JPWO2018070489A1 - Photosensitive element, semiconductor device, and method for forming resist pattern - Google Patents

Abstract

A support, a photosensitive layer, and a protective layer are provided in this order, and the support has an olefin resin layer or an amino alkyd resin layer as a surface layer on the photosensitive layer side, and the photosensitive layer and the protective layer The ratio of the peel strength between the photosensitive layer and the support to the peel strength between them is 1.0 or more, and the peel strength between the photosensitive layer and the support is 6.0 N / m or less. A photosensitive element is disclosed.

Description

  The present disclosure relates to 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, it contains a photosensitive resin composition containing components such as a novolak resin, an epoxy resin and a photoacid generator that are soluble in an alkaline aqueous solution, a component such as an alkali-soluble epoxy compound having a carboxyl group and a photocationic polymerization initiator. A photosensitive resin composition has been proposed (see, for example, Patent Documents 1 to 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, there is a continuous need for the photosensitive resin composition to improve the resolution even in units of 1 μm.

  Incidentally, it is necessary to provide vias (openings) for electrically connecting the upper and lower wiring layers in the interlayer insulating material of the printed wiring board. If the number of flip chip pins mounted on the printed wiring board increases, it is necessary to provide vias corresponding to the number of pins.

  In recent years, as the miniaturization of semiconductor elements has progressed and the number of pins has increased from tens of thousands to hundreds of thousands of pins, vias formed in the interlayer insulating material of the printed circuit board have also been adjusted to the number of pins of the semiconductor elements. There is a need to reduce the diameter. Recently, development of a printed wiring board in which a via is provided by a laser using a thermosetting resin material has been advanced (for example, see Patent Document 5 below).

Japanese Patent Application Laid-Open No. 06-059444 JP 09-087366 A International Publication No. 2008/010521 JP 2003-215802 A JP 2001-217543 A

  However, in the conventional method for manufacturing a multilayer printed wiring board, it is necessary to introduce new equipment such as a laser, it is difficult to provide a via having a relatively large diameter or a minute via having a diameter of 60 μm or less, There are problems that it is necessary to use different lasers according to the aperture diameter, and it is difficult to provide a special shape. In addition, when forming vias using a laser, each via must be formed one by one, which takes time when it is necessary to provide a large number of fine vias. Furthermore, since a resin residue remains around the via opening, there is a problem that the reliability of the obtained multilayer printed wiring board is lowered unless the residue is removed.

  The photosensitive layer of the photosensitive element is transferred to the substrate by peeling the protective layer from the photosensitive element, laminating the photosensitive layer and the substrate using a laminator, and peeling the support. When the protective layer is peeled off, the photosensitive layer may be transferred to the unintended protective layer side. Further, when the support is peeled off, the photosensitive layer may be transferred to the unintended support side. The site where unintentional transcription occurs cannot be used, so that productivity at the time of manufacture is lowered. Therefore, from the viewpoint of productivity, it is required not to transfer the photosensitive layer of the photosensitive element to the protective layer, preferably to the protective layer and the support.

  A first object of the present disclosure is to provide a photosensitive element in which a photosensitive layer is difficult to transfer to a protective layer and a support.

  A second object of the present disclosure is to provide a photosensitive element that can form a resist pattern that is difficult to transfer to a protective layer and that is particularly excellent in resolution.

  Another object of the present disclosure is to provide a semiconductor device obtained using the photosensitive element and a method for forming a resist pattern using the photosensitive element.

  As a result of intensive studies to solve the above problems, the present inventors have found a photosensitive element having excellent characteristics. That is, the photosensitive element of the first embodiment of the present disclosure includes a support, a photosensitive layer, and a protective layer in this order, and the support is an olefin resin layer or amino acid as a surface layer on the photosensitive layer side. An alkyd resin layer, the ratio of the peel strength between the photosensitive layer and the support to the peel strength between the photosensitive layer and the protective layer is 1.0 or more, and the photosensitive layer The peel strength between the support and the support is 6.0 N / m or less.

  In the above embodiment, the photosensitive layer is composed of (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: an aromatic ring, a heterocyclic ring, and an alicyclic ring. A compound having at least one selected from the group consisting of at least one of a methylol group and an alkoxyalkyl group; and component (D): an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group, Provided is a photosensitive element formed from a photosensitive resin composition containing an aliphatic compound having two or more functional groups selected from the group consisting of a vinyl ether group and a hydroxyl group. By having the said structure, a photosensitive layer can be made especially excellent in resolution.

  The photosensitive element of the second embodiment of the present disclosure includes a support, a photosensitive layer, and a protective layer in this order, and the protective layer has a silicone resin layer as a surface layer on the photosensitive layer side, The photosensitive layer is selected from the group consisting of (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: an aromatic ring, a heterocyclic ring and an alicyclic ring. It is formed from a photosensitive resin composition containing at least one kind and a compound having at least one of a methylol group and an alkoxyalkyl group.

  In the above embodiment, the photosensitive resin composition is one or more selected from the group consisting of component (D): acryloyloxy group, methacryloyloxy group, glycidyloxy group, oxetanyl alkyl ether group, vinyl ether group and hydroxyl group. Provided is a photosensitive element further containing an aliphatic compound having two or more functional groups.

  1st and 2nd embodiment provides the photosensitive element whose content of the said (D) component is 1-70 mass parts with respect to 100 mass parts of said (A) component.

  1st and 2nd embodiment provides the photosensitive element in which the said photosensitive resin composition further contains the compound which has (G) component: Si-O bond.

  1st and 2nd embodiment provides a semiconductor device provided with the hardened | cured material of the photosensitive layer in the said photosensitive element.

  Furthermore, the first and second embodiments include a step of forming a photosensitive layer on a substrate using the photosensitive element, a step of exposing the photosensitive layer to a predetermined pattern, and a photosensitive layer after exposure. And a step of heat-treating the obtained resin pattern. A method for forming a resist pattern is provided.

  According to the first embodiment of the present disclosure, it is possible to provide a photosensitive element in which the photosensitive layer is difficult to transfer to the protective layer and the support. In addition, according to the second embodiment of the present disclosure, it is possible to provide a photosensitive element that can form a resist pattern that is difficult to transfer to a protective layer and that is particularly excellent in resolution. According to the first and / or second embodiments of the present disclosure, it is possible to provide a semiconductor device obtained using the photosensitive element and a method of forming a resist pattern using the photosensitive element.

It is a schematic cross section of the photosensitive element which concerns on 1st Embodiment. It is a schematic cross section of the photosensitive element which concerns on 2nd Embodiment. It is a schematic diagram which shows the manufacturing method of the multilayer printed wiring board in this embodiment.

  Hereinafter, although embodiment of this indication is described concretely, this indication is not limited to these. In the following embodiments, it is needless to say that the constituent elements (including element steps and the like) are not necessarily indispensable unless otherwise specified or apparently essential in principle. This also applies to numerical values and ranges, and should not be construed to unduly limit the present disclosure.

  In this specification, the terms “layer” and “film” refer to a structure formed in part in addition to a structure formed over the entire surface when observed as a plan view. Is included. The term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. In the name of the compound, “EO-modified” means a compound having a (poly) oxyethylene group, and “PO-modified” means a compound having a (poly) oxypropylene group. . Here, “(poly) oxyethylene group” means at least one of an oxyethylene group and a polyoxyethylene group in which two or more ethylene groups are linked by an ether bond. The “(poly) oxypropylene group” means at least one of an oxypropylene group and a polyoxypropylene group in which two or more propylene groups are linked by an ether bond. The term “Si—O bond” indicates a bond between a silicon atom and an oxygen atom, and may be a part of a siloxane bond (Si—O—Si bond). The numerical range indicated by 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 numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. “A or B” only needs to include either A or B, and may include both. The materials exemplified below can be used singly or in combination of two or more unless otherwise specified. The content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

[Photosensitive Element of First Embodiment]
The photosensitive element according to the first embodiment will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view of a photosensitive element 10 according to the first embodiment. As shown in FIG. 1, the photosensitive element 10 according to the present embodiment includes a support 11, a photosensitive layer 15, and a protective layer 17 in this order. The photosensitive element 10 can be used for manufacturing the semiconductor device of this embodiment.

<Support>
In the photosensitive element 10, the support 11 has a support substrate 12 and an olefin resin layer 13. The olefin resin layer 13 forms a surface layer on the photosensitive layer 15 side of the support 11 and is disposed so as to be in contact with the photosensitive layer 15. The support 11 may include an amino alkyd resin layer at the same position instead of the olefin resin layer 13. As the support substrate 12, for example, a polymer film having heat resistance and solvent resistance, such as polyester (polyethylene terephthalate, etc.), polypropylene, and polyethylene can be used. As the support 11, for example, a polymer film having an olefin resin layer or an aminoalkyd resin layer on at least one surface can be used.

  When the support 11 has the olefin resin layer 13 or the amino alkyd resin layer as the surface layer on the photosensitive layer 15 side, when the photosensitive layer 15 is laminated on the substrate, the photosensitive layer 15 is easily transferred to the substrate, Productivity can be improved.

