide modified bisphenol A diacrylate, ethylene oxide modified bisphenol A dimethacrylate, etc. may be mentioned. These can be contained singly 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 or a sulfonic acid group. The alkali-soluble resin (B) preferably contains one or more resins selected from the group consisting of polyimide precursors, polyamideimides, polyimides, polybenzoxazole precursors, and polybenzoxazoles. These resins can be polymers having an imide ring, an oxazole ring, and other cyclic structures by heating or catalysis. More preferable examples include polyimides having a closed ring, polyamic acids and polyamic acid esters of polyimide precursors, and polyhydroxyamides of polybenzoxazole precursors. By forming the annular structure, heat resistance and chemical resistance are dramatically improved. Examples of resins other than polyimide precursors, polyamideimides, polyimides, polybenzoxazole precursors, and polybenzoxazoles include radical polymerizable resins having acrylic acid, phenol-novolak resins, polyhydroxystyrenes, polysiloxanes, and the like. . Moreover, you may protect the acidic group of these resin, and may adjust 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, sodium carbonate and the like in addition to tetramethylammonium hydroxide. Two or more of these alkali-soluble resins may be contained, but the proportion of the polyimide precursor, polyamideimide, polyimide, polybenzoxazole precursor, and all other alkali-soluble resins other than polybenzoxazole is 70% by mass or less. It is preferable at the point which can obtain the resin film of the outstanding film | membrane physical property after thermosetting.

  A polyimide can be obtained by reacting a tetracarboxylic acid, corresponding tetracarboxylic acid dianhydride, tetracarboxylic acid diester dichloride or the like with a diamine, a corresponding diisocyanate compound, trimethylsilylated diamine or the like, and a tetracarboxylic acid residue And diamine residues. For example, the polyamic acid which is one of the polyimide precursors obtained by making tetracarboxylic dianhydride and diamine react can be obtained by carrying out the dehydration ring-closing by heat processing. At the time of the heat treatment, a solvent which azeotropes with water, such as m-xylene, can also be added. Alternatively, it can also be obtained by dehydration ring closure by a chemical heat treatment by adding a dehydration condensation agent such as carboxylic acid anhydride or dicyclohexylcarbodiimide, or a base such as triethylamine as a ring closure catalyst. Alternatively, it can also be obtained by adding a weakly acidic carboxylic acid compound and subjecting it to dehydration ring closure by heat treatment at a low temperature of 100 ° C. or lower.

  The 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, polyhydroxyamide, which is one of polybenzoxazole precursors obtained by reacting a bisaminophenol compound and a dicarboxylic acid, can be obtained by dehydration ring closure by heat treatment. Alternatively, it can be obtained by dehydration ring closure by chemical treatment after adding phosphoric anhydride, a base, a carbodiimide compound or the like.

In the photosensitive resin composition of the present invention, from the viewpoint of solubility in an alkaline aqueous solution, the polyimide is a tetracarboxylic acid residue and / or a diamine residue OR ²⁷ , SO ₃ R ²⁷ , CONR ²⁷ R ²⁸ , COOR ²⁷ , 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. Note that the acidic group shows a case ^{where R 27} and ^{R 28} are all hydrogen atoms, the acid group derivative shows a case that contains a monovalent organic group having 1 to 20 carbon atoms in ^{R 27} and ^{R 28.} Examples of the organic group include an alkyl group, an alkoxyl group, and an ester group.

In addition, polybenzoxazole is an acidic group or acid represented by OR ²⁹ , SO ₃ R ²⁹ , CONR ²⁹ R ³⁰ , COOR ²⁹ , SO ₂ NR ²⁹ R ³⁰ or the like for dicarboxylic acid residue and / or bisaminophenol residue. It is preferable to have a group derivative, and more preferable 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. Note that the acidic group shows a case ^{where R 29} and ^{R 30} are all hydrogen atoms, the acid group derivative shows a case that contains a monovalent organic group having 1 to 20 carbon atoms in ^{R 29} or ^{R 30.} 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, preferred structures of the tetracarboxylic acid residue of polyimide and the dicarboxylic acid residue of polybenzoxazole (hereinafter referred to collectively as an acid residue) include the structures shown below, A structure in which a part of hydrogen atoms in the structure of 1 to 4 are substituted by 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 It 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, preferred structures of the diamine residue of the polyimide and the bisaminophenol residue of the polybenzoxazole (hereinafter referred to collectively as the diamine residue) have the structures shown below, A structure in which a part of hydrogen atoms in the structure is substituted by 1 to 4 carbon atoms 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 Be

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 undergo dehydration ring closure by heat treatment or chemical treatment, and the above-mentioned polyimide, polybenzoxazole and the like. Become. The number of repeating structural units 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 polybenzoxazole precursors include polyhydroxyamides, polyaminoamides, polyamides, polyamideimides and the like, with polyhydroxyamides being preferred.

The polyimide precursor and the polybenzoxazole precursor have OR ³¹ , SO ₃ R ³¹ , CONR ³¹ R ³² , COOR ³¹ , SO ₂ NR ³¹ R ^{31 as} acid residues or diamine residues from the viewpoint of solubility in an alkaline aqueous solution. It is preferable to have an acidic group or an acidic group derivative shown by etc., 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 all of R ³¹ and R ³² are hydrogen atoms, and the acidic group derivative indicates a case where a monovalent organic group having 1 to 20 carbon atoms is included in R ³¹ or R ^32. . Examples of the organic group include an alkyl group, an alkoxyl group, and an ester group.

