JP2009003177A - Photosensitive resin composition, and photosensitive element, forming method of resist pattern and production method of printed wiring board using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition, having satisfactory solubility to a solvent of sensitizer in use of light of wavelength 400-440 nm as exposing light, and providing sufficient sensitivity and sufficient resolution. <P>SOLUTION: The photosensitive resin composition comprises (A) a binder polymer, (B) a photopolymeric compound having at least one polymerizable ethylenic unsaturated bond, (C) a photopolymerization initiator, and (D) a tertiary amino compound represented by the general formula (1). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a resist pattern forming method, and a printed wiring board manufacturing method.

  In the field of manufacturing printed wiring boards, as a resist material used for etching and plating, a photosensitive resin composition and a layer made of this photosensitive resin composition (hereinafter referred to as “photosensitive resin composition layer”) are used. Photosensitive elements (laminates) formed on a support film and having a structure in which a protective film is disposed on a photosensitive resin composition layer are widely used.

  Conventionally, a printed wiring board is manufactured using the above photosensitive element, for example, in the following procedure. That is, first, the photosensitive resin composition layer of the photosensitive element is laminated on a circuit forming substrate such as a copper-clad laminate. At this time, the surface opposite to the surface of the photosensitive resin composition layer in contact with the support film (hereinafter referred to as the “lower surface” of the photosensitive resin composition layer) (hereinafter referred to as the “upper surface of the photosensitive resin composition layer”). ") In close contact with the surface of the circuit forming substrate on which the circuit is to be formed. Therefore, when the protective film is arrange | positioned on the upper surface of the photosensitive resin composition layer, this lamination operation is performed while peeling off the protective film. Next, the photosensitive resin composition layer is thermocompression bonded to the underlying circuit forming substrate (normal pressure laminating method).

  Next, pattern exposure is performed through a mask film or the like. At this time, the support film is peeled off at any timing before or after exposure. Thereafter, the unexposed portion is dissolved or dispersed and removed with a developer. Next, an etching process or a plating process is performed to form a pattern, and finally the cured portion is peeled and removed.

  Here, the etching treatment is a method of removing a resist after etching away a metal surface not covered with a cured resist formed after development. On the other hand, the plating process is a method in which a metal surface not covered with a hardened resist formed after development is subjected to a plating process such as copper and solder, and then the resist is removed and the metal surface covered with the resist is etched. is there.

  By the way, conventionally, a mercury lamp has been mainly used as a light source for the above-described pattern exposure. However, the light from the mercury lamp contains ultraviolet rays (light having a wavelength of 400 nm or less) harmful to the human body, which has a problem in work safety. Although there is an exposure method using a visible light laser as a light source, this method requires a resist sensitive to visible light, and this resist has to be handled in a dark room or under a red lamp.

  In consideration of the above points, a technique has been proposed in which actinic rays obtained by cutting 99.5% or more of light having a wavelength of 365 nm or less using a filter among light emitted from a mercury lamp light source are used for pattern exposure.

  In recent years, a long-lived and high-power gallium nitride blue laser light source that oscillates light having a wavelength of 405 nm has become available at low cost, and a technique for using this also as a light source for pattern exposure has been proposed.

  In recent years, a direct drawing method called a DLP (Digital Light Processing) exposure method has been proposed (for example, see Non-Patent Document 1). Even in this exposure method, there are cases where an actinic ray obtained by cutting 99.5% or more of light having a wavelength of 365 nm or less out of light emitted from a mercury lamp light source using a filter or a blue laser light source is used.

  When an image is formed by this DLP exposure method, the photosensitive element needs to absorb near a wavelength of 405 nm. In addition, since the oscillation wavelength range of each DLP exposure machine varies depending on the manufacturer, it is better that the change in absorption near the wavelength of 405 nm is small.

  However, since the conventional photosensitive element is designed to exhibit optimum photosensitive characteristics with respect to full-wavelength exposure of a mercury lamp light source centered on light having a wavelength of 365 nm, light centered on a wavelength of 405 nm (mercury lamp) Exposure by actinic rays obtained by cutting 99.5% or more of light emitted from a light source with a wavelength of 365 nm or less using a filter, and light of a semiconductor laser having a wavelength of 405 nm including those described in Non-Patent Document 1. Light), the sensitivity of the photosensitive element to light with a wavelength of 400 nm or more is low, so the throughput (productivity per unit time) is low and sufficient resolution is achieved. And a good resist shape could not be obtained.

  Therefore, a photosensitive resin composition that can be applied to direct drawing with a blue-violet laser as described in Patent Documents 1 to 3 below has been proposed.

Japanese Patent Laid-Open No. 2005-208561 JP 2005-338375 A JP 2005-128508 A Electronics Packaging Technology June 2002 (p.74-79)

  However, even the photosensitive resin compositions described in Patent Documents 1 to 3 do not necessarily have sufficient sensitivity when exposure light having a wavelength of about 405 nm is used.

  In order to improve sensitivity, there is a method of increasing the content of the sensitizer to increase the absorbance around 405 nm. However, when the sensitizer has low solubility in a solvent, the photosensitive resin composition is used as a support film. This causes a phenomenon that the sensitizer is deposited after being applied and dried. And in the sensitizer described in the said patent documents 1-3, the solubility with respect to a solvent is inadequate, and there exists a problem that it precipitates easily.

  The present invention has been made in view of the above-described problems of the prior art. In the case where light having a wavelength of 400 to 440 nm is used as exposure light, the solubility of the sensitizer in the solvent is good and sufficient. It is an object of the present invention to provide a photosensitive resin composition capable of obtaining sensitivity and sufficient resolution, a photosensitive element using the same, a method for forming a resist pattern, and a method for producing a printed wiring board.

  One of the main reasons why the conventional photosensitive resin compositions such as those described in Patent Documents 1 to 3 described above are low in sensitivity to light having a wavelength of 400 to 440 nm is the sensitivity to the wavelength region. Since the optical density of the photosensitive resin composition is small, the light in the above wavelength region cannot be sufficiently absorbed, and the photopolymerization of the photopolymerizable compound in the photosensitive resin composition cannot be efficiently started. I found it.

  And as a result of intensive studies, the present inventors have found that the above-mentioned problems of the prior art can be achieved by constituting a photosensitive resin composition using a specific photosensitizer.

  That is, the present invention includes (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) the following general formula. The photosensitive resin composition containing the tertiary amino compound represented by (1) is provided.

