WO2014021590A1 - Resin composition having photocurable property and thermosetting property, and dry film solder resist - Google Patents

Abstract

The present invention relates to a resin composition having a photocurable property and a thermosetting property, and a DFSR, wherein the resin composition enables the formation of a DFSR having a micro-undulated surface without an extra treating process such as a plasma treating process. The resin composition having a photocurable property and a thermosetting property comprises: an acid modified oligomer having a carboxyl group (-COOH) and an unsaturated functional group which can be photocured; a polyimide-based resin; a photopolymeric monomer having two or more unsaturated functional groups which can be photocured; a thermosetting binder having a functional group which can be thermoset; and a photoinitiator.

Description

 [Specifications

 [Name of invention]

 Photocurable and thermosetting resin composition, dry film solder resist

 Technical Field

 BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition and a dry film solder resist (DFSR) which are photocurable and thermosetting. More specifically, the present invention relates to a photocurable and thermosetting resin composition and DFSR enabling the formation of DFSR having fine unevenness on the surface without a separate treatment step such as a plasma treatment step.

 Background Art

 Background Art With the miniaturization and light weight of various electronic devices, photosensitive solder resists capable of forming fine opening patterns are used for printed thin substrates, semiconductor package substrates, and flexible circuit boards.

 The solder resist generally requires characteristics such as developability, high resolution, insulation, soldering heat resistance, and gold plating resistance. In addition, when the solder resist is applied to a semiconductor package substrate or the like, fine surface irregularities are formed on the film type solder resist as necessary in order to secure excellent adhesion to subsequent materials and the like during the process.

 However, in order to form such fine surface irregularities, a method of performing a separate surface treatment process such as a plasma treatment process after forming a film type solder resist, for example, DFSR, through a photocuring and thermal curing process Was applied. However, due to the addition of a separate treatment process such as the plasma treatment process, there was a disadvantage that the complexity and economical efficiency of the overall process is greatly caused.

 [Content of invention]

[Problem to solve] The present invention provides a resin composition having photocurability and thermosetting property which enables formation of DFSR having fine unevenness on the surface without a separate treatment step such as a plasma treatment step.

 The present invention also provides a Dry Film Solder Resist (DFSR) which exhibits excellent adhesion to other materials due to the formation of fine irregularities on the surface without a separate treatment step such as a plasma treatment step. .

 The present invention also relates to a circuit board comprising the DFSR. [Measures of problem]

 The present invention is an acid-modified oligomer having a carboxyl group (-COOH) and a photocurable unsaturated functional group; Polyimide resin; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; And photocurable and thermoset comprising photoinitiators. It provides a resin composition.

 In addition, the present invention is an acid-modified oligomer having a carboxy group (-COOH), and a photocurable unsaturated functional group; Polyimide resins; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; And a cured product of a thermosetting binder having a thermosetting functional group, and providing a dry film solder resist (DFSR) having fine irregularities having an average roughness (Rz) of 2 to 20 im on the surface thereof. Hereinafter, a photocurable and thermosetting resin composition and an DFSR according to an embodiment of the present invention will be described in more detail.

 According to one embodiment of the invention, a carboxyl group (-COOH) and an acid-modified oligomer having a photocurable unsaturated functional group; Polyimide resin; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; And a photocurable and thermosetting resin composition comprising a photoinitiator.

In such a resin composition, a predetermined acid-modified oligomer, a photopolymerizable monomer, A polyimide resin is included together with the photoinitiator and the thermosetting binder. The resin composition of this embodiment may be used as a composition for forming DFSR through the following process. First, after apply | coating a resin composition on a board | substrate, it exposes selectively to the resin composition of the part in which DFSR is to be formed. When such exposure is carried out, the unsaturated functional groups contained in the acid-modified oligomer and the unsaturated functional groups contained in the photopolymerizable monomer may cause photocuring to form crosslinks with each other. Can be formed.

 Subsequently, when development is carried out using an alkali developer, the resin composition of the exposed part having the crosslinked structure is left on the substrate as it is, and the resin composition of the remaining non-exposed part may be dissolved in the developer and removed.

 Then, when the heat treatment of the resin composition remaining on the substrate to proceed with the thermal curing, the carboxyl groups contained in the acid-modified oligomer can react with the thermosetting functional groups of the thermosetting binder to form crosslinks, and as a result thermosetting While forming a cross-linked structure by the desired portion on the substrate

DFSR can be formed.

 By the way, when the DFSR formed in this way is applied to a semiconductor package substrate, etc., in order to ensure excellent adhesion to the subsequent materials and the like during the process,

There is a need to form fine surface irregularities on the DFSR. As these fine irregularities are formed on the D ^ SR surface, the contact surface area between the DFSR and subsequent processing materials applied on the DFSR can be increased, and as a result, excellent adhesion can be secured.

 However, in order to form such fine concavities and convexities, a method of performing a separate surface treatment process such as a plasma treatment process after forming the DFSR through the above-described photocuring and thermosetting process is applied. However, the addition of such a plasma treatment process, there is a disadvantage such as causing the complexity of the overall process.

In contrast, the resin composition of one embodiment includes a polyimide-based resin, and thus may solve this disadvantage. That is, the polyimide The resin does not deteriorate photocurability, is not easily miscible with the acid-modified oligomer, and may exhibit properties that can be dissolved in a developer. Due to the characteristics of these polyimide resins, when the development process is performed on the resin composition after the exposure exposure, the resin composition including the polyimide resin may be substantially dissolved and removed by the development in the non-exposed part where photocuring is not advanced. Can be. On the other hand, in the exposed portion, the polyimide-based resin may cause fine phase separation with other components of the resin composition due to the incompatibility with the acid-modified oligomer, and the like. It may be present substantially separate from the components. Such a polyimide resin may be selectively removed by melting with a developer, and only other components such as an acid-modified oligomer having a crosslinked structure may remain in the exposed portion. Therefore, due to the selective removal of the polyimide resin, fine unevenness may be formed in the exposed portion (see FIG. 1).

