KR101775206B1 - Photosensitive resin composition and photosensitive element using same, resist pattern formation method and printed circuit board manufacturing method - Google Patents

Abstract

(식 중, R¹ 및 R²는 각각 독립적으로 수소 원자 또는 메틸기를 나타내고, n은 0 내지 50의 정수를 나타냄)The present invention relates to a direct imaging method comprising (A) a binder polymer, (B) a photopolymerizable compound and (C) a photopolymerization initiator, wherein (B) the photopolymerizable compound comprises a compound represented by the following formula The present invention also provides a photosensitive resin composition for use in the formation of a resist pattern.

(Wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n represents an integer of 0 to 50)

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method of forming a resist pattern, and a method of manufacturing a printed wiring board. BACKGROUND ART [0002]

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

BACKGROUND ART [0002] In the field of the production of printed wiring boards, photosensitive resin compositions are widely used as resist materials used for etching and plating. The photosensitive resin composition is often used as a photosensitive element comprising a support film and a layer formed using a photosensitive resin composition formed on the support film (hereinafter referred to as a " photosensitive resin layer ").

When a printed wiring board is manufactured using a photosensitive element, for example, a printed wiring board is produced as follows. First, the photosensitive resin layer of the photosensitive element is laminated (laminated) on a substrate (lamination step). Next, in some cases, after the support film is peeled off, a predetermined portion of the photosensitive resin layer is irradiated with an actinic ray to expose and cure the predetermined portion (exposure step). Thereafter, portions (unexposed / uncured portions) other than the predetermined portions are removed (developed) from the substrate to form a resist pattern containing a cured product of the photosensitive resin composition on the substrate (developing step). Subsequently, using this resist pattern as a mask, a substrate on which a resist pattern is formed is subjected to etching or plating to form a circuit pattern, and finally, the resist pattern is peeled off from the substrate (circuit pattern forming step). In this manner, a printed wiring board on which a circuit pattern is formed on a substrate is manufactured.

In the above exposure process, a mask exposure method for irradiating an actinic ray through a mask film having a pattern is conventionally used. As a light source of an active ray, a light source that effectively emits ultraviolet rays such as a carbon arc or a mercury vapor arc, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp is used.

In recent years, as a substitute for the mask exposure method, a direct imaging method for directly irradiating an actinic ray on a screen using digital data without using a mask film has been put into practical use. As a light source used in the direct imaging method, a YAG laser, a semiconductor laser, or the like is used in terms of safety and handleability, and recently, a technology using a gallium nitride blue laser having a long life and a high output has been proposed.

In addition, a direct drawing method called a DLP (Digital Light Processing) exposure method capable of forming a fine pattern in comparison with a conventional one has been introduced in accordance with a high-density and high-density printed wiring board. Generally, in the DLP exposure method, an active ray having a wavelength of 390 to 430 nm is used as a light source of a blue-violet semiconductor laser. In addition, an exposure method using a polygon multi-beam having a wavelength of 355 nm, in which a YAG laser capable of coping with a small variety of products is used as a light source in a general-purpose printed wiring board has been used.

On the other hand, as the developing solution used for removing the unexposed portion of the photosensitive resin layer from the substrate in the above-described developing step, an alkaline developing solution such as an aqueous solution of sodium carbonate or an aqueous solution of sodium hydrogencarbonate is mainly used from the standpoint of environmental and safety . The unexposed portions of the photosensitive resin layer are removed from the substrate by developing with these developers or spraying pressure of water. Therefore, the photosensitive resin composition is required to have excellent tent reliability (tentability), which is not damaged by exposure after development or spraying by water.

As a photosensitive resin composition having excellent tent reliability in a conventional mask exposure method, a photosensitive resin composition containing a bifunctional or trifunctional monomer has been proposed (for example, see Patent Documents 1 and 2).

Japanese Patent No. 3199600 Japanese Patent No. 3251446

However, the photosensitive resin composition containing the bifunctional or trifunctional monomer has excellent tent reliability in the conventional mask exposure method, but the direct drawing method does not have sufficient tent reliability.

Accordingly, it is an object of the present invention to provide a photosensitive resin composition having excellent tent reliability when exposed by a direct imaging method. It is another object of the present invention to provide a photosensitive element using the photosensitive resin composition, a method of forming a resist pattern, and a method of manufacturing a printed wiring board.

The present inventors have conducted intensive investigations to solve the above problems. As a result, it has been found that, by using a compound having a specific chemical structure as a photopolymerizable compound, a photosensitive resin composition having excellent tent reliability when exposed by a direct drawing method And thus the present invention has been accomplished.

That is, the present invention relates to a method for producing a photopolymerizable compound, which comprises (A) a binder polymer, (B) a photopolymerizable compound and (C) a photopolymerization initiator, Is a photosensitive resin composition used for forming a resist pattern. By using the compound represented by the following formula (I) as the (B) photopolymerizable compound, the photosensitive resin composition of the present invention has good sensitivity and excellent tent reliability when exposed by the direct imaging method.

In the formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n represents an integer of 0 to 50. It is preferable that n is an integer of 4 to 25 in that tent reliability is further improved.

The photopolymerizable compound (B) preferably further comprises a compound represented by the following formula (II) in that the peelability is further improved.

In the above formula (II), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrocarbon group having 9 carbon atoms, and m represents an integer of 0 to 20. It is preferable that m is an integer of 4 to 8 in that tent reliability is further improved.

The photopolymerization initiator (C) preferably contains a compound represented by the following formula (III) and / or a compound represented by the following formula (IV) in that sensitivity is further improved.

In the above formula (III), R ⁵ represents an alkylene group, an oxydialkylene group or a thioalkylene group having 2 to 20 carbon atoms.

In the above formula (IV), R ⁶ represents a monovalent aromatic group which may have a substituent.

The present invention also relates to a photosensitive element comprising a support film and a photosensitive resin layer formed using the photosensitive resin composition formed on the support film.

The present invention also provides a process for producing a photosensitive resin composition, which comprises laminating a photosensitive resin layer formed by using the photosensitive resin composition on a substrate, and irradiating the photosensitive resin layer with an actinic ray in an image- And a developing step of removing the unexposed portions of the photosensitive resin layer from the substrate to form a resist pattern including a cured product of the photosensitive resin composition on the substrate.

The present invention also relates to a method of manufacturing a printed wiring board comprising etching or plating a substrate on which a resist pattern is formed by the above method.

