JP7620043B2 - Photosensitive resin composition and photosensitive element - Google Patents

Description

The present invention relates to a photosensitive resin composition and a photosensitive element.

Printed wiring boards are generally manufactured using a photolithography process. Photolithography is a method for forming a desired wiring pattern on a substrate by the following steps: First, a layer made of a photosensitive resin composition is formed on the substrate, and the coating is exposed to light and developed in a pattern to form a resist pattern. Next, a conductor pattern is formed by etching or plating. After that, the resist pattern on the substrate is removed to form the desired wiring pattern on the substrate.

In recent years, with the miniaturization and high density of electronic devices, there is a demand for finer wiring than ever before on wiring boards. As a manufacturing method for wiring boards that meets such demands, MSAP (Modified Semi Additive Process) and SAP (Semi Additive Process) have attracted attention. In order to form fine wiring in these methods, for example, it is necessary to form a resist pattern with a line width of 12 μm or less using a cured film that has excellent adhesion and resolution.

Here, a photosensitive resin composition containing an alkali-soluble polymer having a hydroxyalkyl (meth)acrylate unit has been proposed with the aim of providing a photosensitive resin composition capable of producing a cured film with excellent adhesion, resolution, etc. (see, for example, Patent Document 1).

It is also known to use benzotriazole compounds for the purposes of preventing discoloration of the substrate after resist pattern formation and improving the storage stability of the photosensitive resin composition (see, for example, Patent Documents 2 to 5).

International Publication No. 2014/125884 JP 2013-246387 A JP 2016-139154 A JP 2020-076945 A JP 2009-180795 A

However, the photosensitive resin composition described in Patent Document 1 may cause a problem that the composition becomes unable to be applied as time passes due to the progress of gelation of the composition. Such gelation has an adverse effect on the production efficiency of photosensitive elements. In addition, Patent Documents 2 to 5 also did not consider the gelation of the photosensitive resin composition.
Furthermore, Patent Documents 1 to 5 leave room for further study from the standpoint of improving the resolution of the resist pattern and from the standpoint of improving the adhesion of the resist pattern to a substrate (eg, a copper substrate).

The present invention has been proposed in view of the above-mentioned circumstances. That is, the object of the present invention is to provide a photosensitive resin composition that can realize a resist pattern with good adhesion and resolution and can suppress gelation even after long-term storage, and to provide a photosensitive element obtained using such a photosensitive resin composition.

One aspect of the present invention is as follows.
[1]
Ingredients below:
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator,
A photosensitive resin composition comprising:
The photosensitive resin composition comprises the following components:
(D) (d1) a component having a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton,
and
The component (A) has as its constituent monomer components:
A photosensitive resin composition comprising (a) a compound having a hydroxy group, and (b) styrene.
[2]
The photosensitive resin composition according to item 1, wherein in the component (A), the compound having a hydroxy group (a) is 2-hydroxyethyl methacrylate.
3. The photosensitive resin composition according to item 1 or 2, wherein the ratio of the (b) styrene-containing monomer component in the (A) component is 40 mass% or more.
[4]
4. The photosensitive resin composition according to any one of items 1 to 3, wherein the weight average molecular weight of the component (A) is less than 50,000.
[5]
5. The photosensitive resin composition according to any one of items 1 to 4, wherein the component (D) is a compound having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton in one molecule.
[6]
6. The photosensitive resin composition according to any one of items 1 to 5, wherein the component (D) is a mixture of (d1) a compound having a triazole skeleton and (d2) a compound having a long-chain alkylamine or a long-chain alkylenediamine skeleton.
[7]
7. The photosensitive resin composition according to any one of items 1 to 6, wherein the (d2) long-chain alkylamine or long-chain alkylalkylenediamine skeleton is an alkylamine or alkylalkylenediamine having 16 or more carbon atoms.
[8]
8. The photosensitive resin composition according to any one of items 1 to 7, wherein the component (D) has a carboxyl group.
[9]
9. The photosensitive resin composition according to any one of items 1 to 8, wherein the (d1) triazole skeleton has a carboxybenzotriazole structure.
[10]
10. The photosensitive resin composition according to any one of items 1 to 9, wherein the component (C) comprises a hexaarylbiimidazole compound.
[11]
A photosensitive element comprising: a support film; and a photosensitive resin layer formed on the support film, the photosensitive resin layer including a photosensitive resin composition,
The photosensitive resin composition comprises the following components:
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated bond,
(C) a photopolymerization initiator; and (D) (d1) a component having a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton,
The component (A) has as its constituent unit monomer components:
A photosensitive element comprising: (a) a compound having a hydroxy group; and (b) styrene.
[12]
12. The photosensitive element according to item 11, wherein in the component (A), the compound (a) having a hydroxy group is 2-hydroxyethyl methacrylate.
[13]
13. The photosensitive element according to item 11 or 12, wherein in the component (A), the ratio of the monomer component having styrene (b) is 40% by mass or more.
[14]
14. The photosensitive element of any one of items 11 to 13, wherein the weight average molecular weight of component (A) is less than 50,000.
[15]
15. The photosensitive element according to any one of items 11 to 14, wherein the component (D) is a compound having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton in one molecule.
[16]
16. The photosensitive element according to any one of items 11 to 15, wherein the component (D) is a mixture of (d1) a compound having a triazole skeleton and (d2) a compound having a long-chain alkylamine or a long-chain alkylenediamine skeleton.
[17]
17. The photosensitive element according to any one of items 11 to 16, wherein the (d2) long-chain alkylamine or long-chain alkylalkylenediamine skeleton is an alkylamine or alkylalkylenediamine having 16 or more carbon atoms.
[18]
18. The photosensitive element according to any one of items 11 to 17, wherein the component (D) has a carboxyl group.
[19]
19. The photosensitive element according to any one of items 11 to 18, wherein the triazole skeleton (d1) has a carboxybenzotriazole structure.
[20]
20. The photosensitive element of any one of items 11 to 19, wherein the component (C) comprises a hexaarylbiimidazole compound.
[21]
21. The photosensitive element according to any one of items 11 to 20, which is a laminate of the support film, the photosensitive resin layer, and a protective film.

According to the present invention, it is possible to provide a photosensitive resin composition that can realize a resist pattern with excellent adhesion and resolution and can suppress gelation even after long-term storage.
Furthermore, according to the present invention, it is possible to provide a photosensitive element obtained by using the photosensitive resin composition.

Hereinafter, an exemplary embodiment of the present invention (hereinafter, abbreviated as "the present embodiment") will be described. The present invention is not limited to the present embodiment, and can be practiced with various modifications within the scope of the gist of the present invention. In this specification, the upper limit value and the lower limit value of each numerical range can be arbitrarily combined.
In this specification, numerical ranges expressed using the term "to" include the upper and lower numerical limits.

