JP7340328B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to photosensitive resin compositions, etc., and more specifically to metal foil precision for manufacturing dry film resists, printed wiring boards, lead frames for mounting IC chips (hereinafter referred to as lead frames), metal masks, etc. Processing, manufacturing of semiconductor packages such as thin film transistors such as liquid crystal display elements, BGA (ball grid array), and CSP (chip size package), manufacturing of indium tin oxide (ITO) electrodes, address electrodes, electromagnetic shielding, etc. in the flat panel display field. A photosensitive resin composition that can be developed with an alkaline aqueous solution and a photosensitive resin laminate using the same in the production of parts and the production of resist patterns suitable as protective mask members when processing base materials by sandblasting, etc. Regarding their uses.

A photosensitive resin composition containing a novolac type phenol resin and a 1,2-naphthoquinone diazide compound was used as a raw material for an image forming method used for patterning semiconductor integrated circuits, liquid crystal display elements, printed wiring boards, etc. A method using a positive photoresist is known. When a positive photoresist is formed by coating this photosensitive resin composition, the coating thickness is generally 0.5 to several μm. Using this positive photoresist, image patterning over a wide range of dimensions is created. The size range is wide ranging, for example, from sub-half micron region of about 0.3 μm to considerably large size width of several tens to hundreds of μm. It makes processing possible.
In the field of liquid crystal displays (LCDs) and the like, the line width of images has become narrower with the advancement of technologies such as thin film transistor (TFT) liquid crystals and super twisted nematic (STN) liquid crystals, and the trend towards further miniaturization is increasing. For example, in devices using conventional twisted nematic (TN) or STN liquid crystals, the image design size is about 200 μm to several hundred μm, but recently, with the development of new technology, the minimum image design size is 100 μm. It is as follows. Furthermore, in TFT display elements with good responsiveness or image quality, the image design dimensions have been improved to the level of several μm.

Characteristics expected of photoresist materials include maintaining the above-mentioned fine processing ability and being able to handle larger areas. That is, this is a response to liquid crystal displays, whose substrates have recently become larger, and plasma display panels (PDPs), which have been aimed at large screens from the beginning. For these substrates, improving in-plane film thickness uniformity is becoming an important technology. Further, common issues in large-area displays include further cost reduction and reduction in the amount of photoresist used during manufacturing.
Among the above-mentioned problems, in order to further improve the in-plane film thickness uniformity of the photoresist and achieve liquid saving of the photoresist raw material, studies have been continued on coating methods. As a result, new slit coatings have been developed as an alternative to the conventionally common spin coatings. These techniques are beginning to be applicable to substrates with a size of 550 mm x 680 mm or less. However, when aiming for even larger substrates, it is expected that it will be difficult to apply these techniques.

By the way, in the field of printed wiring boards, so-called negative dry film photoresists are widely used. Negative dry film photoresist uses a polyester film with a thickness of 15 to 25 μm as a support, on which a negative photosensitive resin composition with a thickness of 3 to 100 μm is coated, and on top of that, A polyolefin film with a thickness of ~40 μm is laminated as a protective film. This negative dry film photoresist technology is also used for printed wiring boards with a width of about 600 mm. However, when used in the field of printed wiring boards, the resolution required for negative dry film photoresists is approximately 10 to 300 μm at most.
The production of a printed wiring board using a negative dry film photoresist will be briefly explained. First, if there is a protective film on the negative dry film photoresist, remove it, laminate it so that the negative photosensitive resin composition is in contact with a base material for making a printed wiring board, and irradiate active light through the support. The photosensitive resin composition is cured by exposure. Next, generally, the unexposed photosensitive resin composition is dispersed and removed using a weak alkaline aqueous solution, such as a sodium carbonate aqueous solution having a concentration of 1% by mass, and then developed. Thereafter, the copper on the substrate is etched with an aqueous cupric chloride solution, and all of the cured photosensitive resin composition is peeled off with an aqueous solution of caustic soda or aqueous potassium hydroxide at a concentration of 2 to 3% by mass.

However, as mentioned above, the image processing technology required for manufacturing TFTs for LCDs has a resolution of, for example, about 2 to 10 μm, which is much higher than that in the field of printed wiring boards. In addition, techniques for metal ion-free development, stripping using an organic stripping solution, and etching processing of metal thin films such as ITO, Ta, and Al, and inorganic thin films such as SiN _x and ITO are also needed. In order to cope with these problems, photoresists must have a film thickness of several μm, improved adhesion to various sputtered metal thin films or inorganic thin films, further improvement of film thickness uniformity, and irregularities of about 1 μm. There are demands for improvements in followability to TFT preceding patterns and for faster lamination on substrates with a width of 1 to 2 meters, completely exceeding the limits of conventional dry film photoresists. In other words, in order to meet the demands of the LCD and PDP industries, there are limits to the conventional method of applying a positive liquid resist directly to a substrate or the method of transferring a negative dry film resist to a substrate. In order to solve these problems, it is possible to use a positive dry film resist, but there is no practical one yet.

As materials for conventional positive photoresists, for example, Patent Documents 1 and 2 disclose resin compositions containing phenol novolak resin as a main component and 1,2-naphthoquinonediazide sulfonic acid ester as a photosensitive component. There is. However, when directly applied to dry film photoresists, it is not possible to coat thickly on the support due to poor coating properties, and even if it is possible to coat thinly, the film quality is brittle and flexible. Due to the lack of properties, it is difficult to make it into a roll product. Patent Document 3 also discloses that a compound obtained by reacting a phenol resin with a drying oil is introduced to soften the film. However, positive dry film photoresists using these materials have not been put into practical use because resolution deteriorates due to the time required for winding up the roll after exposure. Conventional manufacturing methods and problems with positive dry film photoresist rolls will be described in detail below.

A roll-shaped product having a desired film width is obtained as follows. First, a wide roll is usually formed by coating a positive photosensitive resin composition onto a support. The roll is then cut with slits so that it has the desired film width. In addition, in order to laminate a photosensitive resin composition on a substrate on which an image pattern is formed, a dry film photoresist is usually pulled out from the roll-shaped product and thermally transferred while being pressed onto the substrate using a laminator. . During or after lamination, the dry film photoresist is cut to a predetermined length in the longitudinal direction of the substrate.

When a dry film photoresist having a brittle film-like positive photosensitive resin composition is used, chips of the positive photosensitive resin composition (hereinafter simply referred to as chips) are generated during the slitting. The problem arises. Furthermore, when the dry film photoresist is cut into a predetermined length in the longitudinal direction of the substrate during lamination, chips are likely to be generated from the cut surface. These chips become dust, contaminate the operating environment of the substrate or the laminator, and adhere to the support laminated on the substrate. As a result, defects are likely to occur in the image pattern.
Patent Document 3 describes a photosensitive resin composition that, when formed as a dry film, sufficiently suppresses the generation of chips even when the film is cut. Patent Document 4 discloses that by using an alkali-soluble resin containing hydroxystyrene, pattern formation is possible, and when formed as a dry film, the photosensitive resin composition is flexible and does not cut easily even when the film is cut. A photosensitive resin composition in which generation of debris is sufficiently suppressed is disclosed.

Japanese Patent Application Publication No. 06-027657 Japanese Patent Application Publication No. 2000-105466 Japanese Patent Application Publication No. 2007-316577 Patent No. 5155389

However, conventional positive photosensitive resin compositions still have room for improvement in resolution, film flexibility, visibility of exposed areas, and image quality after 24 hours of exposure.

The present invention has been made in view of the above circumstances, and provides a photosensitive resin composition that is excellent in resolution, film flexibility, visibility of exposed areas, and image quality after 24 hours after exposure, and a photosensitive resin composition that is excellent in resolution, film flexibility, visibility of exposed areas, and image quality after 24 hours after exposure. An object of the present invention is to provide a method for producing a photosensitive resin laminate and a resist pattern using the present invention.

｛式中、Ａ^１は、非置換又は置換の１価の芳香族基であり、Ａ^２は、非置換又は置換のアミノ基であり、Ａ^３及びＡ^４は、それぞれ独立に、水素原子、又は非置換若しくは置換の炭素数１～１０のアルキル基であり、ｐは、０～５の整数であり、かつＣＡ^－は、カウンターアニオンである｝
で表されるカチオン染料である、項目１に記載のポジ型感光性樹脂組成物。
［３］
さらに、（Ｃ）フェノールアラルキル樹脂を含む、項目１又は２に記載のポジ型感光性樹脂組成物。
［４］
前記（Ａ）アルカリ可溶性樹脂が、ノボラック樹脂である、項目１～３いずれか１項に記載のポジ型感光性樹脂組成物。
［５］
前記（Ａ）アルカリ可溶性樹脂が、クレゾールノボラック樹脂である、項目４に記載のポジ型感光性樹脂組成物。
［６］
前記ポジ型感光性樹脂組成物が、エポキシ基又はビニル基含有化合物を含まない、項目１～５いずれか１項に記載のポジ型感光性樹脂組成物。
［７］
前記（Ａ）アルカリ可溶性樹脂を２０～９０質量％、前記（Ｂ）キノンジアジド基含有化合物を１～４５質量％、かつ前記（Ｄ）カチオン染料を０．００１～５質量％含む、項目１～６いずれか１項に記載のポジ型感光性樹脂組成物。
［８］
支持体と、項目１～７いずれか１項に記載のポジ型感光性樹脂組成物を含む感光性樹脂層とを含む感光性樹脂積層体。
［９］
項目８に記載の感光性樹脂積層体の前記感光性樹脂層側を基板上に積層する積層工程；
該感光性樹脂層を露光する露光工程；及び
感光した感光性樹脂層を除去する現像工程；
を含むレジストパターンの製造方法。
［１０］
前記露光工程において、前記感光性樹脂層に直接描画して露光する、項目９に記載のレジストパターンの製造方法。
［１１］
項目９又は１０に記載のレジストパターンの製造方法によってレジストパターンを形成した基板を、エッチング又はめっきする工程を含むプリント配線板の製造方法。
［１２］
項目９又は１０に記載のレジストパターンの製造方法によってレジストパターンを形成した基板を、エッチングする工程を含むリードフレームの製造方法。
［１３］
項目９又は１０に記載のレジストパターンの製造方法によってレジストパターンを形成した基板を、エッチング又はめっきする工程を含む半導体パターンの製造方法。
［１４］
項目９又は１０に記載のレジストパターンの製造方法によってレジストパターンを形成した基板を、エッチング又はめっきする工程を含む薄膜トランジスタの製造方法。
［１５］
項目９又は１０に記載のレジストパターンの製造方法によってレジストパターンを形成した基板を、エッチングする工程を含むタッチパネルの製造方法。 The present inventors have conducted studies to solve the above problems, and have found that the above problems can be solved by using a photosensitive resin composition having the following configuration, and have accomplished the present invention. The present invention is as follows.
[1]
(A) an alkali-soluble resin having a phenolic hydroxyl group;
(B) a quinonediazide group-containing compound;
(D) a cationic dye;
A positive photosensitive resin composition containing.
[2]
The cationic dye (D) has the following general formula (D1):