Examples of acid components constituting acid residues of polyimide precursors and polybenzoxazole precursors include terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyldicarboxylic acid, benzophenone as an example of dicarboxylic acid Examples of tetracarboxylic acids such as dicarboxylic acid and triphenyl dicarboxylic acid, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid as examples of tricarboxylic acid, and pyromellitic acid, 3,3 ′, 4,4 ′ as examples of tetracarboxylic acid -Biphenyltetracarboxylic acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid , 2, 2 ', 3, 3'- Ben Zophenone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 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, Aromatic tetracarboxylic acids such as 3,5,6-pyridine tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, butane tetraca Bon acid, cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, bicyclo [2.2.1. ] Heptanetetracarboxylic acid, bicyclo [3.3.1. ] Tetracarboxylic acid, bicyclo [3.1.1. ] Hept-2-ene tetracarboxylic acid, bicyclo [2.2.2. Aliphatic tetracarboxylic acids such as octane tetracarboxylic acid and adamantane tetracarboxylic acid can be mentioned. In addition, a part of the hydrogen atoms of the dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids exemplified above is an acid 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 preferable to substitute with a group or an acidic group derivative, and it is more preferable to substitute 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 they are or as acid anhydrides or active esters. Moreover, you may use 2 or more types of these.

  Also, by using a silicon atom-containing tetracarboxylic acid such as dimethylsilane diphthalic acid or 1,3-bis (phthalic acid) tetramethyldisiloxane, adhesion to a substrate, oxygen plasma used for cleaning, UV ozone, etc. Resistance to treatment can be enhanced. The silicon atom-containing tetracarboxylic acid is preferably used in an amount of 1 to 30% by mole of the total acid component, and 1% by mole or more is preferable in terms of the substrate adhesion and the effect on plasma treatment. If it is 30 mol% or less, it is preferable in terms of the solubility of the obtained resin in an aqueous alkaline solution.

Examples of the diamine component constituting the diamine residue of the polyimide precursor and the polybenzoxazole precursor include: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-) Hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino- 4-hydroxy) biphenyl, hydroxyl group-containing diamine such as bis (3-amino-4-hydroxyphenyl) fluorene, carboxyl group-containing diamine such as 3,5-diaminobenzoic acid, 3-carboxy-4,4'-diaminodiphenyl ether , 3-sulfonic acid-4,4'-diaminodipheny Sulfonic acid-containing diamines such as ether, dithiohydroxyphenylene diamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'- Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diamino diphenyl sulfide, 4,4'-diamino diphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, m-phenylenediamine P-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-ami Phenoxy) 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, or the hydrogen atom of these aromatic rings And a compound in which a part of R is substituted with an alkyl group or a halogen atom such as F, Cl, Br or I, or an aliphatic diamine such as cyclohexyldiamine or methylenebiscyclohexylamine. Furthermore, these diamines have a portion of hydrogen atoms as alkyl groups having 1 to 10 carbon atoms such as methyl and ethyl, C 1 to C 10 fluoroalkyl groups such as trifluoromethyl and the like, F, Cl, Br, It may be substituted by a halogen atom such as I. Also, diamines exemplified above ^preferably has a _{^{OR 35, SO 3 R 35,}} CONR 35 R 36, COOR 35 acidic group or an acidic group derivative represented by, SO ^{2 NR} 35 ^{R 36,} have a hydroxyl group Is more preferred. 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 they are or as corresponding diisocyanate compounds, trimethylsilylated diamines. Moreover, you may use 2 or more types of these. In applications where heat resistance is required, it is preferable to use an aromatic diamine at 50 mol% or more of the total diamine.

  In addition, adhesion to the substrate 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 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% by mole based on the total diamine components, and 1% by mole or more is preferable in terms of improving adhesion and resistance to plasma treatment. If it is 30 mol% or less, it is preferable in terms of the solubility of the obtained resin in an aqueous alkaline solution.

  Moreover, it is preferable to seal the terminal 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 or an acid chloride. Two or more of these may be used. By having the above-described group at the resin end, the dissolution rate of the resin in an aqueous alkali solution can be easily adjusted to 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-a Nosalicylic 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 and the like can be mentioned.

  Preferred examples of the acid anhydride, monocarboxylic acid and acid chloride include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride, acid anhydrides such as 3-hydroxyphthalic acid anhydride, and the like. 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 the like, and their carboxyl groups as acids Loridated monoacid chloride compounds, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dichloronaphthalene A monoacid chloride compound in which only one carboxyl group of dicarboxylic acids such as carboxynaphthalene is acid chlorided, a monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide The active ester compound etc. which are obtained by reaction can be mentioned.

  The content of monoamine, acid anhydride, monocarboxylic acid and acid chloride to be used as the above-mentioned end capping agent is preferably in the range of 0.1 to 60% by mole based on the number of moles of acid component monomer or diamine component monomer. And 5 to 50 mol% are more preferable. By setting it as such a range, the viscosity of the solution at the time of apply | coating a photosensitive resin composition can be moderate, and the photosensitive resin composition which had the outstanding film physical property can be obtained.

The end capping agent introduced into the alkali soluble resin (B) can be easily detected by the following method. For example, a resin into which an end capping agent has been introduced is dissolved in an acidic solution, decomposed into a diamine component and an acid component which are constituent units of the resin, and the end is measured by gas chromatography (GC) or NMR. The sealant can be easily detected. Aside from this, it is also possible to detect the resin into which the end capping agent has been introduced by directly measuring the pyrolysis gas chromatograph (PGC), infrared spectrum and 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, assuming that the total amount of the photosensitive resin composition excluding the solvent is 100 parts by mass. It is preferable at the point from which the film characteristic excellent in the mechanical characteristic derived from alkali-soluble resin (B), etc. are obtained as it is 40 mass parts or more, More preferably, it is 45 mass parts or more. It is preferable at the point of the sensitivity improvement at the time of high output laser exposure being it being 80 mass parts or less, More preferably, it is 75 mass parts or less.