 Therefore, when the DFSR is formed by applying the resin composition of one embodiment, the DFSR having fine irregularities on the surface may be formed even without a separate plasma treatment process. In particular, even if only the development process that should be applied for the formation of the original DFSR proceeds, since the formation of the DFSR formed on the surface of the fine unevenness is possible, the formation process of the DFSR can be simplified, and excellent adhesion with the subsequent process materials and the like. It is possible to form a DFSR indicating. Hereinafter, the resin composition according to one embodiment will be described in more detail for each component.

 Acid denatured oligomer

The resin composition of one embodiment includes a carboxyl group (-COOH) and an acid-modified oligomer having a photocurable unsaturated functional group. These acid-modified oligomers form crosslinks with other components of the resin composition, ie, photopolymerizable monomers and / or thermosetting binders, by photocuring to enable the formation of DFSR, including carboxyl groups. Have sex. Such acid-modified oligomers are oligomers having a carboxyl group and a photocurable functional group, for example, a curable functional group having a curable functional group having an acrylate group or an unsaturated double bond in the molecule, and have all been known to be usable in the photocurable resin composition. The ingredients can be used without any restriction. For example, the main chain of the acid-modified oligomer may be a novolac epoxy or polyurethane, and may be used as the acid-modified oligomer having a carboxyl group and an acrylate column introduced into the main chain. The photocurable functional group may be suitably an acrylate group, wherein the acid-modified oligomer may be obtained as a oligomer form by copolymerizing a polymerizable monomer having a carboxyl group and a monomer including an acrylate compound. . More specifically, specific examples of the acid-modified oligomer usable in the resin composition include the following components.

 (1) Obtained by copolymerizing unsaturated carboxylic acids (a) such as (meth) acrylic acid with compounds (b) having unsaturated double bonds such as styrene, α-methylstyrene, lower alkyl (meth) acrylate and isobutylene Carboxyl group-containing resins;

 (2) ethylenically unsaturated groups such as vinyl groups, allyl groups, (meth) acryloyl groups, and epoxy groups, acid chlorides, and the like, as part of the copolymer of the unsaturated carboxylic acid (a) and the compound (b) having an unsaturated double bond Carboxyl group-containing photosensitive resin obtained by reacting a compound having a reactive group, for example, glycidyl (meth) acrylate and adding an ethylenically unsaturated group as a pendant;

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

(4) 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; Carboxyl group-containing photosensitive resin obtained by making compound (f) which has one hydroxyl group, such as hydroxy oxyalkyl (meth) acrylate, and one or more ethylenically unsaturated double bonds react;

 (5) an epoxy group of a polyfunctional epoxy resin in which a hydroxy group of a polyfunctional epoxy compound having two or more epoxy groups (g) or a polyfunctional epoxy compound is further epoxidized with epichlorohydrin, and (meth) The carboxyl groups of unsaturated monocarboxylic acid (h) such as acrylic acid are subjected to esterification reaction (full esterification or partial esterification, preferably total esterification), and saturated or unsaturated polybasic acid anhydrides ( carboxyl group-containing photosensitive compound obtained by reacting d);

 (6) 1 in 1 molecule of an alkyl group having 2 to 17 carbon atoms, an aromatic group-containing alkyl carboxylic acid, etc., in the epoxy group of the copolymer of the compound (b) having an unsaturated double bond and glycidyl (meth) acrylate A carboxyl group-containing resin obtained by reacting an organic acid (i) having two carboxyl groups and not having an ethylenically unsaturated bond and reacting the produced secondary hydroxy group with a saturated or unsaturated polybasic anhydride (d);

 (7) diisocyanates (j) such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; and carboxyl group-containing dialcohol compounds (k) such as dimethyl-propionic acid and dimethylolbutanoic acid, And a compound having a polycarbonate poly, a polyether polyol, a polyester poly, a polyolefin poly, an acrylic polyol, a bisphenol A alkylene oxide adduct, a phenolic hydroxyl group and an alcoholic hydroxyl group. Carboxyl group-containing urethane resin in which the middle part of diol compounds (m), such as these, are obtained by reaction;

 (8) diisocyanate (j), bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol bisphenol A epoxy resin, bisphenol

(Meth) acrylates of bifunctional epoxy resins such as F type epoxy resins, bisphenol S type epoxy resins, bixylenol type epoxy resins, and biphenol type epoxy resins or partial acid anhydride modified substances (n) thereof, and carboxyl group-containing di An alcohol compound (k), and Photosensitive carboxyl group-containing urethane resin in which the middle part of a diol compound (m) is obtained by reaction;

 (9) Compound (f) having one hydroxy group such as hydroxyalkyl (meth) acrylate and one or more ethylenically unsaturated double bonds is added during the synthesis of the resin of the above (7) or (8), and is unsaturated at the terminal. Carboxyl group-containing urethane resin which introduce | transduced the double bond;

 (10) One isocyanate group and one or more (meth) acryloyl groups in a molecule such as an equimolar semi-flour of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin (7) or (8). Carboxyl group-containing urethane resin which added the compound which has, and was terminal (meth) acrylated;

 (11) Saturated or unsaturated polybasic acids with respect to the primary hydroxy group in the modified oxetane compound obtained by reacting unsaturated monocarboxylic acid (h) with a polyfunctional oxetane compound having two or more oxetane rings in the molecular weight as described later. Carboxyl group-containing photosensitive resin obtained by making anhydride (d) react;

 (12) Carboxyl group-containing photosensitive resin obtained by introducing an unsaturated double bond into the reaction product of a bisepoxy compound and bisphenols, and then reacting saturated or unsaturated polybasic anhydride (d);

 (13) Novolak-type phenol resins, alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and / or ethylene carbonate, propylene carbon The reaction product obtained by reacting unsaturated monocarboxylic acid (h) with a reaction product with cyclic carbonates such as carbonate, butylene carbonate, 2,3-carbonate propyl methacrylate, and saturated or unsaturated polybasic acid Carboxyl group-containing photosensitive resin obtained by reacting anhydride (d);

Among the above-mentioned components, in the said (7)-(10), when the isocyanate group containing compound used for resin synthesis becomes diisocyanate which does not contain a benzene ring, and in said (5) and (8), The polyfunctional and bifunctional epoxy resins used for the synthesis are bisphenol A skeleton, bisphenol F In the case of the compound having a linear structure having a skeleton, a biphenyl skeleton or a bixylenol skeleton, or a hydrogenated compound thereof, a component which can be preferably used as an acid-modified oligomer in terms of flexibility of the DFSR can be obtained. In addition, in another aspect, the modified product of the resins of the above (7) to (10) is preferable for the bending including the urethane bond in the main chain.