  The olefin resin layer 13 should just contain an olefin resin. Although it does not specifically limit as an olefin component which is a monomer which comprises olefin resin, It is C2-C6 alkene, such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, 1-hexene. Etc., and a mixture thereof may be used. Moreover, a (meth) acrylic acid ester component, an acid-modified component, etc. may be contained in the olefin resin. The content of the olefin resin in the olefin resin layer 13 may be, for example, 1 to 100% by mass, or 50 to 100% by mass.

  The amino alkyd resin layer should just contain an amino alkyd resin. The amino alkyd resin is a resin obtained by using an amino resin and an alkyd resin.

  The olefin resin layer 13 or the amino alkyd resin layer may be formed, for example, by treating at least the surface of the support substrate 12 on the photosensitive layer 15 side with an olefin resin or an amino alkyd resin. The treatment with the olefin resin or amino alkyd resin refers to a chemical treatment in which the olefin resin containing the olefin component or the like or the amino alkyd resin is thinly coated (coated) on the surface of the support substrate 12.

  When applying (coating) the olefin resin or aminoalkyd resin to the support substrate 12, it is preferable to apply (coat) thinly as long as the effect of releasing is obtained. After coating (coating), the olefin resin or aminoalkyd resin may be fixed to the support substrate 12 by heat, UV treatment or the like. It is more preferable to apply an undercoat layer to the support substrate 12 before applying (coating) the olefin resin or aminoalkyd resin.

  The preferred thickness of the olefin resin layer 13 or amino alkyd resin layer is about 0.005 to 1 μm, and particularly preferably 0.01 to 0.1 μm. When the thickness of the olefin resin layer 13 or the amino alkyd resin layer is within the above range, the adhesion between the support substrate 12 and the olefin resin layer 13 or the amino alkyd resin layer is improved.

  As a PET film treated with an olefin resin, for example, a product name “A170” manufactured by Unitika Ltd. is available. Moreover, as a PET film processed with amino alkyd resin, the product name "NSP-5" by Fujimori Kogyo Co., Ltd. can be obtained, for example.

  Each of the support 11 and the support substrate 12 may have a thickness of 5 to 100 μm, preferably 15 to 100 μm, and more preferably 25 to 50 μm. When the thickness of the support 11 or the support substrate 12 is 15 μm or more, the strain at the time of treatment with the olefin resin or aminoalkyd resin is less likely to remain, and the wrinkle is generated when the film is wound. There is a tendency to be suppressed. When the thickness of the support 11 is 50 μm or less, bubbles tend not to be caught between the substrate and the photosensitive layer 15 during thermocompression bonding when the photosensitive layer 15 is laminated on the substrate.

<Protective layer>
As the protective layer 17 in the photosensitive element 10, for example, a polymer film having heat resistance and solvent resistance such as polyester (polyethylene terephthalate, etc.), polypropylene, and polyethylene can be used. The thickness of the protective layer 17 is preferably 5 to 100 μm.

  From the viewpoint of the peelability of the support 11 from the photosensitive layer 15, the 180 ° peel strength at 23 ° C. between the surface of the support 11 on the olefin resin layer 13 or aminoalkyd resin layer side and the photosensitive layer 15 is 0 0.1 to 6.0 N / m, more preferably 0.2 to 5.5 N / m, still more preferably 0.2 to 4.0 N / m, and 1.0 to Particularly preferred is 2.0 N / m. When the 180 ° peel strength is 1.0 N / m or more, the adhesive strength between the photosensitive layer 15 and the support 11 is sufficiently high, and when the protective layer 17 is peeled from the photosensitive layer 15, the photosensitive layer 15 is supported by the support. 11 is sufficiently maintained, and the photosensitive layer 15 tends to be less easily transferred to the protective layer 17. When the 180 ° peel strength is 4.0 N / m or less, the adhesive strength between the photosensitive layer 15 and the support 11 is sufficiently low, and after the photosensitive layer 15 is laminated on the substrate, the support from the photosensitive layer 15 to the support is obtained. 11 tends to be more easily peeled off.

  In the photosensitive element 10 according to this embodiment, the ratio of the peel strength between the photosensitive layer 15 and the support 11 to the peel strength between the photosensitive layer 15 and the protective layer 17 is 1.0 or more. When the ratio is within the above range, the adhesive strength between the photosensitive layer 15 and the support 11 is relatively high, and the photosensitive layer 15 is adhered to the support 11 when the protective layer 17 is peeled off from the photosensitive layer 15. The state is sufficiently maintained and the photosensitive layer 15 tends to be difficult to be transferred to the protective layer 17. As the peel strength, a value of 180 ° peel strength at 23 ° C. is used. The ratio of the peel strength between the photosensitive layer 15 and the support 11 to the peel strength between the photosensitive layer 15 and the protective layer 17 may be 1.1 to 4.0, and 1.2 to 3. 0 is preferable, and 1.3 to 2.0 is more preferable.

  The 180 ° peel strength can be measured by a general method (for example, a method conforming to JIS K6854-2) using an adhesive tape (manufactured by Nitto Denko Corporation, product name: “NITTO31B”). .

<Photosensitive layer>
The photosensitive layer 15 can be formed by applying a photosensitive resin composition described later on the support 11 or the protective layer 17. 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 15 varies depending on the use, it is preferably 1 to 100 μm, more preferably 3 to 60 μm, still more preferably 5 to 60 μm after the photosensitive layer 15 is dried, It is especially preferable that it is 5-40 micrometers, and it is very preferable that it is 5-25 micrometers. Further, from the viewpoint of excellent insulation reliability (insulation between wirings in the thickness direction of the layer) and productivity in mounting a chip, the thickness of the photosensitive layer 15 is preferably over 20 μm. 20 μm or less.

[Photosensitive Element of Second Embodiment]
The photosensitive element 20 of 2nd Embodiment is demonstrated referring FIG. FIG. 2 is a schematic cross-sectional view of the photosensitive element 20 according to this embodiment. As shown in FIG. 2, the photosensitive element 20 according to this embodiment includes a protective layer 21, a photosensitive layer 25, and a support 27 in this order. The photosensitive element 20 can be used for manufacturing the semiconductor device of this embodiment.

<Protective layer>
In the photosensitive element 20, the protective layer 21 has a protective layer base material 22 and a silicone resin layer 23. The silicone resin layer 23 forms a surface layer on the photosensitive layer 25 side of the protective layer 21 and is disposed so as to be in contact with the photosensitive layer 25. As the protective layer base material 22, for example, a polymer film having heat resistance and solvent resistance, such as polyester (polyethylene terephthalate, etc.), polypropylene, and polyethylene can be used. The thickness of the protective layer 21 is preferably 5 to 100 μm. As the protective layer 21, for example, a polymer film having a silicone resin layer on at least one surface can be used.

  Since the protective layer 21 has the silicone resin layer 23 as the surface layer on the photosensitive layer 25 side, when the protective layer 21 is peeled from the photosensitive layer 25, the photosensitive layer 25 is difficult to transfer to the protective layer 21 and productivity is increased. Can be improved. The silicone resin layer 23 may be formed, for example, by treating at least the surface of the protective layer base material 22 on the photosensitive layer 25 side with a silicone resin. The treatment with a silicone resin refers to a chemical treatment in which a silicone compound such as a silicone surfactant or silicone resin is thinly coated (coated) on the surface of the protective layer substrate 22. Examples of the silicone resin include silicone-modified resin and polydimethylsiloxane.

  When a silicone resin is applied (coated) to the protective layer base material 22, it is preferably applied (coated) thinly to the extent that a release effect can be obtained. After application (coating), the silicone resin may be fixed to the protective layer base material 22 by heat, UV treatment or the like. It is more preferable to apply an undercoat layer to the protective layer base material 22 before applying (coating) the silicone resin.

  A preferable thickness of the silicone resin layer 23 is about 0.005 to 1 μm, and particularly preferably 0.01 to 0.1 μm. When the thickness of the silicone resin layer 23 is in the above range, the adhesion between the protective layer base material 22 and the silicone resin layer 23 becomes good.

  As a PET film treated with a silicone resin, for example, a product name “38-T25C-4” manufactured by Mitsui Chemicals Tosero Co., Ltd. is available.

  The thicknesses of the protective layer 21 and the protective layer base material 22 are each preferably 15 to 50 μm, and more preferably 25 to 40 μm. When the thickness of the protective layer 21 or the protective layer base material 22 is 15 μm or more, distortion during the treatment with the silicone resin hardly remains, and when the film is wound, the generation of wrinkles tends to be suppressed. is there.

