KR101648555B1 - Photo-curable and thermo-curable resin composition and dry film solder resist - Google Patents

Abstract

The present invention relates to an acid-modified oligomer; Photopolymerizable monomer; Thermosetting binder resin; Photoinitiators; Organic solvent; And an epoxy resin to which a carboxyl group-terminated butadiene / acrylonitrile copolymer is added; a dry film solder resist obtained from the resin composition; and a circuit including the dry film solder resist Substrate.

Description

[0001] PHOTO-CURABLE AND THERMO-CURABLE RESIN COMPOSITION AND DRY FILM SOLDER RESIST [0002]

The present invention relates to a photosensitive resin composition, a dry film solder resist, and a circuit board, and more particularly, to a dry film solder resist (DFSR) capable of sufficiently securing mechanical properties such as excellent durability and impact resistance while having high heat resistance and elasticity A dry film solder resist, and a circuit board including the dry film solder resist.

BACKGROUND ART [0002] As electronic devices have become smaller and lighter in weight, photosensitive protective films capable of forming fine opening patterns have been used in printed circuit boards (PCBs), semiconductor package substrates, flexible printed circuit boards (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. Such a dry film type solder resist has the above-described characteristics, and also has the effect of simplifying the process for forming a resist and reducing the amount of the solvent discharged at the time of forming a resist.

Protective films for printed circuit boards should satisfy various physical properties such as high thermal stability, mechanical properties, chemical resistance and hygroscopicity.

In general, when the formulation for improving mechanical properties is poor in heat resistance and the composition for improving heat resistance is inferior in mechanical properties, development of a composition having excellent mechanical properties and heat resistance has been required.

Japanese Patent Application Laid-Open No. 2008-189803 discloses a photosensitive resin composition comprising a reaction product of (A) a polycarboxylic epoxy compound (a) and an unsaturated group-containing monocarboxylic acid (b) with a polybasic acid anhydride (c) (C) a photopolymerization initiator, (D) a thermosetting component having at least two cyclic ether groups and / or cyclic thioether groups in one molecule, and (E) a diluent, wherein the photopolymerizable thermosetting resin Compositions are disclosed.

Japanese Patent Application Laid-Open No. 2007-310380 discloses a photopolymerizable composition comprising (a) a binder polymer having a carboxyl group, (b) a photopolymerizable monomer having at least one ethylenic unsaturated group, (c) a polyurethane compound, and (C) a photosensitive resin composition characterized in that a polyurethane compound is reacted with an epoxy acrylate compound having an ethylenic unsaturated group and two or more hydroxyl groups, a diisocyanate compound, and a diol compound having a carboxyl group have.

Japanese Patent Application Laid-Open No. 2008-250305 discloses an epoxy resin composition which is synthesized from an epoxy compound, a phenol compound, an unsaturated monobasic acid, and a polybasic acid anhydride and which is a crystalline epoxy resin having a melting point of 90 ° C or higher as at least a part of an epoxy compound, There is disclosed a solder resist containing an acid-modified vinyl ester obtained using a bisphenol-S skeleton.

However, the above methods still do not satisfy the heat resistance and the mechanical properties at the same time, and new technology development is required.

The present invention provides a dry film solder resist (DFSR) capable of sufficiently securing mechanical properties such as excellent durability and impact resistance while having high heat resistance and elasticity, and also to provide a resin composition having photo-curability and thermosetting property will be.

The present invention also provides a dry film solder resist obtained from the resin composition having the photocurable and thermosetting properties.

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

The present invention relates to an acid-modified oligomer; Photopolymerizable monomer; Thermosetting binder resin; Photoinitiators; Organic solvent; And an epoxy resin to which a carboxyl group-terminated butadiene / acrylonitrile copolymer is added. The present invention also provides a photocurable and thermosetting resin composition.

The present invention also provides a dry film solder resist (DFSR) produced using a photosensitive resin composition.

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

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition, the dry film solder resist and the circuit board having photo-curable properties and thermosetting properties according to specific embodiments of the present invention will be described in more detail below.

According to one embodiment of the invention, acid-modified oligomers; Photopolymerizable monomer; Thermosetting binder resin; Photoinitiators; Organic solvent; And an epoxy resin to which a carboxyl-terminated butadiene / acrylonitrile copolymer is added, may be provided.

The resin composition having photo-curable properties and thermosetting properties of the above-mentioned embodiment includes an epoxy resin to which the carboxyl-terminated butadiene / acrylonitrile copolymer is added, so that the dry film solder resist or other coating film obtained from the resin composition has high flexibility and elasticity Accordingly, it is possible to prevent the substrate such as the SRO (Silicon Rich Oxide) thin film from being broken, and to minimize the defect caused by the difference in thermal expansion coefficient between the substrates.