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

  A photoinitiator is a compound which generate | occur | produces active species, such as a radical, by irradiation of light. By containing the photopolymerization initiator (C) and the photopolymerizable monomer (A), active radicals generated in the light irradiated portion cause radical polymerization of the photopolymerizable monomer (A) to proceed 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-piperidone, 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone.

  7-diethylamino-3-tenonyl coumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1-methylbenzimidazolyl) coumarin, 3 -Coumarins such as (2-benzothiazolyl) -7-diethylamino coumarin.

  Anthraquinones such as 2-t-butyl anthraquinone, 2-ethyl anthraquinone, 1,2-benzanthraquinone and the like.

  Benzoines such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether.

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

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

  1-phenyl-1,2-butanedione-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) isophthalic, "IRGACURE" (registered) Trademark OXE-01 (trade name, manufactured by BASF Japan Ltd.), "IRGACURE" (registered trademark) OXE-02 (trade name, manufactured by BASF Japan Ltd.), NCI-831 (trade name, manufactured by ADEKA Co., Ltd.) And other oximes.

  2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, “IRGACURE Α-aminoalkylphenones such as “registered trademark” 907 (trade name, manufactured by BASF Japan Ltd.), 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl Such as biimidazole.

  Among them, those having the above oxime structure are preferable in terms of improvement of the residual film rate after development, and more preferable 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 (trade name) Co., Ltd.), “IRGACURE” (registered trademark) OXE-02 (trade name, manufactured by BASF Japan 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 to cause a photocrosslinking reaction to progress, and the residual film ratio after development is improved, and is preferably 10 parts by mass or less The irradiated light is transmitted from the coating film surface to the bottom, and the photocrosslinking reaction proceeds in the entire coating film, and the residual film ratio after development is improved.

  Moreover, the photosensitive resin composition of this invention may contain a thermal crosslinking agent (E). For example, as one having a thermally crosslinkable group, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.) And PA-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as having DM-BI 25X-F, 46 DMOC, 46 DMOIPP, 46 DMOEP (all trade names, Asahi Organic Materials Co., Ltd.) DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC -P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSB , DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "Nikalac" (registered trademark) MX-290 (trade name, ( Co., Ltd. Sanwa Chemical Co., Ltd.), B-a-type benzoxazine, B-m-type benzoxazine (all trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2 TriML-P, TriML-35 XL, TriML-Tris CR-HAP (trade names, Honshu Chemical Industries, Ltd.) as having three such as 6, 6-dimethoxymethyl-p-cresol, 2, 6-diacetoxymethyl-p-cresol, etc. TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-B, etc. as having four such as manufactured by Co., Ltd. , TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "Nikalac" (registered trademark) MX-280, "Nikalac" (registered trademark) HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all trade names, Honshu Chemical Industries, Ltd.) as having six such as MX-270 (all trade names, manufactured by Sanwa Chemical Co., Ltd.) Co., Ltd.), "Nicalac" (registered trademark) MW-390, "Nicalac" (registered trademark) MW-100 LM (trade names, manufactured by Sanwa Chemical Co., Ltd.).

  The structure of the thermal crosslinking agent (E) which is particularly preferably used for the photosensitive resin composition of the present invention is shown below.

  These thermal crosslinking agents (E) can be contained singly or in combination of two or more.

  The content of the thermal 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). And 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 thermal 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 the thermal curing of the resin composition film can be improved. it can. On the other hand, by setting the content to 0.5 parts by mass or more, the heat resistance of the resin composition film is improved by the molecular weight increasing effect by the crosslinking.

  In addition, in order to adjust the alkali developability of the photosensitive resin composition of the present invention, a compound having a phenolic hydroxyl group can be contained.

  As a compound which has a phenolic hydroxyl group which can be used by the photosensitive resin composition of this invention, Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP are mentioned, for example. -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 (Tetrakis P-DO-BPA), TrisP-HAP, TrisP-PA, BisOFP-Z, BisRSP-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bi 26X-OCHP, BisOCHP-OC, Bis236T-OCHP, methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR -PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.).

  Among these, preferred compounds having a 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 the compound having a phenolic hydroxyl group, the obtained negative photosensitive resin composition has improved solubility in an alkali developer in the unexposed area, and development contrast due to difference in solubility with the exposed area. It is preferable from the point 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. The adhesion improver may, for example, be an alkoxysilane-containing compound. Two or more of these may be contained. By containing these compounds, the adhesion 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, N-phenylamino Butyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxy Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrichlorosilane, vinyltris (beta-methoxyethoxy) silane and the like.

  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). If it is 0.01 mass part or more, it is preferable at the point which can improve the adhesiveness of the film | membrane and base material after hardening. If the amount is 15 parts by mass or less, it is preferable in that the adhesiveness is improved without the alkali developability being lowered due to excessive adhesion.

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

  As the surfactant, "FLUORAD" (registered trademark) (manufactured by 3M Japan Ltd.), "Megafuck" (registered trademark) (manufactured by DIC Corporation), "Surflon" (registered trademark) (Asahi Glass Co., Ltd.) Fluorine-based surfactants such as KP 341 (trade name, Shin-Etsu Chemical Co., Ltd.), DBE (trade name, Chisso Co., Ltd.), Granol (trade name, Kyoeisha Chemical Co., Ltd.), Organic siloxane surfactants such as BYK (registered trademark) (Bic Chemie Co., Ltd.) and acrylic polymer surfactants such as polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) Available from

  In the photosensitive resin composition of the present invention, the components (A) to (C), (D) other photopolymerizable monomers, a thermal crosslinking agent (E), a compound having a phenolic hydroxyl group, an adhesion improver and an interface The activator is preferably contained in a state of being dissolved or dispersed in an organic solvent. As the organic solvent, one having a boiling point of 80 ° C. to 250 ° C. at atmospheric pressure can be preferably contained.

