JP6439291B2 - Photosensitive resin composition, photosensitive element, semiconductor device, and method for forming resist pattern - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element, a semiconductor device, and a method for forming a resist pattern.

  In manufacturing a semiconductor element or a printed wiring board on which the semiconductor element is mounted, for example, a negative photosensitive resin composition is used to form a fine pattern. In this method, a photosensitive layer is formed on a base material (for example, a chip in the case of a semiconductor element or a substrate in the case of a printed wiring board) by application of a photosensitive resin composition, and irradiated with actinic rays through a predetermined pattern. By doing so, the exposed portion is cured. Furthermore, the resist pattern which is a cured film of the photosensitive resin composition is formed on a base material by selectively removing an unexposed part using a developing solution. Therefore, the photosensitive resin composition is required to have high sensitivity to actinic rays and to be able to form a fine pattern (resolution). Therefore, a photosensitive resin composition containing a novolak resin, an epoxy resin, a photoacid generator, etc. soluble in an alkaline aqueous solution, a photosensitive resin composition containing an alkali-soluble epoxy compound having a carboxyl group, a photocationic polymerization initiator, etc. A thing etc. are proposed (for example, refer patent documents 1-3).

  Furthermore, the surface protection film and the interlayer insulating film used in the semiconductor element are required to have insulation reliability such as heat resistance, electrical characteristics, and mechanical characteristics. Thus, a photosensitive resin composition in which the photosensitive resin composition further contains a crosslinkable monomer has been proposed (see, for example, Patent Document 4).

  On the other hand, in recent years, with the improvement in performance of electronic devices, higher integration and higher reliability of semiconductor elements are progressing year by year. As semiconductor elements are highly integrated, it is required to form finer patterns. Therefore, a photosensitive resin composition capable of forming a resist pattern with high resolution is required.

  Further, by forming the interlayer insulating film thick, the insulation between the wirings in the thickness direction of the layers can be improved and the short circuit of the wiring can be prevented, so that the reliability regarding the insulation between the wirings is improved. In addition, when a chip is mounted, since the semiconductor element has a thick interlayer insulating film, the stress applied to the solder bump pad can be relieved, so that connection failure hardly occurs during mounting. Therefore, from the viewpoint of insulation reliability and productivity when mounting a chip, it is also required that a film of a thick photosensitive resin composition exceeding 20 μm can be formed.

Japanese Patent Application Laid-Open No. 06-059444 JP 09-087366 A International Publication No. 2008/010521 JP 2003-215802 A

  However, for example, in the photosensitive resin composition described in Patent Document 1 or 4, when the thickness of the coating film is 10 μm or less, good resolution with a space width of about 5 μm is obtained. When it is converted into a good resolution, good resolution cannot be obtained. Further, in the photosensitive resin composition described in Patent Document 2, when the thickness of the coating film is 50 μm, the resolution is such that the space width is about 40 μm, which is insufficient for highly integrated semiconductor elements. is there. Furthermore, in the conventional photosensitive resin composition, even when good resolution is obtained, the sensitivity to actinic rays (for example, i-line) is low (see Comparative Examples 1 to 3), so long-time exposure. Or exposure with high irradiation intensity is required, and there are concerns about productivity and cost.

  An object of the present invention is to solve the problems associated with the prior art as described above and to provide a photosensitive resin composition excellent in resolution and sensitivity. Moreover, the objective of this invention is providing the formation method of the resist pattern using the photosensitive element and semiconductor device which are obtained using the said photosensitive resin composition, and the said photosensitive resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have found a photosensitive resin composition having excellent characteristics. That is, the photosensitive resin composition of the present invention is selected from the group consisting of (A) component: novolak resin, (B) component: photosensitive acid generator, and (C) component: methylol group and alkoxyalkyl group. And a cross-linking agent having at least one kind, wherein the molar extinction coefficient of the component (B) with respect to light having a wavelength of 365 nm is 100 L / (mol · cm) or more.

  The photosensitive resin composition of the present invention comprises a component (D): a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3) It is preferable to further contain at least one selected from the group consisting of compounds represented by the following general formula (4).

[In the formulas (1) to (4), R ¹¹ _, R ²¹ , R ⁴² and R ⁴⁵ are each independently a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the formula (5). R ¹² , R ¹³ , R ¹⁴ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ _, R ³⁴ , R ³⁵ , R ³⁶ , R ⁴¹ , R ⁴³ , R ⁴⁴ and R ⁴⁶ are Each independently represents a hydroxyl group, a glycidyl ether group, an oxetanyl alkyl ether group, a vinyl ether group, an acryloyloxy group, a methacryloyloxy group, a group represented by formula (6), or a group represented by formula (7); wherein (5), R ⁵ represents a hydroxyl group, glycidyl ether group, oxetanyl alkyl ether group, a vinyl ether group, acryloyloxy group or methacryloyloxy group, the formula (6) and During 7), R ⁶ and R ⁷ are hydroxyl groups independently glycidyl ether group, oxetanyl alkyl ether group, vinyl ether group, an acryloyloxy group or a methacryloyloxy group, m and n are each independently from 1 to 10 Indicates an integer. ]

  Moreover, this invention provides a photosensitive element provided with a support body and the photosensitive layer containing the said photosensitive resin composition provided on this support body.

  Furthermore, this invention provides a semiconductor device provided with the hardened | cured material of the said photosensitive resin composition.

  The present invention also includes a step of applying the photosensitive resin composition onto a substrate, drying the photosensitive resin composition to form a photosensitive layer, exposing the photosensitive layer to a predetermined pattern, and exposing A step of performing a post-heat treatment (hereinafter, this heat treatment is also referred to as “post-exposure bake”), and developing the photosensitive layer after the heat treatment (post-exposure bake), and heat-treating the resulting resin pattern. And a method of forming a resist pattern.

  Furthermore, the present invention includes a step of arranging the photosensitive layer of the photosensitive element on a substrate, a step of exposing the photosensitive layer to a predetermined pattern, and performing a post-exposure heat treatment (post-exposure baking), And developing the photosensitive layer after heat treatment (post-exposure baking), and heat-treating the resulting resin pattern.

  The photosensitive resin composition of the present invention is excellent in resolution and sensitivity. According to such a photosensitive resin composition, a resist pattern having high sensitivity and excellent resolution can be produced. Moreover, the photosensitive resin composition of the present invention is excellent in resolution and sensitivity even when a coating film having a thickness exceeding 20 μm is formed.

It is a schematic diagram which shows the manufacturing method of the multilayer printed wiring board of this embodiment.

  Hereinafter, although one embodiment of the present invention is described concretely, the present invention is not limited to this.

  Note that in this specification, the term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view. In this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used if the intended purpose of the process is achieved. included. In this specification, the numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the present specification, the term “siloxane bond” indicates a bond between a silicon atom and an oxygen atom, that is, a “Si—O bond”.