In addition, the epoxy resin to which the butadiene / acrylonitrile copolymer at the terminal of the carboxyl group has been added has excellent heat resistance and elasticity, and also has excellent mechanical properties such as durability and impact resistance Of the total area.

The epoxy resin to which the carboxyl-terminated butadiene / acrylonitrile copolymer is added refers to a compound formed by adding a butadiene / acrylonitrile copolymer having a terminal carboxyl group functional group to an epoxy resin.

The epoxy resin to which the carboxyl-terminated butadiene / acrylonitrile copolymer is added may have a viscosity of 5,000 to 300,000 cps or 10,000 to 200,000 cps at 25 ° C.

The epoxy resin to which the carboxyl group-terminated butadiene / acrylonitrile copolymer is added may contain 25% by weight to 60% by weight of the carboxyl-terminated butadiene / acrylonitrile copolymer. That is, the content of the carboxyl-terminated butadiene / acrylonitrile copolymer added to the epoxy resin may be 25 wt% to 60 wt%, or 30 wt% to 50 wt%.

The epoxy resin may be an epoxy resin commonly used in the related art of dry film solder resists (DFSR) without limitation. Specifically, the epoxy resin may include bisphenol A or a derivative thereof.

The dry film solder resist (DFSR) produced by using the resin composition of one embodiment has high heat resistance and elasticity, and at the same time, it is preferable to use bisphenol A as the epoxy resin to sufficiently ensure mechanical properties such as excellent durability and impact resistance And diglycidyl ether.

The resin composition of one embodiment may include 1 wt% to 40 wt%, or 2 wt% to 20 wt% of the epoxy resin to which the carboxyl-terminated butadiene / acrylonitrile copolymer is added.

If the content of the epoxy resin to which the carboxyl-terminated butadiene / acrylonitrile copolymer is added in the resin composition having photo-curability and thermosetting property is too small, the obtained dry film solder resist or other coating film produced from the resin composition of the embodiment Flexibility and elasticity may not be sufficient. If the content of the epoxy resin to which the carboxyl-terminated butadiene / acrylonitrile copolymer is added is too high in the resin composition having photo-curable properties and thermosetting properties, the resulting dry film solder resist or other coating film produced from the resin composition of the embodiment The heat resistance may be deteriorated.

Meanwhile, DFSR can be formed by the following process using the resin composition of one embodiment. First, a film is formed from a resin composition, and after laminating the film on a predetermined substrate, the resin composition in the portion where the DFSR is to be formed is selectively exposed. 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 can cause photopolymerization to form crosslinking bonds with each other, and as a result, crosslinking structure due to photo- .

Thereafter, when development is carried out using an alkali developing solution, the resin composition of the exposed portion where the crosslinked structure is formed is left on the substrate as it is, and the remaining resin composition of the unexposed portion is dissolved in the developer and can be removed.

Then, when the resin composition remaining on the substrate is heat-treated and thermally cured, the carboxyl group contained in the acid-modified oligomer, for example, an iminocarbonate compound, reacts with thermosetting functional groups of the thermosetting binder, Bonding, and as a result, a DFSR can be formed at a desired portion on the substrate while forming a crosslinked structure by thermal curing.

That is, when the DFSR is formed using the resin composition, since the basic cross-linking structure is included in the cured product of the resin composition constituting the DFSR, the thermal expansion coefficient of the DFSR is lowered to 40 or less when α1 and 150 or less when α2 . Accordingly, the heat resistance reliability of the DFSR can be further improved, and the difference in thermal expansion coefficient between the semiconductor substrate and the package substrate material is reduced, thereby minimizing the warpage problem.

On the other hand, the acid-modified oligomers contained in the resin composition having photo-curable properties and thermosetting properties include photo-curable functional groups such as photo-curable functional groups having an acrylate group or an unsaturated double bond and oligomers having a carboxyl group in the molecule, All components previously known to be usable in resin compositions for forming DFSR can be used without limitation.

For example, the main chain of the additional acid-modified oligomer may be novolac epoxy or polyurethane, and a component in which a carboxyl group and an acrylate group are introduced into the main chain may be used as an additional acid-modified oligomer. The photocurable functional group can be preferably an acrylate group, wherein the acid-modified oligomer can be obtained as an oligomer form by copolymerizing a monomer containing a carboxyl group-containing polymerizable monomer and an acrylate-based compound.

