JP2013195712A - Photosensitive resin composition, photosensitive element, resist pattern forming method, and printed wiring board manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in all of resolution, adhesion, resist shapes, releasability, flexibility, and chemical resistance.SOLUTION: The photosensitive resin composition contains: as (A) component, a binder polymer; as (B) component, a photopolymerizable compound containing a compound represented by the specified general formula (1); and, as (C) component, a photoinitiator. [In the general formula (1); Y represents a hydrogen atom or a methyl group; R represents a C1-C4 alkylene group; n is from 0 to 2; and X represents a C6-C14 organic group including a cyclic structure.]

Description

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

  In the field of manufacturing printed wiring boards, photosensitive resin compositions are widely used as resist materials used for etching and plating processes. A photosensitive resin composition includes a support film and a photosensitive element (laminated layer) including a layer formed on the support film using the photosensitive resin composition (hereinafter also referred to as “photosensitive resin composition layer”). Often used as a body).

  A printed wiring board is manufactured as follows, for example. First, the photosensitive resin composition layer of the photosensitive element is laminated (laminated) on the circuit forming substrate (lamination step). Next, after peeling off and removing the support film, the exposed portion is cured by irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays (exposure step). Thereafter, by removing (developing) the unexposed portion from the substrate, a resist pattern made of a cured product of the photosensitive resin composition is formed on the substrate (developing step). An etching process or a plating process is performed on the obtained resist pattern to form a circuit on the substrate (circuit forming process), and finally the resist is peeled and removed to produce a printed wiring board (peeling process).

  As an exposure method, conventionally, a method of exposing via a photomask using a mercury lamp as a light source has been used. In recent years, a direct drawing exposure method called DLP (Digital Light Processing) or LDI (Laser Direct Imaging), which directly draws pattern digital data on a photosensitive resin composition layer, has been proposed. This direct drawing exposure method is being introduced for the production of a high-density package substrate because it has better alignment accuracy than the exposure method through a photomask and a high-definition pattern can be obtained.

  In general, in the exposure process, it is necessary to shorten the exposure time in order to improve production efficiency. However, in the above-described direct drawing exposure method, in addition to using monochromatic light such as a laser as a light source and irradiating a light beam while scanning the substrate, a long exposure time is required as compared with an exposure method using a conventional photomask. Tend. Therefore, in order to shorten the exposure time and increase the production efficiency, it is necessary to improve the sensitivity of the photosensitive resin composition than before.

  In the stripping step, it is necessary to shorten the resist stripping time in order to improve production efficiency. Furthermore, in order to prevent the resist strips from reattaching to the circuit board and improve the production yield, it is necessary to reduce the size of the strips. Thus, the photosensitive resin composition excellent in the peeling characteristics (peeling time, peeling piece size, etc.) after hardening is requested | required.

  On the other hand, with the recent increase in the density of printed wiring boards, there is an increasing demand for a photosensitive resin composition excellent in resolution (resolution) and adhesion. In particular, a photosensitive resin composition capable of forming a resist pattern having an L / S (line width / space width) of 10/10 (unit: μm) or less in package substrate production is required.

  In a high-density package substrate, since the width between circuits is narrow, it is also important that the resist shape is excellent. If the cross-sectional shape of the resist is trapezoidal or inverted trapezoidal, or if there is resist skirting, there is a possibility that a short circuit or disconnection may occur in a circuit formed by subsequent etching or plating. Therefore, it is desirable that the cross-sectional shape of the resist is rectangular, has no skirting, and has no cracks or chips.

  Conventionally, various photosensitive resin compositions have been studied in response to these requirements. For example, Patent Documents 1 to 5 disclose a photosensitive resin composition having improved sensitivity and the like by using a specific sensitizing dye. Patent Documents 6 to 9 disclose a photosensitive resin composition having improved peelability or scum generation by using a cyclic organic compound having one ethylenically unsaturated bond in a specific molecular structure. ing.

JP 2007-101940 A JP 2007-101941 A JP 2007-279381 A International Publication No. 07/004619 Pamphlet JP 2009-003177 A JP-A-6-161103 JP 2001-154349 A JP 2006-154666 A JP 2008-209880 A

  However, conventional photosensitive resin compositions have room for improvement in terms of resolution, adhesion, or resist shape. In particular, it is difficult to obtain a photosensitive resin composition capable of forming a resist pattern having an L / S (line width / space width) of 10/10 (unit: μm) or less. However, it is strongly required to improve the resolution and adhesion of the photosensitive resin composition in units of 1 μm.

  In addition, the resist pattern formed from the resist pattern formed from the photosensitive resin composition can be improved in chemical resistance from the viewpoint of preventing a short circuit of the copper wiring pattern due to the formation of plating resist in the formed resist pattern. It is requested. Furthermore, it is also necessary to improve the flexibility of the resist pattern formed from the photosensitive resin composition from the viewpoint of preventing a short circuit due to resist chipping or cracking.

  Accordingly, the present invention relates to a photosensitive resin composition capable of forming a resist pattern excellent in all of resolution, adhesion, resist shape, peelability, flexibility, and chemical resistance, and a photosensitive element using the same. An object of the present invention is to provide a resist pattern forming method and a printed wiring board manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have combined a compound having one ethylenically unsaturated bond in the molecule and containing a specific cyclic structure as a photopolymerizable compound. The inventors have found that a photosensitive resin composition capable of forming a resist pattern that is excellent in all of resolution, adhesion, resist shape, peelability, flexibility, and chemical resistance is obtained, and the present invention has been completed. It was.

  That is, the first aspect of the present invention is a photosensitive resin composition containing (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: photopolymerization initiator. Wherein the component (B) contains a mono (meth) acrylate compound having a structure selected from a phenyl group, a benzyl group, a dicyclopentanyl group, a dicyclopentenyl group, or a biphenyl group. It is a resin composition.

  In addition, the second aspect of the present invention includes (A) component: binder polymer, (B) component: a photopolymerizable compound containing a compound represented by the following general formula (1), and (C) component: light. A photosensitive resin composition containing a polymerization initiator.

  In general formula (1), Y represents a hydrogen atom or a methyl group. R represents an alkylene group having 1 to 4 carbon atoms. n shows 0-2. X shows a C6-C14 organic group containing a cyclic structure.

  The photosensitive resin composition of the present invention takes any one of resolution, adhesion, resist shape, peelability after curing, flexibility, and chemical resistance by taking the first aspect or the second aspect. Also excellent. According to the photosensitive resin composition of the present invention, a resist pattern having L / S (line width / space width) of 10/10 (unit: μm) or less can be formed.

  X in the general formula (1) is preferably a phenyl group, a benzyl group, a dicyclopentanyl group, a dicyclopentenyl group, or a biphenyl group from the viewpoints of development resistance after curing and peelability.

  In addition, the photosensitive resin composition further includes a sensitizing dye having an absorption maximum at 340 nm to 430 nm from the viewpoint of further improving sensitivity, resolution, adhesion, flexibility, and release property after curing. It is preferable to contain.

  Moreover, it is preferable that the said photosensitive resin composition further contains (E) component: amine type compound from a viewpoint which further improves a sensitivity.

  3rd aspect of this invention is a photosensitive element provided with a support film and the photosensitive resin composition layer which is a coating film of the photosensitive resin composition of said 1st aspect provided on the said support film. It is. By using such a photosensitive element, it is possible to efficiently and efficiently form a resist pattern excellent in resolution, adhesion, and resist shape.

  According to a fourth aspect of the present invention, there is provided a lamination step of laminating a photosensitive resin composition layer, which is a coating film of the photosensitive resin composition of the first aspect, on a substrate, and the photosensitive resin composition layer. An exposure step of irradiating at least a part of the region with actinic rays to expose the region to form a cured product region, and removing regions other than the cured product region of the photosensitive resin composition layer from the substrate And a developing process for forming a resist pattern comprising the cured product region on the substrate. According to the method for forming a resist pattern, a resist pattern that is excellent in resolution, adhesion, resist shape, peelability after curing, flexibility, and chemical resistance can be efficiently formed with high sensitivity. it can.

  In the resist pattern forming method, the wavelength of the actinic ray to be irradiated is preferably in the range of 340 nm to 430 nm. As a result, a resist pattern with better resolution, adhesion, and resist shape can be efficiently formed with higher sensitivity.

  A fifth aspect of the present invention is a method for manufacturing a printed wiring board, including a step of etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern. According to this manufacturing method, a printed wiring board having high-density wiring such as a high-density package substrate can be efficiently manufactured with high accuracy.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can form the resist pattern which is excellent in all of resolution, adhesiveness, resist shape, peelability, flexibility, and chemical resistance, and the photosensitive element using the same A resist pattern forming method and a printed wiring board manufacturing method can be provided.

It is a schematic cross section which shows one Embodiment of the photosensitive element of this invention.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or the corresponding methacrylate, and (meth) acryloyloxy group means An acryloyloxy group or a corresponding methacryloyloxy group is meant. The (poly) oxyethylene group means at least one oxyethylene group or a polyoxyethylene group in which two or more oxyethylene groups are linked by an ether bond, and the (poly) oxypropylene chain is an oxypropylene group or two or more. Means at least one polyoxypropylene group in which the oxypropylene groups are linked by an ether bond. Further, “EO-modified” means a compound having a (poly) oxyethylene group, and “PO-modified” means a compound having a (poly) oxypropylene group. “PO-modified” means a compound having both a (poly) oxyethylene group and a (poly) oxypropylene group.