[Photosensitive resin composition]
The photosensitive resin composition of this embodiment is selected from the group consisting of (A) component: novolak resin, (B) component: photosensitive acid generator, and (C) component: methylol group and alkoxyalkyl group. And a cross-linking agent having at least one kind. In the photosensitive resin composition of the present embodiment, the molar extinction coefficient of the component (B) with respect to light having a wavelength of 365 nm is 100 L / (mol · cm) or more.

  The present inventors consider the reason why the photosensitive resin composition of the present embodiment is excellent in resolution and sensitivity as follows. First, the inference about high resolution will be described. In the unexposed area, the solubility of the component (A) in the developer is improved by the addition of the component (C). Next, in the exposed portion, due to the catalytic effect of the acid generated from the component (B), methylol groups or alkoxyalkyl groups in the component (C), or methylol groups or alkoxyalkyl groups in the component (C) and (A ) Component reacts with dealcoholization, so that the solubility of the composition in the developer is greatly reduced. Thereby, when developed, sufficient resolution can be obtained due to a remarkable difference in solubility in the unexposed and exposed portion of the developer.

  Next, an inference about high sensitivity will be described. The component (B) is a compound that generates an acid by absorbing actinic rays or the like. The light absorption probability depends on the molar extinction coefficient of the photosensitive acid generator. In this embodiment, the light absorption probability is improved by using a light-sensitive acid generator having a large molar extinction coefficient compared to the conventional one, and the amount of acid required for curing by irradiation with an actinic ray or the like with a small exposure amount. Since this occurs, the sensitivity can be increased. Based on these facts, the inventors of the present invention have excellent resolution and sensitivity of the photosensitive resin composition of the present embodiment. By using such a photosensitive resin composition, the sensitivity is high and resolution is high. It is assumed that a resist pattern can be formed.

  If necessary, the photosensitive resin composition of the present embodiment includes (D) component: a compound represented by any one of general formulas (1) to 4 described later, (E) component: sensitizer, (F ) Component: solvent, (G) component: a compound having a siloxane bond, and the like.

<(A) component>
The novolak resin as the component (A) is not particularly limited, but is preferably a resin that is soluble in an alkaline aqueous solution. The novolak resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3 -Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol Catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.

  Specific examples of the novolak resin include phenol-cresol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and the like. (A) A component can be used individually by 1 type or in mixture of 2 or more types.

  The weight average molecular weight of the component (A) is preferably 100000 or less, more preferably 1000 to 80000, and more preferably 2000 to 50000 from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance and the like of the cured film obtained. Is more preferable, 2000-20000 is particularly preferable, and 5000-15000 is very preferable.

  The content of the component (A) is preferably 10 to 90% by mass, based on the total amount of the photosensitive resin composition (when the component (F) is used, the total amount of the components excluding the component (F)), 80 mass% is more preferable, and 40-60 mass% is still more preferable. (A) The ratio of a component is the said range, The developability by the aqueous alkali solution in the film | membrane formed using the photosensitive resin composition obtained is more excellent.

<(B) component>
The photosensitive acid generator (B) is a compound that generates an acid upon irradiation with actinic rays or the like. Due to the catalytic effect of the acid generated from the light-sensitive acid generator, the methylol groups or alkoxyalkyl groups in component (C) or the methylol group or alkoxyalkyl group in component (C) and component (A) Reacts with dealcoholization, so that the solubility of the composition in the developer is greatly reduced, and a negative pattern can be formed.

  The molar extinction coefficient of the light-sensitive acid generator of component (B) for light having a wavelength of 365 nm is 100 L / (mol · cm) or more. The molar extinction coefficient of the photosensitive acid generator can be evaluated, for example, by the following procedure.

  First, acetonitrile solutions of photosensitive acid generators having different concentrations of 4 or more points (unit: mol / L) are prepared at room temperature (25 ° C., the same applies below) using a volumetric flask and a whole pipette. . The concentration “mol / L” is obtained by dividing the mass “g” of the photosensitive acid generator contained in the volumetric flask by the molecular weight “g / mol” of the photosensitive acid generator, and further, the volume “L” of the volumetric flask. It can be calculated by dividing by. Examples of a method for measuring the molecular weight “g / mol” of the photosensitive acid generator include mass spectrometry. The prepared acetonitrile solution of the photosensitive acid generator is filled in a quartz cell having an optical path length of 1 cm, and an ultraviolet-visible spectrophotometer (for example, Hitachi High-Technologies Corporation, trade name: Hitachi spectrophotometer U-3310) is used. The absorption spectrum of the photosensitive acid generator is measured. The spectrophotometer is used after the light source is stabilized, and then a background measurement is performed in a 1 cm quartz cell filled with acetonitrile, and then the absorption spectrum of the photo-sensitive acid generator is used. As measurement conditions, the temperature is the temperature at which the solution is prepared, the slit width is 2 nm, the scan speed is 300 nm / min, the sampling interval is 0.50 nm, and the measurement range is 600 nm to 300 nm. In each measurement, it is confirmed that the absorbance at a wavelength of 365 nm does not exceed 2.0. The vertical axis represents the absorbance of the photosensitive acid generator with respect to light having a wavelength of 365 nm, the horizontal axis represents the product of the concentration of the photosensitive acid generator and the optical path length, and an approximate straight line is drawn by the method of least squares. It is confirmed that the determination coefficient is 0.999 or more. From the Lambert-Beer law, the slope of the obtained straight line is calculated as the molar extinction coefficient (L / (mol · cm)) at a wavelength of 365 nm.

  In the photosensitive resin composition of the present embodiment, the molar extinction coefficient of the component (B) is 100 L / (mol · cm) or more. Among them, the lower limit value of the molar extinction coefficient of the component (B) is preferably 150 L / (mol · cm) or more, more preferably 200 L / (mol · cm) or more, and further preferably 500 L / (mol · cm) or more. The upper limit of the molar extinction coefficient of the component (B) is not particularly limited, but is preferably 10,000 L / (mol · cm) or less, more preferably 5000 L / (mol · cm) or less, and 3000 L / (mol · cm) or less. More preferred is 1000 L / (mol · cm) or less. When the molar extinction coefficient of the component (B) is in such a range, the sensitivity, resolution, and pattern shape of the photosensitive resin composition of the present embodiment tend to be further improved.

  The component (B) is not particularly limited as long as it is a compound that generates an acid upon irradiation with an actinic ray or the like and has a molar extinction coefficient with respect to light having a wavelength of 365 nm of 100 L / (mol · cm) or more. And onium salt compounds. Specific examples of onium salt compounds are shown below.