According to the present invention, it becomes possible to provide a photosensitive resin composition having excellent sensitivity and excellent tent reliability when exposed by a direct imaging method. Further, by providing the photosensitive element using the photosensitive resin composition, a method of forming a resist pattern, and a method of manufacturing a printed wiring board, it is possible to produce a printed wiring board having a highly precise circuit pattern.

1 is an end view showing an embodiment of the photosensitive element of the present invention.
2 is a top view of a substrate for measuring the number of hole tears used for evaluation of tent reliability.

Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratios in the drawings are not limited to the illustrated ratios. In the present specification, "(meth) acrylic acid" means "acrylic acid" and the corresponding "methacrylic acid", and "(meth) acrylate" means "acrylate" and the corresponding "methacrylate" , And the term "(meth) acryloyl group" means "acryloyl group" and the corresponding "methacryloyl group".

(Photosensitive resin composition)

The photosensitive resin composition of the present embodiment is a photopolymerizable compound (hereinafter sometimes referred to as a "component (B)") and (C) a photopolymerization initiator (Hereinafter also referred to as a " component (C) "), which is used for forming a resist pattern by a direct drawing method. Here, the " direct drawing method " is an exposure method for drawing a desired pattern directly on a photosensitive resin layer by irradiating an active ray such as a laser beam onto the photosensitive resin layer based on digital data without using a mask film or the like .

≪ Component (B): photopolymerizable compound >

The photosensitive resin composition of the present embodiment includes a compound represented by the following formula (I) as a photopolymerizable compound which is a component (B). Thus, the photosensitive resin composition of the present embodiment has excellent tent reliability when exposed by the direct drawing method. Here, " tent reliability " means a property (tentability) that is not damaged by the spraying pressure of development or washing after exposure, and the reliability of the tent is evaluated using the substrate for measuring the number of hole tears shown in Fig. And the tent tear rate (%).

In the compound represented by the above formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. It is preferable that R ¹ and R ² are methyl groups. In the compound represented by the above formula (I), n represents an integer of 0 to 50. The n is preferably an integer of 4 to 25, more preferably an integer of 9 to 24, and still more preferably an integer of 9 to 14 in that tent reliability is further improved.

Examples of the compound represented by the above formula (I) include di (meth) acrylic acid anhydride (n = 0) and (poly) ethylene glycol di (meth) acrylate (n = 1 to 50). (Poly) ethylene glycol di (meth) acrylate is obtained by reacting (poly) ethylene glycol with (meth) acrylic acid. Examples of commercially available compounds represented by the above formula (I) include polyethylene glycol dimethacrylates such as 9G, 14G and 23G (all available from Shin-Nakamura Chemical Co., Ltd.).

The content of the compound represented by the above formula (I) is preferably 5 to 90% by mass based on the total mass of the component (B) in view of a good balance of sensitivity and resolution. The content is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more from the viewpoint of excellent tent reliability. The content is preferably 90% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less.

The photosensitive resin composition of the present embodiment may further comprise a component (B) other than the compound represented by the above formula (I). The component (B) is not particularly limited as long as it has an ethylenic unsaturated bond and is capable of photo-crosslinking, and examples thereof include the following compounds (B1) to (B5). These may be used alone or in combination of two or more.

(B1) bisphenol A based di (meth) acrylate compound

(B2) a compound having one ethylenic unsaturated bond

(B3) a compound obtained by reacting an?,? - unsaturated carboxylic acid with a polyhydric alcohol

(B4) A compound obtained by reacting an?,? - unsaturated carboxylic acid with a glycidyl group-containing compound

(B5) a urethane monomer such as a (meth) acrylate compound having a urethane bond

Among them, the component (B) preferably contains a bisphenol A di (meth) acrylate compound (B1) in view of excellent sensitivity and resolution. (Meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4 - ((meth) acryloxypolypropoxy) phenyl) Propane, and 2,2-bis (4 - ((meth) acryloxypolyethoxypolypropoxy) phenyl) propane.

Examples of the 2,2-bis (4 - ((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis Bis (4 - ((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4- (Meth) acryloxypentaethoxy) phenyl) propane, 2,2-bis (4 - ((meth) acryloxypentaethoxy) Bis (4 - ((meth) acryloxynoethoxy) phenyl) propane, 2,2-bis Propane, 2,2-bis (4 - ((meth) acryloxydecaethoxy) phenyl) propane, 2,2- Bis (4 - ((meth) acryloxytridecahexoxy) phenyl) propane, 2,2-bis (4 (meth) acryloxydodecaethoxy) - ((meth) acrylate Bis (4 - ((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis Propoxy) phenyl) propane. 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd.) - (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more.

Examples of the 2,2-bis (4 - ((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis Bis (4 - ((meth) acryloxytetra propoxy) phenyl) propane, 2,2-bis (4 Bis (4 - ((meth) acryloxypentapropoxy) phenyl) propane, 2,2-bis Bis (4 - ((meth) acryloxynonapropoxy) phenyl) propane, 2,2-bis 2-bis (4 - ((meth) acryloxydecaproxy) phenyl) propane, 2, 2-bis (4 - ((meth) acryloxydodecaproxy) phenyl) propane, 2,2-bis 2, 4-bis (4 - ((meth) acryloxytetradecapropoxy) phenyl) propane, 2-bis (4 - ((meth) acryloxyhexadecapropoxy) phenyl) propane. These may be used alone or in combination of two or more.

Examples of the 2,2-bis (4 - ((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4 - ((meth) acryloxy diethoxyoxapropoxy) Bis (4 - ((meth) acryloxyhexaethoxyhexapropoxy) propane, 2,2-bis (4- Phenyl) propane. These may be used alone or in combination of two or more.

The content of the component (B) in the case of containing the bisphenol A di (meth) acrylate compound (B1) is preferably 20 to 80% by mass, more preferably 30 to 70% by mass based on the total mass of the component (B) % Is more preferable.

In addition, from the viewpoint of excellent tent reliability, it is preferable that the component (B) includes the compound (B2) having one ethylenic unsaturated bond in the molecule. (B2) include nonylphenoxime (meth) acrylate compounds represented by the following formula (II),? -Chloro-? -Hydroxypropyl-? '- (meth) acryloyloxyethyl- -Hydroxyethyl-beta '- (meth) acryloyloxyethyl-o-phthalate, and beta -hydroxypropyl-beta' - (meth) acryloyloxyethyl-o-phthalate. Among them, a nonylphenoxime (meth) acrylate compound represented by the following formula (II) is preferred.