 In addition, commercially available components may be used as the acid-modified oligomer, and specific examples of such components may include ZAR-2000, ZFR-1031, ZFR-1121 or ZFR-1122 manufactured by Nippon Chemical Co., Ltd.

On the other hand, the above-mentioned acid-modified oligomer has weight one embodiment about 15 with respect to the total weight of the resin composition to 75 _{^0/0, and} black is about 20 to 50 parts by weight _^0/0, or from about 25 to 45 it may be included in an amount in weight% have. When the content of the acid-modified oligomer is too small, the developability of the resin composition may be lowered and the strength of the DFSR may be lowered. On the contrary, when the content of the acid-modified oligomer is too high, not only the resin composition may be excessively developed, but also uniformity may be decreased during coating. In addition, the acid value of the acid-modified oligomer may be about 40 to 120 mgKOH / g, or about 50 to 110 mgKOH / g, or 60 to 90 _mg KOH / g. When the acid value is too low, alkali developability may be lowered. On the contrary, when the acid value is too high, it may be difficult to form a photocurable part, for example, an exposed part, by a developing solution, which makes it difficult to form a normal pattern of DFSR.

 Photopolymerizable monomer

On the other hand, the resin composition of one embodiment includes a photopolymerizable monomer. Such a photopolymerizable monomer may be, for example, a compound having a photocurable unsaturated functional group, such as two or more polyfunctional vinyl groups, and may form a crosslink with the unsaturated functional group of the acid-modified oligomer described above to provide photocuring during exposure. Crosslinked structure can be formed. This ensures that the part where the DFSR is to be formed _. The resin composition of the corresponding exposure part can be made to remain on a board | substrate without alkali developing.

As the photopolymerizable monomer, a liquid phase may be used at room temperature, and accordingly, the viscosity of the resin composition of one embodiment may be adjusted according to a coating method, It can also play a role of further improving alkali developability of the non-exposed part.

 As said photopolymerizable monomer, the (meth) acrylate type compound which has 2 or more, 3 or more, or 3-6 photocurable unsaturated functional groups in a molecule | numerator can be used, More specifically, a pentaery Hydroxy group-containing polyfunctional acrylate compounds such as trirol triacrylate or dipentaerythritol pentaacrylate; Water-soluble polyfunctional acrylate compounds such as polyethylene glycol diacrylate or polypropylene glycol diacrylate; Polyfunctional polyester acrylate-based compounds of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythrite; Acrylate-based compounds of ethylene oxide adducts and / or propylene oxide adducts of polyfunctional alcohols such as trimethyl-propane or hydrogenated bisphenol A, or polyhydric phenols such as bisphenol A and biphenol; A polyfunctional or monofunctional polyurethane acrylate compound which is an isocyanate modified product of the hydroxy group-containing polyfunctional acrylate compound; Epoxy acrylate compounds that are (meth) acrylic acid adducts of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, or phenol novolac epoxy resins; Caprolactone-modified acrylates such as caprolactone-modified ditrimethylolpropane tetraacrylate, acrylate of ε-caprolactone-modified dipentatrile, or caprolactone-modified hydroxypivalate neopentyl glycol ester diacrylate One or more compounds selected from the group consisting of photosensitive (meth) acrylate-based compounds such as (meth) acrylate-based compounds and the above-mentioned acrylate-based compounds, and these may be used alone or in combination of two or more. It can also be used in combination.

 Among these, as said photopolymerizable monomer, the polyfunctional which has 2 or more, or 3 or more, or 3 to 6 (meth) acryloyl groups in 1 molecule.

(Meth) acrylate-based compounds can be preferably used, especially pentatritriacrylate, trimethylolpropanetriacrylate, Hexaacrylate or caprolactone-modified ditrimethyl can be suitably used as the dipentaerythrate. As an example of a commercially available photopolymerizable monomer, Kaylarad DPEA-12 etc. are mentioned.

Content is about 7 to 20 weight _^0/0, about 5 to 30 parts by weight _^0/0, the black is based on the total amount of the black resin composition of the above-described photo-polymerization monomer may be about 7 to 15% by weight. If the content of the photopolymerizable monomer is too small, the photocuring may not be divided, and if the content is excessively large, the drying property of the DFSR may deteriorate and the physical properties may be degraded.

 Polyimide resin

 On the other hand, the resin composition of one embodiment is a polyimide-based. Resin. Such polyimide-based resins do not exhibit photocurability, and are not commonly reacted or reacted with the acid-modified oligomers, photopolymerizable monomers, and the like, and may exhibit properties that can be dissolved in a developer. Due to the characteristics of such a polyimide resin, when the development process is performed after exposing the resin composition of one embodiment, only the polyimide resin which does not have photocurability in the exposed portion subjected to photocuring is selectively dissolved in the developer. It can be removed, and only acid-modified oligomers and the like whose crosslinked structure is formed by the remaining photocuring can remain. This is because polyimide-based resins exhibit incompatibility and non-reactivity with acid-modified oligomers and the like, and thus cause fine phase separation after photocuring. As a result, only polyimide-based resins are selectively removed in the exposed portion. As a result, minute unevenness may be formed on the DFSR surface remaining in the exposed portion.

