TWI479261B - A photosensitive resin composition and a photosensitive member using the same, a method of forming a photoresist pattern, and a method of manufacturing the printed circuit board - Google Patents

Description

Photosensitive resin composition, photosensitive element using the same, method for forming photoresist pattern, and method for producing printed circuit board

The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for forming a photoresist pattern, and a method for producing a printed wiring board.

In the field of manufacturing printed circuit boards, a photosensitive resin composition or a photosensitive element (laminate) is widely used as a photoresist material for etching or plating.

The printed circuit board can be manufactured, for example, as follows. First, a photosensitive resin composition layer of a photosensitive element is laminated on a circuit formation substrate. Next, the predetermined portion of the photosensitive resin composition layer is irradiated with active light, and the predetermined portion is exposed and hardened. Thereafter, after the support film is removed by peeling off, a portion other than the predetermined portion (unexposed or unhardened portion) is removed (developed) from the substrate to form a cured product of the photosensitive resin composition on the substrate. The light resistance pattern. The resulting photoresist pattern is subjected to an etching treatment or a plating treatment to form a circuit on the substrate, and finally the photoresist is peeled off to produce a printed circuit board.

The etching treatment is a method in which the conductor layer of the circuit-forming substrate which is not covered by the photoresist pattern is removed by etching, and the photoresist is removed. On the other hand, the plating treatment is performed by performing a plating treatment such as copper or solder on the conductor layer of the circuit-forming substrate which is not covered by the photoresist pattern, and then removing the photoresist and performing the photoresist-coated metal surface. Soft etching method.

As a method of the above exposure, a mercury lamp has been used as a light source in the past, and a method of exposing it by a photomask is used. In addition, in recent years, a direct drawing exposure method in which a digital data of a pattern such as DLP (Digital Light Processing) or LDI (Laser Direct Imaging) is directly drawn on a photosensitive resin composition layer has been proposed (for example, refer to the non-patent literature). 1). Since the direct drawing exposure method can more accurately position the film than the exposure method through the photomask, and can obtain a high-definition pattern, it can be applied to the fabrication of a high-density package substrate.

In the exposure step, in order to increase production efficiency, it is necessary to shorten the exposure time as much as possible. However, in the direct drawing exposure method described above, since the light source uses monochromatic light such as laser light, the light is irradiated while scanning the substrate, which tends to require more exposure time than the exposure method in which the photomask is pasted. Therefore, the sensitivity of the photosensitive resin composition must be further improved as compared with the past.

On the other hand, with the increase in density of printed circuit boards in recent years, demands for high resolution and high adhesion have been increasing for photosensitive resin compositions. In particular, in the production of a package substrate, it is expected that a photosensitive resin composition having a photoresist pattern having a line width/pitch width (L/S) of 10/10 (unit: μm) or less can be formed.

Further, in the high-density package substrate, since the width between the circuits is narrow, it is important that the shape of the photoresist is excellent. When the cross-sectional shape of the photoresist is trapezoidal or inverted trapezoidal, or the photoresist has a bottom edge folded, the circuit formed by the etching treatment or the plating treatment may have a possibility of short circuit or disconnection, and thus is not good. The shape of the photoresist is rectangular and it is preferred that the bottom side is not folded.

Moreover, for the photosensitive resin composition, it is required to be peeled after hardening. Excellent sex. That is, by shortening the peeling time of the photoresist, the production efficiency of the peeling step can be improved, and by reducing the size of the peeling sheet of the photoresist, the peeling sheet can be prevented from adhering to the circuit board again, and the productivity can be improved.

In Patent Document 1, a photosensitive resin composition which is excellent in sensitivity to the direct drawing exposure method, and a photosensitive resin composition using a specific binder polymer or a sensitizing dye, has been disclosed.

Patent Document 2 discloses a photosensitive resin composition in which a crosslinking property is increased by introducing a polyfunctional acrylate compound into a substrate.

Patent Document 3 discloses that a photosensitive resin composition using a polymerization inhibiting agent such as catechol or hydroquinone is used to improve the contrast (imaging property) between the exposed portion and the unexposed portion.

(prior technical literature) [Patent Literature]

Patent Document 1: JP-A-2005-122123

Patent Document 2: JP-A-2003-215799

Patent Document 3: JP-A-2000-162767

[Non-patent literature]

Non-Patent Document 1: "Electronic Mounting Technology", June 2002 issue, p. 74~79

In the photosensitive resin composition, it is required to improve various characteristics such as sensitivity, resolution, adhesion, photoresist shape, and peeling property after hardening in a well-balanced manner.

However, the photosensitive resin composition of Patent Document 1 is excellent in sensitivity or peeling property, but is not necessarily sufficient for resolution and adhesion.

The photosensitive resin composition of the patent document 2 has favorable adhesiveness, but conversely, it is not sufficient for peeling characteristics, and it is difficult for the cured product to peel off from the substrate.

The photosensitive resin composition of Patent Document 3 is excellent in resolution, adhesion, and image formation, but the sensitivity is not sufficient, and it is necessary to use a direct exposure time for a direct exposure method.

As described above, in the conventional photosensitive resin composition, it is impossible to balance the characteristics required for the photosensitive resin composition after the formation of the photoresist pattern to a level that is sufficiently satisfactory.

The present invention provides a photosensitive resin composition which is excellent in sensitivity, resolution, adhesion, photoresist shape, and peeling property after curing, and a photosensitive element using the same, a method of forming a photoresist pattern, and printing The manufacturing method of the circuit board is for the purpose.

In order to achieve the above object, the present invention provides a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a sensitizing dye, wherein A) Adhesive polymerization The compound has a structural unit based on (meth)acrylic acid, a structural unit based on benzyl (meth)acrylate or a benzyl (meth)acrylate derivative, and (B) the photopolymerizable compound contains one ethylene. The compound of the unsaturated bond, (D) the sensitizing dye contains the compound represented by the following general formula (1).

In the formula (1), R ¹ and R ² each independently represent a substituted or unsubstituted phenyl, thienyl or furyl group, and R ³ represents an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. Or an alkyl ester group having 1 to 10 carbon atoms, a and b each independently represent an integer of 0 to 2, m represents an integer of 0 to 5, and m represents 2 to 5, and the plural R ³ may be the same or phase different. ]

In other words, the photosensitive resin composition of the present invention has the above-described configuration, and is excellent in sensitivity, resolution, adhesion, resist shape, and peeling property after curing. The present inventors presumed that by using a (A) binder polymer having a specific structural unit, the resolution and the peeling property after hardening can be improved; by using a compound containing a compound having one ethylenic unsaturated bond (B) The photopolymerizable compound can improve the resolution, the adhesion, the resist shape, and the peeling property after curing in a balanced manner; and the sensitivity can be improved by using the (D) sensitizing dye containing the compound of the above general formula; Combine these to get full A photosensitive resin composition having all of the above characteristics.

In the photosensitive resin composition of the present invention, the (B) photopolymerizable compound may contain a compound represented by the following general formula (2) or the following general formula (3).

In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom, a methyl group or a halogenated methyl group, and R ⁶ represents an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. A hydroxyl group or a halogen atom, n represents an integer of 0 to 4, p represents an integer of 1 to 4, and n represents 2 to 4, and R ^{6 in the} plural may be the same or different from each other. ]

In the formula (3), R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group or a halogen atom, and r represents an integer of 1 to 12 , k represents an integer from 0 to 5, and k represents 2 to 5, and R ^{8 in} which the plural exists may be the same or different from each other. ]

Thereby, the resolution, the adhesion, the photoresist shape, and the peeling property after curing of the photosensitive resin composition can be improved in a well-balanced manner.

Further, the (B) photopolymerizable compound may further contain bisphenol A-based di Methyl) acrylate compound. Thereby, the alkali developability, the resolving property, and the peeling property after hardening can be further improved.

Further, the (B) photopolymerizable compound may further contain a trimethylolpropane tri(meth)acrylate compound having a (poly)oxyethylidene chain or a (poly)oxypropanylene chain. Thereby, the alkali developability, the reproducibility, the adhesion, and the peeling property after hardening of the photosensitive resin composition can be further improved.

Further, the (B) photopolymerizable compound may further contain a polyalkylene glycol di(meth)acrylate having a (poly)oxyethylidene chain and a (poly)oxypropanylene chain. Thereby, the flexibility of the cured product (cured film) of the photosensitive resin composition can be improved.

In the photosensitive resin composition of the present invention, when the (A) binder polymer further has a structural unit based on an alkyl (meth)acrylate, the alkali developability and the peeling property after curing can be further improved. Further, the (A) binder polymer may further have a structural unit based on styrene or a styrene derivative, whereby the resolution and adhesion of the photosensitive resin composition can be further improved.