［式（１）中、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に、炭素数１〜１０のアルキル基、炭素数１〜４のシクロアルキル基、フェニル基（但し、炭素数１〜４のアルキル基、水酸基、ハロゲン原子、シアノ基、カルボキシル基、フェニル基、炭素数１〜４のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基の１個以上で置換されてもよい）、水酸基、ハロゲン原子、シアノ基、カルボキシル基、炭素数１〜６のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基、ベンジル基（但し、炭素数１〜６のアルキル基、水酸基、ハロゲン原子、シアノ基、カルボキシル基、フェニル基、炭素数１〜６のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基の１個以上で置換されてもよい）、炭素数２〜１０のアルカノイル基、ベンゾイル基（但し、炭素数１〜６のアルキル基、水酸基、ハロゲン原子、シアノ基、カルボキシル基、フェニル基、炭素数１〜６のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基の１個以上で置換されてもよい）、又は、下記一般式（２）で表される基を示し、Ｒ^１、Ｒ^２及びＲ^３の少なくとも２つは下記一般式（２）で表される基を示し、ａ、ｂ及びｃは、ａ＋ｂ＋ｃの値が２以上となるように選ばれる０〜５の整数を示す。］

[In the formula (1), R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 4 carbon atoms, a phenyl group (however, having 1 to 4 carbon atoms) An alkyl group, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an alkoxycarbonyl group having 2 to 6 carbon atoms). Hydroxyl group, halogen atom, cyano group, carboxyl group, alkoxy group having 1 to 6 carbon atoms, phenoxy group, alkoxycarbonyl group having 2 to 6 carbon atoms, benzyl group (however, alkyl group having 1 to 6 carbon atoms, hydroxyl group, halogen) (It may be substituted with one or more of an atom, a cyano group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms) , An alkanoyl group having 2 to 10 carbon atoms, a benzoyl group (however, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group, Or a group represented by the following general formula (2), and at least two of R ¹ , R ² and R ³ may be substituted with one or more alkoxycarbonyl groups having 2 to 6 carbon atoms) The group represented by following General formula (2) is shown, a, b, and c show the integer of 0-5 chosen so that the value of a + b + c may be 2 or more. ]

［式（２）中、Ｒ^４は炭素数１〜１０のアルキル基、炭素数１〜４のシクロアルキル基、フェニル基（但し、炭素数１〜４のアルキル基、水酸基、ハロゲン原子、シアノ基、カルボキシル基、フェニル基、炭素数１〜４のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基の１個以上で置換されてもよい）、ベンジル基（但し、炭素数１〜６のアルキル基、水酸基、ハロゲン原子、シアノ基、カルボキシル基、フェニル基、炭素数１〜６のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基の１個以上で置換されてもよい）、炭素数２〜１０のアルカノイル基、又は、ベンゾイル基（但し、炭素数１〜６のアルキル基、水酸基、ハロゲン原子、シアノ基、カルボキシル基、フェニル基、炭素数１〜６のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基の１個以上で置換されてもよい）を示し、ｄは１〜１０の整数を示す。］

[In the formula (2), R ⁴ represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 4 carbon atoms, a phenyl group (provided that an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, a cyano group. , A carboxyl group, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, one or more alkoxy groups having 2 to 6 carbon atoms, and a benzyl group (provided that the carbon number is 1 to 6 And may be substituted with one or more of an alkyl group, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms) , An alkanoyl group having 2 to 10 carbon atoms, or a benzoyl group (however, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a phenyl group, or an alkyl group having 1 to 6 carbon atoms) And may be substituted with one or more of an alkoxy group, a phenoxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms), and d represents an integer of 1 to 10. ]

  According to the photosensitive resin composition of the present invention having the above configuration, the compound represented by the general formula (1) having two or more groups represented by the general formula (2) is used as a sensitizer. Thus, good light absorption characteristics can be exhibited with respect to light having a wavelength of 400 to 440 nm, and sufficient sensitivity and sufficient resolution can be obtained. Furthermore, the sensitizer represented by the general formula (1) can exhibit excellent solubility in the solvent used in the photosensitive resin composition, and is a good resist without sensitizer precipitation. Shape can be obtained.

  In the photosensitive resin composition of the present invention, the tertiary amino compound (D) has a maximum absorption wavelength in the range of 370 nm to 440 nm and a molar extinction coefficient at a wavelength of 405 nm of 50,000 or more. It is preferable that Thereby, the photosensitive resin composition can show more suitable light absorption characteristics with respect to light having a wavelength of 400 to 440 nm, can obtain more sufficient sensitivity and more sufficient resolution, and is excellent. A resist shape can be obtained.

  Moreover, it is preferable that the photosensitive resin composition of this invention contains the tertiary amino compound represented by following General formula (3) as said (D) tertiary amino compound.

［式（３）中、Ｒ^５、Ｒ^６及びＲ^７はそれぞれ独立に、炭素数１〜１０のアルキル基、炭素数１〜４のアルコキシ基を示し、ｅ、ｆ及びｇは、ｅ＋ｆ＋ｇの値が１以上となるように選ばれる０〜５の整数を示す。］

[In Formula (3), R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and e, f and g are values of e + f + g. Represents an integer of 0 to 5 selected so that is 1 or more. ]

  By containing the tertiary amino compound represented by the general formula (3), the photosensitive resin composition can exhibit more preferable light absorption characteristics with respect to light having a wavelength of 400 to 440 nm, and is more sufficiently Sensitivity and more sufficient resolution can be obtained. Further, the tertiary amino compound represented by the general formula (3) can exhibit better solubility in the solvent used in the photosensitive resin composition, and there is no precipitation of the sensitizer. A good resist shape can be obtained.

  Moreover, it is preferable that the photosensitive resin composition of this invention contains the 2,4,5-triaryl imidazole dimer represented by following General formula (4) as said (C) photoinitiator. .

［式（４）中、Ａｒ^１、Ａｒ^２、Ａｒ^３及びＡｒ^４はそれぞれ独立に、アルキル基、アルケニル基及びアルコキシ基からなる群より選ばれる少なくとも１つの置換基を有していてもよいアリール基を示し、Ｘ^１及びＸ^２はそれぞれ独立に、塩素原子、アルキル基、アルケニル基又はアルコキシ基を示し、ｐ及びｑはそれぞれ独立に１〜５の整数を示す。但し、Ｘ^１及びＸ^２の少なくとも１つは塩素原子を示す。］

[In formula (4), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have an aryl which may have at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group. Represents a group, X ¹ and X ² each independently represent a chlorine atom, an alkyl group, an alkenyl group or an alkoxy group, and p and q each independently represents an integer of 1 to 5. However, at least one of X ¹ and X ² represents a chlorine atom. ]

  By containing the 2,4,5-triarylimidazole dimer represented by the general formula (4), the photosensitive resin composition is sufficiently and uniformly cured with light having a wavelength of 400 to 440 nm, More sufficient sensitivity and more sufficient resolution can be obtained, and a better resist shape can be obtained.

  Furthermore, the photosensitive resin composition of the present invention contains a binder polymer having a structural unit represented by the following general formula (5) and a structural unit represented by the general formula (6) as the (A) binder polymer. It is preferable to do.

［式（５）中、Ｒ^１１は水素原子、又は、メチル基を示し、Ｒ^１２は炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、水酸基、又は、ハロゲン原子を示し、ｒは０〜５の整数を示す。］

[In the formula (5), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, or a halogen atom, r shows the integer of 0-5. ]

［式（６）中、Ｒ^１３は水素原子、又は、メチル基を示す。］

[In the formula (6), R ¹³ represents a hydrogen atom or a methyl group. ]

  By containing the binder polymer having the structural unit represented by the general formula (5) and the structural unit represented by the general formula (6), the photosensitive resin composition has excellent alkali developability. The adhesion of the formed resist to the substrate can be improved.

  The present invention also provides a photosensitive element comprising a support and a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention formed on the support.