  In addition, in this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. It is. Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. Furthermore, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment comprises (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: photopolymerization initiator, and the (B) component. Is a photosensitive resin composition containing a mono (meth) acrylate compound having a structure selected from a phenyl group, a benzyl group, a dicyclopentanyl group, a dicyclopentenyl group, or a biphenyl group.
The photosensitive resin composition of the present embodiment includes (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: photopolymerization initiator. ) Component may be a photosensitive resin composition containing a photopolymerizable compound represented by the following general formula (1).

  In general formula (1), Y represents a hydrogen atom or a methyl group. R represents an alkylene group having 1 to 4 carbon atoms. n shows 0-2. X shows a C6-C14 organic group containing a cyclic structure.

A photosensitive resin composition that can form a resist pattern that is excellent in resolution, adhesion, resist shape, peelability, flexibility, and chemical resistance by including a compound having a specific structure as a photopolymerizable compound. Things can be configured. Although the detailed reason for the above effect is not necessarily clear, the present inventors have a mono (meta) having a structure selected from a phenyl group, a benzyl group, a dicyclopentanyl group, a dicyclopentenyl group, or a biphenyl group. ) Since the acrylate compound has a cyclic structure and one unsaturated group, it is possible to form a rough crosslinked network while having low swelling, and to improve the mutually conflicting properties of adhesion and peelability in a balanced manner. I guess.
More specifically, in the compound represented by the general formula (1), the above effect is exhibited by the organic group X having an appropriately bulky cyclic structure having 6 to 14 carbon atoms and one unsaturated group. I guess. In addition, it is considered that flexibility is further improved by having a flexible partial structure represented by-(RO) _n- in the general formula (1).

(A) component: Binder polymer The said photosensitive resin composition contains at least 1 sort (s) of a binder polymer as (A) component. The binder polymer is obtained, for example, by radical polymerization of a polymerizable monomer (monomer).

  As the polymerizable monomer (monomer), (meth) acrylic acid; (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid benzyl, (meth) acrylic acid benzyl derivative, ( (Meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid isobornyl, (meth) acrylic acid adamantyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dimethylaminoethyl, (meta) ) Diethylaminoethyl acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, α-bromoacrylic acid, α -Chloracrylic acid, (meth) acrylic acid dicyclopenteni Ruoxyethyl, dicyclopentanyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, adamantyloxyethyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxypropyloxyethyl, dicyclopentanyloxypropyloxyethyl (meth) acrylate, dicyclopentenyloxypropyloxyethyl (meth) acrylate, adamantyloxypropyloxyethyl (meth) acrylate, β-furyl (meth) (Meth) acrylic acid esters such as acrylic acid and β-styryl (meth) acrylic acid; styrene; polymerizable styrene derivatives substituted at the α-position or aromatic ring such as vinyltoluene and α-methylstyrene; Acrylamide such as rilamide; acrylonitrile; ether compound of vinyl alcohol such as vinyl-n-butyl ether; maleic acid; maleic anhydride; maleic acid monoester such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate; fumaric acid, Examples thereof include cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and other unsaturated carboxylic acid derivatives. These may be used alone or in any combination of two or more.

  Component (A) is at least one polymerizable monomer selected from the group consisting of benzyl (meth) acrylate, benzyl (meth) acrylate, styrene and styrene derivatives, from the viewpoint of improving resolution and adhesion. It is preferable to have a structural unit derived from the body. Moreover, it is more preferable that both at least one selected from the group consisting of benzyl (meth) acrylate and a benzyl derivative (meth) acrylate and at least one selected from the group consisting of styrene and a styrene derivative are included. That is, the component (A) is preferably obtained by radical polymerization of these polymerizable monomers, and preferably has a structural unit derived from these polymerizable monomers. .

  When the component (A) has a structural unit derived from benzyl (meth) acrylate or a derivative thereof, the content of the polymerizable monomer constituting the component (A) is excellent in resolution and peelability. 3 mass% to 85 mass%, more preferably 5 mass% to 75 mass%, more preferably 10 mass% to 70 mass%, based on the total mass of (100 mass%, the same applies hereinafter). It is further more preferable that it is 10 mass%-50 mass%. In terms of excellent resolution, the content is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. In terms of excellent peelability and adhesion, the content is preferably 85% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, and 50% by mass. % Or less is particularly preferable.

  When the component (A) has a structural unit derived from styrene or a derivative thereof, the content ratio is the total mass of the polymerizable monomer constituting the component (A) in terms of excellent adhesion and peelability. The reference is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 60% by mass, and still more preferably 20% by mass to 55% by mass. In terms of excellent adhesion, the content is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. In view of excellent peelability, the content is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less.

  Moreover, it is preferable that (A) component has a structural unit derived from (meth) acrylic-acid alkylester from a viewpoint of improving alkali developability and peeling characteristics.

  The (meth) acrylic acid alkyl ester is preferably a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms. Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic. Hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, (meth) An example is dodecyl acrylate. These may be used alone or in any combination of two or more.

  When the component (A) has a structural unit derived from a (meth) acrylic acid alkyl ester, the content is high in peelability, resolution and adhesion, and the polymerizable monomer constituting the component (A). It is preferably 1% by mass to 30% by mass, more preferably 2% by mass to 20% by mass, and still more preferably 3% by mass to 10% by mass based on the total mass of the body. In terms of excellent peelability, the content is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more. In view of excellent resolution and adhesion, the content is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less.

  The component (A) includes (EO) -modified dicyclopentenyl (meth) acrylate, (EO) -modified dicyclopentanyl (meth) acrylate and (EO) from the viewpoint of improving the flexibility and adhesion of the resist pattern to be formed. (EO) modified isobornyl (meth) acrylate, (EO) modified adamantyl (meth) acrylate, and (EO) at least one (meth) acrylate selected from the group consisting of modified cyclohexyl (meth) acrylate (hereinafter referred to as “(EO)”). It is preferable to have a structural unit derived from “modified alicyclic (meth) acrylate”. Among these, it is preferable to contain at least one selected from the group consisting of (EO) -modified dicyclopentenyl (meth) acrylate and (EO) -modified dicyclopentanyl (meth) acrylate. More preferably, it contains cyclopentenyl (meth) acrylate.

  When the component (A) has a structural unit derived from (EO) -modified alicyclic (meth) acrylate, the content is 3 based on the total mass of the polymerizable monomer constituting the component (A). The mass is preferably from 85% by mass to 85% by mass, more preferably from 4% by mass to 70% by mass, and still more preferably from 5% by mass to 50% by mass. This content is preferably 3% by mass or more, more preferably 4% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of better adhesion, flexibility, and flexibility. . Further, from the viewpoint of better resolution, the content is preferably 85% by mass or less, more preferably 70% by mass or less, and further preferably 50% by mass or less.

  The acid value of the component (A) is preferably 90 mgKOH / g to 250 mgKOH / g, more preferably 100 mgKOH / g to 240 mgKOH / g, and 120 mgKOH / g to 120 mgKOH / g in terms of excellent developability and adhesion. It is more preferable that it is 235 mgKOH / g, and it is especially preferable that it is 130 mgKOH / g-230 mgKOH / g. From the viewpoint of shortening the development time, the acid value is preferably 90 mgKOH / g or more, more preferably 100 mgKOH / g or more, further preferably 120 mgKOH / g or more, and 130 mgKOH / g or more. It is particularly preferred. The acid value is preferably 250 mgKOH / g or less, more preferably 240 mgKOH / g or less, and 235 mgKOH / g or less, from the viewpoint of obtaining sufficient adhesion of the cured product of the photosensitive resin composition. Is more preferable, and 230 mgKOH / g or less is particularly preferable. In addition, when performing solvent image development, it is preferable to prepare the polymerizable monomer (monomer) which has carboxy groups, such as (meth) acrylic acid, in a small quantity.

  The weight average molecular weight (Mw) of the component (A) is 10,000 to 200,000 in terms of excellent developability and adhesion when measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene). It is preferable that it is 20000-100,000, It is more preferable that it is 25000-80000, It is especially preferable that it is 30000-60000. In terms of excellent developability, it is preferably 200000 or less, more preferably 100000 or less, still more preferably 80000 or less, and particularly preferably 60000 or less. In the point which is excellent in adhesiveness, it is preferable that it is 10,000 or more, It is more preferable that it is 20000 or more, It is further more preferable that it is 25000 or more, It is especially preferable that it is 30000 or more.

  The dispersity (weight average molecular weight / number average molecular weight) of component (A) is preferably 3.0 or less, more preferably 2.8 or less, in terms of excellent resolution and adhesion. More preferably, it is 5 or less.

  Moreover, (A) component may have the characteristic group which has photosensitivity with respect to the light which has a wavelength within the range of 340 nm-430 nm in the molecule | numerator as needed. Examples of the characteristic group include a group constituted by removing at least one hydrogen atom from a sensitizing dye described later.

  As the component (A), one type of binder polymer may be used alone, or two or more types of binder polymers may be used in any combination.

  The content of the component (A) in the photosensitive resin composition is 30 parts by mass to 70 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B) in terms of excellent film formability, sensitivity, and resolution. Part, preferably 35 parts by weight to 65 parts by weight, and particularly preferably 40 parts by weight to 60 parts by weight. From the viewpoint of formability of the film (photosensitive resin composition layer), the content is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, and particularly preferably 40 parts by mass or more. preferable. In view of sufficiently obtaining sensitivity and resolution, the content is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, and still more preferably 60 parts by mass or less.