{In the formula, A ¹ is an unsubstituted or substituted monovalent aromatic group, A ² is an unsubstituted or substituted amino group, and A ³ and A ⁴ are each independently a hydrogen atom, or an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, p is an integer of 0 to 5, and CA ^- is a counter anion}
The positive photosensitive resin composition according to item 1, which is a cationic dye represented by:
[3]
The positive photosensitive resin composition according to item 1 or 2, further comprising (C) a phenol aralkyl resin.
[4]
The positive photosensitive resin composition according to any one of items 1 to 3, wherein the alkali-soluble resin (A) is a novolak resin.
[5]
The positive photosensitive resin composition according to item 4, wherein the alkali-soluble resin (A) is a cresol novolak resin.
[6]
The positive photosensitive resin composition according to any one of items 1 to 5, wherein the positive photosensitive resin composition does not contain an epoxy group- or vinyl group-containing compound.
[7]
Items 1 to 6 containing 20 to 90% by mass of the alkali-soluble resin (A), 1 to 45% by mass of the quinonediazide group-containing compound (B), and 0.001 to 5% by mass of the cationic dye (D). The positive photosensitive resin composition according to any one of the items.
[8]
A photosensitive resin laminate comprising a support and a photosensitive resin layer containing the positive photosensitive resin composition according to any one of items 1 to 7.
[9]
A laminating step of laminating the photosensitive resin layer side of the photosensitive resin laminate according to item 8 on a substrate;
an exposure step of exposing the photosensitive resin layer; and a developing step of removing the exposed photosensitive resin layer;
A method for manufacturing a resist pattern including:
[10]
The method for producing a resist pattern according to item 9, wherein in the exposure step, the photosensitive resin layer is directly drawn and exposed.
[11]
A method for manufacturing a printed wiring board, including a step of etching or plating a substrate on which a resist pattern is formed by the method for manufacturing a resist pattern according to item 9 or 10.
[12]
A method for manufacturing a lead frame, including a step of etching a substrate on which a resist pattern is formed by the method for manufacturing a resist pattern according to item 9 or 10.
[13]
A method for manufacturing a semiconductor pattern, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method for manufacturing a resist pattern according to item 9 or 10.
[14]
A method for manufacturing a thin film transistor, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method for manufacturing a resist pattern according to item 9 or 10.
[15]
A method for manufacturing a touch panel, including a step of etching a substrate on which a resist pattern is formed by the method for manufacturing a resist pattern according to item 9 or 10.

According to the present invention, it is possible to form a pattern using a photosensitive resin composition, and when the photosensitive resin composition is formed as a dry film, the film has excellent flexibility, and the visibility of the exposed area is good, and the Excellent image quality and resolution over time.

FIG. 1 is a schematic cross-sectional view of a photosensitive resin laminate according to an embodiment of the present invention. FIG. 2 is a flow diagram for explaining a method for manufacturing a touch panel using a negative photosensitive resin composition using schematic cross-sectional views (a) to (h). FIG. 3 is a flow diagram for explaining a method for manufacturing a touch panel using a positive photosensitive resin composition using schematic cross-sectional views (a) to (f). FIG. 4 is a top view of a touch panel obtained using a photosensitive resin composition according to an embodiment of the present invention.

Embodiments of the present invention will be described in detail below. The present invention is not limited to the following embodiments, and various modifications can be made without departing from the gist thereof.

<Photosensitive resin composition>
The photosensitive resin composition according to this embodiment has the following components:
(A) an alkali-soluble resin having a phenolic hydroxyl group;
(B) a quinonediazide group-containing compound; and (D) a cationic dye;
including. By containing components (A), (B), and (D), the photosensitive resin composition enables pattern formation, has good film flexibility when formed as a dry film, and has good film flexibility in exposed areas. Excellent visibility, image quality after 24 hours of exposure, and resolution. In addition, since the photosensitive resin composition contains (D) a cationic dye and (B) a quinonediazide group-containing compound, the (D) cationic dye is decomposed by the acid generated after exposure, and only the exposed area can be decolored. This tends to improve visibility of exposed areas, image quality after 24 hours of exposure, and resolution.

If desired, the photosensitive resin composition according to the present embodiment may include the following components in addition to components (A), (B), and (D):
(C) Phenol aralkyl resin;
(D) Dyes other than component;
plasticizer;
surfactant;
Adhesion aid;
acid;
Solvents, such as high boiling point solvents; and/or other additives, such as sensitizers, crosslinking agents, pigments, fillers, flame retardants, stabilizers, adhesion agents, release promoters, antioxidants, Fragrances, imaging agents, thermal crosslinking agents, etc.;
can include.

The photosensitive resin composition according to the present embodiment is suitable as a positive photoresist from the viewpoints of flexibility and handling of the dry film, suppression of resin scattering during handling of the dry film, production of thin film transistors or touch panels, etc. Can be used for

(A) Alkali-soluble resin having phenolic hydroxyl group (A) Alkali-soluble resin having phenolic hydroxyl group (hereinafter referred to as alkali-soluble phenol resin) is made from, for example, a phenol compound and an aldehyde and/or ketone as raw materials. , by condensation polymerization reaction or by synthesizing monomers in which the hydroxyl group of vinylphenols is protected with an acetyl group, trimethylsilyl group, t-butyl group, t-butoxycarbonyl group, etc., and polymerizing in the presence of a cation, anion, or radical initiator. It can then be obtained by removing the protecting group. In this specification, component (A) does not include a phenol aralkyl resin that corresponds to the compound of component (C).

Examples of the above-mentioned phenolic compounds include phenol, cresol, xylenol; alkylphenols such as ethylphenol, butylphenol, and trimethylphenol; alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol; alkenylphenols such as vinylphenol and allylphenol. Arylphenols such as phenylphenol; Aralkylphenols such as benzylphenol; Alkoxycarbonylphenols such as methoxycarbonylphenol; Arylcarbonylphenols such as benzoyloxyphenol; Halogenated phenols such as chlorophenol; Polyhydroxybenzenes such as catechol and resorcinol; Bisphenols such as bisphenol A and bisphenol F; and naphthol compounds such as α- or β-naphthol, p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol, p-hydroxyphenyl-4-butanol, etc. Hydroxyalkylphenol; hydroxyalkyl cresol such as hydroxyethyl cresol; monoethylene oxide adduct of bisphenol; alcoholic hydroxyl group-containing phenolic compound such as monopropylene oxide adduct of bisphenol; and p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid , p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid, diphenolic acid, and other carboxyl group-containing phenol compounds.
The above-mentioned phenol compounds may be used alone or in combination of two or more.

Examples of the aldehydes and/or ketones include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone, and glyceraldehyde. . Examples of aldehydes and/or ketones include glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate, and pyruvic acid. , leplic acid, 4-acetylbutyric acid, acetone dicarboxylic acid, and 3,3'-4,4'-benzophenonetetracarboxylic acid. Further, formaldehyde precursors such as paraformaldehyde and trioxane may also be used. These may be used alone or in combination of two or more.

It is preferable to use an acidic catalyst in the polycondensation reaction. By using this acidic catalyst, it becomes easier to obtain a novolac type phenol resin as described below, and generation of chips can be more effectively prevented. Such acidic catalysts include, for example, hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. One type of acidic catalyst may be used alone or two or more types may be used in combination. Note that the conditions for synthesizing the alkali-soluble phenol resin may be known conditions.
The content of aldehyde and/or ketone in the raw material for obtaining the alkali-soluble phenolic resin is preferably 0.7 to 1 mol per 1 mol of the above-mentioned phenolic compound. In this case, the polycondensation reaction can proceed more quickly.
Furthermore, the alkali-soluble phenol resin (A) may be a condensation product of the above-mentioned phenol compound and a compound other than phenol, such as m-xylene. In this case, the molar ratio of the compound other than phenol to the phenol compound used in the polycondensation is preferably less than 0.5.

(A) The weight average molecular weight of the alkali-soluble phenol resin measured by gel permeation chromatography in terms of polystyrene is preferably 300 to 100,000, from the viewpoint of improving coating properties and suppressing deterioration of developability. 000 to 50,000, or more preferably 3,000 to 20,000. The weight average molecular weight is preferably 300 or more from the viewpoint of coating properties, and preferably 100,000 or less from the viewpoint of developability.
In addition, if the weight average molecular weight of the phenolic resin is smaller than a predetermined value (for example, 300), the phenol resin is multimerized using a chain extender to increase the molecular weight so that it falls within the weight average molecular weight range described above. You may let them. Examples of the chain extender include diepoxy compounds or dioxazoline compounds capable of reacting with carboxyl groups, and diisocyanate compounds capable of reacting with hydroxyl groups.

(A) The alkali-soluble phenol resin may be used alone or in combination of two or more. Examples of alkali-soluble phenolic resins when two or more types are used in combination include two or more types of alkali-soluble phenolic resins obtained from mutually different types of monomers, and two or more types of alkali-soluble phenolic resins having mutually different weight average molecular weights. Examples include phenolic resins and two or more alkali-soluble phenolic resins having mutually different degrees of dispersion.
(A) The blending ratio of the alkali-soluble phenol resin in the photosensitive resin composition is preferably 20 to 90% by mass, and preferably 30 to 80% by mass based on the total amount of the photosensitive resin composition. The amount is more preferably 35 to 75% by weight, even more preferably 40 to 70% by weight. This blending ratio is preferably 20% by mass or more from the viewpoint of improving pattern formability, and preferably 90% by mass or less from the viewpoint of preventing brittleness of the resist film.

In the photosensitive resin composition of this embodiment, the component (A) is preferably a novolak resin from the viewpoint of exhibiting flexibility when formed into a film while maintaining excellent pattern formability.

Novolac resins are obtained by polycondensing phenols and aldehydes by a known method. It may contain a combination of two or more types of novolac resins. Preferred examples of the above phenols include phenol, bisphenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2 , 3,5-trimethylphenol, 3,4,5-trimethylphenol and the like. In particular, phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol and 2,3,5-trimethylphenol are more preferred, and phenol, More preferred are m-cresol and p-cresol, and two or more of these phenols may be used in combination.

Preferred examples of the aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like. Among these, formalin is particularly preferred. Two or more of these aldehydes may be used in combination. The amount of aldehydes used is preferably 0.6 mol or more, more preferably 0.7 mol or more, per 1 mol of phenols. Moreover, 3 mol or less is preferable, and 1.5 mol or less is more preferable.

Among them, from the viewpoint of heat resistance and solubility in an alkaline developer, phenol novolak resin, m-cresol novolak resin, and p-cresol novolak resin are preferable, and m-cresol novolak resin and p-cresol novolak resin are more preferable. preferable.