  Specifically as an organic solvent which can be preferably contained in the photosensitive resin composition of the present invention, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ale, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, Ethers such as ethylene glycol diethyl ether, 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 Acetate, methyl lactate, ethyl lactate, butyl lactate and other acetates, acetylacetone, Ketones such as methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, Alcohols such as 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-dimethylpropyleneurea, 3-methoxy-N, N-dimethylpropionamide, delta valerolactone Etc. These can be contained singly or in combination of two or more.

  Among these, the photopolymerizable monomer (A) having a structure represented by the general formula (1), the alkali-soluble resin (B), and the photopolymerization initiator (C) are dissolved and the atmospheric pressure boiling point is Particularly preferred is a temperature of 100 ° C to 210 ° C. If the boiling point is in this range, excessive volatilization of the organic solvent is suppressed at the time of application of the photosensitive resin composition to improve the coatability, and the drying temperature of the photosensitive resin composition does not have to be increased. There is no restriction on the material of the substrate. In addition, the base substrate can be obtained by using the photopolymerizable monomer (A) having a structure represented by the general formula (1), the alkali-soluble resin (B), and the organic solvent capable of dissolving the photopolymerization initiator (C). Can form a coating film with good uniformity.

  As particularly preferred organic solvents having such a boiling point, specifically, cyclopentanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, methyl lactate, ethyl lactate, diacetone alcohol, 3-methyl -3-Methoxybutanol, gamma butyrolactone, 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). The amount is preferably 800 parts by mass or less, more preferably 500 parts by mass or less.

  Next, the manufacturing method of the photosensitive resin composition of this invention is demonstrated. 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) or (E) The photosensitive resin composition can be obtained by dissolving the components and the like. The dissolution method may, for example, be stirring or heating. When heating, the heating temperature is preferably set in the range that does not impair the performance of the photosensitive resin composition, and is usually 20 ° C to 80 ° C. Further, the order of dissolution of the respective components is not particularly limited, and there is, for example, a method of sequentially dissolving from the compound having low solubility. In addition, with regard to components that are likely to generate air bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, other components are dissolved and then added last, resulting in the dissolution failure of other components due to the generation of air bubbles. You can prevent.

  The resulting photosensitive resin composition is preferably filtered using a filter to remove dust and particles. Examples of the filter pore size include, but not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.03 μm, 0.02 μm, 0.01 μm, and 0.005 μm. The material of the filtration filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE) and the like, and PE and NY are preferable.

  Next, an example is given and demonstrated about the method to manufacture a cured film using the photosensitive resin composition of this invention.

  First, the photosensitive resin composition is applied onto a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, etc. may be used, but it 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 in which 0.5 to 20% by mass of the aforementioned coupling agent is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate The surface is treated by spin coating, dipping, spray coating, steam treatment, etc. In some cases, the reaction between the substrate and the above-mentioned coupling agent can also proceed by subsequently applying a temperature of 50 ° C. to 300 ° C.

  The photosensitive resin composition may be applied by spin coating using a spinner, spray coating, roll coating or the like. The thickness of the applied film varies depending on the application method, the solid content concentration of the composition, the viscosity and the like, but in general, the film is preferably applied so that the 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 pre-bake. Drying is preferably performed in the range of 70 to 140 ° C. for 1 minute to several hours using an oven, a hot plate, an infrared ray or the like. When a hot plate is used, the coated film can be held and heated directly on the plate or on a jig such as a proxy pin placed on the plate. The material of the proxy pin is a metal material such as aluminum or stainless steel, or a polyimide resin or a synthetic resin such as "Teflon" (registered trademark), and any material may be used if it is heat resistant. . The height of the proxy pin varies depending on the size of the substrate, the type of coating film, the purpose of heating, etc., but is preferably 0.1 to 10 mm.

  Next, the photosensitive coating film is exposed to actinic radiation through a mask having a desired pattern. The actinic radiation used for exposure includes ultraviolet light, visible light, electron beam, X-ray, etc. In the present invention, Y-ray (355 nm) of YAG laser, mercury ray i-line (365 nm), h-line (405 nm), g-line (g-line) It is preferable to use 436 nm), more preferably YAG laser (355 nm). When it has negative photosensitivity, the exposed part is cured and becomes insoluble in a developer.

  Next, bake processing after exposure is performed as necessary. As this temperature, the range of 50-150 degreeC is preferable, and the range of 60-140 degreeC is especially more preferable. The time is not particularly limited, but it is preferably 10 seconds to several hours from the viewpoint of the subsequent developability.

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

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

  After development, the pattern of the applied film obtained 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 be carried out for 5 minutes to 5 hours while selecting a temperature and raising the temperature stepwise or selecting a certain temperature range while raising the temperature continuously. As an example, the method of heat-processing for 30 minutes each at 130 degreeC, 200 degreeC, and 350 degreeC, the method of heating up linearly from room temperature to 220 degreeC over 2 hours, etc. are mentioned.

  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 make the photosensitive resin composition of the present invention into a photosensitive resin sheet, it is preferably formed on a support and used. The method for applying the photosensitive resin composition of the present invention to a support film includes spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure Examples of the method include a coater, a screen coater, and a slit die coater. The thickness of the applied film varies depending on the application method, the solid content concentration of the composition, the viscosity and the like, but in general, the thickness after drying is preferably 0.5 μm to 100 μm.

