KR101432634B1 - Photo-sensitive resin composition and dry film solder resist prepared therefrom having superior heat resistance - Google Patents

Abstract

The present invention relates to a photosensitive resin composition exhibiting excellent heat resistance reliability and a dry film solder resist formed thereby. Specifically, the photosensitive resin composition includes an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator and a metal grafting porous structure .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition having excellent heat resistance and a dry film solder resist formed therefrom. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a photosensitive resin composition and a dry film solder resist. More particularly, the present invention relates to a photosensitive resin composition capable of providing a photosensitive material exhibiting excellent visibility and hiding power without using a pigment and having improved heat resistance reliability and mechanical properties, To a dry film solder resist obtained by using a resin composition.

BACKGROUND ART [0002] As various electronic devices have become smaller and lighter, a photosensitive protective film capable of forming a fine opening pattern is used in a printed circuit board (PCB), a semiconductor package substrate, a flexible printed circuit board (FPCB) and the like.

Protective films are also called solder resists, and generally require properties such as developability, high resolution, insulation, soldering heat resistance, and gold plating resistance. Particularly, for solder resist for package substrate, in addition to these characteristics, resistance to cracking and high-accelerated stress test (HAST) between temperature tester (TCT) of 55 ° C to 125 ° C Is required.

In recent years, dry film type solder resist (DFSR: dry film solder resist), which has good film thickness uniformity, surface smoothness, and thin film formability, has attracted attention as a solder resist. By using such a dry film type solder resist, the process for forming a resist can be simplified, and the effect of reducing the amount of the solvent discharged at the time of forming a resist can be obtained.

On the other hand, in the conventional photosensitive resin composition for a solder resist, a pigment is added for imparting hue to a solder resist. However, in recent years, the kinds of pigments that can be used due to halogen regulations are limited, There has been a problem of heat resistance reliability of a solder resist to which such a pigment is added.

The present invention is to provide a photosensitive resin composition which can exhibit excellent visibility and hiding power without the use of a pigment and which can provide a photosensitive material having improved heat resistance and mechanical properties.

The present invention also provides a dry film solder resist which can be applied to a circuit board to realize improved heat resistance reliability and mechanical properties.

Further, the present invention is to provide a circuit board having improved heat resistance reliability and mechanical properties.

The present invention provides a photosensitive resin composition comprising an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, and a metal grafting porous structure.

The present invention also provides a dry film solder resist formed from the photosensitive resin composition.

The present invention also provides a circuit board comprising the dry film solder resist.

A photosensitive resin composition according to a specific embodiment of the present invention, a dry film solder resist formed from the photosensitive resin composition, and a circuit board including the dry film solder resist will be described in detail below.

According to one embodiment of the present invention, a photosensitive resin composition comprising an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, and a metal grafting porous structure may be provided.

The present inventors have confirmed through experimentation that when a metal grafting porous structure is added to a photosensitive resin composition in place of a conventional pigment, the heat resistance reliability can be improved while expressing hue in the photosensitive resin composition, Respectively. Particularly, the metal grafting porous structure can exhibit visibility and hiding power to replace defects such as scratches, as well as improve the heat resistance stability, dimensional stability by heat, and resin adhesion , And a filler function to enhance color.

The 'metal grafting porous structure' refers to a complex formed by adsorbing or physically / chemically bonding a certain metal to an inorganic material formed with many fine pores.

As the metal grafting porous structure, it is possible to use an inorganic material having a porous structure Metal grafted structures can be used, for example, metal grafting porous structures known to be commonly used in catalysts, carriers for catalysts, adsorbents, and the like. Specifically, it is preferable to use a structure in which a metal is grafted to a molecular sieve containing a silicate with the metal grafting porous structure. When such a silicate-containing molecular sieve is used, a low linear expansion coefficient and excellent high temperature stability .

The silicate-containing molecular sieve may comprise a zeolite, a silica molecular sieve with uniformly formed micropores, or a mixture thereof.

Specific examples of the zeolite include mordenite, ferrierite, ZSM-5,? -Zearite, Ga-silicate, Ti-silicate, Fe-silicate or Mn-silicate, It is not limited to the example.

In addition, the silica molecular sieve in which the micropores are uniformly formed means a silica molecular sieve in which pores having a diameter of several nanometers to several tens of nanometers or less (for example, a diameter of 1 to 30 nm) are uniformly formed, MCM-22, MCM-41, MCM-48, or a mixture thereof.

The molecular sieve of MCM (Mobil Crystalline Material) series was developed in the United States. In particular, MCM-41 has a hexagonal array of linear pores having a uniform size on a silica plate, that is, As shown in Fig. MCM-41 is known to be produced through a liquid crystal mold path according to recent studies. That is, a surfactant forms a liquid crystal structure in an aqueous solution, silicate ions surround the surroundings, a hydrothermal reaction forms a conjugate of the surfactant and the MCM-41 material, and the chelating agent is heated to 500 to 600 ° C To remove MCM-41.

When such a metal grafting porous structure in which a metal is grafted to a molecular sieve containing silicate is applied to a photosensitive resin composition, it is possible to improve heat resistance stability, high temperature stability or heat resistance reliability while allowing the composition to have a hue .

As the grafting metal, a metal that can exist as a metal ion when hydrated can be used. Preferably, one or more selected from the group consisting of nickel, copper, iron and aluminum can be used . Considering the color of the composition expressed by the metal ion, the metal grafting porous structure may include at least one selected from the group consisting of Ni / MCM-41, Fe / MCM-41 and Cu / MCM-41 Is preferably used.

