JP2013246387A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition and a photosensitive resin laminate, which are excellent in resolution, in preventing a reddish surface of a substrate, and in contamination resistance in a copper sulfate plating solution, and to provide a method for forming a resist pattern and a method for forming a conductive pattern by using the photosensitive resin laminate.SOLUTION: The photosensitive resin composition comprises (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, (D) a sensitizer, and (E) an additive. The photosensitive composition contains, on the basis of the total amount of (A) to (E), 0.01 to 10 mass% of a hexaarylbiimidazole compound as the (C) photopolymerization initiator, 0.01 to 1 mass% of a bisbenzoxazolyl thiophene derivative and/or a bisbenzoxazolyl naphthalene derivative as the (D) sensitizer, and 0.01 to 5 mass% of carboxyl banzotriazoles as the (E) additive.

Description

  The present invention relates to a photosensitive resin composition and the like.

  For electronic devices such as personal computers or mobile phones, printed wiring boards and the like are used for mounting components or semiconductors. As a resist for production of printed wiring boards and the like, conventionally, a photosensitive resin laminate in which a photosensitive resin layer is laminated on a support film, and a protective film is laminated on the photosensitive resin layer as necessary, A so-called dry film resist (hereinafter sometimes referred to as DF) is used.

  As the photosensitive resin layer used here, an alkali developing type using a weak alkaline aqueous solution as a developing solution is generally used. To produce a printed wiring board using DF, if there is a protective film, first peel off the protective film and then use a laminator or the like on a permanent circuit production board such as a copper-clad laminate or a flexible board. Laminate DF and expose through a wiring pattern mask film. Next, if necessary, the support film is peeled off, and the photosensitive resin layer of the unexposed part (in the case of negative type) is dissolved or dispersed and removed by a developer, and a cured resist pattern (hereinafter simply referred to as a resist pattern) is formed on the substrate. (Sometimes called).

  The process of forming a circuit after forming a resist pattern is roughly divided into two methods. The first method is a method in which a substrate surface not covered with a resist pattern (for example, a copper surface of a copper clad laminate) is removed by etching, and then the resist pattern portion is removed with an alkaline aqueous solution stronger than a developer (etching method). It is. In the second method, after plating the surface of the substrate with copper, solder, nickel, tin or the like, the resist pattern portion is similarly removed, and the substrate surface that appears again (for example, the copper surface of a copper-clad laminate) This is a method of etching (plating method). For the etching, a solution of cupric chloride, ferric chloride, a copper ammonia complex or the like is used.

  In such a manufacturing process, high sensitivity is demanded from the viewpoint of improving productivity. On the other hand, the exposure methods are also diversified according to applications, and maskless exposure, which eliminates the need for a photomask by direct drawing with a laser, has been rapidly expanding in recent years. As a light source for maskless exposure, light having a wavelength of 350 to 410 nm, particularly i-line or h-line (405 nm) is often used. Therefore, it is important to be able to form a resist pattern with high sensitivity and high resolution with respect to these wavelength ranges, particularly with respect to h-line light sources. Furthermore, along with miniaturization and weight reduction of electronic devices, printed wiring boards are becoming finer and higher density, and high-performance DF excellent in resolution and the like is required.

  As a photosensitive resin composition that realizes such high sensitivity and high resolution, Patent Document 1 describes a blue-violet laser photosensitive composition.

Japanese Patent No. 4337485

  However, the technique described in Patent Document 1 does not satisfy simultaneously the resolution, the prevention of blushing of the substrate, the performance as a resist for use in copper sulfate plating, and the like, and still has room for improvement. It was. In particular, after laminating DF on the substrate, both the problem that the substrate is blushed due to the organic matter adhering to the substrate surface and the problem that contamination occurs when using a copper sulfate plating solution in the plating process, Patent Document 1 is not considered.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition excellent in resolution, substrate blush prevention, and contamination resistance when using a copper sulfate plating solution.

  As a result of intensive studies and experiments to solve the above problems, the present inventor has found that the problems can be solved by the following technical means.

  That is, it is as follows.

[1] The following components (A) to (E):
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated double bond,
(C) a photopolymerization initiator,
(D) a sensitizer, and (E) an additive,
The component (C) is a hexaarylbiimidazole compound based on the total amount of the component (A), the component (B), the component (C), the component (D), and the component (E). Including 10 mass%,
The component (D) is a bisbenzoxazolyl thiophene derivative or a bisbenzoxazolyl naphthalene derivative or both of them in a total amount, the component (A), the component (B), the component (C), (D) 0.01 to 1% by mass based on the total amount of component and component (E),
The component (E) contains carboxyl benzotriazoles in an amount of 0.01 to 0.01 based on the total amount of the component (A), the component (B), the component (C), the component (D), and the component (E). A photosensitive resin composition containing 5% by mass.
[2] The component (A) is one or more components selected from the group consisting of the following (a-1) and (a-2):
(A-1) Derived from a polymerization component containing 15 to 60% by mass of styrene and one or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester. Acrylic copolymer;
(A-2) 20 to 85% by mass of benzyl methacrylate and one or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester other than benzyl methacrylate An acrylic copolymer derived from a polymerization component;
In the above [1], the total amount of the component (A), the component (B), the component (C), the component (D), and the component (E) is 30 to 60% by mass based on the total amount. The said photosensitive resin composition of description.
[3] The photosensitive resin composition according to the above [1] or [2], wherein the component (B) contains a compound having more than two (meth) acryloyl groups in one molecule.
[4] A photosensitive resin laminate in which a photosensitive resin layer made of the photosensitive resin composition according to any one of [1] to [3] is laminated on a support.
[5] A resist pattern forming method including the steps of laminating the photosensitive resin laminate according to the above [4] on a substrate, exposing and developing.
[6] A method for manufacturing a circuit board, comprising: laminating the photosensitive resin laminate according to [4] above on a base material, exposing, developing, and plating.
[7] A method for producing a circuit board, comprising: laminating the photosensitive resin laminate according to [4] above on a base material, exposing, developing, and etching.
[8] The method for manufacturing a circuit board according to [6] or [7], wherein the exposure is performed by direct drawing of a drawing pattern.
[9] A step of forming a resist pattern on a semiconductor package substrate as a base material by the resist pattern forming method described in [5] above, and etching the semiconductor package substrate on which the resist pattern is formed, or A method for manufacturing a semiconductor package, including a step of plating.

  The present invention provides a photosensitive resin composition excellent in resolution, substrate blush prevention, and contamination resistance when using a copper sulfate plating solution.

  Hereinafter, exemplary modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

<Photosensitive resin composition>
In the embodiment, the photosensitive resin composition comprises the following components (A) to (E): (A) an alkali-soluble polymer (also referred to as component (A) in the present disclosure), (B) A compound having a saturated double bond (also referred to as component (B) in the present disclosure), (C) a photopolymerization initiator (also referred to as component (C) in the present disclosure), (D) a sensitizer (in the present disclosure (D ) Component) and (E) additive (also referred to as component (E) in the present disclosure). Hereinafter, each component will be described in order.