Specifically, specific examples of acid-modified oligomers usable in the resin composition include the following components:

(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,? -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 carboxyl group-containing photosensitive resin obtained by reacting a compound having a reactive group, for example, glycidyl (meth) acrylate, and 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? -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 hydroxy 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) an epoxy group of a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a polyfunctional epoxy compound (g) or a polyfunctional epoxy compound having two or more epoxy groups in the molecule as described below with epichlorohydrin and ) The unsaturated monocarboxylic acid (h) such as acrylic acid or the like is subjected to an esterification reaction (entire esterification or partial esterification, preferably complete 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) Diisocyanates (j) such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, dialcohol compounds (k) containing carboxyl groups such as dimethylolpropionic acid and dimethylolbutanoic acid, A diol compound such as a polyol-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic-based polyol, a bisphenol A-based alkylene oxide adduct diol, a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group m) is obtained by a reaction of a carboxyl group-containing urethane resin;

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

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

(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 (Meth) acrylated urethane resin containing a carboxyl group;

(11) A process 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 give a saturated or unsaturated polybasic acid anhydride (d);

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

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

As the above-mentioned additional acid-modified oligomers, commercially available components may be used. Specific examples of such components include ZAR-1035, CCR-1235 or ZFR-1122 manufactured by Nippon Yakushi Kasei.

More specific examples of the acid-modified oligomer include an epoxy (meth) acrylate-based compound. The epoxy (meth) acrylate compound means a reaction product between an epoxy compound or a polyepoxy compound and 2) a (meth) acrylate compound or a hydroxy (meth) acrylate compound.

The use of the epoxy (meth) acrylate-based compound allows the flexibility of the DFSR to be sufficiently ensured, exhibits a lower thermal expansion coefficient and improved heat resistance reliability, and can be suitably used as a package substrate material for semiconductor devices. Can be provided.

As the epoxy (meth) acrylate compound, an epoxy (meth) acrylate compound derived from cresol novolak or an epoxy (meth) acrylate compound derived from bisphenol F can be used. The epoxy (meth) acrylate compound is prepared by mixing an epoxy (meth) acrylate compound derived from cresol novolak and an epoxy (meth) acrylate compound derived from bisphenol F in a weight ratio of 4: 1 to 1: : 1 to 2: 1.

The epoxy (meth) acrylate compound may have a weight average molecular weight of 5,000 to 50,000, or 6,000 to 20,000. If the weight average molecular weight of the epoxy (meth) acrylate compound is too large, the photo-curable acrylate ratio may be relatively decreased, resulting in deterioration of the developability or strength of the DFSR. If the weight average molecular weight of the epoxy (meth) acrylate compound is too small, precipitation or aggregation of the components to be used may occur, and the resin composition of one embodiment may be excessively developed.

The above-mentioned acid-modified oligomer may be contained in an amount of about 5 to 75% by weight, or about 20 to 50% by weight, or about 25 to 45% by weight based on the total weight of the resin composition of one embodiment. When the content of the acid-modified oligomer is too small, the developability of the resin composition is deteriorated and the strength of the DFSR may be lowered. On the other hand, if the content of the acid-modified oligomer is excessively high, the resin composition may not only be excessively developed, but also may be uneven in coating.

On the other hand, the photopolymerizable monomer may include a polyfunctional compound having two or more vinyl groups.

Such a photopolymerizable monomer may be a compound having a photocurable unsaturated functional group such as two or more polyfunctional vinyl groups and may form a crosslinked bond with an unsaturated functional group of the above-mentioned acid-modified oligomer, A crosslinked structure can be formed. Thereby, the resin composition of the exposed portion corresponding to the portion where the DFSR is to be formed can be left on the substrate without alkali development.

Such a photopolymerizable monomer may be a liquid at room temperature, and accordingly, the viscosity of the resin composition of one embodiment may be adjusted according to the application method, and the alkali developability of the unexposed portion may be further improved.

As the photopolymerizable monomer, an acrylate compound having at least two photocurable unsaturated functional groups can be used. As specific examples thereof, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol Triacrylate, dipentaerythritol pentaacrylate and the like; Water-soluble acrylate-based compounds such as polyethylene glycol diacrylate, and polypropylene glycol diacrylate; Polyfunctional polyester acrylate-based compounds of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate; Acrylate compounds of ethylene oxide adducts and / or propylene oxide adducts of polyhydric alcohols such as trimethylol propane or hydrogenated bisphenol A or polyhydric phenols such as bisphenol A and biphenol; A polyfunctional or monofunctional polyurethane acrylate-based compound which is an isocyanate-modified product of the hydroxyl group-containing acrylate; An epoxy acrylate-based compound which is a (meth) acrylic acid adduct of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolac epoxy resin; Caprolactone-modified acrylate compounds such as caprolactone-modified ditrimethylolpropane tetraacrylate, acrylate of? -Caprolactone-modified dipentaerythritol, or caprolactone-modified hydroxypivalic acid neopentyl glycol ester diacrylate, And a photosensitive (meth) acrylate compound such as a methacrylate compound corresponding to the above-mentioned acrylate compound may be used alone, or a combination of two or more thereof may be used .

