JP2020020978A - Photosensitive resin composition and photosensitive resin laminate including the same - Google Patents

Abstract

To provide a photosensitive resin composition that allows patterning; is flexible when formed as a dry film; and sufficiently suppresses the scattering of a resin when the film is handled, and provide a photosensitive resin laminate including the same.SOLUTION: A photosensitive resin composition has (A) an alkali soluble phenolic resin; (B) a quinonediazide group -containing compound; and (D) a compound containing at least one structure selected from the group consisting of a phenol novolac type structure, cresol novolac type structure, xylenol novolac type structure and bisphenol novolac type structure, and at least one non-phenolic hydroxyl group.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photosensitive resin composition and the like, and more particularly, to the manufacture of a printed wiring board, the manufacture of a lead frame for mounting an IC chip (hereinafter, referred to as a lead frame), the metal foil precision processing such as the manufacture of a metal mask, and the liquid crystal display. Manufacturing of semiconductor packages such as thin film transistors such as elements, BGA (ball grid array), and CSP (chip size package); manufacturing of members such as indium tin oxide (ITO) electrodes, address electrodes, or electromagnetic wave shields in the field of flat panel displays; And a photosensitive resin composition developable with an alkaline aqueous solution in the production of a resist pattern suitable as a protective mask member when processing a substrate by a sandblasting method, a photosensitive resin laminate using the same, and uses thereof .

As an image forming method used for patterning of semiconductor integrated circuits, liquid crystal display elements, printed wiring boards, etc., a photosensitive resin composition containing a novolak type phenol resin and a 1,2-naphthoquinonediazide compound was used as a raw material. A method using a positive photoresist is known. When a positive photoresist is formed through application of the photosensitive resin composition, the applied thickness is generally 0.5 to several μm. When this positive photoresist is used, an image pattern is formed over a wide range of dimensions. The dimensional range is wide, for example, from a sub-half micron region of about 0.3 μm to a considerably large dimensional width of about several tens to several hundreds μm. Processing is possible.
In the field of liquid crystal display (LCD) and the like, the line width of an image is becoming narrower with the development of thin film transistor (TFT) liquid crystal and super-twisted nematic (STN) liquid crystal, and the tendency for further miniaturization is increasing. For example, a device using a conventional twisted nematic (TN) or STN liquid crystal has an image design dimension of about 200 μm to several hundred μm, but recently, the minimum design dimension of an image is 100 μm due to the development of a new technology. It is as follows. Further, in a TFT display element having good responsiveness or image quality, the image design dimension has been improved to a level of several μm.

Properties expected of a photoresist material include not only maintaining the above-mentioned fine processing capability but also coping with an increase in area. That is, it is compatible with a liquid crystal display whose substrate has recently become larger and a plasma display panel (PDP) which has a large screen oriented from the beginning. In these substrates, it is becoming an important technique to further improve the in-plane uniformity of the film thickness. In addition, common problems 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 uniformity of the film thickness in the plane of the photoresist and achieve the saving of the liquid of the photoresist raw material, the study of the coating method has been continued. As a result, a new slit coating has been developed as an alternative to the conventional spin coating. These technologies are gaining promise for substrates with a size of 550 mm × 680 mm or less. However, when aiming for an even larger substrate, it is expected that these techniques will be difficult to apply.

In the field of printed wiring boards, a so-called negative dry film photoresist is widely used. A negative dry film photoresist is a polyester film having a thickness of 15 to 25 μm as a support, on which a negative photosensitive resin composition, usually having a thickness of 3 to 100 μm, is applied. A polyolefin film having a thickness of ４０40 μm is laminated as a protective film. The technology of the negative type dry film photoresist has been adopted for a printed wiring board having a width of about 600 mm. However, when used in the field of printed wiring boards, the resolution required for a negative-type dry film photoresist is at most about 10 to 300 μm.
The production of a printed wiring board using a negative type dry film photoresist will be briefly described. First, if there is a protective film in the negative dry film photoresist, remove the protective film, laminate it so that the negative photosensitive resin composition is in contact with the substrate for producing a printed wiring board, and pass active light through the support. Exposure is performed to cure the photosensitive resin composition. Then, generally, the unexposed photosensitive resin composition is dispersed and removed using a weak alkaline aqueous solution represented by an aqueous solution of sodium carbonate having a concentration of 1% by mass and developed. Thereafter, the copper on the substrate is etched with an aqueous cupric chloride solution, and all the cured photosensitive resin composition is peeled off with an aqueous solution of caustic soda or potassium hydroxide having a concentration of 2 to 3% by mass.

However, as described above, the image processing technology required in the manufacture of TFTs for LCDs has, for example, about 2 to 10 μm, which is much higher in resolution than in the field of printed wiring boards. In addition, there is also a need for techniques of metal ion-free development, stripping with an organic stripper, and etching of a thin metal film such as ITO or Ta or Al and an inorganic thin film such as SiN _x or ITO. In order to cope with these, the photoresist has a thickness of several μm, improves the adhesion to various sputtered metal thin films or inorganic thin films, further improves the uniformity of the thickness, and has unevenness of about 1 μm. There is a demand for an improvement in the ability to follow a TFT preceding pattern and an increase in the speed of lamination on a substrate having a width of 1 to 2 m, which completely exceeds the limitations of conventional dry film photoresists. That is, in order to meet the demands in the LCD and PDP industries, there is a limit in a method of directly applying a conventional positive type liquid resist to a substrate or a method of transferring a negative type dry film resist to a substrate. In order to solve such problems, it is conceivable to employ a positive dry film resist, but there is still no practical one.

  As a conventional positive photoresist material, for example, Patent Documents 1 and 2 disclose a resin composition containing a phenol novolak resin as a main component and 1,2-naphthoquinonediazidosulfonic acid ester as a photosensitive component. There is. However, when this is applied to dry film photoresist as it is, it cannot be applied thickly on the support due to poor coatability, and even if it can be applied thinly, the film quality is brittle and flexible. Due to lack of properties, it is difficult to make it into a roll-shaped product. Patent Document 3 also discloses that a compound obtained by reacting a drying oil with a phenol resin is introduced to soften a film. However, at present, positive dry film photoresists using these materials have not been put to practical use. The conventional manufacturing method and problems of the positive type dry film photoresist roll 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 through application of a positive photosensitive resin composition to a support or the like. Then, the roll is cut by a slit so as to have a desired film width. In addition, in order to laminate the photosensitive resin composition on the substrate on which the image pattern is formed, usually, a dry film photoresist is drawn from the roll-shaped product and thermally transferred while being pressed onto the substrate using a laminator. . During or after the lamination, the dry film photoresist is cut to a predetermined length in the longitudinal direction of the substrate.

JP-A-06-027675 JP 2000-105466 A JP 2007-316577 A

When a dry film photoresist having a brittle film-type positive photosensitive resin composition is used, chips (hereinafter simply referred to as chips) of the positive photosensitive resin composition are generated at the time of the slit. Problem occurs. Also, when the dry film photoresist is cut to a predetermined length in the longitudinal direction of the substrate during lamination, chips are easily 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 tend to occur in the image pattern.
The present invention has been made in view of the above circumstances, is capable of pattern formation, and when formed as a dry film, the photosensitive resin composition is flexible, and when the film is handled, the resin It is an object of the present invention to provide a photosensitive resin composition in which the scattering of water is sufficiently suppressed, and a photosensitive resin laminate using the same.