(A) Alkali-soluble polymer (A) An alkali-soluble polymer is a polymer that is easily soluble in an alkali substance. Specifically, a functional group that contributes to alkali solubility (for example, a carboxyl group) is dissolved in a desired alkali substance. It is a polymer that has a sufficient amount to do. Moreover, typically, the amount of the carboxyl group contained in the (A) alkali-soluble polymer is 100 to 600, preferably 250 to 450, in terms of acid equivalent. The acid equivalent means the mass (unit: gram) of a linear polymer having 1 equivalent of a carboxyl group in the molecule. (A) The carboxyl group in the alkali-soluble polymer is necessary for providing the photosensitive resin layer with developability and peelability with respect to an aqueous alkali solution. Setting the acid equivalent to 100 or more is preferable from the viewpoint of improving development resistance, resolution, and adhesion, and it is preferable to set the acid equivalent to 250 or more. On the other hand, the acid equivalent is preferably 600 or less from the viewpoint of improving developability and peelability, and the acid equivalent is preferably 450 or less.

  (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. Setting the weight average molecular weight to 500,000 or less is preferable from the viewpoint of improving resolution and developability, more preferably setting the weight average molecular weight to 300,000 or less, and further to 200,000 or less. preferable. On the other hand, setting the weight average molecular weight to 5,000 or more is preferable from the viewpoint of controlling the properties of the development aggregate and the properties of the unexposed film such as the edge fuse property and the cut chip property of the photosensitive resin laminate, The weight average molecular weight is more preferably 10,000 or more, and further preferably 20,000 or more. The edge fuse property refers to a phenomenon in which the photosensitive resin layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll. The cut chip property refers to a phenomenon in which a chip flies when an unexposed film is cut with a cutter. If the chip adheres to the upper surface of the photosensitive resin laminate, the chip is transferred to a mask in a later exposure process or the like, resulting in a defective product.

  (A) The degree of dispersion of the alkali-soluble polymer (sometimes referred to as molecular weight distribution) may be about 1 to 6, preferably 1 to 4. The degree of dispersion is represented by the ratio between the weight average molecular weight and the number average molecular weight, and (dispersion degree) = (weight average molecular weight) / (number average molecular weight). A weight average molecular weight and a number average molecular weight are the values measured by polystyrene conversion using gel permeation chromatography.

  (A) The alkali-soluble polymer is preferably a copolymer obtained from at least one first monomer described later and at least one second monomer described later.

  The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like. Particularly preferred is (meth) acrylic acid. In this specification, (meth) acryl indicates acrylic and / or methacrylic. The same applies hereinafter.

  The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl alcohol esters such as acetic acid Examples include vinyl, (meth) acrylonitrile, styrene, and styrene derivatives. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate are preferable. From the viewpoint of improving the resolution and adhesion of the resist pattern, styrene and benzyl (meth) acrylate are preferred.

  The copolymerization ratio of the first monomer and the second monomer is 10-60% by mass of the first monomer from the viewpoint of adjusting the alkali solubility of the (A) alkali-soluble polymer. And the second monomer is preferably 40 to 90% by mass, more preferably the first monomer is 15 to 35% by mass, and the second monomer is 65 to 85% by mass. %.

  (A) The synthesis of the alkali-soluble polymer is carried out by diluting a mixture of the first monomer and the second monomer with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to carry out by adding an appropriate amount of a radical polymerization initiator such as butyronitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

  (A) an alkali-soluble polymer (a mixture of a plurality of types of alkali-soluble polymers) is used as (A) component, (B) component, (C) component, (D) component, and The proportion of the component (E) in the total amount (hereinafter, sometimes referred to as the component (A) to component (E)) is preferably in the range of 10 to 90% by mass, more preferably 30 to 70. It is mass%, More preferably, it is 40-60 mass%. The ratio of the component (A) to the total amount of the components (A) to (E) is preferably 90% by mass or less from the viewpoint of controlling the development time, while the total amount of the components (A) to (E). Setting the ratio of the component (A) to 10% by mass or more is preferable from the viewpoint of improving the edge fuse property.

In particular, the photosensitive resin composition has, as the component (A), one or more components selected from the group consisting of the following (a-1) and (a-2):
(A-1) Derived from a polymerization component containing 15 to 60% by mass of styrene and one or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester. Acrylic copolymer;
(A-2) 20 to 85% by mass of benzyl methacrylate and one or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester other than benzyl methacrylate An acrylic copolymer derived from a polymerization component;
It is preferable that high resolution is exhibited. As a proportion of the total amount of the component (a-1) and the component (a-2) in the total amount of the components (A) to (E), 10 to 60% by mass expresses high resolution. Is preferable. The above ratio is preferably 20% by mass or more, more preferably 30% by mass or more from the viewpoint of resolution, and preferably 55% by mass or less, more preferably 50% by mass or less from the viewpoint of cut-tip properties.

  The polymerization component in (a-1) may consist only of styrene and the above acrylic monomer, or may further contain other monomers. Moreover, the polymerization component in (a-2) may consist only of benzyl methacrylate and the above acrylic monomer, or may further contain other monomers. As a particularly preferred example of the combination of the polymerization components, styrene is 15 to 60% by mass, methacrylic acid is 20 to 35% by mass, the remainder is methyl methacrylate, and styrene is 30 to 50% by mass of methacrylic acid. 20 to 40% by mass, 10 to 20% by mass of 2-ethylhexyl acrylate, the remaining is a combination of 2-hydroxyethyl methacrylate, 20 to 60% by mass of benzyl methacrylate, 10 to 30% by mass of styrene, and the rest is methacrylic A combination of acids, benzyl methacrylate is 60 to 85% by mass, 2-ethylhexyl acrylate is 0 to 15% by mass, and the remainder is methacrylic acid.

(B) Compound having ethylenically unsaturated double bond (B) Compound having ethylenically unsaturated double bond is an acryloyl group in the molecule from the viewpoint of curability and compatibility with (A) alkali-soluble polymer. It is preferable that the compound which has this is included. Examples of the compound having an acryloyl group in the molecule include a compound in which (meth) acrylic acid is added to one end of polyalkylene oxide, or (meth) acrylic acid is added to one end and the other end is alkyl. Examples include etherified or allyl etherified compounds.

  As such a compound, phenoxyhexaethylene glycol mono (meth) acrylate, which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to a phenyl group, or an average of 2 moles of propylene oxide (hereinafter sometimes abbreviated as PO). 4-normal nonyl phenoxyheptaethylene glycol diglycol, which is a (meth) acrylate of a compound obtained by adding polyethylene glycol added with an average of 7 moles of ethylene oxide (hereinafter also abbreviated as EO) to nonylphenol. Add propylene glycol (meth) acrylate, polypropylene glycol with an average of 1 mol of propylene oxide and polyethylene glycol with an average of 5 mol of ethylene oxide to nonylphenol All compounds are (meth) acrylate 4-n-nonylphenoxy pentaethylene glycol monopropylene glycol (meth) acrylate. Examples also include 4-normalnonylphenoxyoctaethylene glycol (meth) acrylate (for example, M-114 manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol with an average of 8 moles of ethylene oxide added to nonylphenol.