In the compound represented by the above formula (II), R ³ represents a hydrogen atom or a methyl group. From the standpoint of improving the developing ability, R ³ is preferably a hydrogen atom. R ⁴ represents a hydrocarbon group having 9 carbon atoms. In the compound represented by the above formula (II), m represents an integer of 0 to 20. M is preferably an integer of 4 to 15, more preferably an integer of 4 to 10, and still more preferably an integer of 4 to 8, in that tent reliability is further improved.

Examples of the compound represented by the formula (II) include nonylphenoxy (meth) acrylate (m = 0) and nonylphenoxy (poly) ethylene glycol (meth) acrylate (m = 1 to 20). Nonylphenoxy (poly) ethylene glycol (meth) acrylate is obtained by reacting (poly) ethylene glycol with nonylphenol and (meth) acrylic acid. Examples of the nonylphenoxy (poly) ethylene glycol (meth) acrylate include nonylphenoxy tetraethylene glycol (meth) acrylate and nonylphenoxy octaethylene glycol (meth) acrylate. Examples of commercially available compounds represented by the above formula (II) include nonylphenoxy (poly) ethylene glycol acrylates such as FA-314A and FA-318A (all products of Hitachi Chemical Industry Co., Ltd.) have.

The content of the compound represented by the formula (II) is preferably 5 to 90% by mass based on the total mass of the component (B) in view of excellent balance of sensitivity and resolution. The content is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more from the viewpoint of excellent tent reliability. The content is preferably 90% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less.

Examples of the compound (B3) obtained by reacting the above polyhydric alcohol with an?,? - unsaturated carboxylic acid include polypropylene glycol di (meth) acrylate having 2 to 14 oxypropylene groups, trimethylolpropane di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate (having repeating total number of oxyethylene groups of 1 to 5), PO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, tetraethylene glycol di And pentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more. Here, "EO-modified" means a compound having a (poly) oxyethylene chain block structure (polyoxyethylenated compound), and "PO-modified" means a compound having a (poly) oxypropylene chain Refers to a compound (polyoxypropylene compound), and "EO.PO. denatured" means a compound having a block structure of (poly) oxyethylene chain and (poly) oxypropylene chain (polyoxyethylene and polyoxypropylene ). ≪ / RTI > These may be used alone or in combination of two or more.

Examples of the urethane monomer (B5) include a (meth) acrylic monomer having a hydroxyl group at the? -Position and an isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate and 1,6- (Meth) acryloxytetraethylene glycol isocyanate), hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and diisocyanate compounds such as methylene diisocyanate. ) Acrylate, and the like. Examples of the EO-modified urethane di (meth) acrylate include trade name UA-11 manufactured by Shin Nakamura Chemical Industry Co., Ltd. Examples of the EO and PO modified urethane di (meth) acrylate include UA-13 (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd.). Further, tris ((meth) acryloxytetraethylene glycol isocyanate) Hexamethyleneisocyanurate includes, for example, UA-21 (trade name) manufactured by Shin Nakamura Chemical Industry Co., Ltd. Among them, UA-21 is preferably 5 to 25% by weight, more preferably 7 to 15% by weight in view of further improving tent reliability. These may be used alone or in combination of two or more.

The content of the component (B) (photopolymerizable compound) is preferably 20 to 60 parts by mass based on 100 parts by mass of the total of the components (A) and (B). In order to improve the sensitivity and resolution, the content of the component (B) is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and further preferably 30 parts by mass or more. The content of the component (B) is preferably 60 parts by mass or less, more preferably 55 parts by mass or less, and further preferably 50 parts by mass or less, from the viewpoint of imparting film properties and excellent resist shape after curing.

≪ Component (A): Binder polymer >

The binder polymer as component (A) is not particularly limited as long as it is soluble in an aqueous alkali solution and can form a film, and examples thereof include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, , And phenolic resins. Among them, an acrylic resin is preferable in view of alkali developability. These may be used alone or in combination of two or more.

The component (A) can be produced, for example, by radical polymerization of a polymerizable monomer (monomer). As the polymerizable monomer, for example, styrene; polymerizable styrene derivatives substituted in the? -position or aromatic ring such as? -methylstyrene, vinyltoluene and the like; Acrylamide such as diacetone acrylamide; Acrylonitrile; Ethers of vinyl alcohol such as vinyl-n-butyl ether; (Meth) acrylic acid alkyl ester, (meth) acrylic acid benzyl ester, (meth) acrylate tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, diethylaminoethyl (meth) acrylate, glycidyl (Meth) acrylic acid esters such as esters, 2,2,2-trifluoroethyl (meth) acrylate and 2,2,3,3-tetrafluoropropyl (meth) acrylate; (Meth) acrylic acid derivatives such as (meth) acrylic acid, alpha -bromo (meth) acrylic acid, alpha -chloro (meth) acrylic acid, beta-furyl (meth) acrylic acid and beta -styryl (meth) acrylic acid; Maleic acid derivatives such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; And organic acid derivatives such as fumaric acid, cinnamic acid,? -Cyanosinic acid, itaconic acid, crotonic acid and propiolic acid. These may be used alone or in combination of two or more.

Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following formula (V).

In the above formula (V), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an alkyl group having 1 to 12 carbon atoms.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁸ in the above formula (V) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, An undecyl group, a dodecyl group, and a structural isomer thereof.

Examples of the compound represented by the above formula (V) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (Meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl Esters, and (meth) acrylic acid dodecyl esters. These may be used alone or in combination of two or more.

Examples of the (meth) acrylic acid alkyl ester include compounds in which the alkyl group is substituted with a hydroxyl group, an epoxy group, a halogen group or the like in the compound represented by the formula (V).

The component (A) preferably contains a carboxyl group from the viewpoint of alkali developability. The component (A) containing a carboxyl group can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers. As the polymerizable monomer having a carboxyl group, (meth) acrylic acid is preferable, and methacrylic acid is more preferable.