Among these, as the photopolymerizable monomer, a polyfunctional (meth) acrylate compound having at least two (meth) acryloyl groups in one molecule can be preferably used. In particular, pentaerythritol triacrylate, trimethylol propane Triacrylate, dipentaerythritol hexaacrylate, caprolactone-modified ditrimethylol propane tetraacrylate, and the like can be suitably used. Examples of commercially available photopolymerizable monomers include DPEA-12 of Kayarad and the like.

The content of the photopolymerizable monomer may be about 1 to 40% by weight, or about 5 to 30% by weight, or about 7 to 15% by weight based on the total weight of the resin composition. If the content of the photopolymerizable monomer is too small, the photocuring may become insufficient. If the content of the photopolymerizable monomer is excessively large, the dryness of the DFSR may deteriorate and the physical properties may deteriorate.

Meanwhile, the photoinitiator may be a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, an? -Amino acetophenone compound, an acylphosphine oxide compound, An imidazole-based compound, and a triazine-based compound.

Specifically, known photoinitiators can be used, and benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; Anthraquinones such as 2-methyl anthraquinone, 2-amylanthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone and 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone Can be used.

Further, it is also possible to use 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- -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 acetophenones such as Irugacure (registered trademark) 907, Irugacure 369, Irugacure 379, etc., manufactured by Chiba Specialty Chemicals (now Ciba Japan) Trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide As commercially available products, mention may be made of acylphosphine oxides such as Lucinyl (registered trademark) TPO manufactured by BASF, and IRGACURE 819 manufactured by Ciba Specialty Chemicals, Inc. as a preferred photoinitiator.

Examples of preferred photoinitiators include oxime esters. Specific examples of oxime esters include 2- (acetyloxyiminomethyl) thioxanthien-9-one, (1,2-octanedione, 1- [4- (phenylthio) phenyl] ), (Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] - and 1- (O-acetyloxime). Examples of commercially available products include GGI-325, Irgacure OXE01, Irugacure OXE02, ADEKA N-1919, and Ciba Specialty Chemicals Darocur TPO, all of which are commercially available products.

The content of the photoinitiator may be about 0.1 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. If the content of the photoinitiator is too small, the photo-curing may not occur properly. On the other hand, if the content is excessively large, the resolution of the resin composition may be lowered and the reliability of the DFSR may not be sufficient.

Meanwhile, the thermosetting binder resin may contain 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 resin composition of one embodiment of the present invention also includes a thermosetting binder having at least one selected from a thermosetting functional group, for example, an epoxy group, an oxetanyl group, a cyclic ether group, and a cyclic thioether group. These thermosetting binders can form cross-links with acid-modified oligomers and the like by thermal curing to ensure the heat resistance or mechanical properties of DFSR.

The thermosetting binder may have a softening point of about 70 to 100 캜, thereby reducing irregularities during lamination. If the softening point is low, the tackiness of the DFSR increases, and if it is high, the flowability may deteriorate.

As the thermosetting binder, a resin having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as a cyclic (thio) ether group) in the molecule can be used, and a bifunctional epoxy resin can be used have. Other diisocyanates or their bifunctional block isocyanates may also be used.

The thermosetting binder having at least two cyclic (thio) ether groups in the molecule may be a compound having at least two, three or 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 epoxy groups in the molecule, a polyfunctional oxetane compound having at least two oxetanyl groups in the molecule, or an episulfide resin having two or more thioether groups in the molecule Or the like.

Specific examples of the polyfunctional epoxy compound 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 resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, biquilene type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, Epoxy-containing epoxy resins, epoxy-modified epoxy resins, dicyclopentadiene-phenolic epoxy resins, diglycidyl phthalate resins, heterocyclic epoxy resins, tetraglycidylsilaneoyl ethane resins, silicone modified epoxy resins ,? -caprolactone-modified epoxy resin, and the like. Further, in order to impart flame retardancy, a phosphorus or other atom introduced into the structure may be used. These epoxy resins improve the properties such as adhesiveness of the cured film, solder heat resistance, and electroless plating resistance by thermosetting.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (P-hydroxystyrene), cardo-type bisphenols, caries alenes, caries-threzine isomers, or silsesquioxanes such as novolac resins, poly And ether of a resin having a hydroxy group such as quinoxane. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

Examples of the compound having two or more cyclic thioether groups in the molecule include a bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., 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.

The resin composition having photo-curable properties and thermosetting properties may contain 0.5 to 40% by weight of a thermosetting binder. The thermosetting binder may be contained in an amount corresponding to about 0.8 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the acid-modified oligomer.