[Photosensitive element]
The photosensitive element of the present embodiment includes a support film and a photosensitive resin layer containing a photosensitive resin composition formed on the support film.
The photosensitive resin composition comprises the following components:
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated bond,
(C) a photopolymerization initiator, and (D) (d1) a component having a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton,
Including,
The component (A) has as its constituent monomer components:
It has (a) a compound having a hydroxy group, and (b) styrene.

The present inventors
Comonomer components as follows:
It was found that by combining the (A) component having a structural unit derived from (a) a compound having a hydroxy group and (b) styrene with the (B) to (D) components, the adhesion and resolution are good and the gelation of the photosensitive resin composition is unlikely to occur. As a result of the investigation, it is considered that in the case of the (A) component having a hydrophilic repeating unit such as hydroxyalkyl (meth)acrylate, metal impurities are likely to be contained in the synthesis process of the (A) component and the preparation process of the photosensitive resin composition, and therefore, gelation tends to occur easily as the crosslinking reaction proceeds in the solution state. That is, according to the present embodiment, it is possible to provide a photosensitive resin composition that has good adhesion and resolution and can suppress gelation, and a photosensitive element using such a photosensitive resin composition can be provided.

<Support film>
The support film of the present embodiment is preferably a layer or film for supporting the photosensitive resin layer, and is preferably a transparent base film that transmits actinic rays.

Examples of the transparent substrate film include films made of synthetic resins such as polyethylene, polypropylene, polycarbonate, polyethylene terephthalate, etc. In general, polyethylene terephthalate (PET) is preferably used because of its suitable flexibility and strength.
Among these, it is preferable to use a high-quality film with few internal foreign matters. Specifically, as the high-quality film, it is more preferable to use a PET film synthesized using a Ti-based catalyst, a PET film with a small diameter of lubricant and a small content, a PET film containing a lubricant only on one side of the film, a thin PET film, a PET film with a smoothing treatment applied to at least one side, a PET film with a roughening treatment such as plasma treatment applied to at least one side, etc.
This allows the exposure light to be irradiated onto the photosensitive resin layer without being blocked by internal foreign matter, and as a result, the resolution of the photosensitive element can be improved.

The thickness of the support film is preferably 5 to 25 μm, and more preferably 6 to 20 μm. The thinner the support film, the fewer the number of internal foreign objects, and therefore the easier it is to prevent a decrease in resolution. However, if the film thickness is less than 5 μm, the film is prone to deformation due to stretching in the winding direction caused by tension during the coating and winding manufacturing process, and tears due to minute scratches. In addition, the strength of the film is insufficient, and wrinkles are likely to occur during lamination.

At least one side of the support film may be subjected to a smoothing treatment using a calendar device or the like. This reduces the surface roughness of one side of the support film, particularly the side that comes into contact with the photosensitive resin layer, and can enhance the effects of the present invention.

The haze of the support film is preferably 0.01% to 1.5%, more preferably 0.01% to 1.2%, and even more preferably 0.01% to 0.95%, from the viewpoint of improving the parallelism of the light beam irradiated to the photosensitive resin layer, thereby making it easier to obtain high resolution after exposure and development of the photosensitive element.

<Photosensitive resin layer and photosensitive resin composition>
The photosensitive resin layer is laminated on a support film.
The photosensitive resin layer of the present embodiment contains the photosensitive resin composition of the present embodiment.
The photosensitive resin composition of the present embodiment comprises the following components:
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator,
Includes.
The photosensitive resin composition comprises the following components:
(D) (d1) a component having a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton,
and
The component (A) has as its constituent monomer components:
It has (a) a compound having a hydroxy group, and (b) styrene.

<Component (A): Alkali-soluble polymer>
In this embodiment, as described above, the component (A) has (a) a compound having a hydroxy group and (b) a structural unit derived from styrene.
In this embodiment, a plurality of (A) components may be used in combination, and in this case, at least one of the (A) components used in combination has (a) a compound having a hydroxyl group and (b) a structural unit derived from styrene. By having a structural unit derived from such a compound, it becomes easier to control the developability of the photosensitive resin layer, and therefore it becomes possible to obtain a resist pattern having excellent adhesion, resolution, etc.

The (a) compound having a hydroxy group is preferably a hydroxyalkyl (meth)acrylate. As the hydroxyalkyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate is preferred, and 2-hydroxyethyl methacrylate is more preferred. This is easy to obtain, and yet allows easy control of developability, making it possible to obtain a resist pattern with excellent adhesion and resolution.
The content of component (a) in component (A) is preferably 1.0 to 50 mass%, more preferably 1.0 to 30 mass%, even more preferably 1.0 to 14 mass%, and most preferably 1.0 to 5.0 mass%.

The copolymerization ratio of (b) styrene is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total mass of all monomer components, from the viewpoint of excellent adhesion and resolution. A copolymerization ratio of 90% by mass or less is preferable from the viewpoint of excellent developability and resolution, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

The above-mentioned (A) component preferably further has a repeating unit consisting of at least one type of first monomer described below, and more preferably has a repeating unit consisting of at least one type of first monomer and at least one type of second monomer described below.

The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, from the viewpoint of excellent adhesion and resolution, (meth)acrylic acid is preferred, and methacrylic acid is more preferred.
In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acryloyl group" means acryloyl group or methacryloyl group, and "(meth)acrylate" means "acrylate" or "methacrylate".

The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. The copolymerization ratio of 10% by mass or more is preferable from the viewpoint of excellent adhesion and resolution, more preferably 15% by mass or more, even more preferably 18% by mass or more, even more preferably 21% by mass or more, particularly preferably 23% by mass or more, and most preferably 24% by mass or more. The copolymerization ratio of 50% by mass or less is preferable from the viewpoint of excellent adhesion and resolution, more preferably 35% by mass or less, even more preferably 30% by mass or less, even more preferably 29% by mass or less, particularly preferably 27% by mass or less, and most preferably 26% by mass or less.
When two or more kinds of first monomers are polymerized and used, it is preferable that the total copolymerization ratio of each of them is within the above range.

The second monomer is a monomer that is non-acidic, except for styrene, and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and the like. (meth)acrylates such as phenoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, etc.; styrene derivatives such as methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile, etc.

The second monomer preferably contains a compound having an aromatic structure. The copolymerization ratio of the monomer having an aromatic structure and styrene is preferably 10 to 90% by mass based on the total mass of all monomer components. The copolymerization ratio of 10% by mass or more is preferable from the viewpoint of excellent adhesion and resolution, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more. The copolymerization ratio of 90% by mass or less is preferable from the viewpoint of excellent developability, and more preferably 80% by mass or less.
When two or more types of second monomers are polymerized and used, the total copolymerization ratio of each monomer is preferably within the above range.