Further, the acid value of the (A) binder polymer is preferably from 100 to 250 mgKOH/g. Thereby, the alkali developability of the photosensitive resin composition can be further improved.

Further, the weight average molecular weight of the (A) binder polymer is preferably from 10,000 to 100,000. Thereby, the alkali developability and adhesion of the photosensitive resin composition can be improved more satisfactorily.

The photosensitive resin composition of the present invention may further contain (E) an amine compound from the viewpoint of further improving the sensitivity of the photosensitive resin composition.

Further, the present invention provides a photosensitive element comprising a support film and a photosensitive resin composition layer formed of the photosensitive resin composition formed on the support film. By using the photosensitive element of the present invention, a photoresist pattern having excellent resolution, adhesion, photoresist shape, and peeling property after curing can be formed with good sensitivity and efficiency.

The present invention further provides a method for forming a photoresist pattern comprising: a lamination step of laminating a photosensitive resin composition layer formed of the photosensitive resin composition on a substrate; and a photosensitive resin composition layer An exposure step of irradiating the predetermined portion with the active light to expose the predetermined portion to be cured; and removing a portion other than the predetermined portion of the photosensitive resin composition layer from the substrate to form a photosensitive resin on the substrate The imaging step of the photoresist pattern formed by the hardened material. Thereby, the photoresist pattern which is excellent in resolution, adhesion, photoresist shape, and peeling property after hardening can be formed with good sensitivity and efficiency.

The wavelength of the above active light is preferably 390 to 420 nm. Thereby, it is possible to form a photoresist pattern which is more excellent in resolution, adhesion, and photoresist shape with better sensitivity and efficiency.

Moreover, the present invention provides a method of manufacturing a printed circuit board comprising the step of etching or plating a substrate on which a photoresist pattern is formed by the above-described photoresist pattern forming method. According to this manufacturing method, a printed circuit board having a high-density wiring such as a high-density package substrate and a tantalum wafer rewiring can be manufactured with high precision and efficiency.

According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in sensitivity, resolution, adhesion, photoresist shape, and peeling property after hardening, and a photosensitive element and a resist pattern using the composition. A method of forming and a method of manufacturing a printed circuit board.

(Formation of implementing the invention)

The best mode for carrying out the invention will be described in detail below. However, the present invention is not limited to the following embodiments. Further, in the present specification, (meth)acrylic acid means acrylic acid or methacrylic acid, so-called (meth)acrylic acid ester means acrylate or methacrylate, and so-called (meth)acrylylene group means acrylonitrile or methyl group. Acryl sulfhydryl. Further, the (poly)oxyethyl group represents an oxygen-extended ethyl group or a polyoxyalkylene group, and the (poly)oxy-propion group represents an oxygen-extended propyl group or a polyoxy-propion-propylene group.

<Photosensitive resin composition>

The photosensitive resin composition of the present embodiment contains (A) a binder polymer (hereinafter also referred to as "(A) component)", and (B) a photopolymerizable compound (hereinafter also referred to as "(B) component)"), (C) Photopolymerization initiator (hereinafter also referred to as "(C) component") and (D) sensitizing dye (hereinafter also referred to as "(D) component").

Hereinafter, each component constituting the photosensitive resin composition of the present invention will be described in more detail.

[(A) component: binder polymer]

The binder polymer of the component (A) has a structural unit based on (meth)acrylic acid and a structural unit based on benzyl (meth)acrylate or a benzylmethyl (meth)acrylate derivative. Such a binder polymer can be produced, for example, by radical polymerization of (meth)acrylic acid, with benzyl (meth)acrylate or a benzyl (meth)acrylate derivative. Further, other polymerizable monomers may be copolymerized as necessary.

The benzyl (meth)acrylate derivative may, for example, be a benzyl group of benzyl (meth)acrylate and/or a phenyl group having a substituent.

The content of the structural unit based on the benzyl (meth)acrylate or the benzyl (meth)acrylate derivative in the component (A) is determined by the resolution and the peelability after curing. A) The total mass of the component is preferably 5 to 65 mass%, more preferably 10 to 55 mass%, and still more preferably 20 to 45 mass%. When the content is less than 5% by mass, sufficient resolution is not obtained. When the content exceeds 65% by mass, the release sheet tends to be large and the peeling time tends to be long.

Examples of the polymerizable monomer other than (meth)acrylic acid, benzyl (meth)acrylate or benzyl (meth)acrylate derivative include styrene, vinyl toluene, and α-methylbenzene. a polymerizable styrene derivative in which an ethylene or the like is substituted in an α-position or an aromatic ring; an acrylamide such as diacetone acrylamide; a vinyl alcohol ester such as vinyl n-butyl ether; or an alkyl (meth)acrylate Ester, cycloalkyl (meth) acrylate, decyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylate Mercaptoester, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylamino(meth)acrylate Ethyl ester, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate (meth) acrylate; α-bromo (meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl (meth)acrylic acid, β-styryl (meth)acrylic acid, etc. (methyl Acrylic acid derivatives; maleic acid derivatives such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate; fumaric acid, cinnamic acid, α- Organic acid derivatives such as cyano cinnamic acid, itaconic acid, crotonic acid, and propiolic acid, and acrylonitrile. These can be used individually or in combination of 2 or more types.

(A) The binder polymer preferably contains a structural unit based on an alkyl (meth)acrylate from the viewpoint of improving alkali developability and peeling properties. (A) When the binder polymer contains a structural unit based on an alkyl (meth)acrylate, the content is based on the total mass of the component (A) from the viewpoint of alkali developability and peeling characteristics. ~50% by mass is preferred. In addition, the content is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. Further, from the viewpoint of further improving the resolution and adhesion after alkali development, the content is preferably 50% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass or less. .

The alkyl (meth)acrylate may, for example, be a compound represented by the following general formula (4). In the formula (4), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ¹⁰ in the formula (4) 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 and a decyl group. , mercapto, undecyl, dodecyl and their structural isomers. From the viewpoint of further improving the peeling property, the alkyl group is preferably a carbon number of 4 or less.

Examples of the compound represented by the above general formula (4) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Ester, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( Methyl) decyl acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate. These can be used individually or in combination of 2 or more types.

(A) The binder polymer may further contain a structural unit based on styrene or a derivative thereof from the viewpoint of improving the resolution, adhesion, and peeling properties in a well-balanced manner. (A) When the binder polymer has a structural unit based on styrene or a derivative thereof, the content is based on the total mass of the component (A) from the viewpoints of resolution, adhesion, and peeling characteristics. It is preferably 5 to 65 mass%. In addition, the content is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and 20% by mass, from the viewpoint of further improving the resolution and the adhesion. The above is especially good It is excellent in 30% by mass or more. In addition, the content is preferably 65% by mass or less, more preferably 60% by mass or less, more preferably 55% by mass or less, and particularly preferably 50% by mass or less.

(A) The acid value of the binder polymer is preferably from 100 to 250 mgKOH/g. Further, from the viewpoint of improving the alkali developability, the acid value of the binder polymer is preferably 100 mgKOH/g or more, more preferably 120 mgKOH/g or more, still more preferably 140 mgKOH/g or more, and 150 mgKOH. Above /g is especially good. Further, the acid value of the binder polymer is preferably 250 mgKOH/g or less, more preferably 230 mgKOH/g or less, and 220 mgKOH/g or less, from the viewpoint of excellent liquid resistance (adhesion). Preferably, it is particularly preferably 210 mgKOH/g or less. Further, in the case of performing solvent development, it is preferred to prepare a polymerizable monomer having a carboxyl group such as (meth)acrylic acid in a small amount.

(A) When the weight average molecular weight (Mw) of the binder polymer is measured by a gel permeation chromatography (GPC) (converted using a standard polystyrene as a calibration curve), it is preferably 10,000 to 100,000. In addition, the Mw of the binder polymer is preferably 10,000 or more, and more preferably 20,000 or more, and 25,000, from the viewpoint of improving the liquid resistance (adhesion) of the cured product of the photosensitive resin composition. The above is better. Further, from the viewpoint of excellent alkali developability, the Mw of the binder polymer is preferably 100,000 or less, more preferably 80,000 or less, and still more preferably 70,000 or less.

(A) The dispersity of the binder polymer (Mw/Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. Excellent view of adhesion and resolution In view of the above, it is preferably 3.0 or less, and preferably 2.0 or less.

(A) The binder polymer may have a characteristic group having sensitivity to light having a wavelength in the range of 350 to 440 nm in the molecule as necessary.