  According to such a photosensitive element, by providing the photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention, it is possible to exhibit good light absorption characteristics with respect to light having a wavelength of 400 to 440 nm. Sufficient sensitivity and sufficient resolution can be obtained. In addition, a good resist shape without sensitizer precipitation can be obtained.

  The present invention also includes a step of laminating a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention on a circuit forming substrate, and irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays. Provided is a resist pattern forming method in which an exposed portion is photocured and then a portion other than the exposed portion is removed.

  The present invention further provides a method for producing a printed wiring board, in which a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern of the present invention is etched or plated.

  Since the resist pattern forming method of the present invention and the printed wiring board manufacturing method of the present invention use the above-described photosensitive resin composition of the present invention, light having a wavelength of 400 to 440 nm is used as exposure light. In addition, sufficient sensitivity and sufficient resolution can be obtained, and a resist pattern having a good resist shape can be obtained. And according to the manufacturing method of the above-mentioned printed wiring board of the present invention, a high-density printed wiring board can be manufactured efficiently and with high throughput.

  According to the present invention, when light having a wavelength of 400 to 440 nm is used as exposure light, the sensitizer has good solubility in a solvent, and sufficient sensitivity and sufficient resolution can be obtained. It is possible to provide a photosensitive resin composition capable of obtaining a good resist shape without sensitizer deposition, a photosensitive element using the same, a method for forming a resist pattern, and a method for producing a printed wiring board.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. In the present invention, (meth) acrylic acid indicates acrylic acid or methacrylic acid corresponding thereto, (meth) acrylate means acrylate or methacrylate corresponding thereto, and (meth) acryloyl group means acryloyl group or Means a methacryloyl group;

(Photosensitive resin composition)
The photosensitive resin composition of the present invention comprises (A) a binder polymer (hereinafter sometimes referred to as “component (A)”) and (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond. (Hereinafter referred to as “component (B)” in some cases), (C) photopolymerization initiator (hereinafter referred to as “component (C)” in some cases), and (D) represented by the following general formula (1). A tertiary amino compound (hereinafter referred to as “component (D)” in some cases). Hereinafter, each component will be described in detail.

  First, the binder polymer as component (A) will be described.

  Examples of the (A) binder polymer include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. From the viewpoint of alkali developability, an acrylic resin is preferable. These can be used individually by 1 type or in combination of 2 or more types.

  The (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyl toluene, α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, vinyl, and the like. -Esters of vinyl alcohol such as n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meta ) Acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid , Α-bu Mo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, Examples include maleic acid monoesters such as monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. You may use these individually by 1 type or in combination of 2 or more types arbitrarily.

As said (meth) acrylic-acid alkylester, the compound etc. which the hydroxyl group, the epoxy group, the halogen group, etc. substituted to the compound represented by following General formula (7) and the alkyl group of these compounds are mentioned, for example. However, in the following general formula (7), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents an alkyl group having 1 to 12 carbon atoms.
^{_{CH 2 = C (R 21)}} -COOR 22 (7)

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ²² in the general formula (7) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Nonyl group, decyl group, undecyl group, dodecyl group and structural isomers thereof can be mentioned.

  Examples of the monomer represented by the general formula (7) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (Meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (Meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester and the like. These can be used alone or in any combination of two or more.

  (A) When an acrylic resin is used as the binder polymer, from the viewpoint of improving both the adhesion and release characteristics of the photosensitive resin composition layer having the photosensitive resin composition as a constituent material to the circuit forming substrate, this (A It is preferable that a structural unit based on styrene or a styrene derivative as shown in the general formula (5) is contained in the molecule of the binder polymer. In the present invention, the “styrene derivative” refers to a compound in which a hydrogen atom in styrene is substituted with a substituent (an organic group such as an alkyl group or a halogen atom).

  The content of structural units based on styrene or styrene derivatives is preferably 3 to 30% by mass, more preferably 4 to 28% by mass, and more preferably 5 to 27% by mass based on the mass of the binder polymer. It is particularly preferred. If this content is less than 3% by mass, the above-mentioned adhesion tends to be inferior. If this content exceeds 30% by mass, the peel piece tends to be large and the peel time tends to be long.

  From the viewpoint of alkali developability and resolution, the (A) binder polymer preferably contains a structural unit based on (meth) acrylic acid as shown in the general formula (6).

  The content of the structural unit based on (meth) acrylic acid is preferably 20 to 50% by mass, more preferably 23 to 40% by mass based on the mass of the binder polymer, and 25 to 35% by mass. It is particularly preferred. When the content of the structural unit based on (meth) acrylic acid is less than 20% by mass, the alkali solubility is inferior, the peeling piece tends to be large, and the peeling time tends to be long. If this content exceeds 50% by mass, There is a tendency for image quality to decrease.

  From the viewpoint of resolution and peelability, the (A) binder polymer more preferably has a structural unit based on benzyl (meth) acrylate or a benzyl (meth) acrylate derivative.

  The content of the structural unit based on benzyl (meth) acrylate or benzyl (meth) acrylate is preferably 10 to 60% by mass, and preferably 15 to 50% by mass based on the mass of the binder polymer. Further preferred is 20 to 50% by mass. If the content of the structural unit based on benzyl (meth) acrylate or a benzyl derivative (meth) acrylate is less than 10% by mass, the resolution tends to be inferior. It tends to be large and the peeling time is long.

  The (A) binder polymer in the present invention is preferably composed of one or more kinds of polymers having a carboxyl group from the viewpoint of developability when alkali development is performed using an alkaline solution. Such a (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer.

  (A) It is preferable that the acid value of a binder polymer is 30-200 mgKOH / g, and it is more preferable that it is 45-150 mgKOH / g. When the acid value is less than 30 mg KOH / g, the development time tends to be long, and when it exceeds 200 mg KOH / g, the developer resistance of the photocured resist tends to be lowered. Moreover, when performing solvent image development as a image development process, it is preferable to prepare the polymerizable monomer which has a carboxyl group in a small quantity.

  In the photosensitive resin composition, as the binder polymer (A), one type of binder polymer may be used alone, or two or more types of binder polymers may be used in any combination. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components (including different repeating units as constituent components), two or more types of binders having different weight average molecular weights Examples thereof include polymers and two or more types of binder polymers having different degrees of dispersion. In addition, a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.

  (A) The Mw of the binder polymer is preferably 5000 to 150,000, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 50,000. When Mw is less than 5000, the developer resistance tends to decrease, and when it exceeds 150,000, the development time tends to be long.

  Moreover, (A) The dispersion degree (Mw / Mn) of the binder polymer is preferably 1.0 to 3.0, and more preferably 1.0 to 2.0. When the degree of dispersion exceeds 3.0, the adhesion and resolution tend to decrease.

  In addition, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of (A) binder polymer can be measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene).

  The content of the component (A) in the photosensitive resin composition is preferably 30 to 70% by mass, and 40 to 60% by mass based on the total solid content of the component (A) and the component (B). It is more preferable. If this content is less than 30% by mass, a good resist shape tends to be difficult to obtain, and if it exceeds 70% by mass, good sensitivity and resolution tend to be difficult to obtain.

  Next, the photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond (hereinafter referred to as “(B) photopolymerizable compound” in some cases) as component (B) will be described.