The compound having an aromatic structure preferably contains benzyl (meth)acrylate. The proportion of benzyl (meth)acrylate is preferably 1 to 60 mass%, more preferably 1 to 30 mass%, and particularly preferably 1 to 20 mass%, based on the total mass of all monomer components.

The weight average molecular weight Mw of component (A) is preferably 10,000 to 60,000. From the standpoint of achieving both flexibility and resolution of the resist pattern, it is preferable to keep the weight average molecular weight Mw at 60,000 or less, and from the same standpoint, it is more preferable to keep it at 55,000 or less, and even more preferably less than 50,000.
From the same viewpoint, the weight average molecular weight Mw is preferably 10,000 or more, more preferably 14,000 or more, and even more preferably 25,000 or more.

The polydispersity of component (A) is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

When multiple (A) components are used in combination, it is preferable that the monomer content, molecular weight, and polydispersity of the multiple (A) components are selected so that the weighted average value, with the content ratio as the weight, falls within the above range.

The synthesis of component (A) is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring the solution. In some cases, the synthesis is carried out while dropping a portion of the mixture into the reaction solution. After the reaction is completed, further solvent may be added to adjust the concentration to the desired level. As a synthesis method, in addition to solution polymerization, living radical polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used.

The ratio of component (A) to the total solid mass of the photosensitive resin composition may be 10% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more. It may also be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.

It is preferable to set the ratio of the alkali-soluble polymer (A) to the photosensitive resin composition to 90% by mass or less from the viewpoint of controlling the development time. On the other hand, it is preferable to set the ratio of the alkali-soluble polymer (A) to the photosensitive resin composition to 10% by mass or more from the viewpoint of improving edge fuse resistance, that is, suppressing bleeding of the photosensitive resin layer from the film edge surface.

<Component (B): Compound Having an Ethylenically Unsaturated Bond>
In this embodiment, the component (B) preferably contains a (meth)acryloyl group, and more preferably contains a compound having a bifunctional or higher functional ethylenically unsaturated bond. The term "a compound having a bifunctional or higher functional ethylenically unsaturated bond" refers to a compound having two or more ethylenically unsaturated bonds in one molecule.

The compound having an ethylenically unsaturated bond is preferably a (meth)acrylate compound. From the viewpoint of adhesion and flexibility of the resist pattern, the compound having an ethylenically unsaturated bond preferably includes a bifunctional compound having an ethylenically unsaturated bond and a trifunctional or higher ethylenically unsaturated bond. The compound having an ethylenically unsaturated bond may include, for example, a tetrafunctional, pentafunctional, or hexafunctional compound having an ethylenically unsaturated bond.

Examples of compounds having a bifunctional ethylenically unsaturated bond include alkyl di(meth)acrylate, 1,3-bis(meth)acryloyloxy-2-propanol, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, tricyclodecanol di(meth)acrylate, ethoxylated (hydrogenated) bisphenol A di(meth)acrylate, propoxylated (hydrogenated) bisphenol A di(meth)acrylate, and tetramethylene glycoxylated (hydrogenated) bisphenol A di(meth)acrylate.

Commercially available compounds having bifunctional ethylenically unsaturated bonds include, for example, NK Ester (registered trademark) A-HD-N, A-NOD-N, A-DOD-N, A-NPG, 701A, A-200, A-400, A-600, A-1000, APG-200, APG-400, APG-700, A-PTMG65, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-BPE-20, HD-N, and NOD- N, DOD-N, NPG, 701, 2G, 3G, 4G, 9G, 14G, 23G, 9PG, DCP, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BP E-1300N, NK Oligo (registered trademark) UA-4200, UA-160TM, UA-290TM, UA-W2A, UA-4400, UA-122P, U-200PA (manufactured by Shin-Nakamura Chemical Co., Ltd.), LightAc Related (registered trademark) 3EG-A, 4EG-A, 9EG-A, 14EG-A, PTMGA-250, NP-A, MPD-A, 1.6HX-A, 1.9ND-A, DCP-A, BP-4EAL, BP-4PA, HPP-A, Light Ester G-201P (all manufactured by Kyoeisha Chemical Co., Ltd.), Fancryl (registered trademark) FA-124AS, FA-023M, FA-121M, FA-124M, FA-125M, FA-129AS , FA-137M, FA-220M, FA-222A, FA-240A, FA-240M, FA-320M, FA-3218M, FA-321A, FA-321M, FA-324A, FA-731A, FA-P240A, FA-P270A, FA-PTG9A, FA-PTG9M, FA-PTG28A, FA-PTG49A (all manufactured by Showa Denko Materials Co., Ltd.), DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYL PEG200DMA (all manufactured by Daicel Allnex Co., Ltd.), SR212, SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, S R9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036 (all manufactured by Arkema Co., Ltd.), KAYARAD (registered trademark) NPGDA, PEG400DA, FM-400, R-167, HX-220, HX-620, R-551, R-712, R-604, R-684 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

Examples of compounds having three or more functional ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, ditrimethylolpropane (tetra/penta/hexa)(meth)acrylate, dipentaerythritol (tetra/penta/hexa)(meth)acrylate, etc.

Examples of compounds having trifunctional or higher ethylenically unsaturated bonds include alkylene oxide-modified tri(meth)acrylate of trimethylolpropane, alkylene oxide-modified tri(meth)acrylate of glycerin, alkylene oxide-modified isocyanuric acid tri(meth)acrylate, alkylene oxide-modified pentaerythritol (tri/tetra)(meth)acrylate, alkylene oxide-modified ditrimethylolpropane (tetra/penta/hexa)(meth)acrylate, and alkylene oxide-modified dipentaerythritol (tetra/penta/hexa)(meth)acrylate.

Commercially available compounds having three or more functional ethylenically unsaturated bonds include, for example, NK Ester (registered trademark) A-TMPT, A-TMPT-9EO, AT-20E, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-9300, A-9200YN, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMMT, ATM-35E, AD-TMP, A-DPH, and A-9550. A-DPH-12E, TPOA-50, NK Oligo (registered trademark) UA-7100, UA-1100H, U-6LPA, UA-33H, U-10HA, U-10PA, U-15HA (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate (registered trademark) TMP-A, cPE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.), FA-731A (manufactured by Showa Denko Materials Co., Ltd.), TMPTA, EBECRYL 160S, OTA 480, PETIA, PETRA, EBECRYL 40, PETA, EBECRYL 140, EBECRYL 1140, EBECRYL 1142, DPHA, EBECRYL 895, EBECRYL 896, EBECRYL TMPTMA (all manufactured by Daicel Allnex Co., Ltd.), SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, D9021, SR9035, SR295, SR355, SR399, SR494, SR9041 (all manufactured by Arkema Co., Ltd.), KAYARAD (registered trademark) GPO-303, TMPTA, THE-330, TPA-330, PET-30, T-1420(T), RP-1040, DPHA, DPEA-12, D-310, DPCA-20 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

The ratio of the compound having an ethylenic unsaturated bond (B) to the total solids mass of the photosensitive resin composition is preferably 30% by mass or more, and more preferably 35% by mass or more, from the viewpoints of sensitivity, tackiness, and followability. Also, from the viewpoints of edge fuse resistance, tackiness, and resolution, it is preferably 50% by mass or less, more preferably 45% by mass or less, and more preferably 42% by mass or less.