  The support is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, polyimide film and the like can be used. The bonding surface between the support and the resin sheet may be subjected to surface treatment with silicone, a silane coupling agent, an aluminum chelating agent, polyurea or the like in order to improve adhesion and releasability. 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 more from the viewpoint of drying property, and is preferably 150 ° C. or less from the viewpoint of not impairing the photosensitivity. Under the present circumstances, it is preferable that the film thickness of the photosensitive resin sheet is 5 micrometers or more from a viewpoint of level difference embedding property at the time of lamination, and it is preferable that it is 150 micrometers or less from a viewpoint of film thickness uniformity.

  Moreover, the photosensitive resin sheet of this invention may have a protective film on a film in order to protect the surface. Thus, the surface of the photosensitive resin sheet can be protected from contaminants in the atmosphere, such as dust and dirt.

  As a protective film, a polyolefin film, a polyester film, etc. are mentioned. The protective film preferably has a small adhesion to the photosensitive resin sheet.

  Next, a method for producing a cured film using a photosensitive resin sheet will be described by way of examples.

  When using a photosensitive resin sheet, the photosensitive resin sheet is bonded to a 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 in which circuit constituent materials are disposed on these boards, etc. . Examples of organic circuit boards include glass-clad copper-clad laminates such as glass cloth and epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven and epoxy copper-clad laminates, polyetherimide resin substrates, and polyethers A heat-resistant thermoplastic substrate such as a ketone resin substrate or a polysulfone resin substrate, a flexible substrate such as a polyester copper-clad film substrate, or a polyimide copper-clad film substrate can be mentioned. Further, examples of the inorganic circuit board include a ceramic board such as an alumina board, an aluminum nitride board, and a silicon carbide board, and a metal board such as an aluminum base board or an iron base board. Examples of the constituent material of the circuit include a conductor containing a metal such as silver, gold and copper, a resistor containing an inorganic oxide, a low dielectric containing a glass material and / or a resin, a resin and a high Examples thereof include high dielectrics containing dielectric inorganic particles and the like, and insulators containing a glass-based material and the like.

  When the photosensitive resin sheet has a protective film, it is peeled off, the photosensitive resin sheet and the substrate are made to face each other, and they are pasted together by thermocompression bonding to obtain a resin film. The thermocompression bonding can be performed by a heat press process, a heat lamination process, a heat vacuum lamination process or the like. The bonding temperature is preferably 40 ° C. or more, more preferably 50 ° C. or more, from the viewpoint of adhesion to a substrate and embeddability. Moreover, in order to prevent that the resolution of pattern formation in an exposure and development process worsens, 150 degreeC or less of bonding temperature is preferable. Moreover, at the time of thermocompression bonding, in order to remove air bubbles, you may carry out under pressure reduction.

  A cured film can be obtained by performing exposure, post-exposure baking, development, and heat curing on the resin film obtained from the photosensitive resin sheet as in the case of the photosensitive resin composition described above.

  The photosensitive resin composition of the present invention or a cured film obtained from the photosensitive resin sheet is a surface protective film of a semiconductor component, an insulating film for rewiring, an electronic component such as a thin film inductor, and interlayer insulation of multilayer wiring for high density mounting. It is suitably used for applications such as films and insulating layers of organic electroluminescent devices. Next, an application example to a semiconductor device having bumps using the photosensitive resin composition of the present invention will be described using the drawings (Application Example 1). FIG. 1 is an enlarged sectional view of a pad portion of a semiconductor device having a bump of the present invention. As shown in FIG. 1, a passivation film 3 is formed on a silicon wafer 1 on an input / output aluminum (hereinafter referred to as Al) pad 2, and a via hole is formed in the passivation film 3. Furthermore, an insulating film 4 is formed thereon as a pattern of a cured film of the photosensitive resin composition of the present invention, and a metal (Cr, Ti, etc.) film 5 is formed to be connected to the Al pad 2. Metal wiring (Al, Cu, etc.) 6 is formed by electrolytic plating or the like. A pattern of the cured film of the photosensitive resin composition of the present invention is formed as the insulating layer 7 on the metal wiring 6, and the barrier metal 8 and the solder bump 9 are formed in the opening. Further, scribing lines 10 for dicing and dividing into chips are formed by the openings of the insulating film 4 and the insulating film 7. Since the cured film of the photosensitive resin composition of the present invention is excellent also in high elongation, deformation of the cured film itself can relieve stress from the sealing resin even at the time of mounting. Damage to the low-k layer can be prevented, and a highly reliable semiconductor device can be provided.

  Next, a detailed manufacturing method of the semiconductor device is described in FIG. As shown in FIG. 2A, an Al pad 2 for input / output and a passivation film 3 are formed on a silicon wafer 1, and an insulating film 4 is formed as a pattern of a cured film of the photosensitive resin composition of the present invention. Subsequently, a metal (Cr, Ti, etc.) film 5 is formed to be connected to the Al pad 2 as shown in 2b of FIG. 2, and as shown in 2c of FIG. 6) form a film by plating. Next, as shown in 2 d ′ of FIG. 2, the photosensitive resin composition of the present invention is applied, and a photolithographic process is performed to form a cured film, and an insulating film 7 is formed as a pattern as shown in 2 d of FIG. 2. Wiring (so-called rewiring) can be further formed on the insulating film 7. In the case of forming a multilayer wiring structure of two or more layers, the above steps are repeated to form an interlayer insulating film, which is a cured film obtained by re-wiring two or more layers from the photosensitive resin composition of the present invention. Separated multilayer wiring structures can be formed. There is no upper limit to the number of layers in the multilayer 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 bumps 9 are formed. Then, dicing is performed along the last scribe line 10 to separate chips.