｛式中、Ａは、非フェノール性水酸基を有する有機基を表し、Ｓは、アルキル基、ハロゲン、又はアリーレン基を有する有機基を表し、ｔは、０〜２の整数であり、かつｌは、２以上の整数である。Ｓは重合性不飽和基を有していても良い。｝
で表される繰り返し単位を含む、項目１又は２に記載の感光性樹脂組成物。
［４］
前記（Ｄ）成分が、下記一般式（Ｉ）：

｛式中、Ｒ^１及びＲ^２は、水素、メチル基、ハロゲン原子又は下記一般式（ＩＩ）：

（式中、Ｒ^１、Ｒ^２及びＲ^３は、一般式（Ｉ）において定義されており、かつＲ^５は、水素又はメチル基を表す。）
で表される１価の基を表し、Ｒ^３は、メタクリロイル基、アクリロイル基、又はＣ_１〜Ｃ_２４の飽和若しくは不飽和の脂肪酸の残基を表し、Ｒ^４は、多塩基酸無水物に由来するカルボキシル基を有する原子団を表し、かつｍ及びｎは、０又は正の整数である。｝
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、項目１〜３のいずれか１項に記載の感光性樹脂組成物。
［５］
前記（Ｂ）成分として、下記一般式（ＩＩＩ）：

｛式中、Ｒ_１〜Ｒ_６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_７及びＲ_８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_９〜Ｒ_１１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。｝
で表される化合物のキノンジアジドスルホン酸エステルを含有する、項目１〜４のいずれか１項に記載の感光性樹脂組成物。
［６］
前記（Ｂ）成分として、下記一般式（ＩＶ）：

｛式中、Ｒ_１〜Ｒ_６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。｝
で表される化合物のキノンジアジドスルホン酸エステルを含有する、項目１〜５のいずれか１項に記載の感光性樹脂組成物。
［７］
支持体と、項目１〜６のいずれか１項に記載の感光性樹脂組成物から成る感光性樹脂層とを含む感光性樹脂積層体。
［８］
項目７に記載の感光性樹脂積層体がロール状であるレジストロール。
［９］
項目７に記載の感光性樹脂積層体の感光性樹脂層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形成方法。
［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形成方法。
［１１］
項目９又は１０に記載のレジストパターンの形成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形成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形成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形成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形成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。 Means for Solving the Problems The present inventors have studied to solve the above problems, and 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 phenolic resin;
(B) a quinonediazide group-containing compound; and (D) at least one structure selected from the group consisting of a phenol novolak structure, a cresol novolak structure, a xylenol novolak structure, and a bisphenol novolak structure, and at least one non-phenol A compound having a hydroxyl group;
A photosensitive resin composition containing:
[2]
Item 2. The photosensitive resin composition according to Item 1, comprising 20 to 90% by mass of the component (A), 1 to 45% by mass of the component (B), and 1 to 40% by mass of the component (D).
[3]
The component (D) has the following general formula (P):

In the formula, A represents an organic group having a non-phenolic hydroxyl group, S represents an organic group having an alkyl group, a halogen, or an arylene group, t is an integer of 0 to 2, and l is Is an integer of 2 or more. S may have a polymerizable unsaturated group. ｝
3. The photosensitive resin composition according to item 1 or 2, comprising a repeating unit represented by the formula:
[4]
The component (D) has the following general formula (I):

In the formula, R ¹ and R ² represent hydrogen, a methyl group, a halogen atom or the following general formula (II):

(Wherein R ¹ , R ² and R ³ are defined in the general formula (I), and R ⁵ represents hydrogen or a methyl group.)
R ³ represents a methacryloyl group, an acryloyl group, or a residue of a C _{1 to} C ₂₄ saturated or unsaturated fatty acid, and R ⁴ represents a polybasic acid anhydride. Represents an atomic group having a carboxyl group derived therefrom, and m and n are 0 or a positive integer. ｝
4. The photosensitive resin composition according to any one of items 1 to 3, which is at least one selected from the group consisting of compounds represented by
[5]
As the component (B), the following general formula (III):

In the formula, R _{1 to} R ₆ are each independently hydrogen, halogen, a C _{1 to} C ₄ alkyl group, alkenyl group or hydroxyl group, and R ₇ and R ₈ are each independently hydrogen, halogen or C ₁ -C ₄ alkyl and R ₉ -R ₁₁ are each independently hydrogen or C ₁ -C ₄ alkyl. ｝
The photosensitive resin composition according to any one of items 1 to 4, comprising a quinonediazidesulfonic acid ester of a compound represented by the formula:
[6]
As the component (B), the following general formula (IV):

In the formula, R _{1 to} R ₆ are each independently hydrogen, halogen, a C _{1 to} C ₄ alkyl group, alkenyl group or hydroxyl group. ｝
6. The photosensitive resin composition according to any one of items 1 to 5, comprising a quinonediazidesulfonic acid ester of a compound represented by the formula:
[7]
7. A photosensitive resin laminate comprising a support and a photosensitive resin layer comprising the photosensitive resin composition according to any one of items 1 to 6.
[8]
Item 8. A resist roll wherein the photosensitive resin laminate according to Item 7 is in a roll shape.
[9]
A laminating step of laminating the photosensitive resin layer of the photosensitive resin laminate according to item 7 on a substrate;
An exposing step of exposing the photosensitive resin layer; and a developing step of removing the exposed photosensitive resin layer;
A method for forming a resist pattern comprising:
[10]
Item 10. The method for forming a resist pattern according to Item 9, wherein, in the exposing step, the photosensitive resin layer is directly drawn and exposed.
[11]
A method for manufacturing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern has been formed by the method for forming a resist pattern according to Item 9 or 10.
[12]
A method for manufacturing a lead frame, comprising: etching a substrate on which a resist pattern has been formed by the method for forming a resist pattern according to item 9 or 10.
[13]
A method for producing a semiconductor pattern, comprising a step of etching or plating a substrate on which a resist pattern has been formed by the method for forming 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 has been formed by the method for forming a resist pattern according to Item 9 or 10.
[15]
A method for manufacturing a touch panel, comprising a step of etching a substrate on which a resist pattern has been formed by the method for forming a resist pattern according to Item 9 or 10.

  According to the present invention, a pattern can be formed using a photosensitive resin composition, and the photosensitive resin composition is flexible when formed as a dry film, and the scattering of resin is suppressed when the film is handled. Can be done.

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

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

<Photosensitive resin composition>
The photosensitive resin composition according to the present embodiment includes the following components:
(A) an alkali-soluble phenolic resin;
(B) a quinonediazide group-containing compound; and (D) at least one structure selected from the group consisting of a phenol novolak structure, a cresol novolak structure, a xylenol novolak structure, and a bisphenol novolak structure, and at least one non-phenol A compound having a hydroxyl group;
including. The photosensitive resin composition includes the components (A), (B) and (D), thereby enabling pattern formation, being flexible at the time of forming a dry film, and suppressing scattering of the resin at the time of handling the film. be able to.

If desired, the photosensitive resin composition according to this embodiment may further comprise the following components in addition to the components (A), (B), and (D):
(C) an alkali-soluble resin having a group derived from an aromatic hydroxy compound in a side chain;
A plasticizer other than the component (D);
Surfactant;
Adhesive aid;
acid;
Solvents, such as high-boiling solvents; and / or other additives, such as sensitizers, light absorbers (dyes), crosslinkers, pigments, fillers, flame retardants, stabilizers, adhesion promoters, peeling accelerators Agents, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc .;
Can be included.

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

(A) Alkali-soluble phenol resin (A) The alkali-soluble phenol resin is obtained, for example, by a condensation polymerization reaction using a phenol compound and an aldehyde and / or ketone as raw materials. In this specification, the component (A) does not include the novolak corresponding to the compound of the component (D).

  Examples of the phenol compound include phenol, cresol, and 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 α Or a naphthol compound such as β-naphthol, a hydroxyalkylphenol such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol, p-hydroxyphenyl-4-butanol; a hydroxyalkylcresol such as hydroxyethylcresol; bisphenol An alcoholic hydroxyl group-containing phenol compound such as bisphenol monopropylene oxide adduct; and p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, and p-hydroxycinnamic acid And carboxyl group-containing phenol compounds such as hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid and diphenolic acid.