  (B) As the photopolymerizable compound, for example, a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol, a bisphenol A-based (meth) acrylate compound, a glycidyl group-containing compound with α, β- Compounds obtained by reacting unsaturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond in the molecule, nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, (meth) acrylic acid alkyl esters, etc. It is done. These are used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of plating resistance and adhesion, it is preferable to use a bisphenol A-based (meth) acrylate compound or a (meth) acrylate compound having a urethane bond in the molecule as an essential component. Also, a photopolymerizable unsaturated compound having one polymerizable ethylenically unsaturated bond in the molecule and a photopolymerizable unsaturated compound having two or more polymerizable ethylenically unsaturated bonds in the molecule. Use in combination is preferable from the viewpoint of obtaining the effect of the present invention more reliably.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. 14 polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meta) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. These are used individually by 1 type or in combination of 2 or more types. Here, “EO” represents ethylene oxide, and an EO-modified compound represents one having a block structure of an ethylene oxide group. “PO” represents propylene oxide, and a PO-modified compound has a propylene oxide group block structure.

  Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane and the like It is done. Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynona) Toxi) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like.

  2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis (4 -(Methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). The number of ethylene oxide groups in one molecule of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane is preferably 4-20, and more preferably 8-15. . These are used alone or in any combination of two or more.

  Examples of the (meth) acrylate compound having a urethane bond in the molecule include, for example, a (meth) acryl monomer having an OH group at the β-position and a diisocyanate compound (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate). , 1,6-hexamethylene diisocyanate, etc.), tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate Etc. Examples of the EO-modified urethane di (meth) acrylate include UA-11 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). Examples of the EO and PO-modified urethane di (meth) acrylate include UA-13 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). These are used individually by 1 type or in combination of 2 or more types.

  Examples of the nonylphenoxypolyethyleneoxyacrylate include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxynonaethylene Examples include oxyacrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate. These are used alone or in any combination of two or more.

  Examples of the phthalic acid compounds include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloloxyalkyl-o-phthalate. Etc. These are used alone or in any combination of two or more.

  The component (B) preferably includes a bisphenol A (meth) acrylate compound or a (meth) acrylate compound having a urethane bond in the molecule from the viewpoint of plating resistance and adhesion. Moreover, it is preferable that a bisphenol A type (meth) acrylate compound is included from a viewpoint which can improve a sensitivity and a resolution.

  Furthermore, the component (B) preferably contains polyalkylene glycol di (meth) acrylate having both an ethylene glycol chain and a propylene glycol chain in the molecule from the viewpoint of improving the flexibility of the cured film. This (meth) acrylate is not particularly limited as long as it has both an ethylene glycol chain and a propylene glycol chain (n-propylene glycol chain or isopropylene glycol chain) as alkylene glycol chains in the molecule. In addition, this (meth) acrylate further includes an n-butylene glycol chain, an isobutylene glycol chain, an n-pentylene glycol chain, a hexylene glycol chain, an alkylene glycol chain having about 4 to 6 carbon atoms such as a structural isomer thereof. You may have.

  When there are a plurality of ethylene glycol chains and propylene glycol chains, the plurality of ethylene glycol chains and propylene glycol chains do not need to be continuously present in blocks, but may be present randomly. In the isopropylene glycol chain, the secondary carbon of the propylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.

  Examples of the polyalkylene glycol di (meth) acrylate having both an ethylene glycol chain and a propylene glycol chain in the molecule in the component (B) include compounds represented by the following general formula (8), Examples thereof include a compound represented by (9) and a compound represented by the following general formula (10).

Here, the general formula (8), the general formula (9) and the general formula ^(10), in each of R 31 ^{to R 36} independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, EO is ethylene A glycol chain is shown, PO is a propylene glycol chain, and m ^{1 to} m ⁴ and n ^{1 to} n ⁴ are each independently an integer of 1 to 30. These compounds can be used individually by 1 type or in combination of 2 or more types.

In R ^{31 to} R ³⁶ of the general formulas (8) to (10), examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.

The total number (m ¹ + m ² , m ³ and m ⁴ ) of ethylene glycol chain repeats in the general formulas (8) to (10) is an integer of 1 to 30, and an integer of 1 to 10. Is preferable, an integer of 4 to 9 is more preferable, and an integer of 5 to 8 is particularly preferable. If the number of repetitions exceeds 30, the tent reliability and the resist shape tend to deteriorate.

The repeating number total number of propylene glycol chain in the above general formula ^{(8) ~ (10) (} n 1, n 2 + n 3 and ^{n 4)} is an integer of 1 to 30, an integer of 5-20 Is preferable, an integer of 8 to 16 is more preferable, and an integer of 10 to 14 is particularly preferable. If the number of repetitions exceeds 30, the resolution deteriorates and sludge tends to be generated.

Specific examples of the compound represented by the general formula (8) include, for example, vinyl in which R ³¹ = R ³² = methyl group, m ¹ + m ² = 4 (average value), and n ¹ = 12 (average value). And compounds (trade name: FA-023M, manufactured by Hitachi Chemical Co., Ltd.). Specific examples of the compound represented by the general formula (9) include, for example, R ³³ = R ³⁴ = methyl group, m ³ = 6 (average value), n ² + n ³ = 12 (average value) A certain vinyl compound (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-024M) is exemplified. Furthermore, specific examples of the compound represented by the general formula (10) include, for example, vinyl in which R ³⁵ = R ³⁶ = hydrogen atom, m ⁴ = 1 (average value), and n ⁴ = 9 (average value). Examples thereof include compounds (manufactured by Shin-Nakamura Chemical Co., Ltd., sample name: NK ester HEMA-9P). These compounds can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (B) in the photosensitive resin composition is preferably 30 to 70% by mass, and 40 to 60% by mass based on the total solid content of the component (A) and the component (B). It is more preferable. If this content is less than 30% by mass, good sensitivity and resolution tend to be difficult to obtain, and if it exceeds 70% by mass, a good resist shape tends to be difficult to obtain.

  Next, the photoinitiator which is (C) component is demonstrated.

  (C) As the photopolymerization initiator, for example, 4,4′-bis (diethylamino) benzophenone, benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl Aromatic ketones such as -1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, quinones such as alkyl anthraquinones, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, Benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (O-Fluorophenyl) -4,5-diphenylimidazo 2,4,5- such as dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Examples include triarylimidazole dimer, 9-phenylacridine, acridine derivatives such as 1,7-bis (9,9′-acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds.

  Moreover, the substituents of the two aryl groups in 2,4,5-triarylimidazole may give the same and symmetric compounds, or differently give asymmetric compounds. From the viewpoint of adhesion and sensitivity, 2,4,5-triarylimidazole dimer is preferable, and 2,4,5-triarylimidazole dimer represented by the general formula (4) is more preferable. preferable. These are used individually by 1 type or in combination of 2 or more types.

  The content of the component (C) in the photosensitive resin composition is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the component (A) and the component (B). It is more preferably 6 parts by mass, and particularly preferably 3.5 to 5 parts by mass. If this content is less than 0.1 parts by mass, good sensitivity and resolution tend to be difficult to obtain, and if it exceeds 10 parts by mass, a good resist shape tends to be difficult to obtain.