(B) Component: Photopolymerizable Compound Next, the photopolymerizable compound (hereinafter also referred to as “component (B)”) will be described. The photopolymerizable compound as component (B) comprises at least one mono (meth) acrylate compound having a structure selected from a phenyl group, a benzyl group, a dicyclopentanyl group, a dicyclopentenyl group, or a biphenyl group. Contains as an essential ingredient. More specifically, it is preferable to include a compound represented by the following general formula (1).

  In general formula (1), Y represents a hydrogen atom or a methyl group. R represents an alkylene group having 1 to 4 carbon atoms. n shows 0-2. X shows a C6-C14 organic group containing a cyclic structure.

The compound represented by the general formula (1) has a bulky cyclic structure contained in the organic group X, and thus has excellent peelability while maintaining low swelling due to physical interaction after photocuring. Furthermore, the flexibility can be further improved by having a flexible partial structure of-(RO) _n- .

  In the general formula (1), X represents an organic group having 6 to 14 carbon atoms including a cyclic structure. The organic group represented by X only needs to have at least one cyclic group, and may have a linear or branched alkyl group in addition to the cyclic group. Examples of the cyclic group include a saturated or unsaturated aliphatic hydrocarbon ring group, an aromatic hydrocarbon ring group, a saturated or unsaturated aliphatic heterocyclic group, and an aromatic heterocyclic group. The cyclic group may be any of a single ring, a condensed ring, a bridged ring, a spiro ring, a ring assembly in which a plurality of rings are connected by a covalent bond, and the like.

  Examples of the cyclic group include a monocyclic, condensed ring or bridged saturated aliphatic hydrocarbon ring group, a monocyclic, condensed ring or bridged unsaturated aliphatic hydrocarbon ring group, or a single ring, condensed ring or ring. It is preferably an aggregated aromatic hydrocarbon group. Further, from the viewpoint of further improving the resolution, X is more preferably a phenyl group, a benzyl group, a dicyclopentanyl group, a dicyclopentenyl group, or a biphenyl group, and a phenyl group, a dicyclopentanyl group. Or a dicyclopentenyl group is more preferable.

  In the general formula (1), R represents an alkylene group having 1 to 4 carbon atoms. R is preferably an ethylene group or a propylene group, and more preferably an ethylene group. The propylene group may be either an n-propylene group or an isopropylene group.

  In the said General formula (1), n shows 0-2. Here, n indicates how much an alkyleneoxy group having 1 to 4 carbon atoms is added to the molecule. Therefore, an integer value is shown for a single molecule, but a rational number that is an average value is shown as an aggregate of a plurality of types of molecules.

  The compound represented by the general formula (1) has a boiling point of preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher at normal pressure. When the boiling point is 150 ° C. or higher at normal pressure, when producing a photosensitive element using the photosensitive resin composition, it is possible to suppress volatilization of the compound represented by the general formula (1) in the drying step. Become.

  The compound represented by the general formula (1) preferably has a molecular weight of 100 to 500, more preferably 120 to 400, and further preferably 130 to 360 from the viewpoint of further improving the resolution. preferable.

  The content of the compound represented by the general formula (1) in the photosensitive resin composition is (A) component and (B) from the viewpoint of physically suppressing swelling due to the bulkiness in the crosslinked network after photocuring. The total amount of the components is preferably 1 part by mass to 30 parts by mass, more preferably 3 parts by mass to 25 parts by mass, and still more preferably 5 parts by mass to 20 parts by mass. Moreover, it is preferable that it is 30 mass parts or less in the point which is excellent in the bottom part sclerosis | hardenability of a resist, it is preferable that it is 25 mass parts or less, and it is preferable that it is 20 mass parts or less.

  As the compound represented by the general formula (1), a commercially available product may be used, or a compound synthesized by a conventional method may be used. The compound represented by the general formula (1) is, for example, an organic compound containing (meth) acrylic acid, (poly) alkylene glycol, a cyclic structure having 6 to 14 carbon atoms, and a leaving group such as a hydroxyl group or a halogen atom. It can be obtained by reacting with a compound.

  Industrial production methods for (meth) acrylate compounds include transesterification and dehydration esterification. An example of a synthesis method by transesterification is shown below. An alkylene oxide is added to an alcohol containing a cyclic structure having 6 to 14 carbon atoms. (Meth) acrylic acid having an organic group having 6 to 14 carbon atoms including a cyclic structure and a (poly) alkyleneoxy group by transesterification of the obtained alkylene oxide-added alcohol derivative and (meth) acrylic acid ester An ester compound is obtained.

  As a commercial product of the compound represented by the general formula (1), as a compound in which X represents a dicyclopentenyl group, dicyclopentenyloxyethyl methacrylate (FA-512MT, manufactured by Hitachi Chemical Co., Ltd.), X is di Dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) as a compound showing a cyclopentanyl group, benzyl methacrylate (FA-BZM, Hitachi Chemical Co., Ltd.) as a compound where X shows a benzyl group And phenoxyethyl methacrylate (FA-310M, manufactured by Hitachi Chemical Co., Ltd.) and biphenyloxyethyl methacrylate as the compound where X represents a biphenyl group.

  In the compound represented by the general formula (1), from the viewpoint of resolution, X is a phenyl group, a benzyl group, a dicyclopentanyl group, a dicyclopentenyl group, or a biphenyl group, and R is an ethylene group or a propylene group. Wherein n is 0 or 1, and preferably a group consisting of dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and biphenyloxyethoxyethyl methacrylate. More preferably, it is at least one selected from more.

In the photosensitive resin composition, as the compound represented by the general formula (1), X is a phenyl group, a benzyl group, a dicyclopentanyl group, a dicyclopentenyl group, or a biphenyl group, and R is an ethylene group. Or it is preferable that 1 mass part-30 mass parts is included in 100 mass parts of total amounts of (A) component and (B) component at least 1 sort (s) of the compound which is a propylene group and n is 0 or 1.
At least one selected from the group consisting of dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and biphenyloxyethoxyethyl methacrylate is used, and the total amount of component (A) and component (B) is 100 masses. More preferably, 3 parts by mass to 25 parts by mass is included in the part.

  The said photosensitive resin composition can contain other photopolymerizable compounds other than the compound represented by General formula (1) as (B) component. Other photopolymerizable compounds are not particularly limited as long as photopolymerization is possible. The other photopolymerizable compound is preferably a compound having an ethylenically unsaturated bond. The compound having an ethylenically unsaturated bond includes a compound having one ethylenically unsaturated bond in the molecule, a compound having two ethylenically unsaturated bonds in the molecule, and three ethylenically unsaturated bonds in the molecule. Examples thereof include the compounds described above.

  When the component (B) contains other photopolymerizable compound, the content of the compound represented by the general formula (1) in the component (B) is physically swollen due to the bulkiness in the crosslinked network. From the viewpoint of suppressing, the total amount of component (B) is preferably 2 parts by mass to 60 parts by mass, more preferably 6 parts by mass to 50 parts by mass, and more preferably 10 parts by mass to 40 parts by mass in 100 parts by mass. More preferably, it is part.

  The component (B) preferably contains at least one compound having two ethylenically unsaturated bonds in the molecule as the other photopolymerizable compound. When the component (B) contains a compound having two ethylenically unsaturated bonds in the molecule as the other photopolymerizable compound, the content is 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably 5 to 60 parts by mass, more preferably 5 to 55 parts by mass, and still more preferably 10 to 50 parts by mass.

  Examples of compounds having two ethylenically unsaturated bonds in the molecule include bisphenol A di (meth) acrylate compounds, hydrogenated bisphenol A di (meth) acrylate compounds, and di (meta) having urethane bonds in the molecule. ) Acrylate compounds, polyalkylene glycol di (meth) acrylates and trimethylolpropane di (meth) acrylates having both (poly) oxyethylene groups and (poly) oxypropylene groups in the molecule.

  From the viewpoint of improving resolution and release characteristics, the component (B) is a bisphenol A di (meth) acrylate compound, a hydrogenated bisphenol A di (meth) acrylate compound, and an intramolecular Including at least one compound having two ethylenically unsaturated bonds in the molecule selected from the group consisting of a polyalkylene glycol di (meth) acrylate having a (poly) oxyethylene group and a (poly) oxypropylene group It is preferable.

  Examples of the bisphenol A-based di (meth) acrylate compound include compounds represented by the following general formula (4).

In the general formula (4), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an oxyethylene group or an oxypropylene group. (XO) m ₁ , (XO) m ₂ , (YO) n ₁ , (YO) n ₂ represent a (poly) oxyethylene group or a (poly) oxypropylene group. m ₁ , m ₂ , n ₁ and n ₂ each independently represent 0 to 40. When XO is an oxyethylene group and YO is an oxypropylene group, m ₁ + m ₂ is 1 to 40, and n ₁ + n ₂ is 0 to 20. When XO is an oxypropylene group and YO is an oxyethylene group, m ₁ + m ₂ is 0-20, and n ₁ + n ₂ is 1-40. m ₁ , m ₂ , n ₁ and n ₂ represent the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the same applies to the number of structural units.

In terms of excellent resolution, in the general formula (4), a compound in which m ₁ + m ₂ is in the range of ₈ to 40 and a compound in which m ₁ + m ₂ is in the range of 1 to 7 are used in combination. Are preferably used.

  Among the compounds represented by the above general formula (4), 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) or It is commercially available as FA-321M (manufactured by Hitachi Chemical Co., Ltd., product name), and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (Shin Nakamura) The product is commercially available as a product name manufactured by Chemical Industry Co., Ltd. These may be used alone or in any combination of two or more.

  When the photosensitive resin composition contains a bisphenol A di (meth) acrylate compound as the component (B), the content thereof is 1 mass in 100 parts by mass of the total amount of the components (A) and (B). Part to 50 parts by weight, and more preferably 5 parts to 50 parts by weight.

