KR20180125965A - A photosensitive resin composition, a photosensitive element, a method of manufacturing a substrate with a resistor pattern, and a method of manufacturing a printed wiring board - Google Patents

Abstract

The photosensitive resin composition comprises a binder polymer having a structural unit derived from (meth) acrylic acid, a photopolymerizable compound comprising a bisphenol A di (meth) acrylate having an ethyleneoxy group having a structural unit number of less than 6, a photopolymerization initiator, And a styrylpyridine compound represented by the formula (1). A, b, and c each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or the like; and each of R ¹ , R ² , and R ³ independently represents an alkyl group having 1 to 20 carbon atoms, Represents an integer.

Description

A photosensitive resin composition, a photosensitive element, a method of manufacturing a substrate with a resistor pattern, and a method of manufacturing a printed wiring board

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

BACKGROUND ART [0002] In the field of manufacturing printed wiring boards, a photosensitive resin composition is widely used as a resistor material used when an etching or plating treatment is performed on a substrate for circuit formation. The photosensitive resin composition is often used as a photosensitive element (laminate) comprising a support and a layer using a photosensitive resin composition provided on the support (hereinafter also referred to as a " photosensitive layer ").

The printed wiring board is manufactured, for example, as follows. First, a photosensitive layer is formed on a substrate for circuit formation using a photosensitive element (photosensitive layer forming step). Next, a predetermined portion of the photosensitive layer is irradiated with an actinic ray to cure the exposed portion (exposure step). Thereafter, the support is peeled and removed, and then the unexposed portion of the photosensitive layer is removed (developed) from the substrate to form a resist pattern made of a cured product of the photosensitive resin composition on the circuit formation substrate (developing step). (Circuit forming process) on the substrate by performing the etching process or the plating process on the substrate using the formed resistor pattern as a resistor, and then finally deleting and removing the resist pattern (stripping process) To produce a printed wiring board.

As a method of exposure, conventionally, a method of exposing through a photomask using a mercury lamp as a light source is used. Recently, a direct drawing exposure method has been proposed, which is called DLP (Digital Light Processing) or LDI (Laser Direct Imaging), in which a pattern is directly drawn on a photosensitive layer. This direct imaging exposure method has been introduced for manufacturing a high-density package substrate in that it has better alignment accuracy than the exposure method using a photomask, and can obtain a high-precision pattern.

In general, in the exposure step, it is desired to shorten the exposure time for improvement of the production efficiency. However, in the direct imaging exposure method described above, since monochromatic light such as a laser is used for a light source, and a light beam is irradiated while a substrate is being scanned, a much longer exposure time is required compared with a conventional exposure method using a photomask . Therefore, in order to shorten the exposure time and increase the production efficiency, it is necessary to improve the sensitivity of the photosensitive resin composition.

On the other hand, with the recent increase in the density of printed wiring boards, there is a growing demand for photosensitive resin compositions capable of forming resist patterns having excellent resolution (resolution) and adhesion.

In response to these demands, various photosensitive resin compositions have been studied in the past. For example, Patent Document 1 proposes a photosensitive resin composition in which the aforementioned required properties are improved by using a styrylpyridine compound as a sensitizing dye. In Patent Documents 2 to 5, a photosensitive resin composition in which the above-mentioned required properties are improved by using a specific binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a sensitizing dye is proposed.

Patent Document 1: Chinese Patent Application Publication No. 101738861 Patent Document 2: JP-A-2005-122123 Patent Document 3: Japanese Patent Application Laid-Open No. 2007-114452 Patent Document 4: International Publication No. 10/098183 Patent Document 5: International Publication No. 12/067107

However, the resist pattern formed by the photosensitive resin composition is preferably excellent in chemical resistance. In the case where a plating process is performed on a substrate using a register pattern in which a chemical resistance is insufficient as a resistor, plating intrusion may occur. Here, " plating intrusion " means a phenomenon in which plating solution is flooded between the resistor pattern and the substrate. Particularly, in recent years, since the printed wiring board has been made denser, when the plating intrusion occurs, there is a possibility that the conductor pattern is continuously connected and short-circuited.

However, although the sensitivity of the photosensitive resin compositions disclosed in Patent Documents 1 to 5 is relatively high, there is still room for improvement in the chemical resistance of the formed resistor pattern.

Disclosed herein is a photosensitive resin composition capable of forming a resist pattern excellent in chemical resistance with excellent sensitivity, and a photosensitive element using the photosensitive resin composition, a method of manufacturing a substrate with a resistor pattern, and a method of manufacturing a printed wiring board do.

Specific means for solving the above-mentioned problems include the following embodiments.

(1) a binder polymer having a structural unit derived from (meth) acrylic acid,

A photopolymerizable compound comprising a bisphenol A type di (meth) acrylate having an ethyleneoxy group having a structural unit number of less than 6,

A photopolymerization initiator,

A photosensitive resin composition comprising a styryl pyridine compound represented by the following formula (1).

Wherein R ¹ , R ² and R ³ are each independently selected from the group consisting of 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, an amino group, A, b, and c each independently represent an integer of 0 to 5, and (c) an alkyl group having 1 to 20 carbon atoms, a carboxyl group, a cyano group, a nitro group, an acetyl group, or a (meth) acryloyl group;

<2> The photosensitive resin composition according to <1>, wherein the photopolymerization initiator comprises 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.]

<3> A photosensitive element comprising a support and a photosensitive layer formed using the photosensitive resin composition according to <1> or <2> provided on the support.

(4) a step of forming a photosensitive layer on the substrate using the photosensitive resin composition described in <1> or <2>

Irradiating at least a part of the region of the photosensitive layer with an actinic ray to photo-cure the region to form a cured region,

And removing at least a part of the photosensitive layer other than the hardened region from the substrate to form a resist pattern on the substrate.

&Lt; 5 &gt; The method of manufacturing a substrate with a resist pattern according to &lt; 4 &gt;, wherein a wavelength of the active ray is within a range of 340 to 430 nm.

&Lt; 6 &gt; A method for manufacturing a printed wiring board, comprising the step of etching a substrate on which a resistor pattern is formed by the method for manufacturing a substrate with a resistor pattern according to &lt; 4 &gt;

&Lt; 7 &gt; A method for manufacturing a printed wiring board, comprising the step of plating a substrate on which a resistor pattern is formed by a method of manufacturing a substrate with a resistor pattern as set forth in any one of &lt; 4 &gt;

According to the present disclosure, it is possible to provide a photosensitive resin composition capable of forming a resist pattern excellent in chemical resistance with excellent sensitivity, a photosensitive element using the photosensitive resin composition, a method of manufacturing a substrate with a resistor pattern, and a method of manufacturing a printed wiring board .

1 is a schematic cross-sectional view showing an example of a photosensitive element;
2 is a perspective view schematically showing an example of a manufacturing process of a printed wiring board by a semi-insulating method;

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

In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acryloyl" , Acryloyl or methacryloyl. The term "(poly) ethyleneoxy group" means at least one of an ethyleneoxy group (hereinafter also referred to as "EO group") or a polyethyleneoxy group in which two or more ethylene groups are linked by an ether bond. The term "(poly) propyleneoxy group" means at least one of a propyleneoxy group (hereinafter also referred to as "PO group") or a polypropyleneoxy group in which two or more propylene groups are linked by an ether bond. Refers to a compound having a (poly) ethyleneoxy group, and the term "PO-modified" means a compound having a (poly) propyleneoxy group, and the term "EO.PO. Quot; means a compound having both an oxy group and a (poly) propyleneoxy group.

In the present specification, the term &quot; layer &quot; includes a case where a region in which the layer is present is observed only in a part of the region, in addition to the case where the region is formed over the entire region. The term &quot; lamination &quot; refers to a lamination of two or more layers, or two or more layers may be removable.

Furthermore, in this specification, the term &quot; process &quot; is included in the term when the intended purpose of the process is achieved, even when it is not clearly distinguishable from other processes as well as independent processes.