(A) Adhesive Polymer One type of binder polymer may be used alone, or two or more types of binder polymers may be used in combination. The binder polymer in the case of using two or more kinds of the binder polymer may be, for example, two or more kinds of different copolymerized components (including a different monomer unit as a copolymerization component), a binder polymer, and a different weight. Two or more kinds of binder polymers having an average molecular weight and two or more kinds of binder polymers having different dispersities. Further, a polymer having a multimodal molecular weight distribution described in JP-A-H11-327137 can also be used.

The content of the component (A) (the binder polymer) is preferably 30 to 70 parts by mass based on 100 parts by mass of the total of the components (A) and (B). From the viewpoint of imparting film properties, it is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, and still more preferably 40 parts by mass or more. In addition, from the viewpoint of excellent sensitivity and resolution, it is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, and still more preferably 60 parts by mass or less.

[(B) component: photopolymerizable compound]

The photopolymerization of the component (B) into a compound contains a compound having one ethylenically unsaturated bond in the molecule. From the viewpoint of improving the resolution, the adhesion, the resist shape, and the peeling property after hardening, the content is 1 to 30 in terms of 100 parts by mass of the entire mass of the component (B). The mass fraction is preferably as good as 3 to 25 parts by mass, preferably 5 to 20 The mass parts are better.

Examples of the photopolymerizable compound having one ethylenically unsaturated bond in the molecule include a compound represented by the following general formula (2) or the following general formula (3), and the aforementioned (meth)acrylic acid. The alkyl ester is preferably a compound represented by the following general formula (2) or the following general formula (3) from the viewpoint of further improving the effects of the present invention.

In the formula (2), R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents a hydrogen atom, a methyl group or a halogenated methyl group, preferably a methyl group or a halogenated methyl group, more preferably a halogenated methyl group. The halogenated methyl group may, for example, be a methyl group which may be substituted by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a ruthenium atom. R ⁶ represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group or a halogen atom, and the above alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms may be linear. It can also be branched. Further, p represents an integer of 1 to 4, and preferably an integer of 1 to 3. n represents an integer from 0 to 4, and n represents 2 to 4, and R ^{6 in the} plural may be the same or different.

Examples of the compound represented by the above formula (2) include γ -chloro-β-hydroxypropyl-β'-(meth)acryloxyethyl-phthalate and β-hydroxyl group. Ethyl-β'-(meth)acrylomethoxyethyl-phthalate, and β-hydroxypropyl-β'-(meth)acryloxyethyl-phthalic acid The ester is preferably γ -chloro-β-hydroxypropyl-β'-(meth)acryloxyethyl-phthalate. γ -Chloro-β-hydroxypropyl-β'-methacryloxymethoxyethyl-phthalate is commercially available as FA-MECH (trade name, manufactured by Hitachi Chemical Co., Ltd.). These can be used individually or in combination of 2 or more types.

In the above general formula (3), R ⁷ represents a hydrogen atom or a methyl group. R ⁸ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group or a halogen atom, preferably an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 6 to 12 carbon atoms. good. r represents an integer of 1 to 12, preferably an integer of 3 to 10, and more preferably an integer of 4 to 8. k represents an integer from 0 to 5, and k represents 2 to 5, and R ^{8 in the} plural may be the same or different.

Examples of the compound represented by the above general formula (3) include mercaptophenoxytrixenyl ethoxyacrylate, mercaptophenoxytetraethylene ethoxyacrylate, and mercaptophenoxy quinone Oxy acrylate, nonylphenoxy hexaethoxy acrylate, decyl phenoxy heptaethylene ethoxy acrylate, nonyl phenoxy octaethoxy acrylate, decyl phenoxy IX Ethoxy acrylate, nonylphenoxy decyl ethoxy acrylate, nonyl phenoxy eleven ethoxy acrylate. These can be used individually or in combination of 2 or more types.

Further, the component (B) is preferably a photopolymerizable compound having two or more ethylenically unsaturated bonds in the molecule, from the viewpoint of improving sensitivity, resolution, and adhesion. Examples of the photopolymerizable compound having two or more ethylenically unsaturated bonds in the molecule include a bisphenol A-based di(meth)acrylate compound and a reaction of a polyol with an α ,β-unsaturated carboxylic acid. a compound obtained by reacting a urethane monomer such as a (meth) acrylate compound having a urethane bond in a molecule, a compound containing a propylene group, and an α ,β-unsaturated carboxylic acid Compound. These can be used individually or in combination of 2 or more types.

(B) The photopolymerizable compound is preferably a bisphenol A-based di(meth)acrylate compound from the viewpoint of improving the resolution and the peeling property after curing.

Examples of the bisphenol A-based di(meth)acrylate compound include 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane, 2,2- Bis(4-((meth)propenyloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy)oxy)phenyl)propane, 2 , 2-bis(4-((meth)propenyloxypolyethoxypolypropoxy)phenyl)propane. Among them, 2,2-bis(4-((meth)acryloxycarbonylpolyethoxy)phenyl)propane is preferred from the viewpoint of further improving the resolution and the peeling property.

Examples of the 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane include 2,2-bis(4-((meth)acryloxy)oxy group. Diethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy)triethoxy)phenyl)propane, 2,2-bis(4-((methyl)) Propylene decyloxytetraethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypentaethoxy)phenyl)propane, 2,2-bis(4-( (methyl) Propylene decyloxyhexaethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxyheptaethoxy)phenyl)propane, 2,2-bis(4-( (Meth) propylene decyloxy octaethoxy) phenyl) propane, 2,2-bis(4-((methyl) propylene oxy) ethoxy) phenyl) propane, 2, 2- bis (4-((meth)propenyloxylethoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxyundecyl)phenyl)propane, 2,2-bis(4-((meth)propenyloxydodecyloxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy)tridecyloxy Phenyl)propane, 2,2-bis(4-((meth)propenyloxytetradecyloxy)phenyl)propane, 2,2-bis(4-((methyl)propene) Hexadecane ethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxyhexadecyloxy)phenyl)propane. Among them, 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane has an oxygen number of 4 to 20, preferably 8 to 15 .

Among them, 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane can be used as BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name) or FA-321M (Production by Hitachi Chemical Co., Ltd., trade name) is commercially available. 2,2-bis(4-(methacrylomethoxypentadecyl ethoxy)phenyl)propane is commercially available as BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). These can be used individually or in combination of 2 or more types.

Examples of the 2,2-bis(4-((meth)propenyloxypolypropoxy)phenyl)propane include 2,2-bis(4-((meth)acryloxy). Propoxy)phenyl)propane, 2,2-bis(4-((meth)propene oxime) Oxyl tripropoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxytetrapropoxy)phenyl)propane, 2,2-bis(4-((A) Acryloxypentapropoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxyhexapropoxy)phenyl)propane, 2,2-bis (4) -((Meth)propenyloxyheptaethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy)oxypropenyl)propane, 2,2 - bis(4-((meth)propenyloxynonylpropoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxydapoxy)phenyl)propane , 2,2-bis(4-((meth)propenyloxy eleven propoxy)phenyl)propane, 2,2-bis(4-((methyl) propylene oxy oxy 12 propylene oxide) Phenyl)propane, 2,2-bis(4-((meth)propenyloxytridecyloxy)phenyl)propane, 2,2-bis(4-((methyl)propene oxime) Ethyltetradecyloxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypentadecapropoxy)phenyl)propane, 2,2-bis(4-( (Meth)propylene decyloxyhexadecyloxy)phenyl)propane.

As 2,2-bis(4-((meth)propenyloxypolyethoxypolypropoxy)phenyl)propane, for example, 2,2-bis(4-((meth)propene) Nonyloxydiethoxyoctapropoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxytetraethoxytetrapropoxy)phenyl)propane, 2, 2-bis(4-((meth)propenyloxyhexaethoxyhexapropyloxy)phenyl)propane.

When the component (B) contains a bisphenol A-based (meth) acrylate compound, the content is preferably 20 to 80% by mass, and preferably 30 to 70% by mass based on the total mass of the component (B). .

Examples of the compound obtained by reacting a polyhydric alcohol with an α ,β-unsaturated carboxylic acid include polyethylene glycol di(meth)acrylate having a vinyl group number of 2 to 14, and a number of propylene groups of 2 ~14 polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tris(A) Acrylate (the total number of repeats of oxygen-extended ethyl group is 1 to 5), PO modified trimethylolpropane tri(meth)acrylate, EO, PO modified trimethylolpropane tri(methyl) Acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate. These can be used individually or in combination of 2 or more types. The term "EO modification" means a compound having a block structure of a (poly)oxyethyl group (a polyoxyethylated compound), and the "PO modification" means having a (poly)oxypropyl group. a compound having a block structure of a chain (a compound which is subjected to polyoxyalkylation), the so-called "EO.PO modification" means a block structure having a (poly)oxyethylidene chain and a (poly)oxypropionyl propyl chain. a compound (a compound which is subjected to polyoxyethylation and polyoxyalkylation).