  For example, a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain, or a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are bonded randomly or in blocks. be able to.

  Examples of such compounds include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, and octaethylene glycol di (meth). Polyethylene glycol (meth) acrylates such as acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, a compound having (meth) acryloyl groups at both ends of 12 mol of ethylene oxide chain, Examples thereof include polypropylene glycol di (meth) acrylate and polybutylene glycol di (meth) acrylate. Examples of the polyalkylene oxide di (meth) acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound include, for example, a glycol obtained by adding an average of 3 moles of ethylene oxide to both ends of polypropylene glycol added with an average of 12 moles of propylene oxide. And diglycolate of glycol obtained by adding an average of 15 moles of ethylene oxide to both ends of polypropylene glycol having an average of 18 moles of propylene oxide added thereto.

  Further, a compound in which bisphenol A is modified with alkylene oxide and has (meth) acryloyl groups at both ends is preferable from the viewpoint of resolution and adhesion. Examples of the alkylene oxide modification include ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, and hexylene oxide modification. Further, from the viewpoint of resolution and adhesion, a compound in which bisphenol A is modified with ethylene oxide and has (meth) acryloyl groups at both ends is particularly preferable.

  Examples of such a compound include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane (for example, NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) (Acryloxypentaethoxy) phenyl) propane (for example, NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxyheptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) Lopan, 2,2-bis (4-((meth) acryloxynonaethoxy) 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) acryl) Loxytridecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl ) 2,2-bis (4-((meth) acrylic) such as propane, 2,2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl) propane Alkoxy polyethoxy) phenyl) propane. Furthermore, di (meth) acrylate of polyalkylene glycol obtained by adding an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide to both ends of bisphenol A, or an average of 2 moles of propylene oxide and an average of 15 moles to both ends of bisphenol A, respectively. From the viewpoints of resolution and adhesiveness, ethylene oxide-modified and propylene oxide-modified compounds such as poly (alkylene glycol) di (meth) acrylates to which ethylene oxide is added are also preferred. The number of moles of ethylene oxide with respect to 1 mole of bisphenol A in a compound having a (meth) acryloyl group at both ends modified with alkylene oxide from bisphenol A is from the viewpoint of improving resolution, adhesion and flexibility. 10 mol or more and 30 mol or less are preferable.

  In the present embodiment, (B) the compound having an ethylenically unsaturated double bond includes a compound having more than two (meth) acryloyl groups in one molecule, and exhibits high resolution. Preferred above. The number of (meth) acryloyl groups in one molecule is more preferably 3 or more. The number of (meth) acryloyl groups in one molecule is preferably 6 or less, more preferably 4 or less, from the viewpoint of peelability. A compound having more than two (meth) acryloyl groups in one molecule has 3 moles or more of groups that can add an alkylene oxide group in the molecule as a central skeleton (that is, 3 or more per central skeleton). It can be obtained by forming a (meth) acrylate from an alcohol to which an alkylene oxide group such as an ethylene oxide group, a propylene oxide group or a butylene oxide group is added, and (meth) acrylic acid. If the central skeleton is alcohol, it can also be obtained by directly forming (meth) acrylic acid and (meth) acrylate. Examples of the compound that can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.

  Such compounds include trimethylolpropane EO3 mol modified triacrylate, trimethylolpropane EO6 mol modified triacrylate, trimethylolpropane EO9 mol modified triacrylate, trimethylolpropane EO12 mol modified triacrylate, glycerol EO3. Mole modified triacrylate (for example, A-GLY-3E manufactured by Shin-Nakamura Chemical Co., Ltd.), EO9 mol-modified triacrylate of glycerol (for example, A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), EO6 mol PO6 of glycerol Mole modified triacrylate (A-GLY-0606PE), glycerol EO9 mol PO9 mol modified triacrylate (A-GLY-0909PE), pentaerythritol 4EO modified tetraacrylate (eg Sartoma) Japan Co., Ltd. SR-494), 35EO modified tetraacrylate pentaerythritol (e.g. Shin Nakamura Kagaku Kogyo Co., Ltd. NK Ester ATM-35E), dipentaerythritol tetraacrylate, and the like.

  Among them, preferred examples of the compound (B) having an ethylenically unsaturated double bond are those having a melting point lower than room temperature and not easily solidified at the time of storage, particularly from the viewpoint of handleability, and particularly EO3 molar modification of trimethylolpropane. 4EO-modified tetraacrylate of triacrylate and pentaerythritol is preferable.

  The content of the compound having more than two (meth) acryloyl groups in one molecule is preferably 50 to 100% by mass of the compound (B) having an ethylenically unsaturated double bond. The content is preferably 50% by mass or more, more preferably 60% by mass or more from the viewpoint of resolution. The content may be 100% by mass, but is preferably 95% by mass or less, more preferably 90% by mass or less, from the viewpoint of peelability.

  The component (B) can appropriately contain, for example, the following compounds in addition to the above-described compounds. For example, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 2-di (p-hydroxyphenyl) propanedi (meth) acrylate, 2,2-bis [(4- (Meth) acryloxypolypropyleneoxy) phenyl] propane, 2,2-bis [(4- (meth) acryloxypolybutyleneoxy) phenyl] propane, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Polyoxypropyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, β-hydroxypropyl-β '-(acryloyloxy) propyl Examples thereof include talates, nonylphenoxypolypropylene glycol (meth) acrylate, nonylphenoxypolybutylene glycol (meth) acrylate, and polypropylene glycol mono (meth) acrylate. Furthermore, the following urethane compounds are also mentioned. For example, hexamethylene diisocyanate, tolylene diisocyanate or diisocyanate compound (for example, 2,2,4-trimethylhexamethylene diisocyanate) and a compound having a hydroxyl group and a (meth) acryl group in one molecule, for example, 2-hydroxypropyl Examples thereof include urethane compounds with acrylates and oligopropylene glycol monomethacrylates. Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (for example, Bremer PP1000 manufactured by NOF Corporation). Moreover, di- or tri (meth) acrylates of isocyanuric acid esters modified with polypropylene glycol or polycaprolactone are also included. Moreover, the urethane oligomer obtained by making the terminal of the urethane compound obtained as a polyadduct of diisocyanate and a polyol react with the compound which has an ethylenically unsaturated double bond and a hydroxyl group etc. can be mentioned, for example.

  (B) It is preferable that the ratio with respect to the total amount of the said (A) component-(E) component of the compound which has an ethylenically unsaturated double bond is 5-70 mass%. Setting this ratio to 5% by mass or more is preferable from the viewpoint of sensitivity, resolution, and adhesion, and this ratio is more preferably 10% by mass or more, and further preferably 20% by mass or more. On the other hand, setting this ratio to 70% by mass or less is preferable from the viewpoint of suppressing the peeling delay of the edge fuse and the cured resist, and this ratio is more preferably 60% by mass or less, and further preferably 50% by mass or less. .

