TWI567494B - Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for producing printed wiring board - Google Patents

Description

Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board

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

In the field of manufacturing printed wiring boards, a photosensitive resin composition is widely used as a resist material used in an etching process or a plating process. In many cases, the photosensitive resin composition is used as a support film, and a layer formed by using a photosensitive resin composition on the support film (hereinafter referred to as a "photosensitive resin composition layer") Sexual component (layered body).

The printed wiring board is manufactured, for example, in the following manner. First, a photosensitive resin composition of a photosensitive element is laminated (laminated) on a substrate (layering step). Next, after the support film is removed by peeling off, a predetermined portion of the photosensitive resin composition layer is irradiated with active light rays to cure the exposed portion (exposure step). Thereafter, a resist pattern containing a cured product of the photosensitive resin composition is formed on the substrate by removing (developing) the unexposed portion from the substrate (developing step). After the etching process or the plating process is performed on the obtained resist pattern to form a circuit on the substrate (circuit formation step), the resist is peeled off and finally a printed wiring board is produced (peeling step).

As an exposure method in the exposure step, a method of exposing via a photomask using a mercury lamp as a light source has been used. Moreover, in recent years, a resist called Digital Light Processing (DLP) or Laser Direct Imaging (LDI) has been proposed. The digital data of the pattern is directly plotted on the photosensitive resin composition layer by direct drawing exposure. This direct drawing exposure method has a good alignment accuracy and a high-definition pattern as compared with the exposure method via a photomask, and thus is being introduced step by step in order to produce a high-density package substrate.

In the exposure step, in order to increase production efficiency, it is necessary to shorten the exposure time. However, in the above direct drawing exposure method, monochromatic light such as laser is used in the light source, and in addition, scanning is performed on the substrate, and light is irradiated on one side, so that it is required compared with the previous exposure method via the photomask. The tendency to longer exposure times. Therefore, in order to shorten the exposure time and increase the production efficiency, it is necessary to increase the sensitivity of the photosensitive resin composition as compared with the prior art.

In the peeling step, in order to improve the production efficiency, it is necessary to shorten the peeling time of the resist pattern. Further, in order to prevent the peeling sheet of the resist from adhering again to the circuit board and to improve the production yield, it is necessary to reduce the size of the peeling sheet. In this manner, a photosensitive resin composition having excellent peeling properties (peeling time and release sheet size) of the resist pattern after curing is required.

In addition, in recent years, with the increase in the density of the printed wiring board, the requirements for the resolution (analytical property) of the formed resist pattern and the photosensitive resin composition excellent in adhesion are gradually increased. In particular, in the production of a package substrate, a photosensitive resin composition capable of forming a resist pattern of L/S (line width/space width) 10/10 (unit: μm) or less is required.

Further, in the high-density package substrate, the width between the circuits is narrow, and therefore it is also important that the shape of the resist pattern (hereinafter, simply referred to as "resist The agent shape is excellent. When the cross-sectional shape of the resist pattern is trapezoidal or inverted trapezoidal, or when the resist pattern has a hemming bottom, it is formed by etching treatment or plating treatment thereafter. The possibility of a short circuit or wire break in the circuit. Therefore, the resist is required to have a rectangular shape and no skirt-like bottom.

Further, it is preferable that the formed resist pattern is excellent in tenting property and flexibility. In the case where these characteristics are lacking, the resist pattern is liable to cause defects, which is a cause of short-circuiting of the copper wiring pattern in the subsequent step.

Further, it is desirable that the formed resist pattern is excellent in chemical resistance. In the case where this characteristic is lacking, plating plating is likely to occur in the plating step, which causes a short circuit of the copper wiring pattern.

In response to such a request, various photosensitive resin compositions have been studied (for example, refer to Patent Document 1 to Patent Document 8).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-279381

[Patent Document 2] International Publication No. 2007/004619

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-003177

[Patent Document 4] Japanese Patent Laid-Open No. Hei 11-327137

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2004-004294

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2004-317874

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2008-276194

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2010-085605

However, in the case of the conventional photosensitive resin composition, it is difficult to say that it is sufficient in terms of resolution, adhesion, or resist shape. In particular, it is difficult to form a resist pattern having an L/S (line width/gap width) of 10/10 (unit: μm) or less. Therefore, a photosensitive resin composition capable of improving resolution and adhesion in units of 1 μm is strongly required.

In the case where a resist pattern is formed on a thin plate substrate of 0.5 mm or less, if the resist pattern is peeled off from the substrate due to bending of the substrate or the like, the copper wiring pattern is short-circuited in the subsequent step. Therefore, good bending property is required for the formed resist pattern.

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

In order to solve the above problems, the inventors of the present invention have conducted intensive studies, and as a result, it has been found that a particularly good resolution, adhesion, and flexibility can be obtained by using a binder polymer containing a specific copolymerization composition. The photosensitive resin composition of the resist pattern excellent in resist shape is completed, and the present invention has been completed. That is, the present invention is as follows.

<1> A photosensitive resin composition comprising: (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein the (A) binder polymer is derived from ( a structural unit of methyl)acrylic acid, and a modified (meth)acrylic acid bicyclic ring selected from (ethylene oxide (Ethylene Oxide, EO)) modified (meth)acrylic acid dicyclopentenyl ester (EO) Amyl ester, (EO) at least one selected from the group consisting of isodecyl (meth)acrylate, (EO) modified adamantyl (meth)acrylate, and (EO) modified cyclohexyl (meth)acrylate a structural unit of (meth) acrylate.

In the above-described embodiment, the photosensitive resin composition is excellent in sensitivity at the time of forming a resist pattern, and is particularly excellent in resolution, adhesion, flexibility, and resist shape. According to the photosensitive resin composition described above, a resist pattern having an L/S (line width/gap width) of 10/10 (unit: μm) or less can be formed.

The photosensitive resin composition as described in <1>, wherein the (A) binder polymer further includes a polymerizable single derived from at least one selected from the group consisting of styrene and a styrene derivative. The structural unit of the body. Thereby, the resolution and adhesion of the formed resist pattern can be further improved.

The photosensitive resin composition as described in <1>, wherein the (B) photopolymerizable compound includes a bisphenol A-based di(meth)acrylate compound. Thereby, the alkali developability at the time of forming a resist pattern, the resolution of the formed resist pattern, and the peeling characteristic can be improved.

The photosensitive resin composition according to any one of <1> to <3> wherein the (C) photopolymerization initiator comprises a 2,4,5-triarylimidazole dimer. Thereby, the sensitivity at the time of forming a resist pattern is excellent, and the resolution and adhesiveness of the formed resist pattern can be improved more.

The photosensitive resin composition according to any one of <1> to <4> which further comprises (D) a sensitizing dye having an absorption maximum at 340 nm to 430 nm. Thereby, the resist pattern formation can be further improved The sensitivity of time.

<6> A photosensitive member comprising: a support film; and a photosensitive resin composition layer formed on the support film, and the photosensitive resin composition according to any one of <1> to <5> The coating of the object. By using such a photosensitive element, a resist pattern excellent in resolution, adhesion, resist shape, and flexibility can be formed with good sensitivity and high efficiency.

<7> A method of forming a resist pattern, comprising: a step of laminating: a photosensitive resin which is a coating film of a photosensitive resin composition according to any one of <1> to <5> a composition layer or a photosensitive resin composition layer of the photosensitive element according to <6>; and an exposure step of irradiating at least a part of the photosensitive resin composition layer with active light rays to harden the region to form photohardening And a developing step of forming a resist pattern including the photocured material of the photosensitive resin composition on the substrate by removing a region other than the photocured portion of the photosensitive resin composition layer from the substrate . According to this formation method, a resist pattern having excellent resolution, adhesion, resist shape, and flexibility can be formed with good sensitivity and high efficiency.

<8> A method of producing a printed wiring board, comprising the step of forming a conductor pattern by performing an etching treatment or a plating treatment on a substrate on which a resist pattern is formed by the forming method according to <7>. According to this manufacturing method, a printed wiring board having a high-density wiring such as a high-density package substrate can be manufactured with high precision and high efficiency.

According to the present invention, it is possible to provide an especially resolution and closeness A photosensitive resin composition of a resist pattern excellent in properties, flexibility, and resist shape, a photosensitive element using the same, a method of forming a resist pattern, and a method of producing a printed wiring board.

Hereinafter, embodiments for carrying out the invention will be described in detail. However, the present invention is not limited to the following embodiments. Further, in the present specification, the term "(meth)acrylic acid means acrylic acid or methacrylic acid; the so-called (meth) acrylate means acrylate or a methacrylate corresponding thereto; so-called (meth) propylene Sulfhydryl, meaning acryl fluorenyl or methacryl fluorenyl. Further, the (poly)oxyethylene chain means oxyethylene or polyoxyethylene; the so-called (poly)oxypropylene chain means oxypropylene or polyoxypropylene. Further, the term "(EO) upgrading" means a compound having a (poly)oxyethylene chain; the term "(Propylene Oxide (PO)) modified" means having a (poly)oxypropylene chain. Compound; "(EO) ‧ (PO) modified" means a compound having both (poly)oxyethylene chain and (poly)oxypropylene chain. Moreover, in the present specification, the word "step" is not only an independent step, but may also be achieved in the present term if it is not possible to clearly distinguish it from other steps. Further, the numerical range indicated by "~" is a range indicating the numerical values described before and after including "~" as the respective minimum and maximum values. Further, when the content of each component in the composition is such that a plurality of substances satisfying the respective components are present in the composition, unless otherwise specified, it means the total amount of the plurality of substances present in the composition.