Among them, tetramethylolethane triacrylate can be commercially obtained as A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name), and EO-modified trimethylolpropane trimethacrylate The ester is commercially available as TMPT21E and TMPT30E (trade name, manufactured by Hitachi Chemical Co., Ltd.).

Further, the component (B) may be contained in a viewpoint of further improving the alkali developability, the resolving property, the adhesion, and the peeling property after curing. a trimethylolpropane tri(meth) acrylate compound having a (poly)oxyethylidene chain or a (poly)oxypropyl propyl chain in the molecule, which contains a (poly)oxyethylidene chain in the molecule The trimethylolpropane tri(meth) acrylate compound is preferred. When the component (B) contains these compounds, the content is preferably 5 to 50% by mass, and preferably 10 to 40% by mass based on the total mass of the (B) photopolymerizable compound.

Further, the component (B) may contain (poly)oxyethylidene chain and (poly)oxypropanyl propyl group from the viewpoint of improving the flexibility of the cured product (cured film) of the photosensitive resin composition. Chain polyalkylene glycol di(meth)acrylate. When the component (B) contains these compounds, the content is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, based on the total mass of the (B) photopolymerizable compound.

a (poly)oxyalkylene chain as a polyalkylene glycol di(meth)acrylate having a (poly)oxyethylidene chain and a (poly)oxypropanyl chain ((poly)oxy group) Preferably, a propyl group chain or a (poly)oxyisopropion propyl chain is preferred. Further, the polyalkylene glycol di(meth)acrylate may further have a (poly)oxy-n-butyl group, a (poly)oxyisobutylene chain, a (poly)oxy-n-pentyl chain, and a (poly)oxy group. A (poly)oxyalkylene chain having a carbon number of from 4 to 6 such as a hexyl chain or a structural isomer thereof.

In the molecule of the polyalkylene glycol di(meth) acrylate, the (poly)oxyethylidene chain and the (poly)oxypropanyl propyl chain may each be present in a block form continuously or in a random manner. Further, in the (poly)oxyisoproion chain, the propyl group 2 carbon may be bonded to the oxygen atom, or the first stage carbon may be bonded to the oxygen source. child.

As the polyalkylene glycol di(meth)acrylate, a compound represented by the following general formula (5), (6) or (7) is particularly preferable. These can be used individually or in combination of 2 or more types.

In the above formulae (5), (6) and (7), R each independently represents a hydrogen atom or a methyl group, EO represents an oxygen-extended ethyl group, and PO represents an oxygen-extended propyl group. m ₁ , m ₂ , m ₃ and m ₄ represent the number of repeats of the structural unit formed by the oxygen-extended ethyl group, and n ₁ , n ₂ , n ₃ and n ₄ represent repeats of the structural unit formed by the oxygen-extended propyl group. The number, repeat total number of oxygen-extended ethyl groups m ₁ + m ₂ , m ₃ and m ₄ (average value) each independently represent an integer from 1 to 30, and the total number of repeats of the oxygen-extended propyl group n ₁ , n ₂ + n ₃ and n ₄ (average value) each independently represents an integer from 1 to 30.

In the compound of the above general formula (5), (6) or (7), the total number of repeats of the oxygen-extended ethyl group m ₁ + m ₂ , m ₃ and m ₄ is an integer of 1 to 30, wherein 1 to 10 The integer is preferably an integer of 4 to 9 and more preferably an integer of 5 to 8. The total number of repetitions of the oxygen-extended ethyl group is preferably 30 or less, preferably 10 or less, more preferably 9 or less, and 8 or less, from the viewpoints of excellent resolution, adhesion, and photoresist shape. It is especially good.

Further, the total number of repetitions of oxygen-extended propyl groups n ₁ , n ₂ + n ₃ and n ₄ is an integer of 1 to 30, wherein an integer of 5 to 20 is preferable, and an integer of 8 to 16 is preferable, and 10 to An integer of 14 is preferred. The total number of repetitions of the oxygen-extended propyl group is preferably 30 or less, more preferably 20 or less, more preferably 16 or less, and particularly preferably 14 or less from the viewpoint of improvement in resolution and reduction in soil.

The compound represented by the general formula (5) is a vinyl compound of R = methyl group, m ₁ + m ₂ = 6 (average value), and n ₁ = 12 (average value) (manufactured by Hitachi Chemical Co., Ltd.) , the product name "FA-023M") and so on. The compound represented by the general formula (6) is a vinyl compound of R = methyl group, m ₃ = 6 (average value), and n ₂ + n ₃ = 12 (average value) (manufactured by Hitachi Chemical Co., Ltd.) , the product name "FA-024M") and so on. The compound represented by the general formula (7) is a vinyl compound (manufactured by Shin-Nakamura Chemical Co., Ltd.), which is a product of R = hydrogen atom, m ₄ =1 (average value), and n ₄ = 9 (average value). Name "NK ester HEMA-9P"). These can be used individually or in combination of 2 or more types.

Examples of the (meth) acrylate compound having a urethane bond in the molecule include a (meth)acrylic monomer having a OH group at the β -position and a diisocyanate compound (isophorone diisocyanate). Addition reaction of 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc., ginseng ((meth) propylene oxime tetraethylene glycol isocyanate) Hexamethylene isocyanate, EO modified urethane di(meth) acrylate, EO, PO modified urethane di(meth) acrylate. UA-11 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name) is exemplified as the EO-modified urethane di(meth)acrylate. In addition, as EO, the PO modified urethane di(meth)acrylate is UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). These can be used individually or in combination of 2 or more types.

When the content of the component (B) (photopolymerizable compound) is 100 parts by mass based on the total amount of the component (A) and the component (B), it is preferably 30 to 70 parts by mass. The content of the component (B) is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, and more preferably 40 parts by mass or more, from the viewpoint of improving the sensitivity and the resolution. The content of the component (B) is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, and 60 parts by mass or less, from the viewpoint of imparting film properties and the shape of the photoresist after curing. good.

[(C) component: photopolymerization initiator]

As the (C) photopolymerization initiator, it is sufficient to select only the wavelength of the light used in the exposure machine and the wavelength necessary for the function of the (C) photopolymerization initiator to be used. Special restrictions. Examples of the (C) photopolymerization initiator include benzophenone and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1. An aromatic ketone such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-acetone-1; an anthracene such as an alkyl group; a benzoin such as a benzoin alkyl ether Ether compound; benzoin compound such as benzoin or alkyl benzoin; benzyl derivative such as benzyl dimethyl ketal; 2-(o-chlorophenyl)-4,5-diphenyl 2,4,5-triarylimidazole dimer such as imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer; 9-phenyl acridine, 1,7- An acridine derivative such as (9,9'-acridinyl)heptane. These can be single It can be used alone or in combination of two or more.

The content of the component (C) (photopolymerization initiator) is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B). The content of the component (C) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, more preferably 2 parts by mass or more, from the viewpoint of excellent sensitivity, resolution, or adhesion. More than 3 parts by mass is particularly good. Moreover, the content of the component (C) is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, even more preferably 6 parts by mass or less, from the viewpoint of excellent shape of the photoresist after curing. The following parts are particularly good.

[(D) component: sensitizing pigment]

The sensitizing dye of the component (D) contains the compound represented by the following general formula (1).

In the formula (1), R ¹ and R ² each independently represent a substituted or unsubstituted phenyl group, a thienyl group or a furyl group, and a substituted or unsubstituted phenyl group is preferred from the viewpoint of further improving the resolution. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl ester group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms or a carbon number. The alkoxy group of 1 to 10 is preferred, and an alkyl group having 3 to 8 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is preferred. a and b each independently represent an integer of 0-2.

R ³ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkyl ester group having 1 to 10 carbon atoms. Among them, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is preferred, and an alkyl group having 3 to 8 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is preferred. m represents an integer from 0 to 5. When m is 2 to 5, a plurality of R ^{3 's} may be the same or different from each other.

The substituent of R ¹ to R ³ is preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 10 carbon atoms from the viewpoint of further improving sensitivity and solubility in a solvent.

