KR101755018B1 - Photo-curable and thermo-curable resin composition and dry film solder resist - Google Patents

Abstract

The present invention relates to a resin composition comprising an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, an inorganic filler, a silicone epoxy copolymer and an organic solvent, wherein the content of the inorganic filler in the solid content excluding the organic solvent is 20 wt% %, Photocurable and thermosetting, a dry film solder resist obtained from the resin composition, and a circuit board comprising the dry film solder resist.

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, which not only have excellent photosensitivity, plating resistance, A dry film solder resist, and a circuit board including the dry film solder resist (DFSR) capable of minimizing the warpage phenomenon.

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. By using such a dry film type solder resist, the process for forming a resist can be simplified, and the effect of reducing the amount of the solvent discharged at the time of forming a resist can be obtained.

On the other hand, the semiconductor package product is a composite material including an epoxy molding, a non-conductor such as a solder resist, a semiconductor such as a dip die, a conductor such as a circuit pattern of a substrate, etc. In order to produce such a composite material, various processes involving severe thermal shock conditions . However, due to the difference in the coefficient of thermal expansion (CTE) of each component included in the semiconductor package product, for example, the non-conductor, the semiconductor, and the conductor, the dimensional stability is largely reduced or the warpage phenomenon . This diminished dimensional stability or warpage may cause inconsistency in position between the chip and the substrate when the chip die and the semiconductor substrate are connected by solder balls or gold wires, and may cause uniformity and breakage of the product due to shear stress , Which can shorten the life of the product. Further, as the thickness of the substrate becomes thinner, the dimensional stability and the warping phenomenon can be further intensified. Therefore, there is a demand for a substrate material and a solder resist having a lower thermal expansion coefficient depending on the miniaturization and lighter weight of various electronic apparatuses It is a fact that it is getting bigger.

The present invention relates to a dry film solder resist (DFSR) which not only has excellent photocuring properties, plating resistance, mechanical properties and heat resistance but also exhibits a low thermal expansion coefficient (CTE) to minimize dimensional stability and warpage, Which is capable of providing photo-curable and thermosetting resin compositions.

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 a resin composition comprising an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, an inorganic filler, a silicone epoxy copolymer and an organic solvent, wherein the content of the inorganic filler in the solid content excluding the organic solvent is 20 wt% %, Photo-curing property and thermosetting property.

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 an embodiment of the present invention, there is provided a photosensitive resin composition comprising an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, an inorganic filler, a silicone epoxy copolymer and an organic solvent, By weight to 55% by weight, based on the total weight of the composition.

Various fillers have been applied to improve the physical properties of dry film solder resist (DFSR), for example, development, PCT heat resistance, glass transition temperature and thermal expansion coefficient. However, when filler content is exceeded, And the physical properties and quality of the DFSR or the circuit board finally manufactured can be lowered.

On the contrary, the resin composition having photo-curable property and thermosetting property according to one embodiment of the present invention includes the silicone epoxy copolymer, and the content of the inorganic filler in the solid content excluding the organic solvent is 20% by weight or 20% by weight to 55% %, The heat resistance can be improved without lowering the physical properties and the coefficient of linear expansion can be lowered.

Accordingly, when the resin composition having the photo-curability and the thermosetting property is used , not only the photo-curing property , the plating resistance, the mechanical property, and the heat resistance are exhibited but also the low thermal expansion coefficient (CTE) A dry film solder resist (DFSR) capable of minimizing the thickness of the solder resist layer can be provided.

The photocurable and thermosetting resin composition may have a thermal expansion coefficient (alpha 1) of 10 ppm / C to 40 ppm / C, or 15 ppm / C to 25 ppm / C after photocuring and thermosetting. The photocuring and the thermosetting may be carried out sequentially sequentially or both at the same time.

The silicone epoxy copolymer refers to a polymer compound containing a silicone repeating unit derived from a silicone compound or polysilicon compound and an epoxy repeating unit derived from an epoxy compound or a polyepoxy compound.

The silicone epoxy copolymer may include 20 to 80% by weight of silicone repeating units.

If the content of the silicone repeating unit in the silicone epoxy copolymer is too small, the effect of preventing breakage of the hole may not be exhibited. If the content of the silicone repeating unit is too high, phase separation may occur, And can be uniform.

The silicone epoxy copolymer may have a kinematic viscosity at 25 ° C of 10,000 to 400,000 mPa · s.

The silicone epoxy copolymer may include a linear silicone epoxy copolymer in which an epoxy group is substituted at the terminal.

