TW201800852A - Photosensitive resin composition, photosensitive element, manufacturing method for substrate with resist pattern, and manufacturing method for printed wiring board - Google Patents

Abstract

A photosensitive resin composition comprises: a binder polymer having a structural unit derived from a (meth)acrylic acid, a photopolymerizable compound containing bisphenol A type di(meth)acrylate in which a number of structural units of ethyleneoxy groups is less than 6, a photopolymerization initiator, and a styrylpyridine compound represented by formula (I). In formula (I), each of R1, R2, and R3 independently represents an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or the like, and each of a, b and c independently represents an integer of from 0 to 5.

Description

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

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

In the field of the production of printed wiring boards, a photosensitive resin composition is widely used as a resist material used for etching or plating a circuit for forming a circuit. The photosensitive resin composition is often used as a photosensitive element (layered body), and the photosensitive element includes a support and a layer provided on the support and using a photosensitive resin composition (hereinafter also referred to as " Photosensitive layer").

The printed wiring board is manufactured, for example, in the following manner. First, a photosensitive layer is formed on a substrate for circuit formation using a photosensitive element (photosensitive layer forming step). Then, the predetermined portion of the photosensitive layer is irradiated with actinic rays to harden the exposed portion (exposure step). Then, after the support is peeled off, a resist pattern containing a cured product of the photosensitive resin composition is formed on the circuit-forming substrate by removing (developing) the unexposed portion of the photosensitive layer from the substrate (developing) step). The substrate is subjected to an etching treatment or a plating treatment using the formed resist pattern as a resist, thereby forming a conductor pattern (circuit) on the substrate (circuit forming step), and finally removing the resist pattern ( A stripping step)) was used to manufacture a printed wiring board.

As a method of exposure, a method of using a mercury lamp as a light source and exposing it via a photomask has been previously used. In addition, in recent years, there has been proposed a direct drawing exposure method called Digital Light Processing (DLP) or Laser Direct Imaging (LDI), which directly draws on a photosensitive layer. pattern. Compared with the exposure method via a photomask, the direct drawing exposure method has good alignment precision and a high-definition pattern can be obtained, and thus is continuously introduced for producing a high-density package substrate.

Generally, in the exposure step, in order to improve production efficiency, it is desirable to shorten the exposure time. However, in the direct drawing exposure method, in addition to monochromatic light such as laser light for a light source, light is irradiated while scanning a substrate, and thus there is a need for a large exposure time as compared with the conventional exposure method via a photomask. tendency. 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.

On the other hand, with the recent increase in the density of the printed wiring board, the demand for a photosensitive resin composition capable of forming a resist pattern having excellent resolution (resolution) and adhesion is improved.

In response to these requirements, various photosensitive resin compositions have been previously studied. For example, Patent Document 1 proposes a photosensitive resin composition which is characterized in that the desired property is improved by using a styrylpyridine compound as a sensitizing dye. Further, Patent Literatures 2 to 5 propose a photosensitive resin composition obtained by using a specific binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a sensitizing dye. Improve the characteristics of the requirements. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. /098183 [Patent Document 5] International Publication No. 12/067107

[Problems to be Solved by the Invention] It is preferable that the resist pattern formed of the photosensitive resin composition is excellent in resistance to liquid. In the case where the substrate is subjected to a plating treatment using a resist pattern lacking a solvent-resistant liquid as a resist, plating penetration may occur. Here, "plating infiltration" means a phenomenon in which a plating solution is infiltrated between a resist pattern and a substrate. In particular, in recent years, printed wiring boards have become denser. Therefore, when plating penetration occurs, conductor patterns are connected and short-circuited.

However, although the sensitivity of the photosensitive resin composition described in Patent Document 1 to Patent Document 5 is relatively high, there is still room for improvement in the resistance liquid property of the formed resist pattern.

An object of the present invention is to provide a photosensitive resin composition which can form a resist pattern having excellent resistance to liquidity with excellent sensitivity, and a photosensitive element using the photosensitive resin composition and a substrate with a resist pattern. Manufacturing method and manufacturing method of printed wiring board. [Means for solving the problem]

Specific means for solving the above problems include the following embodiments. <1> A photosensitive resin composition comprising: a binder polymer having a structural unit derived from (meth)acrylic acid; and a bisphenol A type II having a number of structural units containing an ethyloxy group of less than 6 A photopolymerizable compound of a acrylate; a photopolymerization initiator; and a styrylpyridine compound represented by the following formula (1).

[Chemical 1]

In the formula (1), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, and an amine. a group, an alkylamino group having 1 to 20 carbon atoms, a carboxyl group, a cyano group, a nitro group, an ethyl group or a (meth) acryl group, and a, b and c each independently represent an integer of 0 to 5]

<2> The photosensitive resin composition according to <1>, wherein the photopolymerization initiator comprises a 2,4,5-triarylimidazole dimer represented by the following formula (2).

[Chemical 2]

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

<3> A photosensitive element comprising: a support; and a photosensitive layer provided on the support and using a photosensitive resin composition as described in <1> or <2>.

<4> A method of producing a substrate with a resist pattern, comprising: forming a photosensitive layer using the photosensitive resin composition according to <1> or <2> on a substrate; a step of irradiating at least a portion of the photosensitive layer with actinic rays and curing the region to form a cured region; and removing at least a portion of the photosensitive layer other than the cured region from the substrate A step of forming a resist pattern on the substrate.

<5> The method for producing a substrate with a resist pattern according to <4>, wherein the actinic ray has a wavelength in a range of 340 nm to 430 nm.

<6> A method of producing a printed wiring board, comprising the step of performing etching treatment on a substrate on which a resist pattern is formed by a method of manufacturing a substrate with a resist pattern as described in <4> or <5> .

<7> A method of producing a printed wiring board, comprising: performing a plating treatment on a substrate on which a resist pattern is formed by a method of manufacturing a substrate with a resist pattern as described in <4> or <5> step. [Effects of the Invention]

According to the present disclosure, it is possible to provide a photosensitive resin composition which can form a resist pattern having excellent resistance to liquidity with excellent sensitivity, and a photosensitive element using the photosensitive resin composition and a substrate with a resist pattern. Manufacturing method and manufacturing method of printed wiring board.

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. In the following embodiments, constituent elements (including element steps and the like) are not essential unless otherwise specified. The numerical values and ranges thereof are also the same and do not limit the invention.

In the present specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryl fluorenyl group" is Refers to propylene fluorenyl or methacryl fluorenyl. The term "(poly)ethylideneoxy" means an exoethyloxy group (hereinafter, also referred to as "EO(ethylene oxy) group") or a stretching of two or more exoethyl groups bonded by an ether bond. At least one of ethyloxy groups. The term "(poly)propyl propyloxy" means a stretching propyloxy group (hereinafter also referred to as "PO (propylene oxy) group) or two or more stretching propyl groups which are linked by an ether bond. At least one of propyloxy groups. The term "ethylene oxide (EO) modification" refers to a compound having a (poly)ethyloxy group. The so-called "propylene oxide (PO) modification" means having a (poly) extension. The propyloxy group-containing compound, "EO·PO-modified" means a compound having both (poly)ethyloxy group and (poly)propyloxy group.

In the present specification, the term "layer" refers to a case where only a part of the area is formed, except when it is formed in the entire area. The term "layered" means that layers are stacked, and two or more layers may be combined, or two or more layers may be desorbed. In addition, in this specification, the term "step" includes not only independent steps, but even if it is not clearly distinguishable from other steps, it is included in the term as long as the desired purpose of the step is achieved. In addition, in the present specification, the numerical range represented by "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical range recited in the specification, the upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. In addition, in the numerical range described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the examples. In addition, in the present specification, when the content of each component in the composition is such that a plurality of substances corresponding to the respective components are present in the composition, unless otherwise specified, it means the total of the plurality of substances present in the composition. the amount.

<Photosensitive Resin Composition> The photosensitive resin composition of the present embodiment contains: (A) component: a binder polymer having a structural unit derived from (meth)acrylic acid, and (B) component: a structure containing an EO group. a photopolymerizable compound of a bisphenol A type di(meth)acrylate (hereinafter also referred to as "specific photopolymerizable compound") having a unit number of less than 6, a component (C): a photopolymerization initiator, and (D) Component: a styrylpyridine compound represented by the formula (1). The photosensitive resin composition may contain other components as needed.

By a binder polymer containing a structural unit derived from (meth)acrylic acid, a photopolymerizable compound containing a specific photopolymerizable compound, a photopolymerization initiator, and a styrylpyridine compound represented by the formula (1) It is possible to form a photosensitive resin composition which can form a resist pattern excellent in drug-resistant liquidity (especially resistance to a plating solution) with excellent sensitivity. The detailed reason for exerting the above effects is not necessarily clear, but the inventors of the present invention estimated the following. It is presumed that a specific photopolymerizable compound which is hydrophobic and has an effect on low swellability of a resist pattern and a styrylpyridine compound which is excellent in photosensitivity can be used to form an anti-swelling property and to improve the reaction rate. Etch pattern. Thereby, the crosslinked network in the resist pattern is further densified, and the liquid resistance is improved.

