WO2014204173A1 - Photocurable and thermosetting resin composition and dry film solder resist - Google Patents

Abstract

The present invention relates to a resin composition which is photocurable and thermosetting, and which comprises an acid-modified oligomer, a photo-polymerizable monomer, a thermosetting binder resin, a photoinitiator, at least two types of spherical alumina particles having mutually different particle sizes, and an organic solvent; a dry film solder resist obtained from the resin composition; and a circuit board comprising the dry film solder resist.

Description

 【Specification】

 [Name of invention]

 Resin composition and dry film solder resist having photocurability and thermosetting

 Technical Field

 The present invention relates to a resin composition, a dry film solder resist, and a circuit board having photocurability and thermosetting.

 [Technique to become background of invention]

 With the miniaturization and light weight of various electronic devices, photosensitive protective films capable of forming fine opening patterns are used for printed circuit boards (PCBs), semiconductor package substrates, and flexible printed circuit boards (FPCBs).

The protective film is also called a solder resist, and generally requires characteristics such as developability, high resolution, insulation, solder heat resistance, and gold plating resistance. In particular, for solder resists for package substrates, in addition to these characteristics, for example, crack resistance to a temperature cycle test (TCT) of 55 ^° C. to 125 ^° C. or HAST (Highly Accelerated Stress Test) between fine wirings. Characteristics are required.

 In recent years, a dry film type solder resist (DFSR: Dry Film Solder Resist) having good film 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 solvent emissions during the resist formation can be obtained.

On the other hand, semiconductor package products are composite materials including epoxy molding, insulators such as solder resists, semiconductors such as chip dies, and conductors such as substrate circuit patterns. do. However, due to the different coefficients of thermal expansion (CTE) of the respective components included in the semiconductor package products, for example, insulators, semiconductors, and conductors, dimensional stability is greatly reduced or warpage occurs. May appear. Such Deterioration or warpage of the dimensional stability may cause misalignment between the chip and the substrate when the chip die and the semiconductor substrate are connected with solder balls or gold wires, and may cause product uniformity and breakage due to shear forces. This can shorten the life of the product. In addition, as the thickness of the substrate becomes thinner, the dimensional stability deterioration and the warpage phenomenon can be intensified. Therefore, the demand for substrate materials and solder resists having a lower coefficient of thermal expansion than para is required for miniaturization and weight reduction of various electronic devices. It is getting bigger.

 As electronic devices and electronic components tend to be light and short in recent years, the degree of integration of electric devices is increasing, and the amount of heat generated by electric devices operating by electric energy is also increasing. Accordingly, there is an increasing demand for an improvement in heat dissipation characteristics for effectively dissipating and dissipating heat generated inside an electronic device.

 Accordingly, various studies have been made on methods for improving heat dissipation characteristics by effectively dissipating and dissipating heat generated from electrical devices. For example, in order to improve the heat dissipation characteristics of various electric elements, a method including a heat sink for conducting heat and dissipating it to the outside or a silicon rubber sheet having excellent thermal conductivity has been proposed. The back has a limitation in that it is difficult to firmly adhere to the electric elements and exhibits insufficient heat dissipation characteristics.

 [Content of invention]

 Problem to be solved

 The present invention not only has excellent photocuring properties, plating resistance, mechanical properties and heat resistance, but also it can minimize dimensional stability degradation and warpage, and provide a dry film solder resist (DFSR) having high heat dissipation properties. It is to provide a resin composition having photocurable and thermosetting properties.

In addition, the present invention is to provide a dry film solder resist ^■ obtained from the resin composition having the above-mentioned photo-curing and thermosetting. In addition, the present invention is a circuit comprising the dry film solder resist It is for providing a substrate.

 [Measures of problem]

 In the present specification, an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, two or more spherical alumina particles having different particle diameters, a carbon compound and an organic solvent surface-coated with a thermally conductive ceramic compound, photocurable And a resin composition having thermosetting properties. Moreover, in this specification, the dry film soldering resist (DFSR) manufactured using the photosensitive resin composition is provided.

Moreover, in this specification, the circuit board containing the said dry film soldering resist is provided. ^'

 Hereinafter, a resin composition, a dry film solder resist, and a circuit board having photocurable and thermosetting properties according to specific embodiments of the present invention will be described in more detail. According to an embodiment of the present invention, an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, two or more spherical alumina particles having different particle diameters, a carbon compound coated with a surface conductive ceramic compound, and an organic solvent are included. In addition, a resin composition having photocurability and thermosetting property can be provided.

 Various fillers are applied to improve the physical properties of dry film solder resist (DFSR), such as development, PCT heat resistance, glass transition temperature and coefficient of thermal expansion. This can reduce the physical properties and quality of the final DFSR or circuit board produced.

On the contrary, the photocurable and thermosetting resin composition of one embodiment of the present invention includes two or more types of spherical alumina particles having different particle diameters, while greatly increasing the content of the inorganic column and improving heat resistance without deteriorating overall physical properties. The coefficient of linear expansion can be lowered, and the heat dissipation characteristics can be greatly improved without lowering the insulation characteristics of the dry film solder resist to be produced. ' In addition, by using the photocurable and thermosetting resin composition of the embodiment of the present invention can be provided a dry film type solder resist, according to the precipitation or agglomeration of the filler that is a problem in the previously known liquid solder resist The fall of preservation stability can be solved.

 In addition, the use of the resin composition having photocurability and thermosetting properties not only has excellent photocuring properties, plating resistance, mechanical properties and heat resistance, but also exhibits low coefficient of thermal expansion (CTE) to reduce dimensional stability and warpage. Minimized dry film solder resist (DFSR) may be provided.

 As described above, the resin composition having photocurability and thermosetting property may include two or more types of spherical alumina particles having different particle diameters. As such, by including two or more types of spherical alumina particles having different particle diameters, it is possible to minimize the voids between the spherical alumina particles in the resin matrix, thereby improving the heat dissipation effect. According to the use of two or more spherical alumina particles having different particle diameters, a larger synergy effect or a composite effect may be realized compared to the quantitative sum of the effects of using each of the two spherical alumina particles. The embodiment alumina particles refers to alumina particles having a spherical shape or near three-dimensional shape.