In the present specification, the numerical range indicated by using &quot; ~ &quot; indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively. , The upper limit value or the lower limit value described in one numerical range may be replaced by the upper limit value or the lower limit value of the numerical range of other stepwise description. In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the embodiment.

In the present specification, the content of each component in the composition means the total amount of the plural kinds of substances present in the composition, unless a plurality of substances corresponding to each component exist in the composition, unless otherwise specified .

<Photosensitive resin composition>

(A) component: a binder polymer having a structural unit derived from (meth) acrylic acid, and (B) a bisphenol A type di (meth) acrylate having a structural unit number of EO groups of less than 6 (C) component: a photopolymerization initiator, and Component (D): a styrylpyridine compound represented by the formula (1), wherein the photopolymerizable compound is a compound represented by the following formula . The photosensitive resin composition may contain other components as needed.

(Specifically, a binder polymer having 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) , Resistance to plating solution) can be formed with excellent sensitivity. Detailed reasons for exhibiting the above effects are not necessarily clear, but the present inventors have assumed the following. By using a specific photopolymerizable compound that is effective for low swelling properties of a resistor pattern as a hydrophobic property and a styrylpyridine compound having excellent sensitivity to photosensitivity, a resist pattern can be formed with a low swelling property and a high reaction rate have. Thus, it is presumed that the crosslinking network in the resistor pattern becomes more densified and the chemical resistance is improved.

Further, in the embodiment of Japanese Patent Application Laid-Open No. 58-1142, by using a combination of a specific linear copolymer and a bisphenol A type dimethacrylate having the number of structural units of EO group of 10, Is improved. (Resistance to the plating solution) is improved by using the combination of the bisphenol A type di (meth) acrylate having the number of structural units of the EO group of less than 6 and the styrylpyridine compound represented by the formula (1) It's amazing.

(A) Component: Binder polymer

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

The content ratio of the structural unit derived from (meth) acrylic acid is preferably from 100% by mass or less to 100% by mass or less based on the total mass of the polymerizable monomer constituting the specific binder polymer, 15 to 40 mass%, may be 18 to 38 mass%, and may be 20 to 35 mass%. From the viewpoint of further improving the developability, the content may be 15 mass% or more, 18 mass% or more, and 20 mass% or more. From the viewpoint of further improving the adhesion of the resistor pattern, the content may be 40 mass% or less, 38 mass% or less, and 35 mass% or less.

The specific binder polymer may further have a structural unit derived from styrene or? -Methylstyrene. When the specific binder polymer further has a structural unit derived from styrene or? -Methylstyrene, the content ratio of the structural unit derived from styrene or? -Methylstyrene is preferably in the range from May be 10 to 70 mass%, preferably 15 to 60 mass%, or 20 to 55 mass%, based on the total mass of the polymerizable monomer constituting the binder polymer. From the viewpoint of further improving the adhesion of the resistor pattern, the content may be 10 mass% or more, 15 mass% or more, and 20 mass% or more. From the viewpoint of further improving the releasability of the resist pattern, the content may be 70 mass% or less, 60 mass% or less, or 55 mass% or less.

The specific binder polymer may have other structural units other than the structural units described above. As other structural units, for example, structural units derived from the following other polymerizable monomers can be mentioned.

Other polymerizable monomers are not particularly limited as long as they are polymerizable monomers which can be polymerized with (meth) acrylic acid, styrene or? -Methylstyrene and are different from (meth) acrylic acid, styrene and? -Methylstyrene. Examples of other polymerizable monomers include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid hydroxyalkyl ester, benzyl (meth) acrylate, furfuryl (meth) acrylate, (Meth) acrylate, dicyclohexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, dicyclopentenyloxyethyl Dicyclopentanyloxyethyl acrylate, cyclohexyloxyethyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, adamantyloxyethyl (meth) acrylate, dicyclopentenyloxypropyloxyethyl (meth) acrylate, Methacrylic acid (Meth) acrylic acid esters such as cyclopentanyloxypropyloxyethyl (meth) acrylate, and adamantyloxypropyl (meth) acrylate; α-bromoacrylic acid, α-chloroacrylic acid, Acrylates such as diacetone acrylamide; acrylonitrile; ether compounds of vinyl alcohols such as vinyl-n-butyl ether; (meth) acrylic acid derivatives such as methacrylic acid and the like; polymerizable styrene derivatives substituted in aromatic rings; Maleic anhydride, maleic acid monoester such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc., fumaric acid, cinnamic acid,? -Cyanosinic acid, itaconic acid, crotonic acid, propiolic acid, etc. Unsaturated carboxylic acid derivatives, and the like. These polymerizable monomers may be used singly or in combination of two or more kinds.

In the case where the specific binder polymer has other structural units, the content ratio of the other structural units is preferably from 1 to 50% by weight based on the total mass of the polymerizable monomers constituting the specific binder polymer from the viewpoint of further improving the resolution and releasability of the resist pattern , 3 to 85 mass%, 5 to 75 mass%, 10 to 70 mass%, and 10 to 50 mass%, respectively.

The specific binder polymer can be obtained, for example, by copolymerizing (meth) acrylic acid as the polymerizable monomer (monomer), styrene or? -Methylstyrene and other polymerizable monomers, , And radical polymerization.

As the component (A), a specific binder polymer may be used singly or two or more kinds of specific binder polymers may be arbitrarily used in combination. Further, 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 90 to 250 mgKOH / g, may be 100 to 240 mgKOH / g, may be 120 to 235 mgKOH / g, may be 130 to 230 mgKOH / g . From the viewpoint of further shortening the development time, the acid value may be 90 mgKOH / g or more, 100 mgKOH / g or more, 120 mgKOH / g or 130 mgKOH / g or more. The acid value may be 250 mgKOH / g or less, 240 mgKOH / g or less, 235 mgKOH / g or 230 mgKOH / g or less from the viewpoint of further improving the adhesion of the resist pattern.

When the weight average molecular weight (Mw) of a specific binder polymer is measured by gel permeation chromatography (GPC) (in terms of a calibration curve using standard polystyrene), 10000 And may be in the range of 15,000 to 100,000, in the range of 20,000 to 80,000, or in the range of 23,000 to 600,000. From the viewpoint of further shortening the development time, the weight average molecular weight may be 200,000 or less, 100,000 or less, 80000 or less, or 60000 or less. From the viewpoint of further improving the adhesion of the resist pattern, the weight average molecular weight may be 10,000 or more, 15,000 or more, 20,000 or more, 23,000 or more, and 25,000 or more.

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

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

The content of the component (A) in the photosensitive resin composition is preferably 100 parts by mass or more per 100 parts by mass of the total amount of the component (A) and the component (B) from the viewpoint of further improving the formability, May be 30 to 70 parts by mass, may be 35 to 65 parts by mass, and may be 40 to 60 parts by mass. From the viewpoint of further improving the formability of the photosensitive layer, the content may be 30 parts by mass or more, 35 parts by mass or more, and 40 parts by mass or more. The content may be 70 parts by mass or less, and may be 65 parts by mass or less and 60 parts by mass or less from the viewpoint of further improving the sensitivity and resolution of the resistor pattern.

(B) Component: Photopolymerizable compound

The photosensitive resin composition is a photopolymerizable compound which is a component (B), and includes at least one bisphenol A di (meth) acrylate (specific photopolymerizable compound) having an EO group of less than 6 structural units. The component (B) may further contain a photopolymerizable compound other than the specific photopolymerizable compound, if necessary.

In a 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) may be referred to as indicating how much EO group is added to the molecule. Thus, for a single molecule, it represents an integer value. Hereinafter, the number of structural units in the structural unit is the same.

In addition, 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 chemical resistance of the resist pattern. The lower limit value 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).

In the formula (3), R ⁴ and R ⁵ independently represent a hydrogen atom or a methyl group. XO independently represent an EO group. (XO) _m1 and (XO) _m2 each represent a (poly) ethyleneoxy group. m1 and m2 can be independently from 0 to 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.