Examples of the onium salt compounds include iodonium salts, sulfonium salts (for example, arylsulfonium salts such as triarylsulfonium salts), phosphonium salts, diazonium salts, pyridinium salts, and the like. Specific examples of preferred onium salt compounds include [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium trifluoromethanesulfonate, [4- (4-biphenylylthio) phenyl] -4-biphenylyl. Phenylsulfonium nonafluorobutanesulfonate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium heptadecafluorooctanesulfonate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenyl Sulfonium p-toluenesulfonate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium hexafluoroantimonate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfone Um hexafluorophosphate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, [4- (4-biphenylylthio) phenyl] -4-biphenyl Rylphenylsulfonium tetrafluoroborate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, [4- (4-biphenylylthio) phenyl] -4-biphenyl Rylphenylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium trifluoromethanesulfonate, (2-methyl) phenyl [4- (4-Biphenylylthio) phenyl] 4-biphenylylsulfonium nonafluorobutanesulfonate, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium heptadecafluorooctanesulfonate , (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium p-toluenesulfonate, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenyl Rylsulfonium hexafluoroantimonate, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium hexafluorophosphate, (2-methyl) phenyl [4- (4-biphenylylthio) Phenyl] 4-biphenylylsulfonium tri (Pentafluoroethyl) trifluorophosphate, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium tetrafluoroborate, (2-methyl) phenyl [4- (4-biphenylyl) Ruthio) phenyl] 4-biphenylylsulfonium tetrakis (pentafluorophenyl) borate, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium tris [(trifluoromethyl) sulfonyl] methanide , [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium trifluoromethanesulfonate, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium nona Fluorobutanesulfone [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium heptadecafluorooctanesulfonate, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenyl Rylphenylsulfonium p-toluenesulfonate, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium hexafluoroantimonate, [4- (4-biphenylylthio) -3-methylphenyl ] 4-biphenylylphenylsulfonium hexafluorophosphate, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, [4- (4-biphenyl) Rylthio) -3-methylphenyl] -Biphenylylphenylsulfonium tetrafluoroborate, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, [4- (4-biphenylylthio)- 3-methylphenyl] 4-biphenylylphenylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium trifluoro Lomethanesulfonate, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium nonafluorobutanesulfonate, (2-methyl) phenyl [4- (4-biphenylylthio) ) -3-Methylphenyl] 4- Biphenylylsulfonium heptadecafluorooctanesulfonate, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium p-toluenesulfonate, (2-methyl) phenyl [4- (4-Biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium hexafluoroantimonate, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium Hexafluorophosphate, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium tris (pentafluoroethyl) trifluorophosphate, (2-methyl) phenyl [4- (4-Biphenylylthio) -3-methyl Phenyl] 4-biphenylylsulfonium tetrafluoroborate, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium tetrakis (pentafluorophenyl) borate, (2-methyl) ) Phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium trifluoromethanesulfonate, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium nonafluorobutanesulfonate, (2- Methoxy) phenyl [4- (4-bi Phenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium heptadecafluorooctanesulfonate, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium p-toluenesulfonate , (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium hexafluoroantimonate, (2-methoxy) phenyl [4- (4-biphenylylthio)- 3-methoxyphenyl] 4-biphenylylsulfonium hexafluorophosphate, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium tris (pentafluoroethyl) trifluorophosphate , (2 -Methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium tetrafluoroborate, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl ] 4-Biphenylylsulfonium tetrakis (pentafluorophenyl) borate, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium tris [(trifluoromethyl) sulfonyl] Methanide, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium trifluoromethanesulfonate, (2-ethoxy) phenyl [4- (4-biphenylylthio)- 3-Ethoxyphenyl] 4-biphenylylsulfoniu Nonafluorobutanesulfonate, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium hepadecafluorooctanesulfonate, (2-ethoxy) phenyl [4- (4- Biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium p-toluenesulfonate, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium hexafluoroantimo (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium hexafluorophosphate, (2-ethoxy) phenyl [4- (4-biphenylylthio)- 3-Ethoxyphenyl] 4-biphenylyls Rufonium tris (pentafluoroethyl) trifluorophosphate, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium tetrafluoroborate, (2-ethoxy) phenyl [4 -(4-Biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium tetrakis (pentafluorophenyl) borate, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4 -Biphenylylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, (2-butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium trifluoromethanesulfonate, (2-butoxy ) Phenyl [4- ( -Biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium nonafluorobutanesulfonate, (2-butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium heptadeca Fluorooctanesulfonate, (2-butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium p-toluenesulfonate, (2-butoxy) phenyl [4- (4-biphenylyl) (Ruthio) -3-butoxyphenyl] 4-biphenylylsulfonium hexafluoroantimonate, (2-butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium hexafluorophosphate, ( 2-Butoxy) pheny [4- (4-Biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium tris (pentafluoroethyl) trifluorophosphate, (2-butoxy) phenyl [4- (4-biphenylylthio) -3- Butoxyphenyl] 4-biphenylylsulfonium tetrafluoroborate, (2-butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium tetrakis (pentafluorophenyl) borate, (2- Butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium trifluor Lomethanesulfone Tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium nonafluorobutanesulfonate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium heptadecafluorooctanesulfonate, tris [4- (4-acetyl) Phenylsulfanyl) phenyl] sulfonium p-toluenesulfonate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium hexafluoroantimonate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium hexafluorophosphate, tris [ 4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, tris [4- (4-acetyl Enylsulfanyl) phenyl] sulfonium tetrafluoroborate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [(tri Fluoromethyl) sulfonyl] methanide, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium trifluoromethanesulfonate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium nonafluorobutane Sulfonate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium heptadecafluorooctane sulfonate, tris [4- (4-acetyl-3-methylphenol) Nylthio) phenyl] sulfonium p-toluenesulfonate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium hexafluoroantimonate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] Sulfonium hexafluorophosphate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] Sulfonium tetrafluoroborate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfo Nitris [(trifluoromethyl) sulfonyl] methanide, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium trifluoromethanesulfonate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl ] Sulfonium nonafluorobutanesulfonate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium heptadecafluorooctanesulfonate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium p Toluenesulfonate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium hexafluoroantimonate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium hexafluorophor Sulfate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium tetrafluoro Borate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium tris [(tri Fluoromethyl) sulfonyl] methanide, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium trifluoromethanesulfonate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium nonafluoro Tansulfonate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium heptadecafluorooctanesulfonate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium p-toluenesulfonate, Tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium hexafluoroantimonate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium hexafluorophosphate, tris [4- ( 4-acetyl-3-butylphenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium tetrafluoroborate, tris [4- 4-acetyl-3-butylphenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium tris [(trifluoromethyl) sulfonyl] methanide, etc. And triarylsulfonium salts thereof.

  The onium salt compound used as the component (B) is trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluoroantimonate, hexafluorophosphate, tetrafluoroborate, tris (pentafluoroethyl) in terms of further excellent sensitivity and resolution. ) A compound having trifluorophosphate or tetrakis (pentafluorophenyl) borate is preferred. Moreover, (B) component can be used individually by 1 type or in mixture of 2 or more types.