The alkyl group having 1 to 10 carbon atoms or the alkoxy group having 1 to 10 carbon atoms may be linear or branched. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a tertiary butyl group, an isopentyl group, and a tertiary octyl group. However, the alkyl group is not limited thereto. . Further, the sum of a and b in the general formula (1) is preferably 1 to 6, preferably 1 to 4, more preferably 1 to 3.

Examples of the compound represented by the above formula (1) include 1-(4-methoxyphenyl)-3-styryl-5-phenyl-pyrazoline and 1-phenyl-3-. (4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1,5-bis-(4-methoxyphenyl)-3-(4-methoxy Styryl)-pyrazoline, 1-(4-isopropylphenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4-isopropyl Styryl)-5-(4-isopropylphenyl)-pyrazoline, 1,5-bis-(4-isopropylphenyl)-3-(4-isopropylstyryl)- Pyrazoline, 1-(4-methoxyphenyl)-3-(4-tributyl-styryl)-5-(4-tri-butyl-phenyl)-pyrazoline, 1 -(4-tertiary butyl-phenyl)-3- (4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(4-tertiary butyl- Styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-tri-butyl-phenyl)-3-(4-isopropyl-styryl) -5-(4-isopropyl-phenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(4-isopropylstyryl)-5-(4-isopropyl Phenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline , 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3 ,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl -5-(2,6-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-di Methoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline , 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, 1-(4-methoxybenzene 3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-(4-methyl Oxyphenyl)-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-(4-methoxybenzene 3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)- 3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-( 2,3-Dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2,4 -dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, 1-(4-tri-butyl-phenyl)-3-(3,5- Dimethoxybenzene Vinyl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-(4-tributyl-phenyl)-3-(3,4-dimethoxystyrene 5-(3,4-dimethoxyphenyl)-pyrazoline, 1-(4-tributyl-phenyl)-3-(2,6-dimethoxystyryl) -5-(2,6-Dimethoxyphenyl)-pyrazoline, 1-(4-tributyl-phenyl)-3-(2,5-dimethoxystyryl) -5-(2,5-dimethoxyphenyl)-pyrazoline, 1-(4-tributyl-phenyl)-3-(2,3-dimethoxystyryl)- 5-(2,3-dimethoxyphenyl)-pyrazoline, 1-(4-tributyl-phenyl)-3-(2,4-dimethoxystyryl)-5 -(2,4-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(3,5-dimethoxystyryl)-5-( 3,5-Dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(3,4-dimethoxystyryl)-5-(3, 4-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2,6-dimethoxystyryl)-5-(2,6- Dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2,5-dimethoxystyryl)-5-(2,5-dimethyl Oxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxy benzene )-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)- Pyrazoline, 1-(4-tributyl-phenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4-tributyl-styrene 5-(4-tert-butyl-phenyl)-pyrazoline, 1,5-bis-(4-tert-butyl-phenyl)-3-(4-tertiary butyl-benzene Vinyl)-pyrazoline, 1-(4-trioctyl-phenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4-trioctyl) - styryl)-5-(4-tertiary octyl-phenyl)-pyrazoline, 1,5-bis-(4-tertiary octyl-phenyl)-3-(4-tris Xin - styryl)-pyrazoline, 1-(4-dodecyl-phenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4- Dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-dodecyl-phenyl)-3-(4-dodecane -(styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-trioctyl-phenyl)-3-(4-tributyl-benzene Vinyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-tri-butyl-phenyl)-3-(4-trioctyl-styryl) -5-(4-tertiary octyl-phenyl)-pyrazoline, 1-(4-dodecyl-phenyl)-3-(4-tributyl-styryl)-5- (4-tertiary butyl-phenyl)-pyrazoline, 1-(4-tributyl-phenyl)-3-(4-dodecyl-styryl)-5-(4- Dodecyl-phenyl)-pyrazoline, 1-(4-dodecyl-phenyl)-3-(4-trioctyl-styryl)-5-(4-tertiary octyl -Phenyl)-pyrazoline, 1-(4-trioctyl-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-benzene -Pyrazoline, 1-(2,4-dibutyl-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl) -pyrazoline, 1-phenyl-3-(3,5-di-tertiary butyl-styryl)-5-(3,5-di-three Butyl-phenyl)-pyrazoline, 1-phenyl-3-(2,6-di-tert-butyl-styryl)-5-(2,6-di-tertiary butyl-benzene -Pyrazoline, 1-phenyl-3-(2,5-di-tert-butyl-styryl)-5-(2,5-di-tertiary butyl-phenyl)-pyridyl Oxazoline, 1-phenyl-3-(2,6-di-n-butyl-styryl)-5-(2,6-di-n-butyl-phenyl)-pyrazoline, 1-( 3,4-di-tertiary butyl-phenyl)-3-styryl-5-phenyl-pyrazoline, 1-(3,5-di-tertiary butyl-phenyl)-3- Styryl-5-phenyl-pyrazoline, 1-(4-tributyl-phenyl)-3-(3,5-di-tertiary butyl-phenyl)-pyrazoline, 1 -(3,5-di-tertiary butyl-phenyl)-3-(3,5- Di-tertiary butyl-styryl)-5-(3,5-di-tri-butyl-phenyl)-pyrazoline, 1-phenyl-3-(2-thienyl)-5- (4-tertiary butylphenyl)-pyrazoline, 1-phenyl-3-(2-thienyl)vinyl-5-(2-thienyl)-pyrazoline, 1-phenyl-3 -(2-Thienyl)-5-(2-thienyl)-pyrazoline, 1-phenyl-3-(2-thienyl)-5-styyrylpyrazoline and the like. These can be used individually or in combination of 2 or more types.

Among the above compounds, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline is used from the viewpoint of improving the ease of synthesis and sensitivity. It is especially good. Further, from the viewpoint of easiness of synthesis and solubility in a solvent, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)- Pyrazolines are particularly preferred.

In the component (D), the content of the compound represented by the above formula (1) is preferably from 10 to 100% by mass based on the total mass of the component (D), from the viewpoint of excellent sensitivity and resolution. It is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.

Further, in the photosensitive resin composition of the present invention, a sensitizing dye other than the compound represented by the above general formula (1) may be added in such a manner as not to impair the effects of the present invention. Specific examples thereof include dialkylaminobenzophenones, anthraquinones, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, and benzothiazoles. , triazoles, anthracenes, triazines, thiophenes, naphthyl imines, triarylamines. These may be used alone or in combination of two or more.

The content of the component (D) is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B). Sensitivity and solution The content of the component (D) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more. The content of the component (D) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less, from the viewpoint of the excellent shape of the resist after curing.

[(E) component: amine compound]

The photosensitive resin composition of the present embodiment may contain an amine compound as the component (E) from the viewpoint of further improving the sensitivity. Examples of the (E) amine compound include bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, and reduced crystal violet. These can be used individually or in combination of 2 or more types.

When the photosensitive resin composition contains the component (E) (amine compound), the content is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B). The content of the component (E) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, from the viewpoint of excellent sensitivity. After the formation of the film, in order to prevent the excessive (E) amine compound from being precipitated as a foreign matter, the content of the component (D) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less. good.

[Other ingredients]

The photosensitive resin composition of the present embodiment may contain, as necessary, a photopolymerizable compound having at least one cationically polymerizable cyclic ether group in the molecule. a substance (such as a propylene oxide compound), a cationic polymerization initiator, a dye such as malachite green, a photochromic agent such as tribromophenylphosphonium or reduced crystal violet, a thermochromic preventive agent, or a p-toluidinesulfonate Agents, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion imparting agents, coating agents, release promoters, antioxidants, perfumes, imaging agents, thermal crosslinking agents. These can be used individually or in combination of 2 or more types. The content of these is preferably from 0.01 to 20 parts by mass per 100 parts by mass of the total of the components (A) and (B).

<Solution of photosensitive resin composition>

The photosensitive resin composition of the present embodiment can be dissolved in an organic solvent and 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 stilbene, ethyl siroli, toluene, N, N-dimethylformamide, and propylene glycol monomethyl ether. Or a mixed solvent of these.

The coating liquid is applied onto a surface of a metal plate or the like and dried to form a photosensitive resin composition layer made of the photosensitive resin composition of the present embodiment. Examples of the metal plate include an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron, or stainless steel, and copper, a copper-based alloy, and an iron-based alloy are preferable.

The thickness of the photosensitive resin composition layer varies depending on the application, and the thickness after drying is preferably from 1 to 100 μm. It is also possible to protect the surface of the film from the side opposite to the metal plate of the photosensitive resin composition layer. The protective film may be a polymer film such as polyethylene or polypropylene.