When m-cresol and p-cresol are used in combination, the ratio (m/p) of m-cresol and p-cresol as structural units in the cresol novolac resin is not particularly limited, but for example, It can be from 8/2 to 2/8.

Specific examples of such cresol novolac resins include TR4020G (product name, same hereinafter), TR4080G, TR5010G, manufactured by Asahi Yokuzai Co., Ltd., PR-X18153, manufactured by Sumitomo Bakelite Co., Ltd., and PR-X18153, manufactured by Aica Kogyo Co., Ltd. , Shonol (registered trademark) CKM-957, MCM-709, Gunei Chemical Co., Ltd., PS-2808, GTR-B9 (trade name), and the like.

Structure example of cresol novolac:

In this embodiment, the polystyrene equivalent weight average molecular weight (hereinafter referred to as "Mw") of the novolac resin is preferably 1,000 or more, and more preferably 2,000 or more. Further, it is preferably 20,000 or less, more preferably 15,000 or less. Within this range, the positive photosensitive resin composition of the present invention is excellent in workability when applied to a substrate and in solubility in an alkaline developer.

When component (A) contains a novolak resin, the proportion of novolak resin in component (A) is preferably 20% by mass to 90% by mass, more preferably 30% by mass to 80% by mass. This blending ratio is preferably 20% by mass or more from the viewpoint of improving pattern formability, and preferably 90% by mass or less from the viewpoint of preventing brittleness of the resist film.

(B) Quinonediazide group-containing compound (B) The quinonediazide group-containing compound can have, for example, a 1,2-quinonediazide group, a 1,2-naphthoquinonediazide group, etc. as the quinonediazide group. Component (B) can be obtained by, for example, reacting an organic compound having a hydroxyl group or an amino group (hereinafter simply referred to as an "organic compound") with a 1,2-naphthoquinonediazide compound having a sulfo group and/or a sulfonyl chloride group. It is a compound that is In this case, the hydroxyl group or amino group of the organic compound and the sulfo group or sulfonyl chloride group of the 1,2-quinonediazide compound are bonded. It is sufficient that at least one bond exists in the molecule of the obtained 1,2-quinonediazide compound. (B) When the quinonediazide group-containing compound is included in the photosensitive resin composition, visibility of exposed areas may be improved.

Examples of the 1,2-quinonediazide compounds having a sulfo group and/or sulfonyl chloride group include 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfone acid, 1,2-naphthoquinone-2-diazido-4-sulfonyl chloride, and 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride. Among the 1,2-quinonediazide compounds having a sulfo group and/or sulfonyl chloride group, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid, One or more compounds selected from the group consisting of 1,2-naphthoquinone-2-diazido-4-sulfonyl chloride and 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride are preferred. These 1,2-quinonediazide compounds having a sulfo group and/or a sulfonyl chloride group are advantageously soluble in a solvent, so that the reaction efficiency with an organic compound can be increased.

Examples of the above-mentioned organic compounds include polyhydroxybenzophenones, bis[(poly)hydroxyphenyl]alkanes, tris(hydroxyphenyl)methanes or methyl substituted products thereof, bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes, or Its methyl substituted products, phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, 4,4' -Diaminobenzophenone, novolak, pyrogallol-acetone resin, homopolymers of hydroxystyrene or copolymers with monomers copolymerizable therewith. These may be used alone or in combination of two or more.

Examples of the polyhydroxybenzophenones include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, and 2,3,6-trihydroxybenzophenone. , 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4, 4',6-pentahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4', Examples include 5',6-hexahydroxybenzophenone and 2,3,3',4,4',5'-hexahydroxybenzophenone. These may be used alone or in combination of two or more.

Examples of bis[(poly)hydroxyphenyl]alkanes include bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2 -(4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2 -(2',3',4'-trihydroxyphenyl)propane, 4,4'-{1-[4-[2-(4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol, and 3 , 3'-dimethyl-{1-[4-[2-(3-methyl-4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol. These may be used alone or in combination of two or more.

Examples of tris(hydroxyphenyl)methanes or methyl substituted products thereof include tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4- Hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)- 2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, and bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane can be mentioned. These may be used alone or in combination of two or more.

Examples of bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes or methyl substituted products thereof include bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl) )-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis( 5-Cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2- hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3- Hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl- 2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, and bis(5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane is mentioned. These may be used alone or in combination of two or more.

Among these, the organic compounds include polyhydroxybenzophenones, bis[(poly)hydroxyphenyl]alkanes, tris(hydroxyphenyl)methanes, and/or bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes. It is preferable that It is more preferable that the organic compound is at least one compound selected from the group consisting of compounds represented by the following general formula (5). In this case, the difference in solubility in the developer before and after the photosensitive resin composition is irradiated with light becomes large, so there is an advantage that the image contrast is better.

｛式中、Ｒ_７～Ｒ_１２は、それぞれ独立に、水素、ハロゲン、Ｃ_１～Ｃ_４のアルキル基、アルケニル基又は水酸基であり、Ｒ_１３及びＲ_１４は、それぞれ独立に、水素、ハロゲン又はＣ_１～Ｃ_４のアルキル基であり、そしてＲ_１５～Ｒ_１７は、それぞれ独立に、水素又はＣ_１～Ｃ_４のアルキル基である。｝
で表される化合物、下記一般式（６）：

｛式中、Ｒ_１８～Ｒ_２３は、それぞれ独立に、水素、ハロゲン、Ｃ_１～Ｃ_４のアルキル基、アルケニル基又は水酸基である。｝
で表される化合物、下記一般式（７）：

｛式中、Ｒ_２４～Ｒ_２７は、それぞれ独立に水素原子、置換若しくは無置換の炭素数１～５のアルキル基、又は置換若しくは無置換の炭素数１～５のアルコキシ基である。｝で表される化合物、及び下記一般式（８）：

｛式中、Ｒ_２８～Ｒ_３１は、それぞれ独立に、水素原子、置換若しくは無置換の炭素数１～５のアルキル基、又は置換若しくは無置換の炭素数１～５のアルコキシ基であり、そしてＸは、単結合、酸素原子又はフェニレン基である。｝で表される化合物から成る群より選ばれる少なくとも一種であることが、感度の観点から更に好ましい。 Among them, the following general formula (5):

{In the formula, R ₇ to R ₁₂ are each independently hydrogen, halogen, a C ₁ to C ₄ alkyl group, alkenyl group, or hydroxyl group, and R ₁₃ and R ₁₄ are each independently hydrogen, halogen, or It is a C ₁ -C ₄ alkyl group, and R ₁₅ - R ₁₇ are each independently hydrogen or a C ₁ -C ₄ alkyl group. }
A compound represented by the following general formula (6):

{In the formula, R ₁₈ to R ₂₃ are each independently hydrogen, halogen, a C ₁ to C ₄ alkyl group, an alkenyl group, or a hydroxyl group. }
A compound represented by the following general formula (7):

{In the formula, R ₂₄ to R ₂₇ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms. } and the following general formula (8):

{In the formula, R ₂₈ to R ₃₁ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, and X is a single bond, an oxygen atom or a phenylene group. } is more preferable from the viewpoint of sensitivity.

The organic compound is at least one compound selected from the group consisting of a compound represented by the above general formula (5), a compound represented by the above general formula (7), and a compound represented by the above general formula (8). In some cases, the 1,2-quinonediazide compound having a sulfo group and/or a sulfonyl chloride group is 1,2-naphthoquinone-2-diazido-4-sulfonic acid, 1,2-naphthoquinone-2-diazido-5-sulfonic acid , 1,2-naphthoquinone-2-diazido-4-sulfonyl chloride, and/or 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride. These 1,2-quinonediazide compounds having a sulfo group and/or a sulfonyl chloride group include a compound represented by the above general formula (5), a compound represented by the above general formula (7), and a compound represented by the above general formula (8). Since it has good compatibility with at least one compound selected from the group consisting of compounds represented by, it reduces the amount of aggregates generated when component (A) and component (B) are mixed. be able to. Moreover, when a photosensitive resin composition containing these is used as a photosensitive component of a photoresist, it becomes more excellent in sensitivity, image contrast, and heat resistance. From the same viewpoint, it is preferable that at least one of the groups R ₁ to R ₆ in general formula (6) is a hydroxyl group.

で表される化合物からなる群より選ばれる少なくとも一種の化合物であることがより好ましい。この場合、光感度により優れるという利点がある。中でも一般式（９）で表される化合物が溶解抑止の観点から好ましく、また、一般式（１２）又は（１３）で表される化合物が感度の観点から好ましい。 Furthermore, at least one compound selected from the group consisting of the compound represented by the above general formula (5), the compound represented by the above general formula (7), and the compound represented by the above general formula (8) is as follows: Chemical formulas (9) to (13):

More preferably, it is at least one compound selected from the group consisting of compounds represented by: In this case, there is an advantage that the photosensitivity is better. Among these, the compound represented by the general formula (9) is preferred from the viewpoint of dissolution inhibition, and the compound represented by the general formula (12) or (13) is preferred from the viewpoint of sensitivity.

Examples of the method for synthesizing a 1,2-naphthoquinonediazide compound using at least one compound selected from the group consisting of compounds represented by the above general formulas (5) to (8) include the following method. That is, for example, at least one compound selected from the group consisting of compounds represented by the above general formulas (5) to (8) and 1,2-naphthoquinone-2-diazide-sulfonyl chloride are mixed in dioxane and THF. Examples include a method in which the compound is added to such a solvent and reacted in the presence of an alkali catalyst such as triethylamine, triethanolamine, alkali carbonate, or alkali hydrogen carbonate. At this time, the hydroxyl group of at least one compound selected from the group consisting of compounds represented by the above general formulas (5) to (8) and the sulfonyl group of 1,2-naphthoquinone-2-diazide-sulfonyl chloride are condensed. A photosensitizer containing a 1,2-naphthoquinone diazide group is synthesized. In addition, in the molecule of the resulting photosensitizer containing a 1,2-naphthoquinonediazide group, a hydroxyl group of at least one compound selected from the group consisting of compounds represented by general formulas (5) to (8), and 1, It is sufficient that 2-naphthoquinone-2-diazide-sulfonyl chloride has at least one bond with the sulfonyl group.
In addition, as 1,2-naphthoquinone-2-diazido-sulfonyl chloride, 1,2-naphthoquinone-2-diazido-4-sulfonyl chloride or 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride is preferable. be. These may be used alone or in combination of two or more.