As a commercially available product of the compound represented by the formula (3), 2,2-bis (4- (methacryloxy diethoxy) phenyl) propane (EO group: 4 mol (average value)) (manufactured by Hitachi Kasei Co., (ABE-300, manufactured by Shin-Nakamura Kagaku Kogyo KK), 2,2-bis (4- (acryloxypolyethoxy) phenyl) propane (Bis (4- (methacryloxyethoxy) phenyl) propane (EO group: 2.6 mol (average)) (Shin-Nakamura Kagaku Kogyo KK, "BPE-100"), 2,2- Propane (EO group: 2.3 mol (average value)) (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd., &quot; BPE-80N &quot;). These compounds may be used singly or in combination of two or more kinds.

The content of the specific photopolymerizable compound in the photosensitive resin composition is preferably such that the total amount of the component (A) and the component (B) in the crosslinking network is from the viewpoint of suppressing the swelling by inhibiting the molecular motion in the crosslinking network after curing, May be 1 to 60 parts by mass, preferably 5 to 55 parts by mass, and may be 10 to 50 parts by mass, based on 100 parts by mass of the resin.

The photosensitive resin composition may contain, as the component (B), other photopolymerizable compounds other than the specific photopolymerizable compound. The other photopolymerizable compound is not particularly limited as far as it is capable of photopolymerization. The other photopolymerizable compound may be a compound having an ethylenically unsaturated bonding group. Examples of the compound having an ethylenically unsaturated bonding group include compounds having one ethylenically unsaturated bonding group in the molecule, compounds having two ethylenically unsaturated bonding groups in the molecule, and compounds having three or more ethylenically unsaturated bonding groups in the molecule .

When the component (B) contains other photopolymerizable compound, the content of the specific photopolymerizable compound is preferably within a range from (1) to (3), from the viewpoint of suppressing swelling by inhibiting molecular motion in the crosslinking network after curing, May be from 1 to 60 parts by mass, preferably from 6 to 50 parts by mass, and from 10 to 40 parts by mass, based on 100 parts by mass of the total amount of the components.

The component (B) may be another photopolymerizable compound, and it may contain at least one compound having two ethylenically unsaturated bonding groups in the molecule (however, excluding the specific photopolymerizable compound). When the component (B) is another photopolymerizable compound and contains a compound having two ethylenically unsaturated bonding groups in the molecule, the content thereof is preferably 5% or less, more preferably 5% or less based on 100 parts by mass of the total amount of the components (A) To 60 parts by mass, and may be 5 to 55 parts by mass, and may be 10 to 50 parts by mass.

As the compound having two ethylenically unsaturated bonding groups in the molecule, bisphenol A type di (meth) acrylate, hydrogenated bisphenol A type di (meth) acrylate which are different from specific photopolymerizable compounds, EO group and PO group in the molecule (Meth) acrylate having at least one side thereof, di (meth) acrylate having a urethane bond in the molecule, trimethylolpropane di (meth) acrylate, and the like.

The component (B) is preferably a bisphenol A type di (meth) acrylate, a hydrogenated bisphenol A type di (meth) acrylate, or a bisphenol A type di (Meth) acrylate, and a polyalkylene glycol di (meth) acrylate having at least one of EO group and PO group in the molecule, at least one kind of compound having two ethylenically unsaturated bonding groups in the molecule .

As the bisphenol A type di (meth) acrylate which is different from the specific photopolymerizable compound, a compound represented by the following formula (4) can be mentioned.

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 each represent a (poly) ethyleneoxy group or a (poly) propyleneoxy group. x1, x2, y1, and y2 may be independently 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 3 or more, from the viewpoint of improving the resolution of the resist pattern. The number of structural units of the PO group in the molecule may be 5 or less from the viewpoint of improving developability.

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. The number of structural units of the EO group in the molecule may be 16 or less, or 14 or less, from the viewpoint of improving the resolution of the resist pattern.

Examples of commercially available products of the compound represented by the formula (4) include 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (EO group: 12 mol (average value), PO group: (EO group: 10 mol (average value)) (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd., product of Hitachi Chemical Co., Ltd., "FA-3200MY") and 2,2- (EO group: 10 mol (average value)) (manufactured by Hitachi Chemical Co., Ltd., &quot; FA-321M &quot;), 2,2-bis (4- (methacryloxypentaethoxy) , And 2-bis (4- (methacryloxypolyethoxy) phenyl) propane (EO group: 30 mol (average value)) (Shin-Nakamura Kagaku Kogyo Co., Ltd., "BPE-1300"). These compounds may be used singly or in combination of two or more kinds.

When the component (B) contains bisphenol A di (meth) acrylate which is different from the specific photopolymerizable compound, the content of the bisphenol A-type di (meth) acrylate is preferably such that the swelling is suppressed by inhibition of molecular motion in the crosslinking network after curing, From 1 to 65 parts by mass, preferably from 5 to 60 parts by mass, and from 10 to 55 parts by mass, based on 100 parts by mass of the total amount of the component (A) and the component (B). The content of the bisphenol A type di (meth) acrylate having the total number of structural units of the EO group and the PO group of 10 or less is preferably from 0.1 to 10 parts by weight, May be 55 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, and 40 parts by mass or less based on 100 parts by mass of the total amount of the component (B). The content of the bisphenol A di (meth) acrylate having a total number of structural units of the EO group and the PO group of 10 or less is preferably from 0.1 to 10 parts by weight, May be 70 parts by mass or less, and may be 65 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, and 40 parts by mass or less based on 100 parts by mass of the total amount.

As the hydrogenated bisphenol A type di (meth) acrylate, for example, 2,2-bis (4- (methacryloxypentaethoxy) cyclohexyl) propane can be given.

When the component (B) contains hydrogenated bisphenol A type di (meth) acrylate, the content thereof is preferably in the range of from May be 1 to 50 parts by mass, and may be 5 to 40 parts by mass based on 100 parts by mass of the total amount of the component (A) and the component (B).

The component (B) is preferably a polyalkylene glycol di (meth) acrylate having at least one of an EO group and a PO group in the molecule as another photopolymerizable compound, from the viewpoint of improving the flexibility, resolution, Acrylate, and the like. When the component (B) contains polyalkylene glycol di (meth) acrylate, the content of the polyalkylene glycol di (meth) acrylate is preferably within a range from 100 parts by mass to 100 parts by mass of the total amount of the component (A) , 1 to 30 parts by mass, and may be 2 to 20 parts by mass, or 2 to 15 parts by mass.

The polyalkylene glycol di (meth) acrylate may be EO-PO-modified polyalkylene glycol di (meth) acrylate. In the molecule of the polyalkylene glycol di (meth) acrylate, the (poly) ethyleneoxy group and the (poly) propyleneoxy group may be present in block form continuously or randomly. The PO group in the (poly) propyleneoxy group may be any one of n-propyleneoxy group and isopropyleneoxy group. Further, in the (poly) isopropyleneoxy group, the secondary carbon of the propylene group may be bonded to the oxygen atom, or the primary carbon may be bonded to the oxygen atom.

The polyalkylene glycol di (meth) acrylate is at least one member selected from the group consisting of (poly) n-butyleneoxy group, (poly) isobutyleneoxy group, (poly) n- (Poly) alkyleneoxy group having about 4 to 6 carbon atoms, and the like.

The component (B) may be at least one kind of photopolymerizable compound having three or more ethylenically unsaturated bonding groups in the molecule as the other photopolymerizable compound.

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

Examples of commercially available products of photopolymerizable compounds having three or more ethylenically unsaturated bonding groups in the molecule include EO-modified trimethylolpropane trimethacrylate ("TMPT21E" and "TMPT30E" manufactured by Hitachi Chemical Co., Ltd.), pentaerythritol triacrylate A-TMH-3 "), Dipentaerythritol hexaacrylate (" Shin-Nakamura "," A-DPH "manufactured by Shin-Nakamura Chemical Co., Pentaerythritol tetraacrylate (&quot; ATM-35E &quot;, manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.) and the like.