Further, in the examples of Japanese Patent Laid-Open Publication No. SHO 58-1142, it is disclosed that a specific linear copolymer and a bisphenol A type dimethacrylate having an EO group of 10 are used in combination. Improve resistance to plating solutions. It is shocking to use a combination of bisphenol A type di(meth)acrylate having an EO group of less than 6 and a styrylpyridine compound represented by formula (1). It is an increase in resistance to the plating solution.

(A) component: the binder polymer The photosensitive resin composition contains the binder polymer (hereinafter, also referred to as "specific binder polymer") having a structural unit derived from (meth)acrylic acid as (A). )ingredient. The (A) component may also contain a binder polymer other than the specific binder polymer, as needed.

The balance between the developability and the adhesion of the resist pattern is good and excellent, and based on the total mass of the polymerizable unit constituting the specific binder polymer (100% by mass, the same applies hereinafter). The content of the structural unit derived from (meth)acrylic acid may be 15% by mass to 40% by mass, may be 18% by mass to 38% by mass, and may be 20% by mass to 35% by mass. In view of further improving the developability, the content may be 15% by mass or more, 18% by mass or more, and 20% by mass or more. In addition, from the viewpoint of further improving the adhesion of the resist pattern, the content may be 40% by mass or less, 38% by mass or less, or 35% by mass or less.

The specific binder polymer may also have more structural units derived from styrene or alpha-methylstyrene. In the case where the specific binder polymer further has a structural unit derived from styrene or α-methylstyrene, the specific adhesive is formed from the viewpoint of further improving the adhesion and the releasability of the resist pattern. The content of the structural unit derived from styrene or α-methylstyrene may be 10% by mass to 70% by mass, and may be 15% by mass to 60% by mass based on the total mass of the polymerizable monolith of the polymer. % may also be 20% by mass to 55% by mass. The content ratio may be 10% by mass or more, may be 15% by mass or more, and may be 20% by mass or more from the viewpoint of further improving the adhesion of the resist pattern. In addition, from the viewpoint of further improving the peeling property of the resist pattern, the content ratio may be 70% by mass or less, may be 60% by mass or less, and may be 55% by mass or less.

The specific binder polymer may also have other structural units than the structural unit. Other structural units include, for example, structural units derived from other polymerizable single bodies described below.

The other polymerizable monomer is polymerizable with (meth)acrylic acid, styrene or α-methylstyrene, and is different from (meth)acrylic acid, styrene, and α-methylstyrene. There is no particular limitation on the single body. Examples of the other polymerizable monovalent body include alkyl (meth)acrylate, cycloalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, and benzyl (meth)acrylate. Base) decyl acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentyl (meth) acrylate, ( Methyl) dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, (methyl) ) isobornyl acrylate ethyl acrylate, cyclohexyloxyethyl (meth) acrylate, adamantyl ethyl (meth) acrylate, dicyclopentenyloxy propyl (meth) acrylate (meth) acrylate such as ethyl ethyl ester, dicyclopentyloxypropyloxyethyl (meth)acrylate, adamantyloxypropyl ethyl (meth)acrylate; α-bromoacrylic acid , α-chloroacrylic acid, β-furanyl (methyl) a (meth)acrylic acid derivative such as an acid or a β-styryl (meth)acrylic acid; a polymerizable styrene derivative substituted in an aromatic ring; a acrylamide such as diacetone acrylamide; an acrylonitrile An ether compound of vinyl alcohol such as vinyl-n-butyl ether; maleic acid; maleic anhydride; monomethyl maleate, monoethyl maleate, maleic acid a maleic acid monoester such as isopropyl ester; an unsaturated carboxylic acid derivative such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid or propiolic acid. These polymerizable single-body bodies may be used alone or in combination of two or more.

In the case where the specific binder polymer has other structural units, the total mass of the polymerizable unitary body constituting the specific binder polymer is from the viewpoint of further improving the resolution and the releasability of the resist pattern. The content of other structural units may be 3% by mass to 85% by mass, may be 5% by mass to 75% by mass, may be 10% by mass to 70% by mass, and may be 10% by mass to 50% by mass. %.

The specific binder polymer is, for example, a (meth)acrylic acid which is a polymerizable monovalent (monomer), and optionally styrene or α-methylstyrene and the like by using a usual method. The polymerizable monomer is obtained by radical polymerization.

The component (A) may be a specific binder polymer alone, or two or more specific binder polymers may be used arbitrarily in combination. In addition, other binder polymers other than the specific binder polymer may be used together with the specific binder polymer.

The acid value of the specific binder polymer may be from 90 mgKOH/g to 250 mgKOH/g, or may be 100 mgKOH/g, in terms of good balance between the developability and the adhesion of the resist pattern. ～240 mgKOH/g, also from 120 mgKOH/g to 235 mgKOH/g, and from 130 mgKOH/g to 230 mgKOH/g. The acid value may be 90 mgKOH/g or more, may be 100 mgKOH/g or more, or may be 120 mgKOH/g or more, and may be 130 mgKOH/g or more from the viewpoint of further shortening the development time. Moreover, from the viewpoint of further improving the adhesion of the resist pattern, the acid value may be 250 mgKOH/g or less, 240 mgKOH/g or less, or 235 mgKOH/g or less, or 230 mgKOH/g or less.

When the measurement is carried out by Gel Permeation Chromatography (GPC) (converted from a standard curve using standard polystyrene), the balance between the developability and the adhesion of the resist pattern is good. In an excellent aspect, the specific binder polymer may have a weight average molecular weight (Mw) of 10,000 to 200,000, 15,000 to 100,000, 20,000 to 80,000, and 23,000 to 60,000. From the viewpoint of further shortening the development time, the weight average molecular weight may be 200,000 or less, may be 100,000 or less, may be 80,000 or less, or may be 60,000 or less. The weight average molecular weight may be 10,000 or more, may be 15,000 or more, may be 20,000 or more, may be 23,000 or more, or may be 25,000 or more from the viewpoint of further improving the adhesion of the resist pattern.

The degree of dispersion (weight average molecular weight / number average molecular weight) of the specific binder polymer may be 3.0 or less, or may be 2.8 or less, or may be 2.8 or less, from the viewpoint of further improving the resolution and adhesion of the resist pattern. 2.5 or less.

The specific binder polymer may also have a characteristic group in its molecule as needed, which is photosensitive to light having a wavelength in the range of 340 nm to 430 nm. The characteristic group may be a group formed by removing at least one hydrogen atom from a sensitizing dye such as the component (D) described later.

The photosensitive resin composition is 100 parts by mass based on the total amount of the components (A) and (B) from the viewpoint of further improving the formability of the photosensitive layer, the sensitivity, and the resolution of the resist pattern. The content of the component (A) may be 30 parts by mass to 70 parts by mass, or may be 35 parts by mass to 65 parts by mass, or may be 40 parts by mass to 60 parts by mass. The content may be 30 parts by mass or more, or may be 35 parts by mass or more, and may be 40 parts by mass or more from the viewpoint of further improving the formability of the photosensitive layer. In addition, from the viewpoint of further improving the sensitivity and the resolution of the resist pattern, the content may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less.

(B) Component: Photopolymerizable Compound The photosensitive resin composition contains at least one of bisphenol A type di(meth)acrylate (specific photopolymerizable compound) having an EO group of less than 6 as (B) The component is a photopolymerizable compound. The component (B) may further contain a photopolymerizable compound other than the specific photopolymerizable compound, as needed.

In the specific photopolymerizable compound, the number of structural units of the EO group is less than 6. Here, the number of structural units of the EO group (structural unit) also means the number of EO groups which are added to the molecule. Thus, integer values are shown for a single molecule. Hereinafter, the number of structural units of the structural unit is also the same. Further, in the specific photopolymerizable compound, the number of structural units of the EO group may be less than 4 or less than 3 from the viewpoint of improving the liquid resistance of the resist pattern. Further, the lower limit of the number of structural units of the EO group is 0 or more, and may be 2 or more.

The specific photopolymerizable compound may be a compound represented by the following formula (3).

[Chemical 3]

In the formula (3), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group. XO independently represents the EO group. (XO) _m1 and (XO) _m2 represent a (poly)ethyloxy group, respectively. M1 and m2 may independently take values of 0 or more and less than 6, respectively. M1+m2 is 0 or more and less than 6. M1 and m2 represent the number of structural units of the structural unit.

A commercially available product of the compound represented by the formula (3): 2,2-bis(4-(methylpropenyloxydiethoxy)phenyl)propane (EO group: 4 mol (average value)) (Manufactured by Hitachi Chemical Co., Ltd., "FA-324ME"), 2,2-bis(4-(acryloxypolyethoxy)phenyl)propane (EO group: 3 mol (average)) (new Manufactured by Nakamura Chemical Industry Co., Ltd., "ABE-300"), 2,2-bis(4-(methacryloxyethoxy)phenyl)propane (EO group: 2.6 mol (average value)) Manufactured by Shin-Nakamura Chemical Co., Ltd., "BPE-100"), 2,2-bis(4-(methacryloxyethoxy)phenyl)propane (EO group: 2.3 mol (average value)) (Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "BPE-80N"). These compounds may be used alone or in combination of two or more.

The photosensitive resin is 100 parts by mass based on the total amount of the components (A) and (B) from the viewpoint of suppressing swelling of the molecules in the crosslinked network and suppressing swelling and improving the liquid resistance. The content of the specific photopolymerizable compound in the composition may be 1 part by mass to 60 parts by mass, may be 5 parts by mass to 55 parts by mass, and may be 10 parts by mass to 50 parts by mass.