  Next, the tertiary amino compound as component (D) will be described.

上記一般式（１）中、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に、炭素数１〜１０のアルキル基、炭素数１〜４のシクロアルキル基、フェニル基（但し、炭素数１〜４のアルキル基、水酸基、ハロゲン原子、シアノ基、カルボキシル基、フェニル基、炭素数１〜４のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基の１個以上で置換されてもよい）、水酸基、ハロゲン原子、シアノ基、カルボキシル基、炭素数１〜６のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基、ベンジル基（但し、炭素数１〜６のアルキル基、水酸基、ハロゲン原子、シアノ基、カルボキシル基、フェニル基、炭素数１〜６のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基の１個以上で置換されてもよい）、炭素数２〜１０のアルカノイル基、ベンゾイル基（但し、炭素数１〜６のアルキル基、水酸基、ハロゲン原子、シアノ基、カルボキシル基、フェニル基、炭素数１〜６のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基の１個以上で置換されてもよい）、又は、下記一般式（２）で表される基を示し、Ｒ^１、Ｒ^２及びＲ^３の少なくとも２つは下記一般式（２）で表される基を示し、ａ、ｂ及びｃは、ａ＋ｂ＋ｃの値が２以上となるように選ばれる０〜５の整数を示す。なお、ａが２以上の場合、複数存在するＲ^１は同一でも異なっていてもよく、ｂが２以上の場合、複数存在するＲ^２は同一でも異なっていてもよく、ｃが２以上の場合、複数存在するＲ^３は同一でも異なっていてもよい。また、Ｒ^１、Ｒ^２及びＲ^３の少なくとも２つは下記一般式（２）で表される基を示すが、Ｒ^１、Ｒ^２又はＲ^３が２以上存在する場合には、下記一般式（２）で表される基は、２以上のＲ^１、２以上のＲ^２、又は、２以上のＲ^３のいずれかとしてのみ存在していてもよい。すなわち、例えばａが２以上であり、且つ、２以上のＲ^１が下記一般式（２）で表される基であれば、Ｒ^２及びＲ^３は下記一般式（２）で表される基以外であってもよい。 The tertiary amino derivative as component (D) is represented by the following general formula (1).

In the general formula (1), R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 4 carbon atoms, or a phenyl group (however, the number of carbon atoms is 1 to 4). And may be substituted with one or more of an alkyl group, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms) , A hydroxyl group, a halogen atom, a cyano group, a carboxyl group, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group, an alkoxycarbonyl group having 2 to 6 carbon atoms, a benzyl group (however, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, Substituted with one or more of a halogen atom, a cyano group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms Good), alkanoyl group having 2 to 10 carbon atoms, benzoyl group (however, alkyl group having 1 to 6 carbon atoms, hydroxyl group, halogen atom, cyano group, carboxyl group, phenyl group, alkoxy group having 1 to 6 carbon atoms, phenoxy) A group represented by the following general formula (2), or at least 2 of R ¹ , R ² and R ³ : One represents a group represented by the following general formula (2), and a, b and c represent an integer of 0 to 5 selected so that the value of a + b + c is 2 or more. When a is 2 or more, a plurality of R ¹ may be the same or different, and when b is 2 or more, a plurality of R ² may be the same or different, and c is 2 or more A plurality of R ³ may be the same or different. Further, at least two of R ¹ , R ² and R ³ represent a group represented by the following general formula (2), but when two or more R ¹ , R ² or R ³ are present, the following general formula The group represented by (2) may be present only as ^one of two or more R ¹ , two or more R ² , or two or more R ³ . That is, for example, when a is 2 or more and R ¹ or more is a group represented by the following general formula (2), R ² and R ³ are groups represented by the following general formula (2). It may be other than.

上記一般式（２）中、Ｒ^４は炭素数１〜１０のアルキル基、炭素数１〜４のシクロアルキル基、フェニル基（但し、炭素数１〜４のアルキル基、水酸基、ハロゲン原子、シアノ基、カルボキシル基、フェニル基、炭素数１〜４のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基の１個以上で置換されてもよい）、ベンジル基（但し、炭素数１〜６のアルキル基、水酸基、ハロゲン原子、シアノ基、カルボキシル基、フェニル基、炭素数１〜６のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基の１個以上で置換されてもよい）、炭素数２〜１０のアルカノイル基、又は、ベンゾイル基（但し、炭素数１〜６のアルキル基、水酸基、ハロゲン原子、シアノ基、カルボキシル基、フェニル基、炭素数１〜６のアルコキシ基、フェノキシ基、炭素数２〜６のアルコキシカルボニル基の１個以上で置換されてもよい）を示し、ｄは１〜１０の整数を示す。

In the general formula (2), R ⁴ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 4 carbon atoms, a phenyl group (provided that the alkyl group has 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, cyano, A group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an alkoxycarbonyl group having 2 to 6 carbon atoms, a benzyl group (provided that the carbon number is 1 to May be substituted with one or more of 6 alkyl groups, hydroxyl groups, halogen atoms, cyano groups, carboxyl groups, phenyl groups, alkoxy groups having 1 to 6 carbon atoms, phenoxy groups, and alkoxycarbonyl groups having 2 to 6 carbon atoms. ), An alkanoyl group having 2 to 10 carbon atoms, or a benzoyl group (however, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a phenyl group, 1 carbon atom) And may be substituted with one or more of an alkoxy group of -6, a phenoxy group, or an alkoxycarbonyl group having 2 to 6 carbon atoms, and d represents an integer of 1 to 10.

  Moreover, as a compound represented by the said General formula (1), the compound represented by the following general formula (3) is preferable from a viewpoint of acquiring the effect of this invention more fully.

In the general formula (3), R ⁵ , R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and e, f and g are represented by e + f + g. The integer of 0-5 chosen so that a value may become 1 or more is shown. When e is 2 or more, a plurality of R ⁵ may be the same or different, and when f is 2 or more, a plurality of R ⁶ may be the same or different, and when g is 2 or more A plurality of R ⁷ may be the same or different.

  Specific examples of the compound represented by the general formula (3) include, for example, compounds represented by the following formulas (11) to (12).

  Moreover, as a compound represented by the said General formula (1), as a specific example other than the compound represented by the said General formula (3), the compound represented by following formula (13)-(15) is mentioned, for example. It is mentioned as preferable.

  Further, from the viewpoint of obtaining excellent sensitivity and resolution, the maximum absorption wavelength of the (D) tertiary amino compound is preferably in the range of 370 nm to 440 nm, more preferably in the range of 380 nm to 420 nm, It is particularly preferable that it is in the range of 390 nm to 415 nm.

  Further, from the viewpoint of obtaining excellent sensitivity and resolution, the molar extinction coefficient of the (D) tertiary amino compound at a wavelength of 405 nm is preferably 50,000 or more, more preferably 60,000 or more, 65 000 to 80,000 is particularly preferable.

  The content of the component (D) in the photosensitive resin composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the components (A) and (B). It is more preferable to set it as 0.05-5 mass parts, and it is especially preferable to set it as 0.1-2 mass parts. If this content is less than 0.01 parts by mass, good sensitivity and resolution tend not to be obtained, and if it exceeds 10 parts by mass, a good resist shape tends to be not obtained.