If the content of the thermosetting binder becomes too small, a carboxyl group may remain in the DFSR after curing, resulting in deterioration of heat resistance, alkali resistance, electrical insulation and the like. On the other hand, when the content is excessively large, a cyclic (thio) ether group having a low molecular weight remains in the dried coating film, and the strength or the like of the coating film is lowered.

The resin composition having photo-curability and thermosetting property of the embodiment may further include an inorganic filler. The inorganic filler serves to improve heat stability, dimensional stability by heat, and resin adhesion. It also acts as an extender pigment by enhancing the color.

Specific examples of such inorganic fillers include barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide (alumina) have.

The content of the filler is preferably about 2 to 50% by weight based on the total weight of the composition. When it is used in an amount of more than 50% by weight, the viscosity of the composition is increased and the coating property is lowered or the curing degree is lowered.

As described above, the content of the inorganic filler in the solid content excluding the organic solvent may be 20 wt% to 55 wt%, or 25 wt% to 45 wt%.

In order to dissolve the resin composition having the photocurable property and the thermosetting property, or to give an appropriate viscosity, one or more solvents may be used in combination.

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; But are not limited to, 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, dipropylene glycol monomethyl ether acetate And the like; 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 dimethylacetamide and dimethylformamide (DMF), and the like. These solvents may be used alone or as a mixture of two or more thereof.

The content of the solvent may be about 1 to 90% by weight, or 10 to 50% by weight based on the total weight of the resin composition.

The resin composition having photo-curable properties and thermosetting properties may further comprise a thermosetting agent, a pigment, a leveling agent or a dispersing agent.

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

Examples of the thermosetting agent include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as 1-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- compound; Hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus 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.

The present invention is not limited thereto and may be a thermal curing catalyst for an epoxy resin or an oxetane compound or a catalyst for accelerating a reaction between an epoxy group and / or an oxetanyl group and a carboxyl group, or a mixture of two or more thereof may be used .

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 And S-triazine derivatives such as adducts may be used. Preferably, a compound that also functions as such an adhesion-imparting agent can be used in combination with the above-mentioned thermosetting agent.

The content of the thermosetting agent may be about 0.3 to 15% by weight based on the total weight of the resin composition in view of adequate thermosetting property.

The pigment exhibits visibility and hiding power, and serves to hide defects such as scratches on circuit lines.

As the usable pigment, red, blue, green, yellow, black pigment and the like can be used. As blue pigments, 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, have. Green pigments include Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like. Examples of the yellow pigment include anthraquinone type, isoindolinone type, condensed azo type, and benzimidazolone type. Examples thereof include Pigment Yellow 108, Pigment Yellow 147, Pigment Yellow 151, Pigment Yellow 166, Mention Yellow 181, Pigment Yellow 193, and the like.

The content of the pigment is preferably about 0.5 to 3% by weight based on the total weight of the resin composition. If it is used in an amount less than 0.5% by weight, visibility and hiding power will be lowered, and if it is used in an amount exceeding 3% by weight, heat resistance will be deteriorated.

Other usable additives may include additives that remove bubbles in the resin composition, remove the popping or crater on the surface during film coating, provide flame retardant properties, control viscosity, and catalyze .

Specifically, known thickeners such as fine silica, organic bentonite, and montmorillonite; Defoaming agents and / or leveling agents such as silicone, fluorine, and high molecular weight; Silane coupling agents such as imidazole, thiazole and triazole; Flame retardants such as phosphorus flame retardants and antimony flame retardants, and the like.

For example, BYK-380N, BYK-307, BYK-378, and BYK-350 of BYK-Chemie GmbH can be used as the leveling agent in removing the popping or craters on the surface during film coating.

The content of the other additives is preferably about 0.01 to 10% by weight based on the total weight of the resin composition.

According to another embodiment of the present invention, there is also provided an acid-modified oligomer; Photopolymerizable monomer; Thermosetting binder resin; Photoinitiators; Organic solvent; And an epoxy resin to which a carboxyl-terminated butadiene / acrylonitrile copolymer is added, may be provided. The dry film solder resist (DFSR) may be prepared using a photocurable and thermosetting resin composition.

The acid-modified oligomer; Photopolymerizable monomer; Thermosetting binder resin; Photoinitiators; Organic solvent; And an epoxy resin to which a carboxyl-terminated butadiene / acrylonitrile copolymer is added, may have a high flexibility and elasticity, and thus a SRO (Silicon Rich oxide) thin film can be prevented from being broken and the defect caused by the difference in coefficient of thermal expansion between the substrates can be minimized.

In addition, the dry film solder resists or other coating films of the above embodiments can have high heat resistance and elasticity, and at the same time, have excellent mechanical properties such as excellent durability and impact resistance.