The photosensitive resin composition may contain a photopolymerizable compound other than the specific photopolymerizable compound as the component (B). The other photopolymerizable compound is not particularly limited as long as it is a photopolymerizable compound. The other photopolymerizable compound may be a compound having an ethylenically unsaturated bond group. Examples of the compound having an ethylenically unsaturated bond group include a compound having one ethylenically unsaturated bond group in the molecule, a compound having two ethylenically unsaturated bond groups in the molecule, and three or more ethylene groups in the molecule. A compound that is unsaturated with a bond group or the like.

When the component (B) contains another photopolymerizable compound, it is resistant to swelling by the molecular motion in the crosslinked network after curing, and the liquid resistance is improved, and the component (B) is used. The content of the specific photopolymerizable compound may be from 1 part by mass to 60 parts by mass, and may be from 6 parts by mass to 50 parts by mass, and may also be from 10 parts by mass to 40 parts by mass, based on 100 parts by mass of the total amount.

The component (B) may contain at least one of a compound having two ethylenically unsaturated bond groups in the molecule (excluding a specific photopolymerizable compound) as another photopolymerizable compound. When the component (B) contains a compound having two ethylenically unsaturated bond groups in the molecule as the other photopolymerizable compound, the total amount of the component (A) and the component (B) is 100 parts by mass. The content of the compound having two ethylenically unsaturated bonding groups in the molecule may be 5 parts by mass to 60 parts by mass, may be 5 parts by mass to 55 parts by mass, and may be 10 parts by mass to 50 parts by mass.

Examples of the compound having two ethylenically unsaturated bonding groups in the molecule include bisphenol A type di(meth)acrylate and hydrogenated bisphenol A type di(meth)acrylate which are different from the specific photopolymerizable compound. a polyalkylene glycol di(meth)acrylate having at least one of an EO group and a PO group in the molecule, a di(meth)acrylate having a urethane bond in the molecule, and a trimethylolpropane di(III) Methyl) acrylate or the like.

The component (B) may further contain a bisphenol A type di(meth)acrylate different from the specific photopolymerizable compound, and hydrogenated bisphenol A, from the viewpoint of improving the resolution and the releasability of the resist pattern. a group consisting of a type of di(meth)acrylate and a polyalkylene glycol di(meth)acrylate having at least one of an EO group and a PO group in the molecule, and having two ethylene groups in the molecule At least one of the compounds having a saturated bond group is used as another photopolymerizable compound.

The bisphenol A type di(meth)acrylate different from the specific photopolymerizable compound is a compound represented by the following formula (4).

[Chemical 4]

In the formula (4), R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an EO group or a PO group. (XO) _x1 , (XO) _x2 , (YO) _y1 and (YO) _y2 represent a (poly)-extended ethyloxy group or a (poly)-extended propyloxy group, respectively. X1, x2, y1, and y2 can each independently take a value from 0 to 40. X1, x2, y1, and y2 represent the number of structural units of the structural unit.

When the compound represented by the formula (4) has a PO group, the number of structural units of the PO group in the molecule may be 2 or more, or may be 3 or more, from the viewpoint of improving the resolution of the resist pattern. Further, from the viewpoint of improving developability, the number of structural units of the PO group in the molecule may be 5 or less.

When the compound represented by the formula (4) has an EO group, the number of structural units of the EO group in the molecule may be 6 or more, or 8 or more, from the viewpoint of improving developability. Further, from the viewpoint of improving the resolution of the resist pattern, the number of structural units of the EO group in the molecule may be 16 or less, or may be 14 or less.

A commercially available product of the compound represented by the formula (4): 2,2-bis(4-(methacryloxyethoxyethoxypropoxy)phenyl)propane (EO group: 12 mol (average value) ), PO group: 4 mol (average value) (manufactured by Hitachi Chemical Co., Ltd., "FA-3200MY"), 2,2-bis(4-(methacryloxypolyethoxy)phenyl) Propane (EO group: 10 mol (average value)) (manufactured by Shin-Nakamura Chemical Co., Ltd., "BPE-500"), 2,2-bis(4-(methacryloxy)pentaethoxy)benzene Propane (EO group: 10 mol (average value)) (manufactured by Hitachi Chemical Co., Ltd., "FA-321M"), 2,2-bis(4-(methacryloxyloxypolyethoxy)benzene Propane (EO group: 30 mol (average value)) (manufactured by Shin-Nakamura Chemical Co., Ltd., "BPE-1300"). These compounds may be used alone or in combination of two or more.

When the component (B) contains a bisphenol A type di(meth)acrylate different from the specific photopolymerizable compound, it inhibits swelling and improves the drug resistance liquid by inhibiting molecular motion in the crosslinked network after curing. From the viewpoint of the above, the content of the bisphenol A type di(meth)acrylate different from the specific photopolymerizable compound may be 1 with respect to 100 parts by mass of the total of the components (A) and (B). The mass fraction to 65 parts by mass may be 5 parts by mass to 60 parts by mass, and may be 10 parts by mass to 55 parts by mass. In addition, from the viewpoint of improving the resolution, adhesion, and chemical resistance of the resist pattern, the EO group and the PO group are 100 parts by mass based on the total amount of the components (A) and (B). The content of the bisphenol A type di(meth)acrylate having a total number of structural units of 10 or less may be 55 parts by mass or less, may be 50 parts by mass or less, may be 45 parts by mass or less, or may be 40 masses. The following. In addition, the total number of structural units of the EO group and the PO group with respect to 100 parts by mass of the total amount of the component (B) from the viewpoint of the resolution of the resist pattern, the adhesiveness, and the resistance to liquidity The content of the bisphenol A type di(meth)acrylate of 10 or less may be 70 parts by mass or less, may be 65 parts by mass or less, may be 55 parts by mass or less, or may be 50 parts by mass or less. It is 45 mass parts or less, and may be 40 mass parts or less.

Examples of the hydrogenated bisphenol A type di(meth)acrylate include 2,2-bis(4-(methacryloxypentapentaethoxy)cyclohexyl)propane. When the component (B) contains hydrogenated bisphenol A type di(meth)acrylate, it is relatively hard to suppress swelling and improve drug resistance by inhibiting molecular motion in the crosslinked network after hardening. The content of the hydrogenated bisphenol A type di(meth)acrylate may be 1 part by mass to 50 parts by mass, or may be 5 parts by mass to 100 parts by mass of the total of the component (A) and the component (B). 40 parts by mass.

The component (B) may further contain a polyalkylene glycol having at least one of an EO group and a PO group in the molecule, from the viewpoint of improving the flexibility, the resolution, and the adhesion of the resist pattern in a well-balanced manner. At least one of the di(meth)acrylates is used as another photopolymerizable compound. When the component (B) contains a polyalkylene glycol di(meth)acrylate, the total amount of the component (A) and the component (B) is from the viewpoint of the resolution and the flexibility of the resist pattern. The content of the polyalkylene glycol di(meth)acrylate may be from 1 part by mass to 30 parts by mass, may also be from 2 parts by mass to 20 parts by mass, and may also be from 2 parts by mass to 15 parts by mass per 100 parts by mass. Share.

The polyalkylene glycol di(meth)acrylate may be an EO·PO modified polyalkylene glycol di(meth)acrylate. In the molecule of the polyalkylene glycol di(meth)acrylate, the (poly)ethyloxy group and the (poly)propyloxy group may be present in a continuous block or may be present in a random manner. Further, the PO group in the (poly)propyloxy group may be any of a propyloxy group and an isopropyloxy group. Further, in the (poly)extended isopropyloxy group, the secondary carbon which may be a propyl group is bonded to the oxygen atom, or the primary carbon may be bonded to the oxygen atom.

The polyalkylene glycol di(meth)acrylate may also have (poly)-n-butyloxy group, (poly)isobutyloxy group, (poly)-n-pentyloxy group, (poly)exyloxy group, The structural isomers of these groups, etc., are (poly)alkyloxy groups having a carbon number of about 4 to 6.

The component (B) may contain at least one of photopolymerizable compounds having three or more ethylenically unsaturated bond groups in the molecule as another photopolymerizable compound.

Examples of the compound having three or more ethylenically unsaturated bonding groups include trimethylolpropane tri(meth)acrylate and EO-modified trimethylolpropane tri(meth)acrylate (EO-based). The number of structural units is 1 to 5), PO modified trimethylolpropane tri(meth)acrylate, EO·PO modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(methyl) Acrylate, pentaerythritol tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. These compounds may be used alone or in combination of two or more.

A commercially available product of a photopolymerizable compound having three or more ethylenically unsaturated bond groups in the molecule is EO-modified trimethylolpropane trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., "TMPT21E" And "TMPT30E"), pentaerythritol triacrylate (manufactured by Sartomer, "SR444" and manufactured by Shin-Nakamura Chemical Co., Ltd., "A-TMM-3"), dipentaerythritol hexaacrylate (Xinzhongcun) Manufactured by Chemical Industry Co., Ltd., "A-DPH", EO-modified pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., "ATM-35E").