When the component (B) contains a photopolymerizable compound having three or more ethylenically unsaturated bonding groups in the molecule, the content thereof is preferably from a viewpoint of improving the balance of the resist pattern shape and the resolution, adhesion and releasability of the resist pattern, May be from 3 to 30 parts by mass, preferably from 5 to 25 parts by mass, and from 5 to 20 parts by mass, based on 100 parts by mass of the total amount of the component (A) and the component (B).

The component (B) is preferably used as other photopolymerizable compound in view of improving the resolution, adhesion and releasability of the resist pattern in a balanced manner, or suppressing the generation of scum, And may contain a photopolymerizable compound having one unsaturated bond group.

Examples of the photopolymerizable compound having one ethylenically unsaturated bonding group in the molecule include nonylphenoxypolyethyleneoxy (meth) acrylate, phthalic acid compound, and (meth) acrylic acid alkyl ester. Among them, nonylphenoxypolyethyleneoxy (meth) acrylate or a phthalic acid compound may be contained from the viewpoint of improving the balance of the resist pattern shape and the resist pattern resolution, adhesion, and peelability.

When the component (B) contains a photopolymerizable compound having one ethylenically unsaturated bond group in the molecule, the content thereof is preferably from 1 to 20 parts by mass per 100 parts by mass of the total amount of the components (A) and (B) And may be 3 to 15 parts by mass, and may be 5 to 12 parts by mass.

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

(C): Photopolymerization initiator

The photosensitive resin composition contains, as a component (C), at least one kind of a photopolymerization initiator. (C) component is preferably 2,4,5-triarylimidazole 2 represented by the following formula (2) in view of improving the sensitivity and the resolution and adhesion of the resistor pattern while maintaining the chemical resistance of the resist pattern. Or may contain a monomer.

In 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 each of p and q independently represents an integer of 1 to 5. When p is 2 or more, plural X ^{1 s} present may be the same or different from each other. When q is 2 or more, plural X ^{2 s} present may be the same or different.

X ¹ and X ² each independently represent a halogen atom (fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms . It is preferable 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, and more preferably 1.

Examples of the aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ include a phenyl group, a naphthyl group and an anthracenyl group, preferably a phenyl group.

Examples of the substituent which Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have include at least one kind 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 Lt; / RTI &gt; When each of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ independently has the above substituent, the number of substituents is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 . When Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ each independently have such a substituent, the substitution position is not particularly limited and is preferably an ortho or para position. It is preferable that all of Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are unsubstituted.

Examples of the 2,4,5-triarylimidazole dimer represented by the formula (2) include 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, 2- ( 2- (2-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2-methoxyphenyl) imidazole dimer, 2- Phenyl) -4,5-diphenylimidazole dimer, and 2- (4-methoxyphenyl) -4,5-diphenylimidazole dimer. The substituents of the aryl groups of the two 2,4,5-triarylimidazoles may be the same and symmetrical, or an asymmetric compound may be imparted in a different manner. The 2,4,5-triarylimidazole dimer represented by the formula (2) may be used singly or in combination of two or more kinds.

When the component (C) contains 2,4,5-triarylimidazole dimer represented by the formula (2), the content thereof is preferably 25 parts by mass or more based on 100 parts by mass of the total amount of the component (C) And may be 50 parts by mass or more, or 75 parts by mass or more.

As the photopolymerization initiator which is the component (C), other photopolymerization initiators usually used may be contained in addition to the 2,4,5-triarylimidazole dimer represented by the formula (2). Examples of other photopolymerization initiators include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, benzyl dimethyl ketal and the like, benzoin methyl ketal and the like Benzyl derivatives, and acridine derivatives such as 9-phenylacridine and 1,7- (9,9'-acridinyl) heptane.

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

(D) Component: The styrylpyridine compound represented by the formula (1)

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

In 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, A, b, and c each independently represent an integer of 0 to 5, provided that at least one of R 1, R 2, R 3, R 4, R 5, R 6, When a is 2 or more, plural R ^{1 s} may be the same or different. When b is 2 or more, plural R ^{2 s} may be the same or different from each other. When c is 2 or more, ³ may be the same or different from each other.

The carbon number of the alkyl ester group means the carbon number of the alkyl portion.

(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 group having 1 to 6 carbon atoms An alkyl group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 carbon atoms.

Each of a, b, and c independently represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2.

Examples of the styrylpyridine compound represented by the formula (1) include 3,5-dibenzylidene dicyclopentano [b, e] -4-phenylpyridine, 3,5-bis (4-methylbenzylidene) (4-methoxybenzylidene dicyclopentano [b, e]) - 4- (4-methoxybenzylidene) cyclopentano [b, e] (4-aminophenyl) pyridine, 3,5-bis (4-aminobenzylidene dicyclopentano [b, e]) -4- (4-carboxybenzylidene dicyclopentano [b, e]) - 4- (4-dimethylaminophenyl) pyridine, ), 4- (4-acetylphenyl) pyridine, 3,5-bis (4-cyanobenzylidene dicyclopentano [b, (4-nitrophenyl) pyridine, 3,5-bis (4-nitrobenzylidene dicyclopentano [b, e]) - 4- (4-cyanophenyl) (4-acryloylbenzylidene dicyclopentano [b, e]) - 4- (4-acryloylphenyl) (Methoxycarbonyl) benzylidene dicyclopentano [b, e]) - 4- (4- (methoxycarbonyl) phenyl) pyridine and 3,5 -Bis (2,4-dimethoxybenzylidene dicyclopentano [b, e]) - 4- (2,4-dimethoxyphenyl) pyridine.

The styrylpyridine compound represented by the formula (1) can be synthesized by, for example, 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 from 0.01 to 10 parts by mass, preferably from 0.05 to 5 parts by mass, more preferably from 0.08 to 5 parts by mass based on 100 parts by mass of the total amount of the components (A) 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 excellent in chemical resistance tends to be easily obtained. When the content of the component (D) is 10 parts by mass or less, a good resist pattern shape tends to be easily obtained.

(E) Component: Amine compound

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

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

(Other components)

The photosensitive resin composition may contain, if necessary, a photopolymerizable compound (e.g., oxetane compound) having at least one cation polymerizable cationic polymerizable group in the molecule, a cationic polymerization initiator, a sensitizing dye other than the component (D) Dyes such as malachite green, victoria pure blue, brilliant green and methyl violet, photo-coloring agents such as tribromophenylsulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline and 2-chloroaniline, , And other components such as a plasticizer such as 4-toluenesulfonamide, a pigment, a filler, a defoaming agent, a flame retardant, a stabilizer, an adhesion promoter, a leveling agent, a peel accelerator, an antioxidant, a perfume, an imaging agent and a thermal crosslinking agent. These other components may be used singly or in combination of two or more kinds for each component.

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

[Solution of photosensitive resin composition]

The photosensitive resin composition may further contain at least one organic solvent. 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; aromatic hydrocarbon solvents such as toluene; And non-protonic polar solvents such as N, N-dimethylformamide. These organic solvents may be used singly or in combination of two or more kinds. The content of the organic solvent contained in the photosensitive resin composition may be appropriately selected depending on the purpose and the like. For example, an organic solvent may be contained in the photosensitive resin composition to be used as a solution having a solid content of about 30 to 60% by mass. Hereinafter, the photosensitive resin composition containing an organic solvent is also referred to as &quot; coating liquid &quot;.

The above-mentioned coating liquid is applied on the surface of a support, a metal plate or the like to be described later, and dried, whereby a photosensitive layer which is a coating film of the photosensitive resin composition can be formed. 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 copper, a copper-based alloy, and a metal plate such as an iron-based alloy such as nickel, chromium, iron, and stainless steel. As the metal plate, a metal plate such as copper, a copper-based alloy, or an iron-based alloy is preferable.