  From the viewpoint of peelability of the protective layer 21 from the photosensitive layer 25, the 180 ° peel strength at 23 ° C. between the surface of the protective layer 21 on the silicone resin layer side and the photosensitive layer 25 is 0.010 to 0.30 N. / Cm, more preferably 0.015 to 0.25 N / cm, and still more preferably 0.020 to 0.20 N / cm. When the 180 ° peel strength is 0.020 N / cm or more, the adhesive strength between the photosensitive layer 25 and the protective layer 21 is sufficiently high, and the photosensitive resin composition is coated on the support 27 and dried. There exists a tendency for the laminating property of the layer 25 and the protective layer 21 to become favorable. When the 180 ° peel strength is 0.20 N / cm or less, the adhesive strength between the photosensitive layer 25 and the protective layer 21 is sufficiently low, and the photosensitive layer 25 is transferred to the protective layer 21 when the protective layer 21 is peeled off. There is a tendency to become difficult. The 180 ° peel strength can be measured by a general method (for example, a method conforming to JIS K6854-2) using an adhesive tape (manufactured by Nitto Denko Corporation, product name: “NITTO31B”). .

<Support>
As the support 27 in the photosensitive element 20, for example, a polymer film having heat resistance and solvent resistance such as polyester (polyethylene terephthalate, etc.), polypropylene, and polyethylene can be used. The thickness of the support (polymer film) 27 is preferably 5 to 100 μm. The support (polymer film) 27 may have a silicone resin layer, an olefin resin layer, or the like as a release layer.

<Photosensitive layer>
The photosensitive layer 25 can be formed by applying a photosensitive resin composition described later on the support 27 or the protective layer 21. 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 25 varies depending on the use, it is preferably 1 to 100 μm after drying the photosensitive layer 25, more preferably 3 to 60 μm, still more preferably 5 to 60 μm, It is especially preferable that it is 5-40 micrometers, and it is very preferable that it is 5-25 micrometers. In addition, from the viewpoint of excellent insulation reliability (insulation between wirings in the thickness direction of the layer) and productivity in mounting a chip, the thickness of the photosensitive layer 25 is preferably over 20 μm. 20 μm or less.

[Photosensitive resin composition]
The photosensitive resin composition for forming the photosensitive layer 15 in the first embodiment includes (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: A compound having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and having at least one of a methylol group and an alkoxyalkyl group; and component (D): an acryloyloxy group, a methacryloyloxy group, And an aliphatic compound having two or more functional groups selected from the group consisting of a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group and a hydroxyl group. In the present specification, these components may be simply referred to as (A) component, (B) component, (C) component and the like. If the photosensitive layer is formed from the photosensitive resin composition, the resolution of the resulting resist pattern tends to be particularly excellent.

  The photosensitive resin composition for forming the photosensitive layer 25 in the second embodiment includes (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: And a compound having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring and having at least one of a methylol group and an alkoxyalkyl group. The photosensitive resin composition in this embodiment is selected from the group consisting of component (D): an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, and a hydroxyl group as necessary. An aliphatic compound having two or more kinds of functional groups can be contained.

  The present inventors consider the reason why the photosensitive resin composition is excellent in resolution as follows. 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 area, due to the catalytic effect of the acid generated from the component (B), the methylol groups or alkoxyalkyl groups in the component (C) or the methylol groups or alkoxyalkyl groups in the component (C) When the component (A) reacts with dealcoholization, 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.

  Hereinafter, the photosensitive resin composition common in the first and second embodiments will be described. As necessary, the photosensitive resin composition may contain (E) component: benzophenone compound, (F) component: solvent, (G) component: compound having Si—O bond, (H) component: sensitizer, etc. Can be contained.

((A) component)
The photosensitive resin composition in the present embodiment contains a resin having a phenolic hydroxyl group. Although it does not specifically limit as resin which has a phenolic hydroxyl group, Resin soluble in alkaline aqueous solution (alkali-soluble resin) is preferable, and a novolak resin is more preferable from a viewpoint of further improving resolution. The novolak resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst.

  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 can be mentioned. Phenols can be used alone or in combination of two or more.

  Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like. Aldehydes can be used singly or in combination of two or more.

  As the novolac resin, for example, a cresol novolac resin can be used. Specific examples of novolak resins include phenol / formaldehyde condensed novolak resins, phenol-cresol / formaldehyde condensed novolak resins, cresol / formaldehyde condensed novolak resins, phenol-naphthol / formaldehyde condensed novolak resins, and the like.

  Examples of the component (A) other than the novolak resin include polyhydroxystyrene and a copolymer thereof, a phenol-xylylene glycol condensed resin, a cresol-xylylene glycol condensed resin, and a phenol-dicyclopentadiene condensed resin.

  (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 100,000 or less, 1000 to 80000, 2000 to 50000, from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance and the like of the resulting resin pattern (cured film). 2000-20000, 3000-15000, or 5000-15000 may be sufficient.

In addition, in this embodiment, the weight average molecular weight of each component can be measured on condition of the following by the gel permeation chromatography method (GPC) using a standard polystyrene calibration curve, for example.
Equipment used: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (manufactured by Hitachi Chemical Co., Ltd., trade name, total of 3)
Column specification: 10.7mmφ × 300mm
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 ml / min Detector: L-3300RI (manufactured by Hitachi, Ltd.)

  The content of the component (A) is 10 to 90% by mass, 30 to 90% by mass based on the total amount of the photosensitive resin composition (however, when the component (F) is used, the component (F) is excluded). 30 to 80% by mass, 40 to 80% by mass, or 40 to 60% by mass. When the content of the component (A) is in the above range, the developability of the photosensitive layer formed using the photosensitive resin composition with respect to the aqueous alkali solution tends to be further improved.

((B) component)
The photosensitive resin composition in the present embodiment contains a photosensitive acid generator. The photosensitive acid generator is a compound that generates an acid upon irradiation with an actinic ray or the like. Due to the catalytic effect of the acid generated from the photosensitive acid generator, the methylol groups in the component (C) or the alkoxyalkyl groups, or the methylol group or the alkoxyalkyl group in the component (C) and the component (A) However, by reacting with dealcoholization, the solubility of the composition in the developer is greatly reduced, and a negative pattern can be formed.

  The component (B) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or the like. Examples of the component (B) include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds. Among these, from the viewpoint of excellent availability, the component (B) is preferably at least one selected from the group consisting of an onium salt compound and a sulfonimide compound. In particular, when a solvent is used, the component (B) is preferably an onium salt compound from the viewpoint of excellent solubility in the solvent.

  Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Specific examples of preferred onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium heptadecafluorooctanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate Diaryl iodonium salts such as diphenyliodonium tris (pentafluoroethyl) trifluorophosphate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium tris [(trifluoromethyl) sulfonyl] methanide; Such as sulfonium salt and the like. Among these, a sulfonium salt is preferable from the viewpoint of further improving sensitivity and thermal stability, and a triarylsulfonium salt is more preferable from the viewpoint of further improving thermal stability. An onium salt compound can be used singly or in combination of two or more.

  As the triarylsulfonium salt of the component (B), for example, a compound represented by the following general formula (b1), a compound represented by the following general formula (b2), a compound represented by the following general formula (b3), And at least one cation selected from the group consisting of compounds represented by the following general formula (b4), a tetraphenylborate skeleton, an alkyl sulfonate skeleton having 1 to 20 carbon atoms, a phenyl sulfonate skeleton, and a 10-camphor sulfonate skeleton A sulfonium salt having an anion having at least one skeleton selected from the group consisting of a trisalkylsulfonylmethanide skeleton having 1 to 20 carbon atoms, a tetrafluoroborate skeleton, a hexafluoroantimonate skeleton, and a hexafluorophosphate skeleton. Can be mentioned.

  The hydrogen atom of the phenyl group in the general formulas (b1) to (b4) includes a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, and carbon. It may be substituted with at least one selected from the group consisting of several to 12 alkoxycarbonyl groups, and when there are a plurality of substituents, they may be the same or different.

  The hydrogen atom of the phenyl group of the tetraphenylborate skeleton is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, It may be substituted with at least one selected from the group consisting of an alkylcarbonyl group having 2 to 12 carbon atoms and an alkoxycarbonyl group having 2 to 12 carbon atoms. Or different.

  The hydrogen atom of the alkyl sulfonate skeleton is at least one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, and an alkoxycarbonyl group. It may be substituted, and when there are a plurality of substituents, they may be the same or different.

  The hydrogen atom of the phenyl group of the phenylsulfonate skeleton is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, carbon It may be substituted with at least one selected from the group consisting of a C2-C12 alkylcarbonyl group and a C2-C12 alkoxycarbonyl group, and when there are a plurality of substituents, they are mutually identical. May be different.

  The hydrogen atom of the trisalkylsulfonylmethanide skeleton is at least selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, and an alkoxycarbonyl group. It may be substituted with one kind, and when there are a plurality of substituents, they may be the same or different.

  The fluorine atom of the hexafluorophosphate skeleton may be substituted with at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a perfluoroalkyl group having 1 to 12 carbon atoms, When there are a plurality of substituents, they may be the same or different.

  The sulfonium salt used as the component (B) has, as a cation, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium, (2) from the viewpoint of further excellent sensitivity, resolution, and insulation. -Methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium, (2-ethoxy) Having at least one selected from the group consisting of phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium and tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium A compound is preferred.