When the component (B) contains a photopolymerizable compound having three or more ethylenically unsaturated bond groups in the molecule, the resolution of the resist pattern and the balance are improved, and the resolution of the resist pattern is improved. From the viewpoint of the adhesion and the releasability, the photopolymerizable compound having three or more ethylenically unsaturated bond groups in the molecule is contained in an amount of 100 parts by mass based on the total of the components (A) and (B). The content may be from 3 parts by mass to 30 parts by mass, may be from 5 parts by mass to 25 parts by mass, and may also be from 5 parts by mass to 20 parts by mass.

The component (B) may also contain intramolecular points in terms of the shape of the resist pattern and the viewpoint of improving the resolution, adhesion, and releasability of the resist pattern, or suppressing the generation of scum. A photopolymerizable compound having one ethylenically unsaturated bonding group is used as another photopolymerizable compound.

Examples of the photopolymerizable compound having an ethylenically unsaturated bonding group in the molecule include a nonylphenoxy polyethyloxy (meth) acrylate, a phthalic acid compound, and an alkyl (meth) acrylate. Base ester. In the above, the mercaptophenoxy polyethylene group may be contained from the viewpoint of improving the resist pattern shape and the balance, the adhesion, and the releasability of the resist pattern. (Meth) acrylate or phthalic acid compound.

When the component (B) contains a photopolymerizable compound having one ethylenically unsaturated bond group in the molecule, the molecule has one in the molecule with respect to 100 parts by mass of the total of the components (A) and (B). The content of the photopolymerizable compound of the ethylenically unsaturated bonding group may be 1 part by mass to 20 parts by mass, may be 3 parts by mass to 15 parts by mass, or may be 5 parts by mass to 12 parts by mass.

The content of the component (B) in the photosensitive resin composition may be 30 parts by mass to 70 parts by mass, or may be 35 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). 65 parts by mass. When the content of the component (B) is 30 parts by mass or more, the sensitivity and the resolution of the resist pattern tend to be improved. When the content of the component (B) is 70 parts by mass or less, the photosensitive layer tends to be easily formed and a favorable resist pattern shape tends to be easily obtained.

(C) Component: Photopolymerization Initiator The photosensitive resin composition contains at least one of photopolymerization initiators as the component (C). The component (C) may contain 2, 4 represented by the following formula (2) in terms of maintaining the chemical resistance of the resist pattern, improving the sensitivity, and the resolution and adhesion of the resist pattern. , 5-triaryl imidazole dimer.

[Chemical 5]

In the formula (2), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group which may be substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group. X ¹ and X ² each independently represent a halogen atom, an alkyl group, an alkenyl group or an alkoxy group, and p and q each independently represent an integer of 1 to 5. In the case where p is 2 or more, a plurality of X ¹ may be the same or different, and when q is 2 or more, a plurality of X ² may be the same or different.

X ¹ and X ² may each independently be a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or the like), an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkane having 1 to 6 carbon atoms. Oxygen. It is preferred that at least one of X ¹ and X ² is a chlorine atom. The substitution position of X ¹ and X ² is not particularly limited, and is preferably an ortho or para position. p and q are each independently an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1.

The aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may, for example, be a phenyl group, a naphthyl group or a fluorenyl group, and is preferably a phenyl group. The substituent which the Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. At least one substituent in the group. When Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have the substituent, the number of the substituent is preferably from 1 to 5, more preferably from 1 to 3, still more preferably 1. Further, when Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have the substituent, the substitution position thereof is not particularly limited, and is preferably an ortho or para position. Ar ¹ , Ar ² , Ar ³ and Ar ^{4 are} preferably both unsubstituted.

Examples of the 2,4,5-triaryl imidazole dimer represented by the formula (2) include 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2- Chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(2-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2-A Oxyphenyl)-4,5-diphenylimidazole dimer and 2-(4-methoxyphenyl)-4,5-diphenylimidazole dimer. Further, the substituents of the aryl groups of the two 2,4,5-triarylimidazoles may be the same to provide a symmetrical compound, and may also provide an asymmetric compound. The 2,4,5-triaryl imidazole dimer represented by the formula (2) may be used alone or in combination of two or more.

When the component (C) contains the 2,4,5-triarylimidazole dimer represented by the formula (2), the formula (2) is represented by 100 parts by mass of the total amount of the component (C). The content of the 2,4,5-triaryl imidazole dimer may be 25 parts by mass or more, 50 parts by mass or more, and 75 parts by mass or more.

The photopolymerization initiator as the component (C) may contain, in addition to the 2,4,5-triarylimidazole dimer represented by the formula (2), another photopolymerization initiator which is usually used. Other photopolymerization initiators include benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl- An aromatic ketone such as 1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; an anthracene compound such as an alkyl hydrazine; a benzoin ether compound such as a benzoin alkyl ether; benzoin, an alkyl group A benzoin compound such as benzoin; a benzyl derivative such as benzyl dimethyl ketal; an acridine derivative such as 9-phenyl acridine or 1,7-(9,9'-acridinyl)heptane.

The content of the component (C) in the photosensitive resin composition may be 0.1 parts by mass to 10 parts by mass, or may be 1 part by mass, based on 100 parts by mass of the total of the components (A) and (B). 7 parts by mass may be 2 parts by mass to 6 parts by mass, and may also be 3 parts by mass to 5 parts by mass. When the content of the component (C) is 0.1 part by mass or more, the sensitivity and the resolution of the resist pattern and the adhesion tend to be improved. When the content of the component (C) is 10 parts by mass or less, a favorable resist pattern shape tends to be easily obtained.

(D) component: the styrylpyridine compound represented by the formula (1) The photosensitive resin composition contains at least one of the styrylpyridine compounds represented by the following formula (1) as the component (D). The component (D) may be used alone or in combination of two or more.

[Chemical 6]

In the formula (1), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, or an amine group. And an alkylamino group having 1 to 20 carbon atoms, a carboxyl group, a cyano group, a nitro group, an ethyl fluorenyl group or a (meth) acrylonitrile group, and a, b and c each independently represent an integer of 0 to 5. In the case where a is 2 or more, a plurality of R ^{1 's} may be the same or different. When b is 2 or more, a plurality of R ^{2 's} may be the same or different, and c is 2 In the above case, a plurality of R ³ may be the same or different. Further, the carbon number of the alkyl ester group means the carbon number of the alkyl moiety.

In the formula (1), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number. An alkyl ester group of 1 to 6, an amine group or an alkylamino group having 1 to 20 carbon atoms. Further, a, b and c each independently represent an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

The styrylpyridine compound represented by the formula (1) may, for example, be 3,5-dibenzylidenedicyclopenta[b,e]-4-phenylpyridine or 3,5-bis(4-methyl). Benzobenzylidene dicyclopenta[b,e])-4-(4-methylphenyl)pyridine, 3,5-bis(4-methoxybenzylidene dicyclopenta[b, e]) 4-(4-methoxyphenyl)pyridine, 3,5-bis(4-aminobenzylidenedicyclopenta[b,e])-4-(4-aminobenzene Pyridine, 3,5-bis(4-dimethylaminobenzylidene dicyclopenta[b,e])-4-(4-dimethylaminophenyl)pyridine, 3,5 - bis(4-carboxybenzylidene dicyclopenta[b,e])-4-(4-carboxyphenyl)pyridine, 3,5-bis(4-ethylmercaptobenzylidene dicyclopentane And [b,e])-4-(4-ethylmercaptophenyl)pyridine, 3,5-bis(4-cyanobenzylidenebicyclopenta[b,e])-4-(4 -Cyanophenyl)pyridine, 3,5-bis(4-nitrobenzylidenedicyclopenta[b,e])-4-(4-nitrophenyl)pyridine, 3,5-double (4-Propylmercaptobenzylidene dicyclopenta[b,e])-4-(4-propenylphenyl)pyridine, 3,5-bis(4-(methoxycarbonyl)benzene Methyldicyclopenta[b,e])-4-(4-(methoxycarbonyl)phenyl)pyridine and 3,5-bis(2,4-dimethoxybenzylidene dicyclopentane) And [b,e])-4-(2,4-dimethoxy Yl) pyridine.

The styrylpyridine compound represented by the formula (1) can be synthesized, for example, by a condensation reaction of a benzaldehyde derivative, a cyclic alkyl ketone, and ammonium acetate.

The content of the component (D) in the photosensitive resin composition may be 0.01 parts by mass to 10 parts by mass, or may be 0.05 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). 5 parts by mass may be 0.08 parts by mass to 3 parts by mass. When the content of the component (D) is 0.01 parts by mass or more, the sensitivity and the resolution of the resist pattern are improved, and a resist pattern having excellent drug resistance is easily obtained. When the content of the component (D) is 10 parts by mass or less, a favorable resist pattern shape tends to be easily obtained.

(E) component: amine compound The photosensitive resin composition may contain at least one of the amine compounds as the component (E). Examples of the amine compound include bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, leuco crystal violet, and the like. These amine compounds may be used alone or in combination of two or more.

When the photosensitive resin composition contains the component (E), the content of the component (E) may be 0.01 parts by mass to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B). The mass part may be from 0.05 parts by mass to 5 parts by mass, and may also be from 0.1 part by mass to 2 parts by mass. When the content of the component (E) is 0.01 parts by mass or more, sufficient sensitivity tends to be easily obtained. When the content of the component (E) is 10 parts by mass or less, the component (E) which is excessive after the formation of the photosensitive layer is prevented from being precipitated as a foreign matter.