  The content of the component (B) is 0.1 to 100 parts by mass of the component (A) from the viewpoint of easily ensuring the sensitivity, resolution, pattern shape and the like of the photosensitive resin composition of the present embodiment. 15 mass parts is preferable, 0.3-10 mass parts is more preferable, 1-10 mass parts is still more preferable, and 3-10 mass parts is especially preferable. In addition, in this specification, 100 mass parts of (A) component means that it is 100 mass parts of solid content of (A) component.

<(C) component>
The photosensitive resin composition of this embodiment contains the crosslinking agent which has at least 1 type selected from the group which consists of a methylol group and an alkoxyalkyl group as (C) component. When the photosensitive resin composition contains the component (C), when it is cured by exposure and post-exposure heat treatment, the methylol groups in the component (C) or the alkoxyalkyl groups, or the component (C) When the methylol group or alkoxyalkyl group therein reacts with the component (A) with dealcoholization, the solubility of the composition in the developer is greatly reduced, and a negative pattern can be formed. As the component (C), specifically, a compound having a phenolic hydroxyl group and a compound having a hydroxymethylamino group are preferable. However, the component (C) does not include the component (A). (C) A component can be used individually by 1 type or in mixture of 2 or more types.

［式（８）中、Ｚは、単結合又は２価の有機基を示し、Ｒ^８１及びＲ^８２は、それぞれ独立に水素原子又は１価の有機基を示し、Ｒ^８３及びＲ^８４は、それぞれ独立に１価の有機基を示し、ａ及びｂは、それぞれ独立に１〜３の整数を示し、ｃ及びｄは、それぞれ独立に０〜３の整数を示す。］ As the compound having a phenolic hydroxyl group, a conventionally known compound can be used, but the compound represented by the following general formula (8) is effective in promoting the dissolution of the unexposed area and curing the photosensitive resin film. It is preferable because of its excellent balance with the effect of preventing melting of the resin.

[In Formula (8), Z represents a single bond or a divalent organic group, R ⁸¹ and R ⁸² each independently represent a hydrogen atom or a monovalent organic group, and R ⁸³ and R ⁸⁴ each represent Each independently represents a monovalent organic group, a and b each independently represent an integer of 1 to 3, and c and d each independently represents an integer of 0 to 3. ]

  In the general formula (8), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by Z include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group; an alkylidene having 2 to 10 carbon atoms such as an ethylidene group. An arylene group having 6 to 30 carbon atoms such as a phenylene group; a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms; a sulfonyl group; a carbonyl group; an ether bond Thioether bond; amide bond and the like. Among these, Z is preferably a divalent organic group represented by the following general formula (9).

［式（９）中、Ｘは、単結合、アルキレン基（例えば炭素原子数が１〜１０のアルキレン基）、アルキリデン基（例えば炭素原子数が２〜１０のアルキリデン基）、それらの水素原子の一部又は全部をハロゲン原子で置換した基、スルホニル基、カルボニル基、エーテル結合、チオエーテル結合又はアミド結合を示す。Ｒ^９は、水素原子、ヒドロキシル基、アルキル基又はハロアルキル基を示し、ｅは、１〜１０の整数を示す。複数のＲ^９は互いに同一でも異なっていてもよい。］

[In the formula (9), X is a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), or a hydrogen atom thereof. A group, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond or an amide bond, which is partially or entirely substituted with a halogen atom. R ⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group or a haloalkyl group, and e represents an integer of 1 to 10. A plurality of R ⁹ may be the same or different from each other. ]

  Examples of the compound having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N -Nitrogen-containing compounds obtained by alkyl etherifying all or part of methylol groups such as -hydroxymethyl) urea. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specific examples include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl) urea and the like.

  (C) As for content of a component, 5-80 mass parts is preferable with respect to 100 mass parts of (A) component, 10-70 mass parts is more preferable, 15-55 mass parts is still more preferable, 20-40 mass parts Part is particularly preferred. When the content of component (C) is 5 parts by mass or more, chemical resistance and heat resistance tend to be good, and when it is 80 parts by mass or less, resolution tends to be further improved.

<(D) component>
The photosensitive resin composition of this embodiment is represented by the compound represented by the following general formula (1), the compound represented by the following general formula (2), and the following general formula (3) as the component (D). And at least one selected from the group consisting of compounds represented by the following general formula (4). When the photosensitive resin composition contains the component (D), flexibility can be imparted to the coating film, and the dissolution rate of the unexposed area when developing with an alkaline aqueous solution can be increased.

［式（１）〜（４）中、Ｒ^１１ _、Ｒ^２１、Ｒ^４２及びＲ^４５は、それぞれ独立に水素原子、メチル基、エチル基、水酸基、又は、式（５）で表される基を示し、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^３１、Ｒ^３２、Ｒ^３３ _、Ｒ^３４、Ｒ^３５、Ｒ^３６、Ｒ^４１、Ｒ^４３、Ｒ^４４及びＲ^４６は、それぞれ独立に水酸基、グリシジルエーテル基、オキセタニルアルキルエーテル基、ビニルエーテル基、アクリロイルオキシ基、メタクリロイルオキシ基、式（６）で表される基、又は、式（７）で表される基を示し、式（５）中、Ｒ^５は、水酸基、グリシジルエーテル基、オキセタニルアルキルエーテル基、ビニルエーテル基、アクリロイルオキシ基又はメタクリロイルオキシ基を示し、式（６）及び式（７）中、Ｒ^６及びＲ^７は、それぞれ独立に水酸基、グリシジルエーテル基、オキセタニルアルキルエーテル基、ビニルエーテル基、アクリロイルオキシ基又はメタクリロイルオキシ基を示し、ｍ及びｎは、それぞれ独立に１〜１０の整数を示す。オキセタニルアルキルエーテル基中のアルキル基としては、メチル基、エチル基、プロピル基等が挙げられるが、メチル基が好ましい。］

[In the formulas (1) to (4), R ¹¹ _, R ²¹ , R ⁴² and R ⁴⁵ are each independently a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the formula (5). R ¹² , R ¹³ , R ¹⁴ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ _, R ³⁴ , R ³⁵ , R ³⁶ , R ⁴¹ , R ⁴³ , R ⁴⁴ and R ⁴⁶ are Each independently represents a hydroxyl group, a glycidyl ether group, an oxetanyl alkyl ether group, a vinyl ether group, an acryloyloxy group, a methacryloyloxy group, a group represented by formula (6), or a group represented by formula (7); wherein (5), R ⁵ represents a hydroxyl group, glycidyl ether group, oxetanyl alkyl ether group, a vinyl ether group, acryloyloxy group or methacryloyloxy group, the formula (6) and During 7), R ⁶ and R ⁷ are hydroxyl groups independently glycidyl ether group, oxetanyl alkyl ether group, vinyl ether group, an acryloyloxy group or a methacryloyloxy group, m and n are each independently from 1 to 10 Indicates an integer. Examples of the alkyl group in the oxetanyl alkyl ether group include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable. ]

  As the component (D), specifically, a compound having a glycidyl ether group, an oxetanyl alkyl ether group, a vinyl ether group, an acryloyloxy group or a methacryloyloxy group is preferable, and two or more glycidyl ether groups or two or more acryloyl groups are preferable. A compound having an oxy group is more preferable, and a compound having three or more glycidyl ether groups or three or more acryloyloxy groups is more preferable. (D) A component can be used individually by 1 type or in mixture of 2 or more types.