The above-mentioned phenol compounds are used alone or in combination of two or more.
Examples of the aldehyde and / or ketone include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone, and glyceraldehyde. . Examples of the aldehyde and / or ketone include glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formyl acetate, 2-formylpropionic acid, methyl 2-formylpropionate, and pyruvate. , Repulinic acid, 4-acetylbutyric acid, acetonedicarboxylic acid, and 3,3'-4,4'-benzophenonetetracarboxylic acid. Further, a precursor of formaldehyde such as paraformaldehyde and trioxane may be used. These may be used alone or in combination of two or more.

It is preferable to use an acidic catalyst for the condensation polymerization reaction. By using this acidic catalyst, a novolak-type phenol resin is easily obtained, and the 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. The acidic catalyst may be used alone or in combination of two or more. The conditions for synthesizing the alkali-soluble phenol resin may be known conditions.
The content of the aldehyde and / or ketone in the raw material for obtaining the alkali-soluble phenol resin is preferably 0.7 to 1 mol based on 1 mol of the phenol compound. In this case, the polycondensation reaction can proceed more quickly.
Further, (A) the alkali-soluble phenol resin may be a condensation polymerization 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 for the condensation polymerization is preferably less than 0.5.

(A) The weight average molecular weight in terms of polystyrene of the alkali-soluble phenolic resin by gel permeation chromatography is preferably from 300 to 100,000 from the viewpoint of improving the coatability and suppressing the decrease in developability. More preferably, it is 2,000 to 20,000. The weight average molecular weight is preferably 300 or more from the viewpoint of coatability, and is preferably 100,000 or less from the viewpoint of developability.
When the weight average molecular weight of the phenol resin is smaller than a predetermined value (for example, 300), the phenol resin is polymerized using a chain extender, and the molecular weight is increased so as to be in the range of the weight average molecular weight. May be. Examples of the chain extender include a diepoxy compound or a dioxazoline compound capable of reacting with a carboxyl group, and a diisocyanate compound capable of reacting with a hydroxyl group.

(A) The alkali-soluble phenol resin is used alone or in combination of two or more. When two or more kinds are used in combination, examples of the alkali-soluble phenolic resin include two or more kinds of alkali-soluble phenolic resins obtained from different kinds of monomers, and two or more kinds of alkali-soluble phenolic resins having mutually different weight average molecular weights. Phenolic resins, and two or more alkali-soluble phenolic resins having different degrees of dispersion from each other.
(A) The blending ratio of the alkali-soluble phenol resin in the photosensitive resin composition is preferably 20 to 90% by mass, and 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, particularly preferably 40 to 70% by mass. The compounding ratio is preferably 20% by mass or more from the viewpoint of improving the pattern formability, and is preferably 90% by mass or less from the viewpoint of preventing the brittleness of the resist film.

(B) Quinonediazide Group-Containing Compound The (B) quinonediazide group-containing compound can have, for example, a 1,2-quinonediazide group, a 1,2-naphthoquinonediazide group, or the like as a quinonediazide group. The component (B) is obtained, for example, by reacting an organic compound having a hydroxyl group or an amino group (hereinafter simply referred to as “organic compound”) with a 1,2-naphthoquinonediazide compound having a sulfo group and / or a sulfonyl chloride group. Compound. In this case, a hydroxyl group or an amino group of the organic compound is bonded to a sulfo group or a sulfonyl chloride group of the 1,2-quinonediazide compound. In addition, at least one bond may be present in the molecule of the obtained 1,2-quinonediazide compound.
Examples of the 1,2-quinonediazide compound having a sulfo group and / or a sulfonyl chloride group include 1,2-naphthoquinone-2-diazide-4-sulfonic acid and 1,2-naphthoquinone-2-diazide-5-sulfone. Acids, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. Among the 1,2-quinonediazide compounds having a sulfo group and / or a 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-diazide-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 dissolved in a solvent, so that the reaction efficiency with an organic compound can be increased.

  Examples of the organic compound include polyhydroxybenzophenones, bis [(poly) hydroxyphenyl] alkanes, tris (hydroxyphenyl) methanes or methyl-substituted products thereof, bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes, Methyl substituted product thereof, 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, hydroxystyrene homopolymer or copolymer with a monomer 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 ′, 5 ', 6-hexahydroxybenzophenone and 2,3,3', 4,4 ', 5'-hexahydroxybenzophene Non, and the like. 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 and 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. It is. These are used alone or in combination of two or more.

  Tris (hydroxyphenyl) methanes or methyl-substituted products thereof include, for example, 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 Is mentioned. These may be used alone or in combination of two or more.

  Examples of bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methane or a methyl-substituted product thereof include bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane and 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- (Droxyphenyl) -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-hi B hydroxyphenyl methane and the like. 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 preferred that The organic compound is more preferably at least one compound selected from the group consisting of compounds represented by the following general formulas (I), (II) and (III). In this case, the difference in solubility in the developing solution between before and after light irradiation of the photosensitive resin composition is increased, and therefore, there is an advantage that image contrast is more excellent.

｛式中、Ｒ_１〜Ｒ_６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_７及びＲ_８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_９〜Ｒ_１１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（ＩＶ）：

｛式中、Ｒ_１〜Ｒ_６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（Ｖ）：

｛式中、Ｒ_１２〜Ｒ_１５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（ＶＩ）：

｛式中、Ｒ_１６〜Ｒ_１９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 (III):

In the formula, R _{1 to} R ₆ are each independently hydrogen, halogen, a C _{1 to} C ₄ alkyl group, alkenyl group or hydroxyl group, and R ₇ and R ₈ are each independently hydrogen, halogen or C ₁ -C ₄ alkyl and R ₉ -R ₁₁ are each independently hydrogen or C ₁ -C ₄ alkyl. ｝
A compound represented by the following general formula (IV):

In the formula, R _{1 to} R ₆ are each independently hydrogen, halogen, a C _{1 to} C ₄ alkyl group, alkenyl group or hydroxyl group. ｝
A compound represented by the following general formula (V):

In the formula, R _{12 to} R ₁₅ 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 a compound represented by the following general formula (VI):

In the formula, R _{16 to} R ₁₉ 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. It is more preferable that it is at least one selected from the group consisting of the compounds represented by｝ from the viewpoint of sensitivity.

The organic compound is at least one compound selected from the group consisting of the compound represented by the general formula (III), the compound represented by the general formula (V), and the compound represented by the general formula (VI). In some cases, the 1,2-quinonediazide compound having a sulfo group and / or a sulfonylchloride group is 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid , 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and / or 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. These 1,2-quinonediazide compounds having a sulfo group and / or a sulfonyl chloride group include a compound represented by the general formula (III), a compound represented by the general formula (V), and a compound represented by the general formula (VI) Has good compatibility with at least one compound selected from the group consisting of compounds represented by the formula (1), thereby reducing the amount of aggregates generated when component (A) and component (B) are mixed. be able to. Further, when a photosensitive resin composition containing these is used as a photosensitive component of a photoresist, sensitivity, image contrast and heat resistance are more excellent. From the same viewpoint, it is preferable that at least one of the groups R _{1 to} R _{6 in} the general formula (IV) 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（ＶＩＩ）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（Ｘ）又は（ＸＩ）で表される化合物が感度の観点から好ましい。 Further, at least one compound selected from the group consisting of the compound represented by the general formula (III), the compound represented by the general formula (V), and the compound represented by the general formula (VI) is as follows: Chemical formulas (VII) to (XI):

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 light sensitivity is better. Among them, the compound represented by the general formula (VII) is preferable from the viewpoint of suppressing dissolution, and the compound represented by the general formula (X) or (XI) is preferable from the viewpoint of sensitivity.