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

  EXAMPLES The present invention will now be described by way of examples, but the present invention is not limited by these examples. The evaluation of the photosensitive resin composition and the cured film in the examples was performed by the following method.

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

<Measurement method of film thickness>
Dainippon Screen Mfg. Co., Ltd. product lambda ace STM-602J was used, and the film thickness measurement was performed as a refractive index 1.63 targeting a photosensitive coating film.

<Evaluation of residual film rate after development by LDI method>
A photosensitive coating film formed on a silicon wafer of 8 inches was exposed at an exposure amount of 50 mJ / cm ² at a laser output of 0.5 W using a laser direct writing exposure apparatus DW-3000 (manufactured by SCREEN Co., Ltd.) The

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

  Assuming that the film thickness after prebaking is T1 (μm) and the film thickness after development is T2 (μm), the film remaining ratio after development is defined as T2 / T1 × 100 (%). After development, the residual film rate is 90% or more, very good (A), 80% or more and less than 90% good (B), 70% or more and less than 80% possible (C), less than 70% Was insufficient (D).

<Thermal curing (cure)>
The coated film was developed using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.) in an atmosphere in an oven with an oxygen concentration of 20 ppm or less at a temperature rising rate of 3.5 ° C / min from 220C. The temperature was raised to ° C., and heat treatment was performed at 220 ° C. for 1 hour. Thereafter, the film was gradually cooled until the temperature in the oven reached 50 ° C. or less to obtain a cured film.

<Mechanical property evaluation (high elongation)>
The cured film of the photosensitive resin composition formed on a silicon wafer of 8 inches was immersed in 45% by mass of hydrofluoric acid for 3 minutes to separate the cured film from the wafer. This film is cut into strips 1 cm wide and 9 cm long, and a tensile speed of 50 mm / at room temperature 23.0 ° C. and humidity 45.0% RH using TENSILON RTM-100 (manufactured by ORIENTEC Co., Ltd.) It pulled in minutes and measured the elongation at break. The measurement was performed on 10 strips per sample, and the average value of the top 5 points was determined from the results. The elongation at break value is 50% or more, very good (A), 30% or more and less than 50% is good (B), and 10% or more and less than 30% is possible (C), 10 Less than% was regarded as insufficient (D).

Synthesis Example 1 Synthesis of Polyimide
Under a stream of dry nitrogen, 32.9 g (0.09 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF, manufactured by AZ Electronic Materials, Inc.) was dissolved in 500 g of NMP. To this was added 31.0 g (0.1 mol) of ODPA together with 50 g of NMP, and the mixture was stirred at 30 ° C. for 2 hours. Thereafter, 2.18 g (0.02 mol) of 3-aminophenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and the mixture was stirred at 40 ° C. for 2 hours. Furthermore, 5 g of pyridine (manufactured by Tokyo Kasei Co., Ltd.) was diluted with toluene (30 g manufactured by Tokyo Kasei Co., Ltd.), added to the solution, and a cooling pipe was attached to the solution while removing water azeotropically with toluene outside the system. The temperature was raised to 120 ° C. for 2 hours, and further reacted at 180 ° C. for 2 hours. The temperature of this solution was lowered to room temperature, and the solution was poured into 3 liters of water to obtain a white powder. The powder was collected by filtration and washed three more times with water. After washing, the white powder was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide.

Synthesis Example 2 Synthesis of Hydroxyl Group-Containing Diamine Compound (HFHA)>
18.2 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF) in 100 mL of acetone, propylene oxide (manufactured by Tokyo Kasei Co., Ltd.) C.) It was dissolved in 17.4 g (0.3 mol) and cooled to -15.degree. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) dissolved in 100 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the mixture was stirred at -15 ° C for 4 hours and then returned to room temperature. The precipitated white solid was separated by filtration and vacuum dried at 50 ° C.

  30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, 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 further. After completion of the reaction, the reaction product was filtered to remove the catalyst palladium compound and concentrated by a rotary evaporator to obtain a hydroxyl group-containing diamine compound (HFHA) represented by the following formula.

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

Synthesis Example 4 Synthesis of Polybenzoxazole Precursor
Under a stream of dry nitrogen, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP, 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 Japan Pesticide Co., Ltd.) and 5.1 g (0.025 mol) of isophthalic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) to 25 g of γ-butyrolactone The dissolved solution was dropped so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued at -15 ° C for 6 hours. After completion of the reaction, the solution was poured into 3 liters of water containing 10% by mass of methanol to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polybenzoxazole precursor.

Example 1
In a stream of dry nitrogen, 10.01 g (0.05 mol) of 4,4′-diaminodiphenyl ether (DAE manufactured by Wakayama Seika Kogyo Co., Ltd.) and 4-methoxyphenol (MEHQ manufactured by Tokyo Chemical Industry Co., Ltd.) 0. 15 g was dissolved in 40 g of NMP. To this, 7.76 g (0.025 mol) of 3,3 ', 4,4'-diphenylethertetracarboxylic acid dianhydride (manufactured by Shanghai Synthetic Resin Laboratory, ODPA) was added together with 10 g of NMP, and the mixture was allowed to stand overnight at 30 ° C. It stirred. Thereafter, 7.71 g (0.05 mol) of methacrylic anhydride (manufactured by Sigma-Aldrich Co.) was added, and reaction was performed by stirring for 2 hours. The solution was poured into 3 L of water to obtain a white powder. The powder was collected by filtration and washed three more times with water. After washing, the white powder was dried by 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 H-NMR (DMSO): 10.3 (s, 2 H), 9.7 (s, 2 H), 8.0 (d, 2 H), 7.6-7.8 (m, 12 H), 6. 9-7.1 (m, 8 H), 5.8 (s, 2 H), 5.5 (s, 2 H), 1.9 (s, 6 H).