[Photosensitive Resin Composition]

The photosensitive resin composition of the present embodiment contains (A) a binder A photosensitive resin composition of a polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein the (A) binder polymer has a structural unit derived from (meth)acrylic acid And derived from (EO) modified dicyclopentenyl (meth)acrylate, (EO) modified dicyclopentanyl (meth)acrylate, (EO) modified isodecyl (meth)acrylate (EO) A structural unit of (meth) acrylate in which at least one of a group consisting of adamantyl (meth) acrylate and (EO) modified cyclohexyl (meth) acrylate is modified. Thereby, the sensitivity at the time of forming a resist pattern can be excellent, and the resolution, the adhesion, and the flexibility are in addition to the characteristics of the tent hole reliability, the peeling property, and the plating resistance. And a resist pattern excellent in resist shape. Further, a resist pattern of L/S (line width/gap width) of 10/10 (unit: μm) or less can be formed.

It can be considered, for example, as described below. The resist pattern formed by the photosensitive resin composition is excellent in flexibility (high flexibility), but it is easy to swell to the developer, or it is less likely to swell to the developer, but the flexibility is small, so that it is considered to be difficult to completely Satisfy resolution, adhesion, flexibility, and resist shape. Even if the resist pattern formed is excellent in flexibility, there is a tendency that when the developer is easily swollen, a resist pattern may be generated or collapsed (for example, refer to FIGS. 2 and 3). . Further, even if the formed resist pattern is less likely to swell to the developer, there is a tendency that defects or cracks are generated in the resist pattern when the flexibility is small (for example, see FIG. 4). Therefore, in the case where a resist pattern is formed on a thin plate substrate of 0.5 mm or less, it is considered to be necessary to form a photosensitive resin composition which can form a resist pattern which is not easily swollen to the developer and has excellent flexibility. Things. In the present invention, it is considered that the binder polymer contains a structural unit having an oxyethylene chain and a specific aliphatic ring in addition to a structural unit derived from (meth)acrylic acid, thereby making the binder polymer Since the balance between flexibility and rigidity is excellent, it is possible to obtain a photosensitive resin composition which can form a resist pattern which is less likely to swell and has excellent flexibility. Further, it is considered that the binder polymer is composed of a structural unit having an oxyethylene chain and a specific aliphatic ring in addition to a structural unit derived from (meth)acrylic acid, and the active light to be irradiated is irradiated. By utilizing the improvement in efficiency, it is possible to achieve an excellent resist shape and a good resist shape.

<(A) component: binder polymer>

First, the binder polymer (hereinafter also referred to as "(A) component" or "(A) binder polymer") will be described.

The photosensitive resin composition contains at least one of a binder polymer having a structural unit derived from (meth)acrylic acid; and a secondary ring selected from (EO) modified (meth)acrylic acid Pentene ester, (EO) modified dicyclopentanyl (meth)acrylate, (EO) modified isodecyl (meth)acrylate, (EO) modified adamantyl (meth)acrylate and (EO a (meth) acrylate (hereinafter also referred to as "(EO) modified alicyclic (meth) acrylate") of at least one of a group consisting of cyclohexyl (meth) acrylate Structural units.

The (EO)-modified alicyclic (meth) acrylate is not particularly limited as long as it is a (meth) acrylate containing a (poly)oxyethylene chain and having a specific aliphatic ring group. It is especially preferred that the specific aliphatic ring group is ester-bonded to (meth)acrylic acid via at least a (poly)oxyethylene chain. and Further, in this case, in addition to the (poly)oxyethylene chain, a (poly)oxypropylene chain may be further passed. Specific examples of the aliphatic ring group include a dicyclopentenyl group, a dicyclopentyl group, an isodecyl group, an adamantyl group, and a cyclohexyl group. Among them, from the viewpoint of resolution, at least one selected from the group consisting of a dicyclopentenyl group, a dicyclopentyl group, an isodecyl group and an adamantyl group is preferred, and a dicyclopentenyl group is more preferred. Or a dicyclopentyl group, further preferably a dicyclopentenyl group.

The content of the above oxyethylene group can be appropriately selected depending on the purpose. The content of the oxyethylene group is preferably from 1 to 10, more preferably from 1 to 5, still more preferably from 1 to 3, still more preferably 1. Further, the amount of the oxypropylene group to be contained is preferably from 0 to 10, more preferably from 0 to 5, further preferably from 0 to 3, and particularly preferably 0.

Further, the binder polymer is a copolymer containing a structural unit derived from (meth)acrylic acid, in addition to a structural unit derived from the above (EO) modified alicyclic (meth) acrylate. There are no special restrictions. Specifically, a binder polymer having a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II) can be given.

Here, R ¹ each independently represents a hydrogen atom or a methyl group. X represents any one of a dicyclopentenyl group, a dicyclopentyl group, an isodecyl group, an adamantyl group, and a cyclohexyl group. a means 0~10, and b means 1~10. Further, the arrangement order of the oxyethylene group (OC ₂ H ₄ ) and the oxypropylene group (OC ₃ H ₆ ) may be different from the above, and in the case of the three or more constituents, that is, at a+b In the case of 3 or more, the oxyethylene group and the oxypropylene group may be arranged in a random manner or may be arranged in a block form. Further, a and b indicate the number of constituent units constituting the unit. Therefore, an integer value is represented in a single molecule, and as a collection of a plurality of molecules, a rational number as an average value is represented. Hereinafter, the number of constituent units constituting the unit is defined in the same manner.

In the structural unit represented by the above formula (I), a is preferably 0 to 10, more preferably 0 to 5, still more preferably 0 to 3, and particularly preferably 0, from the viewpoint of excellent resolution. .

Further, b is preferably from 1 to 10, more preferably from 1 to 5, still more preferably from 1 to 3, still more preferably 1. When b is 1 or more, the developability tends to be better. Moreover, when it is 10 or less, it becomes easy to acquire sufficient resolution.

Examples of the polymerizable monomer capable of forming the structural unit represented by the above formula (I) include dicyclopentenyloxyethyl (meth)acrylate and dicyclopentyloxyethyl (meth)acrylate. Isomethoxyethyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, adamantylethyl (meth)acrylate, dicyclopentenyl (meth)acrylate Ethyl ester), dicyclopentyl bis(oxyethyl)(meth)acrylate, isodecyl bis(oxyethyl)(meth)acrylate, cyclohexyldi(oxyethyl)(meth)acrylate ), adamantyl (meth) bis(oxyethyl) acrylate, dicyclopentenyloxypropoxyethyl (meth) acrylate, dicyclopentyloxypropoxyethyl (meth) acrylate And adamantyloxypropoxyethyl (meth)acrylate.

(A) a structural unit represented by the formula (I) in a binder polymer The content ratio is preferably from 3% by mass to 85% by mass, more preferably from 4% by mass to 83% by mass, even more preferably from 5% by mass to 80% by mass, even more preferably 10% by mass based on the total mass of the molecule. 80% by mass, and preferably 20% by mass to 80% by mass. When the content is 3% by mass or more, the adhesion, the flexibility, and the flexibility tend to be more excellent. In addition, when the content is 85% by mass or less, the resolution tends to be more excellent.

Examples of the polymerizable monomer capable of forming the structural unit represented by the above formula (II) include acrylic acid and methacrylic acid. (A) The content of the structural unit represented by the formula (II) in the binder polymer is preferably from 10% by mass to 60% by mass, more preferably from 15% by mass to 50% by mass based on the total mass of the molecule. Further, it is preferably 20% by mass to 35% by mass. When the content is 10% by mass or more, the alkaline solubility is further improved, and the peeling time tends to be shorter. In addition, when the content is 60% by mass or less, the resolution tends to be more excellent.

Further, the (A) binder polymer may further contain a structural unit represented by the formula (I) and other structural units other than the structural unit represented by the formula (II). Examples of the polymerizable monomer capable of forming other structural units include alkyl (meth)acrylate, cycloalkyl (meth)acrylate, benzyl (meth)acrylate, and benzyl (meth)acrylate. , (meth) methacrylate, hydroxyalkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isodecyl (meth) acrylate, adamantyl (meth) acrylate, (A) Dicyclopentyl acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylate 2, 2, 2-trifluoroethyl ester, (meth)acrylic acid, 2,2,3,3-tetrafluoropropyl (meth)acrylate Ester; α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth)acrylic acid, β-styryl (meth)acrylic acid, etc. (meth)acrylic acid derivatives; styrene; vinyl toluene, α- a polymerizable styrene derivative substituted with an α-position or an aromatic ring such as methyl styrene; an acrylamide such as diacetone acrylamide; an ester of vinyl alcohol such as acrylonitrile or vinyl-n-butyl ether; Maleic acid; maleic anhydride; maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoisopropyl ester, etc. maleic acid monoester; An unsaturated carboxylic acid such as olefinic acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid or propiolic acid. These may be used alone or in combination of two or more.

The (A) binder polymer preferably further has a polymerizable monomer derived from at least one selected from the group consisting of styrene and a styrene derivative, from the viewpoint of improving the resolution and the adhesion. Structural unit. That is, the (A) binder polymer is preferably obtained by converting at least one of (meth)acrylic acid, at least one of (EO) modified alicyclic (meth) acrylate, and selected from styrene and styrene. The polymerizable monomer of at least one of the groups of the substances is obtained by radical polymerization, and preferably has a structural unit derived from the polymerizable monomers.