As a method for synthesizing a 1,2-naphthoquinonediazide compound using at least one compound selected from the group consisting of the compounds represented by the above general formulas (III) to (VI), the following method is exemplified. That is, for example, at least one compound selected from the group consisting of the compounds represented by the general formulas (III) to (VI) and 1,2-naphthoquinone-2-diazide-sulfonyl chloride are combined with dioxane and THF. Such a solvent may be 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 the compounds represented by the general formulas (III) to (VI) and the sulfonyl group of 1,2-naphthoquinone-2-diazide-sulfonyl chloride are condensed. Thus, a photosensitive agent containing a 1,2-naphthoquinonediazide group is synthesized. In the molecule of the obtained photosensitive agent containing a 1,2-naphthoquinonediazide group, a hydroxyl group of at least one compound selected from the group consisting of compounds represented by formulas (III) to (VI); At least one bond to the sulfonyl group of 2-naphthoquinone-2-diazide-sulfonyl chloride may be sufficient.
In addition, as 1,2-naphthoquinone-2-diazide-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride or 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride is preferable. is there. These may be used alone or in combination of two or more.

In the present embodiment, the component (B) can be used as a photosensitive agent of the photosensitive resin composition.
The proportion of the component (B) in the photosensitive resin composition is preferably from 1 to 45% by mass, more preferably from 3 to 40% by mass, based on the total amount of the photosensitive resin composition. More preferably, it is 5 to 43% by mass, and still more preferably 5 to 20% by mass. The mixing ratio is preferably 1% by mass or more from the viewpoint of improving photosensitivity, and is preferably 45% by mass or less from the viewpoint of preventing brittleness of the resist film.

(C) Alkali-soluble resin having a group derived from an aromatic hydroxy compound in a side chain (C) Examples of the alkali-soluble resin having a group derived from an aromatic hydroxy compound in a side chain include (i) polyhydroxystyrene-based resins. Resin, (ii) a phenol group-containing poly (meth) acrylate resin, (iii) a phenol group-containing polyacrylamide resin, and modified products thereof, and may further include these alkali-soluble resins.

  As a method for producing a polyhydroxystyrene resin, for example, a vinylphenol monomer obtained by various methods such as dehydration of acetoxyphenylmethylcarbinol, decarboxylation of hydroxycinnamic acid, dehydrogenation of ethylphenol, or the like, is subjected to cation or radical initiation. Methods such as homopolymerization or copolymerization with other comonomers in the presence of an agent are known as industrial methods. In addition, a monomer in which the hydroxyl group of vinylphenols is protected with an acetyl group, a trimethylsilyl group, a t-butyl group, a t-butoxycarbonyl group, or the like is synthesized, and polymerized in the presence of a cation, an anion, or a radical initiator. A method for obtaining a polymer by removing a group is also known. In this method, a monodisperse polymer can be produced by so-called living polymerization by selecting the type of the protecting group and the type of the initiator (Japanese Patent Application Laid-Open No. 3-277608). Further, a method of hydrogenating these vinylphenol-based polymers to obtain a modified product having excellent light transmittance (JP-A-1-103604), or various ethers obtained by a reaction of hydroxyl groups of the vinylphenol-based polymer. And methods for producing ester derivatives (JP-A-63-312307, Report of Institute for Textile Polymer Materials, Vol. 128, p. 65 (1981)), and various nucleus-substituted vinylphenol-based polymers (JP-A-51-313). No. 83691) is known.

(I) Examples of the polyhydroxystyrene resin include polyhydroxystyrene, modified polyhydroxystyrene, hydrogenated polyhydroxystyrene, and copolymers of hydroxystyrene with styrene, (meth) acrylate, maleate, and the like. No. The weight average molecular weight of polyhydroxystyrene is generally 1,000 to 1,000,000, preferably 5,000 to 50,000.
Examples of the modified polyhydroxystyrene include those obtained by reacting polyhydroxystyrene with, for example, a benzenesulfonyl chloride derivative, a naphthalene sulfonyl chloride derivative, a benzenecarbonyl chloride derivative, a naphthalene carbonyl chloride derivative, and the like in the presence of a basic catalyst. Can be
Specific examples of the above sulfonyl chloride derivative or carbonyl chloride derivative include p-acetaminobenzenesulfonyl chloride, benzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, naphthylbenzenesulfonyl chloride, p-acetoaminobenzenecarbonylcarbonyl chloride, benzenecarbonyl chloride, p-benzene -Chlorobenzenecarbonyl chloride, naphthylbenzenecarbonyl chloride and the like. In this case, the sulfonyl chloride derivative or the carbonyl chloride derivative is used in an amount of usually 10 to 30 parts by weight, preferably 15 to 25 parts by weight, based on 100 parts by weight of polyhydroxystyrene. Such modified polyhydroxystyrene can have a weight average molecular weight in the range of 3,000 to 50,000, preferably 5,000 to 30,000.

  Hydrogenated polyhydroxystyrene is obtained by hydrogenating a part of the benzene ring of polyhydroxystyrene and a modified polyhydroxystyrene in which a part of the benzene ring is modified by a substituent. The weight average molecular weight of the hydrogenated polyhydroxystyrene is preferably selected in the range of 3,000 to 30,000, more preferably 5,000 to 25,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of mechanical properties or dry etching resistance, and is preferably 30,000 or less from the viewpoint of compatibility.

The proportion of hydroxystyrene when copolymerized with other components is preferably 30% by mass or more and 100% by mass or less from the viewpoint of obtaining sufficient alkali developability upon exposure, and more preferably the ratio of hydroxystyrene is 40% by mass. It is not less than 100% by mass and not more than 100% by mass.
(Ii) Examples of the phenol group-containing poly (meth) acrylate resin include phenol group-containing poly (meth) acrylic acid monomer polymers such as 4-hydroxyphenyl methacrylate and 2- (4-hydroxyphenyl) ethyl methacrylate. And modified forms thereof. The weight average molecular weight of the phenol group-containing poly (meth) acrylate resin is usually 5,000 to 1,000,000, preferably 10,000 to 200,000. Also,
(Iii) Examples of the phenol group-containing polyacrylamide resin include polymers, copolymers and modified products of phenol group-containing acrylamide monomers such as 3,5-dimethyl-4-hydroxybenzylacrylamide. The weight average molecular weight of the phenol group-containing polyacrylamide resin is usually 1,000 to 1,000,000, preferably 5,000 to 100,000.

Plasticizer It is preferable that the photosensitive resin composition contains a plasticizer from the viewpoint that chips can be reduced.
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, and polyoxyethylene poly. Glycol esters such as oxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether; phthalic esters such as diethyl phthalate; o-toluenesulfonic acid amide P-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, acetate 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 ' -Methylene bisphenol) or bisphenol S (4,4'-sulfonyldiphenol) was used to introduce an aliphatic molecular chain such as an alkyl group, an alkylene oxide group, or a polyalkylene oxide group using hydroxyl groups at both terminals. Compounds. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.Examples of the alkylene oxide group include a methylene oxide group, an ethylene oxide group, a propylene oxide group, and a tetramethylene oxide group. Examples include a polyethylene oxide group, a polypropylene oxide group, a polytetramethylene oxide group, or a group composed of a block copolymer or a random copolymer thereof.

(D) A compound having at least one structure selected from the group consisting of a phenol novolak structure, a cresol novolak structure, a xylenol novolak structure, and a bisphenol novolak structure, and at least one non-phenolic hydroxyl group. In the above, as the components contained in the photosensitive resin composition, the component (D) and the plasticizer other than the component (D) are used separately.
The component (D) has at least one structure selected from the group consisting of a phenol novolak structure, a cresol novolak structure, a xylenol novolak structure, and a bisphenol novolak structure, and at least one non-phenolic hydroxyl group. As a prerequisite, the terminal may have at least one hydroxyl group, and / or the terminal of the molecular chain introduced in the item of the plasticizer may have a structure other than the hydroxyl group.
The component (D) contained in the photosensitive resin composition has a viewpoint of exhibiting flexibility when formed into a film while maintaining excellent pattern formability, and a viewpoint of compatibility with the component (A). Compounds derived from at least one compound selected from the group consisting of epoxy compounds of phenol novolak, cresol novolak, xylenol novolak and bisphenol novolak and having at least one hydroxyl group are preferred. The bisphenol novolak may be, for example, bisphenol A novolak.