The content of the carboxyl group of the component (A) (the proportion of the polymerizable monomer having a carboxyl group to the entire polymerizable monomer to be used) is preferably in the range of 12 to 30 mass%, based on the total mass of the component (A) And more preferably 50% by mass. But is preferably not less than 12% by mass, more preferably not less than 15% by mass in terms of excellent alkali developability. From the viewpoint of excellent developer resistance, the content is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

The component (A) preferably contains styrene or a styrene derivative as a polymerizable monomer in view of adhesion and peeling property. When the styrene or styrene derivative is used as a copolymerization component, the content (the ratio of styrene or styrene derivative to the entire polymerizable monomer to be used) By weight based on the total weight of the composition. But is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 1.5% by mass or more, from the viewpoint of excellent adhesiveness. From the viewpoint of excellent releasability, the content is preferably 30% by mass or less, more preferably 28% by mass or less, and further preferably 27% by mass or less.

These component (A) (binder polymer) may be used alone or in combination of two or more. As the binder polymer when two or more kinds are used in combination, for example, two or more binder polymers containing different copolymerization components, two or more different binder polymers having different weight average molecular weights, two or more different binder polymers .

The weight average molecular weight of the component (A) is preferably from 20,000 to 300,000 in view of the balance between the resistance to developing and the alkalinity. But is preferably 20,000 or more, more preferably 40,000 or more, and even more preferably 50,000 or more in view of excellent resistance to developing. The alkali developing property is preferably 150,000 or less, more preferably 120,000 or less. In the present specification, the weight average molecular weight is a value measured by a gel permeation chromatography method and converted by a calibration curve prepared using standard polystyrene.

The content of the component (A) is preferably 40 to 80 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B). From the standpoint of imparting film properties, the amount is preferably not less than 40 parts by mass, more preferably not less than 45 parts by mass, and most preferably not less than 50 parts by mass. Further, the amount is preferably 80 parts by mass or less, more preferably 75 parts by mass or less, and even more preferably 70 parts by mass or less, from the viewpoint of excellent sensitivity and resolution.

≪ Component (C): photopolymerization initiator >

The photopolymerization initiator which is the component (C) preferably contains a compound represented by the following formula (III) and / or a compound represented by the following formula (IV).

In the compound represented by the above formula (III), R ⁵ represents an alkylene group, an oxa-dialkylene group or a thio-alkylene group having 2 to 20 carbon atoms. (C) is a compound represented by the above formula (III) wherein R ⁵ is an alkylene group having 7 carbon atoms (for example, adeka Manufactured by ADEKA, trade name " N-1717 ").

When the component (C) comprises the compound represented by the above formula (IV), the content thereof is preferably 0.01 to 20 parts by mass per 100 parts by mass of the total amount of the components (A) and (B) More preferably from 0.1 to 10 parts by weight, and still more preferably from 0.2 to 5 parts by weight. When the content is less than 0.01 part by weight, sufficient sensitivity tends not to be obtained. When the content exceeds 20 parts by weight, the resist shape becomes inverted trapezoid, and sufficient adhesion and resolution tends not to be obtained.

In the compound represented by the above formula (IV), R ⁶ represents a monovalent aromatic group which may have a substituent. (C) is a compound represented by the above formula (IV) wherein R ⁶ is a phenyl group (for example, a product of Shin-Nittsu Chemical Co., Ltd., trade name "9 -PA "). From the viewpoint of making the sensitivity better, it is preferable that the component (C) includes a compound represented by the above formula (IV) wherein R ⁶ is a phenyl group substituted with an alkyl group, a halogen atom or the like. Examples of such a compound include a compound in which R ⁶ is a p-methylphenyl group, an m-methylphenyl group, an o-methylphenyl group and a p-chlorophenyl group (for example, a trade name "TR-PAD102" TR-PAD103 "," TR-PAD104 "," TR-PAD105 ").

When the component (C) contains the compound represented by the above formula (IV), the content thereof is preferably 0.01 to 10 parts by mass per 100 parts by mass of the total amount of the components (A) and (B) More preferably 0.05 to 5 parts by weight, still more preferably 0.1 to 3 parts by weight. When the content is less than 0.01 part by weight, a sufficient sensitivity tends not to be obtained. When the content is more than 10 parts by weight, the resist shape becomes reverse trapezoid, and sufficient adhesion and resolution tends not to be obtained.

The compound represented by the formula (III) and the compound represented by the formula (IV) can be used alone or in combination, and the compound represented by the formula (III) or the compound represented by the formula (IV) Two or more of them may be used in combination.

Examples of the component (C) (photopolymerization initiator) other than the compound represented by the formula (III) and the compound represented by the formula (IV) include benzophenone, N, N'-tetramethyl- Diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'- Aromatic ketones such as 1- (4-morpholinophenyl) -butanone-1, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; Diethylanthraquinone, 2,3-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di 2-methyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl 1,4-naphthoquinone, and 2,3-dimethyl anthraquinone Quinones such as quinone; Benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; Benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; Benzyl derivatives such as benzyl dimethyl ketal; Substituted anthracenes such as 9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-diphenoxy anthracene; 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o- (O-methoxyphenyl) -4,5-diphenylimidazole dimer and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- 2,4,5-triarylimidazole dimer such as 4,5-diphenylimidazole dimer; Coumarin-based compounds, oxazole-based compounds, and pyrazoline-based compounds. In addition, the substituents of the aryl groups of the two 2,4,5-triarylimidazoles may provide identical and symmetrical compounds, or may provide different, asymmetric compounds. In addition, a thioxanthone compound and a tertiary amine compound may be combined, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid. These may be used alone or in combination of two or more.

The content of the component (C) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B) Do. When the content of the component (C) is within this range, the sensitivity of the photosensitive resin composition and the photocurability of the interior are better.

≪ Other components >

The photosensitive resin composition of the present embodiment may contain dyes such as malachite green, victoria pure blue, brilliant green and methyl violet, if necessary; Photochromic agents such as leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, o-chloroaniline, and tribromomethylsulfone; Anti-colorant; a plasticizer such as p-toluenesulfonamide; Pigments; Fillers; Defoamer; Flame retardant; An adhesion imparting agent; Leveling agents; Release promoter; Antioxidants; Spices; An imaging agent; A thermal crosslinking agent and the like in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the total amount of the component (A) and the component (B). These may be used alone or in combination of two or more.

(Solution of photosensitive resin composition)

The photosensitive resin composition of the present embodiment may be dissolved in an organic solvent to be used as a solution (coating liquid) having a solid content of about 30 to 60% by mass. Examples of the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether or mixed solvents thereof.