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 the additional acid-modified oligomer that can be used 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);

Commercially available components may also be used as the above-mentioned additional acid-modified oligomers. Specific examples of such components include ZAR-2000, CCR-1235, ZFR-1122 and CCR-1291H 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 filler particles may occur during the dispersion of the inorganic filler, 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 filler serves to improve heat stability, dimensional stability by heat, and resin adhesion. It also acts as an extender pigment by enhancing the color.

The filler may be an inorganic filler such as barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide Aluminum, mica, or the like can be used.

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 they may be used alone or in combination of two or more .

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 provided a process for producing an inorganic filler, which comprises an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, an inorganic filler, a silicone epoxy copolymer and an organic solvent, And 20 to 55% by weight of the dry film solder resist (DFSR), which is produced by using a photocurable and thermosetting resin composition.

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, reduces warpage phenomenon, The life span 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.

According to the present invention, it is possible to provide a dry film solder resist (hereinafter referred to as " dry film solder resist ") capable of minimizing the phenomenon of deterioration of dimensional stability and warpage by exhibiting excellent CTE, plating resistance, mechanical property, A resin composition having photo-curable properties and thermosetting properties capable of providing a DFSR 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  To 3

The components shown in Table 1 were mixed to prepare a resin composition. As the acid-modified oligomer, an epoxy (meth) acrylate compound derived from cresol novolak and an epoxy (meth) acrylate compound derived from bisphenol F were mixed at a weight ratio of 3: 1.

The resin composition thus prepared was applied to PET as a carrier film, passed through an oven at 75 deg. C to be dried, and then PE was laminated as a release film to form a carrier film, a photosensitive film (thickness 20 mu m) To prepare a dry film.

After peeling off the cover film of the prepared dry film, the photosensitive film layer was vacuum laminated on the circuit-formed substrate, and the photomask corresponding to the circuit pattern was placed on the photosensitive film layer and exposed by UV. The exposure was carried out at an exposure amount of 350 mJ / cm < 2 > at a wavelength of 365 nm. Thereafter, the PET film was removed, and the film was developed with a 1 wt.% Alkali solution of Na ₂ CO ₃ at 31 ° C for a predetermined time to remove unnecessary portions to form a desired pattern. Subsequently, photo-curing was carried out at an exposure amount of 1000 mJ / cm 2, and finally curing at 160 to 170 ° C for 1 hour to complete a printed circuit board comprising a protective film (solder resist) formed from a photosensitive film.

Composition of Examples 1 to 3 [unit: g] ingredient
Ingredients
(Or product name) Example 1 Example 2 Example 3 Acid-modified oligomer ZFR-1122 15 15 15 CCR-1291H 45 45 45 ZAR-1035 (BPA) ZAR-2000 (BPA) Photopolymerizable monomer M300 10 10 10 Thermosetting binder
(Epoxy resin) NC-300H 10 10 10 YDCN-500-90P 5 5 5 Silicone epoxy copolymer Albiflex 296 10 10 10 Heat curing agent Dicandamide 0.15 0.15 0.15 CXC-1756 0.2 0.2 0.2 Photoinitiator Darocur TPO 2.5 2.5 2.5 Irgacure 819 1.67 1.67 1.67 Darocur ITX 0.83 0.83 0.83 Pigment B15: 3 0.3 0.3 0.3 Y147 0.5 0.5 0.5 Inorganic filler BaSO ₄ 40 60 80 Talc 2.5 2.5 2.5 Content of inorganic filler in solid (wt%) 29.6 38.2 44.9 menstruum DMF 20 20 20

Comparative Example  1 to 4

The components shown in Table 2 were mixed to prepare a resin composition. As the acid-modified oligomer, an epoxy (meth) acrylate compound derived from cresol novolak and an epoxy (meth) acrylate compound derived from bisphenol A were mixed at a weight ratio of 3: 1.

Using the resin composition thus prepared, a dry film was prepared in the same manner as in Example 1, and a printed circuit board including a protective film (solder resist) was formed using the dry film in the same manner as in Example 1 Respectively.