  As the compound selected from the group of epoxy compounds of phenol novolak, cresol novolak, xylenol novolak and bisphenol A novolak, commercially available compounds can be used. For example, NC-3000, NC-3000-L, NC -3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN -502H, EOCN-1020, EOCN-1025, EOCN-1035, EOCN-1045, CER-1020, EPPN-201, BREN-S, BREN-105, RE-3035-L, RE-3105 (Nippon Kayaku) (Made by the company) Manufactured by IC Co., Ltd.)

｛式中、Ａは、非フェノール性水酸基を有する有機基を表し、Ｓは、アルキル基、ハロゲン、又はアリーレン基を有する有機基を表し、ｔは、０〜２の整数であり、かつｌは、２以上の整数であり、好ましくは３以上１０，０以下、より好ましくは３以上５０以下、さらに好ましくは３以上３０以下である。Ｓは重合性不飽和基を有していてもよい。｝
で表される繰り返し単位を含み、より好ましくは、下記一般式（Ｉ）：

｛式中、Ｒ^１及びＲ^２は、水素、メチル基、ハロゲン原子又は下記一般式（ＩＩ）：

（式中、Ｒ^１、Ｒ^２及びＲ^３は、一般式（Ｉ）において定義されており、かつＲ^５は、水素又はメチル基を表す。）
で表される１価の基を表し、Ｒ^３は、メタクリロイル基、アクリロイル基、又はＣ_１〜Ｃ_２４の飽和若しくは不飽和の脂肪酸の残基を表し、Ｒ^４は、多塩基酸無水物に由来するカルボキシル基を有する原子団を表し、かつｍ及びｎは、０又は正の整数である。｝
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。 Further, from the viewpoint of exhibiting flexibility during film formation while maintaining excellent pattern formability, and from the viewpoint of compatibility with the component (A), the component (D) is preferably represented by the following general formula (P) ):

In the formula, A represents an organic group having a non-phenolic hydroxyl group, S represents an organic group having an alkyl group, a halogen, or an arylene group, t is an integer of 0 to 2, and l is And an integer of 2 or more, preferably 3 or more and 10.0 or less, more preferably 3 or more and 50 or less, and further preferably 3 or more and 30 or less. S may have a polymerizable unsaturated group. ｝
And more preferably a repeating unit represented by the following general formula (I):

In the formula, R ¹ and R ² represent hydrogen, a methyl group, a halogen atom or the following general formula (II):

(Wherein R ¹ , R ² and R ³ are defined in the general formula (I), and R ⁵ represents hydrogen or a methyl group.)
R ³ represents a methacryloyl group, an acryloyl group, or a residue of a C _{1 to} C ₂₄ saturated or unsaturated fatty acid, and R ⁴ represents a polybasic acid anhydride. Represents an atomic group having a carboxyl group derived therefrom, and m and n are 0 or a positive integer. ｝
And at least one selected from the group consisting of compounds represented by

Specific examples of the compound represented by the general formula (I) include an epoxy (meth) acrylate compound in which R ^{3 in the} above chemical formula is a methacryloyl group and / or an acryloyl group. It is not particularly limited as long as it is a compound having the above structure, and examples thereof include a compound obtained by reacting an epoxy compound having two or more epoxy groups in one molecule with (meth) acrylic acid.

  The epoxy compound having two or more epoxy groups in one molecule is not particularly limited, and examples thereof include a phenol novolak type, a cresol novolak type, a xylenol novolak type, a bisphenol novolak type, and a halogenated epoxy resin thereof. .

  In the present specification, the (meth) acrylic acid means acrylic acid or methacrylic acid. In the compound obtained by reacting (meth) acrylic acid with an epoxy compound having two or more epoxy groups in one molecule, the (meth) acryl group derived from (meth) acrylic acid is a positive-type photosensitive compound. Does not participate in properties. From the availability, the radical polymerizable monomer used in the negative dry film can be used.

  As the epoxy (meth) acrylate compound which is an example of the compound represented by the above formula (I), a commercially available one can be used. For example, EA-6320, EA-7120 and EA-7420 (the above) And EAM-2160, EAM-2300, ZFA-266H and R-205 (all manufactured by Nippon Kayaku Co., Ltd.), and Ebecryl 3603 (manufactured by Daicel Chemical Co., Ltd.).

  As the epoxy (meth) acrylate compound which is an example of the compound represented by the above formula (I), an acid-modified epoxy (meth) acrylate compound can also be used. Examples of the acid-modified epoxy (meth) acrylate compound include, in the above formula (I), a compound in which n is a positive integer.

  By using such an acid-modified epoxy (meth) acrylate compound, the adhesion of the substrate to copper can be improved. In addition, since the acid-modified epoxy (meth) acrylate compound has an acid group, the solubility of the unexposed portion in an alkali developing solution is increased. Therefore, it is preferable that the integer of n is small.

  By reacting a polybasic anhydride with a hydroxyl group of a compound obtained by reacting an epoxy compound having two or more epoxy groups in one molecule with (meth) acrylic acid, a carboxyl group is added to the compound. By introducing the compound, an acid-modified epoxy (meth) acrylate compound can be obtained.

  The polybasic anhydride is not particularly limited, and examples thereof include dibasic anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride. Products, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride and the like. Among them, tetrahydrophthalic anhydride or succinic anhydride is preferred. The polybasic acid anhydride may be a saturated polybasic acid anhydride or an unsaturated polybasic acid anhydride.

  As the acid-modified epoxy (meth) acrylate compound, commercially available compounds can be used. For example, CCR-1291H, CCR-1235, ZAR-1035, ZAR-2000, ZFR-1401H, ZFR-1491H, ZCR-1569H, ZCR-1601H, ZCR-1797H, PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1159H, PCR-1157H, TCR-1025, TCR-1064, TCR-1286, ZFR- 1122, ZFR-1124, ZFR-1185 (all manufactured by Nippon Kayaku), EA-6340, EA-7140, and EA-7440 (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

  It is preferable that the content of the component (D) is 1% by mass or more and 40% by mass or less based on the total amount of the photosensitive resin composition. The content is preferably 1% by mass or more from the viewpoint of securing the flexibility of the resist film, and is preferably 40% by mass or less from the viewpoint of securing the photosensitivity of the resist film. The content of the component (D) is more preferably 5% by mass or more and 38% by mass or less, further preferably 10.0% by mass or more and 36% by mass or less, and particularly preferably 20-35% by mass. .

Other components The photosensitive resin composition may optionally contain a surfactant for the purpose of improving applicability, defoaming property, leveling property, and the like. Such a surfactant is not particularly limited, but is preferably a fluorinated surfactant. Examples of such a fluorine-based surfactant include BM-1000 and BM-1100 (all manufactured by BM Chemie); Megafac (registered trademark) F142D, Megafac (registered trademark) F172, and 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, Incorporated); Florad FC-135, Florad FC-170C, Florard FC-430, Florard FC-431, Florard FC-4430 (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-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray) Commercially available products such as silicone products) can be used. These may be used alone or in combination of two or more.

The mixing ratio of the surfactant is preferably 5% by mass or less based on the total amount of the photosensitive resin composition. If the compounding ratio exceeds 5% by mass, the pattern formability tends to be lower than when the compounding ratio is in the above range.
The photosensitive resin composition may contain an adhesion aid in order to improve the adhesion to a substrate or the like. As such an adhesion aid, a functional silane coupling agent is preferable. Here, the functional silane coupling agent means a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group. Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, Y-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, Y-glycidoxypropyltrimethoxysilane, trimethoxysilylpropyl Isocyanates and 1,3,5-N-tris (trimethoxysilylpropyl) isocyanate. These may be used alone or in combination of two or more.
It is preferable that the compounding ratio of the above-mentioned adhesion assistant is 20% by mass or less based on the total amount of the photosensitive resin composition. When the compounding ratio is more than 20% by mass, development residues tend to be more easily generated as compared with the case where the compounding ratio is in the above range.