The Ni / MCM-41, the Fe / MCM-41 and the Cu / MCM-41 may be formed of a metal such as Ni, Fe, and Cu, which include silicates of MCM-41, MCM- Quot; means grafted to the molecular sieve.

The metal grafting porous structure is a structure having pores having a diameter of several nanometers to several tens of nanometers or less, and may have a particle diameter of less than 1 mu m. 2 is a Scanning Electron Microscope (SEM) photograph of Ni / MCM-41 used in Examples.

The metal grafting porous structure may have a particle diameter of 10 nm to 2000 nm, preferably 100 nm to 600 nm, in consideration of the use degree of the photosensitive resin composition or the dispersion degree of the storage step.

On the other hand, as a method of grafting a metal to a molecular sieve such as zeolite, methods commonly known to be used as a method for preparing a metal catalyst using zeolite as a carrier can be used without any particular limitation.

In addition to zeolite, methods for preparing molecular sieves of MCM series such as MCM-22, MCM-41 or MCM-48 may be commercially available materials or may be prepared by the following methods.

Specifically, the molecular sieve of the MCM series comprises the steps of: adding a metal chloride to an aqueous alkyltrimethylammonium halide; Adding ammonia water to the mixture and stirring the mixture; Adding dropwise tetraethylorthosilicate after the stirring and stirring; And firing. The schematic contents of such a manufacturing method are shown in Fig. As shown in FIG. 1, a nucleation reaction may proceed by adding a metal chloride to an aqueous solution of alkyltrimethylammonium halide corresponding to a surfactant.

The alkyltrimethylammonium halide compound, which is conventionally known, can be used without limitation, and examples thereof include hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, cetyltrimethyl Ammonium chloride, myristyltrimethylammonium chloride, decyltrimethylammonium bromide, octyltrimethylammonium bromide, hexyltrimethylammonium bromide, and the like can be used.

In addition, the metal chloride can be selected in consideration of the kind of the metal grafted to the molecular sieve containing the silicate. Specific examples of the metal chlorides include nickel dichloride, ferrous chloride, ferric chloride, cuprous chloride, cupric chloride, and mixtures thereof.

Then, ammonia water is added to the mixed solution containing the alkyltrimethylammonium halide and the metal chloride, and the mixture is stirred. Then, tetraethylorthosilicate is further added dropwise and stirred. As shown in FIG. 1, Through the reaction, a molecular sieve precursor in which a liquid crystal template path is formed can be formed. Finally, by firing, the organic material of the molecular sieve precursor is blown off and a porous structure can be obtained.

On the other hand, it is preferable to add the metal chloride to be added in an amount of 1 to 30 mol% based on the total amount of the alkyl halide alkyl trimethyl ammonium solution including the metal chloride in order to improve the reaction yield.

It is preferable that the firing step is performed at a temperature of 300 to 800 ° C in order to incinerate and blow off the organic material contained in the molecular sieve precursor.

The photosensitive resin composition may include 0.5 to 30% by weight, preferably 5 to 25% by weight, of the metal grafting porous structure. If the metal grafting porous structure is added in an excessively small amount, the effect of improving heat resistance reliability is insignificant, and if it is contained in an excessive amount, the mechanical properties of the final product obtained from the composition may be deteriorated.

Meanwhile, the photosensitive resin composition according to the above embodiments includes an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, and a metal grafting porous structure, and may further comprise a heat curing catalyst, an epoxy curing agent, A dispersant, a solvent, and the like.

Specific examples of the structure including the acid-modified oligomer contained in the photosensitive resin composition according to the above embodiment are as follows.

Acid denaturation  Oligomers Acid Modified Oligomer )

Acid Modified Oligomer is an oligomer containing a carboxyl group and a vinyl group, and the main chain of the oligomer is novolac epoxy or polyurethane. The carboxyl group dissolves in an alkaline solution and is alkali-developable and thermoset with epoxy. Vinyl groups are capable of radical photopolymerization.

As the acid-modified oligomer, a compound having a carboxyl group and capable of polymerization and a compound obtained by polymerization with methyl methacrylate, methyl acrylate, ethyl acrylate and the like can be used.

Specifically, those listed below as acid-modified oligomers can be used.

(1) A copolymer obtained by copolymerizing an unsaturated carboxylic acid (a) such as (meth) acrylic acid with a compound (b) having an unsaturated double bond such as styrene, a-methylstyrene, lower alkyl (meth) acrylate or isobutylene A carboxyl group-containing resin;

(Meth) acryloyl group, an epoxy group, an acid chloride, and the like can be added to a part of the copolymer of the unsaturated carboxylic acid (a) and the unsaturated double bond-containing compound (b) A compound having a reactive group can be used. Specifically, a carboxyl group-containing photosensitive resin obtained by reacting glycidyl (meth) acrylate and adding an ethylenically unsaturated group as a pendant;

(3) To a copolymer of a compound (c) having an epoxy group and an unsaturated double bond such as glycidyl (meth) acrylate or a-methyl glycidyl (meth) acrylate and a compound (b) having an unsaturated double bond A carboxyl group-containing photosensitive resin obtained by reacting an unsaturated carboxylic acid (a) with a saturated or unsaturated polybasic acid anhydride (d) such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to the resulting secondary hydroxyl group;

(4) To a copolymer of an acid anhydride (e) having an unsaturated double bond such as maleic anhydride and itaconic anhydride and a compound (b) having an unsaturated double bond, one hydroxyl group such as hydroxyalkyl (meth) A carboxyl group-containing photosensitive resin obtained by reacting a compound (f) having at least one ethylenically unsaturated double bond;