In addition, the DFSR can satisfy various physical properties such as PCT resistance, TCT heat resistance and HAST resistance between fine wirings required for a package substrate material of a semiconductor device, and also reduces warpage phenomenon to reduce defects The life of the product can be increased.

The dry film solder resist may include a cured product or a dried product of the photosensitive resin composition.

The dry film solder resist may have a thermal expansion coefficient (alpha 1) of 10 ppm / C to 40 ppm / C, or 15 ppm / C to 25 ppm / C.

A process for producing a dry film solder resist (DFSR) using a resin composition having photo-curability and thermosetting properties according to one embodiment will be described as follows.

First, a resin composition of the above embodiment is applied to a carrier film as a photosensitive coating material by a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, A spray coater or the like, and then the oven is passed through the oven at a temperature of 50 to 130 캜 for 1 to 30 minutes to dry the laminate. Then, a release film is laminated thereon to form a carrier film, a photosensitive film, Can be produced.

The thickness of the photosensitive film may be about 5 to 100 mu m. As the carrier film, a plastic film such as polyethylene terephthalate (PET), a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film can be used. As the release film, polyethylene (PE) A polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. When the release film is peeled off, 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.

Next, the release film is peeled off, and then the photosensitive film layer is bonded to the substrate on which the circuit is formed by using a vacuum laminator, a hot roll laminator, a vacuum press, or the like.

Next, the substrate is exposed by a light beam (UV or the like) having a certain wavelength band. The exposure may be selectively exposed by a photomask, or may be directly pattern-exposed by a laser direct exposure apparatus. The carrier film peels off after exposure. The exposure dose varies depending on the thickness of the coating film, but is preferably 0 to 1,000 mJ / cm 2. When the above-described exposure is carried out, for example, photocuring occurs in the exposed portion, and cross-linking can be formed between the acid-modified oligomer and the unsaturated functional groups contained in the photopolymerizable monomer or the like. As a result, State. On the other hand, the unexposed portion can be in a state in which the crosslinking and thus the crosslinking structure are not formed, and the carboxyl group is retained and can be alkali-developed.

Next, development is performed using an alkali solution or the like. The alkali 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, only the film of the exposed portion can remain.

Finally, a printed circuit board including the solder resist formed from the photosensitive film is completed by heat curing (Post Cure). A heat curing temperature of 100 ° C or higher is suitable.

Through the above-described method or the like, a DFSR and a printed circuit board including the DFSR can be provided. As the DFSR undergoes light curing and thermosetting, acid-modified oligomers; A photopolymerizable monomer having at least two photocurable unsaturated functional groups; And a cured product of a thermosetting binder having a thermosetting functional group.

The dry film solder resist may be used as a protective film for a printed circuit board. The dry film solder resist can be used for manufacturing a package substrate of a semiconductor device.

According to another embodiment of the present invention, a circuit board including the dry film solder resist may be provided.

The manufacturing method of the circuit board is the same as the manufacturing process of the printed circuit board using the dry film solder resist, and the dry film solder resist can be used as a protective film for a printed circuit board.

According to the present invention, there is provided a dry film solder resist (DFSR) capable of providing a dry film solder resist (DFSR) capable of sufficiently securing mechanical properties such as excellent durability and impact resistance while having high heat resistance and elasticity A resin composition having photo-curable properties and thermosetting properties can be provided.

When the resin composition having photo-curable properties and thermosetting properties is used, a dry film solder resist having the above-described characteristics and a circuit board containing the dry film solder resist can be provided.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example  And Comparative Example : Production of Resin Composition, Dry Film and Printed Circuit Board]

Example 1

(1) Production of resin composition having photo-curable property and thermosetting property

5% by weight of RA 840 (bisphenol A diglycidyl ether to which a carboxyl group-terminated butadiene / acrylonitrile copolymer was added), 35% by weight of CCR-1235 of Japanese explosive as an acid-modified oligomer, 10% by weight of DPEA-12 from Lod, 4% by weight of TPO as a photoinitiator, 15% by weight of YDCN-500-90P by Kukdo Chemical Co. as epoxy resin, 0.1% by weight of dicyandiamide as an epoxy curing agent, 0.1 weight% of Disperbyk-110 as a dispersing agent, 0.1 weight% of BYK-380N as a leveling agent, 0.1 weight% of Disperbyk-110 as a dispersing agent, 15 weight% of BaSO4 as a filler, 0.2 weight% of each of Pigment Blue 15: 3 and Pigment Yellow 151 as pigments, And 15% by weight of DMF as a solvent, to prepare a photosensitive resin composition.

The prepared photosensitive resin composition was applied to PET as a carrier film, then passed through an oven at 75 캜 and dried. Then, PE was laminated as a release film to form a carrier film, a photosensitive film (thickness of 20 탆) To prepare a dry film.