When the (A) binder polymer has a structural unit derived from styrene or a derivative thereof, the content thereof is based on the total mass of the molecule, preferably 10% by mass to 70% by mass, more preferably 15% by mass. %~60% by mass, further preferably 20% by mass to 50% by mass. When the content is 10% by mass or more, sufficient adhesion tends to be easily obtained. In addition, when the content is 70% by mass or less, the release sheet tends to be excessively large, and the peeling time tends to be short.

Further, from the viewpoint of improving alkali developability and peeling characteristics, the (A) binder polymer preferably further has a source derived from alkyl (meth)acrylate and benzyl (meth)acrylate. A structural unit of at least one polymerizable monomer in the group.

The alkyl group in the alkyl (meth)acrylate is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, from the viewpoint of improving alkali developability and peeling properties. The alkyl group is further preferably an alkyl group having 1 to 12 carbon atoms. Specific examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Ethyl methyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

In the case where the (A) binder polymer has a structural unit derived from a polymerizable monomer selected from at least one of a group consisting of alkyl (meth)acrylate and benzyl (meth)acrylate, The content ratio is preferably from 1% by mass to 50% by mass, more preferably from 2% by mass to 40% by mass, even more preferably from 3% by mass to 30% by mass based on the total mass of the molecule. When the content is 1% by mass or more, the release sheet tends to be excessively large, and the peeling time tends to be short. In addition, when the content is 50% by mass or less, it is easy to obtain sufficient resolution and adhesion.

(A) The acid value of the binder polymer is preferably from 90 mgKOH/g to 250 mgKOH/g, more preferably from 100 mgKOH/g to 230 mgKOH/g, further preferably from 110 mgKOH/g to 210 mgKOH/g. More preferably, it is from 120 mgKOH/g to 200 mgKOH/g. If the acid value is 90 mgKOH/g In addition, the developing time tends to be short, and when it is 250 mg KOH/g or less, the developer resistance (adhesiveness) of the cured product of the photosensitive resin composition tends to be sufficiently obtained. Further, in the case of performing solvent development in the development step described below, it is preferred to prepare a small amount of a structural unit derived from a polymerizable monomer having a carboxyl group such as (meth)acrylic acid.

When the weight average molecular weight (Mw) of the (A) binder polymer is measured by Gel Permeation Chromatography (GPC) (by conversion using a calibration curve of standard polystyrene), It is preferably 10,000 to 200,000, more preferably 20,000 to 150,000, still more preferably 25,000 to 120,000. When the weight average molecular weight (Mw) is 10,000 or more, the development liquid property (adhesiveness) of the cured product of the photosensitive resin composition tends to be sufficiently obtained. When the weight average molecular weight (Mw) is 200,000 or less, the development time becomes short. Propensity.

Further, the (A) binder polymer may also have a characteristic group having a sensitivity to light having a wavelength in the range of 340 nm to 430 nm in its molecule. Further, as the component (A), one type of binder polymer may be used alone, or two or more types of binder polymers may be used arbitrarily.

When the total amount of the component (A) and the component (B) is 100 parts by mass, it is preferably 30 parts by mass to 70 parts by mass, and more preferably 35 parts by mass. ~65 parts by mass, particularly preferably 40 parts by mass to 60 parts by mass. When the content is 30 parts by mass or more, the film (photosensitive resin composition layer) tends to be formed. When the content is 70 parts by mass or less, it is easy to sufficiently obtain the sensitivity and the resolution. to.

<(B) component: photopolymerizable compound>

Next, the (B) photopolymerizable compound (hereinafter also referred to as "(B) component)" will be described.

The component (B) is not particularly limited as long as it can be photopolymerized, and a compound having an ethylenically unsaturated bond is preferably used. Examples of the compound having an ethylenically unsaturated bond include a compound having one ethylenically unsaturated bond, a compound having two ethylenically unsaturated bonds, a compound having three or more ethylenically unsaturated bonds, and the like. Among these, the component (B) preferably contains a compound having an ethylenically unsaturated bond and a (poly)oxyethylene chain from the viewpoint of adhesion and developability.

Further, the component (B) is preferably at least one of a compound having two ethylenically unsaturated bonds. In the case where the component (B) contains a compound having two ethylenically unsaturated bonds, the content is preferably 10 mass when the total amount of the component (A) and the component (B) is 100 parts by mass. It is preferably -80 parts by mass, more preferably 30 parts by mass to 70 parts by mass.

Examples of the compound having two ethylenically unsaturated bonds include a bisphenol A-based di(meth)acrylate compound, a hydrogenated bisphenol A-based di(meth)acrylate compound, and a urethane in the molecule. a di(meth)acrylate compound (hereinafter also referred to as "urethane monomer"), a polyalkylene glycol having both (poly)oxyethylene chain and (poly)oxypropylene chain A di(meth)acrylate compound, a trimethylolpropane di(meth)acrylate compound, or the like. Among these, the compound having two ethylenically unsaturated bonds is preferably bisphenol A-based di(methyl)propyl from the viewpoint of plating resistance and adhesion. An enoate compound, a hydrogenated bisphenol A-based di(meth)acrylate compound or a polyalkylene glycol di(meth)acrylate having both (poly)oxyethylene chain and (poly)oxypropylene chain in the molecule An ester compound, more preferably an (EO) modified bisphenol A-based di(meth)acrylate compound, an (EO) modified hydrogenated bisphenol A-based di(meth)acrylate compound, or a (poly)oxyethylene compound A polyalkylene glycol di(meth) acrylate compound of both a chain and a (poly)oxypropylene chain.

In the above, the component (B) preferably contains at least one of a bisphenol A-based di(meth)acrylate compound, and more preferably contains (EO) modified doubles, from the viewpoint of improving sensitivity and resolution. At least one of a phenol A-based di(meth)acrylate compound. By combining at least one of the (EO)-modified bisphenol A-based di(meth)acrylate compound as the component (B) in the above binder polymer, the resolution, the adhesion, and the resist shape can be more excellent. Resist pattern.

The bisphenol A-based di(meth) acrylate compound may, for example, be a compound represented by the following formula (2).

In the above formula (2), 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, and these are different from each other. (XO)m ₁ , (XO)m ₂ , (YO)n ₁ and (YO)n ₂ each independently represent a (poly)oxyethylene chain or a (poly)oxypropylene chain. 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, n ₁ + n ₂ is 0 to 20, and when XO is an oxypropylene group and YO is an oxyethylene group. When m ₁ + m ₂ is 0 to 20, n ₁ + n ₂ is 1 to 40.

Among the compounds represented by the above formula (2), 2,2-bis(4-(methylpropenyloxypentaethoxy)phenyl)propane can be produced by BPE-500 (New Nakamura Chemical Co., Ltd.) , the trade name) or FA-321M (manufactured by Hitachi Chemical Co., Ltd., trade name) is obtained from the mall. Further, 2,2-bis(4-(methacryloxylpentadecane)ethoxypropane) can be BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name), 2,2-double (4-(Methethyloxydiethoxy)phenyl)propane can be obtained from a shopping mall by BPE-200 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). These may be used alone or in combination of two or more.

When the component (B) contains a compound represented by the formula (2), the content of the component (A) and the component (B) is set to 100% in terms of sensitivity and resolution. In the case of a portion, it is preferably from 3 parts by mass to 60 parts by mass, more preferably from 10 parts by mass to 50 parts by mass, even more preferably from 15 parts by mass to 45 parts by mass, particularly preferably from 15 parts by mass to 30 parts by weight. Parts by mass.

Further, from the viewpoint of improving the flexibility of the cured product (cured film) of the photosensitive resin composition, the component (B) preferably contains at least one of a polyalkylene glycol di(meth)acrylate compound. . When the component (B) contains a polyalkylene glycol di(meth)acrylate compound, the content of the component (A) and the component (B) is 100 parts by mass. The amount is preferably from 3 parts by mass to 50 parts by mass, more preferably from 5 parts by mass to 40 parts by mass.

As the polyalkylene glycol di(meth)acrylate compound, a polyalkylene glycol di(meth)acrylate compound having both (poly)oxyethylene chain and (poly)oxypropylene chain is preferred. . In the molecule of the polyalkylene glycol di(meth) acrylate compound, the (poly)oxyethylene chain and the (poly)oxypropylene chain may be present in a continuous block, or may be present in a random manner. Further, the oxypropylene group in the (poly)oxypropylene chain may be any of an oxy-n-propyl group and an oxy-iso-propyl group. Further, in the (poly)oxyisopropenyl propyl chain, the secondary carbon of the exo-propyl group may be bonded to the oxygen atom, or the primary carbon may be bonded to the oxygen atom.

The polyalkylene glycol di(meth) acrylate compound may further have a (poly)oxy-n-butyl group, a (poly)oxyisobutylene chain, a (poly)oxy-n-pentylene chain, (poly) The (poly)oxyalkylene chain having a carbon number of about 4 to 6 such as an oxy-extension group and such a structural isomer.

The polyalkylene glycol di(meth)acrylate compound is preferably at least one of the compounds represented by any one of the following formula (3), formula (4) and formula (5). These may be used alone or in combination of two or more.

In the above formula (3), formula (4) and formula (5), 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 containing an oxyethylene group, and s ₁ , s ₂ , s ₃ and s ₄ represent the number of structural units of the structural unit containing an oxypropylene group, oxyethylene The total number of structural units of the radicals r ₁ +r ₂ , r ₃ and r ₄ (average value) independently represent 1 to 30, and the total number of structural units of the oxypropylene group s ₁ , s ₂ +s ₃ and s ₄ (average value) Respectively represent 1~30.