 Two or more types of spherical alumina particles having different particle diameters The particle size of at least one spherical alumina particle may be 0.1 or less, for example, 0.01 to 0.1;

 In addition, the particle diameter of at least one spherical alumina particles of two or more types of spherical alumina particles having different particle diameters may be 0.2 to 0.7. Accordingly, the two or more spherical alumina particles having different particle diameters may include one spherical alumina particle having a particle size of 0.1 or less and another spherical alumina particle having a particle size of 0.2 kPa to 0.7. .

The photocurable and thermosetting resin composition may include 1 weight ¾> to 75 weight ¾> of two or more kinds of spherical alumina particles having different particle diameters. If the content of the spherical alumina particles is too small, heat radiation Characteristics may be difficult to fully realize, if the content of the spherical alumina particles is too large, it may be difficult to form a film or the like because the uniformity of the resin composition having the photocurable and thermosetting deteriorates or coating is not easy to perform, Due to the deterioration of the adhesion force, the adhesion with the PCB substrate may not be easy.

 On the other hand, the photocurable and thermosetting resin composition may include a carbon compound surface-coated with a thermally conductive ceramic compound in order to greatly improve the heat dissipation characteristics without lowering the insulation properties of the dry film solder resist to be produced .

 The thermally conductive ceramic compound may be included in the photocurable and thermosetting resin compositions coated on the surface of the carbon compound to quickly transfer heat generated from an electric device.

These thermal Specific examples of alumina conductive ceramic compound (A1 ₂ 0 _3), boron nitride (BN), nitride aluminum (A1N), silicon carbide (SiC), oxidized magnetite thoracic (MgO), zinc (ZnO), hydroxide of aluminum oxide ( AK0H) ₃ ) or a mixture thereof, and preferably, alumina or magnesium oxide may be used.

 In addition, when the surface of the carbon compound is coated with a thermally conductive ceramic compound, it is possible to maintain the high thermal conductivity characteristics of the carbon compound and to implement excellent withstand voltage strength, which is included in the photocurable and thermosetting resin composition. The compatibility with other component stones can also be improved.

The carbon compound coated on the surface of the thermally conductive ceramic compound may include 0.5 wt% to 20 wt% of the thermal conductive ceramic compound; And 80 wt% to 99.5 wt% of the carbon compound, and wherein the carbon compound coated on the surface of the thermal conductive ceramic compound includes 1 wt% to 10 wt% of the thermal conductive ceramic compound; And 90% by weight to 99% by weight of a carbon compound. When the content of the thermally conductive ceramic compound is too low, the resin composition having a photocurable and thermosetting property of the embodiment or a product prepared therefrom cannot sufficiently secure physical properties such as voltage resistance or electric thermal resistance, and electronic materials It is disadvantageous for use as an insulating film for use. In addition, of the thermally conductive ceramic compound If the content is too high, it is disadvantageous in the dispersing process due to the formation of coarser fillers during the surface treatment process.

 Specific examples of the carbon compound may include carbon nanotubes, graphene, graphites, or mixtures thereof, and preferably carbon nano-rubbers may be used.

Carbon coated on the surface of the thermally conductive ceramic compound

It may have an average particle diameter of 4 to.

 The photocurable and thermosetting resin composition may include 1.1 wt% or less, preferably 0.2 wt% to 1.0 wt% of the carbon compound coated on the surface of the thermally conductive ceramic compound. When the content of the carbon compound coated on the surface of the thermally conductive ceramic compound in the resin composition is too low, the effect of improving the thermal conductivity may not be very large, and when the content is 1.1% by weight or more, insulation may be greatly reduced. On the other hand, the acid-modified oligomer contained in the photocurable and thermosetting resin composition is a photocurable functional group, for example, a photocurable functional group having an acrylate group or an unsaturated double bond, as an oligomer having a carboxyl group in the molecule , All components previously known to be usable in the resin composition for forming DFSR can be used without particular limitation.

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

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

(1) Unsaturated carboxylic acid (a), such as (meth) acrylic acid, and unsaturated double, such as styrene, (alpha) -methylstyrene, lower alkyl (meth) acrylate, and isobutylene Carboxyl group-containing resin obtained by copolymerizing compound (b) having a bond;

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

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

 (4) One hydroxy group such as hydroxyalkyl (meth) acrylate in a copolymer of an acid anhydride (e) having an unsaturated double bond such as maleic anhydride and itaconic anhydride and a compound (b) having an unsaturated double bond Carboxyl group-containing photosensitive resin obtained by making compound (f) which has 1 or more ethylenically unsaturated double bond react;

 (5) The epoxy group of the polyfunctional epoxy compound (g) which has two or more epoxy groups in the molecule mentioned later, or the polyfunctional epoxy resin in which the hydroxy group of the polyfunctional epoxy compound was further epoxidized with epichlorohydrin, (meth Carboxyl groups of unsaturated monocarboxylic acids (h) such as acrylic acid are esterified (full esterified or partially esterified, preferably total esterified), and the saturated or unsaturated polybasic acid anhydrides (d) Carboxyl group-containing photosensitive compound obtained by making it react;

(6) 1 in 1 molecule of an alkyl group having 2 to 17 carbon atoms, an aromatic group-containing alkyl carboxylic acid, etc., in the epoxy group of the copolymer of the compound (b) having an unsaturated double bond and glycidyl (meth) acrylate Organic acids (i) having two carboxyl groups and no ethylenically unsaturated bonds, and saturated or unsaturated polybasic acid anhydrides in the resulting secondary carboxyl group-containing resin obtained by making (d) react;

 (7) diisocyanates (j) such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; Diols such as carbonate poly, polyether polyol, polyester polyol, polyolefin poly, acryl polyol, bisphenol A alkylene oxide adduct, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups Carboxyl group-containing urethane resin obtained by the polyaddition reaction of compound (m);