  The sulfonium salt used as the component (B) includes trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluoroantimonate, tris [(trifluoromethyl) sulfonyl] methanide, 10-camphorsulfonate, tris (pentafluoroethyl) as anions. A compound having at least one selected from the group consisting of trifluorophosphate and tetrakis (pentafluorophenyl) borate is preferable.

  Specific examples of the sulfonium salt include (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium nonafluorobutanesulfonate, [4- (4-biphenylylthio) Phenyl] -4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, and the like. A sulfonium salt can be used individually by 1 type or in mixture of 2 or more types.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) -1,8- And naphthalimide, N- (10-camphorsulfonyloxy) -1,8-naphthalimide, and the like. A sulfonimide compound can be used individually by 1 type or in mixture of 2 or more types.

  (B) A component can be used individually by 1 type or in mixture of 2 or more types.

  From the viewpoint of further improving the sensitivity, resolution, pattern shape and the like of the photosensitive resin composition of the present embodiment, the content of the component (B) is 0.1 to 100 parts by mass of the component (A). 15 mass parts, 0.3-10 mass parts, 1-10 mass parts, 3-10 mass parts, 5-10 mass parts, or 6-10 mass parts may be sufficient. 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 in the present embodiment is at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic ring as the component (C), and at least selected from the group consisting of a methylol group and an alkoxyalkyl group. A compound having one kind is contained (however, the component (D) and the component (E) are not included). Here, the aromatic ring means an aromatic hydrocarbon group (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic ring means a cyclic group (for example, a cyclic group having 3 to 10 carbon atoms) having at least one hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom, such as a pyridine ring, an imidazole ring, Examples include a pyrrolidinone ring, an oxazolidinone ring, an imidazolidinone ring and a pyrimidinone ring. An alicyclic ring means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring and a cyclohexane ring. Is mentioned. An alkoxyalkyl group means a group in which an alkyl group is bonded to another alkyl group via an oxygen atom. In the alkoxyalkyl group, the two alkyl groups may be the same or different from each other, and may be, for example, an alkyl group having 1 to 10 carbon atoms.

  When the photosensitive resin composition contains the component (C), when exposed to light (or when cured by heat treatment after exposure and exposure), methylol groups or alkoxyalkyl groups in the component (C) Alternatively, the methylol group or alkoxyalkyl group in component (C) reacts with component (A) with dealcoholization to greatly reduce the solubility of the composition in the developer, resulting in a negative pattern. Can be formed. In addition, when the photosensitive layer after the resin pattern is formed is heated and cured, the (C) component reacts with the (A) component to form a bridge structure, thereby preventing the resin pattern from being weakened and melted. .

  Specifically, the component (C) includes a compound having a phenolic hydroxyl group (however, the component (A) is not included), a compound having a hydroxymethylamino group, and a compound having an alkoxymethylamino group. At least one selected from the above is preferred. When the compound having a phenolic hydroxyl group has a methylol group or an alkoxyalkyl group, it is possible to further increase the dissolution rate of the unexposed area when developing with an alkaline aqueous solution, and to further improve the sensitivity of the photosensitive layer. (C) A component can be used individually by 1 type or in mixture of 2 or more types.

  As the compound having a phenolic hydroxyl group, a conventionally known compound can be used, but it is excellent in balance between the effect of promoting dissolution of the unexposed area and the effect of preventing melting at the time of curing of the photosensitive resin composition layer. From the viewpoint, a compound represented by the following general formula (1) is preferable.

In the above general formula (1), 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 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 represent an integer of 0 to 3. Here, examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, and a propyl group; and 2 to 10 carbon atoms such as a vinyl group. An alkenyl group; an aryl group having 6 to 30 carbon atoms, such as a phenyl group; and a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom. When there are a plurality of R ^{81 to} R ⁸⁴ , they may be the same as or different from each other.

  The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).

In the general formula (2), X ¹ represents a single bond or a divalent organic group, and a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). Several R may mutually be same or different.

  Moreover, you may use the compound represented by following General formula (3) as a compound which has the said phenolic hydroxyl group.

  In said general formula (3), several R shows an alkyl group (for example, a C1-C10 alkyl group) each independently. Several R may mutually be same or different.

  In the general formula (1), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. In addition, 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; and 2 to 10 carbon atoms such as an ethylidene group. An alkylidene 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 Ether bond; sulfide bond; amide bond and the like. Among these, Z is preferably a divalent organic group represented by the following general formula (4).

In the general formula (4), X represents 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), A group in which part or all of the hydrogen atoms are substituted with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond, or an amide bond is shown. R ⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms) or a haloalkyl group, and e represents an integer of 1 to 10. A plurality of R ⁹ and X may be the same as or different from each other. Here, the haloalkyl group means an alkyl group substituted with a halogen atom.

  Specifically, the compound having an alkoxymethylamino group is at least one selected from the group consisting of a compound represented by the following general formula (5) and a compound represented by the following general formula (6). preferable.

  In said general formula (5), several R shows an alkyl group (for example, a C1-C10 alkyl group) each independently. Several R may mutually be same or different.

  In said general formula (6), several R shows an alkyl group (for example, a C1-C10 alkyl group) each independently. Several R may mutually be same or different.

  Examples of the compound having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N -Hydroxymethyl) urea and the like. Examples of the compound having an alkoxymethylamino group include nitrogen-containing compounds obtained by alkylating all or part of the methylol groups of the compound having a hydroxymethylamino group. 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 of the compound having an alkoxymethylamino group include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl). Examples include urea.

  The content of the component (C) is 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more with respect to 100 parts by mass of the component (A) from the viewpoint that chemical resistance and heat resistance tend to be good. , 20 parts by mass or more, or 25 parts by mass or more. The content of the component (C) is such that the resolution tends to be further improved, with respect to 100 parts by mass of the component (A), 80 parts by mass or less, 70 parts by mass or less, 55 parts by mass or less, or 40 mass parts or less may be sufficient. The weight average molecular weight of the compound used as the component (C) is preferably 94 to 2000, more preferably 108 to 2000, and further preferably 108 to 1500. In addition, about the compound with a low molecular weight, when it is difficult to measure by the above-mentioned measuring method of the weight average molecular weight, the molecular weight can be measured by another method, and the average can be calculated.

((D) component)
The photosensitive resin composition in the present embodiment includes at least one functional group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, and a hydroxyl group as the component (D). Containing an aliphatic compound having two or more. In addition, (D) component may have at least 1 type of 2 or more types of different functional groups, and may have 2 or more types of 1 type of functional groups. The compound is preferably an aliphatic compound having three or more functional groups. The upper limit of the number of functional groups is not particularly limited, but is 12 for example. The “aliphatic compound” refers to a compound in which the main skeleton is an aliphatic skeleton and does not contain an aromatic ring or an aromatic heterocyclic ring.

  From the viewpoint of excellent workability when forming a photosensitive resin composition layer (photosensitive layer) on a substrate, the photosensitive resin composition is also required to have excellent adhesion to the substrate (tackiness) There is. When a photosensitive resin composition that does not have sufficient tackiness is used, the photosensitive resin composition in the exposed area is easily removed by the development process, and the adhesion between the substrate and the resin pattern (resist pattern) deteriorates. Tend. In this embodiment, when the photosensitive resin composition contains the component (D), there is a tendency that the adhesiveness (that is, tackiness) between the photosensitive resin composition and the substrate is improved. Furthermore, the photosensitive resin composition containing component (D) can impart flexibility to the photosensitive layer (coating film), and increase the dissolution rate of unexposed areas when developing with an alkaline aqueous solution. This tends to improve the resolution of the resin pattern. From the viewpoint of further improving tackiness and solubility in an aqueous alkali solution, the weight average molecular weight of the component (D) may be 92 to 2000, 106 to 1500, or 134 to 1300 in consideration of balance. . In addition, about the compound with a low molecular weight, when it is difficult to measure by the above-mentioned measuring method of the weight average molecular weight, the molecular weight can be measured by another method, and the average can be calculated.

  Specific examples of the component (D) include compounds represented by the following general formulas (7) to (10). In the following general formulas (7) to (13), 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.

In General Formula (7), R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (11), and R ² , R ^3, and R ⁴ are each independently Are an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, a hydroxyl group, a group represented by the following general formula (12), or a group represented by the following general formula (13). .

In General Formula (8), R ⁵ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (11), and R ⁶ , R ^7, and R ⁸ are each independently Are an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, a hydroxyl group, a group represented by the following general formula (12), or a group represented by the following general formula (13). .

In the general formula (9), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently acryloyloxy group, methacryloyloxy group, glycidyloxy group, oxetanyl alkyl ether group, vinyl ether group, hydroxyl group , A group represented by the following general formula (12), or a group represented by the following general formula (13).

In the general formula (10), R ¹⁵ , R ¹⁷ , R ¹⁸ and R ²⁰ are each independently acryloyloxy group, methacryloyloxy group, glycidyloxy group, oxetanyl alkyl ether group, vinyl ether group, hydroxyl group, the following general formula (12 ) Or a group represented by the following general formula (13), R ¹⁶ and R ¹⁹ are each independently a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or the following general formula ( The group represented by 11) is shown.