Comparative Examples 1 to 4 ingredient
Ingredients
(Or product name) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Acid-modified oligomer ZFR-1122 CCR-1291H 45 45 45 45 ZAR-1035 (BPA) ZAR-2000 (BPA) 15 15 15 15 Photopolymerizable monomer M300 10 10 10 10 Thermosetting binder
(Epoxy resin) NC-300H 15 15 15 15 YDCN-500-90P 10 10 10 10 Silicone epoxy copolymer Albiflex 296 - - - - Heat curing agent Dicandamide 0.15 0.15 0.15 0.15 CXC-1756 0.2 0.2 0.2 0.2 Photoinitiator Darocur TPO 2.5 2.5 2.5 2.5 Irgacure 819 1.67 1.67 1.67 1.67 Darocur ITX 0.83 0.83 0.83 0.83 Pigment B15: 3 0.3 0.3 0.3 0.3 Y147 0.5 0.5 0.5 0.5 Inorganic filler BaSO ₄ 20 40 60 80 Talc 2.5 2.5 2.5 2.5 Content of inorganic filler in solid (wt%) 18.2 29.6 38.2 44.9 menstruum DMF 20 20 20 20

< 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 : Developability (Sensitivity) evaluation

3EC-M3-VLP 12 mu m copper clad laminate of Mitsui Metal Co., Ltd. was cut into a size of 5 cm x 5 cm in width X length, and micro-roughness was formed on the surface of the copper foil by chemical etching. After the release films of the dry films prepared in the above 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.) .

Then, a negative type photomask having a hole shape of 80 mu m in diameter was closely contacted, and UV of 365 nm wavelength was exposed at an exposure amount of 350 mJ / cm &lt; ^{2 &} gt ;. Thereafter, the PET film was removed, and developed with a 1 wt% alkali solution of N 留₂ CO ₃ at 31 캜 for a predetermined time to form a pattern.

Then, the shape of the formed pattern was observed with an SEM and evaluated under the following criteria.

1: The cross section is straight shape, no film residue on the floor

2: The cross section is not a straight shape, and undercut or overhang exists in the hole shape

3: Observation in unfinished state

4: Pattern can not be formed by phenomenon

Experimental Example 2 : PCT  Heat resistance and Electroless  Nickel plating resistance

(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 캜, a humidity of 100% saturation 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.

(2) Electroless nickel plated (ENIG) characteristics

Next, the electroless nickel plating resistance was evaluated by treating the above sample with an electroless nickel plating solution (PUWON CHEMICAL, ELN-M, ELN-A) at a temperature of 85 캜 for 30 minutes, -M) for 15 minutes at a temperature of 85 DEG C was observed and evaluated according to the following criteria:

1: No occurrence of whitening of DFSR;

2: some whitening of the DFSR occurred but not less severe than the following 3;

3: DFSR whitening occurs severely.

(3) Electroless Nickel Electroless Palladium Electroless Nickel Electroless Palladium Immersion Gold ENEPIG

The electroless nickel plating resistance was evaluated by treating the above sample with electroless nickel plating solution (PUWON CHEMICAL, ELN-M, ELN-A) at 85 ° C for 30 minutes, , ELP-A) at a temperature of 50 캜 for 15 minutes, and finally the state of the coated film treated for 15 minutes at a temperature of 85 캜 with an electroless gold plating solution (Poongwon Chemical Co., PIG-M) .

1: No occurrence of whitening of DFSR;

2: some whitening of the DFSR occurred but not less severe than the following 3;

3: DFSR whitening occurs severely.

Experimental Example 3 : Absorption measurement

The ICS-25um copper foil of ILJIN Material was cut to a size of 11 cm long and 11 cm wide, and then the dry film prepared in Examples and Comparative Examples was cut into a size of 10 cm * 10 cm in width and 10 cm * After removing the sample, the sample was prepared and mass was measured in the same manner as in the PCT heat resistance measurement.

This specimen was treated for 24 hours under the conditions of a temperature of 85 DEG C and a humidity of 85% using a constant temperature and humidity apparatus (SH-941, manufactured by Espec Co., Ltd.), and the mass thereof was measured.

1) Absorption rate (%) = (Absorption mass / sample nitrogen) * 100

2) Moisture absorbing mass = (Specimen mass after constant temperature and humidity treatment) - (Specimen mass before constant temperature and humidity treatment)

3) Sample mass = (Specimen mass before and after constant temperature and humidity treatment) - (Copper mass)

Experimental Example 4 : Tg  And thermal expansion coefficient

On the Shiny side of the 3EC-M3-VLP 12 占 퐉 copper foil of Mitsui Metal Co., film layers were laminated in the same manner as in the preparation of the measurement specimen such as PCT heat resistance. DFSR specimens were prepared by proceeding to the heat curing in the same manner as in the preparation of the test specimens such as PCT heat resistance, except that a negative type mask having a width of 5 mm and a spacing of 5 mm was placed on the specimen and exposed. Finally, the copper foil was peeled from the specimen to prepare a 5 mm striped test piece for evaluation of TMA (thermal mechanical analysis, METTLER TOLEDO, TMA / SDTA 840).