<Photosensitive element>

As shown in FIG. 1, the photosensitive element 1 of the present invention includes a support film 2 and a photosensitive resin composition layer 3 formed on the support film 2, and further protected on the photosensitive resin composition layer 3 as necessary. Film 4.

The solution of the photosensitive resin composition is applied onto the support film 2, and dried to form a photosensitive resin composition layer 3 made of the photosensitive resin composition on the support film 2. Thus, the photosensitive element 1 of the present embodiment is provided, and the support film 2 and the photosensitive resin composition layer 3 formed on the support film 2 are provided.

As the support film, a polyester film such as polyethylene terephthalate, a polymer film having heat resistance and solvent resistance such as polypropylene or polyethylene can be used. The thickness of the support film (polymer film) is preferably 1 to 100 μm, preferably 5 to 50 μm, and more preferably 5 to 30 μm, in consideration of the influence on the strength and the resolution. When the thickness is less than 1 μm, the support film tends to be easily broken when the support film is peeled off. Further, in order not to affect the resolution, it is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 30 μm or less.

The photosensitive element 1 may have a protective film 4 covering the surface opposite to the support film 2 of the photosensitive resin composition layer 3 as necessary.

As the protective film, the adhesion to the photosensitive resin composition layer is preferably smaller than the adhesion of the support film to the photosensitive resin composition layer, and the film having a low fisheye is preferable. The term "fisheye" means that when a film is produced by heat fusion, kneading, extrusion molding, biaxial stretching, casting, or the like. , foreign matter, undissolved matter, oxidative degradation, etc. of the material enter the film. That is, the "low fisheye" means that the above-mentioned foreign matter or the like is scarce in the film.

As the protective film, specifically, a polymer film such as polyester such as polyethylene terephthalate, polypropylene, polyethylene, or the like, which has heat resistance and solvent resistance can be used. As a sales item, a polyethylene film such as Arufun MA-410, E-200C, and Shin-Etsu Film Co., Ltd. manufactured by Oji Paper Co., Ltd., and PS series such as PS-25 manufactured by Teijin Co., Ltd., etc., may be mentioned. Formate film. And the protective film may be the same as the support film.

The thickness of the protective film is preferably 1 to 100 μm, preferably 5 to 50 μm, more preferably 5 to 30 μm, and particularly preferably 15 to 30 μm. When the thickness is less than 1 μm, when the photosensitive resin composition layer and the protective film are laminated on the substrate, the protective film tends to be easily broken. When it exceeds 100 μm, it is not from the viewpoint of inexpensiveness. Satisfactory.

The coating of the photosensitive resin composition on the support film can be applied by roll coating, Cooma coater, gravure coating, air knife coating, die coater, bar coating. A known method such as cloth is carried out.

The drying of the above solution is preferably carried out at 70 to 150 ° C for 5 to 30 minutes. The amount of the residual organic solvent in the photosensitive resin composition layer after drying is preferably 2 parts by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step.

The thickness of the photosensitive resin composition layer in the photosensitive element differs depending on the application, and the thickness after drying is preferably 1 to 100 μm, and is 1 to 50 μm. Preferably, it is preferably 5 to 40 μm. When the thickness is less than 1 μm, industrial coating tends to be difficult, and when it exceeds 100 μm, sufficient adhesion and resolution tend not to be obtained.

The transmittance of the photosensitive resin composition layer to ultraviolet rays is preferably 5 to 75% for ultraviolet rays having a wavelength of 405 nm. From the viewpoint of excellent adhesion, the transmittance is preferably 5% or more, more preferably 10% or more, and still more preferably 15% or more. From the viewpoint of excellent resolution, it is preferably 75% or less, more preferably 65% or less, and still more preferably 55% or less.

The above transmittance can be measured by a UV spectrometer. As a UV spectrometer, the 228A type W beam spectrophotometer manufactured by Hitachi Co., Ltd. is mentioned.

The photosensitive element may further have an intermediate layer such as a buffer layer, an adhesive layer, a light absorbing layer, a gas blocking layer, or the like.

The obtained photosensitive element may be in the form of a sheet or may be stored in a roll shape on a winding core. When the roll is in the form of a roll, it is preferable to perform winding so that the support film is on the outer side. Examples of the winding core include plastics such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, and an ABS resin (acrylonitrile-butadiene-styrene copolymer). In the end face of the roller-shaped photosensitive element roll thus obtained, it is preferable to provide an end face separator from the viewpoint of end face protection, and to provide a moisture-proof end face separator from the viewpoint of edge fusion It is better. As the packing method, a package wrapped with a black sheet having a small moisture permeability is preferred.

<Formation method of photoresist pattern>

A photoresist pattern can be formed by using the photosensitive resin composition of the present invention. The method for forming a photoresist pattern of the present embodiment includes (i) a lamination step of laminating a photosensitive resin composition layer formed of the photosensitive resin composition on a substrate; (ii) a photosensitive resin composition. And irradiating the active light with a predetermined portion of the layer to expose and harden the predetermined portion; and (iii) removing a portion other than the predetermined portion of the photosensitive resin composition layer from the substrate to form a photosensitive layer on the substrate A step of developing a photoresist pattern formed by a cured product of a resin composition.

(i) lamination step

First, a photosensitive resin composition layer made of a photosensitive resin composition is laminated on a substrate. As the substrate, a substrate (circuit forming substrate) having an insulating layer and a conductor layer formed on the insulating layer can be used.

After laminating the photosensitive resin composition layer on the substrate, for example, after removing the protective film of the photosensitive element, the photosensitive resin composition layer of the photosensitive element is heated and pressed against the substrate. Thereby, a laminate in which the substrate, the photosensitive resin composition layer, and the support film are laminated in this order can be obtained.

This layer of cooperation is preferably carried out under reduced pressure from the standpoint of adhesion and followability. The heating of the photosensitive resin composition layer and/or the substrate at the time of pressing is preferably carried out at a temperature of 70 to 130 ° C, preferably at a pressure of 0.1 to 1.0 MPa (about 1 to 10 kgf/cm ² ). However, these conditions are not particularly limited. Further, when the photosensitive resin composition layer is heated to 70 to 130 ° C, it is not necessary to preheat the substrate, but in order to further improve the laminate property, the substrate may be preheated.

(ii) Exposure step

Next, a predetermined portion of the photosensitive resin composition layer on the substrate is irradiated with active light, and the predetermined portion is exposed and cured. In this case, when the support film which is present on the photosensitive resin composition layer is transparent to the active light, the support film can be irradiated with the active light. However, when the support film is light-shielding, the support film is removed and the photosensitive resin is formed. The layer illuminates the active light.

As the exposure method, a method of irradiating an image with active light by a negative or positive mask pattern called an artwork (mask exposure method) can be mentioned. Further, a method of directly exposing the active light to an image shape by a direct drawing exposure method such as LDI (Laser Direct Imaging) exposure method or DLP (Digital Light Processing) exposure method may be employed.

As the light source of the active light, a known light source can be used. For example, a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, an argon laser or the like, a solid laser such as a YAG laser, or a semiconductor laser can be used. Effectively emit ultraviolet light and visible light.

The wavelength (exposure wavelength) of the active light is preferably in the range of 350 to 420 nm and preferably in the range of 390 to 420 nm from the viewpoint of obtaining the effect of the present invention.

(iii) imaging steps

And by using a portion other than the predetermined portion of the photosensitive resin composition layer The electrode is removed from the substrate, and a resist pattern formed of a cured product of the photosensitive resin composition is formed on the substrate. When the support film is present on the photosensitive resin composition layer, after the support film is removed, the portion (unexposed portion) other than the predetermined portion (exposed portion) is removed (developed). Although wet imaging and dry imaging are used in the development method, wet imaging is widely used.

When performing by wet development, development is performed by a known development method using a developing liquid corresponding to the photosensitive resin composition. Examples of the development method include a method using an immersion method, a puddle method, a spray method, a brushing, a slap, a scraping, a shaking, and the like, and from the viewpoint of improving the resolution, a high-pressure spray method is used. Most suitable. It is also possible to combine these two or more methods for development.

Examples of the developing solution include an alkaline aqueous solution, a water-based developing liquid, and an organic solvent-based developing liquid.

When an alkaline aqueous solution is used as a developing solution, it is safe and stable, and has good workability. As the base of the alkaline aqueous solution, an alkali hydroxide such as a hydroxide of lithium, sodium or potassium; a carbonate such as lithium, sodium, potassium or ammonium carbonate or a bicarbonate; an alkali metal phosphate such as potassium phosphate or sodium phosphate can be used. Salt; alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate.