(5) a polyfunctional epoxy compound (g) having two or more epoxy groups in the molecule as described below or an epoxy group of a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a polyfunctional epoxy compound with epichlorohydrin and (D) a carboxyl group of an unsaturated monocarboxylic acid (h) such as acrylic acid is subjected to an esterification reaction (entire esterification or partial esterification, preferably, a total esterification), and a saturated or unsaturated polybasic acid anhydride (d) A carboxyl group-containing photosensitive compound;

(6) In the epoxy group of the copolymer of the compound (b) having an unsaturated double bond and glycidyl (meth) acrylate, 1 to 5 carbon atoms are contained in an alkylcarboxylic acid having 2 to 17 carbon atoms and an alkylcarboxylic acid having an aromatic group Containing resin obtained by reacting an organic acid (i) having a carboxyl group and no ethylenic unsaturated bond, and reacting the resulting secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride (d);

(7) a diisocyanate (j) such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate and an aromatic diisocyanate, a dialcohol compound (k) containing a carboxyl group such as dimethylolpropionic acid and dimethylolbutanoic acid, A carboxyl group-containing urethane resin obtained by a reaction of a diol compound (m) such as a carbonate-based polyol, a bisphenol-based polyol, a bisphenol A-based alkylene oxide adduct diol, a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group;

(8) A resin composition comprising a diisocyanate (j), a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a brominated bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a bi-xylenol (Meth) acrylate or its partial acid anhydride modification (n) of a bifunctional epoxy resin such as an epoxy resin or a bi-phenol epoxy resin, a carboxyl group-containing dialcohol compound (k), and a diol compound m) of a photosensitive carboxyl group-containing urethane resin obtained by the reaction;

(9) A compound (f) having one hydroxyl group and at least one ethylenic unsaturated double bond such as hydroxyalkyl (meth) acrylate is added to the resin of the above (7) or (8) A carboxyl group-containing urethane resin having a double bond introduced therein;

(10) A process for producing a compound represented by the above formula (7) or (8), wherein a compound having one isocyanate group and at least one (meth) acryloyl group in the molecule such as a molar reaction product of isophorone diisocyanate and pentaerythritol triacrylate And a terminal (meth) acrylated carboxyl group-containing urethane resin;

(11) A method for producing a modified oxetane compound, which comprises reacting an unsaturated monocarboxylic acid (h) with a multifunctional oxetane compound having two or more oxetane rings in a molecule as described below to obtain a saturated or unsaturated polybasic acid anhydride (d) with a carboxyl group-containing photosensitive resin;

(12) A carboxyl group-containing polyester resin obtained by reacting a bifunctional epoxy resin or bifunctional oxetane resin as described below with a dicarboxylic acid and adding a saturated or unsaturated polybasic acid anhydride (d) to the resulting primary hydroxyl group ;

(13) a carboxyl group-containing photosensitive resin obtained by introducing an unsaturated double bond to a reaction product of a bis-epoxy compound and a bisphenol and subsequently reacting a saturated or unsaturated polybasic acid anhydride (d);

(14) A process for producing a novolak type phenol resin, which comprises reacting a novolak type phenolic resin with an alkylene oxide and / or ethylene carbonate such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran and tetrahydropyran, Unsaturated monocarboxylic acid (h) is reacted with a cyclic carbonate such as ethylene carbonate, propylene carbonate, propylene carbonate, propylene carbonate, propylene carbonate, propylene carbonate, And a carboxyl group-containing photosensitive resin obtained by reacting an anhydride (d).

Among the above carboxyl group-containing resins, preferred is a diisocyanate having an isocyanate group (including a diisocyanate) used in the synthesis of the resins (7) to (10) without a benzene ring. The polyfunctional and bifunctional epoxy resin used in the synthesis of the resins of (5), (8) and (12) is a linear structure having a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, Compound and a hydrogenated compound thereof. When the above-mentioned compound is used as an acid-modified oligomer, excellent flexibility is exhibited.

The resins of the above (7) to (10) and the modified materials such as the above (12) have a urethane bond in the main chain and can be preferably used because of their good warping. Resins other than the above-mentioned (1), (6), (7), (11) and (12) are preferred from the viewpoint of photocurability because they contain a photosensitive group (radically polymerizable unsaturated double bond) . Also, as commercially available products, ZAR-2000, a Japanese explosive, etc., can be used.

Meanwhile, the photosensitive resin composition may contain 10 to 60% by weight, preferably 20 to 50% by weight, of the acid-modified oligomer. It is preferable that the acid-modified oligomer is contained in an amount of 10% by weight to 60% by weight based on the total weight of the photosensitive resin composition, because it can optimize developability, prevent the strength of the final formed film from deteriorating and ensure uniformity in coating.

The acid-modified oligomer having an acid value of 40 to 120 mgKOH / g is preferably used since it can optimize developability upon alkali development. When an acid-modified oligomer having an acid value of less than 40 mgKOH / g is used, alkali development may be difficult. On the other hand, when an acid-modified oligomer having an acid value of more than 120 mgKOH / g is used, dissolution of the exposed portion by the developer proceeds, , Or in some cases, dissolving and peeling off as a developing solution without distinction between the exposed portion and the unexposed portion, and it may become difficult to form a normal resist pattern.