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

The above photosensitive resin composition can be applied to the formation of a photosensitive layer of a photosensitive element described later. That is, another embodiment of the present disclosure is a positive resist composition comprising: (A) a binder polymer having a structural unit derived from (meth) acrylic acid; and (B) a bisphenol A type having a structural unit number of EO groups of less than 6 (Meth) acrylate, a component (C): a photopolymerization initiator, and a component (D): a photosensitive resin composition containing a styrylpyridine compound represented by the formula (1) to be.

The above photosensitive resin composition can be used in a method of manufacturing a substrate with a resistor pattern, which will be described later. That is, another embodiment of the present disclosure relates to a resin composition comprising (A) a binder polymer having a structural unit derived from (meth) acrylic acid, (B) a bisphenol A- A method for producing a substrate with a resist pattern of a photosensitive resin composition containing a photopolymerizable compound containing an acrylate, a component (C): a photopolymerization initiator, and a component (D): a styrylpyridine compound represented by the formula (1) .

<Photosensitive element>

The photosensitive element of this embodiment includes a support and a photosensitive layer formed using the photosensitive resin composition provided on the support. The photosensitive layer is a coating film formed using the photosensitive resin composition, and the photosensitive resin composition is in an uncured state. The photosensitive element may have other layers such as a protective layer, if necessary.

Fig. 1 shows an example of a photosensitive element. In the photosensitive element 1 shown in Fig. 1, the support 2, the photosensitive layer 3, and the 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 on the support 2 to form a coating layer and the photosensitive layer 3 is formed by drying the coating layer. The surface of the photosensitive layer 3 opposite to the surface of the support 2 is covered with the protective layer 4 to form the support 2, the photosensitive layer 3 formed on the support 2, and the photosensitive layer 3 The photosensitive element 1 having the protective layer 4 laminated on the photosensitive element 1 can be obtained. The photosensitive element 1 does not necessarily have to be provided with the protective layer 4.

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

The thickness of the support 2 may be 1 to 100 탆 or 5 to 50 탆 or 5 to 30 탆. When the thickness of the support 2 is 1 탆 or more, when the support 2 is peeled off, Tearing of the base material 2 tends to be suppressed. If the thickness of the support 2 is 100 m or less, the decrease in resolution tends to be suppressed.

It is preferable that the adhesive force of the photosensitive layer 3 to the protective layer 4 becomes smaller than the adhesive force of the photosensitive layer 3 to the support 2 as the protective layer 4. Also, a film of a low fish eye is preferred. Here, the term "fish eye" refers to a phenomenon in which when a material is thermally melted and a film is produced by kneading, extruding, biaxial stretching, casting or the like, foreign matter, unsalted material, . That is, the term &quot; low fish eye &quot; 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, polyolefin such as polypropylene and polyethylene, and the like can be used. Commercially available ones include ARPAN MA-410, E-200 manufactured by Oji Seishi Co., Ltd., polypropylene film manufactured by Shin-Etsu Film Co., Ltd., and PS series polyethylene terephthalate film such as PS- have. The protective layer 4 may be the same as the support 2.

The thickness of the protective layer 4 may be 1 to 100 탆, 5 to 50 탆, 5 to 30 탆, or 15 to 30 탆. When the thickness of the protective layer 4 is 1 탆 or more, the protection layer 4 is prevented from being torn when the photosensitive layer 3 and the support 2 are laminated on the substrate while peeling off the protective layer 4 There is a tendency to be able to do. If the thickness of the protective layer 4 is 100 탆 or less, handling and cheapness tend to be excellent.

Specifically, the photosensitive element can be manufactured, for example, as follows. Wherein the component (A) is a binder polymer, the component (B) is a photopolymerizable compound, the component (C) is a photopolymerization initiator, and the component (D) is a styrylpyridine compound represented by the formula (2), forming a coating layer, and drying the coating layer to form a photosensitive layer (3), wherein the coating layer is formed on the support The photosensitive element can be manufactured.

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

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 coating layer is preferably dried at 70 to 150 DEG C for about 5 to 30 minutes. The amount of residual organic solvent in the photosensitive layer 3 after drying may be 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step.

The thickness of the photosensitive layer 3 in the photosensitive element can be appropriately selected depending on the application. The thickness of the photosensitive layer 3 after drying may be 1 to 100 탆, 1 to 50 탆, or 5 to 40 탆. When the thickness of the photosensitive layer 3 is 1 占 퐉 or more, industrial coating tends to be facilitated. If the thickness of the photosensitive layer 3 is 100 m or less, the adhesion of the resist pattern and resolution tends to be sufficiently obtained.

The transmittance of the photosensitive layer 3 with respect to ultraviolet rays may be 5 to 75%, 10 to 65%, or 15 to 55% with respect to ultraviolet rays having a wavelength of 350 to 420 nm. If the transmittance is 5% or more, adhesion of the resistor pattern tends to be sufficiently obtained. When the transmittance is 75% or less, resolution of the resistor pattern tends to be sufficiently obtained. The transmittance can be measured by an ultraviolet spectrometer. As the ultraviolet spectrometer, a 228A type W-beam spectrophotometer of Hitachi, Ltd. is available.

The photosensitive element may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorbing layer, a gas barrier layer, or the like. As the intermediate layer, for example, the intermediate layer described in Japanese Patent Application Laid-Open No. 2006-098982 can be applied to this embodiment.

The shape of the obtained photosensitive element is not particularly limited. The photosensitive element may be, for example, a sheet-like element or a roll-wound form on a core. In the case of winding in the roll, it is preferable to wind the support 2 so as to be on the 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). It is preferable that a cross-section separator is provided on the end face of the roll-shaped photosensitive element roll obtained in this way from the standpoint of protection of the cross section, and a cross section of the moisture-proof cross section separator in terms of edge- It is desirable to install it. As a packaging method, it is preferable to wrap the package in a wrapped black sheet having low moisture permeability.

The photosensitive element can be suitably used, for example, in a manufacturing method of a substrate with a resistor pattern, which will be described later.

&Lt; Method of manufacturing substrate with resist pattern &

Using the above photosensitive resin composition, a resist pattern-attached substrate can be produced. (I) a step of forming a photosensitive layer using the photosensitive resin composition (a photosensitive layer forming step) on a substrate, and (ii) a step of forming a photosensitive layer (Iii) a step of removing at least a part of the photosensitive layer other than the hardened area from the substrate by irradiating an active ray to a part of the area to form a hardened area by photocuring the area; And a step of forming a resist pattern on the substrate (developing step). The method for manufacturing a resist pattern-attached substrate may further include other steps as necessary.

(i) Photosensitive layer forming step

First, the photosensitive layer 3 is formed on the substrate using the above photosensitive resin composition. As the substrate, for example, a substrate (circuit formation substrate) having an insulating layer and a conductor layer formed on the insulating layer can be used. As the insulating layer, for example, a glass epoxy material can be cited. The conductor layer may be, for example, copper foil.

The formation of the photosensitive layer 3 on the substrate can be carried out, for example, when the photosensitive element has the protective layer 4, after removing the protective layer 4, the photosensitive layer 3 of the photosensitive element And pressing it onto the substrate while heating. Thereby, a laminate in which the substrate, the photosensitive layer 3, and the support 2 are laminated in this order can be obtained.

The photosensitive layer forming step is preferably carried out under a reduced pressure in view of adhesion and followability. Heating for at least one of the photosensitive layer 3 and the substrate at the time of pressing is preferably performed at a temperature of 70 ~ 130 ℃ and, 0.1 ~ 1.0MPa approximately (1 ~ 10kgf / cm ² or so) pressing at a pressure of . These conditions are not particularly limited, and are appropriately selected as needed. When the photosensitive layer 3 is heated to 70 to 130 캜, the substrate may not be preheated. The substrate can be preheated to further improve adhesion and followability.

(ii) exposure step

In the exposure step, by irradiating actinic light to at least a part of the region of the photosensitive layer 3 formed on the substrate as described above, the exposed portion irradiated with the actinic light ray is photo-cured to form a latent image. At this time, when the support 2 present on the photosensitive layer 3 is transparent to the active ray, it is possible to irradiate the active ray through the support 2. On the other hand, when the support 2 exhibits light shielding property against the actinic ray, the photosensitive layer 3 is irradiated with an actinic ray after the support 2 is removed.