In the general formula (11), R ²¹ represents an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group or a hydroxyl group.

In General Formula (12), R ²² represents an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, or a hydroxyl group, and n is an integer of 1 to 10.

In General Formula (13), R ²³ represents an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, or a hydroxyl group, and m is an integer of 1 to 10, respectively.

  Specifically, as the component (D), at least selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, and a vinyl ether group from the viewpoint of further improving sensitivity and resolution. A compound having one kind is preferable, a compound having two or more glycidyloxy groups or two or more acryloyloxy groups is more preferable, and a compound having three or more glycidyloxy groups or three or more acryloyloxy groups is further included. preferable. (D) A component can be used individually by 1 type or in mixture of 2 or more types.

  The component (D) includes a compound having an acryloyloxy group, a compound having a methacryloyloxy group, a compound having a glycidyloxy group, a compound having an oxetanyl alkyl ether group, a compound having a vinyl ether group, and a compound having a hydroxyl group. At least one selected from the group can be used. As the component (D), a compound having at least one group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group and a glycidyloxy group is preferable. From the viewpoint of improving the insulation reliability in a fine wiring, acryloyloxy A compound having at least one group selected from the group consisting of a group and a methacryloyloxy group is more preferable. From the viewpoint of further improving developability, the component (D) is preferably an aliphatic compound having two or more glycidyloxy groups, and preferably an aliphatic compound having three or more glycidyloxy groups. More preferably, it is more preferably an aliphatic compound having 3 or more glycidyloxy groups having a weight average molecular weight of 1000 or less.

  Examples of the compound having an acryloyloxy group include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO-modified ditrimethylolpropane tetraacrylate, PO-modified ditrimethylolpropane tetraacrylate, ditrile Methylolpropane 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 trim Triacrylate, trimethylolpropane acrylate, EO-modified glycerol tri acrylate, PO-modified glycerol triacrylate, glycerin triacrylate. The compounds having an acryloyloxy group can be used alone or in combination of two or more.

  Examples of the compound having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, ditriethyl. Methylolpropane 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 Acrylate, PO-modified trimethylolpropane dimethacrylate, trimethylolpropane dimethacrylate, EO modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, glycerine trimethacrylate and the like. The compound which has a methacryloyloxy group can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the compound having a glycidyloxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl. Ether, glycerin diglycidyl ether, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerin triglycidyl ether, Glycerol propoxylay Triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, diglycidyl 1,2-cyclohexane dicarboxylate, and the like. The compound which has a glycidyloxy group can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the compound having a glycidyloxy group include dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, and And at least one selected from the group consisting of glycerin triglycidyl ether is preferred.

  The compound having a glycidyloxy group includes, for example, Epolite 40E, Epolite 100E, Epolite 70P, Epolite 200P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), alkyl type epoxy resin ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L and Denacol EX-850L The name “Denacol” is a commercially available trademark).

  Examples of the compound having an oxetanyl alkyl ether group include a compound having a 3-alkyl-3-oxetanyl alkyl ether group, and a compound having a 3-ethyl-3-oxetanyl alkyl 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. The compound which has oxetanyl alkyl ether can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the compound having a hydroxyl group include polyhydric alcohols such as dipentaerythritol, pentaerythritol, and glycerin. The compound which has a hydroxyl group can be used individually by 1 type or in mixture of 2 or more types.

  Among the components (D), at least one selected from the group consisting of trimethylolethane triglycidyl ether and trimethylolpropane triglycidyl ether is preferable from the viewpoint of further excellent 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. .

  The content of the component (D) is such that the flexibility of the photosensitive layer (coating film) can be further imparted, and the dissolution rate of the unexposed area when developing with an alkaline aqueous solution is likely to further increase, so that the component (A) 100 1 mass part or more, 10 mass parts or more, 20 mass parts or more, 25 mass parts or more, 30 mass parts or more, or 40 mass parts or more may be sufficient with respect to a mass part. The content of the component (D) is 70 parts by mass or less and 65 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint that the photosensitive resin composition tends to form a film on a desired support. Or 50 parts by mass or less.

((E) component)
The photosensitive resin composition in this embodiment may contain a benzophenone compound as the component (E). By containing a benzophenone compound, the resolution of the photosensitive resin composition can be further improved. Moreover, the tolerance of the exposure amount which can form a fine resist pattern can be improved by containing (E) component, and productivity can be improved more. Examples of the benzophenone compound include benzophenone, 4,4′-diaminobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dibutylamino). Benzophenone, 4-ethylaminobenzophenone, 2,4-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetramethoxybenzophenone, 2,2 ′, 4,4′-tetraethoxybenzophenone, 2,2 ′, 4,4′-tetrabutoxybenzophenone 2,2′-dihydroxy-4,4′-dimethoxybenzopheno 2,2′-dihydroxy-4,4′-diethoxybenzophenone, 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, 4,4′-dihydroxybenzophenone, 4,4′-dimethoxybenzophenone, 4, 4,4′-dibutoxybenzophenone, 4,4′-diphenylbenzophenone, and the like.

  Among the components (E), the compound is selected from the group consisting of an amino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a hydroxy group, a methoxy group, an ethoxy group, a butoxy group, and a phenyl group in that the resolution is further improved. A benzophenone compound having one or more groups is preferred, and two or more groups selected from the group consisting of amino group, dimethylamino group, diethylamino group, dibutylamino group, hydroxy group, methoxy group, ethoxy group, butoxy group and phenyl group Benzophenone compounds having more than one, more preferably benzophenone compounds having two or more diethylamino groups or hydroxy groups, particularly 4,4′-bis (dimethylamino) benzophenone and 2,2 ′, 4,4′-tetrahydroxybenzophenone preferable. (E) A component can be used individually by 1 type or in mixture of 2 or more types.

  As for content of (E) component, 0.001-10 mass parts is preferable with respect to 100 mass parts of (A) component, 0.01-1 mass part is more preferable, 0.01-0.8 mass part Is more preferable, and 0.05 to 0.1 part by mass is particularly preferable. When the content of the component (E) is in the range of 0.001 to 10 parts by mass, the resolution of the photosensitive resin composition can be further improved, and the exposure amount that can form a fine resist pattern is sufficient. Tolerance can be further improved and productivity is further improved.

  By including the component (E), the resolution is further improved. For example, it is easy to form a fine resist pattern (that is, a fine resist pattern having a via opening diameter of 10 (unit: μm) or less). For example, when forming a fine resist pattern having a via opening diameter of 10 (unit: μm) or less, it is necessary to appropriately adjust the exposure amount, but by containing the component (E), The width of the exposure amount that can form a simple resist pattern can be widened, that is, the tolerance (allowable range) of the exposure amount can be improved, so that when a mass-produced product or the like is manufactured, a fine resist pattern is formed. In addition, it is not necessary to finely adjust the exposure amount, and productivity is improved.

((F) component)
The photosensitive resin composition in this 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 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 monoethyl Propylene glycol monoalkyl ethers such as 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 nitrate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; methyl ethyl ketone (also known as 2-butanone), 2-heptanone, 3-heptanone, 4- Ketones such as heptanone and cyclohexanone; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and 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) may be 30 to 200 parts by mass or 40 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 in this embodiment may contain a compound having a Si—O bond (excluding compounds corresponding to the components (A) to (F)) as the component (G). The compound having a Si—O bond may be a compound having a siloxane bond. The component (G) is not particularly limited as long as it has a Si—O bond, and examples thereof include silica (silica filler) and silane compounds (such as a silane coupling agent). (G) A component can be used individually by 1 type or in mixture of 2 or more types.

  When the photosensitive resin composition in this embodiment contains an inorganic filler, the thermal expansion coefficient of the resin pattern can be reduced. 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. Moreover, you may use what an inorganic filler has a Si-O bond by processing an inorganic filler with a silane compound. Among inorganic fillers treated with a silane compound, as inorganic fillers other than silica, aluminum oxide, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, or talc, Examples include inorganic fillers derived from mineral products such as mica.

  The average primary particle diameter of the inorganic filler is preferably 100 nm or less, more preferably 80 nm or less, and further preferably 50 nm or less from the viewpoint of further improving the photosensitivity of the photosensitive layer. When the average primary particle size is 100 nm or less, the photosensitive resin composition is less likely to become cloudy, and light for exposure is easily transmitted through the photosensitive layer. As a result, since the unexposed part is easily removed, the resolution of the resin pattern tends to be difficult to decrease. The average primary particle diameter is a value obtained by converting from the BET specific surface area.

The thermal expansion coefficient of silica is preferably 5.0 × 10 ⁻⁶ / ° C. or less. Silica is preferably silica such as fused spherical silica, fumed silica, sol-gel silica, and more preferably fumed silica or sol-gel silica from the viewpoint of easily obtaining a suitable particle size. Moreover, it is preferable that a silica is a silica (nanosilica) with an average primary particle diameter of 5-100 nm.