(C) Photopolymerization initiator (C) The photopolymerization initiator contains a hexaarylbiimidazole compound from the viewpoint of obtaining sensitivity and resolution.

  As the hexaarylbiimidazole compound, 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl)- 4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2'-bis- (2-fluorophenyl) -4,4 ', 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3-difluoromethylphenyl) -4,4 ′, , 5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -Biimidazole, 2,2'-bis- (2,5-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- ( 2,6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4-trifluorophenyl) -4 , 4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,5-trifluorophenyl) -4,4 ′, 5,5′- Tetrakis- (3-methoxyphenyl -Biimidazole, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'- Bis- (2,4,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,4,6- Trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4,5-tetrafluorophenyl) -4, 4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4', 5,5 ' -Tetrakis- (3-methoxyphenyl) -biimidazole And 2,2′-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole and the like. It is done. Among these, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable from the viewpoint of sensitivity and resolution.

  As a photopolymerization initiator that may be contained in addition to the hexaarylbiimidazole compound as the component (C), N-aryl-α-amino acid compounds, quinones, aromatic ketones, acetophenones, acylphosphine oxides, Examples include benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoates, oxime esters, acridines, pyrazoline derivatives, N-aryl amino acid ester compounds, and halogen compounds.

  Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. In particular, N-phenylglycine is preferable because of its high sensitizing effect.

  As quinones, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2 , 3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone and the like.

  Examples of aromatic ketones include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, and 4-methoxy-4′-dimethylaminobenzophenone. be able to.

  Examples of acetophenones include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and 1- (4 -Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-benzyl- Mention may be made of 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

  Examples of acylphosphine oxides include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phosphine oxide, and bis (2,6-dimethoxybenzoyl) -2. , 4,4-trimethyl-pentyl phosphine oxide and the like. Commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

  Examples of benzoin or benzoin ethers include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.

  Examples of dialkyl ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of the thioxanthones include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

  Examples of the dialkylaminobenzoates include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, 2-ethylhexyl-4- (dimethylamino) benzoate and the like.

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

  Examples of acridines include 1,7-bis (9,9′-acridinyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9- Ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- ( 4-tert-butylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9- (4-bromophenyl) acridine Gin, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3- Diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, and 9- (4-pyridyl) Acridine can be mentioned.

  Examples of the pyrazoline derivative include 1- (4-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4- tert-butyl-phenyl) -pyrazoline, 1,5-bis- (4-tert-butyl-phenyl) -3- (4-tert-butyl-styryl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-ethoxy-phenyl) -pyrazoline, 1-phenyl-3- (4-tert- Octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1,5-bis- (4-tert-octyl-phenyl) -3 (4-tert-octyl-styryl) -pyrazoline, 1- (4-dodecyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-dodecyl-styryl) -5- (4 -Dodecyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-dodecyl-stynyl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) ) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-tert-octyl-styryl) ) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-tert-butyl-styryl) -5 (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4 -Dodecyl-phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3- (4-dodecyl) -Styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (2,4-dibutyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1-phenyl-3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2 , 6-Di-tert-butyl-styryl) -5- (2,6-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,5-di-tert-butyl-styryl)- 5- (2,5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,6-di-n-butyl-styryl) -5- (2,6-di-n-butyl) -Phenyl) -pyrazoline, 1- (3,4-di-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (3,5-di-tert-butyl-phenyl) -3- Styryl-5-phenyl-pyrazoline, 1- (4-tert-butyl-phenyl) -3- (3,5-di-tert-butyl-phenyl) -5-phenyl-pyrazoline, 1- (3,5-di -Tert-butyl-phenyl -3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (5-tert-butyl-benzoxazole) 2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4- tert-butyl-phenyl) -pyrazoline, 1- (4- (4-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert- Butyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- ( -(Benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-) Benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzoxazole-2) -Yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) ) -Pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-stynyl) -5- (4-do) Decyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl- Phenyl) -pyrazolin, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -Pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1 -(4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phen L) -pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline 1- (4- (5-tert-octyl-benzooxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (4,6-dibutyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (benzoxazole-2- Yl) phenyl) -3- (3,5-di-tert-butylstyryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoo) Sazol-2-yl) phenyl) -3- (2,6-di-tert-butyl-styryl) -5- (2,6-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzo Oxazol-2-yl) phenyl) -3- (2,5-di-tert-butyl-styryl) -5- (2,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzo Oxazol-2-yl) phenyl) -3- (2,6-di-n-butyl-styryl) -5- (2,6-di-n-butyl-phenyl) -pyrazoline, 1- (4- (4 , 6-Di-tert-butyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (5,7-di-tert-butyl-benzoxazol-2-yl) Yl) phenyl) -3-s Tyryl-5-phenyl-pyrazolin, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (3,5-di-tert-butyl-styryl) -5-phenyl- Pyrazoline, 1- (4- (4,6-di-tert-butyl-benzoxazol-2-yl) phenyl) -3- (3,5-di-tert-butyl-styryl) -5- (3,5 -Di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-amino-phenyl) -pyrazoline, 1-phenyl-3- (4-tert -Butyl-styryl) -5- (4-N-ethyl-phenyl) -pyrazoline and 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-N, N-diethyl-phenyl) - it includes the pyrazoline.

  Further, for example, 1-phenyl-3- (4-biphenyl) -5- (4-n-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl) -Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-isobutyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-n-pentyl) -Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-isopentyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-neopentyl-phenyl) ) -Pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-hexyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-heptyl) -Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-n-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert -Octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-nonyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-decyl) -Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-undecyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-dodecyl-phenyl) ) -Pyrazoline. Among them, from the viewpoint of adhesion and rectangularity of the resist pattern, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-Biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline are preferred.

  Examples of ester compounds of N-aryl amino acids include N-phenylglycine methyl ester, N-phenylglycine ethyl ester, N-phenylglycine n-propyl ester, N-phenylglycine isopropyl ester, and N-phenylglycine. 1-butyl ester, N-phenylglycine 2-butyl ester, N-phenylglycine tertbutyl ester, N-phenylglycine pentyl ester, N-phenylglycine hexyl ester, N-phenylglycine pentyl ester, N -Phenylglycine octyl ester and the like.

  Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds, diallyl iodonium compounds, and the like. In particular, tribromomethylphenylsulfone is preferred. It is preferable that content of the halogen compound in the photosensitive resin composition is 0.01-3 mass% with respect to the total amount of the said (A) component-(E) component from a sensitivity viewpoint.

  These photopolymerization initiators may be used alone or in combination of two or more.

  (C) As for the ratio with respect to the total amount of the said (A) component-(E) component of a photoinitiator, 0.1-20 mass% is preferable. This ratio is preferably 0.1% by mass or more from the viewpoint of obtaining sufficient sensitivity, this ratio is more preferably 0.2% by mass or more, and further preferably 0.5% by mass or more. . On the other hand, setting this ratio to 20% by mass or less is preferable from the viewpoint of obtaining high resolution and suppressing aggregation in the developer, and it is more preferable to set this ratio to 10% by mass or less. .