In the compound represented by the above formula (3), formula (4) or formula (5), the total number of structural units of the oxyethylene group r ₁ + r ₂ , r ₃ and r ₄ is from 1 to 30, but The viewpoint of better resolution, adhesion, and resist shape is more preferably 1 to 10, still more preferably 4 to 9, and particularly preferably 5 to 8.

Further, the total number of structural units s ₁ , s ₂ + s ₃ and s ₄ of the oxypropylene group is 1 to 30, but from the viewpoint of further improving the resolution and suppressing the generation of sludge, it is preferably 5~. 20, more preferably 8 to 16, further preferably 10 to 14.

Examples of the compound represented by the above formula (3) include a vinyl compound having R ⁵ and R ⁶ = methyl group, r ₁ + r ₂ = 6 (average value), and s ₁ = 12 (average value) (Hitachi Chemical Co., Ltd.) Manufactured by Industrial Co., Ltd., trade name: FA-023M). Examples of the compound represented by the above formula (4) include a vinyl compound having R ⁷ and R ⁸ = methyl group, r ₃ = 6 (average value), and s ₂ + s ₃ = 12 (average value) (Hitachi Chemical Co., Ltd.) Manufactured by Industrial Co., Ltd., trade name: FA-024M). The compound represented by the above formula (5) includes a vinyl compound of R ⁹ and R ¹⁰ = a hydrogen atom, r ₄ =1 (average value), and s ₄ = 9 (average value) (Xinzhongcun Chemical Industry Co., Ltd.) Manufactured by the company, sample name: NK ESTER HEMA-9P). These may be used alone or in combination of two or more.

Further, from the viewpoint of the peeling property and the resolution, the component (B) preferably contains at least one of a hydrogenated bisphenol A-based di(meth)acrylate compound. When the component (B) contains a hydrogenated bisphenol A-based di(meth)acrylate compound, the content of the component (A) and the component (B) is preferably 100 parts by mass. It is 3 parts by mass to 50 parts by mass, more preferably 5 parts by mass to 45 parts by mass.

Specific examples of the hydrogenated bisphenol A-based di(meth)acrylate compound include 2,2-bis(4-(methylpropenyloxypentaethoxy)cyclohexyl)propane.

The component (B) is preferably at least one of a compound having one ethylenically unsaturated bond. When the component (B) contains a compound having one ethylenically unsaturated bond, the resolution is improved and the resolution is improved. When the content of the component (A) and the component (B) is 100 parts by mass, the content is preferably 1 part by mass to 30% by mass. The portion is more preferably 3 parts by mass to 25 parts by mass, still more preferably 5 parts by mass to 20 parts by mass, particularly preferably 5 parts by mass to 10 parts by mass.

Examples of the compound having one ethylenically unsaturated bond include a nonylphenoxy poly(ethylene acrylate), a phthalic acid compound, and an alkyl (meth)acrylate.

Among the above, from the viewpoint of improving the resolution, the adhesion, the resist shape and the peeling property in a well-balanced manner, it is preferred to contain a mercaptophenoxy poly(ethoxy acrylate) or a phthalic acid. a compound.

Examples of the above nonylphenoxy poly(ethylene acrylate) include mercaptophenoxytriethoxyethoxyacrylate, mercaptophenoxytetraethylene ethoxyacrylate, and mercaptophenoxy-5. Ethoxy acrylate, nonylphenoxy hexaethoxy acrylate, nonylphenoxy hexamethylene ethoxylate, nonylphenoxy octaethoxy acrylate, mercaptophenoxy Ethylene ethoxy acrylate, nonylphenoxy decyl ethoxy acrylate, nonyl phenoxy eleven ethoxy acrylate, and the like. These may be used singly or in combination of two or more kinds arbitrarily. Further, "nonylphenoxypolyethylene acrylate" is also known as "nonylphenoxy polyethylene glycol acrylate".

Among these, the nonylphenoxy octaethoxy acrylate may be, for example, M-114 (manufactured by Toagosei Co., Ltd., trade name, 4-n-nonylphenoxy octaethoxy acrylate) Obtained from the mall. Furthermore, "4-n-decylphenoxy octaethoxy acrylate" is also known as "4-n-decylbenzene" Oxygen octaethylene glycol acrylate".

Examples of the above-mentioned phthalic acid-based compound include γ-chloro-β-hydroxypropyl-β'-(meth)acryloxyethyl phthalate and β-hydroxyethyl phthalate- ''-(Methyl) propylene methoxyethyl ester, β-hydroxypropyl-β'-(meth) propylene methoxyethyl phthalate, and the like. Among them, γ-chloro-β-hydroxypropyl-β'-(meth)acryloxyethyl phthalate is preferred. Γ-chloro-β-hydroxypropyl-β'-methacryloxymethoxyethyl phthalate can be obtained from the market by FA-MECH (manufactured by Hitachi Chemical Co., Ltd., trade name). These may be used alone or in combination of two or more.

The component (B) is also preferably a photopolymerizable compound containing three or more ethylenically unsaturated bonds. When the component (B) contains a photopolymerizable compound having three or more ethylenically unsaturated bonds, the content thereof is excellent in balance, adhesion, resist shape, and peeling property. When the total amount of the component (A) and the component (B) is 100 parts by mass, it is preferably 3 parts by mass to 30 parts by mass, more preferably 5 parts by mass to 20 parts by mass.

Examples of the compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate and (EO)-modified trimethylolpropane tri(meth)acrylate (oxyethylene). The number of structural units is 1~5), (PO) modified trimethylolpropane tri(meth)acrylate, (EO)‧(PO) modified trimethylolpropane tri(meth)acrylate, Tetramethylolmethanetri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like. These may be used singly or in combination of two or more. In these things, Examples of the compound which can be obtained include A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, tetramethylol methane triacrylate), TMPT21E, TMPT30E (manufactured by Hitachi Chemical Co., Ltd., test The name is (EO) modified trimethylolpropane trimethacrylate).

The photosensitive resin composition may be obtained by combining at least one of (EO) modified bisphenol A-based di(meth)acrylate compound as the component (B), and selected from the group consisting of the above-mentioned binder polymer. a polyalkylene glycol di(meth)acrylate compound of (poly)oxyethylene chain and (poly)oxypropylene chain, and (EO) modified trimethylolpropane tri(meth)acrylate At least one of the constituent groups forms a resist pattern which is more excellent in resolution, adhesion, flexibility, and resist shape.

When the total amount of the component (B) and the component (B) is 100 parts by mass, it is preferably 30 parts by mass to 70 parts by mass, and more preferably 35 parts by mass. The amount is preferably 60 parts by mass to 50 parts by mass. When the content is 30 parts by mass or more, sufficient sensitivity and resolution tend to be easily obtained. In addition, when it is 70 parts by mass or less, the film formability tends to be improved, and a favorable resist shape tends to be easily obtained.

<(C) component: photopolymerization initiator>

Next, the photopolymerization initiator (hereinafter also referred to as "(C) component") will be described.

The photopolymerization initiator as the component (C) is not particularly limited. As a photopolymerization initiator, benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1 can be mentioned. -[4-(methylthio)phenyl]-2-? An aromatic ketone compound such as phenyl-acetone-1; an anthracene compound such as alkyl hydrazine; a benzoin ether compound such as benzoin alkyl ether; a benzoin compound such as benzoin or alkyl benzoin; and a benzyl derivative such as benzyl dimethyl ketal ; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, etc. 2,4,5-triaryl A pyrimidine dimer; an acridine derivative such as 9-phenyl acridine or 1,7-(9,9'-acridinyl)heptane. These may be used alone or in combination of two or more.

The component (C) preferably contains a 2,4,5-triarylimidazole dimer from the viewpoint of improving the sensitivity at the time of forming the resist pattern and the adhesion of the formed resist pattern, and more preferably Containing 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer. In the 2,4,5-triaryl imidazole dimer, the structure may be symmetrical or asymmetric.

When the total amount of the component (A) and the component (B) is 100 parts by mass, the content of the component (C) is preferably from 0.1 part by mass to 10 parts by mass, more preferably from 1 part by mass to 7 parts by mass. Further, it is preferably 2 parts by mass to 6 parts by mass, particularly preferably 3 parts by mass to 5 parts by mass. When the content is 0.1 part by mass or more, it tends to be easy to obtain good sensitivity, resolution, or adhesion. In addition, when it is 10 parts by mass or less, it tends to be easy to obtain a favorable resist shape.

<(D) component: sensitizing pigment>

The photosensitive resin composition preferably further contains at least one of a sensitizing dye (hereinafter also referred to as "(D) component"), and more preferably further contains a maximum absorption at a wavelength of 340 nm to 430 nm. At least one of sensitizing pigments. Hereinafter, the sensitizing dye as the component (D) Be explained.

Examples of the sensitizing dye as the component (D) include a dialkylaminobenzophenone compound, a pyrazoline compound, an anthraquinone compound, a coumarin compound, an onionone compound, a thioxanthone compound, and an evil. An azole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound, a stilbene compound, a triazine compound, a thiophene compound, a naphthyl imine compound, a triarylamine compound, an amine group A pyridine compound or the like. These may be used alone or in combination of two or more.