(Other components) The photosensitive resin composition may optionally contain a photopolymerizable compound (oxetane compound or the like) having at least one cyclic ether group capable of undergoing cationic polymerization in a molecule, and cationic polymerization. Other sensitizing dyes other than the starting agent and the component (D), malachite green, Victoria pure blue, brilliant green, methyl violet, etc., tribromo Photochromic agent such as phenylhydrazine, diphenylamine, benzylamine, triphenylamine, diethylaniline or 2-chloroaniline, thermochromic preventive agent, 4-toluenesulfonamide Plasticizers, pigments, fillers, defoamers, flame retardants, stabilizers, adhesion imparting agents, leveling agents, stripping accelerators, antioxidants, perfumes, imaging agents, thermal crosslinking agents, etc. ingredient. These other components may be used alone or in combination of two or more.

When the photosensitive resin composition contains these other components, the content of the other components may be 0.01 parts by mass per 100 parts by mass of the total of the components (A) and (B). 20 parts by mass or so.

[Solution of Photosensitive Resin Composition] The photosensitive resin composition may further contain at least one of organic solvents. 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 cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; and aromatic hydrocarbons such as toluene. Solvent; aprotic polar solvent such as N,N-dimethylformamide. These organic solvents may be used alone or in combination of two or more. The content of the organic solvent contained in the photosensitive resin composition can be appropriately selected depending on the purpose and the like. For example, the photosensitive resin composition may contain an organic solvent and be used as a solution having a solid content of about 30% by mass to 60% by mass. Hereinafter, the photosensitive resin composition containing an organic solvent is also called "coating liquid."

The coating liquid is applied onto the surface of a support, a metal plate or the like to be described later, and dried to form a photosensitive layer as a coating film of the photosensitive resin composition. The metal plate is not particularly limited and may be appropriately selected depending on the purpose and the like. Examples of the metal plate include metal plates such as copper, a copper alloy, an iron-based alloy such as nickel, chromium, iron, or stainless steel. The metal plate is preferably a metal plate such as copper, a copper-based alloy, or an iron-based alloy.

The thickness of the photosensitive layer to be formed is not particularly limited and may be appropriately selected depending on the use thereof. For example, it may be about 1 μm to 100 μm in terms of the thickness after drying. In the case where a photosensitive layer is formed on a metal plate, the surface of the photosensitive layer may be covered with a protective layer. The protective layer may, for example, be a polymer film such as polyethylene or polypropylene.

The photosensitive resin composition can be applied to a photosensitive layer that forms a photosensitive element to be described later. That is, another embodiment of the present disclosure is an application of a photosensitive resin composition containing: (A) component: having a structural unit derived from (meth)acrylic acid, in a photosensitive resin composition. The binder polymer and the component (B): a photopolymerizable compound of a bisphenol A type di(meth)acrylate having an EO group of less than 6, and a component (C): a photopolymerization initiator, and D) component: a styrylpyridine compound represented by the formula (1). Further, the photosensitive resin composition can be used in a method for producing a substrate with a resist pattern to be described later. That is, another embodiment of the present disclosure is an application of a photosensitive resin composition to a method for producing a substrate with a resist pattern, wherein the photosensitive resin composition contains: (A) component: having a source (a) A binder polymer of a structural unit of acrylic acid, and a component (B): a photopolymerizable compound of bisphenol A type di(meth)acrylate having an EO group of less than 6 and a component (C): light The polymerization initiator and the component (D): a styrylpyridine compound represented by the formula (1).

<Photosensitive Element> The photosensitive element of the present embodiment includes a support and a photosensitive layer provided on the support and using the photosensitive resin composition. Further, the photosensitive layer is a coating film formed using the photosensitive resin composition, and the photosensitive resin composition is an unhardened coating film. The photosensitive element may also include other layers such as a protective layer as needed.

An example of a photosensitive element is shown in FIG. In the photosensitive element 1 shown in FIG. 1, a support 2, a photosensitive layer 3, and a protective layer 4 are laminated in this order. The photosensitive element 1 can be obtained, for example, as follows. A coating liquid as the photosensitive resin composition containing an organic solvent is applied onto the support 2 to form a coating layer, which is dried to form the photosensitive layer 3. Next, the surface of the photosensitive layer 3 opposite to the support 2 is coated by the protective layer 4, whereby the photosensitive element 1 is obtained, which comprises: a support 2, a photosensitive layer 3 formed on the support 2, and a laminate Protective layer 4 on photosensitive layer 3. The photosensitive element 1 does not necessarily include the protective layer 4.

As the support 2, a polyester film such as polyethylene terephthalate or a polymer film having heat resistance and solvent resistance such as polypropylene or polyethylene can be used.

The support 2 may have a thickness of 1 μm to 100 μm, may be 5 μm to 50 μm, or may be 5 μm to 30 μm. When the thickness of the support 2 is 1 μm or more, there is a tendency that the support 2 is prevented from being broken when the support 2 is peeled off. In addition, when the thickness of the support 2 is 100 μm or less, the decrease in the resolution tends to be suppressed.

The protective layer 4 is preferably a layer in which the adhesion of the photosensitive layer 3 to the protective layer 4 is smaller than the adhesion of the photosensitive layer 3 to the support 2. Further, a film of low fisheye is preferred. Here, the term "fisheye" means that when a material is thermally melted and a film is produced by kneading, extrusion, biaxial stretching, casting, or the like, foreign matter, undissolved matter, oxidative degradation or the like of the material enters the film. The middle. In other words, the term "low fisheye" means that the foreign matter or the like in the film is small.

Specifically, as the protective layer 4, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate or polyolefin such as polypropylene or polyethylene can be used. Commercially available products include: Alphan MA-410, E-200 manufactured by Oji Paper Co., Ltd., polypropylene film manufactured by Shin-Etsu Co., Ltd., and PS series such as PS-25 manufactured by Teijin Co., Ltd. Polyethylene terephthalate film or the like. Further, the protective layer 4 may be the same layer as the support 2 .

The protective layer 4 may have a thickness of 1 μm to 100 μm, may be 5 μm to 50 μm, may be 5 μm to 30 μm, or may be 15 μm to 30 μm. When the thickness of the protective layer 4 is 1 μm or more, the protective layer 4 tends to be cracked when the photosensitive layer 3 and the support 2 are laminated on the substrate while the protective layer 4 is peeled off. When the thickness of the protective layer 4 is 100 μm or less, the handling property and the low cost tend to be excellent.

Specifically, the photosensitive element can be produced, for example, in the following manner. The photosensitive member can be produced by a production method comprising the steps of: preparing the component (A): a binder polymer, the component (B): a photopolymerizable compound, and the component (C): photopolymerization a starting agent and a component (D): a coating liquid obtained by dissolving a styrylpyridine compound represented by the formula (1) in the organic solvent; and applying the coating liquid to a support a step of forming a coating layer on the second; and a step of drying the coating layer to form the photosensitive layer 3.

The application of the coating liquid onto the support 2 can be carried out by a known method such as roll coating, notch wheel coating, gravure coating, air knife coating, die coating, or bar coating.

The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. The drying of the coating layer is preferably carried out at 70 ° C to 150 ° C for about 5 minutes to 30 minutes. After drying, the amount of the residual organic solvent in the photosensitive layer 3 can be 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the step described later.

The thickness of the photosensitive layer 3 in the photosensitive element can be appropriately selected depending on the use. The thickness of the photosensitive layer 3 after drying may be 1 μm to 100 μm, may be 1 μm to 50 μm, or may be 5 μm to 40 μm. When the thickness of the photosensitive layer 3 is 1 μm or more, industrial coating tends to be easy. When the thickness of the photosensitive layer 3 is 100 μm or less, the adhesion and the resolution of the resist pattern tend to be sufficiently obtained.

The transmittance of the photosensitive layer 3 to ultraviolet rays may be 5% to 75%, or 10% to 65%, or 15% to 55% for ultraviolet rays having a wavelength in the range of 350 nm to 420 nm. When the transmittance is 5% or more, the adhesion of the resist pattern tends to be sufficiently obtained. When the transmittance is 75% or less, the resolution of the resist pattern tends to be sufficiently obtained. Further, the transmittance can be measured by an ultraviolet spectrometer. As the ultraviolet spectrometer, a 228A W beam spectrophotometer manufactured by Hitachi, Ltd. can be cited.

The photosensitive element may further have an intermediate layer such as a buffer layer, an adhesive layer, a light absorbing layer, and a gas barrier layer. As the intermediate layer, for example, the intermediate layer described in JP-A-2006-098982 can be applied to the present embodiment.

The form of the obtained photosensitive element is not particularly limited. The photosensitive element may be, for example, in the form of a sheet, or may be wound into a roll shape at the core. In the case of winding into a roll shape, it is preferable to wind the support body 2 so that it may become outer side. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). In the end face of the roll-shaped photosensitive element roll obtained in the above manner, in terms of the protection end face, it is preferable to provide an end face separation film, and in terms of edge edge fusion resistance, it is preferable to provide a moisture-proof end face. Separation membrane. As the packing method, it is preferably packaged from a black sheet having a small moisture permeability.

The photosensitive element can be suitably applied to, for example, a method of manufacturing a substrate with a resist pattern described later.