In addition, from the viewpoints of edge fuse resistance, tackiness, and resolution, the value of the solid content of the compound having an ethylenic unsaturated bond (B) relative to the solid content of the alkali-soluble polymer (A) contained in the photosensitive resin composition (i.e., the value of the solid content of the compound having an ethylenic unsaturated bond (B) / the solid content of the alkali-soluble polymer (A)) is preferably 1.4 or less, more preferably 1.3 or less, more preferably 1.2 or less, and more preferably 1.1 or less. The lower limit is preferably 0.7 or more, more preferably 0.8 or more, more preferably 0.9 or more, and more preferably 1.0 or more.

In the photosensitive resin composition of this embodiment, the number of ethylenically unsaturated bonds per 100 g of solid content of the photosensitive resin composition is preferably 0.1 mol to 0.3 mol. By making it 0.1 mol or more, it is possible to prevent the photosensitive resin components from eluting from the cured resist pattern in the water washing step after development, which would cause contamination of the water washing step. By making it 0.3 mol or less, it is possible to prevent the cured resist pattern from chipping and falling off in the water washing step after development, which would cause contamination of the water washing step.

The number of ethylenically unsaturated bonds per 100 g of solid content of the photosensitive resin composition is preferably 0.1 mol or more, more preferably 0.11 mol or more, more preferably 0.12 mol or more, more preferably 0.13 mol or more, and preferably 0.3 mol or less, preferably 0.28 mol or less, preferably 0.25 mol or less, preferably 0.22 mol or less, preferably 0.20 mol or less, preferably 0.18 mol or less, and preferably 0.15 mol or less.
More preferably, it is from 0.1 mol to 0.25 mol, even more preferably from 0.1 mol to 0.2 mol, still more preferably from 0.11 mol to 0.2 mol, and most preferably from 0.11 mol to 0.15 mol.

<Component (C): Photopolymerization initiator>
In this embodiment, the component (C) is not particularly limited, but is preferably a hexaarylbiimidazole compound.

An example of a hexaarylbiimidazole compound is lophine dimer, i.e., a dimer of 2,4,5-triarylimidazole.

Examples of lophine dimers, i.e., dimers of 2,4,5-triarylimidazole, include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)biimidazole, 2-(p-methoxyphenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, and 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole. 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3 -methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5, Examples include 5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole.

From the viewpoints of high sensitivity, resolution, and adhesion, it is preferable that component (C) contains a lophine dimer, and among these, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred. In this case, the content of component (C) (e.g., lophine dimer) in the photosensitive resin composition is preferably 0.1 to 15 mass %, more preferably 0.5 to 10 mass %, based on the total solid content in the photosensitive resin composition.

In addition, it is preferable that the photopolymerization initiator further contains at least one of the group consisting of N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-aryl amino acid ester compounds, and halogen compounds. It is even more preferable that the photopolymerization initiator contains an anthracene derivative.

Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred due to its high sensitizing effect.

Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

Examples of aromatic ketone compounds include benzophenone compounds. Examples of benzophenone compounds include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. From the viewpoint of sensitizing effect and adhesion, another example of aromatic ketone compounds is 4,4'-bis(diethylamino)benzophenone.

In this specification, the term "anthracene derivative" includes both anthracene and compounds derived therefrom. Examples of anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, and 1-chloroanthraquinone. From the viewpoints of sensitization effect and adhesion, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred, and 9,10-diphenylanthracene is particularly preferred.

Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, and the like. Commercially available acetophenone compounds include, for example, the Irgacure series (manufactured by Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide. Commercially available acylphosphine oxide compounds include Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).

Examples of the benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.
Examples of the dialkyl ketal compound include benzyl dimethyl ketal and benzyl diethyl ketal.
Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.
Examples of the dialkylaminobenzoate compound include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, etc. Commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).

As the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred in terms of sensitivity, resolution, availability, etc.

As pyrazoline derivatives, from the viewpoints of adhesion and rectangularity of the resist pattern, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline are preferred.

Examples of ester compounds of N-arylamino acids include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diaryliodonium compounds. Of these, tribromomethylphenyl sulfone is preferred.

The total content of component (C) and other photopolymerization initiators in the photosensitive resin composition is preferably 0.01 to 20% by mass, and more preferably 0.5 to 10% by mass, based on the total solid content in the photosensitive resin composition. By adjusting the content of component (C) and other photopolymerization initiators within the above range, it becomes easier to obtain sufficient sensitivity, making it easier to transmit light sufficiently to the bottom of the photosensitive resin layer, and thus easier to achieve high resolution.

<Component (D)>
In the present embodiment, the photosensitive resin layer contains a component (D) having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkylenediamine skeleton.

In this specification, (d2) long-chain alkylamine or long-chain alkylalkylenediamine skeleton refers to an alkylamine or alkylalkylenediamine having 9 or more carbon atoms. The alkylamine or alkylalkylenediamine preferably has 10 or more carbon atoms, more preferably 12 or more carbon atoms, even more preferably 14 or more carbon atoms, and particularly preferably 16 or more carbon atoms. The number of carbon atoms is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

Here, the (D) component may be a compound having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkyl alkylenediamine skeleton in one molecule, or may be a mixture of (d1) a compound having a triazole skeleton and (d2) a compound having a long-chain alkylamine or long-chain alkyl alkylenediamine skeleton.

で表されるカルボキシベンゾトリアゾールが好ましい。カルボキシ基を有するベンゾトリアゾールを用いることで、ゲル化抑制性能が良好な感光性樹脂組成物の調合液を得易くなる。カルボキシ基とトリアゾール部位が、金属不純物と相互作用することにより、重合反応を抑制するためと考えられる。 (d1) An example of a compound having a triazole skeleton is benzotriazole. Benzotriazole is represented by the following formula (1):

Carboxybenzotriazole represented by the following formula is preferred. By using benzotriazole having a carboxy group, it becomes easier to obtain a preparation of a photosensitive resin composition having good gelation suppression performance. This is thought to be because the carboxy group and the triazole moiety interact with metal impurities to suppress the polymerization reaction.