In particular, when the photosensitive resin composition layer is exposed using active light having a wavelength of 340 nm to 430 nm, the (D) component is preferably at a wavelength of 340 nm to 430 nm from the viewpoint of sensitivity and adhesion. a sensitizing dye having a maximum absorption, more preferably comprising a compound selected from the group consisting of a dialkylaminobenzophenone compound, a pyrazoline compound, an anthraquinone compound, a coumarin compound, a triarylamine compound, a thioxanthone compound, and The sensitizing dye of at least one of the group consisting of the amino acridine compound further preferably contains at least one selected from the group consisting of a pyrazoline compound, an anthracene compound, and a triarylamine compound.

When the total amount of the component (A) and the component (B) is 100 parts by mass, the content of the component (D) is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass. Further, it is preferably from 0.1 part by mass to 3 parts by mass. When the content is 0.01 parts by mass or more, it tends to be easier to obtain a better sensitivity and resolution. In addition, when it is 10 parts by mass or less, it tends to be easy to obtain a sufficiently good resist shape.

The pyrazoline compound is preferably at least one selected from the group consisting of a compound represented by the following formula (6) and a compound represented by the formula (7).

In the above formula (6), R ¹¹ to R ¹³ each independently represent a linear or branched alkyl group having 1 to 12 carbon atoms or a linear or branched chain having 1 to 10 carbon atoms. Alkoxy or halogen atom. Further, 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 or different.

In the above formula (6), at least one of R ¹¹ to R ¹³ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms or a linear chain having 1 to 10 carbon atoms. a branched or branched alkoxy group, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms or a linear or branched alkyl group having 1 to 3 carbon atoms The oxy group is further preferably an isopropyl group, a methoxy group or an ethoxy group.

The pyrazoline compound represented by the above formula (6) is not particularly limited. Specifically, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3-(4) -T-butyl-styryl)-5-(4-t-butyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-A Oxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxybenzene Alkenyl)-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)-pyridyl Oxazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3- (2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxybenzene A pyrazoline compound conforming to a=0 in the above formula (6) such as vinyl)-5-(2,4-dimethoxyphenyl)-pyrazoline.

In the above formula (7), R ¹⁴ to R ¹⁶ each independently represent a linear or branched alkyl group having 1 to 12 carbon atoms or a linear or branched chain having 1 to 10 carbon atoms. Alkoxy group, halogen atom or phenyl group. Further, d, e, and f each independently represent an integer of 0 to 5, and the sum of d, e, and f is 1 to 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 or different.

In the above formula (7), at least one of R ¹⁴ to R ¹⁶ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms or a linear chain having 1 to 10 carbon atoms. Or a branched alkoxy group or a phenyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched chain having 1 to 4 carbon atoms; The alkoxy group or the phenyl group is further preferably a third butyl group, an isopropyl group, a methoxy group, an ethoxy group or a phenyl group.

Further, the pyrazoline compound represented by the above formula (7) is not particularly limited, and examples thereof include 1-phenyl-3,5-bis(4-t-butylphenyl)-pyrazoline. 1-phenyl-3,5-bis(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(4-methoxyphenyl)-5-(4-tert-butyl Phenyl)-pyrazoline, 1-phenyl-3-(4-t-butylphenyl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-( 4-isopropylphenyl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-t-butylphenyl)-5-(4- Isopropylphenyl)-pyrazoline, 1-phenyl-3-(4-methoxyphenyl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3 -(4-isopropylphenyl)-5-(4-methoxyphenyl)-pyrazoline, 1,5-diphenyl-3-(4-tert-butylphenyl)-pyrazole Porphyrin, 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-methoxy-phenyl)-pyrazoline, 1,3-diphenyl-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3,5-bis(4-t-butylphenyl)-pyrazoline, 1 , 5-diphenyl-3-(4-t-butylphenyl)-pyrazoline, etc. a pyrazoline compound conforming to d=0 in the formula (7); 1-phenyl-3-(4-biphenyl)-5-(4-t-butylphenyl)-pyrazoline, 1-benzene a pyrazoline compound such as phenyl-3-(4-biphenyl)-5-(4-t-octylphenyl)-pyrazoline in the above formula (7), wherein e=1, R ¹⁵ =phenyl group, etc. .

The ruthenium compound preferably contains at least one of the compounds represented by the following formula (8).

[Chemical 6]

In the above formula (8), R ¹⁷ and R ¹⁸ each independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl group or a benzyl group. Further, the aromatic ring in the above formula (8) may have a substituent as long as the effects of the present invention are not impaired.

In the above formula (8), examples of R ¹⁷ and R ¹⁸ 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.

Preferably, each of R ¹⁷ and R ^{18 is} independently an alkyl group having 1 to 4 carbon atoms.

Specific examples of the compound represented by the above formula (8) include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 9,10-dibutoxyanthracene.

The triarylamine compound preferably contains at least one of the compounds represented by the following formula (9).

[Chemistry 7]

In the above formula (9), 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, and g, h and i represent An integer of 0 to 5 selected so that the value of g+h+i is 1 or more. Further, when g is 2 or more, a plurality of R ²⁷ may be the same or different, and when h is 2 or more, a plurality of R ²⁸ may be the same or different, and i is In the case of 2 or more, a plurality of R ²⁹ may be the same or different.

<Other ingredients>

The photosensitive resin composition preferably contains bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane or leuco crystal violet. These may be used alone or in combination of two or more. In the case where the photosensitive resin composition contains the above-mentioned compounds, the content thereof is preferably from 0.01 part by mass to 10 parts by mass, based on the total amount of the component (A) and the component (B) being 100 parts by mass. It is more preferably 0.05 parts by mass to 5 parts by mass, particularly preferably 0.1 parts by mass to 2 parts by mass. When the content is 0.01 parts by mass or more, sufficient sensitivity tends to be easily obtained. In addition, when it is 10 parts by mass or less, it is more effective to suppress precipitation of the above-mentioned compound which is excessive after the film formation as impurities.

The photosensitive resin composition of the present embodiment may optionally contain a photopolymerizable compound (such as an oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, and malachite green. Other dyes, tribromomethylphenyl hydrazine, thermal hair color preventive agent, plasticizer such as p-toluenesulfonamide, pigment, filler, antifoaming agent, flame retardant, stabilizer, adhesion imparting agent, homogenization Leveling agent, peeling accelerator, antioxidant, perfume, imaging agent, thermal crosslinking agent, and the like. These may be used singly or in combination of two or more. When the total amount of the component (A) (binder polymer) and the component (B) (photopolymerizable compound) is 100 parts by mass, it is preferably 0.01 parts by mass to 20 parts. The mass is around.

<organic solvent>

The photosensitive resin composition of the present embodiment may contain at least one of organic solvents as needed. The content rate of the organic solvent in the photosensitive resin composition is not particularly limited and may be appropriately selected depending on the purpose. The photosensitive resin composition can be used, for example, as a solution having a solid content of 30% by mass to 60% by mass (hereinafter also referred to as "coating liquid"). Here, the solid component means a residual component from which a volatile component is removed from the photosensitive resin composition.

Examples of the organic solvent include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl stilbene, ethyl celecoxib and propylene glycol monomethyl ether; and hydrocarbons such as toluene. Solvent; aprotic polar solvent such as N,N-dimethylformamide; such mixed solvent and the like.

The above coating liquid can be used to form a photosensitive resin composition layer as follows, for example. The coating liquid can be applied to the surface of a metal plate or the like by The film is dried and dried to form a photosensitive resin composition layer containing the photosensitive resin composition of the present embodiment. Examples of the metal of the metal plate include copper, a copper alloy, an iron-based alloy such as nickel, chromium, iron, and stainless steel, and copper, a copper-based alloy, and an iron-based alloy are preferable.

The thickness of the photosensitive resin composition layer varies depending on the application, and it is preferably about 1 μm to 100 μm after drying. It is also possible to protect the surface of the film-coated photosensitive resin composition layer from the side opposite to the metal plate. Examples of the protective film include polymer films such as polyethylene and polypropylene.

[Photosensitive element]

As shown in FIG. 1, the photosensitive element 1 of the present invention includes a support film 2, and a photosensitive resin composition layer 3 which is formed on the support film 2 as a coating film of the photosensitive resin composition, and optionally further The constituent elements (for example, the protective film 4). By providing the photosensitive resin composition layer formed of the photosensitive resin composition, a resist pattern having particularly excellent resolution, adhesion, flexibility, and resist shape can be formed.

The photosensitive element can be obtained by applying the coating liquid onto a support film and drying it to form a photosensitive resin as a coating film of the photosensitive resin composition on the support film. Composition layer.

The support film is not particularly limited and may be appropriately selected from the polymer films generally used. As the support film, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used.

Further, the thickness of the support film (polymer film) is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, still more preferably from 5 μm to 30 μm. When the thickness is 1 μm or more, it is possible to suppress the film from being broken when the support film is peeled off. In addition, when it is 100 μm or less, it tends to be easy to obtain the resolution sufficiently.

As shown in FIG. 1, the photosensitive element 1 may have a protective film 4 covering the surface of the photosensitive resin composition layer 3 on the opposite side of the support film 2 as needed.

The protective film is preferably a protective film having a lower adhesion to the photosensitive resin composition layer than the support film to the photosensitive resin composition layer, and is preferably a fisheye film. The "low fisheye" refers to a small amount of foreign matter such as foreign matter, undissolved matter, or oxidized deteriorated material in the film.

Specifically, as the protective film, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. Further, the protective film may be the same as the support film.