  The photosensitive resin composition may contain an acid or a high-boiling solvent in order to finely adjust the solubility in an alkali developing solution. Examples of the acid 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-hydroxy acid. Hydroxymonocarboxylic 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 and syringic acid; 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 Melitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1 Polycarboxylic acids such as 2,5,8-naphthalenetetracarboxylic acid, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydroanhydride Phthalic acid, hymic acid anhydride, 1,2,3,4-butanetetracarboxylic acid, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene Acid anhydrides such as glycol bis anhydride trimellitate and glycerin tris anhydride trimellitate are exemplified.

  Examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and 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, Propylene carbonate, phenyl cellosolve acetate and the like. These may be used alone or in combination of two or more.

The mixing ratio of the above-mentioned acid or high-boiling solvent is not particularly limited as long as it can be adjusted according to the use and application method, and can be uniformly mixed with the photosensitive resin composition. For example, the mixing ratio of these acids or high-boiling 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 characteristics of the photosensitive resin composition are not impaired.
Further, the photosensitive resin composition of the present embodiment may contain, if necessary, a sensitizer, a light absorbing agent (dye), a cross-linking agent, a pigment, a filler, a flame retardant, a stabilizer, an adhesion promoter, a peeling accelerator. An additive such as an agent, an antioxidant, a fragrance, an imaging agent, and a thermal crosslinking agent may be contained. These additives may be used alone or in combination of two or more.
The mixing ratio of these additives is not particularly limited as long as the characteristics of the photosensitive resin composition are not impaired, but 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 above.

  The preparation of the photosensitive resin composition may be performed by mixing and stirring by a usual method. When a filler and a pigment are added to the photosensitive resin composition, they may be dispersed and mixed using a disperser, a homogenizer, a three-roll mill, or another disperser. Further, if necessary, filtration may be performed using a mesh, a membrane filter, or the like.

<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 sectional view of the photosensitive resin laminate according to the present 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 of copper, copper-based alloy, iron, iron-based alloy, or the like, or a polymer film of polyethylene terephthalate, polypropylene, polyethylene, polyester, or the like 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 applying the photosensitive resin composition of the present embodiment to the support 2 in a liquid state.
When applying the photosensitive resin composition on a support, if necessary, the photosensitive resin composition is dissolved in a predetermined solvent to form a solution having a solid content of 30 to 60% by mass. May be used. 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 mono Tyl 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 monomethyl ether acetate And organic solvents such as dipropylene glycol monomethyl ether acetate, or a mixed solvent thereof.

Examples of the coating method include a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater. The solvent can be removed, for example, by heating. 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 the residual organic solvent in the photosensitive resin layer thus formed is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in a later step.
The thickness of the photosensitive resin layer varies depending on the application, but the thickness after removing the solvent is preferably about 0.5 to 100 μm.
In the support and the photosensitive resin layer, if necessary, the surface of the photosensitive resin layer opposite to the support may be covered with a protective film.

As the protective layer 6 shown in FIG. 1, a protective film, for example, a polymer film of polyethylene, polypropylene, or the like can be given. In addition, the protective film is preferably a low fisheye film, and the adhesive force 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 strength between the resin layer 4 and the support 2 be smaller.
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, an adhesive layer, a light absorbing layer, and a gas barrier layer. May be further provided.

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

<Method of forming resist pattern>
The method for forming a resist pattern is such that the photosensitive resin layer of the photosensitive resin laminate is laminated on a substrate so that the photosensitive resin layer is in close contact with the substrate, and the exposed portion is removed by development by irradiating actinic rays imagewise. is there. The portion not irradiated with actinic light does not dissolve in alkali because the photosensitive agent containing a 1,2-naphthoquinonediazide group interacts with an alkali-soluble phenol resin and acts as a dissolution inhibitor. However, the photosensitive agent containing a 1,2-naphthoquinonediazide group is photolyzed in the portion irradiated with the actinic ray, and loses the dissolution inhibiting effect. Thereby, the exposed portion irradiated with the actinic ray becomes alkali-soluble.

As a method of laminating the photosensitive resin layer on the base material, when the photosensitive resin laminate has a protective film, the protective film is removed, and the photosensitive resin layer is heated to about 70 to 130 ° C. A method in which the material is pressure-bonded at a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm ² ) using a laminator or the like is used. Such a lamination step may be performed under reduced pressure. The surface of the substrate on which the photosensitive resin layer is laminated is not particularly limited.
The photosensitive resin layer thus laminated on the base material is irradiated with actinic rays imagewise through a negative or positive mask pattern to form an exposed portion. At this time, when the support present on the photosensitive resin layer is transparent to actinic rays, it can be irradiated with actinic rays through the support, and the support exhibits light-shielding properties to actinic rays. In this case, the photosensitive resin layer is irradiated with actinic rays after removing the support. As the light source of the actinic ray, a conventionally known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet light, visible light, or the like is used. Further, a direct drawing method, for example, a laser direct drawing exposure method or the like may be used.

  After the formation of the exposed portion, the photosensitive resin layer in the exposed portion is removed by development to form a resist pattern. As a method of removing the exposed portion, when a support is present on the photosensitive resin layer, the support is removed with an auto peeler or the like, and an alkaline aqueous solution, an aqueous developer, wet development with a developer such as an organic solvent, Alternatively, a method in which the exposed portion is removed by dry development or the like to perform development may be used. Examples of the alkali used for the wet development include, for example, a weak alkali inorganic compound such as sodium carbonate, potassium carbonate and ammonia; an alkali metal compound such as sodium hydroxide and potassium hydroxide; an alkaline earth metal compound such as calcium hydroxide; monomethylamine Weak alkaline organic compounds such as dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, and polyethyleneimine; tetra Methyl ammonium hydroxide, tetraethyl ammonium hydroxide and the like can be mentioned. 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 according to the developability of the photosensitive resin layer. Further, a surfactant, an antifoaming agent, an organic solvent and the like may be mixed in the alkaline aqueous solution. Examples of the developing method include a dip method, a spray method, brushing, slapping, and the like.

In addition, as a process after the development, the resist pattern may be cured by heating at about 60 to 250 ° C. as necessary.
Thus, a resist pattern is obtained. At this time, since the photosensitive resin layer in which the generation of chips is sufficiently prevented is used, contamination of the operating environment of the base material or the laminator due to the chips is sufficiently prevented, and as a result, the resist having sufficiently few defects is obtained. A pattern can be formed. In addition, the exposed portion of the resist film easily dissolves in weak alkali and peels off from the substrate, and by using the photosensitive resin composition of the present invention having extremely good weak alkali developability, a resist pattern can be obtained. Become.

<Manufacturing method of printed wiring board>
The method for manufacturing a printed wiring board according to the present embodiment is performed through 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 conductive pattern is formed on the copper surface of the substrate exposed by development using a known method such as an etching method or a plating method.
After that, the resist pattern is removed again by exposing and developing a liquid to obtain a desired printed wiring board.

<Lead frame manufacturing method>
The manufacturing method of the lead frame according to the present embodiment is performed through the following steps following the above-described method of forming a resist pattern using a metal plate of copper, a copper alloy, an iron-based alloy, or the like as a substrate.
First, a conductive pattern is formed by etching a substrate exposed by development.
Thereafter, the remaining resist pattern is removed by a method similar to the above-described method for manufacturing a printed wiring board, and a desired lead frame is obtained.

<Semiconductor package manufacturing method>
The method of manufacturing a semiconductor package according to the present embodiment is performed through the following steps following the above-described method of forming a resist pattern using a wafer on which circuit formation as an LSI has been completed as a substrate.
A columnar plating of copper, solder, or the like is applied to the opening exposed by the development to form a conductor pattern.
After that, the remaining resist pattern is removed by the same method as the above-described method for manufacturing a printed wiring board, and further, the thin metal layer other than the columnar plating is removed by etching to obtain a desired semiconductor package.

<Method of manufacturing thin film transistor>
The method for manufacturing a thin film transistor (TFT) according to the present embodiment is performed through 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.
After that, a semiconductor layer, a source electrode, a transparent electrode, a protective film, and the like are formed over the substrate having the gate electrode to obtain a desired TFT substrate. Further, the method for manufacturing a semiconductor package described above can be used for forming the semiconductor layer.