By applying the above-mentioned coating liquid on the surface of a metal plate or the like and drying, a photosensitive resin layer formed using the photosensitive resin composition of the present embodiment can be formed. Examples of the metal plate include copper, copper-based alloys, iron-based alloys such as nickel, chromium, iron, and stainless steel, preferably copper, copper-based alloys, and iron-based alloys.

The thickness of the photosensitive resin layer varies depending on the use thereof, but it is preferably about 1 to 100 mu m in thickness after drying. The surface of the photosensitive resin layer opposite to the metal plate may be covered with a protective film. Examples of the protective film include polymer films such as polyethylene and polypropylene.

(Photosensitive element)

Fig. 1 shows an embodiment of the photosensitive element of the present invention. The photosensitive resin layer 3 formed on the support film 2 by using the photosensitive resin composition can be formed by applying the solution of the photosensitive resin composition on the support film 2 and drying the solution. The surface of the photosensitive resin layer 3 opposite to the support film 2 is then covered with a protective film 4 to form a support film 2 and a photosensitive resin layer 3 laminated on the support film 2 , And a protective film 4 laminated on the photosensitive resin layer 3 is obtained. The protective film 4 may not necessarily be provided.

As the support film 2, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. The thickness of the support film 2 (polymer film) is preferably 1 to 100 占 퐉, more preferably 1 to 50 占 퐉, and even more preferably 1 to 30 占 퐉.

If the thickness is less than 1 μm, the support film 2 tends to be torn off when the support film 2 is peeled off. When the thickness exceeds 100 μm, resolution tends not to be sufficiently obtained.

As the protective film 4, it is preferable that the adhesive force to the photosensitive resin layer 3 is smaller than the adhesive force of the support film 2 to the photosensitive resin layer 3, and a film of low fish eye is preferable. Here, "fish eye" means that foreign matter, unheated product, oxidized heat, and the like of the material are introduced into the film when the film is produced by thermally fusing the material, kneading and extruding it, and biaxially stretching or casting . In other words, the term " low fish eye " means that the foreign substance or the like in the film is small.

Specifically, as the protective film 4, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, polyethylene and the like can be used. Examples of commercially available films include polyethylene terephthalate films such as polypropylene films such as ALFAN MA-410, E-200C and Shin-Etsu Film Co., Ltd. manufactured by Oji Seishi Co., Ltd. and PS series such as PS-25 manufactured by Dejina Corporation . The protective film 4 may be the same as the support film 2.

The thickness of the protective film 4 is preferably 1 to 100 占 퐉, more preferably 1 to 50 占 퐉, and even more preferably 1 to 30 占 퐉. When the thickness is less than 1 mu m, the protective film 4 tends to be easily torn when the photosensitive resin layer 3 and the protective film 4 are laminated (laminated) on a substrate. When the thickness exceeds 100 mu m There is a tendency that it is not sufficient in terms of cheapness.

The application of the solution of the photosensitive resin composition onto the support film 2 can be carried out by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater and the like.

The drying of the solution is preferably performed at 70 to 150 DEG C for about 5 to 30 minutes. After drying, the amount of the residual organic solvent in the photosensitive resin layer is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step.

Although the thickness of the photosensitive resin layer 3 in the photosensitive element 1 varies depending on the use, it is preferably 1 to 200 占 퐉, more preferably 5 to 100 占 퐉, and more preferably 10 to 50 占 퐉, More preferable. When the thickness is less than 1 μm, it tends to be difficult to be applied industrially. On the other hand, when the thickness exceeds 200 μm, the sensitivity and the photocurability of the resist bottom portion tend not to be sufficiently obtained.

The photosensitive element 1 may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorbing layer, a gas barrier layer and the like.

The obtained photosensitive element 1 can be wound in a sheet form or in a rolled form by winding. In the case of winding in a roll, it is preferable to wind the support film 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 the end surface of the roll-shaped photosensitive element roll obtained in this way is provided with an end surface separator from the viewpoint of protecting the end surface, and it is preferable to provide a moistureproof end surface separator from the viewpoint of the edge edge fusion. As a wrapping method, it is preferable to wrap wrapped in a black sheet having low moisture permeability.

(Method of forming resist pattern)

A resist pattern can be formed using the above photosensitive resin composition. The method for forming a resist pattern according to the present embodiment includes the steps of (i) laminating a photosensitive resin layer formed using the photosensitive resin composition on a substrate, (ii) activating the photosensitive resin layer by a direct imaging method (Iii) a step of forming a resist pattern including a cured product of the photosensitive resin composition on the substrate by removing the unexposed portion of the photosensitive resin layer from the substrate by irradiating a light ray on the image side to cure the exposed portion And has a developing process.

(i) a laminating step

First, a photosensitive resin layer formed by using a photosensitive resin composition is laminated on a substrate. As the substrate, a substrate (substrate for circuit formation) having an insulating layer and a conductor layer formed on the insulating layer can be used.

The lamination of the photosensitive resin layer on the substrate can be performed by, for example, after removing the protective film 4 of the photosensitive element 1 and pressing the photosensitive resin layer 3 of the photosensitive element 1 on the substrate while heating Is done. Thereby, a laminate in which the substrate, the photosensitive resin layer 3, and the support film 2 are laminated in this order is obtained.

This lamination operation is preferably performed under reduced pressure in view of adhesion and followability. Photosensitive resin layer and / or the heating of the substrate at the time of pressing is preferably pressed at a pressure of preferably, and 0.1 to 1.0 MPa about (1 to 10 kgf / cm ² or so) is performed at a temperature of 70 to 130 ℃ but these Conditions are not particularly limited. When the photosensitive resin layer is heated to 70 to 130 占 폚, it is not necessary to preheat the substrate in advance, but the substrate may be preheated to further improve the lamination property.

(ii) exposure step

Next, exposure is performed by a direct imaging method. That is, a desired pattern is directly drawn on the photosensitive resin layer by irradiating the photosensitive resin layer 3 with an actinic ray such as a laser beam on the basis of digital data without using a mask film. At this time, when the support film 2 present on the photosensitive resin layer 3 is transparent to the active ray, the active ray can be irradiated through the support film 2, In the case of an adult, after the support film 2 is removed, the photosensitive resin layer is irradiated with an actinic ray.

Examples of the direct imaging method include laser direct imaging exposure method and DLP (Digital Light Processing) exposure method. As the light source of the active light beam, a YAG laser, a semiconductor laser, a gallium nitride blue-violet laser, or the like is preferable. However, it is preferable to irradiate effectively the ultraviolet rays such as a carbon arc and a mercury vapor arc, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, A flood bulb for a fluorescent lamp, a solar lamp, or the like.