That is, when the DFSR is formed by applying the resin composition of one embodiment by the action of the polyimide-based resin, DFSR having fine irregularities formed on the surface may be formed even without a separate plasma treatment process. In particular, even if only the development process that should be applied naturally for the formation of the DFSR is possible, the formation of the DFSR formed on the surface of the fine unevenness is possible, so that it is possible to form a DFSR that exhibits excellent adhesion to subsequent process materials and the like in a simplified process. do. As such a polyimide-based resin, any polyimide resin, a precursor thereof or a derivative thereof in the form of any polyimide resin, plymic acid, etc., which exhibits non-coagulant and non-combustibility with an acid-modified ligomer and solubility in a developer, etc. may be used. Can be. For example, the polyimide resin may be a precursor of polyamic acid or polyimide resin obtained by reaction of diamine and dianhydride having an aliphatic or aromatic functional group. In addition, in consideration of the above-described properties of the polyimide resin, the polyimide resin may have a weight average molecular weight of about 10000 to 100000, or a weight average molecular weight of about 20000 to 100000. Such a polyimide resin may be directly synthesized by a method well known to those skilled in the art, or may be obtained by using a commercially available polyimide resin.

In addition, the polyimide content of the imide resin is in the range of about 1 to 30% by weight based on the total amount of the resin composition, or from about 5 to 27 weight _^0/0, the black can be about 10 to 25 wt. / _0. If the content of the polyimide resin is too small, fine irregularities may not be formed well on the final DFSR, and thus, sufficient adhesion may not be ensured with subsequent process materials. The polyimide-based resin may be removed to prevent DFSR having a desired pattern from being properly formed.

 Photoinitiator

 The resin composition of one embodiment includes a photoinitiator. Such photoinitiators serve to initiate radical photocuring, for example, in the exposed portion of the resin composition.

As a photoinitiator, well-known thing can be used and the benzoin type | mold compound which consists of benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and its alkyl ether; Acetophenone-based compounds such as acetophenone, 2,2-dimethec-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4- (lt-butyldioxy-1-methylethyl) acetophenone; Anthraquinone compounds such as methyl anthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloroanthraquinone; Thioxanthone compounds, such as 2, 4- dimethyl thioxanthone, 2, 4- diisopropyl thioxanthone, and 2-chloro thioxanthone; Ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone compounds such as benzophenone, 4- (lt-butyldioxy _1_methylethyl) benzophenone and 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone Substances can be used.

 In addition, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1 -Silver, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, Ν, Ν- dimethylaminoacetophenone ( Examples of commercially available products include α-aminoacetophenone compounds such as Irugacure (trademark) 907, Irugacure 369, Irugacure 379, and the like manufactured by Chiba Specialty Chemical Co., Ltd. (currently, Chiba Japan); 2,4,6-trimethylbenzoyldiphenylphosphineoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphineoxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- Acylphosphine oxide compounds such as pentylphosphine oxide (commercially available products such as Rucillin® TPO from BASF, Arugacure 819 from Chivas Specialty Chemical, etc.) may also be mentioned as suitable photoinitiators.

 And as another suitable photoinitiator, an oxime ester compound is mentioned. As a specific example of an oxime ester compound, 2-

(Acetyloxyiminomethyl) thioxanthene-9-one, (1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (0-benzoyloxime)), (ethanone, 1 -, and the like, l- (0- acetyl oxime)) - ^[9-ethyl-6- (2-methylbenzoyl) - ⁹ H- carbazole-3-yl]. Commercially available products include GGI-325 from Chiba Specialty Chemical, Irugacure OXE01, Irugacure OXE02, ADEKA N-1919, Chiba Specialty Chemical's Darocur TPO, and the like. In addition, biimidazole-based compounds or triazine-based compounds and the like can also be used as suitable photoinitiators.

The content of the photoinitiator may be about 0.5 to 20% by weight, or about 1 to 10% by weight, or about 1 to 5% by weight based on the total weight of the resin composition. When the content of the photoinitiator is too small, the photocuring may not occur properly, on the contrary, when the content of the photoinitiator is too large, the resolution of the water soluble composition may be lowered or the reliability of the DFSR may not be severe. Thermosetting binder

 The resin composition of one embodiment is also selected from thermosetting functional groups such as epoxy groups, oxetanyl groups, cyclic ether groups and cyclic thio ether groups

It includes a thermosetting binder having at least one kind. Such a thermosetting binder may form a crosslinked bond with an acid-modified oligomer and the like by thermosetting to secure heat resistance or mechanical properties of DFSR.

Such a thermosetting binder may have a softening point of about 70 to 100 ^° C., thereby enjoying unevenness during lamination. Low softening points increase the tackiness of the DFSR and high flow rates can deteriorate.

 As the thermosetting binder, a resin having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in a molecule can be used, and a bifunctional epoxy resin can be used. have. Other diisocyanates or their difunctional block isocyanates can also be used. The thermosetting binder having two or more cyclic (thio) ether groups in the molecule may be a compound having any one or two or more of three, four or five membered cyclic ether groups, or cyclic thioether groups in the molecule. have. The thermosetting binder may be a polyfunctional epoxy compound having at least two or more epoxy groups in a molecule, a polyfunctional oxetane compound having at least two or more oxetanyl groups in a molecule, or an episulfide resin having two or more thioether groups in a molecule And so on.

As a specific example of the said polyfunctional epoxy compound, bisphenol-A epoxy resin, hydrogenated bisphenol-A epoxy resin, brominated bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, novolak-type epoxa, for example Resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, N-glycidyl type epoxy resins, bisphenol A novolak type epoxy resins, bixylenol type epoxy resins, biphenol type epoxy resins, chelate type epoxy resins, Glyoxal type epoxy resin, amino group containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenyl yl ethane resin, silicone A modified epoxy resin, (epsilon) -caprolactone modified epoxy resin, etc. are mentioned. In addition, for the purpose of imparting flame retardancy, those in which atoms such as phosphorus are introduced into the structure may be used. By thermosetting these epoxy resins, the adhesiveness of a cured film, solder heat resistance, electroless plating resistance, etc. improve it.

 Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4 Bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3'ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-jade Cetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) methyl In addition to polyfunctional oxetanes such as methacrylates and oligomers or copolymers thereof, oxetane alcohols and novolac resins, poly (Ρ-hydroxystyrene), cardo-type bisphenols, charixarenes, and charixresolecin And etherates with a resin having a hydroxy group such as arene or silsesquioxane. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

 As a compound which has a 2 or more cyclic thioether group in the said molecule | numerator, Japan epoxy resin ^, the bisphenol A episulfide resin YL7000 by V manufacture etc. are mentioned, for example. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used.

 Moreover, as marketed, YDCN-500-80P etc. of Kukdo Chemical Co., Ltd. can be used.

The thermosetting binder can be included in an amount that Daewoong to 0.8 to 2.0 equivalents with respect to the ^carboxylic, diplopia group of 1 equivalent of the acid-modified oligomer. If the content of the thermosetting binder is excessively small, carboxyl groups remain in the DFSR after curing, which may lower heat resistance, alkali resistance, and electrical insulation. On the contrary, when the content is excessively large, the low molecular weight thermosetting binder remains in the dry coating film, which is not preferable because the strength of the coating film is lowered.

In addition to the above-mentioned components, the resin composition of one embodiment includes a solvent; And thermosetting binder catalysts (thermosetting catalysts), fillers, pigments and additives described below. It may further comprise one or more selected from the group consisting of.

 Thermosetting binder catalyst ί thermosetting catalyst)

 The thermosetting binder catalyst serves to promote thermosetting of the thermosetting binder.

As such a thermosetting binder catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Dicyandiamide, benzyldimethylamine, 4- (dimethoxy ^{'butyl-amino)} -Ν, Ν- dimethylbenzylamine, 4-meteuk when -Ν, Ν- dimethylbenzylamine, 4-methyl -Ν, Ν- dimethylbenzylamine, etc. Amine compound; Hydrazine compounds such as adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. As commercially available products, for example, Shikoku Kasei Kogyo Sezo 2ΜΖ-Α, 2ΜΖ-ΟΚ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ (both brand names of imidazole compounds), U-CAT3503N manufactured by San Aprosa, UCAT3502T (All are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. In particular, the present invention is not limited thereto, and may be a thermosetting catalyst of an epoxy resin or an oxetane compound, or may promote reaction of an epoxy group and / or an oxetanyl group with a carboxyl group, or may be used alone or in combination of two or more thereof. . In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl -S-triazine _ isocyanuric acid S-triazine derivatives, such as an adduct, can also be used, Preferably the compound which functions also as these adhesive adhering agents can be used together with the said thermosetting binder catalyst.

 The content of the thermosetting binder catalyst may be about 3 to 15% by weight based on the total weight of the resin composition in terms of suitable thermosetting.

 filler

Filler is characterized by thermal stability, thermal dimensional stability, resin adhesion To improve. In addition, it also serves as a constitution pigment by reinforcing the color. Inorganic or organic layer fillers may be used, for example barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide (alumina ), Aluminum hydroxide, mica and the like can be used.

 The content of the filler is preferably about 5 to 50% by weight based on the total weight of the composition. In the case of using more than 50% by weight, the viscosity of the composition is increased, so that the coating property is lowered or the degree of curing is lowered.

 Pigment

 Pigments exhibit visibility and hiding power to hide defects such as scratches on circuit lines.

 As the pigment, a red, blue, green, yellow, black pigment or the like can be used. Phthalocyanine blue, pigment blue 15: 1, pigment blue 15: 2, pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6, pigment blue 60, etc. have. Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28 and the like can be used as the green pigment. Examples of the yellow pigments include anthraquinones, isoindolinones, condensed azos, and benzimidazolones. For example, Pigment Yellow 108, Pigment Yellow 147, Pigment Yellow 151, Pigment Yellow 166, Pigment. Pigment yellow 181, pigment yellow 193 and the like can be used.

 The content of the pigment is preferably used at about 0.5 to 3% by weight based on the total weight of the resin composition. When used in less than 5% by weight, visibility and hiding power is lowered, and when used in excess of 3% by weight is less heat resistance.

 additive

 The additive may be added to remove bubbles in the resin composition or to remove popping or craters from the surface of the film, impart flame retardancy, adjust viscosity, and catalyze the film.

Specifically, finely divided silica, organic bentonite, montmorillonite and the like Conventional thickeners; antifoaming agents such as silicone-based, fluorine-based, and polymeric-based and / or leveling crabs; Silane coupling agents such as imidazole series, thiazole series, and triazole series; Known and common additives such as flame retardants such as phosphorus flame retardants and antimony flame retardants can be blended.

 Among them, the leveling agent serves to remove the popping or crater of the surface when the film is coated, for example, BYK-Chemie GmbH BYK 80N, BYK-307, BYK-378, BYK-350 and the like can be used.

 The content of the additive is preferably about 0.01 to 10% by weight based on the total weight of the resin composition. One or more solvents may be commonly used to dissolve the resin composition or impart an appropriate viscosity.

As a solvent, Ketones, such as methyl ethyl ketone and cyclonucleanone; 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, di Propylene glycol diethyl ether _: glycol ethers (cellosolve) such as triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate: ethylene glycol monobutyl ether acetate,

Diethylene glycol monoethyl ether acetate,

Diethylene glycol monobutyl ether acetate,

Propylene glycol monomethyl ether acetate,

Acetate esters, such as dipropylene glycol monomethyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and carbyl; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; Amides such as dimethylacetamide and dimethylformamide (DMF). These solvents It can be used alone or as a mixture of two subphases. _,

 The content of the solvent may be about 10 to 50% by weight based on the total weight of the resin composition. If it is less than 10% by weight, the viscosity is high, the coating is inferior, and if it exceeds 50% by weight, the drying is not good, the stickiness increases.