Photopolymerization Monomer

As the photopolymerizable monomer, a compound having at least one polyfunctional vinyl group and capable of crosslinking upon photopolymerization can be used, and polyfunctional epoxy (meth) acrylate can be preferably used. On the other hand, throughout this specification, unless otherwise defined, (meth) acrylate refers to acrylate or methacrylate and (meth) acryloyl group refers to acryloyl or methacryloyl group do.

On the other hand, the polyfunctional epoxy acrylate can be obtained by reacting glycidyl groups of triglycidylisocyanurate (TGIC) with acrylic acid and partially reacting the resulting hydroxyl groups with an anhydride.

Examples of anhydrides which can be used herein include tetrahydrophthalic anhydride (THPA), hexa hydrophthalic anhydride (HHPA), methyl tetrahydrophthalic anhydride (MeTHPA: Methyl tetra hydro phthalic anhydride, Methyl hexahydrophthalic anhydride (MeHHPA), Nadic methyl anhydride (NMA), Hydrolyzed methyl nadic anhydride (HNMA) Hydrolized methyl nadic anhydride, and phthalic anhydride. However, the present invention is not limited to the examples described above.

Specific examples of the photopolymerizable monomer that can be used in the photosensitive resin composition include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) (Meth) acrylate compounds containing hydroxyl group such as erythritol penta (meth) acrylate; Soluble (meth) acrylate compounds such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate; Polyfunctional polyester (meth) acrylate compounds of polyhydric alcohols such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate; (Meth) acrylate compounds of ethylene oxide adducts of polyfunctional alcohols such as trimethylol propane and hydrogenated bisphenol A; (Meth) acrylate compounds of ethylene oxide adducts of polyhydric phenols such as bisphenol A and biphenol; (Meth) acrylate compounds of propylene oxide adducts of polyfunctional alcohols such as trimethylol propane and hydrogenated bisphenol A; (Meth) acrylate compounds of propylene oxide adducts of polyhydric phenols such as bisphenol A and biphenol; Polyfunctional or monofunctional polyurethane (meth) acrylate which is an isocyanate-modified product of the hydroxyl group-containing (meth) acrylate; An epoxy (meth) acrylate compound which is a (meth) acrylic acid adduct of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolac epoxy resin; (Meth) acrylate of caprolactone-modified ditrimethylolpropane tetra (meth) acrylate, (meth) acrylate of? -Caprolactone-modified dipentaerythritol, caprolactone-modified hydroxypivalic acid neopentyl glycol ester di A (meth) acrylate compound modified with lactone; Or a mixture of two or more thereof.

Particularly, as the photopolymerizable monomer which can be used in the photosensitive resin composition, a polyfunctional (meth) acrylate compound having at least two (meth) acryloyl groups in one molecule is more preferable. Examples of such compounds include pentaerythritol (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified ditrimethylolpropane tetra (meth) acrylate and the like. But is not limited thereto. As the photopolymerizable monomer, DPEA-12 or the like manufactured by Nippon Yakushi Kogyo Co., Ltd., which is a commercially available product, may be used.

Meanwhile, the photosensitive resin composition may contain 0.5 to 30% by weight, preferably 1 to 20% by weight, of the photopolymerizable monomer. If the content of the photopolymerizable monomer is too small, photocuring may not occur sufficiently, and if it is too high, film drying may be deteriorated.

Photoinitiator

The photoinitiator serves to initiate radical photocuring. The photoinitiator that can be used is not particularly limited as long as it is generally used in a photosensitive resin composition. Specific examples of photoinitiators that can be used include benzoin compounds such as benzoin, benzoin methyl ether, and benzoin ethyl ether, and alkyl ether compounds thereof; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2,2-diethoxy-2-phenylacetophenone, 4- (1- Methylethyl) acetophenone; Anthraquinone compounds such as 2-methyl anthraquinone, 2-amyl atraquinone, 2-t-butyl anthraquinone, 1-chloro anthraquinone, and 2-ethyl anthraquinone; Thioxanthone compounds such as 2,4-dimethylthioxanthone, 2-4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketal compounds such as acetophenone dimethyl ketal and benzil dimethyl ketal; Benzophenone compounds such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone and 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) And the like.

Further, it is also possible to use 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -One, 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone Examples of commercially available products include α-amino acetophenone compounds such as Irgacure (registered trademark) 907, Irgacure 369, Irgacure 379, etc., manufactured by Chiba Specialty Chemicals (now Ciba Specialty Chemicals); Trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- And acylphosphine oxide compounds such as pentylphosphine oxide (commercially available products such as Lucilin (registered trademark) manufactured by BASR, Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd.) and the like can be preferably used.

The oxime ester compound may also be used as the photoinitiator. Specific examples of the oxime ester compound include 2- (acetyloxyiminomethyl) thioxanthien-9-one, (1,2-octanedione, 1- [4- (phenylthio) phenyl] ), (Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (o-acetyloxime). Examples of commercially available products include GGI-325, Irugacure OXE01, Irugacure OXE02, ADEKA N-199, and Ciba Specialty Chemicals Darocur TPO, which are commercially available from Chiba Specialty Chemicals.

Meanwhile, the photosensitive resin composition may contain 0.1 to 10% by weight, preferably 0.5 to 5% by weight, of the photoinitiator. If the content of the photoinitiator is too small, radical polymerization reaction for photo-curing may be difficult to occur sufficiently, and if it is used in an excess amount, developability of a dry film produced may be deteriorated.

Thermosetting binder resin

The thermosetting binder resin may be a thermosetting resin containing at least one functional group selected from the group consisting of an epoxy group, an oxetanyl group, a cyclic ether group and a cyclic thioether group. These thermosetting binder resins can be thermoset through an epoxy curing agent which is further applied to acid-modified oligomers or photosensitive resin compositions.