(iii) development process

Further, by removing the unexposed portions of the photosensitive resin layer 3 from the substrate, a resist pattern containing a cured product of the photosensitive resin composition is formed on the substrate. When the support film 2 is present on the photosensitive resin layer 3, the support film 2 is removed and unexposed portions are removed (developed). The developing method includes wet phenomenon and dry phenomenon, but wet phenomenon is widely used.

In the case of wet development, a developer corresponding to the photosensitive resin composition is used for development by a known developing method. Examples of the developing method include a dipping method, a batting method, a spraying method, a brushing method, a slapping method, a scraping method, and a method using a rocking dipping method. The two or more methods may be combined to perform development.

Examples of the developer include an alkaline aqueous solution, an aqueous developer, and an organic solvent-based developer.

When used as a developer, the alkaline aqueous solution is safe, stable, and operable. Examples of the base of the alkaline aqueous solution include alkaline hydroxides such as hydroxides of lithium, sodium or potassium; Alkaline 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 sodium pyrophosphate, potassium pyrophosphate and the like are used.

The alkaline aqueous solution is preferably a lean solution of 0.1 to 5 mass% sodium carbonate, a lean solution of 0.1 to 5 mass% potassium carbonate, a lean solution of 0.1 to 5 mass% sodium hydroxide, a lean solution of sodium salt of 0.1 to 5 mass% Do. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted in accordance with the alkali developability of the photosensitive resin layer. 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 aqueous developing solution is, for example, a developer containing water or an alkaline aqueous solution and at least one organic solvent. Examples of the base of the alkaline aqueous solution include, in addition to the above-mentioned materials, borax or sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl- , 3-propanediol, 1,3-diaminopropanol-2, and morpholine.

The pH of the aqueous developing solution is preferably as small as possible within a range in which development is sufficiently carried out, and the pH is preferably 8 to 12, more preferably 9 to 10.

Examples of the organic solvent used in the aqueous developing solution include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, and the like. These may be used alone or in combination of two or more. The concentration of the organic solvent in the aqueous developing solution is preferably 2 to 90% by mass, and the temperature thereof can be adjusted in accordance with the alkali developability. A small amount of a surfactant, defoaming agent or the like may be mixed into the aqueous developing solution.

Examples of the organic solvent-based developer include organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methylisobutylketone, . Water is preferably added to these organic solvents in an amount of 1 to 20% by mass for prevention of flammability.

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

(Manufacturing method of printed wiring board)

The printed wiring board can be manufactured by etching or plating the substrate on which the resist pattern is formed by the above method. Etching or plating of the substrate is performed with respect to the conductor layer or the like of the substrate using the formed resist pattern as a mask.

As the etching solution for etching, a cupric chloride solution, a ferric chloride solution, an alkali etching solution and a hydrogen peroxide etching solution can be mentioned. Among them, the ferric chloride solution is preferably used in that the etching factor is good .

Examples of the plating method for plating include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-speed solder plating, plating with a watt bath (nickel sulfate-nickel chloride plating), nickel plating with nickel sulfamate, Gold plating such as gold plating, soft gold plating and the like.

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

Examples of the method of peeling the resist pattern include an immersion method and a spray method, and they may be used alone or in combination. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole.

<Examples>

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.

[Component (A): Binder polymer]

(Preparation of solution a)

0.8 g of azobisisobutyronitrile as a radical reaction initiator was dissolved in a mixed solution containing the polymerizable monomer (copolymerizable monomer, monomer) shown in Table 1 to prepare &quot; Solution a &quot;.

(Preparation of solution b)

(Solution b) was prepared by dissolving 1.2 g of azobisisobutyronitrile as a radical reaction initiator in 100 g of a mixed solution of 60 g of methyl cellosolve as an organic solvent and 40 g of toluene (mass ratio 3: 2).

(Radical polymerization reaction)

In a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas introducing tube, 400 g of a mixed solution of 240 g of methyl cellosolve as an organic solvent and 160 g of toluene (weight ratio 3: 2) was added. While the nitrogen gas was blown into the flask, the mixed solution was heated with stirring to raise the temperature to 80 캜.

The solution a was dropped into the mixed solution in the flask over a period of 4 hours, and then the solution in the flask was kept at 80 ° C for 2 hours with 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. Further, 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 as component (A).

Acetone was added to the binder polymer solution so that the non-volatile component (solid content) became 50% by mass. The weight average molecular weight of the binder polymer was 80,000.

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

GPC conditions

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

Column: Three of the following

      Gelpack GL-R420

      Gelpack GL-R430

      Gelpack GL-R440 (manufactured by HITACHI KASEI KOGYO CO., LTD., Trade name)

Eluent: tetrahydrofuran

Measuring temperature: 25 ° C

Flow rate: 2.05 mL / min

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

[Solution of photosensitive resin composition]

The component (B) and the component (C) shown in Table 3 were added to a solution of the obtained binder polymer (component (A)) in a blending amount (g) shown in Table 2, (G) shown in the table, a solution of the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 was prepared. The blending amount of the component (A) shown in Table 2 is the mass (solid content) of the nonvolatile component.

Details of each component shown in Table 2 and Table 3 are as follows.

(Light-emitting agent)

· BMPS (trade name, manufactured by Sumitomo Seika Co., Ltd.): tribromomethylphenyl sulfone

LCV (trade name, product of Yamada Chemical Co., Ltd.): Leuco crystal violet (dye)

MKG (trade name, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.): Malachite green

(Component (B): photopolymerizable compound)

(1) The compound represented by the formula (I)

(B-1)

9G (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

Polyethylene glycol # 400 dimethacrylate

In the formula (I), R ¹ and R ² are methyl groups, n = 9

(B-2)

14G (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

Polyethylene glycol # 600 dimethacrylate

In the formula (I), R ¹ and R ² represent a methyl group, n = 14

(B-3)

23G (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

Polyethylene glycol # 1000 dimethacrylate

In the formula (I), R ¹ and R ² represent a methyl group, n = 23

(2) bisphenol A di (meth) acrylate compound (B1)

(B-4)

FA-321M (trade name, manufactured by Hitachi Chemical Industry Co., Ltd.)

2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane

(3) a compound having one ethylenic unsaturated bond (the above-mentioned (B2))

(B-5)

FA-314A (trade name, manufactured by Hitachi Chemical Industry Co., Ltd.)