The thickness of the protective film is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, still more preferably from 5 μm to 30 μm, still more preferably from 15 μm to 30 μm. When the thickness is 1 μm or more, when the photosensitive resin composition layer and the protective film are laminated (laminated) on the substrate, the protective film tends to be less likely to be broken. In addition, when it is 100 μm or less, productivity tends to be improved.

The coating liquid can be applied to the support film by a roll coater, a comma coater, a gravure coater, an air knife coater (air). It is carried out by a known method such as a knife coater, a die coater, or a bar coater.

The drying of the coating layer formed by applying the coating liquid is preferably carried out at 70 ° C to 150 ° C for 5 minutes to 30 minutes. From the viewpoint of preventing the diffusion of the organic solvent in the subsequent step, the amount of the residual organic solvent in the photosensitive resin composition layer after drying is preferably 2% by mass or less.

The thickness of the photosensitive resin composition layer in the photosensitive element varies depending on the application, and is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, still more preferably 5 μm to 40 μm after drying. When the thickness is 1 μm or more, industrial coating tends to be easy, and productivity is further improved. In addition, when it is 100 μm or less, it tends to be easy to sufficiently obtain the adhesion and the resolution.

The obtained photosensitive element can be stored in a sheet shape or wound up in a roll shape by a winding core. In the case of winding up into a roll shape, it is preferable to take up the support film so that it may become outer side.

[Method of Forming Resist Pattern]

The method for forming a resist pattern according to the present invention includes: (i) a laminating step of laminating a photosensitive resin composition layer as a coating film of the photosensitive resin composition or a photosensitive resin composition of the photosensitive member on a substrate (ii) an exposure step of: irradiating at least a part of the photosensitive resin composition layer with active light rays to harden the region to form a photocured portion; (iii) developing step: removing the photosensitive layer from the substrate A resist pattern including the photocured material of the photosensitive resin composition is formed on the substrate in a region other than the photocured portion of the resin composition layer; and other steps are included as necessary. In the method for forming a resist pattern, it is preferable that the stacking step is a photosensitive resin composition layer of the photosensitive element. The step of heating and crimping on the substrate to laminate.

(i) Lamination step

First, a photosensitive resin composition formed using a photosensitive resin composition is laminated on a 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.

The laminate of the photosensitive resin composition layer on the substrate is performed by, for example, removing the protective film of the photosensitive element, and then heating the photosensitive resin composition layer of the photosensitive element while pressing the substrate. Thereby, a laminated body including the substrate, the photosensitive resin composition layer, and the support film, and sequentially laminated thereon can be obtained.

From the standpoint of adhesion and followability, the lamination operation is preferably carried out under reduced pressure. The heating of the photosensitive resin composition layer and/or the substrate at the time of pressure bonding is preferably carried out at a temperature of 70 ° C to 130 ° C, preferably about 0.1 MPa to 1.0 MPa (1 kgf / cm ² to 10 kgf / The pressure is about cm ² ), but the conditions are not particularly limited. In addition, when the photosensitive resin composition layer is heated to 70 to 130 ° C, it is not necessary to preheat the substrate in advance, but in order to further improve the layering property, preheating of the substrate may be performed.

(ii) Exposure step

Then, at least a part of the photosensitive resin composition layer laminated on the substrate is irradiated with active light rays, and the region is exposed and photohardened to form a photocured portion. At this time, when the support film existing on the photosensitive resin composition layer is transmissive to the active light, the active light can be irradiated through the support film. On the other hand, the support film is shaded for active light. In the case of the property, the photosensitive resin composition layer may be irradiated with the active light after the support film is removed.

As the exposure method, a method of irradiating active light into an image by a negative or positive mask pattern called an artwork (mask exposure method) can be cited. Further, a method of irradiating active light into an image by direct drawing exposure such as laser direct imaging (LDI) exposure method or digital light processing (DLP) exposure method may be employed.

The photosensitive resin composition of the present invention can be suitably used in a direct drawing exposure method. That is, one of preferred embodiments of the present invention is the use of a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, and a photosensitive resin composition. And (C) a photopolymerization initiator, the (A) binder polymer having a structural unit derived from (meth)acrylic acid, and derived from (EO) modified dicyclopentenyl (meth)acrylate (EO) modified dicyclopentanyl (meth)acrylate, (EO) modified isodecyl (meth)acrylate, (EO) modified adamantyl (meth)acrylate and (EO) modified A structural unit of a (meth) acrylate of at least one of the group consisting of cyclohexyl (meth)acrylate.

As the light source of the active light, a known light source can be used, and a carbon arc, a mercury vapor arc, a high pressure mercury lamp, a xenon lamp, an argon laser, or the like can be used. A solid laser such as a gas laser or a Yttrium Aluminum Garnet (YAG) laser or a semiconductor laser that emits ultraviolet light, visible light, or the like.

From the viewpoint of obtaining the effect of the present invention more reliably as the wavelength of the active light (exposure wavelength), it is preferably in the range of 340 nm to 430 nm, and more preferably in the range of 350 nm to 420 nm. Inside.

(iii) development step

In addition, a resist pattern containing the photocured material of the photosensitive resin composition is formed on the substrate by removing a region other than the photocured portion of the photosensitive resin composition layer from the substrate. When a support film is present on the photosensitive resin composition layer, the support film is removed, and the portion (unexposed portion) other than the photocured portion (exposed portion) is removed (developed). There are wet development and dry development in the development method, but wet development is widely used.

In the case of using wet development, development is carried out by a known development method using a developer corresponding to the composition of the photosensitive resin composition. Examples of the development method include a dip method, a puddle method, a spray method, a brushing method, a slapping method, a scrubbing, and a shaking immersion method. The high pressure spray method is most suitable from the viewpoint of an increase in resolution. Further, the development method may be carried out by combining two or more methods selected from the above.

The configuration of the developer can be appropriately selected depending on the configuration of the photosensitive resin composition. Specific examples thereof include an alkaline aqueous solution, an aqueous developing solution, and an organic solvent-based developing solution.

After the unexposed portion is removed, the resist pattern may be further cured by heating at about 60 ° C to 250 ° C or exposure at about 0.2 J/cm ² to 10 J/cm ² as needed.

[Manufacturing method of printed wiring board]

A method of manufacturing a printed wiring board according to the present invention includes a step of forming a conductor pattern by performing an etching treatment or a plating treatment on a substrate on which a resist pattern is formed by the method for forming a resist pattern, and includes other components as necessary. step. The etching treatment or the plating treatment of the substrate is performed by using the formed resist pattern as a mask, and the conductor layer of the substrate or the like.

Examples of the etching liquid to be subjected to the etching treatment include a copper chloride solution, a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide etching solution. Among these, in view of the fact that the etch factor is good, it is preferred to use a ferric chloride solution.

Examples of the plating method for performing the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, tin plating lead such as high-throwing tin-plated lead, and Watts bath. Nickel plating (nickel sulfate-nickel chloride), nickel plating such as nickel sulfonate, gold plating such as hard gold plating or soft gold plating.

After the etching treatment or the plating treatment is completed, the resist pattern can be peeled off, for example, by an aqueous solution which is more alkaline than the alkaline aqueous solution used for development. As the strongly alkaline aqueous solution, a 1% by mass to 10% by mass aqueous sodium hydroxide solution, a 1% by mass to 10% by mass aqueous potassium hydroxide solution, or the like can be used. Among them, a 1% by mass to 10% by mass aqueous sodium hydroxide solution or a potassium hydroxide aqueous solution is preferably used, and a 1% by mass to 5% by mass aqueous sodium hydroxide solution or a potassium hydroxide aqueous solution is more preferably used.

Examples of the release method of the resist pattern include a immersion method, a spray method, and the like, and these may be used singly or in combination. Moreover, the printed wiring board forming the resist pattern may be a multilayer printed wiring board, or may have a small diameter Through hole.

The photosensitive resin composition of the present embodiment can be suitably used for producing a printed wiring board. That is, one of preferred embodiments of the present invention is an application of a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, and a photosensitive resin composition. And (C) a photopolymerization initiator, the (A) binder polymer having a structural unit derived from (meth)acrylic acid; and a dicyclopentenyl ester derived from (EO) modified (EO) (EO) modified dicyclopentanyl (meth)acrylate, (EO) modified isodecyl (meth)acrylate, (EO) modified adamantyl (meth)acrylate and (EO) modified A structural unit of a (meth) acrylate of at least one of the group consisting of cyclohexyl (meth)acrylate. Further, a more preferred embodiment is the use of the above-mentioned photosensitive resin composition for producing a high-density package substrate, and is a use of the above-mentioned photosensitive resin composition in a semi-additive process. In addition, an example of the manufacturing process of the wiring board by the semi-additive method is shown in FIG. 5 (a) - FIG. 5 (f).

In FIG. 5(a), a substrate (a substrate for circuit formation) in which the conductor layer 10 is formed on the insulating layer 15 is prepared. The conductor layer 10 is, for example, a metal copper layer. In FIG. 5(b), the photosensitive resin composition layer 32 is laminated on the conductor layer 10 of the substrate by the above-described lamination step. In FIG. 5(c), the photomask 20 is laminated on the photosensitive resin composition layer 32, and the active light ray 50 is irradiated to expose a region other than the region of the laminated photomask 20 to form a photocured portion. In FIG. 5(d), a region other than the photocured portion formed by the above-described exposure step is removed from the substrate by a developing step, whereby a resist pattern 30 as a photocured portion is formed on the substrate. In FIG. 5(e), by using as a light hardening portion The resist pattern 30 is a plating process of a photomask, and a plating layer 42 is formed on the conductor layer 10. In FIG. 5(f), after the resist pattern 30 as the photocured portion is peeled off by the strongly alkaline aqueous solution, a part of the plating layer 42 is removed by the flash etching process. The etchant pattern 30 performs the masked conductor layer 10 to form the circuit pattern 40.