<Method for Producing Substrate with Resist Pattern> A substrate with a resist pattern can be produced using the photosensitive resin composition. The method for producing a substrate with a resist pattern according to the present embodiment includes: (i) a step of forming a photosensitive layer using the photosensitive resin composition on a substrate (photosensitive layer forming step); (ii) a step of exposing actinic rays to at least a portion of the photosensitive layer and photohardening the region to form a cured region (exposure step); and (iii) at least a portion of the photosensitive layer other than the hardened region A step of removing a resist pattern on the substrate to form a resist pattern (developing step). The method of manufacturing the substrate with a resist pattern may also include other steps as needed.

(i) Photosensitive layer forming step First, the photosensitive layer 3 is formed on a substrate by using the photosensitive resin composition. As the substrate, for example, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used. The insulating layer is exemplified by a glass epoxy material. The conductor layer is, for example, a copper foil.

For example, when the photosensitive element has the protective layer 4, the photosensitive layer 3 is formed on the substrate by removing the protective layer 4, and then the photosensitive layer 3 of the photosensitive element is heated while being pressed against the substrate. Come up. Thereby, a laminate in which the substrate, the photosensitive layer 3, and the support 2 are sequentially laminated is obtained.

In terms of adhesion and follow-up, the photosensitive layer forming step is preferably carried out under reduced pressure. The heating of at least one of the photosensitive layer 3 and the substrate at the time of pressure bonding is preferably performed at a temperature of 70 ° C to 130 ° C, and preferably about 0.1 MPa to 1.0 MPa (1 kgf / cm ² to 10 kgf). The pressure of /cm ² or so) is crimped. These conditions are not particularly limited and may be appropriately selected as needed. Further, when the photosensitive layer 3 is heated to 70 ° C to 130 ° C, the substrate may not be preheated in advance. Adhesion and followability can be further improved by preheating the substrate.

(ii) Exposure step In the exposure step, at least a part of the region of the photosensitive layer 3 formed on the substrate as described above is irradiated with actinic rays, whereby the exposed portion irradiated with the actinic rays is photohardened to form a latent image. At this time, when the support 2 existing on the photosensitive layer 3 is transparent to actinic rays, the actinic rays can be irradiated by the support 2 . On the other hand, when the support 2 exhibits light-shielding properties to the actinic rays, the support 2 is removed and the actinic layer 3 is irradiated with actinic rays.

The exposure method may be a method of irradiating actinic rays in an image form by a negative mask pattern or a positive mask pattern called an artwork (mask exposure method). In addition, the following method may be employed: direct exposure method using laser direct imaging (LDI) exposure method, digital light processing (DLP) exposure method, etc., and irradiation of actinic rays in an image form .

The light source of the actinic ray is not particularly limited, and a known light source can be used. Specifically, carbon laser lamps, mercury vapor arc lamps, high pressure mercury lamps, xenon lamps, argon lasers, and the like, solid lasers such as yttrium aluminum garnet (YAG) lasers, semiconductor lasers, A light source that emits ultraviolet light, visible light, or the like, such as a gallium nitride-based blue-violet laser.

The wavelength of the actinic ray (exposure wavelength) may be in the range of 340 nm to 430 nm, or may be in the range of 350 nm to 420 nm. By setting the wavelength of the actinic ray to be in the range of 340 nm to 430 nm, there is a tendency that the resist pattern having excellent drug resistance can be formed more efficiently and with higher sensitivity.

(iii) Developing Step In the developing step, the uncured portion of the photosensitive layer 3 is removed from the substrate by a developing treatment, whereby a resist which is a cured product which is photohardened by the photosensitive layer 3 is formed on the substrate. pattern. In the case where the support 2 is present on the photosensitive layer 3, after the support 2 is removed, the unexposed portion is removed (developed). There are wet development and dry development in development processing, but wet development is widely used.

In the case of wet development, development is carried out by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the development method include a method using an immersion method, a liquid coating method, a spray method, a brushing, a slap, a scrub, a shaking, and the like. From the viewpoint of improving the resolution, the high pressure spray method is preferred. These two or more methods may be combined to perform development.

The developer can be appropriately selected depending on the configuration of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution, an organic solvent developer, and the like.

When the alkaline aqueous solution is used as a developing solution, it is safe and stable, and has good workability. As the base of the alkaline aqueous solution, an alkali hydroxide such as a hydroxide of lithium, sodium or potassium; a carbonate such as lithium, sodium, potassium or ammonium carbonate or a hydrogencarbonate; an alkali metal phosphate such as potassium phosphate or sodium phosphate; Salt; alkali metal pyrophosphate, such as sodium pyrophosphate or potassium pyrophosphate, borax (sodium tetraborate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino 2-hydroxymethyl-1,3-propanediol, 1,3-diamino-2-propanol, morpholine, and the like.

The alkaline aqueous solution used for development is preferably a dilute solution of 0.1% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1% by mass to 5% by mass of potassium carbonate, and 0.1% by mass to 5% by mass of sodium hydroxide. A dilute solution, a dilute solution of 0.1% by mass to 5% by mass of sodium tetraborate, and the like. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11. Further, the temperature thereof can be adjusted in accordance with the alkali developability of the photosensitive layer 3. The alkaline aqueous solution may also contain a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like.

The aqueous alkaline solution may also contain more than one organic solvent. Examples of the organic solvent to be used include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, and diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. These may be used alone or in combination of two or more. When the alkaline aqueous solution contains an organic solvent, the content of the organic solvent is preferably from 2% by mass to 90% by mass based on the total amount of the aqueous alkaline solution.

The organic solvent used in the organic solvent developer may, for example, be 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone or methyl isobutylene. Ketone, γ-butyrolactone and the like. Among these organic solvents, in order to prevent ignition, it is preferred to add water in an amount of from 1% by mass to 20% by mass to prepare an organic solvent developing solution.

The method for manufacturing the substrate with a resist pattern may further include the steps of: after removing the unexposed portion, heating at 60 ° C to 250 ° C as needed or at 0.2 J/cm ² to 10 J/cm ² The amount of energy is exposed to thereby further harden the resist pattern.

<Manufacturing Method of Printed Wiring Board> The method of manufacturing a printed wiring board according to the present embodiment includes the steps of etching and plating a substrate on which a resist pattern is formed by the method for producing a substrate with a resist pattern. At least one treatment of the treatment. In other words, the method of manufacturing a printed wiring board according to the first embodiment includes a step of performing etching processing on a substrate on which a resist pattern is formed by the method for manufacturing a substrate with a resist pattern. Moreover, the method of manufacturing a printed wiring board according to the second embodiment includes a step of performing a plating process on a substrate on which a resist pattern is formed by the method of manufacturing a substrate with a resist pattern. As the substrate, for example, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer is preferably used. The method of manufacturing the printed wiring board may also include other steps such as a resist removal step as needed. The formed resist pattern is used as a mask, and the substrate is etched and plated on the conductor layer of the substrate.

In the etching process, a resist pattern (hardened resist) formed on a substrate is used as a mask, and a conductor layer of the circuit-forming substrate covered with the unhardened resist is etched away to form a conductor pattern. The etching treatment method can be appropriately selected depending on the conductor layer to be removed. Examples of the etching solution include a copper chloride aqueous solution, an aqueous ferric chloride solution, an alkali etching solution, and a hydrogen peroxide etching solution. Among these etching liquids, an aqueous solution of ferric chloride is preferably used in terms of an excellent etch factor.

On the other hand, in the plating process, a resist pattern (hardened resist) formed on a substrate is used as a mask, and copper is plated on the conductor layer of the circuit-forming substrate which is not coated with the resist. , solder, etc. After the plating treatment, the hardened resist is removed, and the conductor layer coated with the hardened resist is etched to form a conductor pattern. The plating treatment may be an electrolytic plating treatment or an electroless plating treatment. Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, and Watt bath (nickel sulfate-chlorination). Nickel plating such as nickel plating or nickel sulfonate, gold plating such as hard gold plating and soft gold plating.

After the etching treatment and the plating treatment, the resist pattern on the substrate is removed (peeled). The removal of the resist pattern can be performed, for example, using an aqueous solution which is more alkaline than the alkaline aqueous solution used in the development step. 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, it is preferred to use a 1% by mass to 10% by mass aqueous sodium hydroxide solution or a 1% by mass to 10% by mass aqueous potassium hydroxide solution, more preferably a 1% by mass to 5% by mass aqueous sodium hydroxide solution or 1% by mass. 5 mass% potassium hydroxide aqueous solution. Examples of the method of providing the resist pattern to the resist pattern are a immersion method, a spray method, and the like. These may be used alone or in combination of two or more.

When the resist pattern is removed after the plating treatment is performed, the conductor layer covered with the hard resist is further removed by an etching process to form a conductor pattern, whereby a desired printed wiring board can be manufactured. The etching treatment method can be appropriately selected depending on the conductor layer to be removed. For example, the etching solution can be applied.