As an exposure method, there is a method (mask exposure method) of irradiating an active ray in the form of a picture image through a negative or positive mask pattern called an artwork. Further, a method of irradiating an active ray on an image plane by a direct imaging exposure method such as LDI (Laser Direct Imaging) exposure method or DLP (Digital Light Processing) exposure method may be employed.

The light source of the active light ray is not particularly limited, and a known light source can be used. Concretely, a gas laser such as a carbon arc, a mercury vapor arc, a high pressure mercury lamp, a xenon lamp, an argon laser, a solid laser such as a YAG laser, a semiconductor laser, a ultraviolet ray such as a gallium nitride blue- Is used.

The wavelength (exposure wavelength) of the active light ray may be in the range of 340 to 430 nm, or in the range of 350 to 420 nm. By setting the wavelength of the active light ray within the range of 340 to 430 nm, it is possible to form the resist pattern with excellent chemical resistance more efficiently with excellent sensitivity.

(iii) development process

In the developing step, the uncured portion of the photosensitive layer 3 is removed from the substrate by the developing process, so that a resist pattern, which is a cured product of the photosensitive layer 3, is formed on the substrate. When the support 2 is present on the photosensitive layer 3, the support 2 is removed and then the unexposed portion is removed (developed). In the developing process, wet phenomenon and dry phenomenon occur, but wet phenomenon is widely used.

In the case of the wet phenomenon, development is carried out by a known developing method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include a dipping method, a paddle method, a spraying method, a brushing method, a slapping method, a scraping method and a method using a dipping immersion method. From the viewpoint of resolution improvement, a high pressure spraying method is most suitable. These two or more methods may be combined to perform development.

The developing solution is appropriately selected depending on the constitution of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution and an organic solvent developer.

When used as a developer, the alkaline aqueous solution is safe or stable, and has good operability. Examples of the base of the alkaline aqueous solution include alkaline hydroxides such as hydroxides of lithium, sodium or potassium; alkali metal carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium; alkali metal phosphates such as potassium phosphate and sodium phosphate; , Alkali metal pyrophosphate such as potassium pyrophosphate, borax (sodium borate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl 1,3-propanediol, 1,3-diamino-2-propanol, morpholine and the like are used.

As the alkaline aqueous solution used for the development, a diluted solution of 0.1 to 5 mass% sodium carbonate, a dilute solution of 0.1 to 5 mass% potassium carbonate, a diluted solution of 0.1 to 5 mass% sodium hydroxide, a diluted solution of 0.1 to 5 mass% Solution or the like is preferable. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11. The temperature is also adjusted in accordance with the alkali developability of the photosensitive layer 3. The alkaline aqueous solution may contain a surface active agent, a defoaming agent, and a small amount of an organic solvent for promoting development.

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

Examples of the organic solvent used in the organic solvent developer include organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methylisobutylketone, . It is preferable to add water to these organic solvents in the range of 1 to 20% by mass for prevention of ignition, to make them organic solvent developers.

The resist pattern-coated substrate manufacturing method may further include a step of removing the unexposed portion and then further heating the resist pattern at 60 to 250 DEG C or an energy amount of 0.2 to 10 J / cm &lt; ² &gt; .

&Lt; Manufacturing method of printed wiring board &gt;

The method of manufacturing a printed wiring board according to the present embodiment includes a step of performing at least one of an etching treatment and a plating treatment on a substrate on which a resistor pattern is formed by the manufacturing method of the substrate with a resistor pattern.

That is, the method for manufacturing a printed wiring board according to the first embodiment has a step of etching the substrate on which the resistor pattern is formed by the method for manufacturing a resist pattern-attached substrate.

The method for manufacturing a printed wiring board according to the second embodiment includes a step of performing a plating process on a substrate on which a resistor pattern is formed by the above method for manufacturing a resist pattern-attached substrate.

As the substrate, for example, it is preferable to use a substrate (substrate for circuit formation) having an insulating layer and a conductor layer formed on the insulating layer. The method of manufacturing the printed wiring board may include other steps such as a resistor removing step if necessary. The etching treatment and the plating treatment of the substrate are carried out with respect to the conductor layer of the substrate and the like, using the formed resist pattern as a mask.

In the etching process, a conductor pattern of a circuit formation substrate not covered with a curing resistor is removed by etching using a resist pattern (curing resistor) formed on the substrate as a mask. The method of the etching treatment is appropriately selected according to the conductor layer to be removed. Examples of the etching solution include an aqueous solution of cupric chloride, a solution of ferric chloride, an alkali etching solution, a hydrogen peroxide etching solution and the like. Among them, it is preferable to use an aqueous ferric chloride solution because of the good etch factor.

On the other hand, in the plating process, copper, solder, or the like is plated on a conductor layer of a substrate for circuit formation which is not covered with a curing resistor, using a resistor pattern (curing resistor) formed on the substrate as a mask. After the plating process, the curing resistor is removed, and the conductor layer covered with the curing resistor 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, copper pyrophosphate plating, high-speed solder plating, nickel plating such as nickel sulfate plating (nickel sulfate-nickel chloride plating), nickel sulfamate plating, hard gold plating, soft gold plating Gold plating and the like.

After the etching treatment and the plating treatment, the resist pattern on the substrate is removed (stripped). The removal of the resistor pattern can be carried out, for example, by using a stronger alkaline aqueous solution than the alkaline aqueous solution used in the developing step. As the strongly alkaline aqueous solution, 1 to 10 mass% aqueous sodium hydroxide solution and 1 to 10 mass% potassium hydroxide aqueous solution are used. Among them, 1 to 10 mass% aqueous sodium hydroxide solution or 1 to 10 mass% potassium hydroxide aqueous solution is preferably used, and more preferably 1 to 5 mass% sodium hydroxide aqueous solution or 1 to 5 mass% potassium hydroxide aqueous solution is used . Examples of the method of applying the strongly alkaline aqueous solution to the resistor pattern include an immersion method and a spray method, and they may be used singly or in combination of two or more kinds.

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

The above-described method for producing a printed wiring board can be applied not only to a single-layer printed wiring board but also to a multilayer printed wiring board, and also to a printed wiring board having a small-diameter through hole.

The above photosensitive resin composition can be suitably used for producing a printed wiring board. That is, one of the suitable embodiments is a resin composition comprising: (A) a binder polymer having a structural unit derived from (meth) acrylic acid and (B) a bisphenol A di (meth) acrylate having a structural unit number of EO groups of less than 6 (C) component: a photopolymerization initiator; and (D): a styrylpyridine compound represented by the formula (1) in the production of a printed wiring board.

Further, a more preferable embodiment is an application to the production of a high-density package substrate of the photosensitive resin composition and application to the semi-adhesive method of the photosensitive resin composition. Hereinafter, an example of a manufacturing process of a wiring board by the semi-insulating method will be described with reference to FIG. The size of the member in Fig. 2 is conceptual, and the relative relationship between the sizes of the members is not limited to this.

2 (a), a substrate (circuit formation substrate) on which a conductor layer 10 is formed on an insulating layer 15 is prepared. The conductor layer 10 is, for example, a metallic copper layer. 2 (b), the photosensitive layer 32 is formed on the conductive layer 10 of the substrate by the photosensitive layer forming step. 2 (c), a mask 20 is disposed on the photosensitive layer 32, the active ray 50 is irradiated to the photosensitive layer 32 by the exposure process, and the mask 20 And exposes an area other than the area to form a light-cured part in the photosensitive layer 32. [ 2 (d), in the photosensitive layer 32, a region other than the light-cured portion is removed from the substrate by a developing process to form a resist pattern 30 which is a photo-cured portion on the substrate. 2E, 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. 2F, the resist pattern 30, which is a photo-cured portion, is peeled off by a strong alkaline aqueous solution, and then a portion of the plating layer 42 and the conductor layer 10 are removed to form the conductor pattern 40. The conductive layer 10 and the plating layer 42 may be made of the same material or different materials.