  Moreover, the compounding quantity of the hexaaryl biimidazole compound as a (C) photoinitiator is 0.01-10 mass% with respect to the total amount of the said (A) component-(E) component. It is necessary from the viewpoint of obtaining sufficient sensitivity that the blending amount be 0.01% by mass or more. The blending amount is preferably 1% by mass or more, more preferably 3% by mass or more. preferable. On the other hand, it is necessary to make the blending amount 10% by mass or less from the viewpoint of obtaining high resolution and suppressing the cohesiveness in the developer, and the blending amount is made 8% by mass or less. It is preferable to make it 6% by mass or less.

  Here, by combining the (D) component and the (E) component of the present disclosure in the presence of a hexaarylbiimidazole compound, sensitivity, resolution, substrate blush prevention, and contamination resistance when using a copper sulfate plating solution are used. The details of the mechanism that realizes the photosensitive resin composition having excellent nation properties are not detailed, but are presumed as follows.

  That is, the light irradiated from the exposure machine is absorbed by the bisbenzoxazolylthiophene derivative or bisbenzoxazolylnaphthalene derivative as component (D), and donates electrons or energy to the hexaarylbiimidazole compound. The hexaarylbiimidazole receiving the electron or energy is cleaved to generate a triarylimidazole radical. This triarylimidazole radical reacts with the component (B) compound having an ethylenically unsaturated double bond to initiate radical polymerization. A combination of a hexaarylbiimidazole compound and a (D) component bisbenzoxazolylthiophene derivative or bisbenzoxazolylnaphthalene derivative is effective for efficiently initiating this photoradical polymerization, that is, high sensitivity. It is considered a thing.

  In addition, when used as a resist for plating, prevention of blushing of the substrate and contamination resistance when using a copper sulfate plating solution are important, and hexaarylbiimidazole and (D) component bisbenzoxazolylthiophene derivative or bis A combination of a benzoxazolyl naphthalene derivative and a carboxyl benzotriazole is considered to be effective in improving blush prevention and contamination resistance when using a copper sulfate plating solution while maintaining high sensitivity.

(D) Sensitizer (D) The sensitizer is a bisbenzoxazolylthiophene derivative or a bisbenzoxazolylnaphthalene derivative or both from the viewpoint of sensitivity and resistance to contamination with a copper sulfate plating solution. Including.

The bisbenzoxazolylthiophene derivative is a compound having a skeleton in which two benzoxazolyl groups are bonded to the 2nd and 5th carbons of thiophene and having a skeleton represented by the following formula (I). .

A bisbenzoxazolyl naphthalene derivative is a compound having a skeleton in which two benzoxazolyl groups are bonded to the 1st and 4th carbons of naphthalene and having a skeleton represented by the following formula (II). .

  Specific examples of the bisbenzoxazolylthiophene derivatives include 2,5-bis (2-benzoxazolyl) thiophene, 2,5-bis (5-methyl-2-benzoxazolyl) thiophene, 2,5 -Bis (5-ethyl-2-benzoxazolyl) thiophene, 2,5-bis (5-tertbutyl-2-benzoxazolyl) thiophene, 2,5-bis (5-phenyl-2-benzoxa) Zolyl) thiophene, 2,5-bis (5-tertoctyl-2-benzoxazolyl) thiophene, and the like. The substituents attached to the two benzoxazolyl groups may be the same or different. Among these, 2,5-bis (5-tertbutyl-2-benzoxazolyl) thiophene is preferable from the viewpoint of sensitivity and solubility in an organic solvent.

  Examples of bisbenzoxazolyl naphthalene derivatives include 1,4-bis (2-benzoxazolyl) naphthalene, 1,4-bis (5-methyl-2-benzoxazolyl) naphthalene, 1,4-bis ( 5-ethyl-2-benzoxazolyl) naphthalene, 1,4-bis (5-tertbutyl-2-benzoxazolyl) naphthalene, 1,4-bis (5-phenyl-2-benzoxazolyl) Naphthalene, 1,4-bis (5-tertoctyl-2-benzoxazolyl) naphthalene, and the like. The substituents attached to the two benzoxazolyl groups may be the same or different. Among these, 1,4-bis (2-benzoxazolyl) naphthalene is preferable from the viewpoint of sensitivity and solubility in an organic solvent.

  (D) As for the ratio with respect to the total amount of said (A) component-(E) component of a sensitizer, 0.01-1 mass% is preferable. Setting this ratio to 0.01% by mass or more is preferable from the viewpoint of obtaining sufficient sensitivity, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more. . On the other hand, setting this ratio to 1% by mass or less is preferable from the viewpoint of obtaining high resolution, and it is more preferable to set this ratio to 0.8% by mass or less, and to 0.5% by mass or less. Further preferred.

  The total amount of the bisbenzoxazolylthiophene derivative and the bisbenzoxazolylnaphthalene derivative is 0.01 to 1% by mass with respect to the total amount of the components (A) to (E). It is necessary to make this blending amount 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and it is preferable that this blending amount be 0.05% by mass or more, and 0.1% by mass or more. More preferably. On the other hand, it is necessary to make this blending amount 1% by mass or less from the viewpoint of obtaining high resolution, and this blending amount is preferably 0.8% by mass or less, and 0.5% by mass or less. More preferably.

(E) Additive In the present disclosure, the “(E) additive” is a component blended to give a desired function to the photosensitive resin composition, and the above-described (A) component, (B) component, Includes components other than the component (C) and the component (D).

  (E) An additive contains carboxyl benzotriazole from a viewpoint of preventing the blush of a board | substrate. Carboxybenzotriazoles are contained in an amount of 0.01 to 5% by mass based on the total amount of the components (A) to (E). From the viewpoint of preventing the blush of the substrate when the photosensitive resin laminate is laminated on a substrate such as a copper-clad laminate and developed after a time, making the blending amount 0.01% by mass or more. This is necessary, and the blending amount is preferably 0.03% by mass or more, and more preferably 0.05% by mass or more. On the other hand, it is necessary from the viewpoint of obtaining high resolution that the blending amount be 5% by mass or less. The blending amount is preferably 3% by mass or less, and preferably 1% by mass or less. Further preferred.

  Examples of carboxyl benzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and an aminomethyl group that may be substituted 1 -[N, N-bis (2-ethylhexyl) aminomethyl] -5-carboxylbenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] -4-carboxylbenzotriazole, 1- [N, N-bis (isopropyl) aminomethyl] -5-carboxylbenzotriazole, 1- [N-hydro-N-3- (2-ethylhexyloxy) -1-propylaminomethyl] -5-carboxylbenzotriazole, 1- [N, N-bis (1-octyl) aminomethyl] -5-carboxylbenzotriazole Examples include 1- [N, N-bis (2-hydroxypropyl) aminomethyl] -5-carboxylbenzotriazole, 1- [N, N-bis (1-butyl) aminomethyl] -5-carboxylbenzotriazole, and the like. It is done. Among these, 1- [N, N-bis (1-butyl) aminomethyl] -5-carboxylbenzotriazole is preferable from the viewpoint of preventing blush. As for the substitution position of the carboxyl group, the 5-position and the 6-position may be mixed in the synthesis process, both of which are preferable, for example, 0.5: 1.5 to 1.5: 5-position substitution product and 6-position substitution product: A 0.5 (mass ratio) mixture, in particular a 1: 1 (mass ratio) mixture, can be used. It may be simply described as “1-N-dibutylaminomethylcarboxylbenzotriazole” to indicate a mixture of a 5-position substituent and a 6-position substituent. As the carboxyl benzotriazole, for example, compounds described in JP-A-2008-175957 can also be used.