（式中、Ｒ_１は、水素原子または、直鎖状又は分岐鎖状アルキル基を表し、Ｒ_２，Ｒ_２’は、各々独立に、直鎖状又は分岐鎖状アルキル基を表す。ただし、Ｒ_２，Ｒ_２’の炭素数の合計が９以上である。）
で表される化合物が挙げられる。 (d2) Examples of the compound having a long-chain alkylamine skeleton include compounds represented by the following general formula (2):

(In the formula, R ₁ represents a hydrogen atom or a linear or branched alkyl group, and R ₂ and R ₂ ′ each independently represent a linear or branched alkyl group, provided that the total number of carbon atoms in R ₂ and R ₂ ′ is 9 or more.)
Examples of the compound include compounds represented by the following formula:

で表されるジ（２－エチルヘキシル）アミンが特に好ましい。 Specific examples of compounds having such a long-chain alkylamine skeleton include dialkylamines such as dipentylamine, dihexylamine, dioctylamine, and di(2-ethylhexyl)amine. Dialkylamines include those represented by the following formula (2a):

Di(2-ethylhexyl)amine represented by the following formula is particularly preferred.

（式中、Ｒ_３は、炭素数９以上の直鎖状又は分岐鎖状アルキル基を表す。また、ｎは１以上の整数である。）
で表される化合物が挙げられる。 Examples of the compound (d2) having a long-chain alkyl alkylenediamine skeleton include compounds represented by the following general formula (3):

(In the formula, _R3 represents a linear or branched alkyl group having 9 or more carbon atoms, and n is an integer of 1 or more.)
Examples of the compound include compounds represented by the following formula:

（式中、Ｒ_３は、牛脂アルキル基を表す。牛脂アルキル基とは主に炭素数１６～１８の飽和又は不飽和の直鎖脂肪族炭化水素を表す。）
で表される牛脂アルキルプロピレンジアミン化合物が挙げられる。
上記式（３ａ）のような化合物として、市販品で利用可能なものとしては、ニッサンアミンＤＴ（日油株式会社製）などがあげられる。 Specific examples of such compounds having a long-chain alkyl alkylenediamine skeleton include those represented by the following formula (3a):

(In the formula, _R3 represents a beef tallow alkyl group. The beef tallow alkyl group represents a saturated or unsaturated linear aliphatic hydrocarbon having mainly 16 to 18 carbon atoms.)
Examples of the alkyl propylene diamine compounds include tallow alkyl propylene diamine compounds represented by the following formula:
As a compound such as the above formula (3a), Nissan Amine DT (manufactured by NOF Corporation) is a commercially available product.

The use of such long-chain alkylamine or long-chain alkyl alkylenediamine compounds makes it easier to obtain a preparation of a photosensitive resin composition with good gelation inhibition performance. It is believed that such amine compounds interact with metal impurities in the preparation, and the long-chain alkyl group has high steric hindrance, which inhibits the polymerization reaction, thereby inhibiting gelation.

When component (D) is a compound having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkyl alkylenediamine skeleton in one molecule, the compound is a compound having (d1) a triazole skeleton and (d2) a long-chain alkylamine or long-chain alkyl alkylenediamine skeleton in one molecule, which is derived from the above-mentioned compound.

（式中、Ｒ_４は、水素原子、または置換基を有していてもよい炭素数１以上の有機基を表す。）
で表わされる化合物が挙げられる。このような化合物を有することで、金属不純物と相互作用し、不純物由来の重合反応を抑制することができると考えられる。 Examples of such compounds include those represented by the following general formula (4):

(In the formula, _R4 represents a hydrogen atom or an organic group having 1 or more carbon atoms which may have a substituent.)
It is believed that the presence of such a compound can interact with metal impurities and inhibit polymerization reactions caused by the impurities.

The organic group having 1 or more carbon atoms represented by _R4 is preferably a methyl group, an ethyl group, a propyl group, a carboxyl group, a hydroxyalkyl group, or an aminoalkyl group, and more preferably a carboxyl group. By having a carboxyl group, developability is improved, and a resist pattern with good resolution can be formed.

In general formula (4), R ₂ and R ₂ ' each represent an alkyl group which may have a substituent, provided that the total number of carbon atoms in R ₂ and R ₂ ' is 9 or more. It is believed that the total number of carbon atoms being 9 or more increases the steric hindrance of the complex formed by the metal impurity and the triazole compound, and reduces the interaction with the compound having an unsaturated bond, thereby suppressing gelation.

Examples of alkyl groups which may have a substituent include n-pentyl, n-hexyl, n-octyl, and 2-ethylhexyl groups. Among these, n-octyl and 2-ethylhexyl groups, which have an alkyl group with 8 or more carbon atoms or a branched structure, are preferred, and 2-ethylhexyl groups are particularly preferred. It is believed that gelation can be suppressed by increasing steric hindrance when an alkyl group with 8 or more carbon atoms or a branched structure is used.

で表される１－（Ｎ，Ｎ－ビス（２－エチルヘキシル）アミノメチル）－５－カルボキシ－１，２，３－ベンゾトリアゾールが好ましい。 Specific examples of such compounds include 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,3-benzotriazole, 1-(N,N-bis(2-ethylhexyl)aminomethyl)-1,2,3-tolyltriazole, 1-(N,N-bis-2-hydroxyethyl)aminomethyl)-1,2,3-benzotriazole, and 1-(N,N-bis(2-ethylhexyl)aminomethyl)-5-carboxy-1,2,3-benzotriazole. Among these, compounds represented by the following formula (4a):

Preferred is 1-(N,N-bis(2-ethylhexyl)aminomethyl)-5-carboxy-1,2,3-benzotriazole represented by the following formula:

The content of component (D) in the photosensitive resin composition is preferably 0.01 to 20 mass % based on the total solid content in the photosensitive resin composition, more preferably 0.01 to 1 mass %, and even more preferably 0.01 to 0.1 mass %. 0.01 to 0.05 mass % is particularly preferred. By adjusting the content of component (D) within the above range, sufficient gelation inhibition performance is achieved, and high resolution and high adhesion are easily achieved.

Other Ingredients
The photosensitive resin composition may contain, if desired, an antioxidant, a stabilizer, a base dye, a sensitizer, a plasticizer, a hindered amine, and the like.

Examples of base dyes include Basic Green 1 [CAS number (hereinafter the same): 633-03-4] (e.g., Aizen Diamond Green GH, product name, manufactured by Hodogaya Chemical Co., Ltd.), Fuchsin [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, product name, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2], etc. Among them, Basic Green 1 is preferred from the viewpoint of improving coloring properties, hue stability, and exposure contrast. These can be used alone or in combination of two or more.

The content of the base dye in the photosensitive resin composition is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, and even more preferably 0.04 to 1 mass %, based on the total solid content in the photosensitive resin composition. From the viewpoint of obtaining good coloring properties, the content of the base dye is preferably equal to or greater than the above lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, the content is preferably equal to or less than the above upper limit.