  Examples of the hydrogenated bisphenol A di (meth) acrylate compound include 2,2-bis (4- (methacryloxypentaethoxy) cyclohexyl) propane. When the said photosensitive resin composition contains hydrogenated bisphenol A type | system | group di (meth) acrylate compound, as the content, 1 mass part-50 in 100 mass parts of total amounts of (A) component and (B) component. It is preferable that it is a mass part, and it is more preferable that it is 5 mass parts-40 mass parts.

  The component (B) contains at least one polyalkylene glycol di (meth) acrylate as another photopolymerizable compound from the viewpoint of improving the flexibility of the cured product (cured film) of the photosensitive resin composition. It is preferable. When the photosensitive resin composition contains a polyalkylene glycol di (meth) acrylate, the content thereof is 5 to 30 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B). It is preferable that it is 10 mass parts-25 mass parts.

  As the polyalkylene glycol di (meth) acrylate compound, polyalkylene glycol di (meth) acrylate having both a (poly) oxyethylene group and a (poly) oxypropylene group in the molecule is preferable. In the molecule of the polyalkylene glycol di (meth) acrylate, the (poly) oxyethylene group and the (poly) oxypropylene group may be continuously present in blocks or randomly. The oxypropylene group in the (poly) oxypropylene group may be either an oxy-n-propylene group or an oxyisopropylene group. In the (poly) oxyisopropylene group, 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.

  Polyalkylene glycol di (meth) acrylate is composed of (poly) oxy-n-butylene group, (poly) oxyisobutylene group, (poly) oxy-n-pentylene group, (poly) oxyhexylene group, and structural isomers thereof. It may have a (poly) oxyalkylene group having about 4 to 6 carbon atoms, such as a body.

  The polyalkylene glycol di (meth) acrylate is preferably a compound represented by any one of the following general formulas (5), (6) and (7). These can be used alone or in combination of two or more.

In formulas (5), (6) and (7), R ^{5 to} R ¹⁰ each independently represent a hydrogen atom or a methyl group, EO represents an oxyethylene group, and PO represents an oxypropylene group. r ₁ , r ₂ , r ₃ and r ₄ represent the number of structural units of the structural unit composed of oxyethylene groups, and s ₁ , s ₂ , s ₃ and s ₄ represent the number of structural units of the structural units composed of oxypropylene group. And the number of structural units r ₁ + r ₂ , r ₃ and r ₄ of the oxyethylene group each independently represents 1 to 30, and the number of structural units s ₁ , s ₂ + s ₃ and s ₄ of the oxypropylene group are each independently 1-30 are shown.

In the compound represented by the general formula (5), (6) or (7), the number of structural units r ₁ + r ₂ , r ₃ and r ₄ of the oxyethylene group is 1 to 30, preferably 1 to 10 More preferably, it is 4-9, Most preferably, it is 5-8. When the total number of structural units is 30 or less, sufficient resolution, adhesion, and resist shape tend to be easily obtained.

The number of structural units s ₁ , s ₂ + s ₃ and s ₄ of the oxypropylene group is 1 to 30, preferably 5 to 20, more preferably 8 to 16, and particularly preferably 10 to 14. . When the total number of the structural units is 30 or less, sufficient resolution is easily obtained, and sludge generation tends to be suppressed.

The compound represented by the general formula (5) is a vinyl compound (Hitachi Chemical Industry Co., Ltd.) in which R ⁵ and R ⁶ are methyl groups, r ₁ + r ₂ = 6 (average value), and s ₁ = 12 (average value). (Product name "FA-023M") etc. are mentioned. As the compound represented by the general formula (6), vinyl compounds (Hitachi Chemical Industry Co., Ltd.) in which R ⁷ and R ⁸ are methyl groups, r ₃ = 6 (average value), and s ₂ + s ₃ = 12 (average value) Product name "FA-024M") and the like. As the compound represented by the general formula (7), R ⁹ and R ¹⁰ are hydrogen atoms, r ₄ = 1 (average value), s ₄ = 9 (average value) vinyl compound (Shin Nakamura Chemical Industry ( Co., Ltd. product, sample name “NK ester HEMA-9P”) and the like. These can be used alone or in combination of two or more.

  The component (B) preferably contains two or more compounds having two ethylenically unsaturated bonds in the molecule as other photopolymerizable compounds from the viewpoint of balancing resolution and flexibility. A di (meth) acrylate compound, a hydrogenated bisphenol A di (meth) acrylate compound, and a polyalkylene glycol di (meth) acrylate having a (poly) oxyethylene group and a (poly) oxypropylene group in the molecule More preferably, the molecule selected from the group consisting of two or more compounds having two ethylenically unsaturated bonds is selected from the group consisting of bisphenol A di (meth) acrylate compounds. More preferably, two or more compounds having two saturated bonds are included.

  The component (B) may contain at least one photopolymerizable compound having three or more ethylenically unsaturated bonds in the molecule as the other photopolymerizable compound.

  Examples of the compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate (having 1 to 5 constituent units of oxyethylene group). , PO-modified trimethylolpropane tri (meth) acrylate, EO / PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate and tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate Or dipentaerythritol hexa (meth) acrylate is mentioned. These can be used alone or in combination of two or more.

  Tetramethylol methane triacrylate is A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name), and EO-modified trimethylol propane trimethacrylate is TMPT21E and TMPT30E (manufactured by Hitachi Chemical Co., Ltd., sample name). ), Pentaerythritol triacrylate is SR444 (manufactured by Sartomer, product name), dipentaerythritol hexaacrylate is A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., product name), and ethoxylated penta Erythritol tetraacrylate is commercially available as ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)).

  When the component (B) contains a photopolymerizable compound having three or more ethylenically unsaturated bonds in the molecule as the other photopolymerizable compound, the content thereof is resolution, adhesion, resist shape and after curing. From the viewpoint of improving the release properties in a well-balanced manner, the total amount of the component (A) and the component (B) is preferably 3 parts by mass to 30 parts by mass, and preferably 5 parts by mass to 25 parts by mass. It is more preferable that it is 5 to 20 parts by mass.

  From the viewpoint of improving the resolution, adhesion, resist shape, suppression of scum generation, or improving the release characteristics after curing, the above component (B) is an ethylenically unsaturated bond in the molecule as another photopolymerizable compound. One photopolymerizable compound may be included.

  Examples of other photopolymerizable compounds having one ethylenically unsaturated bond in the molecule include nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, and (meth) acrylic acid alkyl esters. Among the above, it is preferable that nonylphenoxypolyethyleneoxyacrylate or a phthalic acid-based compound is included from the viewpoint of improving the resolution, adhesion, resist shape, and release property after curing in a well-balanced manner.

  When the component (B) includes a photopolymerizable compound having one ethylenically unsaturated bond in the molecule as the other photopolymerizable compound, the content thereof is a total of 100 components (A) and (B). The mass part is preferably 1 part by mass to 20 parts by mass, more preferably 3 parts by mass to 15 parts by mass, and still more preferably 5 parts by mass to 12 parts by mass.

The component (B) is composed of at least one compound represented by the general formula (1) and a compound having two ethylenically unsaturated bonds in the molecule from the viewpoints of resolution, peelability, and flexibility. Preferably including at least one species,
More preferably, it contains at least one compound represented by the general formula (1) and at least two compounds having two ethylenically unsaturated bonds in the molecule,
At least one of the compounds represented by the general formula (1), a bisphenol A di (meth) acrylate compound, a hydrogenated bisphenol A di (meth) acrylate compound, and a (poly) oxyethylene group in the molecule And more preferably two or more compounds having two ethylenically unsaturated bonds in the molecule selected from the group consisting of polyalkylene glycol di (meth) acrylates having a (poly) oxypropylene group,
Two or more compounds selected from the group consisting of at least one compound represented by the above general formula (1) and a bisphenol A di (meth) acrylate compound and having two ethylenically unsaturated bonds in the molecule It is particularly preferable to include it.

The component (B) is composed of at least one compound represented by the general formula (1) (hereinafter, also referred to as “B ₁ component”) in the molecule from the viewpoint of resolution, peelability, and flexibility. at least one ethylenically unsaturated bond and having two compounds (hereinafter also referred to as "B ₂ component") and a, B ₂ B ₁ component content ratio to component (B ₁ component / B ₂ components) 0 0.05 to 1.0 is preferable, 0.10 to 0.8 is more preferable, and 0.12 to 0.5 is still more preferable.

  The total content of the component (B) in the photosensitive resin composition is preferably 30 parts by mass to 70 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B), and 35 parts by mass. It is more preferable to set it as -65 mass parts, and it is especially preferable to set it as 35 mass parts-50 mass parts. When the content is 30 parts by mass or more, sufficient sensitivity and resolution tend to be easily obtained. When it is 70 parts by mass or less, a film (photosensitive resin composition layer) tends to be easily formed, and a good resist shape tends to be easily obtained.

Component (C): Photopolymerization initiator The photosensitive resin composition contains at least one photopolymerization initiator as the component (C). There is no restriction | limiting in particular as a photoinitiator which is (C) component, It can select suitably from the photoinitiator used normally. As the photopolymerization initiator, benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Aromatic ketones such as propanone-1; quinones such as alkylanthraquinones; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl)- 2,4,5-triarylimidazole dimer such as 4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer; 9-phenylacridine, 1, Acridine derivatives such as 7- (9,9′-acridinyl) heptane Is mentioned. These can be used alone or in combination of two or more.