A 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 a photopolymerizable monomer (A), 1.50 g of RA1 of a photopolymerizable monomer,
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
0.43 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties 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 a photopolymerizable monomer (A), 3.00 g of RA1 of a photopolymerizable monomer,
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
0.43 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties 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 a photopolymerizable monomer (A), 4.50 g of RA1 of a photopolymerizable monomer,
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
0.43 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties were carried out by the above method.

Example 4
The following substances were 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 RA1 of the photopolymerizable monomer,
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
0.43 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties 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,
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
0.43 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties 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,
10.00 g of the polyimide precursor of Synthesis Example 1 as an alkali-soluble resin (B)
0.43 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties 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 a photopolymerizable monomer (A), 7.00 g of RA1 of a photopolymerizable monomer,
10.00 g of the polybenzoxazole precursor of Synthesis Example 1 as the alkali-soluble resin (B),
0.43 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties were carried out by the above method.

[Example 8]
The following substances were added to 16.71 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
7.50 g of a photopolymerizable monomer RA1 as a photopolymerizable monomer (A),
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
0.43 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties were carried out by the above method.

[Example 9]
The following substances were added to 13.29 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As a photopolymerizable monomer (A), 3.00 g of RA1 of a photopolymerizable monomer,
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
As photopolymerization initiator (C), 0.20 g of NCI-831,
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties were carried out by the above method.

[Example 10]
The following substances were added to 13.87 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As a photopolymerizable monomer (A), 3.00 g of RA1 of a photopolymerizable monomer,
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
As photopolymerization initiator (C), 1.00 g of NCI-831,
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties were carried out by the above method.

[Example 11]
The following substances were added to 13.22 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As a photopolymerizable monomer (A), 3.00 g of RA1 of a photopolymerizable monomer,
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
As photopolymerization initiator (C), 0.10 g of NCI-831,
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties 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 a photopolymerizable monomer (A), 3.00 g of RA1 of a photopolymerizable monomer,
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
1.10 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties were carried out by the above method.

[Example 13]
The following substances were added to 13.45 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
As a photopolymerizable monomer (A), 3.00 g of RA1 of a photopolymerizable monomer,
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
0.43 g of "IRGACURE" 907 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties 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 a photopolymerizable monomer (A), 3.00 g of RA1 of a photopolymerizable monomer,
10.00 g of the polyimide precursor of Synthesis Example 3 as an alkali-soluble resin (B)
0.43 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties 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 a photopolymerizable monomer (A), 3.00 g of RA1 of a photopolymerizable monomer,
10.00 g of the PBO precursor of Synthesis Example 4 as an alkali-soluble resin (B)
0.43 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties were carried out by the above method.

[Example 16]
In a stream of dry nitrogen, 5.41 g of 1,4-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.05 g of 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd., MEHQ) in 40 g of NMP 40 g Dissolved in To this, 7.76 g (0.025 mol) of 3,3 ', 4,4'-diphenylethertetracarboxylic acid dianhydride (manufactured by Shanghai Synthetic Resin Laboratory, ODPA) was added together with 10 g of NMP, and the mixture was allowed to stand overnight at 30 ° C. It stirred. Thereafter, 7.71 g (0.05 mol) of methacrylic anhydride (manufactured by Sigma-Aldrich Co.) was added, and reaction was performed by stirring for 2 hours. The solution was poured into 3 L of water to obtain a white powder. The powder was collected by filtration and washed three more times with water. After washing, the white powder was dried by 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 H-NMR (DMSO): 10.3 (s, 2 H), 9.7 (s, 2 H), 7.9 (d, 2 H), 7.6-7.8 (m, 8 H), 6. 9-7.1 (m, 4 H), 5.8 (s, 2 H), 5.5 (s, 2 H), 1.9 (s, 6 H).

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 a photopolymerizable monomer (A), 3.00 g of RA2 of a photopolymerizable monomer,
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
0.43 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties were carried out by the above method.

[Example 17]
In a stream of dry nitrogen, 5.41 g of 1,4-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.05 g of 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd., MEHQ) in 40 g of NMP 40 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. Thereafter, 7.71 g (0.05 mol) of methacrylic anhydride (manufactured by Sigma-Aldrich Co.) was added, and reaction was performed by stirring for 2 hours. The solution was poured into 3 L of water to obtain a white powder. The powder was collected by filtration and washed three more times with water. After washing, the white powder was dried by 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 H-NMR (DMSO): 10.3 (s, 2 H), 9.7 (s, 2 H), 8.6 (d, 2 H), 7.6-7.8 (m, 8 H), 5. 8 (s, 2 H), 5.5 (s, 2 H), 1.9 (s, 6 H).

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 RA3 of the photopolymerizable monomer,
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
0.43 g of NCI-831 as a photopolymerization initiator (C),
Does not contain other photopolymerizable monomers (D),
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties were carried out by the above method.