 Dry film solder resist

 According to another embodiment of the invention, there is provided a DFSR formed using the resin composition having the photocurable and thermosetting properties of the embodiment described above. Such DFSRs include carboxyl groups (-COOH) and acid-modified oligomers having photocurable unsaturated functional groups; Polyimide resin; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; And a cured product of a thermosetting binder having a thermosetting functional group, wherein fine unevennesses having an average roughness (Rz) of about 2 to 20 / ιη, or about 3 to 10 // m, or about 4 to about are formed on the surface thereof. It may be. In such DFSR, the microrefractive point may have an average roughness Ra of about 50 nm to 5 / m, or about 50 nm to 5, black to about 100 nm to 3 /, or about 200 nm to i. ,

 First, the process of forming such DFSR is as follows.

The resin composition of the above embodiment is applied to a carrier film as a photosensitive coating material. A comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, or a spray coater. After the coating, etc., it is dried by passing an oven at a temperature of 50 to 130 ^° C for 1 to 30 minutes, and then laminating a release film to form a carrier film, a photosensitive film, a release film from below. The dry film comprised can be manufactured. The thickness of the photosensitive film may be about 5 to 100 IM. In this case, a plastic film such as polyethylene terephthalate (PET), a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film may be used as the carrier film, and polyethylene (PE), Polytetrafluoroethylene film, polypropylene film, surface treated paper, etc. When the release film is peeled off, the adhesive force between the photosensitive film and the release film is preferably lower than that of the photosensitive film and the carrier film. Next, after peeling off a release film, a photosensitive film layer is bonded together on the board | substrate with a circuit using a vacuum laminator, a hot roll laminator, a vacuum press, etc.

 Next, the substrate is exposed to light having a constant wavelength band (UV, etc.). The exposure may be selectively exposed with a photo mask or may be directly pattern exposed with a laser direct exposure machine. The carrier film peels off after exposure. The exposure amount depends on the coating film thickness, but is preferably about 0 to 1,000 mJ / orf. When the exposure is carried out, for example, in the exposed portion, photocuring may occur to form a crosslinking bond between an acid-modified oligomer and a photopolymerizable monomer, and as a result, may not be removed by a subsequent phenomenon. In contrast, the non-exposed portion may be maintained in a carboxyl group as it is, and thus may be in an alkali developable state.

 Next, development is carried out using an alkaline solution or the like. The alkaline solution may be an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like. By this phenomenon, acid-modified oligomers, photopolymerizable monomers, and the like in the non-exposed part can be dissolved in the developer and removed.

 However, the resin composition of one embodiment includes the above-described polyimide resin. Accordingly, through the developing step, not only the resin composition of the non-exposed part but also the polyimide resin of the exposed part may be selectively removed. Therefore, as described above, fine unevenness may be formed on the exposed portion and the finally formed DFSR.

 As a result, through the development process, as shown in Figure 1, a film having fine irregularities on the surface can be formed.

Finally, by heat curing (Post Cure), the DFSR formed from the photosensitive film can be finally formed. Heat curing temperature is more than 100 ^° C. By such heat curing, thermosetting of a thermosetting binder is possible The functional group and the carboxyl group of the acid-modified oligomer may crosslink to form a crosslinked structure. Moreover, as a result of this heat-hardening, the fine unevenness | corrugation formed in the surface by the polyimide resin after the said image development process is reflected,

2 to 20, or about 3 to lO / m, black is about 4 to 8 / m average roughness (Rz), or about 50nm to 5 / ΛΠ, or about 50nm to 5 / im, or about lOOnm to 3 // m, black may be finally formed DFSR with fine irregularities having an average roughness (Ra) of about 200 nm to 2 GPa.

 Through the above-described method, a DFSR and a printed circuit board including the same, for example, a package substrate of a semiconductor device may be provided, and the DFSR contacts a subsequent process material and the like as predetermined fine irregularities are formed on a surface thereof. The surface area can be increased to show good adhesion. In addition, the DFSR is the acid-modified oligomer described above as the photocuring and thermal curing; Photopolymerizable monomers; And a cured product of a thermosetting binder having a thermosetting functional group.

More specifically, in the cured product, the carboxyl group of the acid-modified oligomer may be cross-linked with the thermosetting functional group of the thermosetting semi-unggi group by thermosetting, and the photo-curable unsaturated functional group of the acid-modifying oligomer The crosslinking may be carried out by crosslinking with the unsaturated functional groups included in the photopolymerizable monomer. Again _. As described above, as the polyimide-based resin is removed during the DFSR forming process, the above-described fine unevenness may be formed on the surface of the DFSR.

 As such, it is possible to form DFSR having fine unevenness on the surface while omitting a separate plasma treatment and the like, thereby providing DFSR that exhibits excellent adhesion to subsequent process materials when applied to a semiconductor package substrate. It is possible to provide a DFSR which expresses and maintains excellent physical properties by suppressing a decrease in physical properties of the DFSR by plasma treatment or the like.

 In addition, the DFSR may further include a small amount of photoinitiator remaining in the photocuring in a state of being dispersed in the cured product.

 [Effects of the Invention]

According to the present invention, even without a separate treatment process such as plasma treatment A resin composition and DFSR having photocurable and thermosetting properties which enable the formation of DFSR having fine unevenness on the surface can be provided. The DFSR thus formed can exhibit excellent adhesion to subsequent process materials due to fine concavities and convexities when applied to semiconductor package substrates, and can be formed in a simpler and more economical process by eliminating a separate treatment process such as a plasma treatment process. . In addition, such DFSR can suppress the deterioration of physical properties due to the plasma treatment and the like and can express and maintain excellent seban physical properties.

 [Brief Description of Drawings]

 1 is a schematic diagram showing a process of forming a DFSR having fine unevenness by applying a photocurable and thermosetting resin composition according to an embodiment of the invention.

 2 and 3 are FE-SEM images of the surface state of the DFSR formed in Examples 1 and 2.

 [Specific contents to carry out invention]

 Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific embodiments of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.

<Example>

 Example 1

 (1) Preparation of Polyimide Resin

 To synthesize the polyimide resin, 20 wt% of QDA (4,4 diaminodiphenyl ether) was dissolved in a solvent as a polymerization monomer, and then PMDA (Pyromemtic dian ydride) was added at an ODA and molar ratio of 1: 1. It stirred for 24 hours in bath atmosphere, and obtained PAA (Poly amic acid) which has a weight average molecular weight of 31500.