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

  FIG. 2 is a flow chart for explaining a method of manufacturing a touch panel using a negative photosensitive resin composition with schematic sectional views (a) to (h). The method includes the steps of: forming a metal layer 26 on a laminated base material including 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 the photosensitive resin composition thereon, and etching of the metal layer 26 and the transparent conductive layer 24 to form a remaining portion of the transparent conductive layer 24 and a remaining portion of the metal layer 26 A second step of forming a laminated pattern (24 + 26 in FIG. 2 (d)) consisting of: a transparent electrode composed of the remaining transparent conductive layer 24 and the remainder 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 composed of:

  In the first step, first, as shown in FIG. 2A, the support base material 22, the transparent conductive layer 24 provided on one surface of the support base material 22, and the transparent conductive layer 24 provided on the transparent conductive layer 24 are provided. A negative photosensitive layer 28 is laminated on the metal layer 26 of the laminated base material including the metal layer 26 by using a negative photosensitive resin composition. The photosensitive layer 28 may have a support on the surface opposite to the metal layer 26.

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

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

  The method of the etching treatment is appropriately selected according to the layer to be removed. For example, an etching solution for removing the metal layer includes a cupric chloride solution, a ferric chloride solution, a phosphoric acid solution, and the like. Further, as an etchant for removing the transparent conductive layer, oxalic acid, hydrochloric acid, aqua regia, or the like is used.

FIG. 2C is a view showing a state after the etching process. On the supporting substrate 22, a laminated body including 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. In the method of manufacturing a touch panel using the negative photosensitive resin composition, the resist pattern 29 is removed from the laminate.
For removal of the resist pattern 29, for example, an aqueous solution having a higher alkalinity than an alkaline aqueous solution used in the developing step included in the above-described method for forming a resist pattern can be used. As the strong alkaline aqueous solution, a 1 to 10% by mass aqueous sodium hydroxide solution, a 1 to 10% by mass aqueous potassium hydroxide solution or the like is used. Among them, it is preferable to use a 1 to 10% by mass aqueous solution of sodium hydroxide or potassium hydroxide solution, and it is more preferable to use an 1 to 5% by mass aqueous solution of sodium hydroxide or potassium hydroxide solution. Examples of the method of removing the resist pattern include an immersion method and a spray method, and these may be used alone or in combination.

FIG. 2D is a view showing a state after the resist pattern 29 is peeled off, and a laminated pattern including the remaining part of the metal layer 26 and the remaining part of the transparent conductive layer 24 is formed on the supporting base material 22.
In the third step, a part of the metal layer 26 other than the part for forming the metal wiring is removed from the laminated pattern, and the metal wiring composed of the remaining part of the metal layer 26 and the transparent electrode composed of the remaining part of the transparent conductive layer 24 are removed. To form

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

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

  FIG. 2 (g) is a view showing a state after the etching process, in which a transparent electrode composed of the remaining portion of the transparent conductive layer 24 is formed on the support base material 22, and a metal layer 26 and a resist are formed on some of the transparent electrodes. A laminate composed of the pattern 31 is formed. By removing the resist pattern 31 from this laminated body, as shown in FIG. 2H, a transparent electrode composed of the remaining part of the transparent conductive layer 24 and a metal composed of the remaining part of the metal layer 26 are formed on the supporting base material 22. 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 required. When a photosensitive layer is formed using a positive photosensitive resin composition, the exposed portion can be removed with an alkaline aqueous solution, and the unexposed portion remains as a film. A pattern can be formed.

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

In the first step, first, as shown in FIG. 3A, the support base material 22, the transparent conductive layer 24 provided on one surface of the support base material 22, and the transparent conductive layer 24 provided on the transparent conductive layer 24 are provided. A positive photosensitive layer 40 is laminated using a positive photosensitive resin composition on the metal layer 26 of the laminated base material having the metal layer 26. The photosensitive layer 40 may have a support on the surface opposite to the metal layer 26.
Next, after irradiating active light to a partial area of the photosensitive layer 40 to form an exposed portion, the photosensitive layer in the exposed portion is removed from the laminated base material by development. Thus, as shown in FIG. 3B, a resist pattern 40a including 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 the region not masked by the resist pattern 40a are removed from the support base material 22 by etching.
The method of the etching treatment is appropriately selected according to the layer to be removed. For example, examples of the etchant for removing the metal layer include an ammonium persulfate solution, a sodium persulfate solution, a cupric chloride solution, a ferric chloride solution, and a phosphoric acid solution. Further, as an etchant for removing the transparent conductive layer, oxalic acid, hydrochloric acid, aqua regia, or the like is used.
FIG. 3C is a view showing a state after the etching process. On the supporting base material 22, a laminated body including the remaining part of the metal layer 26, the remaining part of the transparent conductive layer 24, and the resist pattern 40a is formed.

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

Next, the metal layer 26 is removed by an etching process from a portion of the laminated pattern where the resist pattern 40b is not formed. At this time, the same etching solution as the above-described etching solution for removing the metal layer can be used as the etching solution.
FIG. 3E is a view showing a state after the etching process, in which a transparent electrode composed of the remaining portion of the transparent conductive layer 24 is formed on the support base material 22 and a metal layer 26 and a resist are formed on some of the transparent electrodes. A laminate composed of the pattern 40b is formed. By removing the resist pattern 40b from the laminate, as shown in FIG. 2F, a transparent electrode made up of the remaining portion of the transparent conductive layer 24 and a metal made up of the remaining portion of the metal layer 26 are formed on the supporting base material 22. Wiring is formed.
As described above, in the touch panel manufacturing method according to the present embodiment, steps corresponding to (d) and (e) in FIG. 2 can be omitted.
Although the transparent conductive layer 24 contains indium tin oxide (ITO), the positive photosensitive resin composition according to the present embodiment manufactures a touch panel in which the transparent conductive layer 24 is changed from ITO to a metal mesh. The method can also be suitably used.

  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, the X electrodes 52 and the Y electrodes 54, which are transparent electrodes, are alternately arranged in parallel, and the X electrodes 52 provided in the same row in the longitudinal direction are connected to each other by one lead wire 56, 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 described in more detail with reference to examples.
[Examples 1 to 7, Comparative Examples 1 to 3]
<1. Preparation of photosensitive resin composition>
The compounds shown in Table 1 were mixed to prepare a photosensitive resin composition. The values in Table 1 are the solid content.
The symbols in the table are as shown below.
A-1: Cresol novolak resin, weight average molecular weight 10,000, m-form: p-form = 6: 4
A-2: Cresol novolak resin, weight average molecular weight 5,000, m-form: p-form = 6: 4

B-1: Monomer of 1,2-naphthoquinonediazide-4-sulfonic acid of 4,4 ′-(1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene) bisphenol) B-2: 1,2-Naphthoquinonediazide of 4,4 '-(1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene) bisphenol) B-3: 6-diazo-5,6-dihydro-5-oxo-l-naphthalenesulfonic acid mono-, di-, 2-, 3, 4-trihydroxybenzophenone mixture of mono-, di- or triesters of 4-sulfonic acid Or triester B-4: 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid mono of 2,3,4,4'-tetrahydroxybenzophenone Di-, tri- or tetra-ester

D-1: a compound having 3 moles of propylene glycol at both ends of bisphenol A D-2: a bifunctional bisphenol A epoxy acrylate having an average molecular weight of 3,500 D-3: in the above general formula (I), R ¹ R ² is hydrogen, R ³ is an acryloyl group, m = 1, and n = mixture of novolac epoxy acrylate and trimethylol propane triacrylate as a diluent 0 D-4: in the above general formula (I) , R ¹ is a methyl group, R ² is a hydrogen group, R ³ is an acryloyl group, R ⁴ is a carboxylic anhydride residue, m = 2 and n = 2, a propylene glycol of novolak epoxy acrylate Diluent of monomethyl ether acetate solvent

<2. Manufacture of photosensitive resin laminate>
The solvent acetone was added to the photosensitive resin composition having the composition shown in Table 1 until the solid content became 55% by mass, and the mixture was thoroughly stirred and mixed, and the solution of the photosensitive resin composition was coated with a 25 μm-thick polyethylene terephthalate film (25 μm). (A film easily peeled off on one surface of a polyethylene terephthalate film) is uniformly coated with a bar coater and dried in a drier at 95 ° C. for 5 minutes to form a photosensitive resin layer (dry film) having a thickness of 8 μm. did. Next, a 33 μm-thick polyethylene film was laminated on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.