On the other hand, when the thermosetting binder resin has a softening point of 70 to 100 ° C, the unevenness can be minimized during lamination. When the thermosetting binder resin having a low softening point is used, the tackiness of the film is increased and the thermosetting When the binder resin is used, the flowability of the photosensitive resin composition may be deteriorated.

Preferable examples of the thermosetting binder resin include thermosetting resins having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as "cyclic (thio) ether groups"). Of these, bifunctional epoxy resins are preferred, and diisocyanates and bifunctional block isocyanates thereof can also be used.

The thermosetting binder resin having two or more cyclic (thio) ether groups may be a compound having at least two functional groups of one, two, or three kinds of cyclic ether groups or cyclic thioether groups of 3, 4 or 5-membered rings in the molecule .

Specifically, the thermosetting binder resin may be a polyfunctional epoxy resin having at least two epoxy groups, a polyfunctional oxetane resin having at least two oxetanyl groups, and an episulfide resin having at least two thioether groups .

Specific examples of the polyfunctional epoxy resin include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolak type epoxy resin, Phenol novolak type epoxy resins, cresol novolak type epoxy resins, N-glycidyl type epoxy resins, novolak type epoxy resins of bisphenol A, biquilene type epoxy resins, biphenol type epoxy resins, chelate type epoxy resins, Modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidylsilaneoyl ethane resin, silicone modified epoxy resin, silicone modified epoxy resin, caprolactone-modified epoxy resins, and the like. Further, in order to impart flame retardancy, an atom such as phosphorus (P) may be further introduced into the above-mentioned polyfunctional epoxy resin. Such a polyfunctional epoxy resin can improve properties such as adhesiveness of a cured film, solder heat resistance, electroless plating resistance and the like upon thermal curing.

Specific examples of the polyfunctional oxetane resin include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ (3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [ (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, In addition to polyfunctional oxetane compounds such as methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resins, poly (p-hydroxystyrene), cardo type bisphenol compounds, carixarene compounds, An ether compound of a hydroxyl group-containing resin such as silane compound, silsesquioxane or the like. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

On the other hand, as an example of the episulfide resin having two or more thioether groups, a bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins Co., Ltd., which is a commercially available product, may be used, but examples of usable resins are not limited thereto.

An episulfide resin in which the oxygen atom of the epoxy group of the novolac epoxy resin is replaced with a sulfur atom can also be used. As a commercially available product, YDCN-500-80P manufactured by Kukdo Chemical Co., Ltd. can be used.

Meanwhile, the photosensitive resin composition may include 0.5 to 30% by weight, preferably 5 to 25% by weight, of the thermosetting binder resin. When the content of the thermosetting binder resin is too small, a carboxyl group remains in the cured coating to deteriorate the heat resistance, alkali resistance, electrical insulation, etc., and is not preferable. When the content of the thermosetting binder resin is too high, An ether group or the like remains in the dried coating film, and the strength or the like of the coated film is lowered.

Meanwhile, the photosensitive resin composition according to the above-described embodiment of the present invention may further include the following additives.

Thermosetting catalyst

As an additive to be added to the photosensitive resin composition according to the above-described embodiment, the thermosetting catalyst promotes the curing of the thermosetting binder resin upon thermal curing.

As described above, since the photosensitive resin composition according to an embodiment of the present invention may include a thermosetting binder resin having at least two cyclic (thio) ether groups, it may contain a thermosetting catalyst. Examples of the thermosetting catalyst that can be added include imidazole, 2-methylimidazole, 2-ethylquimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole compounds such as cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And compounds such as triphenylphosphine.

2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., U-CAT 3503N and UCAT3502T DBU, DBN, U-CATSA102, and U-CAT5002 (all of bicyclic amidine compounds and salts thereof), and the like.

but. The thermosetting catalyst which can be used is not limited to the above-mentioned examples, and the compounds known as thermosetting catalysts for epoxy resins and oxetane compounds, or thermosetting catalysts for promoting the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups are different Can be used without restrictions.

Further, it is also possible to use one or more compounds selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct S-triazine derivatives such as < RTI ID = 0.0 >

The thermosetting catalyst may be used in an appropriate amount in consideration of the degree of curing of the thermosetting binder resin. For example, the photosensitive resin composition may include 0.01 to 7 wt%, preferably 0.1 to 5 wt% of the thermosetting catalyst .

Epoxy hardener

As the epoxy curing agent, an amine compound, an acid anhydride compound, an amide compound, a phenol compound, or the like can be used. Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetraamine, diaminodiphenylsulfone, isophoronediamine, and the like. Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Can be used. Examples of the amide compound include dicyandiamide, a dimer of linolenic acid and a polyamide resin synthesized from ethylenediamine. Examples of the phenol compounds include polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and terphenyl phenol; Phenolic resins obtained by condensation of phenols with aldehydes, ketones or dienes; Denaturants of phenols and / or phenolic resins; Halogenated phenols such as tetrabromobisphenol A and brominated phenol resin; Other imidazoles, BF3-amine complexes, guanidine derivatives and the like can be used.

The epoxy curing agent may be used in an appropriate amount in consideration of the mechanical properties of the dry film to be produced. For example, the photosensitive resin composition may include 0.01 to 10% by weight, preferably 0.1 to 5% by weight of the epoxy curing agent have.

filler

The filler serves to reinforce heat resistance, hygroscopicity, dimensional stability, and color. In addition, it improves thermal stability, dimensional stability by heat, adhesion of resin, and enhances color to serve as extender pigment.