  The component (C) preferably contains at least one 2,4,5-triarylimidazole dimer from the viewpoint of improving sensitivity and adhesion, and 2- (o-chlorophenyl) -4,5- More preferably, it contains a diphenylimidazole dimer. The 2,4,5-triarylimidazole dimer may be symmetric or asymmetric in structure.

  The content of the component (C) in the photosensitive resin composition is preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is more preferably from 7 parts by mass to 7 parts by mass, still more preferably from 2 parts by mass to 6 parts by mass, and particularly preferably from 3 parts by mass to 5 parts by mass. When this content is 0.1 parts by mass or more, good sensitivity, resolution or adhesion tends to be obtained, and when it is 10 parts by mass or less, a good resist shape tends to be obtained.

(D) component: Sensitizing dye The photosensitive resin composition of this embodiment can contain at least 1 sort (s) of a sensitizing dye as (D) component.

  Examples of the sensitizing dye as component (D) include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds. , Stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. These can be used alone or in combination of two or more.

  In particular, when exposing the photosensitive resin composition layer using actinic rays of 340 to 430 nm, from the viewpoint of sensitivity and adhesion, the component (D) is a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, It preferably contains at least one sensitizing dye selected from the group consisting of a coumarin compound, a triarylamine compound, a thioxanthone compound and an aminoacridine compound, and among them, a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, and a triarylamine compound More preferably, it contains at least one selected from the group consisting of, and more preferably contains at least one pyrazoline compound.

  The content of the component (D) in the photosensitive resin composition is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is more preferable to set it as 05 mass parts-5 mass parts, and it is still more preferable to set it as 0.1 mass parts-3 mass parts. When this content is 0.01 parts by mass or more, sensitivity and resolution tend to be easily obtained, and when it is 10 parts by mass or less, a sufficiently good resist shape tends to be easily obtained.

  The pyrazoline compound is preferably at least one selected from the group consisting of a compound represented by the following general formula (8) and a compound represented by the general formula (9).

In the general formula (8), R ^{11 to} R ¹³ are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkoxy group having 1 to 10 carbon atoms. Or a halogen atom is shown. A, b and c each independently represent an integer of 0 to 5, and the sum of a, b and c is 1 to 6. When the sum of a, b and c is 2 or more, a plurality of R ^{11 to} R ¹³ may be the same as or different from each other.

In the general formula (8), at least one of R ^{11 to} R ¹³ is a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched group having 1 to 10 carbon atoms. It is preferably a linear alkoxy group, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a phenyl group. More preferred is a tert-butyl group, an isopropyl group, a methoxy group, or an ethoxy group.

  The pyrazoline compound represented by the general formula (8) can be used without particular limitation, and specifically, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -Pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butylphenyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4- Methoxyphenyl) -pyrazoline, 1-phenyl-3- (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3,4-dimethoxystyryl) -5 -(3,4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,6-dimethoxystyryl) -5- (2,6-dimethoxyphenyl) -pi Zoline, 1-phenyl-3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,3-dimethoxystyryl) -5- (2, It corresponds to a = 0 in the above general formula (8) such as 3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,4-dimethoxystyryl) -5- (2,4-dimethoxyphenyl) -pyrazoline And pyrazoline compounds.

In the general formula (9), R ^{14 to} R ¹⁶ are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkoxy group having 1 to 10 carbon atoms. Represents a halogen atom or a phenyl group. D, e, and f each independently represent an integer of 0-5, and the sum of d, e, and f is 1-6. When the sum of d, e, and f is 2 or more, a plurality of R ^{14 to} R ¹⁶ may be the same as or different from each other.

In the general formula (9), at least one of R ^{14 to} R ¹⁶ is a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched group having 1 to 10 carbon atoms. Is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a phenyl group. More preferred is a tert-butyl group, isopropyl group, methoxy group, ethoxy group or phenyl group.

Further, the pyrazoline compound represented by the general formula (9) can be used without particular limitation, but 1-phenyl-3,5-bis (4-tert-butylphenyl) -pyrazoline, 1-phenyl- 3,5-bis (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (4-methoxyphenyl) -5- (4-tert-butylphenyl) -pyrazoline, 1-phenyl-3- (4-tert -Butylphenyl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (4-isopropylphenyl) -5- (4-tert-butylphenyl) -pyrazoline, 1-phenyl-3- (4 -Tert-butylphenyl) -5- (4-isopropylphenyl) -pyrazoline, 1-phenyl-3- (4-methoxyphenyl) -5- (4- Sopropylphenyl) -pyrazoline, 1-phenyl-3- (4-isopropylphenyl) -5- (4-methoxyphenyl) -pyrazoline, 1,5-diphenyl-3- (4-tert-butylphenyl) -pyrazoline, 1,3-diphenyl-5- (4-tert-butylphenyl) -pyrazoline, 1,5-diphenyl-3- (4-isopropylphenyl) -pyrazoline, 1,3-diphenyl-5- (4-isopropylphenyl) -Pyrazoline, 1,5-diphenyl-3- (4-methoxyphenyl) -pyrazoline, 1,3-diphenyl-5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3,5-bis (4-tert -Butylphenyl) -pyrazoline, 1,5-diphenyl-3- (4-tert-butylphenyl) -pyrazoline, etc. A pyrazoline compound corresponding to d = 0 in the general formula (9); 1-phenyl-3- (4-biphenyl) -5- (4-tert-butylphenyl) -pyrazoline, 1-phenyl-3- (4 In the above general formula (9) such as -biphenyl) -5- (4-tert-octylphenyl) -pyrazoline, a pyrazoline compound in which e = 1 and R ¹⁵ = phenyl group can be mentioned.

  The anthracene compound preferably includes a compound represented by the following general formula (10).

In the general formula (10), R ¹⁷ and R ¹⁸ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl group, a benzyl group, or 2 carbon atoms. -12 alkanoyl groups or benzoyl groups are shown. R ^{19 to} R ²⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, a cyano group, a carboxyl group, a phenyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a benzoyl group. Show.

Examples of R ¹⁷ and R ¹⁸ in the general formula (10) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the combination of R ¹⁷ and R ¹⁸ include a combination of ethyl groups, a combination of propyl groups, and a combination of butyl groups.

Examples of R ^{19 to} R ²⁶ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an ethoxycarbonyl group. , Hydroxyethoxycarbonyl group, and phenoxy group. As combinations of R ^{19 to} R ²⁶ , all of them are hydrogen atoms; any one of them is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a propenyl group, a butenyl group, a pentenyl group, A xenyl group, a heptenyl group, an ethoxycarbonyl group, a hydroxyethoxycarbonyl group, or a phenoxy group, all of which are hydrogen atoms; any two of them are independently a methyl group, an ethyl group, a propyl group, A group selected from the group consisting of a butyl group, a pentyl group, a hexyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an ethoxycarbonyl group, a hydroxyethoxycarbonyl group, and a phenoxy group; All include combinations such as hydrogen atoms.

R ¹⁷ and R ¹⁸ are preferably each independently an alkyl group having 1 to 4 carbon atoms. R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are preferably hydrogen atoms.

  Specific examples of the compound represented by the general formula (10) include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 9,10-dibutoxyanthracene.

  The triarylamine compound is preferably at least one compound represented by the following general formula (11).

In the general formula (11), R ²⁷ , R ²⁸ and R ²⁹ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. g, h and i are integers of 0 to 5 selected so that the value of g + h + i is 1 or more. When g is 2 or more, a plurality of R ²⁷ may be the same or different. When h is 2 or more, a plurality of R ²⁸ may be the same or different. When i is 2 or more A plurality of R ²⁹ may be the same or different. In the general formula (11), R ²⁷ , R ²⁸ and R ²⁹ are preferably hydrogen atoms.

(E) component: amine compound It is preferable that the said photosensitive resin composition contains at least 1 sort (s) of an amine compound as (E) component. Examples of the amine compound include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leucocrystal violet. These can be used alone or in combination of two or more.

  When the photosensitive resin composition includes the component (E), the content is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass. If this content is 0.01 parts by mass or more, sufficient sensitivity tends to be obtained. If the amount is 10 parts by mass or less, after the film is formed, precipitation of excess (E) component as foreign matter tends to be suppressed.

(Other ingredients)
If necessary, the photosensitive resin composition of the present embodiment includes a photopolymerizable compound (such as an oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, malachite green, Victoria Dyes such as pure blue, brilliant green and methyl violet, photochromic agents such as tribromophenylsulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline and o-chloroaniline, thermochromic inhibitors, p-toluenesulfonamide, etc. Plasticizers, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. . These are used alone or in combination of two or more. When the photosensitive resin composition contains other components, these contents are about 0.01 parts by mass to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), respectively. It is preferable.

[Solution of photosensitive resin composition]
The photosensitive resin composition of this embodiment may further contain at least one organic solvent. Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; N, N- And aprotic polar solvents such as dimethylformamide. These may be used alone or in admixture of two or more. Content of the organic solvent contained in the said photosensitive resin composition can be suitably selected according to the objective etc. For example, it can be used as a solution having a solid content of about 30% by mass to 60% by mass (hereinafter, a photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”).

  The said coating liquid is apply | coated on surfaces, such as a support film mentioned later and a metal plate, and the photosensitive resin layer which is a coating film of the photosensitive resin composition of this embodiment can be formed by making it dry. It does not restrict | limit especially as a metal plate, According to the objective etc., it can select suitably. Examples of the metal plate include metal plates such as copper, copper alloys, iron alloys such as nickel, chromium, iron, and stainless steel. As a metal plate, Preferably, metal plates, such as copper, a copper-type alloy, and an iron-type alloy, are mentioned.