Comparative Example 1
The following substances were added to 9.11 g of γ-butyrolactone and stirred to obtain a photosensitive resin composition of the resin composition.
Does not contain photopolymerizable monomer (A),
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
0.43 g of NCI-831 as a photopolymerization initiator (C),
As a photopolymerizable monomer (D) having no other amide bond, 3.00 g of PDBE-250,
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties 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.
Does not contain photopolymerizable monomer (A),
10.00 g of the polyimide of Synthesis Example 1 as an alkali-soluble resin (B),
0.43 g of NCI-831 as a photopolymerization initiator (C),
As a photopolymerizable monomer (D) having no other amide bond, 3.00 g of DCP-A,
1.43 g of Nicalac MX-270 as a thermal crosslinking agent (E)
0.71 g of KBM-403 as adhesion modifier,
Polyflow No. 1 as a surfactant. 0.01 g of 77.
Using the obtained photosensitive resin composition, evaluation of residual film rate after development and evaluation of mechanical properties were carried out by the above method.

  It shows in Table 1 about Example 1-17 and Comparative Examples 1-2 regarding said composition and evaluation result. There is no problem if the results of residual film rate evaluation after development and mechanical property evaluation are both C or higher by the LDI method.

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 Acrulus NCI-831 (trade name, manufactured by ADEKA Co., Ltd.)
IRGACURE 907: "IRGACURE" (registered trademark) 907 (trade name, manufactured by BASF Japan Ltd.),
PDBE-250: "Blenmar" (registered trademark)
PDBE-250 (trade name, manufactured by NOF Corporation)
DCP-A: Light acrylate DCP-A (trade name, manufactured by Kyoei Chemical Co., Ltd.)
MX-270: Nicarak 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.)
PF 77: Polyflow No. 77 (brand name, manufactured by Kyoei Chemical Co., Ltd.)
GBL: γ-butyrolactone

1 silicon wafer 2 Al pad 3 passivation film 4 insulating film 5 metal (Cr, Ti etc) film 6 metal wiring (Al, Cu etc)
7 insulating film 8 barrier metal 9 solder bump 10 scribe line 11 substrate 12 insulating film 13 insulating film 14 metal (Cr, Ti etc) film 15 metal wiring (Ag, Cu etc)
16 Metal wiring (Ag, Cu etc.)
17 electrode 18 sealing resin

Claims (13)

The photopolymerizable monomer which has a structure represented by General formula (1).

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or a C 1-10 monovalent organic group. L is Any of a divalent aromatic group having one benzene ring, or 2 to 5 benzene rings each having a single bond, an ether bond, an isopropylidene group, a trifluoroisopropylidene group, a carbonyl group, an amido group or a sulfonyl group Represents a divalent organic group having a structure bonded via a heel (the mark * indicates a bond) The photopolymerizable monomer according to claim 1, wherein the photopolymerizable monomer having the structure represented by the general formula (1) has a 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 and each represents a hydrogen atom or a carbon number of 1 to 10) L and M, which may be the same or different, each represents a divalent aromatic group having one benzene ring, or a single bond of 2 to 5 benzene rings, It represents a divalent organic group having a structure bonded by an ether bond, an isopropylidene group, a trifluoroisopropylidene group, a carbonyl group, an amido group or a sulfonyl group, and X represents a single bond, an ether bond, isopropylidene And R 1 represents an organic group having one or more selected from the group consisting of a group, a trifluoroisopropylidene group, a carbonyl group, an amido group and a sulfonyl group.) The photopolymerizable monomer according to claim 2, wherein the photopolymerizable monomer having the structure represented by the general formula (2) has a 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, and each represents a hydrogen atom or a carbon number of 1 to 10 X, Y and Z, which may be the same or different, each represents a single bond, an ether bond, an isopropylidene group, a trifluoroisopropylidene group, a carbonyl group, an amido group or a sulfonyl group Represents an organic group having one or more selected from the group consisting of A photosensitive resin composition comprising the photopolymerizable monomer (A) according to claim 1, an alkali-soluble resin (B), and a photopolymerization initiator (C). The photosensitive resin composition according to claim 4, wherein the photopolymerizable monomer (A) having a structure represented by the general formula (1) has a 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 and each represents a hydrogen atom or a carbon number of 1 to 10) L and M, which may be the same or different, each represents a divalent aromatic group having one benzene ring, or a single bond of 2 to 5 benzene rings, It represents a divalent organic group having a structure bonded by an ether bond, an isopropylidene group, a trifluoroisopropylidene group, a carbonyl group, an amido group or a sulfonyl group, and X represents a single bond, an ether bond, isopropylidene And R 1 represents an organic group having one or more selected from the group consisting of a group, a trifluoroisopropylidene group, a carbonyl group, an amido group and a sulfonyl group.) The photosensitive resin composition according to claim 5, wherein the photopolymerizable monomer (A) having a structure represented by the general formula (2) has a structure represented by a 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, and each represents a hydrogen atom or a carbon number of 1 to 10 X, Y and Z, which may be the same or different, each represents a single bond, an ether bond, an isopropylidene group, a trifluoroisopropylidene group, a carbonyl group, an amido group or a sulfonyl group Represents an organic group having one or more selected from the group consisting of The photosensitive resin according to any one of claims 4 to 6, 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. The photopolymerization initiator (C) has an oxime type structure, and is contained in an amount of 2 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the alkali-soluble resin (B). The photosensitive resin composition as described in any one. The photosensitive resin sheet formed from the photosensitive resin composition in any one of Claims 4-8. The cured film which hardened | cured the photosensitive resin composition in any one of Claims 4-8, or the photosensitive resin sheet of Claim 9. The electronic component or semiconductor component by which the cured film of Claim 10 was arrange | positioned as an interlayer insulation film or a surface protective film. The electronic component or semiconductor component by which the cured film of Claim 10 was arrange | positioned as an interlayer insulation film between rewirings. The electronic component or the semiconductor device by which the cured film of Claim 10 was repeatedly arrange | positioned 2-10 layers as an interlayer insulation film between rewirings.

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