 (8) diisocyanate (j), 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, bixenol type epoxy resin, non Photosensitive property obtained by the polyaddition reaction of the (meth) acrylate of a bifunctional epoxy resin, such as a phenol type epoxy resin, or its partial acid anhydride modified substance (n), a carboxyl group-containing dialcohol compound (k), and a dialel compound (ni) Carboxyl group-containing urethane resin;

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

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

 (11) A saturated or unsaturated polybasic acid anhydride with respect to the primary hydroxy group in the modified oxetane compound obtained by reacting unsaturated monocarboxylic acid (h) with a polyfunctional oxetane compound having two or more oxetane rings in a molecule as described later. carboxyl group-containing photosensitive resin reacted by reaction (d);

(12) Unsaturation in reaction products of bisepoxy compounds and bisphenols Carboxyl group-containing photosensitive resin obtained by introducing a double bond and subsequently reacting saturated or unsaturated polybasic acid anhydride (d);

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

 In addition, as the additional acid-modified oligomer described above, commercially available components may be used, and specific examples of such components may include

ZAR-2000, CCR-1235, ZFR-1122, or CCR—1291H.

 More specific examples of the acid-modified oligomer are epoxy

(Meth) acrylate type compound is mentioned. The said epoxy (meth) acrylate type compound is an epoxy compound or a polyepoxy compound,

2) It means a semi-ungmul product between a (meth) acrylate compound or a hydroxy (meth) acrylate compound.

 By using the epoxy (meth) acrylate compound,

A DFSR can be provided that can sufficiently secure the flexibility of the DFSR, exhibit a lower coefficient of thermal expansion and improved heat resistance, and can be preferably used as a package engine material of a semiconductor device.

 Examples of the epoxy (meth) acrylate compounds include an epoxy (meth) acrylate compound or bisphenol derived from cresol novolak.

Epoxy (meth) acrylate compounds derived from F can be used. In addition, the epoxy (meth) acrylate compound is an epoxy (meth) acrylate compound derived from cresol novolak and an epoxy (meth) acrylate compound derived from bisphenol F 4: 1 to 1: 1 by weight, or 3 It may be included in a weight ratio of 1: 1 to 2: 1.

The epoxy (meth) acrylate-based compound may have a weight average molecular weight of 5,000 to 50,000, or 6,000 to 20,000. The epoxy (Meth) is too large, the weight average molecular weight of the acrylate-based compound ^■ photocurable acrylate ratio is relatively decreased in developability may be degraded, or the strength of the DFSR can be lowered. If the weight average molecular weight of the epoxy (meth) acrylate-based compound is too small, precipitation or congestion of filler particles may occur during inorganic filler dispersion, and the resin composition of one embodiment may be excessively developed.

The acid-modified oligomer may be included in an amount of about 5 to 75 wt%, black about 20 to 50 wt%, or about 25 to 45 wt% 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 may be lowered and the strength of the DFSR may be lowered. On the contrary, when the content of the acid-modified oligomer is too high, not only the resin composition may be excessively developed, but also uniformity may be decreased during coating. The photopolymerizable monomer is at least one selected from the group consisting of a polyfunctional compound having two or more vinyl groups in a molecule and a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in a molecule _. It may include a compound.

 Such a photopolymerizable monomer may be, for example, a compound having a photocurable unsaturated functional group such as two or more polyfunctional vinyl groups, and may be formed by crosslinking with the unsaturated functional group of the acid-modified oligomer described above by photocuring upon exposure. A crosslinked structure can be formed. As a result, the resin composition of the exposed portion facing the portion where the DFSR is to be formed can be left on the substrate without being alkali developed.

 As such a photopolymerizable monomer, in fact, a liquid may be used. Accordingly, the viscosity of the resin composition of one embodiment may be adjusted according to a coating method, or the role of improving the alkali developability of the non-exposed part may also be accompanied.

As the photopolymerizable monomer, an acrylate compound having two or more photocurable unsaturated functional groups may be used. More specifically, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol Triacrylate or dipentaerythritol pentaacrylate Hydroxyl group-containing acrylate compounds such as; Water-soluble acrylate compounds such as polyethylene glycol diacrylate or polypropylene glycol diacrylate; Polyfunctional polyester acrylate compounds of polyhydric alcohols such as trimethyl to propane triacrylate, pentaerythritol to tetraacrylate, or dipentaerythr to nucleated acrylate; Acrylate compounds of ethylene oxide adducts and / or propylene oxide adducts of polyfunctional alcohols such as trimethylolpropane or hydrogenated bisphenol A or polyhydric phenols such as bisphenol A and biphenol; Polyfunctional or monofunctional polyurethane acrylate compounds which are isocyanate modified products of the hydroxyl group-containing acrylate; Epoxy acrylate compounds which are (meth) acrylic acid adducts of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolac epoxy resins; Caprolactone-modified ditrimethyl to propane tetraacrylate, acrylate of _ε -caprolactone-modified dipentaerythrite, or caprolactone-modified acrylate compounds such as caprolactone-modified hydroxypivalatene neopentyl glycol ester diacrylate; And one or more compounds selected from the group consisting of photosensitive (meth) acrylate compounds such as methacrylate compounds corresponding to the above-described acrylate compounds, and these may be used alone or in combination of two or more thereof. .

Among these, as said photopolymerizable monomer, in 1 molecule _. 2 or more

A polyfunctional (meth) acrylate-based compound having a (meth) acryloyl group can be preferably used, and in particular, pentaerythritol triacrylate, trimethylolpropane triacrylate, dipentaerythritol nucleoacrylate, or caprolactone Modified ditrimethylol propane tetraacrylate and the like can be used as appropriate. Examples of commercially available photopolymerizable monomers include Kaylarad's DPEA-12 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. When the content of the photopolymerizable monomer is too small, the photocuring may be uneven, and when too large, the drying property of the DFSR may deteriorate. Physical properties may be reduced. The photoinitiator is a benzoin compound, acetophenone compound, anthraquinone compound, thioxanthone compound, ketal compound, benzophenone compound, α-aminoacetophenone compound, acylphosphine oxide compound, oxime ester compound, biimida It may include one or more selected from the group consisting of a sol-based compound and a triazine-based compound.