  In addition, the photosensitive resin composition includes a photopolymerizable compound (for example, oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, malachite green, and the like, if necessary. Dyes, photochromic agents such as tribromophenylsulfone and leucocrystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion imparting Agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, and the like are each 0.01 to 100 parts by mass of the total solid content of component (A) and component (B). About 20 parts by mass can be contained. These are used individually by 1 type or in combination of 2 or more types.

  The photosensitive resin composition of the present invention is dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. It is good also as a solution about 30-60 mass% of solid content. This solution can be used as a coating solution for forming a photosensitive resin composition layer of a photosensitive element described later.

  In addition, the above coating solution may be used for forming a photosensitive resin composition layer of a photosensitive element by applying and drying on a support film described later, for example, on the surface of a metal plate, After applying and drying as a liquid resist, a protective film may be coated and used. Examples of the metal plate include copper, copper-based alloys, iron-based alloys such as nickel, chromium, iron, and stainless steel, and copper, copper-based alloys, and iron-based alloys are preferable.

  Moreover, although the layer thickness of the photosensitive resin composition layer formed using the photosensitive resin composition changes with uses of the photosensitive element, it is preferable that it is about 1-100 micrometers by the thickness after drying. When the above-mentioned liquid resist is used after being coated with a protective film, examples of the protective film include polymer films such as polyethylene and polypropylene.

(Photosensitive element)
Next, the photosensitive element of the present invention will be described. The photosensitive element of this invention is equipped with a support film (support) and the photosensitive resin composition layer which consists of the said photosensitive resin composition of this invention formed on this support film.

  Here, FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 includes a support film 10 and a photosensitive resin composition layer 14 provided on the support film 10. The photosensitive resin composition layer 14 is a layer made of the above-described photosensitive resin composition of the present invention. Moreover, the photosensitive element 1 of this invention may coat | cover the surface F1 on the opposite side to the support film 10 on the photosensitive resin composition layer 14 with a protective film.

  As the support film 10, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.

  Moreover, it is preferable that thickness is 1-100 micrometers, and, as for a support film (polymer film), it is more preferable that it is 5-25 micrometers. If the thickness is less than 1 μm, the support film tends to be broken when the support film is peeled off before development, and if it exceeds 100 μm, the resolution tends to decrease.

  One polymer film is used as a support for the photosensitive resin composition layer 14 and the other is used as a protective film for the photosensitive resin composition 14 by being laminated on both sides of the photosensitive resin composition layer. May be.

  Moreover, as a protective film, what the adhesive force between the photosensitive resin composition layer 14 and a protective film becomes smaller than the adhesive force between the photosensitive resin composition layer 14 and the support film 10 is used. It is preferable to use it. Moreover, as a protective film, a film of a low fish eye is preferable. "Fish eye" means that when a material is melted by heat, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidized degradation products, etc. It is taken in.

  As the protective film, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. Examples of commercially available products include polypropylene films such as Alphan MA-410 and E-200C manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and PS series such as PS-25 manufactured by Teijin Limited. However, the present invention is not limited to this.

  The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, still more preferably 5 to 30 μm, and particularly preferably 15 to 30 μm. If the thickness is less than 1 μm, the protective film tends to be broken during lamination, and if it exceeds 100 μm, the cost tends to be inferior.

  The photosensitive resin composition layer 14 is prepared by dissolving the photosensitive resin composition of the present invention in a solvent as described above to obtain a solution (coating solution) having a solid content of about 30 to 60% by mass. The coating liquid) can be formed on the support film 10 and dried.

  The coating can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater. Drying can be performed at 70 to 150 ° C. for about 5 to 30 minutes. Moreover, it is preferable that the amount of the residual organic solvent in the photosensitive resin composition layer 14 shall be 2 mass% or less from the point which prevents the spreading | diffusion of the organic solvent in a next process.

  Moreover, although the thickness of the photosensitive resin composition layer 14 changes with uses, it is preferable that it is 1-100 micrometers in the thickness after drying, and it is more preferable that it is 1-50 micrometers. If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the effect of the present invention is reduced, and the adhesive force and resolution tend to decrease.

  The photosensitive element of the present invention may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. Moreover, the obtained photosensitive element can be wound up and stored in a sheet form or a roll around a core. At this time, it is preferable that the support is wound up so as to be the outermost side. An end face separator is preferably installed on the end face of the roll-shaped photosensitive element roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance. Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer).

(Method for forming resist pattern)
Next, the resist pattern forming method of the present invention will be described. In the method for forming a resist pattern of the present invention, a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention is laminated on a circuit forming substrate, and an active portion is formed on a predetermined portion of the photosensitive resin composition layer. This is a method of irradiating a light beam to photocur the exposed portion, and then removing portions other than the exposed portion. The “circuit forming substrate” refers to a substrate including an insulating layer and a conductor layer formed on the insulating layer.

  Lamination of the photosensitive resin composition layer on the substrate is performed, for example, by applying the photosensitive resin composition on the substrate by a method such as screen printing, spraying, roll coating, curtain coating, or electrostatic coating. And it can carry out by drying a coating film at 60-110 degreeC.

Moreover, you may laminate | stack the photosensitive resin composition layer on a board | substrate using the photosensitive element of this invention mentioned above. As a lamination method in that case, when the photosensitive element is provided with a protective film, the protective film is removed, and then the photosensitive resin composition layer is heated to about 70 ° C. to 130 ° C. while being applied to the substrate at 0.1 MPa to 1 MPa. the degree method in which bonding at a pressure of ^{(1kgf / cm 2 ~10kgf / cm} 2 or so) can be mentioned. Such a lamination process is preferably performed under reduced pressure from the viewpoint of adhesion and followability. The surface of the substrate on which the photosensitive resin composition layer is laminated is usually a metal surface, but is not particularly limited.

  Further, if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the circuit forming substrate in advance, but in order to further improve the laminating property, Pre-heat treatment of the substrate can also be performed.

  The exposed portion is photocured by irradiating the photosensitive resin composition layer laminated on the substrate with an actinic ray in an image form through a negative or positive mask pattern called an artwork. At this time, when a photosensitive resin composition layer is laminated using a photosensitive element, a support is present on the photosensitive resin composition layer, but this support is transparent to actinic rays. In the case where the support is capable of irradiating actinic rays through the support, and the support exhibits a light shielding property against the actinic rays, the active resin is exposed to the photosensitive resin composition layer after the support is removed. Irradiate.

  Further, as an exposure method, a method of irradiating actinic rays in an image form by a direct drawing method such as a laser direct drawing exposure method or a DLP (Digital Light Processing) exposure method may be employed.

  As a light source of actinic light, a known light source, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, an Ar ion laser, a semiconductor laser, or the like, effectively emits ultraviolet light, visible light, or the like. Things are used.

  In the present invention, it is desirable to use an actinic ray obtained by cutting 99.5% or more of light having a wavelength of 365 nm or less from a mercury lamp light source using a filter, or light having a wavelength of 405 nm from a semiconductor laser. As a filter for cutting light having a wavelength of 365 nm or less, for example, a sharp cut filter SCF-100S-39L manufactured by Sigma Kogyo Co., Ltd. can be used.