Examples of the filler include inorganic or organic fillers such as barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide , Aluminum hydroxide, mica, and the like.

The filler may be used in an appropriate amount in consideration of the mechanical properties of the dry film to be produced. For example, the photosensitive resin composition may include 0.01 to 20% by weight, preferably 0.1 to 10% by weight of the filler. If the content of the filler is too small, the effect of reinforcing the heat resistance, hygroscopicity and dimensional stability due to the addition of the filler is insignificant. When the filler is used in an excessively large amount, the viscosity of the composition may increase, .

Leveling agent

The leveling agent serves to remove popping or craters on the surface during film coating. Examples of the leveling agent may include a silicone type, a fluorine type, a high molecular type, and the like. For example, BYK-Chemie GmbH BYK -380N, BYK-307, BYK-378 and BYK-350.

The leveling agent may be used in an appropriate amount in consideration of the surface characteristics of the dry film to be produced. For example, the leveling agent may include 0.1 to 20% by weight, preferably 1 to 10% by weight, of the leveling agent . When the leveling agent is added in an excessively small amount, the effect of removing popping or craters is insignificant, and when added in an excessively large amount, bubbles may be generated.

Dispersant

A dispersant may be added to improve dispersion stability of the filler, pigment, and the like. Examples of usable dispersants include Disperbyk-110, Disperbyk-162 and Disperbyk-168 of BYK-Chemie GmbH.

For example, the photosensitive resin composition may contain 0.1 to 30% by weight, preferably 1 to 20% by weight, of a dispersing agent. The dispersing agent may be used in an amount of 0.1 to 30% by weight, . When the addition amount of the dispersing agent is too small, the dispersion is not sufficient. If an excessively large amount of the dispersing agent is added, the heat resistance and reliability may be affected.

On the other hand, in addition to the above-mentioned additives such as fillers, leveling agents and dispersants, silane coupling agents such as imidazole, thiazole and triazole; And / or flame retardants such as phosphorus flame retardants and antimony flame retardants. When such a silane coupling agent and / or a flame retardant is added, it may be added in an amount of 0.01 to 30% by weight, preferably 0.1 to 20% by weight, based on the photosensitive resin composition.

menstruum

The solvent may be used for dissolving the photosensitive resin composition and for imparting a viscosity to a degree suitable for applying the composition.

Specific examples of the solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol ethers (cellosolve) such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Acetic acid esters such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate and dipropylene glycol monomethyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and carbitol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; Amides such as dimethylformamide, dimethylacetamide and dimethylformamide (DMF). These solvents may be used alone or as a mixture of two or more thereof.

The solvent may be used in an appropriate amount in consideration of the dispersibility, solubility, or viscosity of the photosensitive resin composition. For example, the photosensitive resin composition may contain 0.1 to 50% by weight, preferably 1 to 30% by weight, . If the content of the solvent is too small, the viscosity of the photosensitive resin composition may be increased to decrease the coating property. If the content of the solvent is excessively high, the drying may not be performed well,

On the other hand, according to another embodiment of the invention, a dry film solder resist manufactured using the above-described photosensitive resin composition and a circuit board including such a dry film solder resist can be provided.

Such a dry film solder resist can be obtained by applying the above-mentioned photosensitive resin composition onto a certain substrate and drying the same. Specifically, the above-mentioned photosensitive resin composition is coated on a carrier film such as PET, dried by a drying device such as an oven, and a release film is laminated thereon to form a carrier film from below. , A photosensitive film (Photosensitive Film), and a release film.

In the application step, conventional methods and apparatuses known to be usable for applying the photosensitive resin composition can be used. For example, a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, , A gravure coater, a spray coater, or the like can be used.

The thickness of the photosensitive film formed of the photosensitive resin composition may be 5 to 100 탆, more preferably 10 to 40 탆.

As the carrier film, a plastic film such as polyethylene terephthalate (PET), polyester film, polyimide film, polyamideimide film, polypropylene film, and polystyrene film can be used.

As the release film, polyethylene (PE), polytetrafluoroethylene film, polypropylene film, surface-treated paper and the like can be used.

It is preferable that the adhesive force between the photosensitive film and the release film is lower than the adhesive force between the photosensitive film and the carrier film when the release film is peeled off.

The drying temperature in the oven may be 50 to 130 캜, more preferably 70 to 100 캜.

FIG. 3 is a process diagram schematically showing a process of producing a dry film solder resist using the above-described photosensitive resin composition.

The dry film solder resist is applicable to various types of circuit boards. Examples of such a circuit board include, but are not limited to, a printed circuit board (PCB), a semiconductor package substrate, or a flexible printed circuit board (FPCB).

In the practical application of the dry film solder resist, a method may be used in which a release film is peeled off from the surface and a photosensitive film layer is vacuum laminated on a circuit-formed substrate. The vacuum lamination can be performed by using a vacuum laminator, a hot roll laminator, a vacuum press, or the like.

A photomask corresponding to a circuit pattern may be placed on the vacuum laminated photosensitive film layer and exposed to form a predetermined pattern. The light source used for the exposure may be ultraviolet (UV), electron beam, X-ray, or the like. The exposure may be performed by selectively exposing the photomask or by using a laser direct exposure apparatus. The carrier film is peeled off before or after exposure. The exposure dose is preferably from 0 to 1,000 mJ / cm ^{2 though} it depends on the thickness of the coating film.