Specifically, a well-known thing can be used as a photoinitiator, Benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and its alkyl 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-amyl anthraquinone, 2-t-butyl anthraquinone and 1 'chloroanthraquinone; Thioxanthones, such as a 2, 4- dimethyl thioxanthone, a 2, 4 'diisopropyl thioxanthone, and a 2' chloro thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Such as benzophenones such as benzophenone, 4- (lt-butyldioxy-1-methylethyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone Materials can be used. ^'

In addition, 2-methyl '1- [4- (methylthio) phenyl] 2—morpholino propanoone 1,2'benzyl 1 2-dimethylamino-1' (4-morpholinophenyl) -butane-1- One, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1— [4- (4-morpholinyl) phenyl] -1-butanone, Ν, Ν- dimethylaminoacetophenone (commercially available) For example, ε ᅳ aminoacetophenones such as Irugacure (registered trademark) 907, Irugacure 369, Itugacure 379, etc. of Chiba Specialty Chemical Co., Ltd. (currently Chiba Japan Co., Ltd.) _; 2,4,6-trimethylbenzoyldiphenylhospinoxite, bis (2,4,6-trimethylbenzoyl) -phenylphosphineoxide, bis (2,6-dimethoxybenzoyl) —2, 4, 4- Acyl phosphine oxides, such as trimethyl- pentyl phosphine oxide (A commercially available product, Rucillin (R) TP0 by BASF, Irugacure 819 by Chivas Specialty Chemical, etc.) can be mentioned as a preferable photoinitiator.

Moreover, oxime ester is mentioned as a preferable photoinitiator. Specific examples of oxime esters include 2 ′ (acetyloxyiminomethyl) thioxanthene-9-one, (1,2—octanedione, 1- [4- (phenylthio) phenyl] ᅳ, 2— (0-benzoyloxime )), (Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- 3-yl]-, 1- (0-acetyloxime)), etc. are mentioned. Commercially available products include GGI-325 from Chiba Specialty Chemical, Irugacure 0XE01, Irugacure 0XE02, ADEKA N-1919, and Chiba Specialty Chemical's Darocur TP0.

 The content of the photoinitiator may be about 0.1 to 20% by weight, or about 1 to 10% by weight, and black to about 1 to 5% by weight, based on the total weight of the resin composition. If the content of the photoinitiator is too small, photocuring may not occur properly, on the contrary, if the content of the photoinitiator is too large, the resolution of the resin composition may be lowered or the reliability of the DFSR may not be sufficient. The thermosetting binder resin may include at least one functional group selected from the group consisting of an epoxy group, an oxetanyl group, a cyclic ether group and a cyclic thio ether 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 thio ether group. Such a thermosetting binder may form a crosslinked bond with an acid-modified oligomer and the like by thermosetting to secure heat resistance or mechanical properties of DFSR.

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

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

As a specific example of the said polyfunctional epoxy compound, Bisphenol-A epoxy resin, Hydrogenated bisphenol-A epoxy resin, Brominated bisphenol-A epoxy resin, Bisphenol F-type epoxy resin, Bisphenol S-type epoxy resin, Novolak-type epoxy, for example Resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, Glyoxal epoxy resin, amino group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy-resin, tetraglycidyl xylenoyl ethane resin, silicone modified and the caprolactone-modified epoxy resin such as epoxy resin, _ε There. In addition, for the purpose of imparting flame retardancy, those in which atoms such as phosphorus are introduced into the structure may be used. These epoxy resins thermoset to improve characteristics such as adhesion of the cured film, solder heat resistance, electroless plating resistance, and the like.

Examples of the polyfunctional oxetane compound include bis [(3'methyl-1-3'oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4'bis [(3'ethyl-1-3'oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl ) Methyl acrylate, (3-ethyl-3 oxetanyl) methyl acrylate, ₍₃ ᅳ methyl _ ₃ _ oxetanyl) methyl methacrylate, (3-ethyl- 3-oxetanyl) methyl methacrylate In addition to polyfunctional oxetanes such as oligomers or copolymers thereof, oxetane alcohols and novolac resins, poly (ρ-hydroxystyrene), cardo-type bisphenols, carixarenes, carlixresolecinarenes, or Ether ether with resin which has hydroxyl groups, such as a silsesquioxane, etc. are mentioned. In addition, the copolymer of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate etc. are mentioned. As a compound which has 2 or more cyclic thioether group in the said molecule, For example, bisphenol A episulfide resin YL7000 by the Japan epoxy resin company, etc. are mentioned. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used.

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

 The photocurable and thermosetting resin composition may comprise 0.5 to 40% by weight of the thermosetting binder. In addition, the thermosetting binder may be included 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.

When the content of the thermosetting binder is too small, carboxyl groups remain in the DFSR after curing, which may lower heat resistance, alkali resistance, electrical insulation, and the like. On the contrary, when the content is too large, low molecular weight cyclic (thio) ether groups remain in the dry coating film, which is not preferable because the strength of the coating film and the like decrease. One or more solvents may be commonly used to dissolve the resin composition having the photocurable and thermosetting properties or to impart an appropriate viscosity. As the solvent, such as methyl ethyl ketone

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 Glycol ethers (cellosolve) such as monomethyl ether, propylene glycol monoethyl ether dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate,

Ethylene glycol monobutyl ether acetate,

Diethylene glycol monoethyl ether acetate,

Diethylene glycol monobutyl ether acetate,

Propylene glycol monomethyl ether acetate,

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

The amount of the solvent may be about 1 to 90% by weight, or 10 to 50% by weight based on the total amount of the resin composition described above. The photocurable and thermosetting resin compositions include barium sulfate, barium titanate, amorphous silica, crystalline silica, ^' fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide and mica. It may further comprise at least one inorganic filler selected from the group consisting of.