Specifically, such component (B) includes 1,2-4,4'-(1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene)bisphenol). A mixture of mono-, di- or triesters of naphthoquinonediazide-4-sulfonic acid (for example, 4CPA-20 (trade name, the same hereinafter) manufactured by Daito Chemix Co., Ltd.), 4,4'-(1-{4-[1 -(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene)bisphenol), a mixture of mono-, di- or triester of 1,2-naphthoquinonediazide-4-sulfonic acid (for example, 4CPA manufactured by Daito Chemix Co., Ltd.) -27), 1,2-naphthoquinonediazide-5-sulfonic acid ester of α,α,α-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, manufactured by Toyo Gosei Co., Ltd., TS-100G), ester of 2,3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonic acid, 2,3,4,4'-tetramethylbenzophenone and naphthoquinone-1, Ester of 2-diazide-5-sulfonic acid (manufactured by Toyo Gosei Co., Ltd., 4NT-300), ester of 2,3,4-trihydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonic acid (manufactured by Toyo Gosei Kogyo Co., Ltd.) , NT-200), ester of bis(2,4-dihydroxyphenyl)methane and naphthoquinone-1,2-diazide-4-sulfonic acid, bis(p-hydroxyphenyl)ethane and naphthoquinone-1,2-diazide-4 - esters of sulfonic acids, esters of 1,1,1-tri(p-hydroxyphenyl)ethane and naphthoquinone-1,2-diazide-4-sulfonic acids, bis(2,3,4-trihydroxyphenyl)methane and Ester of naphthoquinone-1,2-diazido-4-sulfonic acid, ester of 2,2'-bis(2,3,4-trihydroxyphenyl)propane and naphthoquinone-1,2-diazido-4-sulfonic acid, 1 , 1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane and naphthoquinone-1,2-diazido-4-sulfonic acid.

Structural formula of 4CPA-20 and 4CPA-27:

In this embodiment, component (B) can be used as a photosensitizer in the photosensitive resin composition.
Further, the blending ratio of component (B) in the photosensitive resin composition is preferably 1 to 45% by mass, more preferably 3 to 40% by mass, based on the total amount of the photosensitive resin composition. The content is preferably from 5 to 43% by weight, even more preferably from 5 to 20% by weight. This blending ratio is preferably 1% by mass or more from the viewpoint of improving photosensitivity, and preferably 45% by mass or less from the viewpoint of preventing brittleness of the resist film.

(C) Phenol aralkyl resin The photosensitive resin composition contains (C) phenol aralkyl resin. In this embodiment, component (C) is used in combination with an alkali-soluble resin, and can be used as a photosensitizer in a photosensitive resin composition.
(C) Phenol aralkyl resin is a resin obtained from the reaction of phenols and aralkylphenols (reactive compounds having xylylene units, benzene, biphenyl, etc.), and is not only in the i-line region (365 nm) but also in the vicinity of 248 nm. Because its absorption is very small, it has very high transparency from the conventional g-line (436 nm) and i-line to KrF excimer laser, and its hydroxyl group greatly contributes to its alkali solubility. By combining this resin with a photoreactive component, the alkali solubility is suppressed under normal conditions, and after exposure, the photoreactive component in the exposed area is photodenatured, loses its suppressing effect, and becomes alkali soluble, making it suitable for photolithography. This makes it more useful as a so-called positive photoresist.

｛式中、Ｒ_３２はハロゲン原子、水酸基または炭素数１～４の低級アルコキシ基を表す｝

｛式中、Ｒ_３３はハロゲン原子、水酸基または炭素数１～４の低級アルコキシ基を表す｝
で表されるアラルキルハライド若しくはアラルキルアルコール、又はその誘導体（以下、アラルキル化合物と称する）とを反応させた後、必要により未反応フェノール化合物を留去することにより得られるものである。 This phenol aralkyl resin can be produced using the methods described in Japanese Patent Publication No. 47-15111, Japanese Patent Application Laid-open No. 63-238129, Japanese Patent Application Laid-open No. 06-100667, and the like. That is, an excess amount of a phenol compound and the following general formula (14) or (15):

{In the formula, R ₃₂ represents a halogen atom, a hydroxyl group, or a lower alkoxy group having 1 to 4 carbon atoms}

{In the formula, R ₃₃ represents a halogen atom, a hydroxyl group, or a lower alkoxy group having 1 to 4 carbon atoms}
It is obtained by reacting an aralkyl halide, an aralkyl alcohol, or a derivative thereof (hereinafter referred to as an aralkyl compound) represented by the formula, and then optionally distilling off an unreacted phenol compound.

Phenol compounds used in the reaction include phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,6-xylenol, t-butylphenol, o-phenylphenol, p-phenylphenol, α - Monohydric phenols such as naphthol and β-naphthol, dihydric phenols such as resorcinol, hydroquinone, and catechol, 2-bromophenol, 4-bromophenol, 2-iodophenol, 4-iodophenol, 2-chlorophenol, Examples include halogenated phenols such as 4-chlorophenol, 2,4-dibromophenol, 2,6-dibromophenol, 2,4-diiodophenol, and 2,6-diiodophenol. Among these, preferred phenol compounds include phenol, o-cresol, m-cresol, and p-cresol, which may be used alone or in combination of two or more.

In addition, as aralkyl compounds, m-xylene, α,α'-dichloro-p-xylene, α,α'-dichloro-m-xylene, α,α'-dichloro-o-xylene, α,α'-dibromo -p-xylene, α,α'-dibromo-m-xylene, α,α'-dibromo-o-xylene, α,α'-difluoro-p-xylene, α,α'-difluoro-m-xylene, α , α'-difluoro-o-xylene, α,α'-diiodo-p-xylene, α,α'-diiodo-m-xylene, α,α'-diiodo-o-xylene, α,α'-dihydroxy- p-xylene, α,α'-dihydroxy-m-xylene, α,α'-dihydroxy-o-xylene, α,α'-dimethoxy-p-xylene, α,α'-dimethoxy-m-xylene, α, α'-dimethoxy-o-xylene, α,α'-diethoxy-p-xylene, α,α'-diethoxy-m-xylene, α,α'-diethoxy-o-xylene, α,α'-di-n -propoxy-p-xylene, α,α'-di-n-propoxy-m-xylene, α,α'-di-n-propoxy-o-xylene, α,α'-diisopropoxy-p-xylene, α,α'-diisopropoxy-m-xylene, α,α'-diisopropoxy-o-xylene, α,α'-di-n-butoxy-p-xylene, α,α'-di-n- Butoxy-m-xylene, α,α'-di-n-butoxy-o-xylene, α,α'-di-sec-butoxy-p-xylene, α,α'-di-sec-butoxy-m-xylene , α,α'-di-sec-butoxy-o-xylene, 4,4'-di(halogenomethyl)biphenyl, 2,4'-di(halogenomethyl)biphenyl, 2,2'-di(halogenomethyl) biphenyl, 4,4'-di(alkoxymethyl)biphenyl, 2,4'-di(alkoxymethyl)biphenyl, 2,2'-di(alkoxymethyl)biphenyl, 4,4'-di(hydroxymethyl)biphenyl, 2,4'-di(hydroxymethyl)biphenyl, 2,2'-di(hydroxymethyl)biphenyl, 4,4'-di(alkoxymethyl)biphenyl, 2,4'-di(alkoxymethyl)biphenyl and 2, 2'-di(alkoxymethyl)biphenyl, 1,4-di(halogenomethyl)benzene, 1,4-di(alkoxymethyl)benzene, 1,2-di(halogenomethyl)benzene, 1,2-di(alkoxy Examples include methyl)benzene, 1,3-di(halogenomethyl)benzene, and 1,3-di(alkoxymethyl)benzene. Among these, preferred compounds include α,α'-dichloro-p-xylene, α,α'-dichloro-m-xylene, α,α'-dimethoxy-p-xylene, α,α'-dimethoxy-m-xylene, α,α'-dihydroxy-p-xylene, α,α'-dihydroxy-m-xylene, 4,4'-di(halogenomethyl)biphenyl, 4,4'-di(alkoxymethyl)biphenyl, 4,4' -di(hydroxymethyl)biphenyl, 1,4-di(alkoxymethyl)benzene, 1,2-di(alkoxymethyl)benzene, and 1,3-di(alkoxymethyl)benzene, which may be used alone or in combination. Two or more types are used in combination.

The reaction molar ratio between the phenol compound and the aralkyl compound is basically as long as there is a small excess of the phenol compound, but if the amount of phenol is too small, the molecular weight will increase too much during the reaction and gelation will occur, and if it is too large, it will cause gelation. Since the amount of unreacted phenol compound increases and it is also disadvantageous in terms of volumetric efficiency of the reaction, the phenol/aralkyl compound (molar ratio) is 20 to 1.3, preferably 10 to 1.5, more preferably 8 to It is in the range of 1.5.

In the reaction, Lewis acids such as aluminum chloride, alkanesulfonic acids such as methanesulfonic acid, organic sulfonic acids such as p-toluenesulfonic acid, and perfluoroalkanesulfonic acids such as trifluoromethanesulfonic acid are used. A super strong acid such as Nafion, or an acidic catalyst such as a perfluoroalkanesulfonic acid type ion exchange resin called Nafion or a normal acidic ion exchange resin is used. The amount used is in the range of 0.0005 to 10% by weight, preferably 0.001 to 5% by weight, based on the raw material.

The reaction is carried out by reacting phenol and an aralkyl compound by any method. Specifically, there are methods to terminate the reaction while dropping the aralkyl compound into preheated and stirred phenol, methods to prepare all the raw materials at once in advance, and to gradually raise the temperature while stirring to allow the reaction to occur. The reaction can be carried out in any reaction format. In this reaction, reaction by-products such as hydrogen halide, water, and alcohol are produced depending on the selection of the aralkyl compound, but as the reaction progresses and by-products are produced, it is desirable to sequentially remove these from the system. The reaction temperature is in the range of 40 to 200°C, preferably 60 to 180°C, more preferably 70 to 160°C. Note that in this reaction, it is also possible to use a solvent that does not participate in the reaction.

｛一般式（１）において、Ｘは、それぞれ独立に一般式（２）：

または一般式（３）：

または一般式（４）：

（式中、Ｒ^３～Ｒ^６は、それぞれ独立に水素原子または炭素数１～１２のアルキル基である）で表される芳香族環を含む２価の基を表し、Ｒ^１およびＲ^２は、それぞれ独立に水素原子又は炭素数が１～６個のアルキル基を表し、ｑは、１～１００の整数を表す。｝
で表される樹脂であることが好ましい。 (C) The phenol aralkyl resin has the following general formula (1):

{In general formula (1), each X independently represents general formula (2):

Or general formula (3):

Or general formula (4):

(In the formula, R ³ to R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms), and R ¹ and R ² represent a divalent group containing an aromatic ring. , each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and q represents an integer of 1 to 100. }
It is preferable that it is a resin represented by

In addition, in the photosensitive resin composition, from the viewpoint of flexibility and resolution of the dry film, the cresol novolak resin explained above as a type of component (A) and the phenol having a biphenyl structure as the component (C) are used. It is preferable to use it together with an aralkyl resin. This is because it is possible to balance the hard and brittle properties of the cresol novolak resin with the relatively low softening point of the phenol aralkyl resin having a biphenyl structure. From the same viewpoint, the phenol aralkyl resin preferably has a biphenyl structure represented by the above general formula (3), and also preferably has a softening point of 70° C. or lower.