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

The photosensitive resin composition can be suitably used for producing a printed wiring board. That is, one of the preferred embodiments is the use of a photosensitive resin composition containing: (A) component: having a structural unit derived from (meth)acrylic acid, in the production of a printed wiring board The binder polymer and the component (B): a photopolymerizable compound of a bisphenol A type di(meth)acrylate having an EO group having a structural unit number of less than 6, and a component (C): a photopolymerization initiator; Component (D): a styrylpyridine compound represented by the formula (1). Further, a more preferred embodiment is the use of the photosensitive resin composition in the production of a high-density packaging substrate, and is an application of the photosensitive resin composition in a semi-additive process. Hereinafter, an example of a manufacturing procedure of a wiring board using a semi-additive process will be described with reference to FIG. 2 . The size of the members in Fig. 2 is a conceptual size, and the relative relationship between the sizes of the members is not limited thereto.

In FIG. 2(a), a substrate (circuit forming substrate) on 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. 2(b), the photosensitive layer 32 is formed on the conductor layer 10 of the substrate by the photosensitive layer forming step. In FIG. 2(c), a mask 20 is disposed on the photosensitive layer 32, and the photosensitive layer 32 is irradiated with actinic rays 50 by the exposure step, and an area other than the area in which the mask 20 is disposed is exposed to be exposed. A light hardening portion is formed on the layer 32. In (d) of FIG. 2, in the photosensitive layer 32, a region other than the photocured portion is removed from the substrate by a developing step, whereby a resist pattern 30 as a photocured portion is formed on the substrate. In (e) of FIG. 2, a plating layer 42 is formed on the conductor layer 10 by a plating process using the resist pattern 30 as a photocured portion as a mask. In (f) of FIG. 2, after the resist pattern 30 as the photocured portion is peeled off by an aqueous solution of a strong alkali, a part of the plating layer 42 and the resist pattern 30 are removed by flash etching. The shielded conductor layer 10 is removed to form a conductor pattern 40. The material of the conductor layer 10 and the plating layer 42 may be the same or different. Although the method of forming the resist pattern 30 using the mask 20 has been described in FIG. 2, the resist pattern 30 may be formed by a direct drawing exposure method without using the mask 20. [Examples]

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

(Examples 1 to 6 and Comparative Examples 1 to 4) <Preparation of a solution of a photosensitive resin composition> The components shown in Tables 2 and 3 were formulated in the table. (Unit: g), a solution of the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 was prepared by mixing with 9 g of acetone, 5 g of toluene, and 5 g of methanol. The blending amount of the component (A) shown in Table 2 and Table 3 is the mass (solid content) of the nonvolatile component. The details of each component shown in Table 2 and Table 3 are as follows. In addition, "-" means unprovisioned.

(A) Adhesive polymer [Synthesis of binder polymer (A-1)] 81 g of methacrylic acid, 135 g of styrene, benzyl methacrylate 69 as a polymerizable monomer (monomer) g and 15 g of methyl methacrylate (mass ratio: 27/45/23/5) and 1.5 g of azobisisobutyronitrile were mixed, and the obtained solution was referred to as "solution a".

0.5 g of azobisisobutyronitrile was dissolved in 100 g of a mixture of 60 g of methyl cellosolve and 40 g of toluene (mass ratio: 3:2), and the obtained solution 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, 300 g of a mixture of methyl cellosolve 180 g and toluene 120 g (mass ratio: 3:2) was introduced into the flask. Nitrogen gas was blown in, and the mixture was heated while stirring, and the temperature was raised to 80 °C.

The solution a was added dropwise to the mixed solution in the flask for 4 hours, and then kept 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 at 80 ° C for 3 hours while stirring. Further, the solution in the flask was heated to 90 ° C for 30 minutes, and the mixture was kept at 90 ° C for 2 hours, and then cooled to obtain a solution of the binder polymer (A-1). The binder polymer (A-1) had a nonvolatile content (solid content) of 41.5 mass%, a weight average molecular weight of 44,000, an acid value of 176 mgKOH/g, and a degree of dispersion of 2.2.

Further, the weight average molecular weight is determined by using gel permeation chromatography (GPC) and is converted using a standard curve of standard polystyrene. The conditions of GPC are shown below.

GPC Condition Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.) Pipe column: The following total 3, pipe specifications: 10.7 mmf × 300 mm Gelpack GL-R440 Gelpack GL-R450 Gelpack GL-R400M (above, Hitachi Chemicals Co., Ltd.) Dissolution: tetrahydrofuran (THF) Sample concentration: 120 mg of a resin solution having a solid content of 40% by mass was collected, and dissolved in 5 mL of THF to prepare a sample. Measurement temperature: 40 ° C Injection amount: 200 μL Pressure: 49 kgf/cm ² (4.8 MPa) Flow rate: 2.05 mL/min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

[Synthesis of Binder Polymer (A-2)] In addition to 81 g of methacrylic acid as a polymerizable monomer (monomer), 9 g of 2-hydroxyethyl methacrylate, 141 g of styrene, and a solution obtained by mixing 69 g of benzyl acrylate (mass ratio: 27/3/47/23) and 2.4 g of azobisisobutyronitrile as "solution c", and using solution c instead of solution a, A solution of the binder polymer (A-2) was obtained in the same manner as the solution of the binder polymer (A-1). The binder polymer (A-2) had a nonvolatile content (solid content) of 41.7% by mass, a weight average molecular weight of 38,000, an acid value of 176 mgKOH/g, and a degree of dispersion of 1.8.

Regarding the binder polymer (A-1) and the binder polymer (A-2), the mass ratio (%), the acid value, the weight average molecular weight, and the dispersion degree of the polymerizable monomer (monomer) are shown in the table. 1 in. In addition, "-" means unprovisioned.

[Table 1]

(B) Photopolymerizable compound·BPE-100 (manufactured by Shin-Nakamura Chemical Co., Ltd.): 2,2-bis(4-(methacryloxyethoxy)phenyl)propane (EO group: 2.6 Mol (average)) · BPE-80N (manufactured by Shin-Nakamura Chemical Co., Ltd.): 2,2-bis(4-(methacryloxyethoxy)phenyl)propane (EO group: 2.3 mol) (Average)) · FA-324ME (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (EO group: 4 mol (average Value)) · ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.): 2,2-bis(4-(acryloxypolyethoxy)phenyl)propane (EO group: 3 mol (average value) · FA-321M (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane (EO group: 10 mol (average value)) FA-3200MY (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis(4-(methacryloxyethoxyethoxypropoxy)phenyl)propane (EO group: 12 mol (average value), PO Base: 4 mol (average)) · FA-024M (Hitachi Chemicals) Manufacturing Co., Ltd.) :( PO) (EO) (PO) modified polypropylene glycol # 700 dimethacrylate Furthermore, regarding the number of mol EO groups and PO groups is the number of the respective structural units of EO or PO groups.

(C) Photopolymerization initiator · B-CIM (manufactured by Hampford): 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl Bis-imidazole [2-(2-chlorophenyl)-4,5-diphenylimidazole dimer]

(D) Styrylpyridine compound represented by formula (1) · 2,4-DMOP-DSP: 3,5-bis(2,4-dimethoxybenzylidene dicyclopenta[b,e ])-4-(2,4-Dimethoxyphenyl)pyridine

Other sensitizing dyes other than the component (D) PYR-1 (manufactured by Nippon Chemical Industry Co., Ltd.): 1-phenyl-3-(4-methoxystyryl)-5-(4-A Oxyphenyl)pyrazoline·EAB (manufactured by Hodogaya Chemical Industry Co., Ltd.): 4,4'-diethylaminobenzophenone·H-MOP-DSP: 4,6-double (4- Methoxybenzylidenebicyclohexa[b,e])-5-(4-methoxyphenyl)pyridine

(E) Amine compound · LCV (manufactured by Yamada Chemical Industry Co., Ltd.): leuco crystal violet

Dye ·MKG (made by Osaka Organic Chemical Industry Co., Ltd.): Malachite Green

[Table 2]

[table 3]

<Preparation of Photosensitive Element> A solution of the obtained photosensitive resin composition was applied to a polyethylene terephthalate film having a thickness of 16 μm (manufactured by Toray Co., Ltd., "FB" On -40") (support), a hot air convection dryer at 70 ° C and 110 ° C was sequentially dried to form a photosensitive layer having a film thickness of 25 μm after drying. A polyethylene film ("E-200K" manufactured by Oji Paper Co., Ltd.) (protective layer) was bonded to the photosensitive layer, and a photosensitive member in which a support, a photosensitive layer, and a protective layer were laminated in this order was obtained.

<Preparation of a laminated substrate> A copper-clad laminate containing a glass epoxy material and a copper foil (having a thickness of 16 μm) formed on both surfaces (manufactured by Hitachi Chemical Co., Ltd., "MCL-E-679F") (below) After heating by heating to 80 ° C, the photosensitive elements of Examples 1 to 6 and Comparative Examples 1 to 4 were laminated (laminated) on the copper surface of the substrate. The protective layer was removed, and the photosensitive layer of each photosensitive element was adhered to the copper surface of the substrate, and laminated at a temperature of 110 ° C and a lamination pressure of 4 kgf / cm ² (0.4 MPa). . Thus, a laminated substrate in which a photosensitive layer and a support are laminated on the copper surface of the substrate is obtained. The resulting laminated substrate was left to cool to 23 °C.