Nonylphenoxy tetraethylene glycol acrylate (the average value of the total number of oxyethylene groups is 4)

(B-6)

FA-318A (trade name, manufactured by Hitachi Chemical Industry Co., Ltd.)

Nonylphenoxy octaethylene glycol acrylate (the average value of the total number of oxyethylene groups is 8)

(B-7)

FA-MECH (trade name, manufactured by Hitachi Chemical Industry Co., Ltd.)

? -chloro-? -hydroxypropyl-? '- methacryloyloxyethyl-o-phthalate

(4) urethane monomer (above (B5))

(B-8)

UA-13 (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

EO, PO modified urethane dimethacrylate

(B-9)

UA-21 (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

Tris ((meth) acryloxytetraethylene glycol isocyanate) Hexamethylene isocyanurate

(Component (C): photopolymerization initiator)

(C-1)

N-1717 (trade name, manufactured by Adeka Co., Ltd.)

1,7-bis (9-acridinyl) heptane

The compound represented by the formula (II) (R ³ is an alkylene group having 7 carbon atoms)

(C-2)

9-PA (trade name, manufactured by Shin-Nittsu Chemical Co., Ltd.): 9-phenylacridine

The compound represented by the formula (III) (R ⁴ is a phenyl group)

(C-3)

TR-PAD103 (trade name, manufactured by Sangju Strong Electronics Co., Ltd.)

9- (3-methylphenyl) acridine

The compound represented by the formula (III) (wherein R ⁴ is an m-methylphenyl group)

(C-4)

B-CIM (trade name, manufactured by Hampford)

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole

(C-5)

9,10-dibutoxyanthracene

[Photosensitive element]

The solutions of the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were uniformly coated on a polyethylene terephthalate film (trade name: &quot; G2-16 &quot;, trade name, manufactured by DAICHE Co., Ltd.) And dried in a hot air convection type dryer at 100 캜 for 10 minutes to form a photosensitive resin layer having a film thickness of 38 탆 after drying. (Protective film), each of the photosensitive resin layers formed thereon, and a protective film (trade name &quot; NF-13 &quot;, manufactured by Tama Poly The photosensitive elements of Examples 1 to 10 and Comparative Examples 1 to 4, including the protective film formed thereon, were obtained.

[Laminated Substrate]

The copper surface of a 1.6 mm thick copper-plated laminated board (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) containing a glass epoxy material and a copper foil (thickness 35 μm) (Manufactured by Sankei Co., Ltd.) having a brush of a comparative size, washed with water, and then dried in an air flow. After the copper clad laminate (hereinafter referred to as "substrate") was heated and heated to 80 ° C., the photosensitive elements of Examples 1 to 10 and Comparative Examples 1 to 4 were laminated (laminated) on the copper surfaces on both sides of the substrate . The laminate was heated at a rate of 1.5 m / min by using a heat roll at 110 캜 so that the photosensitive resin layer of each photosensitive element adhered to each copper surface of the substrate while removing the protective film.

[Evaluation test 1: Examples 1 to 10 and Comparative Examples 1 to 4]

(Sensitivity)

The resultant laminated substrate was allowed to cool, and a phototool having a step tablet was brought into close contact with the polyethylene terephthalate film (supporting film) on the surface of the laminated substrate at 23 占 폚. As the step tablet, a 41 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 used. The photosensitive resin layer was exposed through the phototool having the step tablet and the polyethylene terephthalate film. The exposure was carried out at an exposure dose of 20 mJ / cm ² using an exposure machine (trade name "Paragon-9000 m", manufactured by Nippon Orbotech Co., Ltd.) using a semiconductor excited solid state laser as a light source.

After exposure, the polyethylene terephthalate film was peeled from the laminated substrate to expose the photosensitive resin layer. The unexposed portion was removed by spraying (developing) a 1.0 mass% sodium carbonate aqueous solution to the exposed photosensitive resin layer at 30 캜 for 50 seconds. Thus, a cured film containing a cured product of the photosensitive resin composition was formed on the copper surface of the laminated substrate. The sensitivity (light sensitivity) of the photosensitive resin compositions and photosensitive elements of Examples 1 to 10 and Comparative Examples 1 to 4 was evaluated by measuring the number of stages of the step tablets of the obtained cured film. The higher the number of steps of the step tablet, the higher the sensitivity. The results are shown in Table 4.

(Adhesion)

A wiring pattern having a line width / space width of 5/400 to 200/400 (unit: μm) was drawn on the photosensitive resin layer of the above-mentioned laminated board by a direct drawing method using an exposure machine using the laser as a light source. The exposure was performed with an energy amount such that the remaining step number after development of the Hitachi 41-step tablet was 17.0. After exposure, the same development processing as that of the sensitivity evaluation was performed.

The adhesion was evaluated by the minimum line width of the wiring pattern in the case where the line portion (exposed portion) was formed without occurrence of meandering or peeling. The smaller the minimum value, the better the adhesion. The results are shown in Table 4.

(resolution)

A wiring pattern having a line width / space width of 400/5 to 400/200 (unit: μm) was drawn on the photosensitive resin layer of the laminated substrate by a direct drawing method using an exposure machine using the laser as a light source. The exposure was performed with an energy amount such that the remaining step number after development of the Hitachi 41-step tablet was 17.0. After exposure, the same development processing as that of the sensitivity evaluation was performed.

The resolution was evaluated by the minimum value of the space width of the wiring pattern when the space portion (unexposed portion) was removed neatly. The smaller the minimum value, the better the resolution. The results are shown in Table 4.

(Peelability)

A pattern of 60 mm x 45 mm was drawn on the photosensitive resin layer of the laminated substrate by a direct drawing method using an exposure machine using the laser as a light source. The exposure was performed with an energy amount such that the remaining step number after development of the Hitachi 41-step tablet was 17.0. After exposure, the same development processing as that for the evaluation of the sensitivity was carried out to obtain a test piece on which a cured film of 60 mm x 45 mm was formed.

The test piece was allowed to stand at room temperature for one week and then immersed (dipped) in a 3 mass% sodium hydroxide aqueous solution (exfoliating solution) at 50 캜 and stirred by an agitator. The peeling property was evaluated by measuring the time (peeling time (sec)) from the start of stirring until the cured film was completely peeled off from the substrate. The shorter the peeling time, the better the peeling property. The results are shown in Table 4.