  As the component (D), it is preferable to use at least one selected from the group consisting of an epoxy compound, an oxetane compound, an acrylic compound, a methacrylic compound, and a polyhydric alcohol (excluding a compound corresponding to an epoxy compound).

  Examples of the epoxy compound include dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerin triglycidyl ether, and the like. It is done. These epoxy compounds can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the oxetane compound include a compound having a 3-alkyl-3-oxetanylalkyl ether group, and a compound having a 3-ethyl-3-oxetanylalkyl ether group is preferable. Examples of such oxetane compounds include dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3- Oxetanylmethyl) ether, trimethylolethane tris (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, glycerol poly (3-ethyl-3-oxetanylmethyl) ether And glycerin tris (3-ethyl-3-oxetanylmethyl) ether. These oxetane compounds can be used individually by 1 type or in mixture of 2 or more types.

  Examples of acrylic compounds include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO-modified ditrimethylolpropane tetraacrylate, PO-modified ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetraacrylate, EO Modified pentaerythritol tetraacrylate, PO modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO modified pentaerythritol triacrylate, PO modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO modified trimethylolpropane acrylate, PO modified trimethylolpropane acrylate Trimethylol propane acrylate, EO-modified glycerol tri acrylate, PO-modified glycerol triacrylate, glycerin triacrylate. These acrylic compounds can be used individually by 1 type or in mixture of 2 or more types. EO represents an oxyethylene group, and PO represents an oxypropylene group.

  Examples of methacrylic compounds include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetramethacrylate, EO. Modified pentaerythritol tetramethacrylate, PO modified pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, EO modified pentaerythritol trimethacrylate, PO modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO modified trimethylolpropane methacrylate, PO modified trimer Trimethylol propane dimethacrylate, trimethylol propane dimethacrylate, EO modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, glycerine trimethacrylate and the like. These methacrylic compounds can be used singly or in combination of two or more. EO represents an oxyethylene group, and PO represents an oxypropylene group.

  Examples of the polyhydric alcohol include dipentaerythritol, pentaerythritol, and glycerin. These polyhydric alcohols can be used singly or in combination of two or more.

  Among the components (D), trimethylolethane triglycidyl ether and trimethylolpropane triglycidyl ether are preferable because they are further excellent in sensitivity and resolution.

  Component (D) is commercially available as an alkyl type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name ZX-1542), an alkyl type acrylic resin (manufactured by Nippon Kayaku Co., Ltd., trade name: PET-30), and the like. Available.

  When the component (D) is contained, the content of the component (D) is preferably 1 to 70 parts by weight, more preferably 10 to 70 parts by weight with respect to 100 parts by weight of the component (A), and 20 to 70 parts by weight. Part is further preferable, 25 to 65 parts by mass are particularly preferable, and 30 to 50 parts by mass are extremely preferable. When the content of the component (D) is 10 parts by mass or more, flexibility can be further imparted to the coating film, and the dissolution rate of the unexposed part when developing with an alkaline aqueous solution is further likely to increase. There is a tendency that the photosensitive resin composition is easily formed on a desired support.

<(E) component>
The photosensitive resin composition of this embodiment may further contain a sensitizer as the component (E). When the photosensitive resin composition contains the component (E), the sensitivity of the photosensitive resin composition can be further improved. Examples of the sensitizer include 9,10-dibutoxyanthracene. (E) A component can be used individually by 1 type or in mixture of 2 or more types.

  The content of the component (E) is preferably 0.01 to 1.5 parts by mass and more preferably 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the component (A).

<(F) component>
The photosensitive resin composition of the present embodiment may further contain a solvent as the component (F) in order to improve the handleability of the photosensitive resin composition or to adjust the viscosity and storage stability. it can. The component (F) is preferably an organic solvent. The type of organic solvent is not particularly limited as long as it can exhibit the above performance, but ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol mono Propylene glycol monoalkyl ethers such as ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; Propylene glycol monomethyl Ether acetate Propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; methyl lactate, ethyl lactate, Lactic acid esters such as n-propyl lactate and isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, propionate Aliphatic carboxylic acid esters such as isobutyl acid; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate Esters such as methyl acetate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, etc. Ketones; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; and lactones such as γ-butyrolactone. (F) A component can be used individually by 1 type or in mixture of 2 or more types.

  The content of the component (F) is preferably 30 to 200 parts by mass and more preferably 60 to 120 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (F).

<(G) component>
The photosensitive resin composition of this embodiment may contain the compound which has a siloxane bond as (G) component. Although it will not specifically limit as (G) component if it has a siloxane bond, For example, the compound and alkoxy oligomer which have a siloxane bond among an inorganic filler and a silane compound are mentioned. (G) A component can be used individually by 1 type or in mixture of 2 or more types.

  When an inorganic filler is used as the component (G), the inorganic filler is preferably silica such as fused spherical silica, fused pulverized silica, fumed silica, or sol-gel silica. Further, the inorganic filler may have a siloxane bond by treating the inorganic filler with a silane compound. Among inorganic fillers treated with silane compounds, inorganic fillers other than silica include aluminum oxide, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, talc, mica, etc. Inorganic fillers derived from mine.

  When a silane compound is used as the component (G), the silane compound is not particularly limited as long as the silane compound has a siloxane bond. Examples of the silane compound include alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acrylic silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, sulfur silane, styryl silane, alkyl chlorosilane, and the like.

As the silane compound as component (G), a compound represented by the following general formula (10) is preferable.
(R ¹⁰¹ O) _4-f -Si- (R ¹⁰² ) _f (10)

In General Formula (10), R ¹⁰¹ represents an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, or a propyl group, R ¹⁰² represents a monovalent organic group, and f represents 0 An integer of ~ 3 is shown. When f is 0, 1 or 2, the plurality of R ¹⁰¹ may be the same as or different from each other. When f is 2 or 3, the plurality of R ¹⁰² may be the same as or different from each other. R ¹⁰¹ is preferably an alkyl group having 1 to 5 carbon atoms and more preferably an alkyl group having 1 to 2 carbon atoms from the viewpoint of further improving the resolution. When processing with a silane compound in order to improve the dispersibility of a filler, 0-2 are preferable and 0-1 are more preferable from a viewpoint which further improves the dispersibility of a filler.