From the viewpoint of film flexibility, the hydroxyl equivalent of the phenol aralkyl resin (C) is preferably 115 g/eq or more, more preferably 130 g/eq or more. From the viewpoint of heat resistance, the hydroxyl equivalent is preferably 5000 g/eq or less, more preferably 3000 g/eq or less.
Here, the hydroxyl group equivalent means the molecular weight for one hydroxyl group in the phenol resin. The hydroxyl equivalent can be measured according to the neutralization titration method specified in JIS K 0070 (1992).

(C) Phenol aralkyl resins include condensates of tert-butylphenol, m-xylene, and formaldehyde (Nicanor HP-70, Nicanol HP-210), 4,4-bis(methoxymethyl)biphenyl, and phenol. Condensation products with formaldehyde (GPH-65, GPH-103 (Nippon Kayaku Co., Ltd.), MEH-7851 (Meiwa Kasei Co., Ltd.), condensation products of 1,4-di(methoxymethyl)benzene, phenol, and formaldehyde (MEH-7800, MEHC-7800 (Meiwa Kasei Co., Ltd.)), condensate of allylphenol and formaldehyde (MEH-8000 (Meiwa Kasei Co., Ltd.)), manufactured by Mitsui Chemicals, XLC-3L, XL-225 etc. Among them, a condensate of 4,4-bis(methoxymethyl)biphenyl, phenol and formaldehyde, and a condensate of 1,4-di(methoxymethyl)benzene, phenol and formaldehyde are preferred. , 4,4-bis(methoxymethyl)biphenyl, a condensate of phenol and formaldehyde is more preferred.

｛式中、ｎは、２以上の整数である｝ Structure example of GPH-65, MEHC-7851:

{In the formula, n is an integer of 2 or more}

Structure example of MEHC-7800 and MEH-7800:

The blending ratio of component (C) in the photosensitive resin composition is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, based on the total amount of the photosensitive resin composition. More preferably, it is 35 to 75% by mass. This blending ratio is preferably 20% by mass or more from the viewpoint of preventing brittleness of the resist film, and preferably 90% by mass or less from the viewpoint of pattern formability.

(D) Cationic Dye The cationic dye (D) according to the present embodiment can be a dye having a cationic moiety or a salt thereof. The photosensitive resin composition is preferable in terms of visibility because the exposed area develops color by containing the component (D), so that it is possible to distinguish between the exposed area and the unexposed area. In addition, when (D) a cationic dye and (B) a quinonediazide group-containing compound are used together, the (D) cationic dye is decomposed by the acid generated after exposure, and only the exposed area can be decolored, thereby improving the visibility of the exposed area. This is preferable because image quality and resolution tend to improve after 24 hours of exposure.

Examples of cationic dyes include Basic Blue 6, Basic Blue 7 (for example, Hodogaya Chemical Co., Ltd. Eisen Victoria Pure Blue BOH (product name)), Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17, Natural Brown 7, Basic Green 1 (e.g. Hodogaya Chemical Co., Ltd. Eisen Diamond Green GH (product name)), Basic Orange 31, Basic Red 2, Basic Red 12, Basic Red 22, Basic Red 51, Basic Red 76, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 10, Basic Violet 14, Basic Yellow 57, Basic Yellow 87, and mixtures thereof.

｛式中、Ａ^１は、非置換又は置換の１価の芳香族基であり、Ａ^２は、非置換又は置換のアミノ基であり、Ａ^３及びＡ^４は、それぞれ独立に、水素原子、又は非置換若しくは置換の炭素数１～１０のアルキル基であり、ｐは、０～５の整数であり、かつＣＡ^－は、カウンターアニオンである｝
で表されるカチオン染料であることが好ましい。これは、感光性樹脂組成物が、一般式（Ｄ１）で表されるカチオン染料を含むと、露光部の視認性を発現することがあるからである。 The cationic dye (D) has the following general formula (D1):

{In the formula, A ¹ is an unsubstituted or substituted monovalent aromatic group, A ² is an unsubstituted or substituted amino group, and A ³ and A ⁴ are each independently a hydrogen atom, or an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, p is an integer of 0 to 5, and CA ^- is a counter anion}
A cationic dye represented by is preferable. This is because when the photosensitive resin composition contains a cationic dye represented by the general formula (D1), visibility of exposed areas may be improved.

｛式中、Ａ^２は、非置換又は置換のアミノ基であり、かつｐは、０～５の整数である｝

｛式中、Ａ^２は、非置換又は置換のアミノ基であり、かつｐは、０～５の整数である｝
で表される１価の基であることが好ましい。 In general formula (D1), A ¹ is an unsubstituted or substituted monovalent aromatic group, for example, a monocyclic aromatic hydrocarbon such as benzene; or naphthalene, anthracene, naphthacene, chrysene, pyrene, pentacene, It may be a monovalent group having a polycyclic aromatic hydrocarbon structure such as benzopyrene or triphenylene, and may have various substituents. ^A1 is the following formula (D2) and/or (D3) from the viewpoint of visibility of the exposed part:

{wherein A ² is an unsubstituted or substituted amino group, and p is an integer of 0 to 5}

{wherein A ² is an unsubstituted or substituted amino group, and p is an integer of 0 to 5}
A monovalent group represented by is preferable.

に示される１価の基から成る群から選択される少なくとも１つであることができる。一般式（Ｄ１）において、Ａ^３及びＡ^４は、それぞれ独立に、水素原子、又は非置換若しくは置換の炭素数１～１０のアルキル基であり、露光部の視認性の観点から、Ａ^３及びＡ^４の両方が、メチル基、エチル基などのアルキル基であることが好ましい。 In general formulas (D1) to (D3), A ² is an unsubstituted or substituted amino group, for example, the following:

It can be at least one selected from the group consisting of monovalent groups shown in . In general formula (D1), A ³ and A ⁴ are each independently a ^hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms. Preferably both A ⁴ are alkyl groups such as methyl and ethyl groups.

In general formulas (D1) to (D3), p is an integer of 0 to 5, and is preferably an integer of 1 to 4, or 1, 2, or 3 from the viewpoint of visibility of the exposed area. In general formula (D1), CA ^- is a counter anion, such as a halogen ion, hydroxide ion, nitrate ion, nitrite ion, hypochlorite ion, chlorite ion, chlorate ion, acetate ion , hydrogen carbonate ion, dihydrogen phosphate ion, hydrogen sulfate ion, etc. Among these, as CA ^- , from the viewpoint of visibility of the exposed area, halogen ions such as F ^- , Cl ^- , Br ^- , I ^-, and/or HSO ₄ ^- are preferable.

で表される染料が好ましい。 In this embodiment, the cationic dye (D) used is the following formula (D4) and / Or (D5):

Dyes represented by are preferred.

The content of the cationic dye (D) in the photosensitive resin composition is preferably 0.001% by mass to 5% by mass, based on the total solid mass of the photosensitive resin composition. It is more preferably 0.05 to 1% by weight, and even more preferably 0.1 to 0.6% by weight. The content is preferably 0.001% by mass or more from the viewpoint of improving the contrast between exposed and unexposed regions and improving the handleability of the photosensitive resin composition. On the other hand, from the viewpoint of excellent adhesion and resolution even under extremely harsh development conditions such as over-development and over-washing with high developer temperature, and from the viewpoint of maintaining the storage stability of the photosensitive resin composition, It is preferable that the amount is 5% by mass or less.

Dyes other than component (D) Examples of dyes other than component (D) include Solvent Green 3 [128-80-3] (eg, OPLAS Green 533), leuco dyes, fluoran dyes, and the like.

Examples of the leuco dye include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leucomalachite green], and the like.

When the photosensitive resin composition contains component (D) and a dye other than component (D), the total content of the dye in the photosensitive resin composition is the total solid content of the photosensitive resin composition. When the mass is 100% by mass, it is preferably 0.001% to 5% by mass, more preferably 0.05 to 1% by mass, and 0.1 to 0.6% by mass. is even more preferable. The total content is preferably 0.001% by mass or more from the viewpoint of improving the contrast between exposed and unexposed regions and improving the handleability of the photosensitive resin composition. On the other hand, the total It is preferable that the content is 5% by mass or less.

It is preferable to include a plasticizer in the plasticizer photosensitive resin composition from the viewpoint of reducing chips.
The plasticizer may be any compatible low molecular weight component, such as polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene poly Glycol esters such as oxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide , p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, acetyl tri-n-butyl citrate, bisphenol A (2,2-bis(4') -hydroxyphenyl)propane) or bisphenol E (1,1-bis(4-hydroxyphenyl)ethane) or bisphenol F (4,4'-methylenebisphenol) or bisphenol S (4,4'-sulfonyldiphenol). Examples include compounds in which an aliphatic molecular chain such as an alkyl group, an alkylene oxide group, or a polyalkylene oxide group is introduced using a terminal hydroxyl group. Alkyl groups include methyl, ethyl, and propyl groups; alkylene oxide groups include methylene oxide, ethylene oxide, propylene oxide, and tetramethylene oxide; and polyalkylene oxide groups include polymethylene oxide, Examples include groups consisting of polyethylene oxide groups, polypropylene oxide groups, polytetramethylene oxide groups, or block copolymers and random copolymers thereof.

Other Components The photosensitive resin composition may contain a surfactant, if necessary, for the purpose of improving coating properties, antifoaming properties, leveling properties, etc. Such surfactants are not particularly limited, but are preferably fluorosurfactants. Examples of such fluorine-based surfactants include BM-1000, BM-1100 (manufactured by BM Chemie); Megafac (registered trademark) F142D, Megafac (registered trademark) F172, Megafac (registered trademark). ) F173, Megafac (registered trademark) F183, Megafac (registered trademark) R-08, Megafac (registered trademark) R-30, Megafac (registered trademark) R-90PM-20, Megafac (registered trademark) BL -20 (manufactured by Dainippon Ink and Chemicals); Florado FC-135, Florado FC-170C, Florado FC-430, Florado FC-431, Florado FC-4430 (manufactured by Sumitomo 3M); Surflon (registered) Trademark) S-112, Surflon (registered trademark) S-113, Surflon (registered trademark) S-131, Surflon (registered trademark) S-141, Surflon (registered trademark) S-145 (all manufactured by Asahi Glass Co., Ltd.); SH Commercially available products such as -28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicone) can be used. These may be used alone or in combination of two or more.

The blending ratio of the surfactant is preferably 5% by mass or less based on the total amount of the photosensitive resin composition. When this blending ratio exceeds 5% by mass, pattern formability tends to be lower than when the blending ratio is within the above range.
The photosensitive resin composition may contain an adhesion aid in order to improve adhesion to a base material and the like. As such an adhesion aid, a functional silane coupling agent is preferred. Here, the functional silane coupling agent means a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, or an isocyanate group. Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, Y-methacryloxypropyltrimethoxysilane, Y-glycidoxypropyltrimethoxysilane, trimethoxysilylpropyl isocyanate, and 1,3,5-N- Tris(trimethoxysilylpropyl)isocyanate is mentioned. These may be used alone or in combination of two or more.
The blending ratio of the adhesive aid is preferably 20% by mass or less based on the total amount of the photosensitive resin composition. When this blending ratio exceeds 20% by mass, development residues tend to occur more easily than when the blending ratio is within the above range.