  After formation of the exposed portion, the photosensitive resin composition layer (unexposed portion) other than the exposed portion is removed by development to form a resist pattern. As a method for removing such an unexposed portion, when a support is present on the photosensitive resin composition layer, the support is removed with an auto peeler or the like, and a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used. Examples include a method in which an unexposed portion is removed and developed by wet development or dry development.

  For example, in the case of wet development, using a developer corresponding to a photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer, an organic solvent developer, etc., for example, spraying, rocking immersion, brushing, scraping, etc. Development is performed by a known method.

  As the developing solution, a safe and stable solution having good operability such as an alkaline aqueous solution is used. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate, potassium phosphate, and phosphoric acid. Alkali metal phosphates such as sodium and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used.

  Moreover, as alkaline aqueous solution used for image development, 0.1-5 mass% dilute solution of sodium carbonate, 0.1-5 mass% dilute solution of potassium carbonate, 0.1-5 mass% dilute solution of sodium hydroxide, A dilute solution of 0.1 to 5% by mass sodium tetraborate is preferred. Moreover, it is preferable to make pH of the alkaline aqueous solution used for image development into the range of 9-11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, in the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.

  Examples of the aqueous developer include a developer composed of water or an alkaline aqueous solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution, in addition to the substances described above, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1, 3 -Propanediol, 1,3-diaminopropanol-2, morpholine and the like. The pH of the developer is preferably as low as possible within a range where the resist can be sufficiently developed, preferably pH 8-12, more preferably pH 9-10.

  Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. It is done. These are used alone or in combination of two or more. The concentration of the organic solvent is usually preferably 2 to 90% by mass, and the temperature can be adjusted according to the developability. Further, a small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

  These organic solvents preferably add water in the range of 1 to 20% by mass in order to prevent ignition. Moreover, you may use together 2 or more types of image development methods as needed. Development methods include a dip method, a battle method, a spray method, brushing, and slapping, and the high pressure spray method is most suitable for improving the resolution.

Examples of the development method include a dip method, a spray method, brushing, and slapping. As the treatment after development, the resist pattern may be further cured and used by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² as necessary. For the etching of the metal surface performed after development, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like can be used.

(Printed wiring board manufacturing method)
Next, the manufacturing method of the printed wiring board of this invention is demonstrated. The method for producing a printed wiring board of the present invention comprises etching or plating a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern of the present invention.

  Etching and plating of the circuit forming substrate is performed on a conductor layer or the like of the circuit forming substrate using the formed resist pattern as a mask.

  Etching solutions used for etching include cupric chloride solution, ferric chloride solution, alkaline etching solution, and hydrogen peroxide etching solution. It is preferable to use an iron solution.

  Moreover, as a plating method in the case of plating, for example, copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel sulfamate, etc. Nickel plating, hard gold plating, and gold plating such as soft gold plating.

  After completion of etching or plating, the resist pattern can be peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. As this strongly alkaline aqueous solution, for example, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used. Examples of the peeling method include an immersion method and a spray method, and the immersion method and the spray method may be used alone or in combination. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole. Thus, a printed wiring board is obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

[Examples 1-8 and Comparative Examples 1-4]
First, a mixed solvent obtained by mixing methyl cellosolve and toluene at a mass ratio of 3: 2 to a copolymer obtained by copolymerizing the monomers shown in Table 1 below with a copolymerization ratio (unit: parts by mass) shown in the table is solid. Binder polymers A and B were prepared so that the partial concentration was 40% by mass. The weight average molecular weights of the binder polymers A and B are shown in Table 1.

  Next, the composition was mix | blended according to the compounding composition (unit: mass part) shown to the following Tables 2-3, and the solution of the photosensitive resin composition of Examples 1-8 and Comparative Examples 1-4 was obtained. In addition, in the following Tables 2-3, the compounding quantity of each component other than a solvent shows the compounding quantity of solid content.

In addition, the detail of each component in Tables 2-3 is as follows.
<Photopolymerizable compound>
FA-321M: trade name, manufactured by Hitachi Chemical Co., Ltd. FA-023M: trade name, manufactured by Hitachi Chemical Co., Ltd. <photopolymerization initiator>
BCIM: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole <sensitizer>
Sensitizer (1): compound represented by the above formula (11) Sensitizer (2): compound represented by the following formula (16) Sensitizer (3): represented by the following formula (17) Compound Sensitizer (4): Compound represented by the following formula (18) <Coloring agent>
Leuco crystal violet <dye>
Malachite green

Table 4 shows the solubility of the sensitizers (1) to (4) and the molar extinction coefficient at a wavelength of 405 nm. Here, the solubility indicates the amount (g) of acetone necessary for dissolving 0.01 g of the sensitizer. The molar extinction coefficient is calculated based on the absorbance measured as follows using a UV spectrometer (trade name: U-3310 spectrophotometer, manufactured by Hitachi, Ltd.). That is, first, a dilute solution (concentration: 1.0 × 10 ⁻⁵ mol·L ⁻¹ ) of a sensitizer to be measured was prepared using CH ₂ Cl ₂ as a solvent. Next, a diluted solution of a sensitizer in a quartz cell is placed on the measurement side of the UV spectrometer, and a solvent (CH ₂ Cl ₂ ) in the quartz cell is placed on the reference side, and the absorbance mode is set to 550 to 300 nm. Was continuously measured. The absorbance obtained at a wavelength of 405 nm is A, the concentration of the dilute solution is C (mol·L ⁻¹ ), the optical path length of the quartz cell is L (cm), and the sensitizer is expressed by the following formula (I). The molar extinction coefficient α was calculated.

  Next, the obtained photosensitive resin composition solution was uniformly coated on a 16 μm-thick polyethylene polyethylene terephthalate film (PET film) as a support film, and dried in a hot air convection dryer at 70 ° C. and 110 ° C. A photosensitive resin composition layer was formed to obtain a photosensitive element. The film thickness of the photosensitive resin composition layer was 25 μm.

<Evaluation of solubility of sensitizer>
The solutions of the photosensitive resin compositions obtained in Examples and Comparative Examples were allowed to stand at room temperature (23 ° C.) for 2 hours, and then the presence or absence of precipitation of the sensitizer was visually observed to dissolve the sensitizer. Sex was evaluated. The results are shown in Tables 5-6. In addition, when precipitation of a sensitizer is observed in the above evaluation, it is not preferable because precipitates are likely to be generated in the resist pattern, and defects such as disconnection and short circuit are likely to occur during wiring pattern formation.

<Measurement of absorbance>
In the photosensitive element obtained by the Example and the comparative example, the optical density (OD value) with respect to the exposure wavelength of the photosensitive resin composition layer was measured using a UV spectrophotometer (manufactured by Hitachi, Ltd., trade name: U-). 3310 spectrophotometer). O. D. For the measurement of the value, a photosensitive element composed of a support film and a photosensitive resin composition layer is placed on the measurement side, a support film is placed on the reference side, continuous measurement is performed with light having a wavelength of 550 to 300 nm in the absorbance mode, and UV absorption is performed. A spectrum was obtained, in which the absorbance value at a wavelength of 405 nm was read, and O.D. D. Value. The results are shown in Tables 5-6.