[Example]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples.

(Modulation of photosensitive resin composition)

The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 12 were prepared by mixing the components shown in Tables 2 and 3 with the amounts shown in Tables 2 and 3 (unit: parts by mass). a solution of matter. Further, the blending amount of the component (A) shown in Tables 2 and 3 indicates the mass (solid content) of the nonvolatile component, and "-" indicates that the blending amount is not formulated. Further, the details of each component shown in Table 2 and Table 3 are as follows.

<(A) Binder Polymer>

With respect to the binder polymer (A-1) to the binder polymer (A-10), the mass ratio (%), the acid value, and the weight average molecular weight of the polymerizable monomer (monomer) are shown in Table 1. Furthermore, "-" means unprovisioned.

[Synthesis of binder polymer (A-1)]

78 g of methacrylic acid, 75 g of dicyclopentenyloxyethyl methacrylate, 15 g of methyl methacrylate and 132 g of styrene (mass ratio of 26/) were mixed as a polymerizable monomer (monomer). 25/5/44), a solution obtained with 2.5 g of azobisisobutyronitrile was set as "solution a".

A solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 150 g of a mixture of 100 g of methyl racerus and 50 g of toluene (mass ratio of 3:2) was referred to as "solution b".

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

The solution a was added dropwise to the mixture in the flask over 4 hours, and then the mixture was stirred at 80 ° C for 2 hours while stirring. Then, the solution b was added dropwise to the solution in the flask over 10 minutes, and the solution in the flask was stirred while maintaining the temperature at 80 ° C for 3 hours. Further, the solution in the flask was heated to 90 ° C over 30 minutes, and after holding at 90 ° C for 2 hours, it was cooled to obtain a solution of the binder polymer (A-1).

The binder polymer (A-1) had a nonvolatile content (solid content) of 42.8 mass%, a weight average molecular weight of 43,000, and an acid value of 170 mgKOH/g.

Further, the weight average molecular weight was measured by gel permeation chromatography (GPC) and converted using a calibration curve of standard polystyrene. Hereinafter, the conditions of GPC are shown.

GPC condition

Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.)

Column (column): the following total 3

Gelpack GL-R420

Gelpack GL-R430

Gelpack GL-R440 (above, manufactured by Hitachi Chemical Co., Ltd., trade name)

Dissolution: tetrahydrofuran

Measuring temperature: 40 ° C

Flow rate: 2.05 mL/min

Detector: Hitachi L-3300 RI (manufactured by Hitachi, Ltd.)

[Synthesis of binder polymer (A-2)]

A solution obtained by mixing the same material as the binder polymer (A-1) in the same mass ratio and mixing 0.25 g of azobisisobutyronitrile as a polymerizable monomer (monomer) is used. A solution of the binder polymer (A-2) was obtained in the same manner as the solution for obtaining the binder polymer (A-1).

[Synthesis of binder polymer (A-3) ~ binder polymer (A-10)]

The material shown in Table 1 was used as the polymerizable monomer (monomer) in the mass ratio shown in Table 1, and the binder polymerization was obtained in the same manner as the solution for obtaining the binder polymer (A-1). A solution of the (A-3) to the binder polymer (A-10).

<(B) Photopolymerizable Compound>

‧TMPT21E (manufactured by Hitachi Chemical Co., Ltd., sample name): (EO) modified trimethylolpropane trimethacrylate (ethylene oxide average 21 mol adduct)

‧FA-321M (manufactured by Hitachi Chemical Co., Ltd., trade name): 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane

‧BPE-200 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name): 2,2-bis(4-(methylpropenyloxydiethoxy)phenyl)propane

‧ Crosslinker 1: 2,2-bis(4-(methacryloxydiethoxydipropoxy)phenyl)propane

‧ Crosslinker 2: 2,2-bis(4-(methacryloxypentapentaethoxy)cyclohexyl)propane

‧ Crosslinker 3: (EO) ‧ (PO) modified pentaerythritol tetraacrylate (average 8 mol of ethylene oxide and average 8 mol adduct of propylene oxide)

‧FA-024M (manufactured by Hitachi Chemical Co., Ltd., trade name): in the above formula (4), R ⁷ and R ⁸ = methyl group, r ₃ = 6 (average value), s ₂ + s ₃ =12 (average) vinyl compound

‧FA-023M (manufactured by Hitachi Chemical Co., Ltd., trade name): in the above formula (3), R ⁵ and R ⁶ = methyl group, r ₁ + r ₂ = 6 (average value), s ₁ =12 (average) vinyl compound

‧M-114 (Manufactured by Toagosei Co., Ltd., trade name): 4-n-decylphenoxy octaethylene glycol acrylate

<(C) Photopolymerization initiator>

‧B-CIM (manufactured by Hampford, trade name): 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole

<(D) sensitizing pigment>

‧PYR-1 (manufactured by Nippon Chemical Industry Co., Ltd.): 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline

‧DBA (manufactured by Kawasaki Chemical Co., Ltd., trade name): 9,10-dibutoxy oxime

‧J205 (manufactured by Nippon Distillation Co., Ltd., trade name): a triphenylamine derivative represented by the following formula (10)

[化8]

‧EAB (made by Baotu Valley Chemical Industry Co., Ltd., trade name): 4,4'-bis(diethylamino)benzophenone

<(E) amine compound>

‧LCV (manufactured by Yamada Chemical Industry Co., Ltd., trade name): leuco crystal violet

<dye>

‧MKG (Manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name): Malachite Green

(photosensitive element)

The photosensitive resin composition obtained above was uniformly applied to a polyethylene terephthalate film (manufactured by Teijin Co., Ltd., trade name "HTF-01") having a thickness of 16 μm, and used at 70 ° C. The hot air convection dryer at 110 ° C was sequentially dried to form a photosensitive resin composition layer having a film thickness of 25 μm after drying. A protective film (trade name "NF-15", manufactured by TAMAPOLY Co., Ltd.) is laminated on the photosensitive resin composition layer, and a polyethylene terephthalate film (support film) and a photosensitive resin are sequentially laminated. The photosensitive elements of the composition layer and the protective film were obtained as the photosensitive elements of Examples 1 to 13 and Comparative Examples 1 to 12, respectively.

(Laminated substrate)

The copper foil of the core material (manufactured by Hitachi Chemical Co., Ltd., trade name "E-679-F") is roughened, and the build up material (manufactured by Hitachi Chemical Co., Ltd.) After the lamination, the product name "AS-Z3" was subjected to desmear and electroless copper plating manufactured by Atotech. The copper substrate (hereinafter simply referred to as "substrate") had a surface roughness Ra of 0.2 μm and a thickness of 0.5 mm. After heating the substrate to a temperature of 80 ° C, the photosensitive elements of Examples 1 to 13 and Comparative Examples 1 to 12 were laminated (laminated) on the copper surface of the substrate. The lamination is performed by removing the protective film and adhering the photosensitive resin composition layer of each photosensitive element to the copper surface of the substrate at a temperature of 120 ° C and a lamination pressure of 3.9 × 10 ⁵ Pa (4 kgf / cm ^{2 ).} Under the conditions of ).

Thus, a laminated substrate in which a photosensitive resin composition layer and a polyethylene terephthalate film were laminated on the copper surface of the substrate was obtained.

(Evaluation of sensitivity)

The obtained laminated substrate was left to cool, and at a time point of 23 ° C, the polyethylene terephthalate film of the laminated substrate was adhered to have a concentration region of 0.00 to 2.00, a concentration step of 0.05, and an exposure table (tablet). ) A photo tool of a 41-segment staged exposure meter with a size of 20 mm × 187 mm and a size of 3 mm × 12 mm at each stage. Direct-drawing exposure machine "DE-1UH" (trade name) manufactured by Hitachi Via Mechanics Co., Ltd. using a blue-violet laser diode with a wavelength of 405 nm as a light source at 80 mJ/cm The energy (exposure amount) of ² exposes the photosensitive resin composition layer through a light mask and a polyethylene terephthalate film. In addition, the measurement of the illuminance was performed using an ultraviolet illuminometer (manufactured by USHIO Electric Co., Ltd., trade name "UIT-150") using a 405 nm corresponding probe.

After the exposure, the polyethylene terephthalate film was peeled off from the laminated substrate to expose the photosensitive resin composition layer, and a 1 mass% sodium carbonate aqueous solution was sprayed at 30 ° C for 50 seconds to remove the unexposed portion. In this manner, a cured film containing a cured product of the photosensitive resin composition is formed on the copper surface of the substrate. The sensitivity of the photosensitive resin composition was evaluated by measuring the number of remaining stages (the number of stages) of the stage exposure meter obtained as a cured film. The sensitivity is represented by the number of stages in the above stage, meaning that the higher the number of segments, the better the sensitivity. The results are shown in Tables 5 and 6.

(evaluation of resolution and adhesion)

Use a line width (L) / gap width (S) (hereinafter, referred to as "L/S") as a drawing pattern of 3/3 to 30/30 (unit: μm) to make the residual of the 41-stage staged exposure meter The number of stages is 16 stages of energy to expose (plot) the photosensitive resin composition layer of the laminated substrate. After the exposure, the same development treatment as the above sensitivity evaluation was performed.