The photosensitive resin composition may contain an acid or a high boiling point solvent in order to finely adjust the solubility in an alkaline developer. Examples of acids include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso-valeric acid, benzoic acid, and cinnamic acid, lactic acid, 2-hydroxybutyric acid, and 3-hydroxybutyric acid. Hydroxy monocarboxylic acids such as butyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid, sulfur Acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, tricarboxylic acid Polyhydric carboxylic acids such as mellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid, itaconic anhydride, succinic anhydride, citraconic anhydride, anhydride Dodecenylsuccinic acid, tricarbanic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, himic anhydride, 1,2,3,4-butanetetracarboxylic acid, cyclopentanetetracarboxylic dianhydride, anhydride Acid anhydrides such as phthalic acid, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate anhydride, and glycerin tris trimellitate anhydride are mentioned.

Examples of high boiling point solvents include N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl Ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, Examples include propylene carbonate and phenyl cellosolve acetate. These may be used alone or in combination of two or more.

The blending ratio of the above-mentioned acid or high-boiling solvent can be adjusted depending on the application and coating method, and is not particularly limited as long as it can be uniformly mixed into the photosensitive resin composition. For example, the blending ratio of these acids or high boiling point solvents is preferably 60% by mass or less, more preferably 40% by mass or less, based on the total amount of the photosensitive resin composition. In this case, there is an advantage that the properties of the photosensitive resin composition are not impaired.
Furthermore, the photosensitive resin composition of this embodiment may optionally include a sensitizer, a light absorber (dye), a crosslinking agent, a pigment, a filler, a flame retardant, a stabilizer, an adhesion promoter, and a peel promoting agent. It may also contain additives such as antioxidants, fragrances, imaging agents, and thermal crosslinking agents. These additives may be used alone or in combination of two or more.
The photosensitive resin composition may contain a sensitizer in order to finely adjust the sensitivity and the visibility after exposure. As the sensitizer, from the viewpoint of better resolution or solubility, anthracene skeleton, pyrene skeleton, perylene skeleton, carbazole skeleton, phenothiazine skeleton, xanthone skeleton, thioxanthone skeleton, acridine skeleton, pyrazoline skeleton, distyrylbenzene skeleton, and a compound having at least one skeleton selected from the group consisting of a distyrylpyridine skeleton.
The blending ratio of these additives is not particularly limited as long as it does not impair the properties of the photosensitive resin composition, but it is preferably 50% by mass or less based on the total amount of the photosensitive resin composition. .
Each of the above-mentioned components may be combined with any of those exemplified.

The photosensitive resin composition may be prepared by mixing and stirring in a conventional manner. Furthermore, when adding fillers and pigments to the photosensitive resin composition, they may be dispersed and mixed using a dispersing machine such as a dissolver, homogenizer, or three-roll mill. Furthermore, if necessary, it may be further filtered using a mesh, membrane filter, or the like.

The photosensitive resin composition according to this embodiment preferably does not contain an epoxy group- or vinyl group-containing compound. When a compound having a reactive functional group such as an epoxy group or a vinyl group is used, visibility of the exposed area is difficult to develop. This is thought to be because the radicals or acids generated after exposure of the photosensitive resin composition or the laminate containing the same are captured by the reactive functional groups, and the decomposition of the cationic dye (D) does not proceed. Since the photosensitive resin composition does not contain an epoxy group- or vinyl group-containing compound, visibility of exposed areas can be easily improved.

In addition, the photosensitive resin composition of the present embodiment contains component (A) in a proportion of 20 to 90% by mass, component (B) in a proportion of 1 to 45% by mass, and component (D) in a proportion of 0.001 to 5% by mass. It is preferable to contain component (A) in a proportion of 30 to 80% by mass, component (B) in a proportion of 3 to 40% by mass, and component (D) in a proportion of 0.05 to 1% by mass. It is more preferable. This results in excellent resolution, film flexibility, visibility of exposed areas, and image quality 24 hours after exposure.

<Photosensitive resin laminate>
The photosensitive resin laminate has a structure including at least a support and a photosensitive resin layer made of the above-described photosensitive resin composition. The photosensitive resin laminate may further include a protective layer, if desired. FIG. 1 is a schematic cross-sectional view of a photosensitive resin laminate according to this embodiment. In the photosensitive resin laminate 10 shown in FIG. 1, as an example, the support 2, the photosensitive resin layer 4, and the protective layer 6 are laminated in this order.
As the support 2, for example, a metal plate such as copper, a copper alloy, iron, or an iron alloy, or a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. The thickness of the support 2 is preferably 1 to 150 μm.

The photosensitive resin layer 4 shown in FIG. 1 can be formed by making the photosensitive resin composition of the present embodiment into a liquid state and applying it onto the support 2 .
When coating a photosensitive resin composition on a support, if necessary, the photosensitive resin composition is dissolved in a predetermined solvent to form a solution with a solid content of 30 to 60% by mass, and then a coating solution is used. It may also be used as Such solvents include, for example, methanol, ethanol, propanol, ethylene glycol, propylene glycol, octane, decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, toluene, xylene. , tetramethylbenzene, N,N-dimethylformamide, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol Examples include organic solvents such as monomethyl ether acetate and dipropylene glycol monomethyl ether acetate, and mixed solvents thereof.

Examples of the coating method include methods such as a roll coater, comma coater, gravure coater, air knife coater, die coater, and bar coater. Further, the solvent can be removed, for example, by heating, and in that case, the heating temperature is preferably about 70 to 150° C., and the heating time is preferably about 2 to 30 minutes.
The amount of residual organic solvent in the photosensitive resin layer thus formed is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in subsequent steps.
Further, the thickness of the photosensitive resin layer varies depending on the use, but it is preferable that the thickness after removing the solvent is about 0.5 to 100 μm.
In the support and the photosensitive resin layer, the surface of the photosensitive resin layer opposite to the support may be covered with a protective film, if necessary.

The protective layer 6 shown in FIG. 1 may be a protective film, for example, a polymer film such as polyethylene or polypropylene. Further, the protective film is preferably a low fisheye film, and the adhesive strength between the protective film and the photosensitive resin layer 4 is such that the adhesive strength between the protective film and the photosensitive resin layer 4 is such that the protective film can be easily peeled off from the photosensitive resin layer 4. It is preferable that the adhesive force is smaller than the adhesive force between the resin layer 4 and the support body 2.
Further, between the support 2 and the photosensitive resin layer 4 and/or between the photosensitive resin layer 4 and the protective film, an intermediate layer or a protective layer such as a cushion layer, adhesive layer, light absorption layer, gas barrier layer, etc. It may further include.

The photosensitive resin laminate can be, for example, in the form of a flat plate as it is, or rolled into a cylindrical shape or the like by laminating a protective film on one surface of the photosensitive resin layer (on the unprotected and exposed surface). It can be wound onto a core and stored in roll form. The winding core is not particularly limited as long as it is conventionally used, and examples include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). etc. During storage, it is preferable to roll up the support so that it is the outermost side. In addition, it is preferable to install an end separator on the end face of the photosensitive resin laminate wound into a roll from the viewpoint of end face protection, and in addition, it is preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. . Furthermore, when packaging the photosensitive resin laminate, it is preferable to wrap it in a black sheet with low moisture permeability.

<Method for forming resist pattern>
The method for forming a resist pattern is to laminate the photosensitive resin layer of the photosensitive resin laminate on a base material so as to be in close contact with the base material, irradiate the photosensitive resin layer with actinic light in an imagewise manner, and remove the exposed area by development. be. The areas not irradiated with actinic light are not soluble in alkali because the photosensitizer containing 1,2-naphthoquinonediazide groups interacts with the alkali-soluble phenol resin and acts as a dissolution inhibitor. However, in the area irradiated with actinic light, the photosensitizer containing the 1,2-naphthoquinonediazide group is photodecomposed and loses its dissolution inhibiting effect. As a result, the exposed portion irradiated with actinic light becomes alkali-soluble.

The method for laminating the photosensitive resin layer on the base material is that when the photosensitive resin laminate includes a protective film, the protective film is removed, and then the photosensitive resin layer is heated to about 70 to 130°C while the base material is laminated. Examples include a method of crimping the material using a laminator or the like at a pressure of approximately 0.1 to 1 MPa (approximately 1 to 10 kgf/cm ² ). This lamination step may be performed under reduced pressure. The surface of the base material on which the photosensitive resin layer is laminated is not particularly limited.
The photosensitive resin layer laminated on the base material in this manner is imagewise irradiated with actinic light through a negative or positive mask pattern to form exposed areas. At this time, if the support present on the photosensitive resin layer is transparent to actinic rays, the actinic rays can be irradiated through the support, and the support exhibits a light-shielding property against the actinic rays. In some cases, the photosensitive resin layer is irradiated with actinic rays after removing the support. As the active light source, conventionally known light sources such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, and xenon lamps that effectively emit ultraviolet rays, visible light, etc. can be used. Alternatively, a direct writing method such as a laser direct writing exposure method may be used.

After forming the exposed area, the photosensitive resin layer in the exposed area is removed by development, thereby forming a resist pattern. As a method for removing such exposed areas, if a support is present on the photosensitive resin layer, the support is removed using an auto peeler or the like, and wet development is performed using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. Alternatively, a method may be used in which exposed areas are removed by dry development or the like. Examples of the alkali used in wet development include weakly alkaline inorganic compounds such as sodium carbonate, potassium carbonate, and ammonia; alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide; monomethylamine. , dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, polyethyleneimine, and other weakly alkaline organic compounds; tetra Examples include methylammonium hydroxide and tetraethylammonium hydroxide. These may be used alone or in combination of two or more as an aqueous solution. The pH of the alkaline aqueous solution is preferably in the range of 9 to 13, and the temperature is adjusted depending on the developability of the photosensitive resin layer. Moreover, a surfactant, an antifoaming agent, an organic solvent, etc. may be mixed into the alkaline aqueous solution. Examples of the developing method include a dipping method, a spray method, brushing, and slapping.

Note that as a post-development treatment, the resist pattern may be cured by heating at about 60 to 250° C., if necessary.
In this way, a resist pattern is obtained. At this time, since a photosensitive resin layer that sufficiently prevents the generation of chips is used, contamination of the base material or the operating environment of the laminator by chips is sufficiently prevented, and as a result, a resist with sufficiently few defects is produced. A pattern can be formed. Furthermore, by using the photosensitive resin composition of the present invention, which has extremely good weak alkali developability, the exposed portion of the resist film is easily dissolved in a weak alkali and peeled off from the base material, making it possible to obtain a resist pattern. Become.