<3. Preparation of Evaluation Board>
Board leveling:
As a substrate for evaluation, a 0.4 mm thick copper-clad laminate obtained by laminating 35 μm rolled copper foil was used. # 400) was prepared.
laminate:
While peeling off the polyethylene film of the photosensitive resin laminate, it was laminated at a roll temperature of 105 ° C. with a hot roll laminator (AL-700, manufactured by Asahi Kasei Electronics Co., Ltd.) on a copper-clad laminate preliminarily heated to 60 ° C. while peeling off. . The air pressure was 0.35 MPa, and the laminating speed was 0.5 m / min.

exposure:
The support was peeled off, and the evaluation substrate was exposed to light using a chromium glass photomask using an exposure machine having an ultra-high pressure mercury lamp (a parallel light exposure machine (HMW-801, manufactured by Oak Manufacturing Co., Ltd.)).
developing:
The obtained evaluation substrate was developed by a dipping method at a temperature of 30 ° C. for 60 seconds using a 1.0% by mass aqueous solution of potassium hydroxide as an alkali developing solution. Thereafter, at room temperature, the evaluation substrate was washed with pure water for about 20 seconds by a dipping method, and dried with a compressed air gun.

<4. Evaluation>
Image quality evaluation:
The test piece was exposed at an exposure of 100 mJ / cm ² using a chrome glass photomask having a line pattern in which the width of the exposed part and the unexposed part was 1: 1. Thereafter, the resist was developed by the above-mentioned developing method. The minimum mask width in which the resist line was normally formed was taken as the value of the resolution, and the resolution was ranked as follows. It should be noted that the minimum mask width that was normally formed without falling of the cured resist pattern or adhesion between the cured resists was evaluated.
◎: the value of resolution is 5 μm or less;
：: the value of the resolution exceeds 5 μm and 10 μm or less;
X: The value of the resolution exceeds 10 μm.

Evaluation of flexibility of photosensitive resin (bending resistance test according to JIS K5600-5-1):
After laminating a photosensitive resin laminate on a flexible base material (NIKAFLEX F-30VC1 manufactured by Nikkan Industries), peeling off the support from the photosensitive resin laminate, exposing at 400 mJ / cm ² with the above exposure machine, After the development, the flexibility was tested according to the flex resistance item of JIS K5600-5-1. Thereafter, the coating film after the test was observed under a microscope, and the minimum cylindrical diameter (mmφ) at which the coating film did not crack or crack was evaluated.

<5. Evaluation results>
Table 1 shows the evaluation results of the examples and the comparative examples.
As can be seen from Table 1, Examples 1 to 8 were excellent in both image quality evaluation and cylindrical bending resistance test. In Comparative Example 1, since the component (D) used in the present invention was not included, the photosensitive resin layer was very brittle, and the result of the cylindrical bending resistance test was poor. In Comparative Examples 2 and 3, when the same amount of the bisphenol A derivative which is not the component (D) was used, the image quality evaluation was poor, and thus the effectiveness of the component (D) is high. Therefore, it can be seen that there is a specific range of the component (D) to satisfy both characteristics.

  The present invention relates to manufacturing of printed wiring boards, manufacturing of lead frames for mounting IC chips, metal foil precision processing such as metal mask manufacturing, manufacturing of packages such as BGA and CSP, manufacturing of tape substrates such as COF or TAB, manufacturing of semiconductor bumps. The present invention can be suitably used for manufacturing, manufacturing of a partition of a flat panel display such as an ITO electrode or an address electrode, an electromagnetic wave shield, and particularly, a manufacturing method of a touch panel.

Reference Signs List 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 Leader wiring 100 Touch panel

Claims (15)

(A) an alkali-soluble phenolic resin;
(B) a quinonediazide group-containing compound; and (D) at least one structure selected from the group consisting of a phenol novolak structure, a cresol novolak structure, a xylenol novolak structure, and a bisphenol novolak structure, and at least one non-phenol A compound having a hydroxyl group;
A photosensitive resin composition containing:   2. The photosensitive resin composition according to claim 1, comprising 20 to 90% by mass of the component (A), 1 to 45% by mass of the component (B), and 1 to 40% by mass of the component (D). The component (D) has the following general formula (P):

In the formula, A represents an organic group having a non-phenolic hydroxyl group, S represents an organic group having an alkyl group, a halogen, or an arylene group, t is an integer of 0 to 2, and l is Is an integer of 2 or more. ｝
The photosensitive resin composition according to claim 1, comprising a repeating unit represented by the formula: The component (D) has the following general formula (I):

In the formula, R ¹ and R ² represent hydrogen, a methyl group, a halogen atom or the following general formula (II):

(Wherein R ¹ , R ² and R ³ are defined in the general formula (I), and R ⁵ represents hydrogen or a methyl group.)
R ³ represents a methacryloyl group, an acryloyl group, or a residue of a C _{1 to} C ₂₄ saturated or unsaturated fatty acid, and R ⁴ represents a polybasic acid anhydride. Represents an atomic group having a carboxyl group derived therefrom, and m and n are 0 or a positive integer. ｝
The photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin composition is at least one selected from the group consisting of compounds represented by the following formula: As the component (B), the following general formula (III):

In the formula, R _{1 to} R ₆ are each independently hydrogen, halogen, a C _{1 to} C ₄ alkyl group, alkenyl group or hydroxyl group, and R ₇ and R ₈ are each independently hydrogen, halogen or C ₁ -C ₄ alkyl and R ₉ -R ₁₁ are each independently hydrogen or C ₁ -C ₄ alkyl. ｝
The photosensitive resin composition according to any one of claims 1 to 4, comprising a quinonediazidesulfonic acid ester of a compound represented by the formula: As the component (B), the following general formula (IV):

In the formula, R _{1 to} R ₆ are each independently hydrogen, halogen, a C _{1 to} C ₄ alkyl group, alkenyl group or hydroxyl group. ｝
The photosensitive resin composition according to any one of claims 1 to 5, comprising a quinonediazidesulfonic acid ester of a compound represented by the formula:   A photosensitive resin laminate comprising a support and a photosensitive resin layer comprising the photosensitive resin composition according to claim 1.   A resist roll in which the photosensitive resin laminate according to claim 7 is in the form of a roll. A laminating step of laminating the photosensitive resin layer of the photosensitive resin laminate according to claim 7 on a substrate;
An exposing step of exposing the photosensitive resin layer; and a developing step of removing the exposed photosensitive resin layer;
A method for forming a resist pattern comprising:   The method of forming a resist pattern according to claim 9, wherein, in the exposing step, the photosensitive resin layer is directly drawn and exposed.   A method for manufacturing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern has been formed by the method for forming a resist pattern according to claim 9.   A method for manufacturing a lead frame, comprising a step of etching a substrate on which a resist pattern has been formed by the method for forming a resist pattern according to claim 9.   A method of manufacturing a semiconductor pattern, comprising a step of etching or plating a substrate on which a resist pattern has been formed by the method of forming a resist pattern according to claim 9.   A method for manufacturing a thin film transistor, comprising a step of etching or plating a substrate on which a resist pattern has been formed by the method for forming a resist pattern according to claim 9.   A method for manufacturing a touch panel, comprising a step of etching a substrate on which a resist pattern has been formed by the method for forming a resist pattern according to claim 9.

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