  When measuring the particle size of the inorganic filler, a known particle size distribution meter can be used. The particle size distribution meter is a laser diffraction / scattering type particle size distribution meter that calculates the particle size distribution by irradiating the particle group with laser light and calculating from the intensity distribution pattern of the diffracted light and scattered light emitted from the particle group; Examples thereof include a particle size distribution meter of nanoparticles for obtaining a particle size distribution using frequency analysis.

  When the photosensitive resin composition of this embodiment contains a silane compound, the adhesive strength between the photosensitive layer and the substrate after pattern formation can be improved. 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 Si—O 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 (14) is preferable.
(R ¹⁰¹ O) _4-f -Si- (R ¹⁰² ) _f (14)

In General Formula (14), 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 An integer of 0 to 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, more preferably an alkyl group having 1 to 2 carbon atoms, from the viewpoint of further improving resolution. In the case of treating with a silane compound (such as a compound represented by the general formula (14)) in order to improve the dispersibility of the inorganic filler, f is preferably 0 to 2 from the viewpoint of further improving the dispersibility of the inorganic filler. 0 to 1 are more preferable.

  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-dodecyltrimethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylsilanol, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3 Aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3 -(Triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-methacryloyloxyp Pyrtrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- ( 1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane and the like. The component (G) is preferably an epoxy silane having at least one glycidyloxy group, more preferably an epoxy silane having at least one selected from the group consisting of a trimethoxysilyl group and a triethoxysilyl group. .

  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. The content of the component (G) may be 1 to 20 parts by mass or 3 to 10 parts by mass with respect to 100 parts by mass of the component (A).

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

  The content of the component (H) 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).

(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 colorant, an adhesion aid, a leveling agent, and an inorganic filler that does not have a Si—O bond. Examples of the inorganic filler include, but are not limited to, aluminum compounds such as aluminum oxide and aluminum hydroxide; alkali metal compounds; alkalis such as calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, and magnesium hydroxide. Earth metal compounds; inorganic compounds derived from mines. These are pulverized by a pulverizer, classified according to circumstances, and can be dispersed with a maximum particle size of 2 μm or less. The inorganic filler may be used alone or in combination of two or more. Any inorganic filler is preferably dispersed with a maximum particle size of 2 μm or less when dispersed in the photosensitive resin composition. At that time, a silane coupling agent can be used in order to disperse the resin in the resin without aggregation. The content of the inorganic filler is preferably 1 to 70% by mass based on the total amount of the photosensitive resin composition (however, when the component (F) is used, excluding the component (F)). More preferably, it is -65 mass%.

[Method of forming resist pattern]
The resist pattern forming method according to the present embodiment includes a step of forming a photosensitive layer on a substrate using a photosensitive element (photosensitive layer preparation step), a step of exposing the photosensitive layer to a predetermined pattern, and an exposure. Developing the subsequent photosensitive layer, and heat-treating the resulting resin pattern.

  The resist pattern forming method of this embodiment may further include a step of heat-treating (post-exposure baking) the photosensitive layer between the exposure step and the development step. In this case, the method for forming a resist pattern according to this embodiment includes a step of forming a photosensitive layer on a substrate using a photosensitive element, exposing the photosensitive layer to a predetermined pattern, and post-exposure heat treatment (after exposure). And a step of developing the photosensitive layer after the heat treatment (baking after exposure) and heat-treating the obtained resin pattern.

  In the method for forming a resist pattern according to this embodiment, for example, first, the above-described photosensitive layer is formed on a substrate on which a resist pattern is to be formed. The process of forming a photosensitive layer can be performed by arrange | positioning the photosensitive layer of the said photosensitive element on a base material, for example. The photosensitive layer preparation step can also be referred to as a step of obtaining a base material (for example, a substrate) including a photosensitive layer containing a photosensitive resin composition. The photosensitive layer can be formed, for example, by transferring (laminating) the photosensitive layer in the photosensitive element onto a substrate.

  Examples of the substrate include a substrate. As the substrate, for example, a copper foil with resin, a copper clad laminate, a silicon wafer with a metal sputtered film, a silicon wafer with a copper plating film, an alumina substrate, or the like can be used. The surface on which the photosensitive layer is formed on the substrate may be a cured resin layer formed using the photosensitive resin composition. In that case, there exists a tendency for adhesiveness with a base material to improve.

Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of actinic rays used for exposure include rays using a g-line stepper as a light source; ultraviolet rays using a low-pressure mercury lamp, high-pressure mercury lamp, metal halide lamp, i-line stepper and the like as a light source; electron beams; The exposure amount is appropriately selected depending on the light source used, the thickness of the photosensitive layer, and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the exposure amount may be about 100 to 3000 mJ / cm ² when the photosensitive layer has a thickness of 5 to 50 μm.

  By performing the heat treatment after the exposure and before the development (post-exposure baking), the curing reaction of the component (A) and the component (C) by the acid generated from the photosensitive acid generator can be promoted. The post-exposure baking conditions vary depending on the composition of the photosensitive resin composition, the content of each component, the thickness of the photosensitive layer, and the like, but for example, heating at 50 to 150 ° C. for 1 to 60 minutes is preferable, and 60 to It is more preferable to heat at 100 ° C. for 1 to 15 minutes. Moreover, you may heat at 70-150 degreeC for 1 to 60 minutes, and you may heat at 80-120 degreeC for 1 to 60 minutes.

  Next, the photosensitive layer (coating film) that has been subjected to exposure and / or post-exposure baking is developed with an alkaline developer, and the unexposed areas (areas other than the cured areas) are dissolved and removed to obtain a desired resist pattern. Get. 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 in which an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline is dissolved in water so that the concentration becomes 1 to 10% by mass; Is 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 the said alkaline developing solution, it wash | cleans with water and dries. The alkaline developer is preferably tetramethylammonium hydroxide from the viewpoint 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 of the photosensitive resin composition are not particularly limited, but can be adjusted according to the use of the cured product. For example, the photosensitive resin composition can be cured by heating at 50 to 250 ° C. for 30 minutes to 10 hours.

  Moreover, in order to fully advance hardening and / or to prevent the deformation | transformation of the obtained resin pattern, 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. When the heat treatment is performed under the above-described curing conditions, the heating equipment is not particularly limited, and a general oven, infrared furnace, or the like can be used.

<Semiconductor device>
The semiconductor device according to the present embodiment includes a cured product of the photosensitive layer in the present embodiment. The cured product of the photosensitive layer of this embodiment can be suitably used as, for example, a surface protective film and / 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. The semiconductor device of this embodiment includes a circuit substrate (for example, a circuit board) having a cured product of the photosensitive layer of this embodiment.

  FIG. 3 is a view showing a method for producing a multilayer printed wiring board including the cured product of the photosensitive layer according to the present embodiment as a solder resist and / or an interlayer insulating film. The multilayer printed wiring board 100A shown in FIG. 3F has a wiring pattern on the 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 according to an embodiment of the present disclosure will be briefly described with reference to FIG.

  First, an interlayer insulating film 103 is formed on both surfaces of a base material (a copper clad laminate or the like) 101 having a wiring pattern 102 on the surface (see FIG. 3A). The interlayer insulating film 103 can be formed by preparing the above-described photosensitive element in advance and attaching the photosensitive layer of the photosensitive element to the surface of the printed wiring board using a laminator.

  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. 3B). 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. 3C). A photosensitive layer containing a photosensitive resin composition (a semi-additive photosensitive resin composition) is formed on the seed layer 105, and a predetermined pattern is exposed and developed to form a resin pattern 106 (FIG. 3 ( d)).

  Next, a wiring pattern 107 is formed on the portion of the seed layer 105 where the resin pattern 106 is not formed by electrolytic plating, and the resin pattern 106 is removed by a peeling solution, and then the wiring pattern 107 of the seed layer 105 is formed. The part which is not removed is removed by etching (see FIG. 3E).

  The multilayer printed wiring board 100A can be manufactured by repeating the above operation and forming the solder resist 108 containing the cured product of the above-described photosensitive resin composition on the outermost surface (see FIG. 3 (f)). The interlayer insulating film 103 and / or the solder resist 108 can be formed by using the resist pattern forming method described above. Moreover, it can form using the method provided with the process of forming a photosensitive layer, and the process of heat-processing. In the multilayer printed wiring board 100A thus obtained, semiconductor elements are mounted at corresponding locations, and electrical connection can be ensured.

  Hereinafter, although an example and an advantage of this indication are explained in detail by an example, this indication is not limited at all by these examples.

[Test Example 1: Examples 1-1 to 1-2 and Comparative Examples 1-1 to 1-6]
<Preparation of photosensitive resin composition>
Photosensitive acid generator (B-1), alkoxyalkyl compound (C-1), and compound having an acryloyloxy group (D-1) with respect to 100 parts by mass of the resin components (A-1 and A-2) ), A benzophenone compound (E-1), a solvent (F-1), and a compound (G-1) having a Si—O bond at the blending amounts (unit: parts by mass) shown in Table 1. The photosensitive resin composition was obtained by blending.