  The thickness of the photosensitive resin layer to be formed is not particularly limited and can be appropriately selected depending on the application. For example, the thickness after drying is preferably about 1 μm to 100 μm. When the photosensitive resin layer is formed on the metal plate, the surface of the photosensitive resin layer opposite to the metal plate may be covered with a protective film. Examples of the protective film include polymer films such as polyethylene and polypropylene.

  The photosensitive resin composition of this embodiment can be used for formation of the photosensitive resin layer of the photosensitive element mentioned later. That is, another embodiment of the present invention comprises (A) component: binder polymer, (B) component: photopolymerizable compound containing the compound represented by the general formula (1), and (C) component: light. Use of a photosensitive resin composition containing a polymerization initiator for a photosensitive element. Moreover, the photosensitive resin composition of this embodiment can be used for the formation method of the resist pattern mentioned later. That is, another embodiment of the present invention comprises (A) component: binder polymer, (B) component: photopolymerizable compound containing the compound represented by the general formula (1), and (C) component: light. It is use to the formation method of the resist pattern of the photosensitive resin composition containing a polymerization initiator.

<Photosensitive element>
The photosensitive element of this invention is equipped with the support film and the photosensitive resin composition layer which is a coating film of the said photosensitive resin composition provided on this support film. The coating film is one in which the photosensitive resin composition is in an uncured state. The said photosensitive element may have other layers, such as a protective film, as needed.

  FIG. 1 shows an embodiment of the photosensitive element. In the photosensitive element 10 shown in FIG. 1, the support film 2, the photosensitive resin composition layer 4 which is a coating film of the photosensitive resin composition, and the protective film 6 are laminated in this order. The photosensitive element 10 can be obtained as follows, for example. On the support film 2, the coating liquid which is the said photosensitive resin composition containing an organic solvent is apply | coated, a coating layer is formed, and the photosensitive resin composition layer 4 is formed by drying this. Next, the surface opposite to the support film 2 of the photosensitive resin composition layer 4 is covered with a protective film 6, thereby supporting the support film 2, and the photosensitive resin layer 4 laminated on the support film 2, The photosensitive element 10 of this embodiment provided with the protective film 6 laminated | stacked on this photosensitive resin composition layer 4 is obtained. The photosensitive element 10 does not necessarily include the protective film 6.

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

  The thickness of the support film (polymer film) is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, and still more preferably 5 μm to 30 μm. When the thickness of the support film is 1 μm or more, the support film can be prevented from being broken when the support film is peeled off. Moreover, the fall of the resolution is suppressed because it is 100 micrometers or less.

  As a protective film, what has the adhesive force with respect to the photosensitive resin composition layer is smaller than the adhesive force with respect to the photosensitive resin composition layer of a support film is preferable. A low fisheye film is preferred. Here, “fish eye” means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.

  Specifically, a polymer film having heat resistance and solvent resistance, such as polyester such as polyethylene terephthalate, polyolefin such as polypropylene and polyethylene, can be used as the protective film. Examples of commercially available products include polypropylene films such as Alphan MA-410 and E-200 manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and PS series polyethylene terephthalate films such as PS-25 manufactured by Teijin Limited. It is done. The protective film 6 may be the same as the support film 2.

  The thickness of the protective film is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, still more preferably 5 μm to 30 μm, and particularly preferably 15 μm to 30 μm. When the thickness of the protective film is 1 μm or more, the protective film can be prevented from being broken when the photosensitive resin layer and the support film are laminated on the substrate while peeling off the protective film. When it is 100 μm or less, it is excellent in handleability and inexpensiveness.

  Specifically, the photosensitive element of this embodiment can be manufactured as follows, for example. (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) a step of preparing a coating solution in which a photopolymerization initiator is dissolved in the organic solvent, and coating the coating solution on a support. And a process for forming a coating layer and a process for drying the coating layer to form a photosensitive resin composition layer.

  Application of the photosensitive resin composition solution onto the support film can be performed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.

  The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. It is preferable to carry out at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin composition layer is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

  The thickness of the photosensitive resin composition layer in the photosensitive element can be appropriately selected depending on the application. The thickness after drying is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and still more preferably 5 μm to 40 μm. Industrial coating becomes easy because the thickness of the photosensitive resin composition layer is 1 μm or more. When it is 100 μm or less, adhesion and resolution tend to be sufficiently obtained.

  The transmittance of the photosensitive resin composition layer with respect to ultraviolet rays is preferably 5% to 75%, more preferably 10% to 65%, and more preferably 15% to ultraviolet rays having a wavelength in the range of 350 nm to 420 nm. It is particularly preferred that it is ˜55%. When the transmittance is 5% or more, sufficient adhesion tends to be obtained. If it is 75% or less, sufficient resolution tends to be easily obtained. The transmittance can be measured with a UV spectrometer. An example of the UV spectrometer is a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

  The photosensitive element may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. As these intermediate layers, for example, the intermediate layers described in JP-A-2006-098982 can also be applied in the present invention.

  The form of the obtained photosensitive element is not particularly limited. For example, it may be in the form of a sheet, or may be in the form of a roll wound around a core. When it winds up in roll shape, it is preferable to wind up so that a support film may become an outer side. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). From the viewpoint of protecting the end face, it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained, and it is preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. As a packaging method, it is preferable to wrap and package in a black sheet with low moisture permeability.

  The photosensitive element of this embodiment can be used suitably for the formation method of the resist pattern mentioned later, for example.

<Method for forming resist pattern>
A resist pattern can be formed using the photosensitive resin composition. The resist pattern forming method of the present embodiment includes (i) a lamination step of laminating a photosensitive resin composition layer, which is a coating film of the photosensitive resin composition, on a substrate, and (ii) a photosensitive resin composition layer. An exposure step of irradiating the predetermined portion with actinic rays to expose and cure the predetermined portion; and (iii) removing the portion other than the predetermined portion of the photosensitive resin composition layer from the substrate, And a developing step for forming a resist pattern made of a cured product of the photosensitive resin composition. The method for forming the resist pattern may further include other steps as necessary.

(I) Lamination process First, the photosensitive resin composition layer which is a coating film of the said photosensitive resin composition is laminated | stacked on a board | substrate. As the substrate, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used.

  For example, when the photosensitive element has the protective film 6, the photosensitive resin composition layer is laminated on the substrate after the protective film is removed and then the photosensitive resin composition layer of the photosensitive element. This is performed by pressure-bonding to the substrate while heating. Thereby, the laminated body by which the board | substrate, the photosensitive resin composition layer, and the support film were laminated | stacked in this order is obtained.

This lamination step is preferably performed under reduced pressure from the viewpoint of adhesion and followability. Heating at least one of the photosensitive resin composition layer and the substrate during the pressure bonding is preferably performed at a temperature of 70 ° C. to 130 ° C., and is about 0.1 MPa to 1.0 MPa (1 kgf / cm ^{2 to} 10 kgf / cm ^2. It is preferable to press-fit with a pressure of about). These conditions are not particularly limited, and are appropriately selected as necessary. In addition, if the photosensitive resin composition layer is heated to 70 ° C. to 130 ° C., it is not necessary to pre-heat the substrate in advance. Adhesion and follow-up can be further improved by pre-heat treatment of the circuit forming substrate.

(Ii) Exposure Step In the exposure step, at least a part of the photosensitive resin layer formed on the substrate as described above is irradiated with actinic rays so that the exposed portion irradiated with actinic rays is photocured. Thus, a latent image is formed. Under the present circumstances, when the support film which exists on the photosensitive resin composition layer is transparent with respect to actinic light, actinic light can be irradiated through a support film. On the other hand, when a support film shows light-shielding property with respect to actinic rays, actinic rays are irradiated to the photosensitive resin composition layer after removing a support film.

  Examples of the exposure method include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork (mask exposure method). Alternatively, a method of irradiating actinic rays in an image form by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.

  The light source for actinic rays is not particularly limited, and a known light source can be used. For example, carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid-state lasers such as YAG lasers, ultraviolet rays such as semiconductor lasers and gallium nitride blue-violet lasers, visible light, etc. What to do is used.

  The wavelength of the actinic ray (exposure wavelength) is preferably in the range of 340 nm to 430 nm, more preferably in the range of 350 nm to 420 nm, from the viewpoint of obtaining the effects of the present invention more reliably.

(Iii) Development Step In the development step, the uncured portion of the photosensitive resin composition layer is removed from the circuit-forming substrate by a development process, whereby the photosensitive resin composition layer is a cured product that is photocured. A resist pattern is formed on the substrate. When the support film exists on the photosensitive resin composition layer, the support film is removed, and then the unexposed portion is removed (development). Development processing includes wet development and dry development, and wet development is widely used.

  In the case of wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include a method using a dip method, a battle method, a spray method, brushing, slapping, scraping, rocking immersion, and the like. From the viewpoint of improving the resolution, the high pressure spray method is most suitable. You may develop by combining these 2 or more types of methods.

  The developer is appropriately selected according to the configuration of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution, an aqueous developer, an organic solvent developer, and the like.

  The alkaline aqueous solution is safe and stable when used as a developer, and has good operability. 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, sodium phosphate, and the like. Alkali metal phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used.

  Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1% by mass to 5% by mass of potassium carbonate, and 0.1% by mass to 5% by mass of sodium hydroxide. A dilute solution of 0.1 mass% to 5 mass% of sodium tetraborate is preferred. The pH of the alkaline aqueous solution is preferably in the range of 9-11. The temperature is adjusted in accordance with the alkali developability of the photosensitive resin composition layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.