 (2) Preparation of Dry Film Solder Resist

The above as PAA (replicon amic acid) 30% by weight of ZFR-1122 of Nippon Kayaku the polyimide resin in the form of 11.5 weight _^0/0, as an acid-modified oligomer, a photopolymerizable monomer resulting in functional epoxy yarn acrylate (Nippon Kayaku DPEA-12) 10 weight ⁰ /。, As photoinitiator Darocur TPO (Ciba Specialty Chemicals Inc.) 3 parts by weight _^0/0, YDCN-500-80P (Kukdo Chemical Co.) as a thermosetting binder, 16 wt%, the 2-phenyl imidazole as a thermal curing catalyst, 1 parts by weight _^0/0, to a 15% by weight, an additive for B-30 (Sakai Chemical Co., Ltd.) as a filler using 13% by weight and DMF of BYK-333's BYK 0.5 weight _^0/0, as a solvent, and then blending the components and stirring for 3 reulmil equipment The filler was dispersed to prepare a resin composition having photocurability and thermosetting property.

After applying the prepared resin composition to the PET used as a carrier film using a comma coater, and then dried by passing through an oven at 75 ^° C for 8 minutes, by laminating PE as a release film, carrier film, photosensitive film from below And the dry film comprised from the release film was manufactured.

 (3) manufacture of printed circuit boards

After peeling off the release film of the manufactured dry film, the photosensitive film layer was vacuum laminated with a vacuum laminator (MV LP-500 manufactured by Meisei Seisakusho Co., Ltd.) on a substrate on which a circuit was formed, and then 400 mJ / After exposing to cm ² , the PET film was removed. Subsequently, the resultant was immersed in 311: Na ₂ CO ₃ 1% alkaline solution for stirring for 60 seconds, and then developed and heat-cured at 150 ^° C. for 1 hour. The printed circuit board comprising the dry film solder resist (DFSR). Was completed.

 Meanwhile, the substrate on which the circuit is formed is cut into LG Chem's copper-clad laminate LG-T-500GA having a thickness of 0.1 l and a copper thickness of 12 / ΛΠ into a substrate having a width of 5 cm and a length of 5 cm. Was used. Example 2

 (1) Preparation of Plyimide Resin

 In order to synthesize a polyimide resin, ODA (4,4 diaminodiphenyl ether) was dissolved as a polymerization monomer in 20 wt% of iF as a solvent, and then ODPA (4,4'-oxydiphthalic anhydride) in a molar ratio of 1: 1 with ODA. ), And stirred for 24 hours in an ice bath atmosphere to obtain PAA (Poly amic acid) having a weight average molecular weight of 33000.

(2) manufacture of dry film solder resist Photocurable and thermosetting in the same manner as in Example 1, except for using a polyimide resin in the form of PAA (polyamic acid) obtained above and using 30% by weight of ZFR-1121 of Nippon Gunpowder as an acid-modified oligomer. A resin composition having was prepared.

The resin composition prepared above was applied to PET used as a carrier film using a comma coater, and then dried by passing an obon at 75 ^° C. for 8 minutes, and then laminated with PE as a release film, thereby carrying a carrier film and a photosensitive material. The dry film which consists of a film and a release film was manufactured.

 (3) Manufacture of printed circuit board

 A printed circuit board including the DFSR was completed in the same manner as in Example 1 except for using the manufactured dry film.

Comparative Example

 Comparative Example 1

 Instead of using the polyimide-based resin in Example 1, except that 41.5% by weight of acid-modified oligomer ZFR-1122 was used in the same manner as in Example 1 to complete a printed thin substrate containing DFSR.

<Test Example: Evaluation of Properties of Protective Film for Printed Circuit Boards>

 The surface roughness, developability, and heat resistance reliability of the dry film solder resist for printed circuit boards prepared in Examples 1 and 2 and Comparative Example 1 were evaluated as follows.

 Experimental Example 1: Surface Roughness

After peeling off the release film of the DFSR obtained in Examples 1 and 2 and Comparative Example 1 and placing it on the copper foil laminate, vacuum treatment was performed with a vacuum laminator for 20 seconds, lamination at a temperature of 65 ^° C. and a pressure of 0.7 Mpa for 40 seconds. It was.

Then, a negatively drawn quartz photomask was placed on the laminated DFSR, exposed to UV (i band) of 400 mJ / cin ² , and then the PET film used as a carrier film was removed, and Na ₂ ^at 30 ^° C. C0 ₃ 1% Alkali The solution was developed for 60 seconds, washed with water and dried.

The dried samples were observed on the surface state using FE-SEM (Hitachi S-4800), and in Example 1 and Comparative Example 1 in order to accurately measure the difference in the surface roughness OP (Optical profiler, nanoview, Inc.) It was measured by comparing the values of the surface roughness values Rz and Ra using. FE-SEM photographs of the surface conditions of Examples 1 and 2 are as shown in Figs. 2 and 3, and the images measured using OP for Examples 1, 2 and Comparative Example 1, and Rz and Ra values It was as summarized in Table 1 below. Experimental Example 2: Evaluation of developability After peeling off the release film of the DFSR obtained in Examples 1 and 2 and Comparative Example 1 and placing it on the copper foil laminate, vacuum treatment was performed with a vacuum laminator for 20 seconds, a temperature of 65 ^° C. for 40 seconds, and O Mpa. Lamination was carried out under the pressure of.

Then, a negatively drawn quartz photomask was placed on the laminated DFSR, exposed to UV (i band) of 400 mJ / cin ² , and then the PET film used as a carrier film was removed, and Na ₂ ^at 30 ^° C. After developing for 60 seconds in an alkaline solution of C0 ₃ 1%, it was washed with water and dried.

 These developability evaluation criteria and results were summarized in Table 2 below.

 '

 Experimental Example 3: Method for Measuring Thermal Resistance

The protective film for printed circuit board was laminated on CCL, and finished through photocuring, thermal curing and back curing, and then cut to 150mm * 130mm. A temperature of 288 ^° C was set in the bath (electrically heated, temperature-controlled and at least 2.25 kg of lead for testing), and the test specimen was placed with the film on top of the bath. The test specimens were inspected for visible peeling or deformation of the film.