(Tent reliability)

Circular holes and three consecutive holes having a diameter of 4 to 6 mm in diameter were produced in a die cutter in the above-mentioned copper clad laminate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) burr were removed using a polishing machine having a brush equivalent to # 600 (manufactured by Sankei Kogyo Co., Ltd.) to obtain a substrate for measuring the number of hole tears shown in Fig. The substrate for measuring the number of hole tears thus obtained was heated to 80 DEG C and the photosensitive elements of Examples 1 to 10 and Comparative Examples 1 to 4 were laminated on the copper surface at 120 DEG C and 0.4 MPa. The laminate was made such that the photosensitive resin layer of the photosensitive element adhered to the copper surface of the substrate for measuring the number of hole tears while removing the protective film. After the laminating, the substrate for measuring the number of hole tears was cooled, and when the temperature of the substrate for measuring the number of hole tears reached 23 占 폚, the surface of the polyethylene terephthalate film (support film) , And exposure was performed with an energy amount such that the remaining step number after development of the Hitachi 41-step tablet was 17.0 (direct drawing method). After exposure, the film was allowed to stand at room temperature for 15 minutes. Thereafter, the polyethylene terephthalate film was peeled off from the substrate for measuring the number of hole tears. After 50 seconds of the development treatment, the number of hole tears of three continuous holes was measured and evaluated as a release tent tearing rate , And this was defined as the tent reliability (%). The smaller this number, the higher the tent reliability. The results are shown in Table 4.

As is apparent from Table 4, the photosensitive resin compositions of Examples 1 to 10 exhibited photosensitivity of Comparative Examples 1 to 4 which did not contain the compounds (B-1 to B-3) represented by the formula (I) The sensitivity and the tent reliability were superior to those of the resin composition. In particular, the tent reliability of Comparative Examples 1 to 4 was 12 to 23%, while the values of Examples 1 to 10 were significantly lowered to 2 to 6%. Thus, the photosensitive resin composition of the present invention has excellent tent reliability It became clear.

[Evaluation test 2: Reference examples 1 to 2]

(Reference Example 1)

The sensitivity, adhesion, resolution, peelability and tent reliability were evaluated by the same procedure as in Example 1, except that the exposure conditions were changed as follows using the photosensitive resin composition of Example 1. The results are shown in Table 5.

Exposure conditions

   Exposure machine: HMW-201GX (trade name, manufactured by Oak)

   Light source: High pressure mercury lamp

Exposure dose in sensitivity evaluation: 40 mJ / cm ²

   Exposure dose in evaluation other than sensitivity: The amount of energy at which the remaining step number after development of the Hitachi 41-step tablet is 23.0

Exposure method: mask exposure method

(Reference Example 2)

The sensitivity, the adhesion, the resolution, the peelability and the reliability of the tent were evaluated in the same manner as in Comparative Example 1, except that the photosensitive resin composition of Comparative Example 1 was used and the exposure conditions were changed to the same exposure conditions (mask exposure method) . The results are shown in Table 5.

As shown in Table 5, sufficient tent reliability was not obtained in Reference Example 1 in which exposure was performed by the conventional mask exposure method using the photosensitive resin composition of Example 1. On the other hand, as shown in Table 4, excellent tent reliability was obtained in Example 1 in which exposure was performed by a direct drawing method using a laser as a light source using a photosensitive resin composition having the same composition.

Further, as shown in Table 5, sufficient sensitivity and tent reliability were obtained in Reference Example 2 in which exposure was performed by the conventional mask exposure method using the photosensitive resin composition of Comparative Example 1. [ On the other hand, as shown in Table 4, in Comparative Example 1 in which the photosensitive resin composition of the same composition was used for exposure by the direct drawing method using the laser as the light source, neither sufficient sensitivity nor tent reliability was obtained .

By incorporating the above results, the photosensitive resin composition of the comparative example which does not contain the compound represented by the formula (I) as the component (B) has satisfactory sensitivity and tent reliability when exposed by the conventional mask exposure method, , The photosensitive resin composition of the present invention containing the compound represented by the formula (I) is not exposed to light by the conventional mask exposure method, while the photosensitive resin composition containing the compound represented by the formula , It has become clear that the tent reliability is superior to the comparative example in the case of exposure by the direct imaging method.

&Lt; Industrial applicability >

The photosensitive resin composition and the photosensitive element of the present invention have excellent tent reliability when exposed by the direct drawing method, and enable high-precision resist pattern formation and production of a printed wiring board.

1: photosensitive element
2: Support film
3: Photosensitive resin layer
4: Protective film

Claims (7)

(A) a binder polymer, (B) a photopolymerizable compound and (C) a photopolymerization initiator, wherein the photopolymerizable compound (A)
Wherein the photopolymerizable compound (B) comprises a compound represented by the following formula (I)
Wherein the photopolymerization initiator (C) comprises a compound represented by the following formula (III) and / or a compound represented by the following formula (IV)
Wherein the content of the compound represented by the formula (I) is 20 to 50% by mass based on the total mass of the photopolymerizable compound (B).

(Wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n represents an integer of 0 to 50)

(Wherein R ⁵ represents an alkylene group, an oxydialkylene group or a thioalkylene group having 2 to 20 carbon atoms)

(Wherein R ⁶ represents a monovalent aromatic group which may have a substituent) The photosensitive resin composition according to claim 1, wherein the (B) photopolymerizable compound further comprises a compound represented by the following formula (II).

(Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrocarbon group having 9 carbon atoms, and m represents an integer of 0 to 20) The photosensitive resin composition according to claim 1 or 2, wherein n in the compound represented by the formula (I) is an integer of 4 to 25. The photosensitive resin composition according to claim 2, wherein m in the compound represented by the formula (II) is an integer of 4 to 8. A photosensitive element comprising a support film and a photosensitive resin layer formed using the photosensitive resin composition according to claim 1 or 2 formed on the support film. A lamination step of laminating a photosensitive resin layer formed using the photosensitive resin composition according to claim 1 or 2 on a substrate;
An exposure step of irradiating the photosensitive resin layer with an actinic ray in a picture image by a direct imaging method to cure the exposed part,
And removing the unexposed portions of the photosensitive resin layer from the substrate to form a resist pattern including a cured product of the photosensitive resin composition on the substrate. A method for producing a printed wiring board, which comprises etching or plating a substrate on which a resist pattern is formed by the method according to claim 6.

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