Abbreviations in Table 1 are as follows.
A-1: Novolac resin (made by Asahi Organic Materials Co., Ltd., trade name: TR4020G, weight average molecular weight: 13000)
A-2: Novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4080G, weight average molecular weight: 5000)
B-1: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-310B, anion: tetrakis (pentafluorophenyl) borate)
C-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalak MX-270)
D-1: Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: PET-30)
E-1: 4,4′-bis (diethylamino) benzophenone (made by Hodogaya Chemical Co., Ltd., trade name: EAB)
F-1: Methyl ethyl ketone (made 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)
PET-1: Polyethylene terephthalate film (manufactured by Fujimori Kogyo Co., Ltd., product name: NSP-5, film thickness: 38 μm): Film provided with aminoalkyd resin layer PET-2: Polyethylene terephthalate film (manufactured by Unitika Ltd., product name: A170, film thickness: 38 μm): film provided with olefin resin layer PET-3: polyethylene terephthalate film (manufactured by Teijin DuPont Films, product name: G2, film thickness: 25 μm): any of olefin resin layer and aminoalkyd resin layer PET-4: Polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd., product name: PUREX A53, film thickness: 25 μm): Film having a silicone resin layer formed using a silicone-modified resin PET 5: Polyethylene terephthalate film (manufactured by Teijin DuPont Films, Ltd., product name: PUREX A52T1, film thickness: 25 μm): film comprising a silicone resin layer formed using a silicone-modified resin PET-6: polyethylene terephthalate film (Teijin) DuPont Films Co., Ltd., product name: PUREX H52T1, film thickness: 25 μm): film having a silicone resin layer formed using a silicone-modified resin PET-7: polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name: TN608, film thickness: 25 μm): film provided with olefin resin layer PET-8: polyethylene terephthalate film (manufactured by Fujimori Kogyo Co., Ltd., product name: NS-15, film thickness: 38 μm): film provided with aminoalkyd resin layer Film

<Production of photosensitive element>
As the support, those having an olefin resin layer, an aminoalkyd resin layer, or a silicone resin layer formed on a support substrate and those not formed were prepared. The photosensitive resin composition was applied onto a support so that the thickness of the photosensitive resin composition was uniform, and dried for 10 minutes with a hot air convection dryer at 90 ° C. After drying, a polyethylene film (manufactured by Tamapoly Co., Ltd., product name: NF-15) is bonded as a protective layer on the photosensitive layer, and on the support or on the olefin resin layer, aminoalkyd resin layer or silicone resin layer, A photosensitive element in which a photosensitive layer and a protective layer were sequentially laminated and the thickness of the photosensitive layer was 10 μm was obtained.

<Evaluation of peel strength between support and photosensitive layer>
The photosensitive element was cut into 2 cm × 10 cm with a cutter, the protective layer was peeled off, and the laminate was attached to a rigid copper clad laminate with a laminator so that the photosensitive layer and the copper clad laminate were in contact with each other. Lamination was performed at 100 ° C., 1.0 m / min, and 0.4 MPa. Next, the copper-clad laminate with the photosensitive element attached is attached to a rheometer (manufactured by Rheotech Co., Ltd., trade name: FUDOH RHEO METER RT-3010D-CW), peeled off at 23 ° C., 30 cm / min, angle 180 °. Then, the support was peeled from the photosensitive layer, and the peel strength between the support and the photosensitive layer was evaluated. In addition, when the measured value fluctuated in a peak shape instead of a constant value, the average value of the peak was taken as the peel strength. The evaluation results are shown in Table 1.

<Evaluation of peel strength between protective layer and photosensitive layer>
The photosensitive element was cut into 2 cm × 10 cm with a cutter, and attached to a rigid copper-clad laminate with a double-sided tape so that the support and the copper-clad laminate were in contact with each other. Next, the copper-clad laminate with the photosensitive element attached is attached to a rheometer (manufactured by Rheotech Co., Ltd., trade name: FUDOH RHEO METER RT-3010D-CW), peeled off at 23 ° C., 30 cm / min, angle 180 °. Then, the protective layer was peeled from the photosensitive layer, and the peel strength between the protective layer and the photosensitive layer was evaluated. In addition, when the measured value fluctuated in a peak shape instead of a constant value, the average value of the peak was taken as the peel strength.

<Evaluation of peel strength ratio>
The peel strength ratio was evaluated as a value obtained by dividing the peel strength between the support and the photosensitive layer by the peel strength between the protective layer and the photosensitive layer. The evaluation results are shown in Table 1.

<Evaluation of resolution>
The photosensitive element from which the protective layer was peeled was laminated on a 6-inch diameter silicon wafer so that the photosensitive layer was in contact with the silicon wafer to obtain a laminate. Lamination was performed using a vacuum pressurizing laminator with a heater at 60 ° C. (upper), a heater at 60 ° C. (lower), a vacuuming time of 20 seconds, a pressing time of 20 seconds, and a pressure of 0.4 MPa. . Next, the support of the laminate is peeled off, and reduced projection exposure is performed on the photosensitive layer through a mask with i-line (365 nm) using an i-line stepper (trade name: FPA-3000iW, manufactured by Canon Inc.). Went. As the mask, a negative pattern having via openings (unexposed portions) in 1 μm increments from 1 to 30 μm in via diameter was used. The exposure amount is in the range of 100 to 2000 mJ / cm ^2, was subjected to the reduction projection exposure while changing by 100 mJ / cm ^2.

  The exposed photosensitive layer (coating film) was heated at 65 ° C. for 1 minute and then at 75 ° C. for 8 minutes (post-exposure baking). Next, a 2.38 mass% tetramethylammonium hydroxide aqueous solution (manufactured by Tama Chemical Industry Co., Ltd., trade name: TMAH 2.38%) is used as a developer, and a developing machine (trade name: AD- manufactured by Takizawa Sangyo Co., Ltd.) is used. 1200) and spray the developer onto the photosensitive layer (coating film) in a time corresponding to four times the shortest development time (the shortest time to remove the unexposed area) (pump discharge pressure [developer]: 0. 16 MPa) to remove the unexposed area. Subsequently, purified water (trade name: purified water, manufactured by Wako Pure Chemical Industries, Ltd.) was sprayed as a rinse solution for 60 seconds (pump discharge pressure [rinse solution]: 0.12 to 0.14 MPa) to wash away the developer. . And it was made to dry and the resin pattern was formed. The formed resin pattern was observed by enlarging the magnification to 1000 times using a metal microscope. The diameter of the smallest via opening was evaluated as the resolution among the patterns formed without the via opening (unexposed area) being removed cleanly and the insulating resin part (exposed area) being reduced in film thickness and without film roughness. . The evaluation results are shown in Table 1. In Comparative Example 1-1, since the peelability of the support was poor and the photosensitive layer was destroyed, the resolution was not evaluated.

<Evaluation of peelability of protective layer>
The photosensitive element was cut into 15 cm × 15 cm with a cutter, and the protective layer was peeled off from the end portion at 23 ° C. using a cellophane tape. After peeling off the protective layer, the photosensitive layer and the protective layer are observed. “A” indicates that the photosensitive layer is not transferred onto the protective layer, and “B” indicates that the photosensitive layer is partially transferred onto the protective layer. The peelability of the protective layer was evaluated. The evaluation results are shown in Table 1.

<Evaluation of peelability of support>
The protective layer was peeled off, and the photosensitive layer was laminated on a 6-inch silicon wafer so that the photosensitive layer was in contact with the silicon surface. After peeling the support, observe the surface of the support and the silicon wafer, and “A” indicates that the photosensitive layer is formed on the silicon wafer, and “S” indicates that the photosensitive layer remains even partially on the support. The peelability of the support was evaluated as “B”. The evaluation results are shown in Table 1. Laminating is performed using a vacuum pressurizing laminator with a heater at 60 ° C. (upper), a heater at 60 ° C. (lower), a vacuuming time of 20 seconds, a pressurizing time of 20 seconds, and a pressure of 0.4 MPa. went.

  As apparent from Table 1, Examples 1-1 and 1-2 using a support having an olefin resin layer or an aminoalkyd resin layer having a peel strength ratio of 1.0 or more have a peel strength ratio of 1. Compared with Comparative Examples 1-2 to 1-6 of less than 0.0, the peelability of the protective layer was improved from B to A. Examples 1-1 and 1-2 using a support having an olefin resin layer or an amino alkyd resin layer having a peel strength between the support and the photosensitive layer of less than 4.0 N / m are the olefin resin layer and amino Compared with the case where the support body which does not have an alkyd resin layer was used, the peelability of the support body improved from B to A. In addition, Examples 1-1 and 1-2 have a resolution of 7 μm, and it was found that the resolution was extremely good as in Comparative Examples 1-2 to 1-6.