These heat reliability evaluation criteria and results were summarized in Table 2 below. Table 1 Rz and Ra measurement results of Experimental Example 1

Referring to Table 1 above, the DFSR of Examples 1 and 2 is formed from a resin composition comprising a polyimide resin, so that the surface has an average roughness (Rz) of about 6.01 kPa and about ³ 3 ⁵ . Fine unevenness was formed with an average roughness (Ra) of ⁹⁸ nm, an average roughness (Rz) of about ^5.0 l / m, and an average roughness (Ra) of about 317.70 nm.

 In contrast, it was confirmed that the DFSR of Comparative Example 1 did not form fine irregularities on the surface without a separate treatment such as plasma treatment, and had only an average roughness (Rz) of about 0.94 and an average roughness (Ra) of about 48.52 nm.

 Table 2 Measurement Results of Experimental Examples 2 and 3

Referring to Table 2, it was confirmed that the DFSR of the embodiment exhibits excellent heat resistance and developability according to the comparative example in which fine irregularities are not formed on the surface, but fine irregularities are not formed. Therefore, the DFSR of the embodiment can exhibit excellent adhesion as well as excellent physical properties as DFSR.

Claims

[Patent Claims]

 [Claim 1]

 Acid-modified oligomers having a carboxyl group (—COOH) and a photocurable unsaturated functional group;

 Polyimide resin;

 Photopolymerizable monomers having two or more photocurable unsaturated functional groups; Thermosetting binders having thermosetting functional groups; And

 Resin composition which has photocurability and thermosetting containing photoinitiator.

[Claim 2]

 The resin composition according to claim 1, wherein the photocurable functional group of the acid-modified oligomer is an acrylate group.

[Claim 3]

 The resin composition according to claim 1, wherein the acid-modified oligomer comprises a copolymer of a polymerizable monomer having a carboxyl group and a monomer including an acrylate compound.

[Claim 4]

First hangsse in the resin composition contained the acid modified hitting with 15 to 75 parts by weight _^0/0, based on the total weight of the resin composition dimmer.

[Claim 5]

 The resin composition according to claim 1, wherein the acid value of the acid-modified oligomer is 40 to 120 mgKOH / g.

[Claim 6]

The method of claim 1, wherein the polyimide-based resin is a polyimide resin, a precursor or derivative thereof having a weight average molecular weight of 10000 to 100000 Resin composition containing.

[Claim 7]

 The resin composition according to claim 6, wherein the precursor or derivative of the polyimide resin is a polyamic acid.

[Claim 8]

The method of claim 1, wherein the poly-imide resin is a resin composition comprising, based on the total weight of the resin composition to 1 to 30 parts by weight ^_0/0.

[Claim 9]

 The resin composition according to claim 1, wherein the photopolymerizable monomer comprises a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in a molecule.

[Claim 10]

 According to claim 1, wherein the photopolymerizable monomer is a hydroxyl group-containing polyfunctional acrylate compound; Water-soluble polyfunctional acrylate compounds; Polyfunctional polyester acrylate compound of polyhydric alcohol; Acrylate-based compounds of ethylene oxide adducts of polyfunctional alcohols or polyhydric phenols; Acrylate compounds of propylene oxide adducts of polyfunctional alcohols or polyhydric phenols; Polyfunctional or monofunctional polyurethane acrylate compounds; Epoxy acrylate compounds; A resin composition comprising at least one polyfunctional (meth) acrylate compound selected from the group consisting of caprolactone-modified acrylate compounds and photosensitive (meth) acrylate compounds.

[Claim 1 11]

The resin composition of claim 1, wherein the photopolymerizable monomer is included in an amount of 5 to 30 wt% based on the total weight of the resin composition.

[Claim 12]

 The method of claim 1, wherein the photoinitiator is a benzoin compound, acetophenone compound, anthraquinone compound, thioxanthone compound, ketal compound, benzophenone compound, α-aminoacetophenone compound, acylphosphine oxide compound , A resin composition comprising at least one selected from the group consisting of an oxime ester compound, a non-imidazole compound and a triazine compound.

[Claim 13]

 The resin composition of claim 1, wherein the photoinitiator is included in an amount of 0.5 to 20 wt% based on the total weight of the resin composition.

[Claim 14]

 The resin composition according to claim 1, wherein the thermosetting functional group is at least one member selected from the group consisting of an epoxy group, an oxetanyl group, a cyclic ether group, and a cyclic thio ether group.

[Claim 15]

 The resin composition according to claim 1, wherein the thermosetting binder is contained in an amount of 0.8 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the acid-modified oligomer.

[Claim 16]

 A solvent according to claim 1; And at least one selected from the group consisting of a thermosetting binder catalyst, a filler, a pigment, and an additive.

[Claim 17]

Acid-modified oligomers having a carboxyl group (-COOH) and a photocurable unsaturated functional group; Photopolymerizable monomers having two or more photocurable unsaturated functional groups; A dry film soldering resist comprising a cured product of a thermosetting binder having a thermosetting functional group, wherein fine unevenness having an average roughness (Rz) of 2 to 20 is formed on a surface thereof.

【Claim 18】,

 The cured product of claim 17, wherein the cured product comprises: a crosslinked structure in which the carboxyl group of the acid-modified oligomer and the thermosetting functional group are crosslinked; And

 Dry film soldering resist comprising a cross-linked structure cross-linked unsaturated functional groups of the acid-modified oligomer and photopolymerizable monomer.

[Claim 19]

 18. The dry film solder resist of claim 17, further comprising a photoinitiator dispersed in said cured product.

[Claim 20]

 The dry film soldering resist of claim Π, wherein the fine unevenness has an average roughness Ra of 50 nm to 5 / dl.

[Claim 21]

 18. The dry film solder resist according to claim 17, which is used for the manufacture of a package substrate of a semiconductor device.