<Manufacturing method of printed wiring board>
The method for manufacturing a printed wiring board according to the present embodiment is performed by performing the following steps following the above-described resist pattern forming method using a copper-clad laminate or a flexible substrate as a substrate.
First, a conductor pattern is formed on the copper surface of the substrate exposed by development using a known method such as etching or plating.
Thereafter, the resist pattern is removed by exposure and developer again to obtain a desired printed wiring board.

<Lead frame manufacturing method>
The method for manufacturing a lead frame according to the present embodiment is performed by performing the following steps following the above-described method for forming a resist pattern using a metal plate such as copper, copper alloy, or iron-based alloy as a substrate.
First, the substrate exposed by development is etched to form a conductor pattern.
Thereafter, the remaining resist pattern is removed by the same method as the above-described printed wiring board manufacturing method to obtain a desired lead frame.

<Method for manufacturing semiconductor packages>
The method for manufacturing a semiconductor package according to the present embodiment is performed by performing the following steps following the above-described method for forming a resist pattern using a wafer on which circuit formation as an LSI has been completed as a substrate.
Columnar plating with copper, solder, or the like is applied to the openings exposed by development to form a conductor pattern.
Thereafter, the remaining resist pattern is removed by the same method as the above-described printed wiring board manufacturing method, and the thin metal layer in areas other than the columnar plating is removed by etching to obtain a desired semiconductor package.

<Method for manufacturing thin film transistor>
The method for manufacturing a thin film transistor (TFT) according to this embodiment is performed by performing the following steps following the above-described method for forming a resist pattern using a glass substrate on which a gate metal is formed as a substrate.
Etching or plating is performed on the resist pattern formed on the gate metal film, and the resist pattern is removed to form a gate electrode.
Thereafter, a semiconductor layer, a source electrode, a transparent electrode, a protective film, and the like are formed on the substrate having the gate electrode to obtain a desired TFT substrate. Furthermore, the semiconductor package manufacturing method described above can be used to form the semiconductor layer.

<Touch panel manufacturing method>
The positive photosensitive resin composition of this embodiment can be suitably used in a method for manufacturing a touch panel. The touch panel manufacturing method according to the present embodiment includes a step of etching a substrate on which a resist pattern is formed by the above-described resist pattern forming method. The etching process is performed on the conductor layer of the substrate, etc. using the formed resist pattern as a mask. A touch panel is manufactured by forming lead wiring and a pattern of transparent electrodes through an etching process. Hereinafter, a method for manufacturing a touch panel using the positive photosensitive resin composition of this embodiment will be described in comparison with a case where a negative photosensitive resin composition is used.

FIG. 2 is a flow diagram for explaining a method for manufacturing a touch panel using a negative photosensitive resin composition using schematic cross-sectional views (a) to (h). This method uses a metal layer 26 of a laminated base material comprising a support base material 22, a transparent conductive layer 24 provided on one surface of the support base material 22, and a metal layer 26 provided on the transparent conductive layer 24. A first step of forming a resist pattern 29 made of a cured product of a photosensitive resin composition on the top, etching the metal layer 26 and the transparent conductive layer 24, and etching the remainder of the transparent conductive layer 24 and the remainder of the metal layer 26. A second step of forming a laminated pattern (24+26 in FIG. 2(d)) consisting of a transparent electrode consisting of the remaining part of the transparent conductive layer 24 and the remaining part of the metal layer by removing the metal layer from a part of the laminated pattern. and a third step of forming a metal wiring consisting of.

In the first step, first, as shown in FIG. A negative photosensitive layer 28 is laminated on the metal layer 26 of the laminated base material including the metal layer 26 using a negative photosensitive resin composition. The photosensitive layer 28 may include a support on the side opposite to the metal layer 26.

Examples of the metal layer 26 include metal layers containing copper, an alloy of copper and nickel, a molybdenum-aluminum-molybdenum laminate, an alloy of silver, palladium, and copper, and the like. The transparent conductive layer 24 contains indium tin oxide (ITO).
Next, a part of the photosensitive layer 28 is cured by irradiation with actinic light to form a cured product area, and the area other than the cured product area of the photosensitive layer 28 is removed from the laminated base material. As a result, a resist pattern 29 is formed on the laminated base material, as shown in FIG. 2(b).

In the second step, the metal layer 26 and transparent conductive layer 24 in areas not masked by the resist pattern 29 are removed from the support base material 22 by etching.

The etching method is appropriately selected depending on the layer to be removed. For example, examples of the etching solution for removing the metal layer include a cupric chloride solution, a ferric chloride solution, a phosphoric acid solution, and the like. Further, as an etching solution for removing the transparent conductive layer, oxalic acid, hydrochloric acid, aqua regia, etc. are used.

FIG. 2C is a diagram showing the state after the etching process, in which a laminate consisting of the remaining portion of the metal layer 26, the remaining portion of the transparent conductive layer 24, and the remaining portion of the photosensitive layer 28 is formed on the supporting base material 22. In the method for manufacturing a touch panel using a negative photosensitive resin composition, the resist pattern 29 is removed from this laminate.
For removing the resist pattern 29, for example, an aqueous solution that is more alkaline than the alkaline aqueous solution used in the developing step included in the above-described resist pattern forming method can be used. As this strong alkaline aqueous solution, a 1 to 10% by mass aqueous sodium hydroxide solution, a 1 to 10% by mass aqueous potassium hydroxide solution, etc. are used. Among them, it is preferable to use a 1 to 10% by mass aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, and it is more preferable to use a 1 to 5% by mass aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. Examples of methods for removing the resist pattern include a dipping method and a spray method, and these methods may be used alone or in combination.

FIG. 2D is a diagram showing the resist pattern 29 after it has been peeled off, and a laminated pattern consisting of the remainder of the metal layer 26 and the remainder of the transparent conductive layer 24 is formed on the support base material 22.
In the third step, from this laminated pattern, a portion of the metal layer 26 other than a portion for forming the metal wiring is removed, and a metal wiring consisting of the remainder of the metal layer 26 and a transparent electrode consisting of the remainder of the transparent conductive layer 24 are formed. form.

In the method using a negative photosensitive resin composition, if it is desired to partially expose the transparent conductive layer 24 by multi-step etching, it is necessary to form the photosensitive layer again.

That is, in the third step, first, a photosensitive layer 30 is formed using a negative photosensitive resin composition on the laminated base material that has undergone the second step (FIG. 2(e)), and then the photosensitive layer 30 is formed using a negative photosensitive resin composition (FIG. 2(e)). After 30 exposure and development steps, a resist pattern 31 made of the cured photosensitive layer 30 is formed (FIG. 2(f)).
Next, by etching, the metal layer 26 is removed from the portions of the laminated pattern where the resist pattern 31 is not formed. At this time, the etching solution may be the same as the etching solution for removing the metal layer described above.

FIG. 2(g) is a diagram showing the state after the etching process, in which a transparent electrode consisting of the remainder of the transparent conductive layer 24 is formed on the supporting base material 22, and a metal layer 26 and a resist are formed on a part of the transparent electrode. A laminate consisting of patterns 31 is formed. By removing the resist pattern 31 from this laminate, as shown in FIG. wiring is formed.

On the other hand, in the method using the positive photosensitive resin composition according to the present embodiment, when it is desired to partially expose the transparent conductive layer 24 by multi-step etching, the step of forming the photosensitive layer again is not necessary. When a photosensitive layer is formed using a positive photosensitive resin composition, the exposed area can be removed with an alkaline aqueous solution and the unexposed area remains as a film. A pattern can be formed.

FIG. 3 is a flow diagram for explaining a method for manufacturing a touch panel using a positive photosensitive resin composition using schematic cross-sectional views (a) to (f).

In the first step, first, as shown in FIG. A positive photosensitive layer 40 is laminated on the metal layer 26 of a laminated base material including the metal layer 26 using a positive photosensitive resin composition. The photosensitive layer 40 may include a support on the side opposite to the metal layer 26.
Next, a part of the photosensitive layer 40 is irradiated with actinic rays to form an exposed portion, and then the photosensitive layer in the exposed portion is removed from the laminated base material by development. As a result, as shown in FIG. 3(b), a resist pattern 40a consisting of the unexposed portion of the photosensitive layer 40 is formed on the laminated base material.

In the second step, the metal layer 26 and the transparent conductive layer 24 in areas not masked by the resist pattern 40a are removed from the support base material 22 by etching.
The etching method is appropriately selected depending on the layer to be removed. For example, examples of the etching solution for removing the metal layer include ammonium persulfate solution, sodium persulfate solution, cupric chloride solution, ferric chloride solution, phosphoric acid solution, and the like. Further, as an etching solution for removing the transparent conductive layer, oxalic acid, hydrochloric acid, aqua regia, etc. are used.
FIG. 3C is a diagram showing the state after the etching process, in which a laminate consisting of the remaining portion of the metal layer 26, the remaining portion of the transparent conductive layer 24, and the resist pattern 40a is formed on the supporting base material 22.

Next, in the third step, after irradiating a part of the resist pattern 40a with actinic rays to form an exposed area, the photosensitive layer in the exposed area is removed from the laminated base material by development. As a result, as shown in FIG. 3(d), a resist pattern consisting of the resist pattern 40b of the unexposed portion is formed on the laminated base material.

Next, by etching, the metal layer 26 is removed from the portions of the laminated pattern where the resist pattern 40b is not formed. At this time, the etching solution may be the same as the etching solution for removing the metal layer described above.
FIG. 3E is a diagram showing the state after the etching process, in which a transparent electrode consisting of the remainder of the transparent conductive layer 24 is formed on the supporting base material 22, and a metal layer 26 and a resist are formed on a part of the transparent electrode. A laminate consisting of the pattern 40b is formed. By removing the resist pattern 40b from this laminate, as shown in FIG. wiring is formed.
In this way, in the touch panel manufacturing method according to the present embodiment, it is possible to omit the steps corresponding to (d) and (e) in FIG. 2 .
Although the transparent conductive layer 24 contains indium tin oxide (ITO), the positive photosensitive resin composition according to this embodiment can be used in the manufacture of a touch panel in which the transparent conductive layer 24 is changed from ITO to a metal mesh. It can also be suitably used in methods.

Moreover, FIG. 4 is a top view of the touch panel 100 obtained using the photosensitive resin composition according to one embodiment of the present invention. In the touch panel 100, X electrodes 52 and Y electrodes 54, which are transparent electrodes, are arranged in parallel alternately, and the X electrodes 52 provided in the same row in the longitudinal direction are connected to each other by one extraction wiring 56, and The Y electrodes 54 provided in the same row in the width direction are connected to each other by one lead wire 57.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
[Examples 1 to 6, Comparative Examples 1 to 6]
<1. Preparation of photosensitive resin composition>
The compounds shown in Table 1 were mixed to prepare a photosensitive resin composition. The numerical value of each component in Table 1 is the solid content.