  Specific examples of the silane compound as component (G) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and diisopropyl. Dimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyl Trimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Lan, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxy Silyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-meta Liloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene ) -3-aminopropyltriethoxysilane and the like.

  As for content of (G) component, 1.8-420 mass parts is preferable with respect to 100 mass parts of (A) component, and 1.8-270 mass parts is more preferable.

<Other ingredients>
In addition to the component (A), the photosensitive resin composition of the present embodiment may contain a phenolic low molecular compound having a molecular weight of less than 1000 (hereinafter referred to as “phenol compound (a)”). As the phenolic compound (a), 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, Tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl ] Benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- {1 -(4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane Emissions, and the like. Content of these phenolic compounds (a) is the range of 0-40 mass parts (especially 0-30 mass parts) with respect to 100 mass parts of (A) component.

  Moreover, the photosensitive resin composition of this embodiment may contain other components other than the above-mentioned component. Examples of other components include a filler, an adhesion aid, and a leveling agent.

[Photosensitive element]
Next, the photosensitive element of this embodiment will be described.

  The photosensitive element of this embodiment includes a support and a photosensitive layer provided on the support, and the photosensitive layer includes the above-described photosensitive resin composition. The photosensitive element of this embodiment may further include a protective layer that covers the photosensitive layer on the photosensitive layer.

  As said support body, the polymer film which has heat resistance and solvent resistance, such as a polyethylene terephthalate, a polypropylene, polyethylene, polyester, can be used, for example. As for the thickness of the said support body (polymer film), 5-25 micrometers is preferable. In addition, the said polymer film may be laminated | stacked and used for both surfaces of a photosensitive layer by using one as a support body and another as a protective layer.

  As the protective layer, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.

  The photosensitive layer can be formed by applying the photosensitive resin composition on a support or a protective layer. Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, and a spin coating method. Although the thickness of the photosensitive layer varies depending on the application, it is preferably 1 to 100 μm, more preferably 3 to 60 μm, still more preferably 5 to 40 μm after the photosensitive layer is dried. Further, from the viewpoint of insulation reliability and productivity in mounting a chip, the thickness of the photosensitive layer is preferably more than 20 μm, but may be 20 μm or less.

[Method of forming resist pattern]
Next, a resist pattern forming method of this embodiment will be described. The resist pattern forming method of the first embodiment includes a step of applying the photosensitive resin composition on a substrate (for example, a substrate), drying the photosensitive resin composition to form a photosensitive layer, and the photosensitive layer. A step of exposing the layer to a predetermined pattern and performing a post-exposure heat treatment (post-exposure bake); a step of developing the photosensitive layer after the heat treatment (post-exposure bake), and a heat treatment of the resulting resin pattern And including. The resist pattern forming method of the second embodiment includes a step of placing the photosensitive layer of the photosensitive element on a substrate (for example, a substrate), exposing the photosensitive layer to a predetermined pattern, and post-exposure heat treatment ( A step of performing post-exposure baking, and a step of developing the photosensitive layer after the heat treatment (post-exposure baking) and heat-treating the obtained resin pattern.

  In the method for forming a resist pattern of the present embodiment, for example, first, the above-described base material (a copper foil with resin, a copper clad laminate, a silicon wafer with a metal sputtered film, an alumina substrate, etc.) on which a resist is to be formed is formed. A photosensitive layer containing the photosensitive resin composition is formed. As the method for forming the photosensitive layer, the photosensitive resin composition is applied to a substrate (for example, coating), dried, and the solvent is volatilized to form a coating film (photosensitive layer). And a method of transferring the photosensitive layer in the conductive element onto the substrate.

  As a method for applying the photosensitive resin composition to the substrate, for example, a coating method such as a dipping method, a spray method, a bar coating method, a roll coating method, or a spin coating method can be used. Moreover, the thickness of the coating film can be appropriately controlled by adjusting the coating means, the solid content concentration and the viscosity of the photosensitive resin composition.

Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of actinic rays used for exposure include g-line stepper rays; UV rays such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and i-line steppers; electron beams; laser rays. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the thickness is about 100 to 5000 mJ / cm ² when the coating thickness is 10 to 50 μm.

  Further, a heat treatment (post-exposure bake) is performed after the exposure. By performing post-exposure baking, the curing reaction of the (A) component and the (C) component by the generated acid can be promoted. The post-exposure baking conditions vary depending on the content of the photosensitive resin composition, the thickness of the coating film, etc., but for example, heating at 50 to 150 ° C. for 1 to 60 minutes is preferable, and 1 to 15 at 60 to 100 ° C. It is more preferable to heat for a minute.

  Next, the exposed and / or post-exposure baked coating film is developed with an alkaline developer, and a region other than the cured portion (unexposed portion) is dissolved and removed to obtain a desired resist pattern. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The development conditions are, for example, 20 to 40 ° C. and 10 to 300 seconds in the spray development method.

  Examples of the alkaline developer include an alkaline aqueous solution obtained by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline in water so that the concentration becomes 1 to 10% by mass, and alkaline such as aqueous ammonia. An aqueous solution etc. are mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, after developing with this alkaline developing solution, it wash | cleans with water and dries. The alkaline developer is preferably tetramethylammonium hydroxide in terms of further excellent resolution.

  Furthermore, the cured film (resist pattern) of the photosensitive resin composition is obtained by performing a heat treatment to develop the insulating film characteristics. The curing conditions for the photosensitive resin composition are not particularly limited, but for example, according to the use of the cured product, the photosensitive resin composition is cured by heating at 50 to 250 ° C. for 30 minutes to 10 hours. be able to.

  Moreover, in order to fully advance hardening, and in order to prevent the deformation | transformation of the obtained resin pattern shape, it can also heat in two steps. For example, it can be cured by heating at 50 to 120 ° C. for 5 minutes to 2 hours in the first stage and further heating at 80 to 200 ° C. for 10 minutes to 10 hours in the second stage.

  If it is the above-mentioned hardening conditions, there will be no restriction | limiting in particular as heating equipment, A general oven, an infrared furnace, etc. can be used.

[Semiconductor device]
The semiconductor device according to the present embodiment includes a cured product of the photosensitive resin composition according to the present embodiment. The cured product of the photosensitive resin composition of the present embodiment can be suitably used as, for example, a surface protective film or an interlayer insulating film of a semiconductor element, or a solder resist and / or an interlayer insulating film in a multilayer printed wiring board.

  FIG. 1 is a view showing a method for producing a multilayer printed wiring board including a cured product of the photosensitive resin composition of the present embodiment as a solder resist and / or an interlayer insulating film. A multilayer printed wiring board 100A shown in FIG. 1 (f) has a wiring pattern on its surface and inside. The multilayer printed wiring board 100A is obtained by laminating a copper clad laminate, an interlayer insulating film, a metal foil, and the like and appropriately forming a wiring pattern by an etching method or a semi-additive method. Hereinafter, a method of manufacturing the multilayer printed wiring board 100A will be briefly described with reference to FIG.