[Test Example 2: Example 2-1 and Comparative Examples 2-1 to 2-5]
<Preparation of photosensitive resin composition>
Photosensitive acid generator (B-1), alkoxyalkyl compound (C-1), and compound having an acryloyloxy group (D-1) with respect to 100 parts by mass of the resin components (A-1 and A-2) ), A benzophenone compound (E-1), a solvent (F-1), and a compound (G-1) having a Si—O bond at the blending amounts (unit: parts by mass) shown in Table 2. The photosensitive resin composition was obtained by blending.

Abbreviations in Table 2 are as follows.
A-1: Novolac resin (made by Asahi Organic Materials Co., Ltd., trade name: TR4020G, weight average molecular weight: 13000)
A-2: Novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4080G, weight average molecular weight: 5000)
B-1: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-310B, anion: tetrakis (pentafluorophenyl) borate)
C-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalak MX-270)
D-1: Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: PET-30)
E-1: 4,4′-bis (diethylamino) benzophenone (made by Hodogaya Chemical Co., Ltd., trade name: EAB)
F-1: Methyl ethyl ketone (made 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)
PET-1: Polyethylene terephthalate film (Mitsui Chemicals Tosero Co., Ltd., product name: 38-T25C-4, film thickness: 38 μm): Film having a silicone resin layer PE-1: Polyethylene film (Tamapoly Co., Ltd., product name) : NF-15, film thickness: 20 μm): film not provided with a silicone resin layer PE-2: polyethylene film (manufactured by Tamapoly Co., Ltd., product name: GF-3, film thickness: 30 μm): provided with a silicone resin layer No film OPP-1: Biaxially stretched polypropylene film (Futamura Chemical Co., Ltd., product name: FOK-P, film thickness: 20 μm): Film without silicone resin layer OPP-2: Biaxially stretched polypropylene film (Toray Product name: 2500H, film thickness: 60 μm): Silicone resin layer E have no film OPP-3: biaxially oriented polypropylene film (Oji F-TECH scan Ltd., product name: FG-201, thickness: 30 [mu] m): film not provided with a silicone resin layer

<Production of photosensitive element>
The above photosensitive resin composition is formed on a polyethylene terephthalate film (manufactured by Teijin DuPont Films, trade name: Purex A53, "Purex" is a registered trademark) (support), and the thickness of the photosensitive resin composition is uniform. And dried for 10 minutes with a hot air convection dryer at 90 ° C. After drying, any one of PET1, PE1-2, or OPP1-3 as a protective layer was bonded onto the photosensitive layer to obtain a photosensitive element having a photosensitive layer thickness of 10 μm. The protective layer having the silicone resin layer was laminated so that the support, the photosensitive layer, the silicone resin layer, and the protective layer substrate were in this order.

<Evaluation of resolution>
The photosensitive element from which the protective layer was peeled was laminated on a 6-inch diameter silicon wafer so that the photosensitive layer was in contact with the silicon wafer to obtain a laminate. Lamination was performed using a vacuum pressurizing laminator with a heater at 60 ° C. (upper), a heater at 60 ° C. (lower), a vacuuming time of 20 seconds, a pressing time of 20 seconds, and a pressure of 0.4 MPa. . Next, the support of the laminate is peeled off, and reduced projection exposure is performed on the photosensitive layer through a mask with i-line (365 nm) using an i-line stepper (trade name: FPA-3000iW, manufactured by Canon Inc.). Went. As the mask, a negative pattern having via openings (unexposed portions) in 1 μm increments from 1 to 30 μm in via diameter was used. The exposure amount is in the range of 100 to 2000 mJ / cm ^2, was subjected to the reduction projection exposure while changing by 100 mJ / cm ^2.

  The exposed photosensitive layer (coating film) was heated at 65 ° C. for 1 minute and then at 75 ° C. for 8 minutes (post-exposure baking). Next, a 2.38 mass% tetramethylammonium hydroxide aqueous solution (manufactured by Tama Chemical Industry Co., Ltd., trade name: TMAH 2.38%) is used as a developer, and a developing machine (trade name: AD- manufactured by Takizawa Sangyo Co., Ltd.) is used. 1200) and spray the developer onto the photosensitive layer (coating film) in a time corresponding to four times the shortest development time (the shortest time to remove the unexposed area) (pump discharge pressure [developer]: 0. 16 MPa) to remove the unexposed area. Subsequently, purified water (trade name: purified water, manufactured by Wako Pure Chemical Industries, Ltd.) was sprayed as a rinse solution for 60 seconds (pump discharge pressure [rinse solution]: 0.12 to 0.14 MPa) to wash away the developer. . And it was made to dry and the resin pattern was formed. The formed resin pattern was observed by enlarging the magnification to 1000 times using a metal microscope. The diameter of the smallest via opening was evaluated as the resolution among the patterns formed without the via opening (unexposed area) being removed cleanly and the insulating resin part (exposed area) being reduced in film thickness and without film roughness. . The evaluation results are shown in Table 2.

<Evaluation of peelability of protective layer>
The photosensitive element was cut into 15 cm × 15 cm with a cutter, and the protective layer was peeled off from the end portion at 23 ° C. using a cellophane tape. After peeling off the protective layer, the photosensitive layer and the protective layer are observed. “A” indicates that the photosensitive layer is not transferred onto the protective layer, and “B” indicates that the photosensitive layer is partially transferred onto the protective layer. The peelability of the protective layer was evaluated. The evaluation results are shown in Table 2.

  As is apparent from Table 2, in Example 2-1 using the protective layer having the silicone resin layer, the peelability of the protective layer was improved from B to A as compared with Comparative Examples 2-1 to 2-5. did. In addition, Example 2-1 has a resolution of 7 μm, and it was found that the resolution was extremely good as in Comparative Examples 2-1 to 2-5.

  The photosensitive element of the present disclosure can be applied to formation of a material used for a surface protective film or an interlayer insulating film of a semiconductor element, and formation of a material used for a solder resist of a wiring board material or an interlayer insulating film. In particular, the photosensitive layer in the photosensitive element of the first embodiment of the present disclosure was thinned and densified because the resolution, the protective layer peelability, and the support peelability were all good. It is suitably used for a highly integrated package substrate. In addition, the photosensitive element of the second embodiment of the present disclosure has good resolution and protective layer peeling properties, so that it is highly integrated with fine lines and high density. It is suitably used for a package substrate or the like.

DESCRIPTION OF SYMBOLS 10,20 ... Photosensitive element, 11,27 ... Support body, 12 ... Support base material, 13 ... Olefin resin layer, 15, 25 ... Photosensitive layer, 17, 21 ... Protective layer, 22 ... Protective layer base material, 23 DESCRIPTION OF SYMBOLS ... Silicone resin layer, 100A ... Multilayer printed wiring board, 101 ... Base material, 102, 107 ... Wiring pattern, 103 ... Interlayer insulation film, 104 ... Opening part, 105 ... Seed layer, 106 ... Resin pattern, 108 ... Solder resist.

Claims (8)

A support, a photosensitive layer, and a protective layer are provided in this order, and the support has an olefin resin layer or an aminoalkyd resin layer as a surface layer on the photosensitive layer side,
The ratio of the peel strength between the photosensitive layer and the support relative to the peel strength between the photosensitive layer and the protective layer is 1.0 or more, and between the photosensitive layer and the support. A photosensitive element having a peel strength of 6.0 N / m or less.   The photosensitive layer is selected from the group consisting of (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: an aromatic ring, a heterocyclic ring and an alicyclic ring. A compound having at least one and having at least one of a methylol group and an alkoxyalkyl group; and component (D): an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group, a vinyl ether group, and a hydroxyl group The photosensitive element of Claim 1 formed from the photosensitive resin composition containing the aliphatic compound which has 2 or more of 1 or more types of functional groups selected from the group which consists of. A support, a photosensitive layer, and a protective layer are provided in this order, and the protective layer has a silicone resin layer as a surface layer on the photosensitive layer side,
The photosensitive layer is selected from the group consisting of (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: an aromatic ring, a heterocyclic ring and an alicyclic ring. A photosensitive element formed from a photosensitive resin composition comprising at least one compound and a compound having at least one of a methylol group and an alkoxyalkyl group.   The photosensitive resin composition comprises (D) component: one or more functional groups selected from the group consisting of acryloyloxy group, methacryloyloxy group, glycidyloxy group, oxetanyl alkyl ether group, vinyl ether group and hydroxyl group. The photosensitive element according to claim 3, further comprising an aliphatic compound having two or more.   The photosensitive element of Claim 2 or 4 whose content of the said (D) component is 1-70 mass parts with respect to 100 mass parts of said (A) component.   The photosensitive element as described in any one of Claims 2-5 in which the said photosensitive resin composition further contains the compound which has (G) component: Si-O bond.   A semiconductor device provided with the hardened | cured material of the photosensitive layer in the photosensitive element as described in any one of Claims 1-6.   The process of forming a photosensitive layer on a base material using the photosensitive element as described in any one of Claims 1-6, the process of exposing the said photosensitive layer to a predetermined pattern, and the photosensitive layer after exposure Developing, and heat-treating the obtained resin pattern. A method for forming a resist pattern.

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