Examples of antioxidants include triphenyl phosphite (e.g., ADEKA, product name: TPP), tris(2,4-di-tert-butylphenyl)phosphite (e.g., ADEKA, product name: 2112), tris(mononylphenyl)phosphite (e.g., ADEKA, product name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., ADEKA, product name: 329K). These can be used alone or in combination of two or more.

The content of the antioxidant in the photosensitive resin composition is preferably 0.01 to 0.8% by mass, more preferably 0.01 to 0.3% by mass, based on the total solid content in the photosensitive resin composition. The content of the antioxidant is preferably equal to or greater than the above lower limit, from the viewpoint of favorably expressing the hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer. On the other hand, it is preferably equal to or less than the above upper limit, from the viewpoint of favorably expressing the hue stability while suppressing the color development of the resist pattern and improving adhesion.

The stabilizer can be used from the viewpoint of improving the thermal stability and/or storage stability of the photosensitive resin composition. Examples of the stabilizer include at least one of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group. These can be used alone or in combination of two or more.

Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salt (for example, aluminum salt with 3 moles of nitrosophenylhydroxylamine added), diphenylnitrosamine, etc. Among these, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or aluminum salt with 3 moles of nitrosophenylhydroxylamine added is preferred. These can be used alone or in combination of two or more.

Examples of alkylene oxide compounds having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolight 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolight 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (e.g., Epolight 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolight 1600 manufactured by Kyoeisha Chemical Co., Ltd.). These can be used alone or in combination of two or more.

The total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably 0.001 to 3 mass %, more preferably 0.05 to 1 mass %, based on the total solid content in the photosensitive resin composition. From the viewpoint of imparting good storage stability to the photosensitive resin composition, the total content is preferably equal to or greater than the above lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, the total content is preferably equal to or less than the above upper limit.

In this embodiment, a color-developing dye that develops color upon irradiation with light may be included in the photosensitive resin layer. For example, a combination of a leuco dye and a halogen compound is known as a color-developing dye. Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane [leuco crystal violet] and tris(4-dimethylamino-2-methylphenyl)methane [leucomalachite green]. Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and hexachloroethane.

In this embodiment, additives such as plasticizers may be added to the photosensitive resin layer as necessary. Examples of additives include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, etc.

In this embodiment, a hindered amine compound may be contained in the photosensitive resin layer as necessary. Examples of the hindered amine compound include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethyl-1-oxypiperidine, 2,2,6,6-tetramethylpiperidyl methacrylate, and 1,2,2,6,6-pentamethylpiperidyl methacrylate.

By including the above hindered amine compound, excessive crosslinking reaction of the resist pattern is suppressed, and the diffusibility in the stripping solution is improved, making it possible to form a resist pattern with good strippability.

The hindered amine compound preferably has a monofunctional polymerizable group, since this improves the flexibility and peelability of the cured film after the crosslinking reaction. 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate are particularly preferred.

The ratio of the hindered amine compound to the total solid mass of the photosensitive resin composition is preferably 0.001 to 10% by mass. From the viewpoint of excellent peelability, this ratio is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.3% by mass or more. On the other hand, from the viewpoint of improving resolution, this ratio is preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.

The above hindered amine compound may be used as a repeating unit in the alkali-soluble polymer (A).

The thickness of the photosensitive resin layer is preferably 3 to 100 μm, with a more preferred upper limit of 50 μm. As the thickness of the photosensitive resin layer approaches 3 μm, the resolution improves, and as the thickness approaches 100 μm, the film strength improves, so the thickness can be appropriately selected according to the application.

<Protective film>
The photosensitive element of the present embodiment may include a protective film in addition to the support film and the photosensitive resin layer.
The protective film is laminated on the photosensitive resin layer on the side opposite to the support film, and functions as a cover.

Since the adhesive strength between the photosensitive resin layer and the protective film is sufficiently smaller than that between the photosensitive resin layer and the support film, the protective film can be easily peeled off from the photosensitive resin layer. For example, a polyethylene film, a polypropylene film, an oriented polypropylene film, a polyester film, etc. can be preferably used as the protective film.
In addition, a release layer may be provided on the surface of the protective film.

The thickness of the protective film is preferably 10 to 100 μm, more preferably 10 to 50 μm. Examples of protective films include Alphan (registered trademark) EM-501, E-200, E-201F, FG-201, and MA-411 (all manufactured by Oji F-Tex Co., Ltd.), Torayfan (registered trademark) KW37, 2578, 2548, 2500, and YM17S, Therapeel (registered trademark) PJ271, PJ111, HP2, PJ101, WZ, MDA, MFA, TK07, BKE, BX8A, and SY (all manufactured by Toray Industries, Inc.), GF-18, GF-818, and GF-858 (all manufactured by Tamapoly Co., Ltd.), and the like.

[Method of preparing a photosensitive element]
The photosensitive element can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective film on a support film.
A step of mixing the photosensitive resin composition with a solvent capable of dissolving the photosensitive resin composition to obtain a photosensitive resin composition preparation liquid (coating liquid);
A step of applying the coating liquid onto a support film using a bar coater or a roll coater and drying the coating liquid to form a photosensitive resin layer on the support film;
If necessary, a step of laminating a protective film on the photosensitive resin layer;
may have the following structure:

[Photosensitive element roll]
The photosensitive element described above may be used as a roll of a long photosensitive element wound around a core.

[Method of forming a resist pattern]
A method for forming a resist pattern using the photosensitive element of this embodiment includes the following steps:
laminating the photosensitive element to a substrate;
an exposure step of exposing a photosensitive resin layer of a photosensitive element to light; and a development step of developing and removing an unexposed portion of the photosensitive resin layer;
preferably in that order.

Specifically, in the lamination process, after the protective film is peeled off from the photosensitive element, the photosensitive resin layer is heated and pressed onto the surface of a support (e.g., a substrate) using a laminator, and laminated once or multiple times. Examples of materials for the substrate include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). The heating temperature during lamination is generally 40°C to 160°C. Heat-press bonding can be performed using a laminator equipped with rolls, or by repeatedly passing the laminate of the substrate and the photosensitive resin layer through the rolls several times. Heat-press bonding can be performed in a reduced pressure environment, if desired.

In the exposure step, the photosensitive resin layer is exposed to active light using an exposure machine. If desired, exposure can be performed after peeling off the support. When exposure is performed through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and may be measured using an actinometer. In the exposure step, direct imaging exposure may be performed. In direct imaging exposure, exposure is performed directly on the substrate using a drawing device without using a photomask. As the light source, a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350 to 410 nm is used. When the drawing pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the movement speed of the substrate.

The light irradiation method used in the exposure step is preferably at least one method selected from the projection exposure method, the proximity exposure method, the contact exposure method, the direct imaging exposure method, and the electron beam direct writing method, and is more preferably performed by the projection exposure method or the direct imaging exposure method.