  Other additives that may be added as component (E) to the photosensitive resin composition described above include colorants, radical polymerization inhibitors, benzotriazoles other than carboxyl benzotriazoles, bisphenol A epoxy compounds, And plasticizers.

  Examples of the colorant include fuchsin, phthalocyanine green, auramin base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (for example, Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue. 20, Diamond Green (for example, Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), 1,4-bis (4-methylphenylamino) -9,10-anthraquinone (for example, manufactured by Orient Chemical Industry Co., Ltd.) OPLAS GREEN533), 1,4-bis (butylamino) anthraquinone (for example, OIL BLUE 2N, manufactured by Orient Chemical Industry Co., Ltd.), 1,4-bis (isopropylamino) -9,1 - anthraquinone (e.g. Orient Chemical Industries Co., OIL BLUE 630), and the like.

  In addition, the ratio with respect to the total amount of the said (A) component-(E) component of a coloring agent becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.1-5 mass%, More preferably, it is 0.5-2. % By mass, particularly preferably 0.5 to 1% by mass.

  As the colorant, for example, a leuco dye or a fluoran dye may be contained. By containing these, the exposed portion of the photosensitive resin layer is colored, which is preferable from the viewpoint of visibility, and when an inspection machine or the like reads the alignment marker for exposure, the contrast between the exposed portion and the unexposed portion is high. Since the larger one becomes easier to recognize, it is advantageous.

  Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green], and the like. In particular, from the viewpoint of good contrast, it is preferable to use leuco crystal violet as the leuco dye. It is preferable that content of the leuco dye in the photosensitive resin composition is 0.1-10 mass% with respect to the total amount of the said (A) component-(E) component. Setting the content to 0.1% by mass or more is preferable from the viewpoint of improving the contrast between the exposed part and the unexposed part, more preferably setting the content to 0.2% by mass or more. It is particularly preferable that the content be 4% by mass or more. On the other hand, the content is preferably 10% by mass or less from the viewpoint of maintaining storage stability, the content is more preferably 2% by mass or less, and particularly preferably 1% by mass or less. preferable.

  In addition, it is preferable to use a combination of a leuco dye and a halogen compound in the photosensitive resin composition from the viewpoint of optimizing adhesion and contrast. The halogen compound can be derived from the organic halogen compound described above as the component (C), and tribromomethylphenylsulfone is particularly preferable.

  Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. In order not to impair the sensitivity of the photosensitive resin composition, a nitrosophenylhydroxyamine aluminum salt is preferred.

  Examples of benzotriazoles other than carboxyl benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis (N-2-ethylhexyl) aminomethylene-1,2. , 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole, and the like. .

  Examples of the bisphenol A epoxy compounds include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminals.

  The total content of radical polymerization inhibitors, benzotriazoles other than carboxyl benzotriazoles, carboxyl benzotriazoles, and epoxy compounds of bisphenol A is based on the total amount of components (A) to (E). , Preferably it is 0.001-3 mass%, More preferably, it is 0.01-1 mass%. Setting the content to 0.001% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition, while setting the content to 3% by mass or less is photosensitive. This is preferable from the viewpoint of maintaining the sensitivity of the resin composition and suppressing decolorization and color development of the dye.

  Examples of the plasticizer include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and acetyl tricitrate tri-n-. And propyl, acetyl citrate tri-n-butyl, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether. Also, Adecanol SDX-1569, Adecanol SDX-1570, Adecanol SDX-1571, Adecanol SDX-479 (manufactured by Asahi Denka Co., Ltd.), New Pole BP-23P, New Pole BP-3P, New Pole BP-5P, New Pole Pole BPE-20T, New Pole BPE-60, New Pole BPE-100, New Pole BPE-180 (manufactured by Sanyo Chemical Co., Ltd.), Unior DB-400, Unior DAB-800, Unior DA-350F, Unior DA- Examples include compounds having a bisphenol skeleton such as 400, Uniol DA-700 (manufactured by Nippon Oil & Fats Co., Ltd.), BA-P4U glycol, BA-P8 glycol (manufactured by Nippon Emulsifier Co., Ltd.).

  The content of the plasticizer with respect to the total amount of the components (A) to (E) is preferably 1 to 50% by mass, more preferably 1 to 30% by mass. Setting the content to 1% by mass or more is preferable from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, while making the content 50% by mass or less, This is preferable from the viewpoint of suppressing insufficient curing and cold flow.

<Photosensitive resin laminate>
Another embodiment provides a photosensitive resin laminate in which a photosensitive resin layer composed of the photosensitive resin composition as described above is laminated on a support. If necessary, the photosensitive resin laminate may have a protective layer on the surface opposite to the support side of the photosensitive resin layer.

  The support is usually a support film. The support film is preferably a transparent film that transmits light emitted from the exposure light source. Examples of such support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, Examples thereof include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films can be stretched if necessary, and preferably have a haze of 5 or less. The thinner the film is, the more advantageous it is to improve the image forming property and the economical efficiency, but a film having a thickness of 10 to 30 μm is preferably used in order to maintain the strength of the photosensitive resin laminate.

  An important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support in terms of adhesion to the photosensitive resin layer and can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. Further, for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

  When polyethylene is used for the protective layer, there is a gel called fish eye on the surface of the polyethylene film, which may be transferred to the photosensitive resin layer. When the fish eye is transferred to the photosensitive resin layer, air may be entrained during the lamination, resulting in voids, leading to a defect in the resist pattern. From the viewpoint of preventing fish eyes, the protective layer is preferably made of stretched polypropylene. A specific example is Alfane E-200A manufactured by Oji Paper Co., Ltd.

  Although the thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, it is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the film strength. .

  The manufacturing method of the photosensitive resin laminated body is demonstrated. As a method for producing a photosensitive resin laminate by sequentially laminating a support, a photosensitive resin layer, and if necessary, a protective layer, a known method can be employed. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves the photosensitive resin composition into a uniform solution, first applied onto the support film using a bar coater or roll coater, and then dried to form the support film A photosensitive resin layer made of a photosensitive resin composition is laminated thereon. Next, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

  Examples of the solvent include ketones typified by methyl ethyl ketone (MEK), alcohols typified by methanol, ethanol, and isopropanol. It is preferable to add the said solvent to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition apply | coated on a support film may be 500-4000 mPa * s at 25 degreeC.