After development, the unnecessary portions are removed to form a desired pattern. As the developer, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia or amines can be used. On the other hand, it is washed with water after development with an aqueous alkali solution.

After the developing and cleaning step, the substrate is heat cured in an oven at 140 to 160 ° C. for about 0.5 to 2 hours, and finally photocured at an exposure amount of 500 to 2,000 mJ / cm ² (Post Cure) A circuit board may be provided.

According to the present invention, there can be provided a photosensitive resin composition capable of providing a photosensitive material exhibiting excellent visibility and hiding power without using pigments and having improved heat resistance reliability and mechanical properties, and a dry film solder resist obtained using such a photosensitive resin composition have.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a simplified illustration of a process for preparing a silicate-containing molecular sieve according to one embodiment of the present invention.
2 is a scanning electron microscope image of Ni / MCM-41 prepared according to an embodiment of the present invention.
FIG. 3 is a schematic view showing a process for producing a dry film solder resist using a photosensitive resin composition according to an embodiment of the present invention.
FIGS. 4 and 5 show thermogravimetric analysis (TGA) results for a conventional pigment used in a photosensitive resin composition instead of a metal grafting porous structure.
FIG. 6 shows a thermogravimetric analysis (TGA) result of the metal grafting porous structure according to one embodiment of the present invention.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

[ Example ] Dry film Solder Resist  And manufacture of printed circuit boards including the same

[ Example  One]

(1) Dry film Solder Resist  Produce

, 10 weight% of polyfunctional epoxy acrylate (DPEA-12 of Japanese explosive), 3 weight% of Darocur TPO (Ciba Specialty Chemicals) as a photoinitiator, 38 weight% of ZAR-2000 as the acid-modified oligomer, 16% by weight of YDCN-500-80P (National Chemical Industries) as thermosetting binder, 1% by weight of 2-phenylimidazole as thermosetting catalyst, 18.5% by weight of Ni / MCM-41 as a metal grafting porous structure, 0.5% by weight of BYK-333 manufactured by BYK Co., Ltd., and 13% by weight of DMF as a solvent were mixed and stirred, followed by dispersing the filler with a 3-roll mill to prepare a photosensitive resin composition.

The photo-curable photosensitive resin composition thus prepared was applied to PET used as a carrier film using a comma coater, followed by drying in an oven at 75 캜 for 8 minutes and then PE was laminated as a release film, A dry film composed of a photosensitive film and a release film was produced.

(2) Manufacturing of printed circuit boards

After releasing the release film of the dry film, the photosensitive film layer was vacuum-laminated on a circuit-formed substrate with a vacuum laminator (MV LP-500, manufactured by Meiki Seisakusho Co., Ltd.) and then exposed to UV light having a wavelength of 365 nm at 350 mJ / after exposure to the cm ^2, by hot-setting after removing the PET film dipped, and stirred and 60 seconds in an alkali solution of Na ₂ CO ₃ 1% for 31 ℃ in the developing and for 1 hour at 160 ℃, formed from the photosensitive film A printed circuit board including the solder resist is completed.

On the other hand, the substrate on which the circuit was formed was cut into a substrate of LG-T-500GA having a thickness of 0.1 mm and a copper foil thickness of 12 탆 by a substrate having a width of 5 cm and a length of 5 cm and forming a micro roughness on the surface of the copper foil by chemical etching Were used.

 [ Example  2]

(1) Dry film Solder Resist  Produce

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 38% by weight of ZFR-1031 as the acid-modified oligomer was used.

The photocurable photosensitive resin composition prepared above was applied to PET used as a carrier film using a comma coater and then dried in an oven at 75 캜 for 8 minutes and then PE was laminated as a release film, , A photosensitive film, and a release film.

(2) Manufacturing of printed circuit boards

A printed circuit board including the solder resist formed from the photosensitive film was completed in the same manner as in Example 1, except that the dry film prepared above was used.

[ Example  3]

(1) Dry film Solder Resist  Produce

A photosensitive resin composition was prepared in the same manner as in Example 1 except that 18.5% by weight of Fe / MCM-41 was used as the metal grafting porous structure and 0.5% by weight of BYK-380N by BYK as an additive.

The photocurable photosensitive resin composition prepared above was applied to PET used as a carrier film using a comma coater and then dried in an oven at 75 캜 for 8 minutes and then PE was laminated as a release film, , A photosensitive film, and a release film.

(2) Manufacturing of printed circuit boards

A printed circuit board including the solder resist formed from the photosensitive film was completed in the same manner as in Example 1, except that the dry film prepared above was used.

[ Comparative Example ] Dry film Solder Resist  And manufacture of printed circuit boards including the same

[ Comparative Example  One]

18 wt% of barium sulfate (BaSO ₄ ) as a filler, 0.5 wt% of phthalocyanine blue and 0.5 wt% of a pigment 0.5, which is a mixture of phthalocyanine blue and Y147 of Ciba Co., in a ratio of 3: 2 instead of 18.5 wt% of Ni / MCM-41 as a metal grafting porous structure in Example 1 A printed circuit board including the solder resist formed from the photosensitive film was completed in the same manner as in Example 1 except that the weight% was used.

[ Test Example ]

The heat-resistant reliability and developability of the dry film solder resist for a printed circuit board prepared in Examples 1 to 3 and Comparative Examples were evaluated. The results are shown in Table 1 and Figs. 4 to 6. Fig.

1. How to measure heat resistance reliability

The printed circuit board specimens prepared according to Examples 1 to 3 and Comparative Example were left in a 100% pressure cooker test chamber at 121 ° C for 100 hours, and water was removed therefrom. This was placed on a 288 ° C water bath with the film side up. The test specimens were inspected for peeling or deformation of the film in appearance, and the heat resistance reliability was evaluated.