 The inorganic filler serves to improve heat stability, thermal dimensional stability, and resin adhesion. In addition, it also serves as a constitution pigment by reinforcing the color.

 The amount of the inorganic filler can be adjusted in consideration of physical properties and quality of the final dry solder solder resist.

 In the photocurable and thermosetting resin composition, the sum of the contents of the two or more spherical alumina particles having different particle diameters and the inorganic column may be 30% by weight to 60% by weight in the solid content excluding the organic solvent.

 The solid content may include all components other than an organic solvent in the photocurable and thermosetting resin composition, for example, an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, and two or more spherical alumina particles having different particle diameters. Refers to the ingredients. The photocurable and thermosetting resin composition may further include a thermosetting agent, pigment, leveling agent or dispersant.

The thermosetting agent serves to promote thermosetting of the thermosetting binder. As such a thermosetting agent, for example, imidazole, 2-methylimidazole, 2 'ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-2′phenylimidazole and 1- (2-cyanoethyl) -2—ethyl-4-methylimidazole; Dicyandiamide, benzyldimethylamine, 4- (dimethylamino) — Ν, Ν- dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4 'methyl-N, N-dimethylbenzylamine, etc. Amine compounds; Hydrazine compounds such as adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. As commercially available products, for example, Shikoku Kasei Kogyo Co., Ltd., 2ΜΖ-Α, 2ΜΖ-0Κ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ (all brand names of imidazole compounds), U-CAT3503N manufactured by San Aprosa, UCAT3502T (All are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATS A102, U—CAT5002 (both bicyclic amidine compounds and salts thereof) and the like.

In particular, the present invention is not limited thereto, and may be a thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group ^' and / or an oxetanyl group and a carboxyl group, and may be used alone or in combination of two or more thereof. have. .

 In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4'diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4, 6-diamino-S-tri Azine, 2—vinyl-4, 6-diamino-S-triazine isocyanuric acid adduct, 2,4'diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct S-triazine derivatives, such as these, can also be used, Preferably, the compound which functions also as these adhesive imparting agents can be used together with the said 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 terms of appropriate thermosetting.

The pigment serves to hide visibility and defects such as scratching of the circuit line. ^'

As the pigment which can be used, red, blue, green, yellow, or dark pigment can be used. As blue pigment, phthalocyanine blue, pigment blue 15: 1, pigment blue 15: 2 ᅳ pigment blue 15: 3, pigment blue 15: 4, pigment Blue 15: 6, Pigment Blue 60, etc. may be used. Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28 and the like can be used as the green pigment. Examples of the yellow pigments include anthraquinones, isoindolinones, condensed azos and benzimidazolones. Examples include pigment yellow 108, pigment yellow 147, pigment yellow 151, pigment yellow 166 and pig. You can use the ment yellow 181, Pigment Yellow 193 round.

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

 Other usable additives may be to remove bubbles from the resin composition, to remove popping or craters on the surface of the film, to add flame retardancy, to control viscosity, and to add a catalyst. .

 Specifically, known commonly used thickeners such as finely divided silica, organic bentonite and montmorillonite; Antifoaming agents and / or leveling agents such as silicone-based, fluorine-based and polymer-based; Silane coupling agents such as imidazole series, thiazole series, and triazole series; Known and common additives such as flame retardants such as phosphorus flame retardants and antimony flame retardants can be blended.

 Among them, the leveling agent serves to remove the popping and craters of the surface when the film is coated, for example, BYK-380N, BYK-307, BYK-307, BYK-378, BYK-350, etc. of BYK-Chemie GmbH.

The content of the other additives is preferably about 0.01 to 10% by weight based on the total weight of the resin composition. DFSR can be formed by the following process using the resin composition having the photocurable and thermosetting properties of the embodiment. First, after forming a film with a resin composition and laminating such a film on a predetermined board | substrate, exposure is selectively performed to the resin composition of the part in which DFSR is to be formed. When the exposure is carried out, the unsaturated functional groups contained in the acid-modified oligomer, The unsaturated functional groups contained in the photopolymerizable monomer may cause photocuring to form crosslinks with each other, and as a result, a crosslinked structure by photocuring may be formed in the exposed portion.

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

 Then, when the heat treatment of the resin composition remaining on the substrate to proceed with heat curing, the carboxyl groups contained in the acid-modified oligomer, for example, the iminocarbonate-based compound reacts with the thermosetting functional group of the thermosetting binder to crosslink A bond can be formed, and as a result, a DFSR can be formed in a desired portion on the substrate while forming a crosslinked structure by thermal curing.

In other words, when the DFSR is formed using the resin composition, since the basic crosslinked structure is included in the cured product of the resin composition constituting the DFSR, the coefficient of thermal expansion of the DFSR is 40 or less for αΐ and 150 or less for α2. Can be lowered. As a result, the heat resistance reliability of the DFSR can be further improved, and the difference in thermal expansion coefficient with the package substrate material of the semiconductor device can be reduced, thereby minimizing the Warpage problem. According to another embodiment of the present invention, an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, two or more spherical alumina particles having different particle diameters, a carbon compound coated with a surface conductive ceramic compound, and comprises an organic solvent, a dry film solder resist (DFSR) is produced using a resin composition having ^• a photo-curable and thermosetting, may be provided.

 . The dry film solder resist (DFSR) not only meets various physical properties such as PCT resistance, TCT heat resistance, and HAST resistance between fine wirings required for the package substrate material of the semiconductor device, but also reduces warpage. This can reduce defects and extend the life of the product.

In addition, the dry film solder resist (DFSR) greatly increases the content of the inorganic column while improving heat resistance without deteriorating overall physical properties and improving the coefficient of linear expansion. The heat dissipation characteristics can be greatly improved without lowering the insulating properties of the dry film soldering resist to be produced.