  The aqueous developer is, for example, 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, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3 -Propanediol, 1,3-diamino-2-propanol, morpholine and the like. The pH of the aqueous developer is preferably as low as possible within a range where development is sufficiently performed, preferably pH 8 to 12, and more preferably pH 9 to 10.

  Examples of the organic solvent used in the aqueous developer 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. Etc. These are used alone or in combination of two or more. The concentration of the organic solvent in the aqueous developer is usually preferably 2% by mass to 90% by mass. Moreover, the temperature can be adjusted according to alkali developability. A small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.

  Examples of the organic solvent developer include organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. It is preferable to add water to these organic solvents in the range of 1% by mass to 20% by mass in order to prevent ignition.

Above the resist pattern forming method, by performing after the removal of the unexposed portions, the order of 60 ° C. to 250 DEG ° C. heating or 0.2J ^/ cm ² ~10J ^/ cm 2 about the exposure as required, the resist pattern The method may further include a step of further curing.

<Method for manufacturing printed wiring board>
The method for producing a printed wiring board of the present invention includes a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern has been formed by the resist pattern forming method. The manufacturing method of a printed wiring board may include other processes, such as a resist removal process, as needed. Etching or plating of the substrate is performed on the conductor layer of the substrate using the formed resist pattern as a mask.

  In the etching process, using the resist pattern formed on the substrate as a mask, the conductor layer of the circuit forming substrate not covered with the resist is removed by etching to form a conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. Examples of the etching solution include cupric chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching solution and the like. Among these, it is preferable to use a ferric chloride solution because it has a good etch factor.

  On the other hand, in the plating process, copper, solder, or the like is plated on the conductor layer of the circuit forming substrate that is not covered with the resist, using the resist pattern formed on the substrate as a mask. After the plating process, the cured resist is removed, and the conductor layer covered with the resist is etched to form a conductor pattern. The method of plating treatment may be electrolytic plating treatment or electroless plating treatment. The plating treatment includes 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 plating such as nickel sulfamate, hard gold plating, and soft plating. Examples thereof include gold plating such as gold plating.

  After the etching process and the plating process, the resist pattern on the substrate is removed (peeled). The resist pattern can be removed using, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step. As this strongly alkaline aqueous solution, 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. Among them, it is preferable to use a 1 to 10% by mass sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution, and it is more preferable to use a 1 to 5% by mass sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution. Examples of the resist pattern peeling method include an immersion method and a spray method, which may be used alone or in combination.

  When the resist pattern is removed after the plating treatment, a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by the etching treatment to form a conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. For example, the above-described etching solution can be applied.

  The printed wiring board manufacturing method of the present invention can be applied not only to a single-layer printed wiring board but also to a multilayer printed wiring board, and also to a printed wiring board having a small-diameter through hole. .

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(Preparation of solution of photosensitive resin composition)
The photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 9 were prepared by mixing the components (A) to (E) shown in Table 2 and Table 3 in the blending amounts (g units) shown in the same table. A solution of was prepared. The blending amount of the component (A) shown in Tables 2 and 3 is the mass (solid content) of the nonvolatile content. Details of each component shown in Tables 2 and 3 are as follows.

(A) Binder polymer [synthesis of binder polymer (A-1)]
A polymerizable monomer (monomer) of 78 g of methacrylic acid, 15 g of methyl methacrylate, 132 g of styrene and 75 g of benzyl methacrylate (mass ratio 26/5/44/25) and 2.5 g of azobisisobutyronitrile. The solution obtained by mixing was designated as “Solution a”.

  A solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 150 g of a mixed solution (mass ratio 3: 2) of 100 g of methyl cellosolve and 50 g of toluene was designated as “Solution b”.

  A flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube was charged with 300 g of a mixture of 180 g of methyl cellosolve and 120 g of toluene (mass ratio 3: 2), and nitrogen gas was introduced into the flask. The mixture was heated with stirring while being blown, and the temperature was raised to 80 ° C.

  The solution a was added dropwise to the mixed solution in the flask over 4 hours, and then kept at 80 ° C. for 2 hours with stirring. Next, the solution b was added dropwise to the solution in the flask over 10 minutes, and then the solution in the flask was kept at 80 ° C. for 3 hours while stirring. Further, the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a binder polymer (A-1) solution.

  The binder polymer (A-1) had a non-volatile content (solid content) of 42.8% by mass, a weight average molecular weight of 45,000, an acid value of 170 mgKOH / g, and a dispersity of 1.9.

The weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
GPC conditions Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: 3 in total, column specifications: 10.7 mmφ x 300 mm
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M (Hitachi Chemical Industries, Ltd., trade name)
Eluent: Tetrahydrofuran (THF)
Sample concentration: 120 mg of a resin solution having a solid content of 40% was collected and dissolved in 5 mL of THF to prepare a sample.
Measurement temperature: 40 ° C
Injection volume: 200 μL
Pressure: 49Kgf / cm ² (4.8MPa)
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

[Synthesis of Binder Polymers (A-2) to (A-4)]
As the polymerizable monomer (monomer), the binder polymer (A-2) was obtained in the same manner as the solution of the binder polymer (A-1) except that the materials shown in Table 1 were used in the mass ratio shown in the same table. ) To (A-4) were obtained.

  Table 1 shows the mass ratio (%), acid value, weight average molecular weight, and degree of dispersion of the polymerizable monomers (monomers) for the binder polymers (A-1) to (A-4). “-” Means not blended.

(B) Photopolymerizable compound FA-321M (manufactured by Hitachi Chemical Co., Ltd., trade name): 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propaneFA-324M (Hitachi Chemical Industry Co., Ltd.) Product name): 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane

FA-320M (trade name, manufactured by Hitachi Chemical Co., Ltd.): Ethoxylated bisphenol A diacrylate (average 2.0 mol of ethylene oxide adduct)
B-1: 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (addition product of ethylene oxide average 4 mol and propylene oxide average 4 mol)
B-2: 2,2-bis (4- (methacryloxypentaethoxy) cyclohexyl) propane B-3: ethoxylated proxied pentaerythritol tetraacrylate (average 8 mol of ethylene oxide and average 8 mol of propylene oxide adduct)
B-4: Biphenyloxyethoxyethyl methacrylate FA-023M (manufactured by Hitachi Chemical Co., Ltd., trade name): In the above general formula (5), R ⁵ and R ⁶ are methyl groups, r ₁ + r ₂ = 6 ( (Average value), vinyl compound in which s ₁ = 12 (average value) FA-024M (trade name, manufactured by Hitachi Chemical Co., Ltd.): In the general formula (6), R ⁷ and R ⁸ are methyl groups, r ₃ = 6 (average value), s ₂ + s ₃ = 12 (average value) vinyl compound TMPT21E (manufactured by Hitachi Chemical Co., Ltd., sample name): EO-modified trimethylolpropane trimethacrylate (ethylene oxide average 21 mol adduct) )
FA-BZM (manufactured by Hitachi Chemical Co., Ltd., trade name): benzyl methacrylate (in general formula (1), Y is a methyl group, n = 0, X = benzyl group)
FA-512MT (trade name, manufactured by Hitachi Chemical Co., Ltd.): dicyclopentenyloxyethyl methacrylate (in general formula (1), Y is a methyl group, n = 1, X = dicyclopentenyl group)
FA-310M (trade name, manufactured by Hitachi Chemical Co., Ltd.): Phenoxyethyl methacrylate (in general formula (1), Y is a methyl group, n = 1, X = phenyl group)
FA-513M (trade name, manufactured by Hitachi Chemical Co., Ltd.): dicyclopentanyl methacrylate (in general formula (1), Y is a methyl group, n = 0, X = dicyclopentanyl group)
M-114 (trade name, manufactured by Toagosei Co., Ltd.): 4-normalnonylphenoxyoctaethylene glycol acrylate FA-MECH (trade name, manufactured by Hitachi Chemical Co., Ltd.): γ-chloro-β-hydroxypropyl-β '-Methacryloyloxyethyl-o-phthalate

(C) Photopolymerization initiator B-CIM (product name, manufactured by Hampford): 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole

(D) Sensitizing dye PYR-1 (manufactured by Nippon Chemical Industry Co., Ltd.): 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline DBA (Kawasaki Chemical Industry Co., Ltd.) Manufactured, product name): 9,10-dibutoxyanthracene EAB (manufactured by Hodogaya Chemical Co., Ltd., product name): 4,4′-bis (diethylamino) benzophenone J205 (manufactured by Nippon Distillation Co., Ltd., product name) : Triarylamine compound represented by the following formula (11a)

(E) Amine compound LCV (Yamada Chemical Co., Ltd., product name): leuco crystal violet dye MKG (Osaka Organic Chemical Co., Ltd., product name): Malachite Green

<Production of photosensitive element>
The solution of the photosensitive resin composition obtained above was uniformly applied onto a polyethylene terephthalate film (product name “HTF-01” manufactured by Teijin Limited) having a thickness of 16 μm. A photosensitive resin composition layer having a dried film thickness of 25 μm was formed by sequentially drying with a hot air convection dryer. A protective film (manufactured by Tamapoly Co., Ltd., product name “NF-15”) is laminated on the photosensitive resin composition layer, a polyethylene terephthalate film (support film), a photosensitive resin composition layer, and a protective film. A photosensitive element in which was stacked in order was obtained.