2. Developability  evaluation

The release films of the dry film solder resists obtained in Examples 1 to 3 and Comparative Example were peeled off and placed on the copper-clad laminate, followed by vacuum treatment for 20 seconds with a vacuum laminator and lamination was performed at 65 ° C and 0.7 MPa pressure for 40 seconds .

Then, a quartz photomask was drawn on the laminated dry film solder resist in a negative manner and exposed to UV (i band) at 250 mJ / cm 2. Then, the PET film used as the carrier film was removed, Dried for 60 seconds in an alkali solution of 1% Na ₂ CO ₃ , washed with water and dried.

The measurement results of Experimental Examples 1 and 2 are shown in Table 1 below.

Measurement results of Experimental Examples 1 and 2 Heat Resistance Reliability Developability Example 1 OK OK Example 2 OK OK Example 3 OK OK Comparative Example 1 NG OK 1. Evaluation Criteria for Heat Resistance Reliability
(1) OK: 288 ℃, solder floating
(2) NG: 288 ° C, bursting from solder floating

2. Developability
Observation of the Fe-SEM revealed that the developed hole having a mask size of 100 mu was 90 mu m or more in size and evaluated as OK

As shown in Table 1, the dry film solder resists of Examples 1 to 3 and Comparative Examples were not significantly different in terms of developability, but when the dry film solder resists of Examples 1 to 3 were used, the heat resistance reliability was improved The point was confirmed. Specifically, when the dry film solder resists of Examples 1 to 3 were used, there was almost no peeling or deformation of the test specimen even when placed on a 288 ° C water bath. On the other hand, in the case of the test specimen of the comparative example, .

3. Thermogravimetric analysis ( Thermogravimetric 분석 , TGA )

The TGA of the compositions comprising Ni / MCM-41 and previously used pigments, respectively, were measured and are shown in Figures 4 to 6, respectively. 4 is a TGA of a composition (comparative example) comprising Y-147 of Ciba, FIG. 5 is a TGA of a composition (comparison example and pigment only) comprising B15: 3 of Sanyo, ≪ / RTI > (Example 1).

The analytical instrument used was a Q500 instrument from Texas Instrument, and the weight loss to 600 ° C was measured at a temperature rise of 10 ° C per minute at room temperature. At this time, 0.2 g of each sample was sampled and analyzed.

As shown in Figs. 4 to 6, it was confirmed that the dry film solder resist obtained from the photosensitive resin composition of the examples had a relatively low rate of pyrolysis even at a high temperature of 400 캜 or higher, and thus had improved heat resistance. On the other hand, the products of the market or the dry film solder resists of the comparative examples were thermally decomposed by 50% or more at a high temperature of 400 ° C or higher, and exhibited poor heat resistance.

Claims (17)

Acid-modified oligomers; Photopolymerizable monomer; Thermosetting binder resin; Photoinitiators; And a metal grafting porous structure having a metal grafted on a molecular sieve containing a silicate.
delete The method according to claim 1,
Wherein the silicate-containing molecular sieve comprises at least one selected from the group consisting of zeolite and silica molecular sieve having micropores formed uniformly.
The method of claim 3,
Wherein the zeolite is at least one selected from the group consisting of mordenite, ferrierite, ZSM-5,? -Zearite, Ga-silicate, Ti-silicate, Fe-silicate and Mn-silicate.
The method of claim 3,
Wherein the silica molecular sieve having uniform micropores is at least one selected from the group consisting of MCM-22, MCM-41 and MCM-48.
The method according to claim 1,
Wherein the metal is at least one selected from the group consisting of nickel, copper, iron, and aluminum.
The method according to claim 1,
Wherein the metal grafting porous structure comprises a structure in which a metal is grafted to a silica molecular sieve having uniformly formed micropores having a diameter of 1 to 30 nm.
The method according to claim 1,
Wherein the metal grafting porous structure is at least one selected from the group consisting of Ni / MCM-41, Fe / MCM-41 and Cu / MCM-41.
The method according to claim 1,
Wherein the metal grafting porous structure has a particle size of 1 占 퐉 or less.
The method according to claim 1,
10 to 60% by weight of an acid-modified oligomer;
0.5 to 30% by weight of photopolymerizable monomer;
0.5 to 30% by weight of a thermosetting binder resin;
0.1 to 10% by weight of a photoinitiator; And
And 0.5 to 30% by weight of a metal grafting porous structure.
The method according to claim 1,
A thermosetting catalyst, an epoxy curing agent, a filler, a leveling agent, a dispersing agent or a solvent.
The method according to claim 1,
Wherein the acid-modified oligomer is an oligomer comprising a carboxyl group and a vinyl group.
The method according to claim 1,
Wherein the thermosetting binder resin is a thermosetting resin comprising at least one functional group selected from the group consisting of an epoxy group, an oxetanyl group, a cyclic ether group and a cyclic thioether group.
The method according to claim 1,
Wherein the thermosetting binder resin is selected from the group consisting of a polyfunctional epoxy resin having two or more epoxy groups, a polyfunctional oxetane resin having two or more oxetanyl groups, and an episulfide resin having two or more thioether groups Lt; / RTI >
The method according to claim 1,
A photosensitive resin composition for use in the production of a dry film solder resist.
A dry film solder resist formed from the photosensitive resin composition according to claim 1.
A circuit board comprising the dry film solder resist of claim 16.

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