As an alkaline aqueous solution, a thin solution of 0.1 to 5% by mass of sodium carbonate, a thin solution of 0.1 to 5% by mass of potassium carbonate, a thin solution of 0.1 to 5% by mass of sodium hydroxide, and a thinner of 0.1 to 5% by mass of sodium tetraborate The solution is preferred. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature can be adjusted in accordance with the alkali developability of the photosensitive resin composition layer. A surfactant, an antifoaming agent, a small amount of an organic solvent which promotes development, and the like may be mixed in the alkaline aqueous solution.

The aqueous imaging liquid is, for example, a developing solution of water or an aqueous alkaline solution and one or more organic solvents. In addition, examples of the base of the alkaline aqueous solution include borax or sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, and diethylenetriamine. 2-Amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2, morpholine. The pH of the aqueous imaging solution is preferably a small value in a range in which sufficient development can be performed, preferably pH 8 to 12, and preferably pH 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, and butyl alcohol. , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. These can be used individually or in combination of 2 or more types. The concentration of the organic solvent in the aqueous imaging liquid is generally 2 to 90% by mass, and the temperature can be adjusted in accordance with the alkali developability. A small amount of a surfactant, an antifoaming agent, or the like may be mixed into the water-based developing solution.

Examples of the organic solvent-based developing solution include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, and methyl isobutyl ketone. An organic solvent such as γ-butyrolactone. Among these organic solvents, in order to prevent ignition, it is preferred to add water in the range of 1 to 20% by mass.

After the unexposed portion is removed, the photoresist pattern can be further cured by heating at a temperature of about 60 to 250 ° C or an exposure of about 0.2 to 10 J/cm ² as necessary.

<Method of Manufacturing Printed Circuit Board>

By etching the substrate of the photoresist pattern formed by the above method or Plated to make printed circuit boards. The etching or plating of the substrate can be performed by using the formed photoresist pattern as a mask for the conductor layer of the substrate.

Examples of the etching liquid to be etched include a copper chloride solution, a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide etching solution, and these are used from the viewpoint of having an excellent etch factor. A ferric chloride solution is preferred.

Examples of the plating method at the time of plating include copper plating such as copper sulfate plating and copper pyrophosphate plating; solder plating such as high-throw solder plating; and Watt Bath; ) (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfonate; gold plating such as hard gold plating or soft gold plating.

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

Examples of the peeling method of the resist pattern include an immersion method, a spray method, and the like, and these may be used singly or in combination. Further, the printed circuit board forming the photoresist pattern may be a multilayer printed circuit board, or may have a small-diameter through hole, or may be a printed circuit board having a high-density wiring such as a high-density package substrate and a germanium wafer.

[Examples]

The following examples are given to more specifically illustrate the invention. However, the present invention It is not limited to the following examples.

(A) binder polymer (A-1)

150 g of methacrylic acid mixed with a polymerizable monomer, 125 g of benzyl methacrylate, 25 g of methyl methacrylate, and 200 g of styrene (mass ratio 30/25/5/40), and azo The solution obtained by 9.0 g of diisobutyronitrile was referred to as "solution a".

A solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 100 g of a mixture of 60 g of methyl sirolimus and 40 g of toluene (mass ratio: 3:2) was referred to as "solution b".

Into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas introduction tube, 450 g of a mixture of 270 g of methyl sirolimus and 180 g of toluene (mass ratio: 3:2) was placed, and nitrogen was blown into the flask. While stirring, the temperature was raised to 80 ° C by heating.

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

The non-volatile content (solid content) of the binder polymer (A-1) was 47.8% by mass, the weight average molecular weight was 30,000, and the acid value was 196 mgKOH/g. Gel permeation chromatography (GPC) measurement, using a calibration curve of standard polystyrene, derived by conversion. The conditions for GPC are as follows.

(GPC condition)

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

Column: 3 pieces below

Gelpack GL-R420

Gelpack GL-R430

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

Dissolution: tetrahydrofuran

Measuring temperature: 40 ° C

Flow rate: 2.05ml/min

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

(A-2) and (A-3)

In addition to the polymerizable monomer, the material shown in Table 1 was used in the same manner as the mass ratio shown in the same table, and the binder polymer (A-2) was obtained in the same manner as the solution for obtaining the binder polymer (A-1). Solution of (A-3).

[Modulation of Solution of Photosensitive Resin Composition]

The components shown in the following Tables 2 and 3 were mixed in the amounts shown in the same table, and a solution of the photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 3 was prepared. Further, the blending amount of the component (A) shown in Tables 2 and 3 indicates the mass of the nonvolatile matter (solid content).

The details of each component shown in the above table are as follows.

(B) Photopolymerizable compound

TMPT21 (manufactured by Hitachi Chemical Co., Ltd., trade name): EO modified trimethylolpropane triacrylate (in general formula (1), R ¹ = R ² = R ³ = methyl, a + b + c =21 (average) of the compound)

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

FA-024M (manufactured by Hitachi Chemical Co., Ltd., trade name): Compound of the general formula (6), R = methyl group, m ₃ = 6 (average value), n ₂ + n ₃ = 12 (average value)

M-114 (manufactured by Toagosei Co., Ltd., trade name): 4-n-decylphenoxy octaethyl glycol acrylate

BPE-100 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name): EO modified bisphenol A-based dimethacrylate (the total number of repeats of oxygen-extended ethyl group is 2.6)

FA-MECH (manufactured by Hitachi Chemical Co., Ltd., trade name): (2-hydroxy-3-chloro)propyl-2-methylpropenyloxyethyl phthalate

(C) Photopolymerization initiator

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

(D) sensitizing pigment

(D-1): 1-phenyl-3-(4-tert-butylstyryl)-5-(4-tributylphenyl)pyrazoline

(D-2): 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline

(D-3): 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)pyrazoline

(D-4): 1,3-diphenyl-5-(4-isopropylphenyl)pyrazoline

(D-5): 1-phenyl-3-(4-methoxyphenyl)-5-(4-tributylphenyl)pyrazoline

(D-6): 1-phenyl-3-(2-thienyl)-5-(4-tributylphenyl)pyrazoline

(D-7): 1-phenyl-3-(2-thienyl)vinyl-5-(2-thiophene) Pyrazoline

(D-8): 1-phenyl-3-(2-thienyl)-5-(2-thienyl)pyrazoline

(D-9): 1-phenyl-3-(2-thienyl)-5-styrylpyrazoline (The above is manufactured by Nippon Chemical Industry Co., Ltd.)

(E) amine compound

LCV (made by Yamada Chemical Co., Ltd., trade name): reduced crystal violet

(dye)

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

[Photosensitive element]

The solutions of the photosensitive resin compositions of the above examples and comparative examples were uniformly applied to a polyethylene terephthalate film (manufactured by Teijin Co., Ltd., trade name "HTF-01") having a thickness of 16 μm. The hot air convection dryer was dried at 70 ° C and 110 ° C to form a photosensitive resin composition layer having a film thickness of 25 μm after drying. A protective film (trade name "NF-15", manufactured by Tamapoly Co., Ltd.) was bonded to the photosensitive resin composition layer to obtain a polyethylene terephthalate film (support film) and a photosensitive resin composition. A layer, a photosensitive element laminated under the order of the protective film.

[Laminated substrate]

A copper surface of a copper-clad laminate (a thickness of 35 μm) formed of a glass epoxy material (manufactured by Hitachi Chemical Co., Ltd., trade name "MCL-E-67") is used. A grinder (manufactured by Sanqi Co., Ltd.) having a brush equivalent to #600 was ground, washed with water, and dried by 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 14 and Comparative Examples 1 to 3 were laminated on the copper surface of the substrate. After the protective film was removed, the photosensitive resin composition layer of each photosensitive element was adhered to the copper surface of the substrate, and the temperature was 120 ° C and the lamination pressure was 4 kgf/cm ² . Thus, a laminated substrate in which a photosensitive resin composition layer and a polyethylene terephthalate film were laminated on the copper surface of the substrate was obtained.

[Evaluation of Sensitivity]

When the laminated substrate obtained by cooling is placed at a time point of 23 ° C, the polyethylene terephthalate film on the laminated substrate is adhered to a concentration region of 0.00 to 2.00, a concentration gradient of 0.05, and a plate size of 20 mm × 187 mm. The exposure tool (Phototool) of the 41-segment gradient plate having a size of 3 mm × 12 mm for each gradient. A direct exposure machine (manufactured by Hitachi Via Mechanics, trade name "DE-1AH") using a blue-violet laser diode having a wavelength of 405 nm as a light source, with an energy of 70 mJ/cm ² (exposure amount), and an exposure tool (Phototool) and The polyethylene terephthalate film is exposed to the photosensitive resin composition layer. The measurement of the illuminance was carried out using an ultraviolet illuminometer (manufactured by Ushio Electric Co., Ltd., trade name "UIT-150") using a 405 nm corresponding probe.