<Resist pattern formation method>
Another aspect provides a resist pattern forming method including the steps of laminating the above-described photosensitive resin laminate on a substrate, exposing and developing. Below, an example of the method of forming a resist pattern using the photosensitive resin laminated body of this Embodiment is demonstrated. Resist patterns include circuit boards (printed wiring boards), flexible boards, lead frame boards, COF (chip on film) boards, semiconductor package boards, transparent electrodes for liquid crystal panels, TFT wiring for liquid crystal panels, and organic EL displays. Examples thereof include resist patterns formed on wirings, PDP (plasma display panel) electrodes and the like.

The resist pattern can be formed through the following steps.
(1) Lamination process While peeling off the protective layer of the photosensitive resin layer, the photosensitive resin laminate is brought into close contact with a substrate such as a copper clad laminate or a flexible substrate using a hot roll laminator. The laminating conditions may be appropriately set under conventionally known conditions.

(2) Exposure process A mask film having a desired pattern (for example, a wiring pattern) is brought into close contact with the support of the photosensitive resin laminate and exposed using an active light source, or a drawing pattern corresponding to the desired pattern is formed. Exposure by direct drawing. As the exposure wavelength, i-line, h-line, g-line, a mixture thereof, and the like can be used as appropriate. However, the photosensitive resin composition of the present embodiment is high in exposure with i-line or h-line, particularly h-line. This is advantageous in that sensitivity and high resolution can be realized. Thereby, the photosensitive resin composition of this Embodiment is useful especially in direct drawing. The exposure conditions may be appropriately set under conventionally known conditions.

(3) Development Step After the exposure, the support on the photosensitive resin layer is peeled off, and subsequently, the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to form a resist pattern on the substrate. As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2 to 2% by mass and a temperature of about 20 to 40 ° C. is common.

  Although a resist pattern can be obtained through each of the above steps, a heating step at about 100 to 300 ° C. can be further performed in some cases. By carrying out this heating step, chemical resistance can be further improved. For heating, a hot air, infrared, or far infrared heating furnace can be used.

  Another aspect includes a process for producing a circuit board, comprising the steps of laminating, exposing, developing, and plating the above-described photosensitive resin laminate to a substrate, and the above-mentioned photosensitive resin laminate to the substrate. Provided is a method of manufacturing a circuit board, which includes steps of laminating, exposing, developing, and etching. The circuit board can be manufactured by further etching or plating the base material on which the resist pattern is formed by the procedure described above for the resist pattern forming method. In particular, it is advantageous from the viewpoint of productivity to perform exposure by direct drawing of a drawing pattern in the manufacture of a circuit board, because it is not necessary to produce a mask. Etching and plating can be performed as follows.

(4) Etching process or plating process The surface of the base material exposed by the above development (for example, a copper surface in the case of a copper clad laminate) is etched or plated to form a conductor pattern. As the etching and plating methods, conventionally known methods can be appropriately used.

(5) Stripping step Thereafter, the resist pattern is stripped from the substrate with an aqueous solution having alkalinity stronger than the developer. The alkaline aqueous solution for peeling is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of about 2 to 5% by mass and a temperature of about 40 to 70 ° C. is generally used. A small amount of a water-soluble solvent can also be added to the stripping solution.
The circuit board can be manufactured by the procedure as described above.

  In another aspect, a step of forming a resist pattern on a semiconductor package substrate as a base material by the above-described resist pattern forming method, and etching or plating the semiconductor package substrate on which the resist pattern is formed A method of manufacturing a semiconductor package including a process is provided. As the configuration of the semiconductor package substrate and the semiconductor package, any conventionally known one can be adopted as appropriate. Further, the formation of the resist pattern and the etching or plating can be performed by the procedure as described above.

  The photosensitive resin laminate of the present embodiment includes a circuit board (printed wiring board), a flexible board, a lead frame board, a COF (chip on film) board, a semiconductor package board, a transparent electrode for a liquid crystal panel, and a liquid crystal panel. This is a photosensitive resin laminate suitable for the production of conductor patterns such as TFT wiring, organic EL display wiring, and PDP (plasma display panel) electrodes.

  As described above, according to the present embodiment, even in h-line exposure, the sensitivity is high and the resolution is high, the substrate is difficult to blush after being laminated to the substrate, and there is no contamination to the copper sulfate plating solution. It is possible to provide a resin laminate, and a resist pattern formation method and a conductor pattern formation method using the photosensitive resin laminate.

  The various parameters described above are measured according to the measurement methods in the examples described later unless otherwise specified.

  Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless departing from the gist thereof. In addition, the physical property in the form for implementing said invention and the below-mentioned Example was measured with the following method.

<Sensitivity evaluation>
First, a 0.4 mm-thick copper clad laminate on which 35 μm rolled copper foil is laminated is jetted using a grinding material (Nippon Carlit Co., Ltd., Sacradund R (registered trademark # 220)) at a spray pressure of 0.2 MPa. Scrub polished.

  Next, while peeling the polyethylene film of the photosensitive resin laminate, roll the photosensitive resin laminate on a copper clad laminate preheated to 60 ° C. with a hot roll laminator (Asahi Kasei Co., Ltd., AL-700). Lamination was performed at a temperature of 105 ° C. The air pressure was 0.35 MPa in terms of cylinder pressure, the lateral width of the laminated plate was 20 cm, and the laminating speed was 1.5 m / min.

Next, using a direct drawing type exposure apparatus (Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode, main wavelength 405 ± 5 nm) using a stove 21 step tablet as a mask at 40 mJ / cm at 80 mW. The exposure amount was ² .

Further, after the polyethylene terephthalate film is peeled off, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for a predetermined time using an alkali developing machine (manufactured by Fuji Kiko Co., Ltd., a dry film developing machine). The exposed portion was dissolved and removed in a time twice as long as the minimum development time. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion was defined as the minimum development time. The actual development time was twice as long as the minimum development time to obtain a cured resist pattern.

  Regarding the number of remaining film steps after development, the number of remaining film steps where the remaining film area remained 90% or more of the design value of the mask was defined as the number of remaining film steps in the exposure amount.

<Resolution evaluation>
Substrate flattening and lamination were performed in the same manner as the sensitivity evaluation procedure, and a line pattern having a ratio of 1: 1 between the exposed area and the unexposed area was exposed at an exposure amount of 40 mJ / cm ² using the drawing data. Thereafter, development was performed with a development time twice as long as the minimum development time, and the minimum mask width in which a cured resist line was normally formed was defined as a resolution value, and the resolution was ranked as follows.
○: Resolution value of 16 μm or less;
(Triangle | delta): The value of resolution exceeds 16 micrometers and is 20 micrometers or less;
X: The resolution value exceeds 20 μm.