A heating step may be performed between the exposure step and the development step. The heating temperature is preferably about 30 to about 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C. By performing this heating step, it is possible to improve the resolution and adhesion. For heating, a hot air, infrared, or far infrared heating furnace, a thermostatic bath, a hot plate, a hot air dryer, an infrared dryer, a hot roll, or the like can be used.

The time that elapses from the exposure step to the heating step, more precisely the time that elapses from the point at which exposure is stopped to the point at which heating is started, is preferably 10 to 600 seconds, more preferably 20 to 300 seconds. The time that elapses from the point at which heating is started to the point at which heating is stopped is preferably 1 to 120 seconds, more preferably 5 to 60 seconds.

In the development process, the unexposed or exposed areas of the photosensitive resin layer after exposure are removed with a developer using a developing device. If there is a support film on the photosensitive resin layer after exposure, it is removed. Next, the unexposed or exposed areas are developed and removed using a developer consisting of an alkaline aqueous solution to obtain a resist image.

The alkaline aqueous solution is preferably an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ , tetramethylammonium hydroxide, or the like. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ solution with a concentration of 0.2 to 2 mass % is generally used. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, etc. may be added to the alkaline aqueous solution. The temperature of the developer in the development step is preferably kept constant within the range of 20 to 40°C.

In the development step, it is preferable to have a washing step for removing the developer contained in the resist pattern after development. The washing water may be selected according to the characteristics of the photosensitive resin layer, such as pure water or industrial water, and a polyvalent metal salt such as MgSO ₄ may be added at a concentration of 0.001 to 1% by mass in order to improve the resolution and the shape of the resist pattern. The temperature of the washing water in the washing step is preferably kept constant within the range of 20 to 40°C.

The above steps produce a resist pattern, but if desired, a heating step can be further carried out at 60°C to 300°C. By carrying out this heating step, the chemical resistance of the resist pattern can be improved. For the heating step, a heating furnace using hot air, infrared rays, or far infrared rays can be used.

In order to obtain a conductor pattern, after the development step or heating step, a conductor pattern formation step may be performed in which the substrate on which the resist pattern has been formed is etched or plated.

The method for manufacturing the conductor pattern is, for example, to use a metal plate or a metal-coated insulating plate as a substrate, form a resist pattern by the resist pattern formation method described above, and then carry out a conductor pattern formation process. In the conductor pattern formation process, a conductor pattern is formed on the substrate surface (e.g., the copper surface) exposed by development using a known etching method or plating method.

Furthermore, after the conductor pattern is produced by the above-mentioned conductor pattern production method, a stripping process is performed in which the resist pattern is stripped from the substrate using an aqueous solution that is more alkaline than the developer, thereby obtaining a wiring board (e.g., a printed wiring board) having a desired wiring pattern.

The alkaline aqueous solution used for stripping (hereinafter also referred to as the "stripping solution") is not particularly limited, but an aqueous solution of NaOH or KOH with a concentration of 2 to 5% by mass, or an organic amine-based stripping solution is generally used. A small amount of a water-soluble solvent may be added to the stripping solution. Examples of water-soluble solvents include alcohol. The temperature of the stripping solution in the stripping process is preferably within the range of 40 to 70°C.

In this embodiment, the photosensitive element can be used in the manufacture of printed wiring boards; the manufacture of lead frames for mounting IC chips; precision processing of metal foils such as the manufacture of metal masks; the manufacture of packages such as ball grid arrays (BGA) and chip size packages (CSP); the manufacture of tape substrates such as chip-on-film (COF) and tape automated bonding (TAB); the manufacture of semiconductor bumps; and the manufacture of partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic wave shields.
Unless otherwise specified, the values of the above-mentioned parameters are measured according to the measurement methods in the Examples.

The present embodiment will be described in more detail below with reference to examples and comparative examples. The present embodiment is not limited to the following examples. The physical properties in the examples were measured by the following methods.

<Synthesis of component (A)>
The monomers shown in the table were mixed with azobisisobutyronitrile in the amounts shown in the table (units are "parts by mass"). A mixed solution (x) was prepared by mixing methyl cellosolve and toluene in a ratio of 3:2. A mixed solution (b) was prepared by mixing 50 parts by mass of a mixed solution (x) of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene with 0.5 parts by mass of azobisisobutyronitrile. 300 g of the mixed solution (x) was put into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas inlet tube, and then the mixture was stirred while blowing nitrogen gas into the flask, and the temperature was raised to 80°C. The solution (a) was dropped into the mixed solution in the flask at a constant dropping rate over 4 hours. Then, the mixture was stirred at 80°C for 2 hours. Next, solution (b) was added dropwise to the solution in the flask at a constant dropping rate over 10 minutes, and the solution in the flask was then stirred at 80°C for 3 hours. The solution in the flask was then heated to 90°C over 30 minutes and kept at 90°C for 2 hours. Thereafter, stirring was stopped and the solution was cooled to room temperature (25°C), thereby obtaining solutions of alkali-soluble polymers A1 to A9. The non-volatile content (solid content) of each of the solutions of alkali-soluble polymers A1 to A9 was 50 mass%. The weight average molecular weights (Mw) of the alkali-soluble polymers A1 to A9 are shown in the table.

The weight average molecular weight was measured by gel permeation chromatography (GPC) and calculated using a calibration curve of standard polystyrene. The GPC conditions were as follows:
(GPC conditions)
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., product name)
Columns: 3 in total Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440 (the above are product names manufactured by Hitachi Chemical Co., Ltd.)
Eluent: tetrahydrofuran Measurement temperature: 40°C
Flow rate: 2.05 mL/min Detector: Hitachi L-3300 RI (manufactured by Hitachi, Ltd., product name)

[Preparation of evaluation samples]
<Preparation of photosensitive resin composition and photosensitive element>
The components shown in the table (wherein the number for each component indicates the amount (parts by mass) of solid content) were mixed in the amounts shown in the table, and ethanol was added until the solid content concentration reached 60%, followed by thorough stirring. In this way, preparations containing photosensitive resin compositions were obtained (Examples 1A to 20A, and Comparative Examples 1A to 8A).
A 16 μm-thick polyethylene terephthalate film (QS71, manufactured by Toray Industries, Inc.) was used as the support film. The above-mentioned preparation was uniformly applied to the surface of the film using a bar coater, and then dried for 2 minutes and 30 seconds in a dryer at 95° C. to form a photosensitive resin layer with a film thickness of 25 μm. This resulted in the production of photosensitive resin elements (Examples 1 to 10, and Comparative Examples 1 to 8).
Next, a 19 μm polyethylene film (protective film) was attached as a protective layer to the surface of the photosensitive resin layer on the side on which the polyethylene terephthalate film was not laminated.