<Production of laminated substrate>
The copper surface of a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., product name “MCL-E-679F”) made of glass epoxy material and copper foil (thickness 16 μm) formed on both sides thereof is subjected to CZ treatment. A roughened copper substrate was obtained by roughening with a liquid (MEC Co., Ltd.). After heating the roughened copper substrate (hereinafter referred to as “substrate”) to 80 ° C., the photosensitive elements according to Examples 1 to 11 and Comparative Examples 1 to 9 were placed on the copper surface of the substrate. Laminated. Lamination is performed under conditions of a temperature of 120 ° C. and a lamination pressure of 4 kgf / cm ² (0.4 MPa) so that the photosensitive resin composition layer of each photosensitive element is in close contact with the copper surface of the substrate while removing the protective film. Went under. Thus, the laminated substrate by which the photosensitive resin composition layer and the polyethylene terephthalate film were laminated | stacked on the copper surface of the board | substrate was obtained.

<Evaluation of sensitivity>
The obtained laminated substrate was allowed to cool and when the temperature reached 23 ° C., on the polyethylene terephthalate film of the laminated substrate, a concentration region of 0.00 to 2.00, a concentration step of 0.05, and a tablet size of 20 mm × 187 mm. A photo tool having a 41-step tablet having a size of 3 mm × 12 mm for each step was brought into close contact. Photo tool and polyethylene with an energy amount (exposure amount) of 100 mJ / cm ² using a direct exposure tool “DE-1UH” (product name) manufactured by Hitachi Via Mechanics, Inc. using a blue-violet laser diode with a wavelength of 405 nm as a light source Exposure was performed with respect to the photosensitive resin composition layer through the terephthalate film. The illuminance was measured using an ultraviolet illuminometer (product name “UIT-150” manufactured by Ushio Electric Co., Ltd.) to which a 405 nm probe was applied.

  After the exposure, the polyethylene terephthalate film was peeled from the laminated substrate, the photosensitive resin composition layer was exposed, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 60 seconds to remove unexposed portions. Thus, the resist pattern which consists of hardened | cured material of the photosensitive resin composition was formed on the copper surface of a board | substrate. The sensitivity of the photosensitive resin composition was evaluated by measuring the number of remaining steps (step number) of the step tablet obtained as a resist pattern (cured film). The sensitivity is indicated by the number of step steps, and the higher the step number, the better the sensitivity. The results are shown in Tables 5 and 6.

<Evaluation of resolution and adhesion>
The remaining 41-step tablet using a drawing pattern having a line width (L) / space width (S) (hereinafter referred to as “L / S”) of 3/3 to 30/30 (unit: μm) Exposure (drawing) was performed on the photosensitive resin composition layer of the laminated substrate with an energy amount of 16 steps. After the exposure, the same development processing as in the sensitivity evaluation was performed.

  After development, the space portion (unexposed portion) is removed cleanly, and the line portion (exposed portion) is formed without meandering or chipping. Resolution and adhesion were evaluated. A smaller value means better resolution and adhesion. The results are shown in Tables 5 and 6.

<Evaluation of resist shape>
In the evaluation of the resolution and adhesion, the obtained resist shape (cross-sectional shape of the resist pattern) was observed using a Hitachi scanning electron microscope S-500A. When the resist shape is trapezoidal or inverted trapezoidal, or when there is a resist skirt or crack, there is a tendency that a short circuit or disconnection tends to occur in a circuit formed by the subsequent etching process or plating process. Therefore, it is preferable that the resist shape is rectangular (rectangular) and there is no resist skirting or cracking. The term “crack” means that a line portion (exposed portion) of the resist pattern is cracked or cracked, or accompanying this, the line portion is chipped or broken. Evaluation was made as “A” when the resist shape was rectangular and there was no resist skirt or crack, and “B” when resist skirt or crack was observed. The results are shown in Tables 5 and 6.

<Evaluation of peeling properties>
The photosensitive element obtained above was laminated on the roughened copper substrate (substrate), and the resist pattern (cured film) was formed on the substrate by performing exposure and development under the conditions shown in Table 4. A test piece (40 mm × 50 mm) was prepared. After leaving this test piece for a day and night at room temperature, peeling was performed under the conditions shown in Table 4. The time from the start of stirring until the cured film was completely peeled and removed from the substrate was defined as the peeling time (seconds). Moreover, the size of the peeling piece after peeling was observed visually, and the following references | standards evaluated. The shorter the peeling time and the smaller the peeling piece size, the better the peeling characteristics. The results are shown in Tables 5 and 6.
Peeling piece size L: Sheet shape M: 30 mm or more and 40 mm or less corner S: 20 mm or more and less than 30 mm corner SS: Less than 20 mm corner

<Evaluation of flexibility>
The flexibility of the resist pattern was evaluated by evaluating the flexibility as follows. An FPC board (trade name: F-30VC1, board thickness: 25 μm, copper thickness: 18 μm, manufactured by Nikkan Kogyo Co., Ltd.) was heated to 80 ° C., and Examples 1 to 11 and Comparative Examples 1 to 9 were formed on the copper surface. The photosensitive resin composition layer and the support film of the photosensitive element according to the present invention are 1.5 m / min using a 110 ° C. heat roll while peeling off the protective film so that the photosensitive resin composition layer faces the FPC substrate side. Laminated at the speed of The FPC substrate on which the photosensitive resin composition layer and the support were laminated was used as a test piece for evaluating flexibility. For the test piece, a direct exposure machine DE-1UH manufactured by Hitachi Via Mechanics, Inc. using a 405 nm blue-violet laser diode as a light source, the energy of 16 steps in the number of remaining steps after development of a 41-step tablet is obtained. The photosensitive resin composition layer was photocured by exposure in an amount. Thereafter, the support film was peeled and developed to obtain a flexibility evaluation substrate in which a resist pattern was laminated on an FPC substrate.

  The bendability was evaluated by a mandrel test, and the substrate for bendability evaluation was cut into a strip shape having a width of 2 cm and a length of 10 cm, and was rubbed back and forth 5 times at 180 ° with a cylindrical rod. Thereafter, the minimum cylindrical diameter (mm) without peeling between the FPC substrate and the resist pattern was determined. The smaller the diameter of the cylinder, the better the flexibility.

<Evaluation of chemical resistance>
The chemical resistance of the resist pattern was evaluated by evaluating the plating resistance as follows. Using the laminated substrate obtained above, exposure was performed with a predetermined exposure amount under the process conditions shown in Table 4, and then a degreasing solution (product name “PC-455”, 25 mass%, manufactured by Meltex Co., Ltd.) Pretreatment was performed in the order of immersion for 5 minutes, washing with water, immersion in a soft etch solution (ammonium persulfate 150 g / L) for 2 minutes, washing with water, and immersion in 10% by mass sulfuric acid for 1 minute. Next, it was placed in a copper sulfate plating bath (copper sulfate 75 g / L, sulfuric acid 190 g / L, chloride ion 50 ppm, manufactured by Meltex, product name “Capper Gream PCM” 5 mL / L), and room temperature, 2 A / dm ² for 40 minutes. Copper sulfate plating was performed, followed by washing with water.

  After washing with water and drying, cellotape (registered trademark) was immediately applied to the resist pattern in order to examine the plating resistance, and this was peeled off in the vertical direction (90 ° peel-off test), and the presence or absence of peeling of the resist pattern was observed. Further, after the resist was peeled, the presence or absence of copper plating was observed with an optical microscope from above. In the case where the copper plating is stripped, the copper plating deposited by plating is observed.

  As is clear from Tables 5 and 6, the photosensitive resin composition containing the compound represented by the general formula (1) is sensitive, resolution, adhesion, resist shape, peelability, flexibility, chemical resistance. Were all good.

  DESCRIPTION OF SYMBOLS 10 ... Photosensitive element, 2 ... Support film, 4 ... Photosensitive resin composition layer, 6 ... Protective film

Claims (9)

(A) component: binder polymer,
(B) component: a photopolymerizable compound;
Component (C): a photosensitive resin composition containing a photopolymerization initiator, wherein the component (B) is a phenyl group, a benzyl group, a dicyclopentanyl group, a dicyclopentenyl group, or a biphenyl group. A photosensitive resin composition containing a mono (meth) acrylate compound having a structure selected from: (A) component: binder polymer,
(B) component: a photopolymerizable compound;
(C) A photosensitive resin composition containing a component: a photopolymerization initiator, wherein the component (B) contains a compound represented by the following general formula (1) .

[In General Formula (1), Y represents a hydrogen atom or a methyl group. R represents an alkylene group having 1 to 4 carbon atoms. n shows 0-2. X shows a C6-C14 organic group containing a cyclic structure. ]   The photosensitive resin composition according to claim 2, wherein X in the general formula (1) is a phenyl group, a benzyl group, a dicyclopentanyl group, a dicyclopentenyl group, or a biphenyl group.   (D) Component: The photosensitive resin composition of any one of Claims 1-3 which further contains the sensitizing dye which has an absorption maximum in 340 nm-430 nm.   (E) component: The photosensitive resin composition of any one of Claims 1-4 which further contains an amine compound.   A photosensitive element comprising: a support film; and a photosensitive resin composition layer that is a coating film of the photosensitive resin composition according to any one of claims 1 to 5 provided on the support film. . A laminating step of laminating a photosensitive resin composition layer which is a coating film of the photosensitive resin composition according to any one of claims 1 to 5 on a substrate,
An exposure step of irradiating at least a part of the photosensitive resin composition layer with actinic rays to expose the region to form a cured product region;
A development step of removing a region other than the cured product region of the photosensitive resin composition layer from the substrate and forming a resist pattern including the cured product region on the substrate;
A method for forming a resist pattern having   The method for forming a resist pattern according to claim 7, wherein the wavelength of the actinic ray is in a range of 340 nm to 430 nm.   A method for producing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 7 or 8.