<Evaluation of copper sulfate plating solution contamination>
A photosensitive resin laminate of 30 cm × 60 cm × thickness 25 μm is exposed from the polyethylene terephthalate film side with an exposure amount of 40 mJ / cm ² , the polyethylene film is peeled off, and the polyethylene terephthalate film side is faced down to the glass epoxy substrate. The 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed on the photosensitive resin layer side for twice the minimum development time. Thereafter, the polyethylene terephthalate film of the photosensitive resin laminate that had been washed with water and peeled off was peeled off, immersed in 300 mL of a copper sulfate plating solution (Capper Gream 125 bath, manufactured by Meltex), and left at room temperature for 3 days. Thereafter, the photosensitive resin is removed from the plating solution, and 267 mL is put into a copper sulfate plating Hull cell container (Yamamoto plating tester). Phosphorus-containing copper is used for the anode and a brass plate is used for the cathode. Plating was applied. In the copper sulfate plating, air bubbling was performed in the solution, and the brass plate for the cathode was previously immersed in 10% sulfuric acid and washed. After copper sulfate plating is completed, the brass plate sample is washed with water, immediately dried with air, and judged on the appearance of plating on the high current density side as “cloudy”, “discolored”, and “glossy”. The case where there was no gloss and “cloudy” or “burnt” was observed was rated as “x”.

<Blush evaluation>
After substrate leveling and laminating in the same manner as the sensitivity evaluation procedure, the substrate with the photosensitive resin laminate is shielded from ultraviolet rays and visible light, and the temperature and humidity are controlled at 23 ° C. and 50%. Left in a room for 72 hours. After peeling off the polyethylene terephthalate film of the substrate with the photosensitive resin laminate after being left, 1% by mass Na _{2 at} 30 ° C. using an alkali developing machine (Fuji Kiko Co., Ltd., dry film developing machine) as in the sensitivity evaluation procedure. A CO ₃ aqueous solution was sprayed for a predetermined time, and the photosensitive resin layer was dissolved and removed in a time twice as long as the minimum development time. The copper surface of the substrate from which the photosensitive resin layer had been removed was observed. The red color was indicated as x, and the no color change was indicated as ◯. The red surface is generally one in which the substrate appears red due to organic substances adhering to the surface of the substrate, and when copper sulfate plating is applied to the blushed substrate, plating placement failure or plating peeling may occur.

<Weight average molecular weight, dispersity>
Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation [Pump: Gulliver, PU-1580 type, Column: Shodex (trademark) manufactured by Showa Denko KK (KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK)], weight average molecular weight and dispersity are calculated as polystyrene. It was.

<Acid equivalent of alkali-soluble polymer>
Hiranuma Sangyo Co., Ltd. Hiranuma automatic titrator (COM-555) was used, and acid equivalent was measured by potentiometric titration using 0.1 mol / L sodium hydroxide aqueous solution.

[Examples 1 to 10 and Comparative Examples 1 to 3]
The photosensitive resin composition and the solvent having the composition shown in Tables 1 and 2 (where the numbers of the respective components indicate the blending amount (parts by mass) as the solid content) are sufficiently stirred and mixed, and the solid content is 60 masses. % Photosensitive resin composition preparation liquid was obtained. A 16 μm-thick polyethylene terephthalate film (R340G16 manufactured by Mitsubishi Resin Co., Ltd.) was prepared as a support, and the photosensitive resin composition preparation liquid was uniformly applied to the surface of the film using a bar coater. Was dried for 2 minutes and 30 seconds to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 25 μm.

  Next, a 19 μm thick polyethylene film (GF-818 manufactured by Tamapoly Co., Ltd.) was bonded as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate. . Various evaluation was performed about the obtained photosensitive resin laminated body. The results are shown in Table 1.

  From the results of Tables 1 and 2, the following contents can be read.

  First, by comparing the examples and comparative examples, if the photosensitive resin composition of the present embodiment is used, it has high sensitivity and high resolution with respect to h-line exposure, good plating contamination resistance, and the substrate does not blush. It can be seen that the characteristics can be expressed.

  Next, by comparing Examples 1, 5, 6 and 7 with Example 8, when alkali-soluble polymer contains styrene or benzyl methacrylate in the copolymerization component, particularly high resolution is exhibited for h-line exposure. It turns out that the photosensitive resin laminated body which carries out can be obtained.

  Next, by comparing Example 1 and 9 with Example 10, three or four (ie, more than two) (meth) acryloyl compounds having an ethylenically unsaturated double bond are present in one molecule. When the compound which has group is included, it turns out that the photosensitive resin laminated body which expresses especially high resolution with respect to h line exposure can be obtained.

  The photosensitive resin laminate of the present embodiment has a circuit board (printed wiring board), a flexible board, a lead frame board, a COF (chip on film) board, and a semiconductor package board because of its high sensitivity and high resolution. It can be suitably used for the production of conductive patterns in liquid crystal panel transparent electrodes, liquid crystal panel TFT wiring, organic EL display wiring, PDP (plasma display panel) electrodes, and the like.

Claims (9)

Each of the following components (A) to (E),
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated double bond,
(C) a photopolymerization initiator,
(D) a sensitizer, and (E) an additive,
The component (C) is a hexaarylbiimidazole compound based on the total amount of the component (A), the component (B), the component (C), the component (D), and the component (E). Including 10 mass%,
The component (D) is a bisbenzoxazolyl thiophene derivative or a bisbenzoxazolyl naphthalene derivative or both of them in a total amount, the component (A), the component (B), the component (C), (D) 0.01 to 1% by mass based on the total amount of component and component (E),
The component (E) contains carboxyl benzotriazoles in an amount of 0.01 to 0.01 based on the total amount of the component (A), the component (B), the component (C), the component (D), and the component (E). A photosensitive resin composition containing 5% by mass. The component (A) is one or more components selected from the group consisting of the following (a-1) and (a-2):
(A-1) Derived from a polymerization component containing 15 to 60% by mass of styrene and one or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester. Acrylic copolymer;
(A-2) 20 to 85% by mass of benzyl methacrylate and one or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester other than benzyl methacrylate An acrylic copolymer derived from a polymerization component;
The total amount of the component (A), the component (B), the component (C), the component (D), and the component (E) is 30 to 60% by mass based on the total amount. The photosensitive resin composition.   The photosensitive resin composition of Claim 1 or 2 in which the said (B) component contains the compound which has more than two (meth) acryloyl groups in 1 molecule.   The photosensitive resin laminated body by which the photosensitive resin layer which consists of the photosensitive resin composition of any one of Claims 1-3 was laminated | stacked on the support body.   A method for forming a resist pattern, comprising: laminating the photosensitive resin laminate according to claim 4 on a base material, exposing and developing the laminate.   A method for producing a circuit board, comprising: laminating the photosensitive resin laminate according to claim 4 on a base material, exposing, developing, and plating.   A method for producing a circuit board, comprising: laminating the photosensitive resin laminate according to claim 4 on a base material, exposing, developing, and etching.   The method for manufacturing a circuit board according to claim 6, wherein the exposure is performed by direct drawing of a drawing pattern.   A method of forming a resist pattern on a semiconductor package substrate as a base material by a resist pattern forming method according to claim 5 and a step of etching or plating the semiconductor package substrate on which the resist pattern is formed. A method for manufacturing a semiconductor package.