<Substrate surface preparation>
A 0.4 mm thick copper-clad laminate with 18 μm rolled copper foil was prepared. The surface of this substrate was washed with a 10 mass % H ₂ SO ₄ aqueous solution.

<Lamination>
While peeling off the polyethylene film (protective film) of the photosensitive element, the photosensitive element was laminated at a roll temperature of 105°C using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) onto a copper-clad laminate that had been preheated to 50°C after surface preparation by the above method. In this way, a substrate for evaluation was obtained. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m/min.

<Exposure>
Two hours after lamination, the evaluation substrate was exposed to light using a direct imaging (DI) exposure pattern by a direct imaging exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.).

<Heating>
One minute after exposure, the evaluation substrate was heated for 30 seconds in a constant temperature incubator with a constant airflow (DKM600, manufactured by Yamato Scientific Co., Ltd.) set at 60°C.

<Developing>
After peeling off the polyethylene terephthalate film (support film), an alkaline developer (manufactured by Fuji Kiko Co., Ltd., a dry film developer) was used to spray a 1% by mass _{Na2CO3 aqueous} solution at 30°C for a predetermined time (developer spray). The developer spray time was twice the shortest development time, and after development, a water washing spray was also performed, and the water washing spray time was twice the shortest development time. At this time, the shortest time required for the photosensitive resin layer in the unexposed area to completely dissolve was determined as the "shortest development time."

[evaluation]
<Sensitivity>
A Hitachi 41-step tablet was placed on the evaluation substrate that had been subjected to the above surface preparation and lamination, and then exposure and development were performed. The sensitivity was evaluated based on the exposure amount (unit: mJ/ ^cm2 ) that resulted in 15 remaining steps after development. The lower the exposure amount, the higher the sensitivity.

<Adhesion>
The evaluation substrate that had been subjected to the above surface preparation and lamination was exposed to light using a drawing pattern in which line width (L)/space width (S) (hereinafter sometimes referred to as "L/S") was x/3x (x = 1 to 20 (varying at 1 μm intervals)) (unit: μm) with an energy amount that resulted in 17 remaining steps on a Hitachi 41-step step tablet. Thereafter, the above heating and development treatments were performed to form a resist pattern. This resist pattern was observed under an optical microscope, and adhesion was evaluated based on the minimum line width that was formed without causing meandering or chipping of the line portion (exposed portion). The smaller this value, the better the adhesion. Those with adhesion of 7 μm or less were considered to pass.

<Resolution>
Using a drawing pattern with L/S of x/x (x=1 to 20 (varying in 1 μm intervals)) (unit: μm), exposure was performed with an energy amount that resulted in 17 remaining steps on a Hitachi 41-step step tablet. The above-mentioned heating and development treatment was then performed to form a resist pattern. This resist pattern was observed under an optical microscope, and the resolution was evaluated based on the smallest line width at which the line portions (exposed portions) were free of meandering and chipping, and no residue was found in the space portions (unexposed portions) (the unexposed portions were removed). The smaller this value, the better the resolution. A resolution of 12 μm or less was considered to be acceptable.

<Gelling prevention performance>
25 g of the prepared liquid containing the photosensitive resin composition was placed in a 50 ml brown glass screw bottle (manufactured by Maruemu Co., Ltd.) and stored in a closed state in a hot air circulation incubator (manufactured by Espec Corp.) at 50° C. for 25 hours, 50 hours, 100 hours, and 200 hours, respectively. The liquid after storage was visually inspected, and when the container was tilted 90° and held for 30 seconds, those in which flow on the liquid surface was observed were rated as pass, and those in which no flow on the liquid surface was observed due to the composition solidifying or the like were rated as fail. Those in which no gelation was observed after 50 hours of storage were rated as pass.

As is clear from the table, Examples 1 to 20 were good in terms of adhesion, resolution, and gelation inhibition performance.

In contrast, good results were not obtained in Comparative Examples 1 to 8. That is, Comparative Examples 4 to 7, which do not include the (d2) component as the (D) component, failed in gelation inhibition performance. On the other hand, Comparative Example 8, which does not include the (d1) component as the (D) component, had poor adhesion. Also, Comparative Example 1, in which the (A) component does not include the (a) component as its constituent unit, Comparative Example 2, in which the (A) component does not include the (b) component as its constituent unit, and Comparative Example 3, which does not include the (C) component, had poor adhesion and resolution.

The photosensitive resin composition of the present invention can be used to obtain the photosensitive element of the present invention. The use of such a photosensitive element provides good adhesion, resolution, and gelation suppression performance, and therefore the element can be widely used as a photosensitive element for forming resist patterns on printed wiring boards and the like.

Claims (7)

Ingredients below:
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator,
A photosensitive resin composition comprising:
The photosensitive resin composition comprises the following components:
(D) a mixture of (d1) a compound having a triazole skeleton and (d2) a long-chain alkylamine having 9 or more carbon atoms;
Further comprising:
The compound (d1) having a triazole skeleton is represented by the following formula (1):
The carboxybenzotriazole represented by the formula:
The component (C) contains a hexaarylbiimidazole compound,
and,
The component (A) has as its constituent monomer components:
(a) a compound having a hydroxy group, and (b) styrene,
A photosensitive resin composition, wherein the ratio of the component (b) in the component (A) is 30 mass% or more, and the weight average molecular weight of the component (A) is less than 50,000. The photosensitive resin composition according to claim 1, wherein in the component (A), the compound having a hydroxy group (a) is 2-hydroxyethyl methacrylate. The photosensitive resin composition according to claim 1 or 2, wherein the ratio of the monomer component (b) having styrene in the component (A) is 40 mass% or more. A photosensitive element comprising: a support film; and a photosensitive resin layer formed on the support film, the photosensitive resin layer including a photosensitive resin composition,
The photosensitive resin composition comprises the following components:
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated bond,
(C) a photopolymerization initiator; and (D) a mixture of (d1) a compound having a triazole skeleton and (d2) a long-chain alkylamine having 9 or more carbon atoms ,
The compound (d1) having a triazole skeleton is represented by the following formula (1):
The carboxybenzotriazole represented by the formula:
The component (C) contains a hexaarylbiimidazole compound,
The component (A) has as its constituent unit monomer components:
(a) a compound having a hydroxy group, and (b) styrene,
a photosensitive element comprising: the component (A) having a ratio of the component (b) of 30% by mass or more; and the component (A) having a weight average molecular weight of less than 50,000. 5. The photosensitive element according to claim 4 , wherein in the component (A), the compound (a) having a hydroxy group is 2-hydroxyethyl methacrylate. The photosensitive element according to claim 4 , wherein the proportion of the styrene- containing monomer component (b) in the component (A) is 40% by mass or more. The photosensitive element according to claim 4 or 5 , which is a laminate of the support film, the photosensitive resin layer, and a protective film.