The symbols in Table 1 are as shown below.
Component A-1: Cresol novolak resin (weight average molecular weight 10,000, m form: p form = 6:4)
Component A-2: Cresol novolac resin (weight average molecular weight 5,000, m form: p form = 6:4)
Component A-3: Cresol novolak resin (weight average molecular weight 9,750, m form: p form = 5:5)
Component A-4: Cresol novolak resin (weight average molecular weight 6,450, m form: p form = 4:6)

Component C-1: Biphenylaralkyl resin (OH equivalent 200g/eq)

Component B-1: 1,2-naphthoquinonediazide-4-sulfonic acid of 4,4'-(1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene)bisphenol) Mixtures of mono-, di- or triesters ()
Component B-2: 1,2-naphthoquinonediazide-4-sulfonic acid of 4,4'-(1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene)bisphenol) Mixtures of mono-, di- or triesters ()
Component B-3: 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid mono-, di- or triester of 2,3,4-trihydroxybenzophenone ()
Component B-4: 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid mono, di, tri or tetraester of 2,3,4,4'-tetrahydroxybenzophenone ()

Component D-1: [4[4(diethylamino)α[4-(ethylamino)-1-naphthyl]benzylidene]cyclohex-2,5-dien-1-ylidene]diethylammonium chloride Component D-2: Diamond Green Component D-3: 1,4-bis(p-toluidino)anthraquinone

Although not shown in Table 1, the following materials were also prepared:
Component F-1: Novolak epoxy acrylate Component F-2: Hydrogenated bisphenol A diglycidyl ether Component F-3: Bisphenol A PO 2 mol adduct diglycidyl ether

<2. Production of photosensitive resin laminate>
Solvent acetone was added to the photosensitive resin composition having the composition shown in Table 1 until the solid content was 56% by mass, stirred and mixed well, and the solution of the photosensitive resin composition was applied to a polyethylene terephthalate film (Lintech PET-25X; a 25 μm polyethylene terephthalate film (one surface of which has been easily peeled) is coated uniformly using a bar coater and dried for 5 minutes in a dryer at 95°C to form a 5 μm thick photosensitive resin layer. (dry film) was formed. Next, a 33 μm thick polyethylene film (GF-858 manufactured by Tamapoly Co., Ltd.) was laminated onto the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.

<3. Fabrication of evaluation board>
laminate:
While peeling off the polyethylene film of the photosensitive resin laminate, it was laminated onto a PET substrate with a copper layer using a hot roll laminator (AL-700, manufactured by Asahi Kasei Electronics Corporation) at a roll temperature of 105°C. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m/min.

exposure:
The support was peeled off, and the evaluation substrate was exposed to light using a chrome glass photomask using an exposure machine (parallel light exposure machine (manufactured by Oak Seisakusho Co., Ltd., HMW-801)) equipped with an ultra-high pressure mercury lamp.
developing:
The obtained evaluation board was developed by a dipping method using a 1.0% by mass aqueous potassium hydroxide solution as an alkaline developer at a temperature of 30° C. for 60 seconds. Thereafter, the evaluation board was washed with pure water by dipping for about 10 seconds at room temperature and dried with a compressed air gun.

<4. Evaluation>

Flexibility evaluation of photosensitive resin film (JIS K5600-5-1 bending resistance test):
A photosensitive resin laminate was laminated on a flexible substrate (NIKAFLEX F-30VC1 manufactured by Nikkan Kogyo), and the support was peeled off from the photosensitive resin laminate, and then exposed to light at 400 mJ/cm ² using the above exposure machine, and then exposed to light using the above method. After development, the flexibility was tested according to the bending resistance item of JIS K5600-5-1. Thereafter, the coating film after the test was observed under a microscope, and the smallest cylindrical shape (mmφ) without cracks or cracks in the coating film was evaluated.
◎: Minimum cylinder diameter is within 10mmΦ ○: Minimum cylinder diameter is within 15mmΦ ×: Minimum cylinder diameter exceeds 15mmΦ

Resolution evaluation:
The test piece was exposed to light at an exposure dose of 250 mJ/cm ² using a chrome glass photomask having a line pattern with a width ratio of 1:1 between exposed and unexposed areas. Thereafter, development was performed using the above-mentioned development method, and the minimum mask width at which resist lines were normally formed was taken as the value of resolution, and the resolution was ranked as follows. In addition, the minimum mask width that was normally formed without collapse of the cured resist pattern or close contact between the cured resists was evaluated.
◎: Resolution value is 5 μm or less;
○: Resolution value is more than 5 μm and less than 10 μm;
×: Resolution value exceeds 10 μm.

Visibility evaluation after exposure:
The test piece was exposed to light at an exposure dose of 250 mJ/cm ² using a chrome glass photomask having a line pattern with a width ratio of 1:1 between exposed and unexposed areas. One hour after exposure, the substrate was visually observed and evaluated.
〇: Line pattern can be visually identified ×: Line pattern cannot be visually identified

Image quality evaluation after 24 hours after exposure:
The test piece was exposed to light at an exposure dose of 250 mJ/cm ² using a chrome glass photomask having a line pattern with a width ratio of 1:1 between exposed and unexposed areas. The exposed test piece was stored at 25° C. and 50% for 24 hours. Thereafter, development was performed using the above-mentioned development method, and the minimum mask width at which resist lines were normally formed was taken as the value of resolution, and the resolution was ranked as follows. In addition, the minimum mask width that was normally formed without collapse of the cured resist pattern or close contact between the cured resists was evaluated.
◎: Dimensional change rate of 10 μm line pattern before and after 24 hours is within ±5% ○: Dimensional change rate of 10 μm line pattern before and after 24 hours is within ±10% ×: Dimensional change rate of 10 μm line pattern before and after 24 hours More than ±10%

<5. Evaluation results>
The evaluation results of Examples and Comparative Examples are shown in Table 1.
As can be seen from Table 1, the examples containing all of the components (A), (B), and (D) according to the present embodiment have poor film flexibility, resolution, visibility of the exposed area, and 24 hours after exposure. It was excellent in both post-imaging properties.

From the comparison of Comparative Examples 1 to 6, when only component (C-1) is used as a resin without using components (A-1) to (A-4) as in Comparative Example 1, component (C -1) cannot be resolved because it is alkali-insoluble, whereas component (D) is not used as in Comparative Example 2, or the compound containing a quinonediazide group is not contained as in Comparative Example 3, or It can be seen that when only a benzophenone photosensitizer is contained as in Comparative Examples 5 and 6, the visibility of the exposed area deteriorates or resolution cannot be achieved.

Although not shown in Table 1, if a compound (components F-1 to F-3) having a reactive group such as a vinyl group or an epoxy group is present in the positive photosensitive resin composition, It was found that visibility of exposed areas did not develop. This is thought to be because the radicals or acids generated after exposure are captured by the reactive functional groups and the decomposition of the dye does not proceed.

Further, a comparison between Examples 1 to 6 and Comparative Example 4 suggests that the visibility of the exposed area is influenced by the structure of the dye.

The present invention is applicable to the manufacturing of dry film resists, printed wiring boards, lead frames for mounting IC chips, metal foil precision processing such as metal mask manufacturing, manufacturing of packages such as BGA and CSP, and manufacturing of tape substrates such as COF or TAB. , the production of semiconductor bumps, the production of ITO electrodes or address electrodes, the production of partitions for flat panel displays such as electromagnetic wave shields, and especially the production method of touch panels.

2 Support 4 Photosensitive resin layer 6 Protective layer 10 Photosensitive resin laminate 22 Support base material 24 Transparent conductive layer 26 Metal layer 28 Photosensitive layer 29 Resist pattern 30 Photosensitive layer 31 Resist pattern 40 Photosensitive layer 40a, 40b Resist pattern 52 Transparent Electrode (X electrode)
54 Transparent electrode (Y electrode)
56, 57 Output wiring 100 Touch panel

Claims (13)

A photosensitive resin laminate comprising a support and a photosensitive resin layer containing a positive photosensitive resin composition,
the support is a polymer film;
The positive photosensitive resin composition includes:
(A) an alkali-soluble resin having a phenolic hydroxyl group;
(B) a quinonediazide group-containing compound;
(C) a phenol aralkyl resin;
(D) a cationic dye;
Contains
The phenol aralkyl resin (C) has the following general formula (1):
{In general formula (1), each X independently represents general formula (2):
Or general formula (3):
Or general formula (4):
(In the formula, R 3 ^to R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms), and R ¹ and R ² represent a divalent group containing an aromatic ring. , each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and q represents an integer of 1 to 100}
It is a resin represented by, and
The photosensitive resin laminate is a photosensitive resin laminate for producing a resist pattern . The cationic dye (D) has the following general formula (D1):
{In the formula, A ¹ is an unsubstituted or substituted monovalent aromatic group, A ² is an unsubstituted or substituted amino group, and A ³ and A ⁴ are each independently a hydrogen atom, or an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, p is an integer of 0 to 5, and CA ^- is a counter anion}
The photosensitive resin laminate according to claim 1, which is a cationic dye represented by: The photosensitive resin laminate according to claim 1 or 2 , wherein the alkali-soluble resin (A) is a novolak resin. The photosensitive resin laminate according to claim 3 , wherein the alkali-soluble resin (A) is a cresol novolak resin. The photosensitive resin laminate according to any one of claims 1 to 4 , wherein the positive photosensitive resin composition does not contain an epoxy group- or vinyl group-containing compound. Claims 1 to 3, comprising 20 to 90% by mass of the alkali-soluble resin (A), 1 to 45% by mass of the quinonediazide group-containing compound (B), and 0.001 to 5% by mass of the cationic dye (D). 5. The photosensitive resin laminate according to any one of item 5 . A laminating step of laminating the photosensitive resin layer side of the photosensitive resin laminate according to any one of claims 1 to 6 on a substrate;
an exposure step of exposing the photosensitive resin layer; and a developing step of removing the exposed photosensitive resin layer;
A method for manufacturing a resist pattern including: 8. The resist pattern manufacturing method according to claim 7 , wherein in the exposure step, the photosensitive resin layer is directly drawn and exposed. A method for manufacturing a printed wiring board, comprising the step of etching or plating a substrate on which a resist pattern is formed by the method for manufacturing a resist pattern according to claim 7 or 8 . A method for manufacturing a lead frame, comprising the step of etching a substrate on which a resist pattern is formed by the method for manufacturing a resist pattern according to claim 7 or 8 . A method for manufacturing a semiconductor pattern, comprising the step of etching or plating a substrate on which a resist pattern is formed by the method for manufacturing a resist pattern according to claim 7 or 8 . A method for manufacturing a thin film transistor, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method for manufacturing a resist pattern according to claim 7 or 8 . A method for manufacturing a touch panel, comprising the step of etching a substrate on which a resist pattern is formed by the method for manufacturing a resist pattern according to claim 7 or 8 .

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