After the exposure, the polyethylene terephthalate film was peeled off from the laminated substrate to expose the photosensitive resin composition layer, and the unexposed portion was removed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C for 24 seconds. Thus, a cured film made of a cured product of the photosensitive resin composition is formed on the copper surface of the substrate. The sensitivity of the photosensitive resin composition was evaluated by measuring the number of remaining portions of the gradient plate obtained as the cured film. The sensitivity is indicated by the number of segments of the gradient plate, and the higher the number of segments, the better the sensitivity. The results are shown in Tables 5 and 6.

[Evaluation of resolution and adhesion]

The line width (L) / pitch width (S) (hereinafter referred to as "L/S") is a drawing pattern of 5/5 to 30/30 (unit: μm), and the number of remaining segments of the 41-stage gradient plate becomes The energy of the 11th stage was exposed (drawn) to the photosensitive resin composition layer of the laminated substrate. After the exposure, the same development processing as the evaluation of the aforementioned sensitivity is performed.

After development, in the resist pattern in which the pitch portion (unexposed portion) is cleanly removed and the line portion (exposed portion) is not bent or deficient, the resolution is evaluated by the value of the minimum line width/pitch width. Sex. Adhesiveness. The smaller the value, the better the resolution and the adhesion at the same time. The results are shown in Tables 5 and 6.

[Evaluation of photoresist shape]

For the above resolution. Evaluation of adhesion, the resulting photoresist shape (The cross-sectional shape of the photoresist pattern) was observed using a Hitachi scanning electron microscope S-500A. The results are shown in Tables 5 and 6.

When the photoresist shape is trapezoidal or inverted trapezoidal, or when the bottom edge of the photoresist is folded, the circuit formed by the subsequent etching treatment or plating treatment tends to cause short-circuit or disconnection. Therefore, the shape of the photoresist is rectangular (rectangular), and there is no bottom edge of the photoresist, and it is preferable that no developer residue exists. Here, when the shape of the photoresist is good, it is "rectangular", and when the photoresist pattern is observed, the bottom side is folded, and the bottom side is folded. When the development residue is observed, it is "developing residue".

2 is a schematic cross-sectional view for explaining a "bottom edge crimp" in the photoresist pattern. As shown in FIG. 2, when the "bottom edge crimp" is a cross-sectional shape of the photoresist pattern, the post-development photoresist pattern 14 formed on the surface of the copper foil 13 of the substrate 12 is not rectangular. The portion (unexposed portion) has a shape such as a bottom edge crimp. 3 is a schematic cross-sectional view for explaining "development residue" in the photoresist pattern. When the "development residue" is a cross-sectional shape in which the photoresist pattern is observed, the photoresist pattern 14 after development is not rectangular, the bottom edge is significantly folded, and the developer residue 15 is deposited on the line portion at the pitch portion. The state of the room.

[Evaluation of peeling characteristics]

Each of the photosensitive members was laminated on the copper-clad laminate (substrate), and exposure and development were carried out under the conditions shown in Table 4 to produce a test piece (40 mm × 50 mm) in which a cured film was formed on the substrate. After the test piece was allowed to stand at room temperature (25 ° C) for one day, peeling was performed under the conditions shown in Table 4. The time from the start of stirring until the cured film was completely peeled off from the substrate was taken as the peeling time. Further, the size of the peeling sheet after peeling was visually observed and evaluated by the following criteria. The shorter the peeling time, the smaller the peeling sheet size, indicating that the peeling property is better. Further, when the size of the release sheet is a sheet shape, it is represented by "L", when it is 30-40 mm square, it is represented by "M", and when it is 30 mm square, it is represented by "S". The results are shown in Tables 5 and 6.

As can be seen from Tables 5 and 6, the photosensitive resin compositions of Examples 1 to 14 were all excellent in sensitivity, resolution, adhesion, photoresist shape, and peeling properties after curing. On the other hand, Comparative Example 1 in which benzyl (meth)acrylate is not used in the binder polymer, and a photopolymerizable compound which is not used as a photopolymerizable compound having one ethylenically unsaturated bond in the molecule In Comparative Examples 2 and 3, the resolution, the adhesion, the resist shape, and the peeling sheet size were inferior to those of the examples.

[Industrial availability]

The photosensitive resin composition of the present invention can be suitably used as a material for forming a photoresist pattern when manufacturing a printed circuit board. In particular, since the photosensitive resin composition has good sensitivity, resolution, adhesion, photoresist shape, and peeling property after curing, it is also suitable for thinning of a substrate having a high-density package. The photoresist pattern used in the printed circuit board of the high-density wiring is formed.

1‧‧‧Photosensitive components

2‧‧‧Support film

3‧‧‧Photosensitive resin composition layer

4‧‧‧Protective film

12‧‧‧Substrate

13‧‧‧ copper foil

14‧‧‧Light resistance pattern

15‧‧‧Development residue

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

Fig. 2 is a schematic cross-sectional view showing the "bottom edge crimp" used in the description of the photoresist pattern.

Fig. 3 is a schematic cross-sectional view showing the "developing residue" used in the description of the photoresist pattern.

Claims (13)

A photosensitive resin composition which is a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a sensitizing dye, as described above ( A) The binder polymer has a structural unit based on (meth)acrylic acid, a structural unit based on benzyl (meth)acrylate or a benzyl (meth)acrylate derivative, and the above (B) photopolymerizable compound The compound represented by the following general formula (2) or the following general formula (3), wherein the (D) sensitizing dye contains the compound represented by the following general formula (1); In the formula (1), R ¹ and R ² each independently represent a substituted or unsubstituted phenyl, thienyl or furyl group, and R ³ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms or The alkyl ester group having 1 to 10 carbon atoms, a and b each independently represent an integer of 0 to 2, m represents an integer of 0 to 5, and m represents 2 to 5, and the plural R ³ existing may be different or identical to each other. ; In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom, a methyl group or a halogenated methyl group, and R ⁶ represents an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. a hydroxyl group or a halogen atom, p represents an integer of 1 to 4, n represents an integer of 0 to 4, and n represents 2 to 4, and R ^{6 in the} plural may be the same or different; In the formula (3), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group or a halogen atom, and r represents an integer of 1 to 12, k represents an integer from 0 to 5, and k represents 2 to 5, and R ^{8 in the} plural may be the same or different. The photosensitive resin composition of the first aspect of the invention, wherein the (B) photopolymerizable compound further contains a bisphenol A-based di(meth)acrylate compound. The photosensitive resin composition according to claim 1 or 2, wherein the (B) photopolymerizable compound further contains a trihydroxyl group having a (poly)oxyethylidene chain or a (poly)oxypropanyl chain Methylpropane tri(meth) acrylate compound. Photosensitive resin composition as claimed in claim 1 or 2 The (B) photopolymerizable compound further contains a polyalkylene glycol di(meth)acrylate having a (poly)oxyethylidene chain and a (poly)oxypropanylene chain. The photosensitive resin composition of claim 1 or 2, wherein the (A) binder polymer further has a structural unit based on an alkyl (meth)acrylate. The photosensitive resin composition of claim 1 or 2, wherein the (A) binder polymer further has a structural unit based on styrene or a styrene derivative. The photosensitive resin composition of claim 1 or 2, wherein the (A) binder polymer has an acid value of 100 to 250 mgKOH/g. The photosensitive resin composition according to claim 1 or 2, wherein the (A) binder polymer has a weight average molecular weight of 10,000 to 100,000. The photosensitive resin composition of claim 1 or 2, further comprising (E) an amine compound. A photosensitive element comprising a support film and a photosensitive resin composition formed on the support film by the photosensitive resin composition according to any one of claims 1 to 9 Floor. A method for forming a resistive pattern, comprising: laminating a photosensitive resin composition layer formed from the photosensitive resin composition according to any one of claims 1 to 9 on a substrate Lamination step And an exposure step of irradiating the predetermined portion of the photosensitive resin composition layer with the active light, exposing and hardening the predetermined portion; and forming a portion other than the predetermined portion of the photosensitive resin composition layer from the substrate The removal step is performed by forming a resist pattern of a resist pattern formed by a cured product of the photosensitive resin composition on the substrate. The method for forming a photoresist pattern according to claim 11, wherein the wavelength of the active light is in the range of 390 to 420 nm. A method of manufacturing a printed circuit board, comprising the step of etching or plating a substrate having a photoresist pattern formed by the method of claim 11 or 12.