(2) Manufacturing of printed circuit boards

After peeling off the cover film of the prepared dry film, the photosensitive film layer was vacuum laminated on the substrate on which the circuit was formed, and then a photomask corresponding to the circuit pattern was placed on the photosensitive film layer and exposed with UV light. And developed to remove unwanted portions to form a desired pattern, and then photocured, thereby completing a printed circuit board comprising a protective film (solder resist) formed from a photosensitive film.

Example  2

Except that 2 wt% of RA 840 (bisphenol A diglycidyl ether to which a carboxyl group-terminated butadiene / acrylonitrile copolymer was added) was used, and 18 wt% of DMF was used as a solvent A dry film was produced.

Example 3

Except that 10 wt% of RA 840 (bisphenol A diglycidyl ether to which a carboxyl group-terminated butadiene / acrylonitrile copolymer was added) was used, and 10 wt% of DMF was used as a solvent A dry film was produced.

Example  4

10% by weight of KR-170 [(1) Viscosity: cps (at 25?) Of 30,000 to 60,000 and (2) Epoxy Equivalent Weight: about 325 to 360] A dry film was prepared in the same manner as in Example 1, except that 10% by weight of DMF was used.

Comparative Example  One

A dry film and a printed circuit board were prepared in the same manner as in Example 1, except that RA 840 was not used and 20% by weight of DMF was used as a solvent.

Comparative Example  2

A dry film and a printed circuit board were prepared in the same manner as in Example 1 except that CN991 (manufacturer: satomer / aliphatic polyester-based urethane diacrylate oligomer) was used instead of RA 840.

< Experimental Example  >

The properties of the dry film and the printed circuit board prepared in Examples and Comparative Examples were measured by the following methods

Experimental Example 1 : PCT  Heat resistance measurement

A copper clad laminate of LG-T-500GA manufactured by LG Chemical Co., Ltd., having a thickness of 0.1 mm and a thickness of copper foil of 12 mm, was cut into a size of 5 cm x 5 cm in width X and a micro-roughness was formed on the surface of the copper foil by chemical etching. After the release films of the dry films prepared in Examples and Comparative Examples were removed, the film layers were vacuum-laminated on a light-emitting copper clad laminate (substrate) with a vacuum laminator (MV LP-500, manufactured by Meiki Seisakusho Co., Ltd.) , And UV at a wavelength of 365 nm was exposed at an exposure dose of 350 mJ / cm ² . Then, remove the PET film, which was in progress the photocurable at a predetermined time, and the developing, exposure dose of about 1000mJ / cm ² during the Nα2CO ₃ 1% by weight of the alkaline solution 31 ℃. Finally, the specimen was heated and cured at about 170 ° C for 1 hour.

This specimen was treated for 192 hours under conditions of a temperature of 121 占 폚, saturation of 100% humidity and a pressure of 2 atm using a PCT apparatus (Espec Co., Ltd., HAST system TPC-412MD). The observations were evaluated according to the following criteria:

1: No peeling of DFSR, no blisters and discoloration;

2: DFSR peeling, blistering or discoloration occurs, but not less severe than in Example 3;

3: DFSR peeling, blistering and discoloration occur severely.

Experimental Example 2 : Tg  And thermal expansion coefficient

The glass transition temperature (Tg) was measured by the following method. First, the specimen was mounted on a holder to have a length of 10 mm, a force was applied to both ends with 0.05 N, and the length of the specimen was measured at a heating rate of 10 ° C./min from 50 ° C. to 250 ° C. The inflection point shown in the temperature rising section was taken as Tg, and Tg was evaluated by the following method:

1: Tg 150 DEG C or higher;

2: Tg 140 DEG C or more and less than 150 DEG C;

3: Tg 120 DEG C or more and less than 140 DEG C;

4: Tg 100 DEG C or more and less than 120 DEG C;

5: Tg &lt; 100 ° C.

The Tg measurement simultaneously measured and compared the thermal expansion coefficient (CTE) required simultaneously. First, the thermal expansion coefficient α1 at a temperature lower than Tg was calculated from the slope of the specimen increased from 50 ° C to 80 ° C, and the thermal expansion coefficient α2 at a temperature higher than Tg was calculated from the slope of the specimen increased from 170 ° C to 210 ° C. The results of this calculation were evaluated according to the following criteria:

(Thermal expansion coefficient? 1)

1:? 1 less than 20 ppm;

2:? 1 20 ppm or more and less than 30 ppm;

3: alpha 1 30 ppm or more and less than 50 ppm;

4: α1 50 ppm or more.