<Evaluation of Sensitivity> A photo tool having a 41-step trapezoidal plate is disposed on the support of the laminated substrate, and the concentration region of the 41-step trapezoidal plate is 0.00 to 2.00, and the concentration step is 0.05. The size of the plate is 20 mm × 187 mm, and the size of each step is 3 mm × 12 mm. A direct exposure machine (ViaMechanics Co., Ltd., "DE-1UH") using a blue-violet laser diode having a wavelength of 405 nm as a light source, with a predetermined amount of energy (exposure amount), The photosensitive layer is exposed through a light tool and a support. In addition, an ultraviolet illuminometer (manufactured by Ushio Electric Co., Ltd., "UIT-150") using a 405 nm corresponding probe was used for the measurement of the illuminance.

After the exposure, the support was peeled off from the laminated substrate, the photosensitive layer was exposed, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C for 60 seconds to remove the unexposed portion. Thus, a resist pattern 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 steps (step number) of the trapezoidal plate obtained as a resist pattern (cured film). The sensitivity is represented by the number of steps in the case of exposure at 100 mJ/cm ² , and the higher the value, the better the sensitivity. The results are shown in Tables 4 and 5.

<Evaluation of Resolution and Adhesion> A drawing pattern having a line width (L)/space width (S) (hereinafter referred to as "L/S") of 3/3 to 30/30 (unit: μm) is used. The number of remaining steps of the 41-step trapezoidal plate is the amount of energy of 14 steps, and the photosensitive layer of the laminated substrate is exposed (drawn). After the exposure, the same development processing as the evaluation of the sensitivity was performed.

After development, the minimum value of the line width/space width in the resist pattern formed by the space portion (unexposed portion) is completely removed and the line portion (exposed portion) is not defective in bending, defects, or the like. Evaluation of resolution and adhesion. The smaller the value, the better the resolution and adhesion of the resist pattern. Further, the obtained resist pattern was magnified and observed at a magnification of 1,000 times by using an optical microscope to confirm the presence or absence of defects. The results are shown in Tables 4 and 5.

<Evaluation of Reaction Rate> The photosensitive layer of the photosensitive element was exposed to an amount of energy of 14 levels of the remaining number of trapezoidal plates of the 41-stage trapezoidal plate to obtain a photocured material. Before and after the exposure, the photosensitive layer or its photocured material was subjected to FT-IR measurement using a Fourier transform infrared spectroscopy (FT-IR) apparatus (manufactured by Bruker Optics Co., Ltd., "VERTEX 70"). Then, the aromatic-derived peak at 1570 cm ^-1 was taken as an internal standard, and the reaction rate (%) was calculated according to the following formula based on the peak derived from vinyl group observed at 1637 cm ^-1 . The results are shown in Tables 4 and 5. Reaction rate (%) = (1-I/I ₀ ) × 100 I: peak intensity after exposure I ₀ : peak intensity before exposure

<Evaluation of plating liquid resistance (resistance liquid resistance)> After heating a copper-clad laminate (manufactured by Nikkan Kogyo Co., Ltd., "F30VC1") for a flexible printed wiring board, the temperature was raised to 80 ° C, respectively. The photosensitive elements of Examples 1 to 6 and Comparative Examples 1 to 4 were laminated (laminated) on the copper surface of the substrate. The protective layer was removed, and the photosensitive layer of each photosensitive element was adhered to the copper surface of the substrate, and laminated at a temperature of 110 ° C and a lamination pressure of 4 kgf / cm ² (0.4 MPa). . The laminated body for evaluation in which the photosensitive layer and the support were laminated on the copper surface of the substrate was obtained in this manner. The obtained laminated laminate for evaluation was left to cool to 23 °C.

a glass illuminating tool having a wiring pattern having L/S of 5/5, 8/8, 10/10, and 15/15 (unit: μm) is adhered to the support of the laminated body for evaluation, and The amount of remaining step numbers after development is exposed to an amount of energy of 14 steps. Then, the support was peeled off, and a 1 mass% sodium carbonate aqueous solution was sprayed at 30 ° C, whereby the unexposed portion was removed to obtain a substrate for evaluation. The development time is set to be twice the time corresponding to the shortest development time (the shortest time for removing the unexposed portion).

The evaluation substrate was subjected to pretreatment in the following order: immersed in a degreasing liquid (manufactured by Meltex Co., Ltd., "PC-455", 25 mass%) for 5 minutes and washed with water, followed by soft The etching solution (ammonium persulfate 150 g/L) was immersed for 2 minutes, washed with water, and further immersed in 10% by mass of sulfuric acid for 1 minute. Then, it is placed in a copper sulfate plating solution (copper sulfate 75 g/L, sulfuric acid 190 g/L, chloride ion 50 ppm by mass, manufactured by Meltex Co., Ltd., "copper gleam" In PCM" and 5 mL/L), copper plating was performed under the conditions of 1 A/dm ² until the plating thickness was 12 μm.

After the substrate for evaluation after the copper plating treatment was washed with water and dried, the substrate was immersed in a stripping solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., "R-100", 0.2% by volume) at 50 ° C to remove the resist. The pattern was etched with an aqueous solution containing 0.1% by mass of sulfuric acid and 0.1% by mass of hydrogen peroxide. Thereafter, the plating penetration was confirmed by an optical microscope from above, and the plating infiltrator was evaluated as "A (excellent)", and the plating infiltrator was evaluated as "C (bad)". Further, in the case where plating penetration occurs, metallic copper precipitated by copper plating is observed in a region not covered by the resist pattern. The results are shown in Tables 4 and 5.

[Table 4]

[table 5]

It is clear from Tables 4 and 5 that the use of a binder polymer having a structural unit derived from (meth)acrylic acid, a bisphenol A type di(meth)acrylate having an EO group-containing structural unit of less than 6 Examples 1 to 6 of the photosensitive resin composition of the photopolymerizable compound, the photopolymerization initiator, and the styrylpyridine compound represented by the formula (1), the sensitivity and the resistance of the photosensitive resin composition The etchant pattern is excellent in resolution, adhesion, and drug resistance.

On the other hand, in Comparative Example 1 in which a photosensitive resin composition of bisphenol A type di(meth)acrylate having a number of structural units of less than 6 containing no EO group is used, the sensitivity of the photosensitive resin composition is excellent. However, the resolution, adhesion, and chemical resistance of the resist pattern were inferior to those of Examples 1 to 6. In addition, Comparative Example 2 to Comparative Example 4 using a photosensitive resin composition not containing the styrylpyridine compound represented by the formula (1), the sensitivity of the photosensitive resin composition and the resist liquid of the resist pattern The properties were inferior to those of Examples 1 to 6, and in particular, the resolutions and adhesion of the resist patterns of Comparative Example 3 and Comparative Example 4 were also inferior.

The disclosure of Japanese Patent Application No. 2016-053771, filed on Jan. In addition, all the documents, patent applications, and technical specifications described in the specification are incorporated in the specification to the same extent as the specific disclosure and the disclosure of each document, patent application, and technical specification by reference. in.

1‧‧‧Photosensitive components
2‧‧‧Support
3‧‧‧Photosensitive layer
4‧‧‧Protective layer
10‧‧‧Conductor layer
15‧‧‧Insulation
20‧‧‧ mask
30‧‧‧resist pattern
32‧‧‧Photosensitive layer
40‧‧‧ conductor pattern
42‧‧‧ plating layer
50‧‧‧Acradiation rays

FIG. 1 is a schematic cross-sectional view showing an example of a photosensitive element. FIG. 2 is a perspective view schematically showing an example of a manufacturing procedure of a printed wiring board by a half-addition process.

no

Claims (7)

A photosensitive resin composition comprising: a binder polymer having a structural unit derived from (meth)acrylic acid; a bisphenol A type di(meth)acrylic acid having a number of structural units containing an ethyloxy group of less than 6 a photopolymerizable compound of an ester; a photopolymerization initiator; and a styrylpyridine compound represented by the following formula (1), In the formula (1), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, or an amine group. And an alkylamino group having 1 to 20 carbon atoms, a carboxyl group, a cyano group, a nitro group, an ethyl fluorenyl group or a (meth) acrylonitrile group, and a, b and c each independently represent an integer of 0 to 5. The photosensitive resin composition according to the above aspect of the invention, wherein the photopolymerization initiator comprises a 2,4,5-triarylimidazole dimer represented by the following formula (2), In the formula (2), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group which may be substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group. X ¹ and X ² each independently represent a halogen atom, an alkyl group, an alkenyl group or an alkoxy group, and p and q each independently represent an integer of 1 to 5. A photosensitive element comprising: a support; and a photosensitive layer provided on the support and using the photosensitive resin composition according to claim 1 or 2. A method for producing a substrate with a resist pattern, comprising: forming a photosensitive layer on the substrate using the photosensitive resin composition according to claim 1 or 2; a step of irradiating at least a portion of the photosensitive layer with actinic rays and curing the region to form a cured region; and removing at least a portion of the photosensitive layer other than the cured region from the substrate A step of forming a resist pattern on the substrate. The method for producing a substrate with a resist pattern according to claim 4, wherein the actinic ray has a wavelength in a range of 340 nm to 430 nm. A method of producing a printed wiring board, comprising the step of etching a substrate on which a resist pattern is formed by a method of manufacturing a substrate with a resist pattern according to claim 4 or 5 . A method of manufacturing a printed wiring board, comprising: plating a substrate on which a resist pattern is formed by using a method of manufacturing a substrate with a resist pattern according to claim 4 or 5; step.