Although the method of forming the resistor pattern 30 using the mask 20 has been described with reference to Fig. 2, the resistor pattern 30 may be formed by the direct imaging exposure method without using the mask 20. Fig.

Example

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

(Examples 1 to 6 and Comparative Examples 1 to 4)

&Lt; Preparation of solution of photosensitive resin composition &gt;

The photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were prepared by mixing 9 g of acetone, 5 g of toluene and 5 g of methanol in the amounts shown in Tables 2 and 3 (unit: g) Respectively. The compounding amount of the component (A) shown in Table 2 and Table 3 is the mass (solid content) of the nonvolatile matter. Details of each component shown in Table 2 and Table 3 are as follows. In addition, &quot; - &quot; means an unmixed compound.

(A) a binder polymer

[Synthesis of binder polymer (A-1)] [

81 g of methacrylic acid as a polymerizable monomer (monomer), 135 g of styrene, 69 g of benzyl methacrylate, 15 g of methyl methacrylate (mass ratio: 27/45/23/5) and 1.5 g of azobisisobutyronitrile were mixed Solution was referred to as &quot; solution a &quot;.

A solution obtained by dissolving 0.5 g of azobisisobutyronitrile in 100 g of a mixed solution of 60 g of methyl cellosolve and 40 g of toluene (mass ratio: 3: 2) was referred to as &quot; solution b &quot;.

To a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introducing tube, 300 g of a mixed solution of 180 g of methyl cellosolve and 120 g of toluene (mass ratio: 3: 2) was charged, and nitrogen gas was introduced into the flask , And the temperature was raised to 80 캜.

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

The nonvolatile matter (solid content) of the binder polymer (A-1) was 41.5% by mass, the weight average molecular weight was 44,000, the acid value was 176 mgKOH / g, and the dispersion degree was 2.2.

The weight average molecular weight was determined by gel permeation chromatography (GPC) and calculated by using a standard polystyrene calibration curve. The conditions of GPC are shown below.

GPC conditions

Pump: Hitachi L-6000 type (Hitachi SEISAKUSHO Co., Ltd.)

Column: Three columns below, column specification: 10.7 mmφ × 300 mm

Gelpack GL-R440

 Gelpack GL-R450

 Gelpack GL-R400M (manufactured by Hitachi Chemical Co., Ltd.)

Eluent: tetrahydrofuran (THF)

Sample concentration: 120 mg of a resin solution having a solid content of 40% by mass was sampled and dissolved in 5 mL of THF to prepare a sample.

Measuring 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 (Hitachi SEISAKUSHO Co., Ltd.)

[Synthesis of binder polymer (A-2)] [

(Mass ratio: 27/3/47/23), 81 g of methacrylic acid as the polymerizable monomer (monomer), 9 g of 2-hydroxyethyl methacrylate, 141 g of styrene, and benzyl methacrylate (A-1) was obtained in the same manner as in the preparation of the binder polymer (A-1) except that the solution obtained by mixing 2.5 g of the binder polymer (A-1) Solution.

The nonvolatile matter (solid content) of the binder polymer (A-2) was 41.7% by mass, the weight average molecular weight was 38,000, the acid value was 176 mgKOH / g, and the dispersion degree was 1.8.

The mass ratio (%), the acid value, the weight average molecular weight, and the degree of dispersion of the polymerizable monomer (monomer) are shown in Table 1 with respect to the binder polymers (A-1) and (A- In addition, &quot; - &quot; means unmixed.

(B) a photopolymerizable compound

(Average value) of 2,2-bis (4- (methacryloxyethoxy) phenyl) propane (EO group: BPE-100 manufactured by Shin Nakamura Kagaku Kogyo Co.,

Bis (4- (methacryloxyethoxy) phenyl) propane (EO group: 2.3 mol (average value)) was obtained in the same manner as in Example 1, except that BPE-80N (manufactured by Shin Kagaku Kagaku Kogyo Co.,

(4 mol (average value) of EO group) of FA-324 ME (manufactured by Hitachi Chemical): 2,2-bis (4- (methacryloxy diethoxy)

3 mol (average value) of 2,2-bis (4- (acryloxypolyethoxy) phenyl) propane (EO group: ABE-300 manufactured by Shin Kagaku Kagaku Kogyo Co.,

(EO group: 10 mol (average value)) of FA-321 M (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis

(EO group: 12 mol (average value), PO group: 4 mol (average value)), 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane, FA-3200MY (manufactured by Hitachi Chemical Co.,

FA-024M (manufactured by Hitachi Chemical Co., Ltd.): (PO) (EO) (PO) modified polypropylene glycol # 700 dimethacrylate

In addition, the number of moles per EO group and PO group means the number of structural units of each EO group or PO group.

(C) a photopolymerization initiator

B-CIM (manufactured by Hampford): 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole [2- -Diphenylimidazole dimer]

(D) a styrylpyridine compound represented by the formula (1)

2,4-DMOP-DSP: 3,5-bis (2,4-dimethoxybenzylidene dicyclopentano [b, e]) 4- (2,4-dimethoxyphenyl)

(D) other than the component

PYR-1 (Nippon Gakugei Kogyo Co., Ltd.): 1-phenyl-3- (4-methoxystyryl) -5- (4- methoxyphenyl) pyrazoline

· EAB (manufactured by Hodogaya Chemical Industry Co., Ltd.): 4,4'-diethylaminobenzophenone

H-MOP-DSP: 4,6-bis (4-methoxybenzylidene dicyclohexano [b, e]) - 5- (4-methoxyphenyl)

(E) An amine compound

· LCV (manufactured by Yamada Kagaku Kogyo Co., Ltd.): Loico crystal violet

dyes

· MKG (manufactured by Osaka Organic Chemical Co., Ltd.): Marachite Green

&Lt; Preparation of Photosensitive Element &gt;

The solution of the photosensitive resin composition obtained above was applied onto a polyethylene terephthalate film ("FB-40", made by Toray Industries, Inc.) having a thickness of 16 탆 (support) and dried at 70 캜 and 110 캜 in a hot air convection type dryer Followed by successive drying to form a photosensitive layer having a dry thickness of 25 mu m. A polyethylene film (&quot; E-200K &quot;, made by Oji Seishi Co., Ltd.) (protective layer) was laminated on the photosensitive layer to obtain a photosensitive element in which a support, a photosensitive layer and a protective layer were sequentially laminated.

<Fabrication of Laminated Substrate>

MCL-E-679 F "(hereinafter referred to as &quot; substrate &quot;) made of a glass epoxy material and a copper foil (thickness 16 탆 in thickness) formed on both surfaces thereof (multilayer laminate plate (Hitachi Chemical). ) Were heated and heated to 80 DEG C, and the photosensitive elements related to Examples 1 to 6 and Comparative Examples 1 to 4 were laminated (laminated) on the copper surface of the substrate. The laminate was carried out under conditions of a temperature of 110 캜 and a laminate pressure of 4 kgf / cm ² (0.4 MPa) such that the photosensitive layer of each photosensitive element was brought into close contact with the copper surface of the substrate while removing the protective layer. Thus, a laminated substrate having a photosensitive layer and a support laminated on the copper surface of the substrate was obtained. The resultant laminated substrate was allowed to cool to 23 占 폚.

&Lt; Evaluation of sensitivity &

A phototool having a 41 step (stage) step tablet having a concentration range of 0.00 to 2.00, a concentration step of 0.05, a tablet size of 20 mm x 187 mm, and each step size of 3 mm x 12 mm was placed on the support of the laminated substrate. A direct-exposure light exposure apparatus ("DE-1 UH" manufactured by Beer Mechanics Co., Ltd.) having a blue-violet laser diode having a wavelength of 405 nm as a light source was used to expose the photosensitive layer through a phototool and a support at a predetermined energy amount . For the measurement of the illuminance, an ultraviolet illuminometer ("UIT-150" manufactured by Ushio Denki Co., Ltd.) to which a probe corresponding to 405 nm was applied was used.