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 defined as Tg.

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.

Experimental Example 5 : Hole crack  Confirm creation

A copper clad laminate (thickness: 0.1 mm, thickness of copper foil: 12 um, LG Chem LG-T-500GA) was cut into a size of 5 cm in length and 5 cm in length, and 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.) , A negative type photomask having a hole shape with a diameter of 80 mu m was closely contacted, and UV at a wavelength of 365 nm was exposed at an exposure amount of 350 mJ / cm &lt; 2 &gt;.

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.

Then, the shape of the formed pattern was observed with an SEM and evaluated under the following criteria.

1: No crack on hole shape

2: Crack in hole shape

Experimental Example 5 : out Gas  Measured amount of emissions ( FUME )

The specimens were prepared in the same manner as the PCT heat resistant specimens. Fume generated at 250 ℃ for 30 minutes was measured in ug / ㎠ using purege & trap sampler - GC / MSD system (EQC-0176).

The results measured in Experimental Examples 1 to 6 are shown in Table 3 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Sensitivity 11 10 10 12 10 9 8 Electroless nickel gold plating
(ENIG) characteristics 0 0 0 0 0 0 0 Gold plated (ENEPIG)
characteristic 0 0 0 0 0 0 0 Absorbency (%) 0.5 0.6 0.5 0.5 0.6 0.7 1.0 Fume (ppm) 120 110 100 130 120 120 110 PCT heat resistance 0 0 0 0 0 0 0 Coefficient of linear expansion
(a1) 39 25 15 58 46 44 41 Hole crack 0 0 0 0 0 x x

As shown in the results of the measurement and evaluation in Table 3, it was confirmed that the DFSR of the examples exhibited excellent physical properties as compared with the DFSR of the comparative example in terms of not only developability but also various physical properties such as PCT heat resistance, glass transition temperature and thermal expansion coefficient . In particular, the DFSR of the embodiment exhibits a lower coefficient of thermal expansion (CTE) as compared with the comparative example, thereby minimizing the dimensional stability degradation and warpage phenomenon.

Therefore, it is confirmed that the embodiment is suitable for the formation of DFSR showing high temperature thermal reliability.

Claims (20)

An acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, an inorganic filler, a linear silicone epoxy copolymer substituted with an epoxy group at the terminal, and an organic solvent,
Wherein the content of the inorganic filler in the solid content excluding the organic solvent is 20 wt% to 55 wt%
Wherein the linear silicone epoxy copolymer having an epoxy group substituted at the terminal thereof comprises 20 to 80% by weight of silicone repeating units,
The linear silicone epoxy copolymer in which the epoxy group is substituted at the terminal has a kinetic viscosity at 25 ° C of 10,000 to 400,000 mPa · s,
C at a temperature lower than the glass transition temperature (Tg) after photocuring and thermosetting is 10 ppm / C to 40 ppm / C,
Photo-curable resin and thermosetting resin composition.
delete delete delete delete The method according to claim 1,
Wherein the acid-modified oligomer comprises an epoxy (meth) acrylate-based compound.
The method according to claim 6,
The epoxy (meth) acrylate compound has a weight average molecular weight of 6,000 to 20,000.
The method according to claim 1,
Wherein the photopolymerizable monomer is a compound having a photocurable unsaturated functional group.
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.
The method according to claim 1,
Wherein the thermosetting binder resin comprises 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.
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,
5 to 75% by weight of an acid-modified oligomer;
1 to 40% 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;
2 to 50% by weight of an inorganic filler;
1 to 55% by weight of a linear silicone epoxy copolymer having an epoxy group substituted at the terminal thereof; And
1 to 90% by weight of an organic solvent; and a photocurable and thermosetting resin composition.
The method according to claim 1,
A resin composition for photocuring and thermosetting, which further comprises a thermosetting catalyst, a thermosetting agent, a pigment, a leveling agent or a dispersing agent.
A dry film solder resist produced by using the photosensitive resin composition of claim 1.
17. The method of claim 16,
A dry film solder resist comprising a cured product or a dried product of the photosensitive resin composition.
17. The method of claim 16,
Wherein the thermal expansion coefficient (alpha 1) at a temperature lower than the glass transition temperature (Tg) is 10 ppm / C to 40 ppm /
Dry film solder resist.
17. The method of claim 16,
Dry film solder resist used as a protective film for printed circuit boards.
A circuit board comprising the dry film solder resist of claim 16.