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

 The acid-modified oligomer, photopolymerizable monomer, thermosetting binder resin, photoinitiator, two or more types of spherical alumina particles having different particle diameters, an organic solvent, and a resin composition having photocurability and thermosetting properties are described in the above-mentioned invention. Includes the foregoing with respect to embodiments.

 The dry film solder resist may have a thickness of 10 to 150 / mm 3.

 Referring to the process of manufacturing a dry film solder resist (DFSR) using the photocurable and thermosetting resin composition of the embodiment is as follows.

First, a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer coater, gravure coater, or the like as a photosensitive coating material on a carrier film. After coating with a spray coater or the like, the oven ^at 50 to 130 ^° C. is dried for 1 to 30 minutes, and then laminated with a release film, from below to form a carrier film, a photosensitive film, or a release film. The dry film comprised from a film can be manufactured.

 The photosensitive film may have a thickness of about 5 to about 100 / zm. In this case, a plastic film such as polyethylene terephthalate (PET), a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film may be used as the carrier film, and polyethylene (PE), A polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used, and when peeling a release film, it is preferable that the adhesive force of a photosensitive film and a release film is lower than the adhesive force of a photosensitive film and a carrier film.

Next, after peeling off the release film, the photosensitive on the circuit formed substrate The film layer is bonded by using a vacuum laminator, hot laminator, vacuum press or the like.

 Next, the substrate is exposed to light having a constant wavelength band (UV, etc.). The exposure may be selectively exposed with a photo mask or may be directly pattern exposed with a laser direct exposure machine. The carrier film peels off after exposure. The exposure amount depends on the coating film thickness, but preferably 0 to 1,000 niJ / citf. When the exposure is performed, for example, in the exposed portion, photocuring may occur to form a crosslink between the acid-modified oligomer and the unsaturated functional groups included in the photopolymerizable monomer, and as a result, may not be removed by a subsequent phenomenon. Can be in a state. On the contrary, the non-exposed part may not be formed with the crosslink and the crosslinked structure thereof, and thus the carboxyl group may be maintained to become an alkali developable state.

 Next, development is carried out using an alkaline solution or the like. The alkaline solution may be an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like. By this phenomenon, only the film of the exposed portion may remain.

Finally, by heat curing (Post Cure), a printed circuit board including a solder resist formed from the photosensitive film is completed. Heat curing temperature is more than 100 ^° C.

 Through the above-described method, a DFSR and a printed circuit board including the same may be provided. The DFSR may be acid-modified oligomer as it undergoes photocuring and thermosetting; Photopolymerizable monomers having two or more 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 may be used to manufacture a package substrate of a semiconductor device. In addition, according to another embodiment of the 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 described above, the dry film solder resist may be used as a protective film for a printed circuit board.

 【Effects of the Invention】

According to the present invention, dry film solder resist (DFSR) having not only excellent photocuring properties, plating resistance, mechanical properties and heat resistance, but also _minimizing dimensional stability degradation and warpage, and having high heat dissipation characteristics There may be provided a resin composition having a photocurable and thermoset capable of providing.

 In addition, when the resin composition having the photocurable and thermosetting properties is used, a dry film solder resist having the above-described characteristics, and a circuit board including the dry film solder resist may be provided.

 [Specific contents to carry out invention]

 The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the present invention, the content of the present invention is not limited by the following examples.

EXAMPLES AND COMPARATIVE EXAMPLES: Preparation of Resin Composition, Dry Film and Printed Circuit Board

 Examples 1 to 2 and Comparative Example 1

The resin compositions were prepared by mixing the components shown in Table 1 below. In this case, 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 and used in a weight ratio of 3: 1.

 After applying the prepared resin composition to the PET as a carrier film,

After drying by passing through an oven at 75 ^° C., by laminating PE as a release film, a dry film composed of a carrier film, a photosensitive film (thickness 20), a release film from below was prepared.

After peeling off the cover film of the manufactured dry film, the photosensitive film layer was vacuum-laminated on the board | substrate with which the circuit was formed, and the photo mask which rounds a pattern with white The photosensitive film layer was covered with light and exposed to UV light. Exposure progressed UV of 365 nm wavelength band by the exposure amount of 350mJ / cni2. Thereafter, the PET film was removed, and developed with a Na ₂ CO ₃ 1 weight ¾ alkaline solution at 31 ^° C. for a predetermined time to remove unnecessary portions to form a desired pattern. Subsequently, photocuring was performed at an exposure dose of 1000 mJ / cm 2, and finally heat curing was performed at 160 to 170 ^° C. for 1 hour to complete a printed circuit board including a protective film (solder resist) formed from the photosensitive film. .

TABLE 1 Compositions of Examples 1 to 4 [Units]

Comparative Examples 2 to 3

The resin compositions were prepared by mixing the components shown in Table 2 below. At this time, 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 and used in a weight ratio of 3: 1.

 A dry film was manufactured in the same manner as in Example 1 using the prepared resin composition, and a printed circuit board including a protective film (solder resist) was completed in the same manner as in Example 1 using the dry film. It was.

TABLE 2 Compositions of Comparative Examples 2 and 3 [Unit: g]

Experimental Example

 The physical properties of the dry film and the printed circuit board prepared in Examples and Comparative Examples were measured by the following method. Experimental Example 1: Evaluation of developability (sensitivity)

The copper clad laminate of Mitsui Metals 3EC ᅳ M3-VLP 12 was cut into a horizontal X length = 5 cm X 5 cm size. Fine roughness was formed on the copper foil surface by chemical etching. After removing the release film of the dry film manufactured by the said Example and the comparative example, the said film layer was vacuum-laminated by the vacuum laminator (MV LP-500 by Meisei Seisakusho Co., Ltd.) on the copper foil laminated board (substrate) with roughness formed. .