After the exposure, the support was peeled off from the laminated substrate to expose the photosensitive layer, and the 1 wt% sodium carbonate aqueous solution was sprayed at 30 캜 for 60 seconds to remove the unexposed portions. In this manner, a resist pattern made of a cured product of the photosensitive resin composition was 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 step tablet obtained as a resist pattern (cured film). The sensitivity is represented by the step number at the time 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>

The step pattern of the 41 step tablet is obtained by using a drawing pattern having a line width L / space width S (hereinafter referred to as "L / S") of 3/3 to 30/30 (unit: The photosensitive layer of the laminated substrate was exposed (drawn) with an energy amount of 14 stages. After exposure, the same development processing as that of the sensitivity evaluation was performed.

After developing, the space portion (unexposed portion) is cleared away, and the line portion (exposed portion) is formed without causing defects such as meandering or shortage, and the value of the line width / The resolution and the adhesion were evaluated. The smaller this value, the better the resolution and adhesion of the resist pattern. The obtained resist pattern was observed by magnification at a magnification of 1000 times using an optical microscope to confirm the presence or absence of defects. The results are shown in Tables 4 and 5.

&Lt; Evaluation of reaction rate &

The photosensitive layer of the photosensitive element was exposed to an energy amount such that the remaining number of steps of the 41-step tablet was 14 stages to obtain a photo-cured product. Before and after the exposure, FT-IR measurement of the photosensitive layer or its optical product was carried out using a Fourier transform infrared spectroscopy (FT-IR) device ("VERTEX70" manufactured by Burka Optics Co., Ltd.). The reaction rate (%) was calculated from the peak derived from the aromatic group at 1570 cm ^-1 as an internal standard and the peak derived from the vinyl group observed at 1637 cm ^-1 as follows. The results are shown in Tables 4 and 5.

Reaction rate (%) = (1-I / I ₀ ) x 100

I: Peak intensity after exposure

I ₀ : Peak intensity before exposure

&Lt; Evaluation of plating solution resistance (chemical resistance) &gt;

After heating the copper-clad laminate ("F30VC1" manufactured by Nikkan Kogyo Co., Ltd.) for the flexible printed wiring board to 80 ° C, the photosensitive elements related to Examples 1 to 6 and Comparative Examples 1 to 4 were laminated on the copper surface of the substrate (Laminated). The laminate was carried out under conditions of a temperature of 110 캜 and a laminate pressure of 4 kgf / cm ² (0.4 MPa) such that the photosensitive layer of each photosensitive element adhered to the copper surface of the substrate while removing the protective layer. Thus, an evaluation laminate having a photosensitive layer and a support laminated on the copper surface of the substrate was obtained. The obtained evaluation laminate was allowed to cool to 23 占 폚.

A glass phototool having a wiring pattern with L / S of 5/5, 8/8, 10/10, and 15/15 (unit: 占 퐉) was brought into close contact with the support of the evaluation laminate to form a residue And the exposure was performed by an amount of energy of 14 steps. Subsequently, the support was peeled off, and an unexposed portion was removed by spraying a 1 mass% sodium carbonate aqueous solution at 30 캜 to obtain a substrate for evaluation. The developing time was set to a time corresponding to twice the shortest developing time (the shortest time for which the unexposed portion was removed).

The substrate for evaluation was immersed in a degreasing liquid ("PC-455", 25 mass%) for 5 minutes, washed with water, immersed in a soft alcohol solution (ammonium persulfate 150 g / L) for 2 minutes, And then immersed in 10 mass% sulfuric acid for 1 minute. Then, the coating thickness on the copper sulfate plating solution (copper sulfate 75g / L, sulfuric acid 190g / L, chlorine ion 50 mass ppm, maeru Tex Co., Ltd., "Kappa FIG PCM", 5 mL / L) 1 condition A / dm ² to put the Copper plating treatment was carried out until the thickness became 12 탆.

The substrate for evaluation after the copper plating treatment was washed with water and dried, and then the resist pattern was peeled off by immersing it in a peeling liquid (Mitsubishi Gas Co., Ltd., "R-100", 0.2 volume% Was etched with an aqueous solution containing 0.1 mass% sulfuric acid and 0.1 mass% hydrogen peroxide. Thereafter, plating intrusion was confirmed using an optical microscope from above, and it was evaluated as "A (good)" in which no plating intrusion occurred and "C (poor)" in which plating intrusion occurred. Further, when plating intrusion occurs, metallic copper precipitated by copper plating is observed in the region masked with the resist pattern. The results are shown in Tables 4 and 5.

As is apparent from Tables 4 and 5, a photopolymerizable compound comprising a binder polymer having a structural unit derived from (meth) acrylic acid and a bisphenol A di (meth) acrylate having an EO group having a structural unit number of less than 6, Examples 1 to 6 using a photopolymerization initiator and a photosensitive resin composition containing a styrylpyridine compound represented by the formula (1) showed that the sensitivity of the photosensitive resin composition, the resolution of the resist pattern, the adhesion property, and the chemical resistance It was excellent.

On the other hand, Comparative Example 1 using a photosensitive resin composition containing no bisphenol A di (meth) acrylate having a structural unit number of less than 6 in the EO group was excellent in sensitivity of the photosensitive resin composition, but the resolution, The drug solution resistance was inferior to those of Examples 1 to 6.

In Comparative Examples 2 to 4 using the photosensitive resin composition containing no styrylpyridine compound represented by the formula (1), the sensitivity of the photosensitive resin composition and the chemical resistance of the resist pattern were inferior to those of Examples 1 to 6, In particular, the resist patterns of Comparative Examples 3 and 4 were inferior in resolution and adhesion.

The disclosure of Japanese Patent Application No. 2016-053771 filed on March 17, 2016 is incorporated herein by reference in its entirety.

In addition, all documents, patent applications, and technical specifications described in this specification are herein incorporated by reference to the same extent as if each individual document, patent application, and technical specification was specifically and individually recorded as being incorporated by reference. Be used by

One… Photosensitive element, 2 ... Support, 3 ... Photosensitive layer, 4 ... Protective layer, 10 ... Conductor layer, 15 ... Insulation layer, 20 ... Mask, 30 ... Register pattern, 32 ... Photosensitive layer, 40 ... Conductor pattern, 42 ... Plated layer

Claims (7)

A binder polymer having a structural unit derived from (meth) acrylic acid,
A photopolymerizable compound comprising a bisphenol A type di (meth) acrylate having an ethyleneoxy group having a structural unit number of less than 6,
A photopolymerization initiator,
A photosensitive resin composition comprising a styryl pyridine compound represented by the following formula (1).

Wherein R ¹ , R ² and R ³ are each independently selected from the group consisting of 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, an amino group, A, b, and c each independently represent an integer of 0 to 5, and (c) an alkyl group having 1 to 20 carbon atoms, a carboxyl group, a cyano group, a nitro group, an acetyl group, or a (meth) acryloyl group; The method according to claim 1,
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 formed using the photosensitive resin composition according to claim 1 or 2 provided on the support. A step of forming a photosensitive layer on the substrate using the photosensitive resin composition according to claim 1 or 2,
Irradiating at least a part of the region of the photosensitive layer with an actinic ray to photo-cure the region to form a cured region,
And removing at least a part of the photosensitive layer other than the hardened region from the substrate to form a resist pattern on the substrate. The method of claim 4,
Wherein a wavelength of the active ray is within a range of 340 to 430 nm. The method for manufacturing a printed wiring board according to claim 4 or 5, wherein the substrate having the resistor pattern formed thereon is subjected to an etching process. The method for manufacturing a printed wiring board according to claim 4 or 5, further comprising a step of performing a plating process on the substrate on which the resistor pattern is formed by the method of manufacturing a substrate with a resistor pattern.

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