  First, an interlayer insulating film 103 is formed on both surfaces of a copper clad laminate 101 having a wiring pattern 102 on the surface (see FIG. 1A). The interlayer insulating film 103 may be formed by printing a photosensitive resin composition using a screen printing machine or a roll coater. Alternatively, the photosensitive element described above is prepared in advance, and the photosensitive resin composition is prepared using a laminator. The photosensitive layer in the element can also be formed on the surface of the printed wiring board.

  Next, an opening 104 is formed using a YAG laser or a carbon dioxide gas laser in a place that needs to be electrically connected to the outside (see FIG. 1B). Smear (residue) around the opening 104 is removed by desmear treatment.

  Next, a seed layer 105 is formed by an electroless plating method (see FIG. 1C). A photosensitive layer containing the above-described photosensitive resin composition is formed on the seed layer 105, and a predetermined portion is exposed and developed to form a wiring pattern 106 (see FIG. 1D).

  Next, the wiring pattern 107 is formed by an electrolytic plating method, and the cured product of the photosensitive resin composition is removed by a peeling solution, and then the seed layer 105 is removed by etching (see FIG. 1E).

  By repeating the above operation and forming a solder resist 108 containing a cured product of the above-described photosensitive resin composition on the outermost surface, the multilayer printed wiring board 100A can be produced (see FIG. 1 (f)).

  In the multilayer printed wiring board 100A thus obtained, semiconductor elements are mounted at corresponding locations, and electrical connection can be ensured.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these Examples.

<Examples 1-6 and Comparative Examples 1-4>
It represents with a photosensitive acid generator (B-1 to B-7), a crosslinking agent (C-1), and general formula (1) with respect to 100 mass parts of resin components (A-1 to A-3). Compound (D-1), sensitizer (E-1), solvent (F-1), and compound (G-1) having a siloxane bond are shown in Table 1 in amounts (units). : Parts by mass) to obtain a photosensitive resin composition. The resin components (A-1 to A-3) and the photosensitive acid generators (B-1 to B-7) were blended so that the solid content would be parts by mass shown in Table 1.

Abbreviations in Table 1 are as follows.
A-1: Novolac resin (Asahi Organic Materials Co., Ltd., trade name: EP4020G, weight average molecular weight: 13000)
A-2: Novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4020G, weight average molecular weight: 13000)
A-3: p-hydroxystyrene-styrene copolymer (manufactured by Maruzen Petrochemical Co., Ltd., trade name: CST-50)
B-1: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-310B, molecular weight: 1203 g / mol)
B-2: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-300PG, molecular weight: 969 g / mol)
B-3: Arylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-510B, molecular weight: 1090 g / mol)
B-4: Triarylsulfonium salt (manufactured by BASF Japan Ltd., trade name: Irgacure 290, molecular weight: 1393 g / mol)
B-5: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-101A, molecular weight: 607 g / mol)
B-6: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-210S, molecular weight: 817 g / mol)
B-7: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-110B, molecular weight: 1051 g / mol)
C-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: MX-270)
D-1: Trimethylolpropane triglycidyl ether (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: ZX-1542)
E-1: 9,10-dibutoxyanthracene (manufactured by Kawasaki Chemical Industry Co., Ltd., trade name: DBA)
F-1: Methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 2-butanone)
G-1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403)

  On the polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd., trade name: Purex A53) (support), the photosensitive resin composition was applied so that the thickness of the photosensitive resin composition was uniform, It dried for 10 minutes with a 90 degreeC hot air convection dryer. After drying, it was covered with a polyethylene film (trade name: NF-15, manufactured by Tamapoly Co., Ltd.) (protective layer) to obtain a photosensitive element having a photosensitive layer thickness of 25 μm.

<Evaluation of molar extinction coefficient>
Acetonitrile solutions of photosensitive acid generator (B-1) at concentrations of 0.00000 mol / L, 0.00058 mol / L, 0.0012 mol / L, 0.0018 mol / L, and 0.0024 mol / L in a volumetric flask at room temperature. Respectively.
Photosensitive acid generator (B-2) concentrations of 0.00000 mol / L, 0.00047 mol / L, 0.00093 mol / L, 0.0017 mol / L, 0.0020 mol / L, 0.0023 mol / L acetonitrile Solutions were each prepared in a volumetric flask at room temperature.
Acetonitrile solutions of photosensitive acid generator (B-3) at concentrations of 0.00000 mol / L, 0.0023 mol / L, 0.0049 mol / L, and 0.0072 mol / L were respectively prepared in a measuring flask at room temperature.
Acetonitrile solutions of photosensitive acid generator (B-4) at concentrations of 0.00000 mol / L, 0.00046 mol / L, 0.00095 mol / L, 0.0013 mol / L, and 0.0019 mol / L in a volumetric flask at room temperature. Respectively.
Acetonitrile solutions of photosensitive acid generator (B-5) at concentrations of 0.00000 mol / L, 0.0044 mol / L, 0.0092 mol / L, 0.013 mol / L, and 0.019 mol / L in a volumetric flask at room temperature. Respectively.
Acetonitrile solutions of photosensitive acid generator (B-6) at concentrations of 0.00000 mol / L, 0.0044 mol / L, 0.0092 mol / L, 0.013 mol / L, and 0.019 mol / L in a volumetric flask at room temperature. Respectively.
Acetonitrile solutions of photosensitive acid generator (B-7) at concentrations of 0.00000 mol / L, 0.0044 mol / L, 0.0092 mol / L, 0.013 mol / L, and 0.018 mol / L in a volumetric flask at room temperature. Respectively.

  The concentration “mol / L” is obtained by dividing the mass “g” of the photosensitive acid generator contained in the volumetric flask by the molecular weight “g / mol” of the photosensitive acid generator, and further, the volume “L” of the volumetric flask. Calculated by dividing by. As a method for measuring the molecular weight “g / mol” of the photosensitive acid generator, mass spectrometry was used. The prepared acetonitrile solution of the photosensitive acid generator is filled in a quartz cell having an optical path length of 1 cm, and an ultraviolet-visible spectrophotometer (Hitachi High-Technologies Corporation, trade name: Hitachi spectrophotometer U-3310) is used for light The absorption spectrum of the sensitive acid generator was measured. The spectrophotometer was used after stabilizing the light source, and then the background measurement was performed with a 1 cm quartz cell filled with acetonitrile, and then the absorption spectrum of the photosensitive acid generator was used. The measurement conditions were as follows: temperature at the time of solution preparation, slit width of 2 nm, scan speed of 300 nm / min, sampling interval of 0.50 nm, and measurement range of 600 nm to 300 nm. In each measurement, it was confirmed that the absorbance at a wavelength of 365 nm did not exceed 2.0. The vertical axis represents the absorbance of the light-sensitive acid generator with respect to light having a wavelength of 365 nm, the horizontal axis represents the product of the concentration of the light-sensitive acid generator and the optical path length, and an approximate straight line was drawn by the method of least squares. It was confirmed that the coefficient of determination was 0.999 or more. From the Lambert-Beer law, the slope of the obtained straight line was calculated as the molar extinction coefficient (L / (mol · cm)) at a wavelength of 365 nm. The evaluation results are shown in Table 1.