<Measurement of photosensitivity>
About each of the photosensitive element obtained by the Example and the comparative example, the photosensitive resin composition layer was laminated | stacked on the copper clad laminated board with the following method, and the laminated body was obtained. That is, the copper surface of a copper clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-67), which is a glass epoxy agent in which copper foil (thickness 35 mm) is laminated on both sides, is a brush equivalent to # 600. Polishing was performed using a polishing machine (manufactured by Sankei Co., Ltd.), washed with water, and then dried with an air flow. Then, the obtained copper-clad laminate was heated to 80 ° C., the photosensitive element on the copper-clad laminate, and the photosensitive resin composition layer in close contact with the surface of the copper-clad laminate, A laminate was obtained by laminating under conditions of a temperature of 120 ° C. and a pressure of 0.4 MPa.

  The laminate is cooled to 23 ° C., and on the surface of the polyethylene terephthalate film located in the outermost layer of the laminate, a concentration region of 0.00 to 2.00, a concentration step of 0.05, and a tablet (rectangle) A phototool having a 41-step tablet with a size of 20 mm × 187 mm and a size of each step (rectangle) of 3 mm × 12 mm was brought into close contact.

  In this state, using a direct drawing exposure machine (trade name: DE-1AH, manufactured by Hitachi Via Mechanics, Inc.) using a 405 nm blue-violet laser diode as a light source, the number of remaining step stages after development of the 41-step tablet is 17 steps. Exposure was performed with an exposure amount of This exposure amount was defined as sensitivity. The sensitivity evaluation is better as the numerical value is smaller. The results are shown in Tables 5-6.

<Evaluation of resolution>
A laminate was produced in the same manner as in the photosensitivity measurement. This laminated body is cooled to 23 ° C., and a direct drawing exposure machine (manufactured by Hitachi Via Mechanics Co., Ltd.) using a 405 nm blue-violet laser diode as a light source on the polyethylene terephthalate film located in the outermost layer of the laminated body. Name: DE-1AH), the line width / space width is 6/6 to 22/22 (unit: 60 mJ · cm ⁻² , 70 mJ · cm ^−2, and 80 mJ · cm ⁻² ). mm) blank pattern (resolution (removed)) and left pattern (resolution (remaining)) were exposed.

  Here, FIG. 2 is a top view schematically showing the direct drawing data for resolution evaluation. In the blank pattern, the space portion 24 is exposed in the direct drawing data 20 shown in FIG. On the other hand, as for the remaining pattern, the line part 22 is exposed in the direct drawing data 20 shown in FIG.

  Next, the polyethylene terephthalate film was peeled off, and a 1% by mass sodium carbonate aqueous solution was sprayed at 30 ° C. for 24 seconds to remove unexposed portions. The resolution (remaining) was evaluated based on the smallest value of the line width in which the unexposed portion (space portion 24) can be removed cleanly by the development process, and the line is generated without forming a snake shape or chipping. Further, the resolution (extraction) was evaluated based on the smallest value of the space width in which the unexposed part (line part 22) could be removed cleanly by the development process. The smaller the numerical value, the better the resolution evaluation. The results are shown in Tables 5-6.

<Evaluation of presence or absence of precipitates>
In the evaluation of the resolution, the surface of the resist pattern formed under the condition of the exposure (80 mJ · cm ⁻² ) at the time of the evaluation of the resolution (remaining) was observed using a Hitachi scanning electron microscope S-500A. The presence or absence was confirmed. The results are shown in Tables 5-6.

It is a schematic cross section which shows suitable one Embodiment of the photosensitive element of this invention. It is a top view which shows the direct drawing data for resolution evaluation typically.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body (support film), 14 ... Photosensitive resin composition layer, 20 ... Direct drawing data, 22 ... Line part, 24 ... Space part.

Claims (8)

(A) a binder polymer;
(B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond;
(C) a photopolymerization initiator;
(D) a tertiary amino compound represented by the following general formula (1);
Containing a photosensitive resin composition.

[In the formula (1), R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 4 carbon atoms, a phenyl group (however, having 1 to 4 carbon atoms) An alkyl group, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an alkoxycarbonyl group having 2 to 6 carbon atoms). Hydroxyl group, halogen atom, cyano group, carboxyl group, alkoxy group having 1 to 6 carbon atoms, phenoxy group, alkoxycarbonyl group having 2 to 6 carbon atoms, benzyl group (however, alkyl group having 1 to 6 carbon atoms, hydroxyl group, halogen) (It may be substituted with one or more of an atom, a cyano group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms) , An alkanoyl group having 2 to 10 carbon atoms, a benzoyl group (however, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group, Or a group represented by the following general formula (2), and at least two of R ¹ , R ² and R ³ may be substituted with one or more alkoxycarbonyl groups having 2 to 6 carbon atoms) The group represented by following General formula (2) is shown, a, b, and c show the integer of 0-5 chosen so that the value of a + b + c may be 2 or more. ]

[In the formula (2), R ⁴ represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 4 carbon atoms, a phenyl group (provided that an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, a cyano group. , A carboxyl group, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, one or more alkoxy groups having 2 to 6 carbon atoms, and a benzyl group (provided that the carbon number is 1 to 6 And may be substituted with one or more of an alkyl group, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms) , An alkanoyl group having 2 to 10 carbon atoms, or a benzoyl group (however, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a phenyl group, or an alkyl group having 1 to 6 carbon atoms) And may be substituted with one or more of an alkoxy group, a phenoxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms), and d represents an integer of 1 to 10. ]   The photosensitive resin according to claim 1, wherein the tertiary amino compound (D) has a maximum absorption wavelength in the range of 370 nm to 440 nm and a molar extinction coefficient at a wavelength of 405 nm of 50,000 or more. Composition. The photosensitive resin composition of Claim 1 or 2 containing the tertiary amino compound represented by following General formula (3) as said (D) tertiary amino compound.

[In Formula (3), R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and e, f and g are values of e + f + g. Represents an integer of 0 to 5 selected so that is 1 or more. ] The photosensitivity as described in any one of Claims 1-3 which contains the 2,4,5-triaryl imidazole dimer represented by the following general formula (4) as said (C) photoinitiator. Resin composition.

[In formula (4), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have an aryl which may have at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group. Represents a group, X ¹ and X ² each independently represent a chlorine atom, an alkyl group, an alkenyl group or an alkoxy group, and p and q each independently represents an integer of 1 to 5. However, at least one of X ¹ and X ² represents a chlorine atom. ] 5. The binder polymer having a structural unit represented by the following general formula (5) and a structural unit represented by the general formula (6) as the (A) binder polymer. The photosensitive resin composition as described in 2.

[In the formula (5), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, or a halogen atom, r shows the integer of 0-5. ]

[In the formula (6), R ¹³ represents a hydrogen atom or a methyl group. ]   A photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the photosensitive resin composition as described in any one of Claims 1-5 formed on this support body.   A photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 5 is laminated on a circuit forming substrate, and active light is applied to a predetermined portion of the photosensitive resin composition layer. Is used for photocuring the exposed portion and then removing the portion other than the exposed portion. A method for manufacturing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 7.

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