Then, a negative photo mask having a hole shape having a diameter of 80 was brought into close contact with each other, and UV of a 365 漏 wavelength band was exposed at an exposure dose of 350 mJ / cm ² . Thereafter, the PET film was removed, and developed with a Na ₂ CO ₃ 1 wt% alkaline solution at 31 ^° C. for a period of time to form a pattern.

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

 1: The cross section is straight, and no film residue remains on the bottom.

2: The cross section is not straight and there is an under cut or overhang in the hole shape

 3 ： We observe in undeveloped state

 4 ： Pattern formation impossible due to over development Experimental Example 2: Acid resistance measurement

The copper foil laminate (thickness: 0.1 mm, copper foil thickness: 12 ^ m, LG Chem LG—T-500GA) was cut into a horizontal X length = 5 cm X 5 cm size, and fine roughness was formed on the copper foil surface by chemical etching. After removing the release film of the dry film manufactured by the said Example and the comparative example, the said film layer was vacuum-laminated by the vacuum laminator (MV LP-500 by Meisei Seisakusho Co., Ltd.) on the copper foil laminated board (substrate) with roughness formed. . Then, a negative photo mask having a hole shape having a diameter of 80 was brought into close contact with each other, and UV of a 365 nm wavelength band was exposed at an exposure dose of 350 niJ / cm ² . Thereafter, the PET film was removed, developed with a Na ₂ CO ₃ 1 wt% alkaline solution at 31 ^° C. for a predetermined time, and photocured at an exposure dose of about 1000 niJ / cm ² . Then, the specimen was prepared by heat curing at about 170 ^° C for 1 hour.

The specimens were treated in 25 ^° C., 10wt sulfuric acid solution (¾SO ₄ ) for 30 minutes, and then evaluated by the following criteria.

 1: no delamination of DFSR and no discoloration

2: Peeling / discoloration observed with the naked eye of DFSR starts to occur 3: Exfoliation / discoloration of DFSR occurs badly Experimental Example 3 Measurement of Absorbency

 After cutting the copper foil of ICS-25um of ILJIN Material in the width * length = llcm * llcm and measuring the mass, cut the dry film manufactured in the Example and the comparative example in the size of width * length = 10cm * 10cm, and release film After removal, the specimens were prepared in the same manner as the PCT heat resistance measurement sample and the mass was measured.

The specimens were treated for 24 hours using a thermo-hygrostat (spec, SH-941) at a temperature of 85 ^° C. and a humidity of 85%, and the masses were measured.

 1) Hygroscopicity (%) = (hygroscopic mass / sample quantity) * 100

_. 2) Hygroscopic mass = (mass of specimen after treatment with constant temperature and humidity)-(mass of specimen before treatment with constant temperature and humidity)

 3) Sample mass = (mass of specimen before constant temperature and humidity treatment)-(copper mass) Experimental Example 4: Pencil hardness measurement

 Test specimen was prepared in the same manner as in Experimental Example 2 [acid resistance measurement], and was cut to a size of llcm * llcm. Using a pencil set for hardness measurement (Mitsu-Bi Shi) and a pencil hardness tester (manufactured by CK Co., Ltd.), the degree to which the specimen was scratched at a constant speed under a load of 100 g was measured. The hardness of the pencil to which a coating film does not peel was confirmed using the pencil which has the hardness of B-9H of the said pencil set. Experimental Example 5: Insulation Resistance Measurement

 The dry film prepared in the Example and the comparative example was vacuum-laminated on the FR-4 board | substrate with which the comb-shaped electrode of the IPC specification B pattern was formed using the vacuum laminator (MV LP-500 by Meisei Seisakusho Co., Ltd.).

And the negative type photo mask which has a hole shape of diameter 80 was made to adhere to the said board | substrate, and the UV of 365nm wavelength band was exposed by the exposure amount of 350mJ / cm <^2> . Thereafter, the PET film was removed, developed with Na ₂ C0 ₃ 1% increase in alkali solution at 31 ^° C. for a period of time, and photocured at an exposure dose of about 1000 mJ / cm ² . Proceeded. Then, the specimen was prepared by heat curing at about 170 ^° C for 1 hour.

 The insulation resistance value of the electrode which the obtained specimen had was measured at an applied voltage of 500V. Experimental Example 6: Measurement of Thermal Conductivity

 Copper foil laminated sheet of 12 mm (3EC-M3-VLP of Mitsui Metal) Cut into dimensions of * * ^ ^ 15 cm * 15 cm in width, Example and comparison using a vacuum laminator (MV LP-500 manufactured by Meisei Seisakusho Co., Ltd.) The dry film manufactured in the example was vacuum laminated several times on the copper foil laminated plate prepared by the said predetermined | prescribed magnitude | size, and it became thickness of about 100 kPa.

Then, a negative photo mask having a hole shape having a diameter of 12.7 GHz was brought into close contact with the substrate, and UV was exposed at 350 mJ / cm ^{2 at} a 365 nm wavelength band. Thereafter, the PET film was removed, developed with a Na ₂ CO ₃ 1 weight? ¾ alkali solution at 31 ^° C. for a predetermined time, and photocured at an exposure dose of about 1000 mJ / cm ² . Thereafter, heat curing was performed at about 17 (C for 1 hour, and copper foil was removed using an etchant to prepare a thermal conductivity measurement sample.

 The thermal conductivity was obtained by the formula of [density * specific heat * thermal diffusivity], the density was measured by Mettler Toledo, and the specific heat and thermal diffusivity was measured by Netzch's LFA447 device. It is shown in Table 3 below the measurement results of Singh Examples 1 to 6. TABLE 3 Measurement results of Experimental Examples 1 to 6

Table 3 As shown in the measurement and evaluation results of the, embodiment DFSR was confirmed that has an excellent developing property, photo-curing properties and mechanical properties, decreases when the insulating property and has improved heat dissipation properties, without the ^package. Particularly, in the case of the specimen using the dry film of Comparative Example 1, the content of the inorganic filler was 57.7 wt%, and the thermal conductivity calculated by the Bruggemann equat ion and the actual measured thermal conductivity were about 0.5 W / mK. In Example 2, while having an inorganic filler content equivalent to that of the comparative example, a thermal conductivity of 1.00 W / mK or more was realized. In order for the specimen using the dry film of Comparative Example 1 to realize thermal conductivity of 1.00 W / mK or more by the Bruggemann equat ion, the content of the used alumina filler should be 70 wt% or more, and Examples 1 and 2 show the content of the inorganic filler. High thermal conductivity can be achieved without increasing it.