(Thermal expansion coefficient? 2)

1:? 2 less than 100 ppm;

2:? 2 100 ppm or more and less than 120 ppm;

3: alpha 2 120 ppm or more and less than 150 ppm;

3:? 2 150 ppm or more and less than 200 ppm;

4: 200 ppm or more of? 2

Experimental Example 3 : Break Elongation  Measure

The elastic modulus was measured by measuring the elongation through a universal testing machine (UTM). The elongation was measured using a Z010 instrument manufactured by Zwick, Germany. The sample length was measured at a tensile rate of 50.8 mm / min for a sample having a length of 50 mm, and the fracture elongation was calculated according to the following equation .

[Equation 1]

Elongation at break (%) = (L - L ₀ ) / L ₀ * 100

L is the length of the sample when the sample is ruptured at a tensile rate of 50.8 mm / min for a sample having a length of 50 mm, and L ₀ is an initial sample length.

Then, the elongation at break was evaluated under the following criteria.

<Breaking Elongation >

1: 4% or more

2: Less than 3% and less than 4%

3: Less than 2% and less than 3%

4: Less than 2%

The results measured in Experimental Example 1 are shown in Table 1 below.

PCT
Heat resistance Plated
tolerance Glass transition
Temperature (℃) alpha 1 α2 Elongation at break (%) Example 1 One One One One One One Example 2 One One One One One 2 Example 3 One One One One One One Example 4 One One One One One One Comparative Example 1 One One One One One 4 Comparative Example 2 One One 2 2 2 3

In the above examples, it can be seen that the use of the epoxy resin to which the butadiene / acrylonitrile copolymer at the terminal of the carboxyl group is added is superior in both the durability and the mechanical properties. In addition, it was confirmed that the use of 2 wt%, 5 wt%, and 10 wt%, respectively, in a proper amount to improve the mechanical properties with excellent heat resistance.

On the contrary, in Comparative Example 1 in which additives other than those in Examples were used or additives for improving physical properties were not used, heat resistance was secured, but mechanical properties such as elasticity and the like were greatly deteriorated. Particularly, in the case of Comparative Example 2, it was confirmed that a relatively large thermal expansion coefficient was exhibited, and warpage problems caused by a difference in thermal expansion coefficient between the semiconductor device and the package substrate material could be exhibited.

Claims (21)

20 to 50% by weight of an acid-modified oligomer; 5 to 30% by weight of photopolymerizable monomer; 0.5 to 40% by weight of a thermosetting binder resin; 0.1 to 20% by weight of a photoinitiator; 10 to 50% by weight of an organic solvent; 2 to 50% by weight of an inorganic filler and 1 to 40% by weight of a bisphenol A diglycidyl ether resin to which a carboxyl-terminated butadiene / acrylonitrile copolymer is added,
The acid-modified oligomer includes an epoxy (meth) acrylate compound having a weight average molecular weight of 6,000 to 20,000,
Wherein the thermosetting binder resin comprises at least one resin selected from the group consisting of 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 Lt; / RTI &gt;
The photopolymerizable monomer includes a polyfunctional compound having at least two vinyl groups or a polyfunctional (meth) acrylate compound having at least two (meth) acryloyl groups in the molecule,
Wherein the content of the inorganic filler in the solid content excluding the organic solvent is 25 wt% to 45 wt%
Photo-curable resin and thermosetting resin composition.
The method according to claim 1,
Wherein the bisphenol A diglycidyl ether resin to which the carboxyl-terminated butadiene / acrylonitrile copolymer is added has a viscosity of 5,000 to 300,000 cps at 25 占 폚.
The method according to claim 1,
The bisphenol A diglycidyl ether resin to which the carboxyl-terminated butadiene / acrylonitrile copolymer is added contains 25% by weight to 60% by weight of the butadiene / acrylonitrile copolymer at the terminal of the carboxyl group, and the photocurable and thermosetting .
delete delete delete delete delete delete The method according to claim 1,
The photoinitiator may be a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, an? -Amino acetophenone compound, an acylphosphine oxide compound, an oxime ester compound, Based compound and at least one compound selected from the group consisting of a triazine-based compound, and a photocurable and thermosetting resin composition.
delete delete delete delete The method according to claim 1,
The inorganic filler includes at least one selected from the group consisting of barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, Curing, and thermosetting.
The method according to claim 1,
A resin composition having photo-curable and thermosetting properties, which further comprises a thermosetting catalyst, a thermosetting agent, a leveling agent or a dispersing agent.
A dry film solder resist produced by using the resin composition having the photocurable and thermosetting properties of claim 1.
18. The method of claim 17,
A dry film solder resist comprising a cured product or a dried product of the resin composition having photo-curability and thermosetting property.
18. The method of claim 17,
A dry film solder resist having a thermal expansion coefficient of 15 ppm / C to 40 ppm / C.
18. The method of claim 17,
Dry film solder resist used as a protective film for printed circuit boards.
A circuit board comprising the dry film solder resist of claim 17.