<Evaluation of solubility>
The photosensitive resin composition is spin-coated on a 6-inch diameter silicon wafer and heated on a hot plate at 65 ° C. for 2 minutes and then at 95 ° C. for 8 minutes to produce a uniform coating having a thickness of 25 μm. did. The prepared coating film was immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution (manufactured by Tama Chemical Industry Co., Ltd., trade name: TMAH 2.38%) at 23 ° C. It evaluated according to. The evaluation results are shown in Table 1.
(Evaluation criteria)
○: uniformly dissolved △: clouded and dissolved ×: insoluble

<Evaluation of resolution and sensitivity>
On the 6-inch diameter silicon wafer, the protective layer of the said photosensitive element was peeled, this photosensitive element was laminated, and the laminated body was obtained. Lamination was performed using a 100 ° C. heat roll at a pressure of 0.4 MPa and a roll speed of 1.0 m / min. Next, the support of the above laminate is peeled off, and reduced projection onto the photosensitive layer through a mask with i-line (365 nm) using an i-line stepper (manufactured by Canon Inc., trade name: FPA-3000iW). Exposure was performed. As the mask, a mask having a pattern in which the width of the exposed part and the unexposed part is 1: 1 is from 2 μm: 2 μm to 30 μm: 30 μm in 1 μm increments. The exposure amount is in the range of 100~3000mJ / cm ^2, was subjected to the reduction projection exposure while changing by 50 mJ / cm ^2.

  The exposed coating film was heated at 65 ° C. for 1 minute and then at 95 ° C. for 4 minutes (post exposure bake). Next, a 2.38 mass% tetramethylammonium hydroxide aqueous solution (manufactured by Tama Chemical Industry Co., Ltd., trade name: TMAH 2.38%) as a developer, and a developing machine (manufactured by Takizawa Sangyo Co., Ltd., trade name: AD-1200) ) Is sprayed on the coating film for a time corresponding to four times the shortest development time (the shortest time during which the unexposed area is removed) (pump discharge pressure [developer]: 0.16 MPa). Removed. Next, purified water (trade name: purified water) manufactured by Wako Pure Chemical Industries, Ltd. is sprayed as a rinse solution for 30 seconds (pump discharge pressure [rinse solution]: 0.12 to 0.14 MPa), and the developer is washed away. The resist pattern was formed by drying. The formed resist pattern was observed by enlarging the magnification 500 times using a metal microscope. Among the patterns in which the space portion (unexposed portion) is removed cleanly and the line portion (exposed portion) is formed without causing meandering or chipping, the smallest space width value is set as the minimum resolution, and at that time The exposure amount was evaluated as sensitivity. The evaluation results are shown in Table 1.

＊１：パターンを形成できなかったことを示す。

* 1: Indicates that the pattern could not be formed.

As is apparent from Table 1, Examples 1 to 6 using a photo-sensitive acid generator having a molar extinction coefficient with respect to light having a wavelength of 365 nm of 100 L / (mol · cm) or more have a sensitivity of 1500 mJ / cm ² or less. And it was good. On the other hand, Comparative Examples 1 to 3 not using a light-sensitive acid generator having a molar extinction coefficient of 100 L / (mol · cm) or more were insufficient because the sensitivity exceeded 1500 mJ / cm ² . Further, although a photosensitive acid generator having a molar extinction coefficient of 100 L / (mol · cm) or more is used, Comparative Example 4 using no novolak resin develops not only the unexposed area but also the exposed area. Since it was dissolved in the liquid, pattern formation could not be performed. Example 3 was found to be superior in balance between resolution and sensitivity as compared with Examples 1, 2, 4 and 5.

  The photosensitive resin composition of this invention is applied as a material used for the surface protection film or interlayer insulation film of a semiconductor element. Moreover, it is applied as a material used for a solder resist of a wiring board material or an interlayer insulating film. In particular, since the photosensitive resin composition has good resolution and heat resistance after curing, it is suitably used for highly integrated package substrates that are thinned and densified.

  DESCRIPTION OF SYMBOLS 100A ... Multilayer printed wiring board, 101 ... Copper-clad laminate, 102, 106, 107 ... Wiring pattern, 103 ... Interlayer insulating film, 104 ... Opening, 105 ... Seed layer, 108 ... Solder resist.

Claims (5)

(A) component: novolac resin,
(B) component: a photosensitive acid generator containing a sulfonium salt ;
(C) component: a crosslinking agent having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group;
Component (D): a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and the following general formula (4) Containing at least one selected from the group consisting of the compounds represented ,
The photosensitive resin composition whose molar absorption coefficient of the said (B) component with respect to the light whose wavelength is 365 nm is 100 L / (mol * cm) or more.

[In the formulas (1) to (4), R ¹¹ _, R ²¹ , R ⁴² and R ⁴⁵ are each independently a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the formula (5). R ¹² , R ¹³ , R ¹⁴ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ _, R ³⁴ , R ³⁵ , R ³⁶ , R ⁴¹ , R ⁴³ , R ⁴⁴ and R ⁴⁶ are Each independently represents a hydroxyl group, a glycidyl ether group, an oxetanyl alkyl ether group, a vinyl ether group, an acryloyloxy group, a methacryloyloxy group, a group represented by formula (6), or a group represented by formula (7); wherein (5), R ⁵ represents a hydroxyl group, glycidyl ether group, oxetanyl alkyl ether group, a vinyl ether group, acryloyloxy group or methacryloyloxy group, the formula (6) and During 7), R ⁶ and R ⁷ are hydroxyl groups independently glycidyl ether group, oxetanyl alkyl ether group, vinyl ether group, an acryloyloxy group or a methacryloyloxy group, m and n are each independently from 1 to 10 Indicates an integer. ] Comprising a support and a photosensitive layer comprising a photosensitive resin composition according to claim 1 provided on the support, the photosensitive element. A semiconductor device comprising a cured product of the photosensitive resin composition according to claim 1 . Applying the photosensitive resin composition according to claim 1 on a substrate, and drying the photosensitive resin composition to form a photosensitive layer;
Exposing the photosensitive layer to a predetermined pattern and performing a post-exposure heat treatment;
Developing the photosensitive layer after the heat treatment, and heat-treating the obtained resin pattern. Disposing the photosensitive layer of the photosensitive element according to claim 2 on a substrate;
Exposing the photosensitive layer to a predetermined pattern and performing a post-exposure heat treatment;
Developing the photosensitive layer after the heat treatment, and heat-treating the obtained resin pattern.

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