After the development, the gap portion (unexposed portion) is removed without residue, and the value of the line width/gap width in the resist pattern formed without causing defects and defects in the line portion (exposed portion) Minimum value, evaluation resolution and adhesion. It means that the smaller the value, the better the resolution and the adhesion. The results are shown in Tables 5 and 6.

(Evaluation of resist shape)

In the evaluation of the above resolution and adhesion, the obtained resist shape (cross-sectional shape of the resist pattern) was observed using a Hitachi scanning electron microscope S-500A. In the case where the resist shape is trapezoidal or inverted trapezoidal, or in the case where a skirt-like bottom or crack of the resist is present, a circuit formed by etching treatment or plating treatment thereafter becomes easy to be produced. The tendency to short or break. Therefore, it is desirable that the resist has a rectangular shape (rectangular shape) and a slab-like bottom or crack without a resist. In addition, the term "crack" means that a line portion (exposed portion) of the resist pattern is cracked or cracked, or a defect or break occurs in a line portion accompanying the film. The shape of the resist was rectangular, and the case of the skirt-like bottom or crack without the resist was evaluated as "A", and the case where the skirt-like bottom portion of the resist was observed was evaluated as "B", and all of the observation was observed. The case of the skirt bottom of the resist was evaluated as "C". The results are shown in Tables 5 and 6.

(Evaluation of peeling characteristics)

Each of the photosensitive elements was laminated on the copper foil laminate (substrate), and exposed and developed under the conditions shown in Table 4 to prepare a test piece (40 mm) on which a cured film (resist pattern) was formed on the substrate. ×50 mm). After the test piece was allowed to stand at room temperature for one day, peeling was performed under the conditions shown in Table 4. The time from the start of stirring until the cured film was completely peeled off from the substrate was defined as the peeling time (second). Moreover, the shape and size of the peeling sheet after peeling were visually observed, and it evaluated by the following criteria. The peeling sheet size was evaluated by the average value of the length of each side when the peeling sheet was approximated to a rectangular shape. It means that the shorter the peeling time, the smaller the peeling sheet size, and the better the peeling property. The results are shown in Tables 5 and 6.

Peel sheet size

L: flake

M: 30 mm square ~ 40 mm square

S: less than 30 mm square

(Evaluation of cover hole reliability)

The photosensitive member was laminated on both sides of the substrate in which a hole having a diameter of 4 mm was connected three times on a 1.6 mm-thick copper foil laminate in the same manner as above to allow the remaining stage after development. The exposure was performed with an exposure amount of 15.0 segments, and development was performed twice for 50 seconds. After development, the number of hole ruptures was measured for a total of 18 pieces of three connected φ 4 mm holes, and evaluated in the form of a shaped cover hole rupture rate (the following formula), which was set as a cover hole reliability. .

Shaped cover hole breakage rate (%) = (number of hole breaks (pieces) / 18 (pieces)) × 100

(evaluation of bending)

Flexible Print Circuit (FPC) The substrate (trade name: F-30VC1, substrate thickness: 25 μm, copper thickness: 18 μm, manufactured by Nikkan Industrial Co., Ltd.) was heated to 80 ° C on the copper surface to make the photosensitive resin composition The layers were peeled off from the FPC substrate side, and the protective film was peeled off, and the heat-rolling at 110 ° C was used to laminate the examples 1 to 13 and the comparative examples 1 to 12 at a speed of 1.5 m/min. A photosensitive resin composition layer and a support film of the photosensitive element. The FPC board in which the photosensitive resin composition layer and the support were laminated was used as a test piece for evaluating flexibility. The above test piece is a direct-exposed exposure machine DE-1UH manufactured by Hitachivia Machinery Co., Ltd. using a blue-violet laser diode having a wavelength of 405 nm as a light source, so as to make the remaining stage of the development of the 41-stage staged exposure meter. The number of energies of 11 stages was exposed, and the photosensitive resin composition layer was photocured. Thereafter, the support film was peeled off and developed, and a substrate for evaluating the flexibility of the resist pattern on the FPC substrate was obtained.

The flexibility was evaluated by a mandrel test, and the substrate for bending evaluation was cut into short strips having a width of 2 cm and a length of 10 cm, and rubbed into a cylindrical rod at a distance of five times at 180°. . Thereafter, the diameter (mm) of the smallest cylinder which does not peel off between the FPC board and the resist pattern is obtained. The smaller the diameter of the cylinder, the more excellent the flexibility.

(Evaluation of plating resistance)

The evaluation of the plating resistance was carried out in the following manner.

Using the laminated substrate obtained in the above, under the process conditions shown in Table 4, exposure was carried out by a predetermined exposure amount, followed by degreasing liquid (manufactured by Meltex Co., Ltd., product name "PC-455". 25% by mass), immersed in water, washed for 5 minutes, immersed in a soft etching solution (ammonium persulfate 150 g/L), washed with water for 2 minutes, and immersed in 10% by mass of sulfuric acid for 1 minute. Pretreatment, adding to the copper sulfate plating bath (copper sulfate 75 g / L, sulfuric acid 190 g / L, chloride ion 50 ppm, manufactured by Meite, the product name "Copper Gleam PCM" 5 mL / L), Copper sulfate was plated at room temperature and 2 A/dm ² for 40 minutes, and then washed with water.

After washing with water and drying, in order to analyze the plating resistance, Sellotape (registered trademark) was directly attached to the resist pattern, and it was peeled off in a vertical direction (90° peel off test) to observe the presence or absence of resistance. Peeling of the etchant pattern. Further, after the resist pattern was peeled off, the presence or absence of copper plating was observed by an optical microscope from above. In the case of embedding of copper plating, metallic copper precipitated by copper plating in a region shielded by a resist pattern was observed.

According to Tables 5 and 6, it is clear that the photosensitive resin compositions of Examples 1 to 13 have sensitivity, resolution, adhesion, bendability, lid hole reliability, plating resistance, resist shape, and peeling characteristics. good. On the other hand, in the photosensitive resin compositions of Comparative Examples 1 to 12, any one of the resolution, the adhesion, the bendability, the flexibility, the lid hole reliability, the plating resistance, and the resist shape were used. Poor compared to the examples. Further, in Comparative Example 11, the photosensitive resin composition layer was not adhered to the substrate at the time of lamination, and thus evaluation could not be performed.

1‧‧‧Photosensitive components

2‧‧‧Support film

3‧‧‧Photosensitive resin composition layer

4‧‧‧Protective film

10‧‧‧Conductor layer

15‧‧‧Insulation

20‧‧‧Photomask

30‧‧‧resist pattern

32‧‧‧Photosensitive resin composition layer

40‧‧‧ circuit pattern

42‧‧‧ plating layer

50‧‧‧Active light

Fig. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive element of the present invention.

2 is an example of a scanning electron microscope (SEM) photograph in which a ruthenium or collapse occurs in a resist pattern.

Figure 3 is a SEM photograph of a flaw or collapse in a resist pattern An example.

4 is an example of an SEM photograph of defects or cracks in a resist pattern.

5(a) to 5(f) are perspective views schematically showing an example of a manufacturing procedure of a wiring board by a semi-additive method.

1‧‧‧Photosensitive components

2‧‧‧Support film

3‧‧‧Photosensitive resin composition layer

4‧‧‧Protective film

Claims (8)

A photosensitive resin composition comprising: (A) a binder polymer; (B) a photopolymerizable compound; and (C) a photopolymerization initiator; the (A) binder polymer comprising (meth) derived from (meth) a structural unit of acrylic acid, and derived from (EO) modified dicyclopentenyl (meth)acrylate, (EO) modified dicyclopentanyl (meth)acrylate, (EO) modified (methyl) Structure of (meth) acrylate of at least one of a group consisting of isodecyl acrylate, (EO) modified adamantyl (meth) acrylate, and (EO) modified cyclohexyl (meth) acrylate unit. The photosensitive resin composition according to claim 1, wherein the (A) binder polymer further comprises a polymerizable single derived from at least one selected from the group consisting of styrene and a styrene derivative. The structural unit of the body. The photosensitive resin composition according to Item 1 or 2, wherein the (B) photopolymerizable compound includes a bisphenol A-based di(meth)acrylate compound. The photosensitive resin composition according to claim 1 or 2, wherein the (C) photopolymerization initiator comprises a 2,4,5-triarylimidazole dimer. The photosensitive resin composition according to claim 1 or 2, further comprising (D) having a suction at 340 nm to 430 nm. The maximum amount of sensitizing pigment is obtained. A photosensitive element comprising: a support film; and a photosensitive resin composition layer formed on the support film, and is composed of a photosensitive resin according to any one of claims 1 to 5. The coating of the object. A method of forming a resist pattern, comprising: a step of laminating: a photosensitive resin which is a coating film of a photosensitive resin composition according to any one of claims 1 to 5, which is laminated on a substrate a composition layer or a photosensitive resin composition layer of the photosensitive element according to claim 6; and an exposure step of irradiating at least a part of the photosensitive resin composition layer with active light rays to harden the region Forming a photocured portion; and developing a step of forming a photocured material including the photosensitive resin composition on the substrate by removing a region other than the photocured portion of the photosensitive resin composition layer from the substrate Resist pattern. A method of manufacturing a printed wiring board, comprising: performing etching treatment or plating treatment on a substrate on which a resist pattern is formed by a method for forming a resist pattern according to claim 7 of the invention; The steps of the pattern.