 That is, the DFSR of the embodiment may have high thermal conductivity and electromagnetic wave absorption performance without deterioration of the withstand voltage strength by securing electrical insulation, and may realize excellent thermal conductivity, electromagnetic wave absorption performance, and withstand voltage strength even at a relatively thin thickness.

[Reference] Breggmann equat ion

^ iths nal conductivity σί the composites =: th nnaf concluctivf o ^f ceramic filler & K _m : thermal conductivity of Polymer

t ： the volume fraction of ceramics

 * For the specimen of Comparative Example 1, alumina specific gravity 4 and resin specific gravity

Applies to 1.1.

Claims

 Patent Claim

 [Claim 1]

Acid-modified oligomers, photopolymerizable monomers, thermosetting binder resins, photoinitiators, two or more spherical alumina particles having different particle diameters, including ^' carbon compounds and organic solvents coated with a thermally conductive ceramic compound, photocurable and thermosetting Having a resin composition.

[Claim 2]

 In U,

 The resin composition which has photocurability and thermosetting whose particle diameter of at least 1 sort (s) of the said spherical alumina particle is 0.1 GPa or less.

[Claim 3]

 The method of claim 1,

 The resin composition which has photocurability and thermosetting whose particle diameter of at least 1 sort (s) of the said spherical alumina particle is 0.2-.

[Claim 4]

 The method of claim 1,

 The carbon compound surface-coated with the thermally conductive ceramic compound comprises 0.5% to 20% by weight of the thermally conductive ceramic compound and 80% to 99.5% by weight of the carbon compound, the photocurable and thermosetting resin composition

[Claim 5]

 According to claim 1,

 The photocurable and thermosetting resin composition comprises a carbon compound coated with the thermally conductive ceramic compound in less than 1.1% by weight, the photocurable and thermosetting resin composition.

30. Claim 6 The method of claim 1,

The thermally conductive ceramic compound includes alumina (A1 ₂ 0 ₃ ), boron nitride (BN), aluminum nitride (A1N), silicon carbide (SiC), magnesium oxide (MgO), zinc oxide (ZnO) and aluminum hydroxide (A1 ( 0H) 3) a photocurable and thermosetting resin composition comprising at least one member selected from the group consisting of.

[Claim 7]

^According to claim 1,

 The carbon compound comprises at least one selected from the group consisting of graphite, graphene and carbon nanotubes, a photocurable and thermosetting resin composition.

[Claim 8]

 The method of claim 1,

 Resin composition having a photocurable and thermosetting, the carbon compound surface-coated with the thermally conductive ceramic compound has an average particle diameter of 0. mi to 4.

[Claim 9]

 In U,

 The acid-modified oligomer has a photocurable and thermosetting resin composition comprising an epoxy (meth) acrylate-based compound.

[Claim 10]

 The method of claim 9,

 The said epoxy (meth) acrylate type compound has a weight average molecular weight of 5,000-50,000, The resin composition which has photocurability and thermosetting.

[Claim 11]

 The method of claim 1,

The photopolymerizable monomer is a polyfunctional having two or more vinyl groups in a molecule. A resin composition having photocurability and thermosetting, comprising at least one compound selected from the group consisting of a compound and a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in the molecule. [Claim 12]

 In U,

 The photoinitiator is a benzoin compound, acetophenone compound, anthrazonone compound, thioxanthone compound, ketal compound, benzophenone compound α-aminoacetophenone compound, acylphosphine oxide compound, oxime ester compound, biimidazole type A resin composition having photocurability and thermosetting, comprising at least one member selected from the group consisting of a compound and a triazine compound.

[Claim 13]

The method of claim 1 wherein ^'

 The thermosetting binder resin includes at least one functional group selected from the group consisting of an epoxy group, an oxetanyl group, a cyclic ether group and a cyclic thio ether group, a photocurable and thermosetting resin composition.

[Claim 14]

 The method of claim 1

 The thermosetting binder resin is at least one selected from the group consisting of a polyfunctional epoxy resin having two or more epoxy groups, a polyfunctional oxetane resin having two or more oxetanyl groups, and an episulfide resin having two or more thioether groups The resin composition which has resin, and has photocurability and thermosetting.

[Claim 15]

 The method of claim 1,

 5% to 75% acid denatured oligomer;

 1 to 40% by weight of the photopolymerizable monomer,

0.5-40% by weight of thermosetting binder resin, 0.1 to 20% by weight photoinitiator;

 1 to 75% by weight of two or more spherical alumina particles having different particle diameters;

 0.2 wt% to 1.0 wt% of a carbon compound coated with a thermally conductive ceramic compound, and

 1 to 90 weight% of an organic solvent; The resin composition which has photocurability and thermosetting.

[Claim 16]

 The method of claim 1,

 Further comprising at least one inorganic filler 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, aluminum hydroxide and mica ， Resin composition having photocurability and thermosetting.

[Claim 17]

 The method of claim 16,

 The sum of the content of the two or more spherical alumina particles having different particle diameters and the inorganic column is 30% by weight to 60% by weight in the solid content excluding the organic solvent, the photocurable and thermosetting resin composition.

[Claim 18]

 The dry film soldering resist manufactured using the photosensitive resin composition of Claim 1.

[Claim 19]

 The method of claim 18,

Dry film soldering resist containing hardened | cured material or dry matter of the said photosensitive resin composition. [Claim 20]

 The method of claim 18,

 Dry film solder resist used as a protective film for printed circuit boards. [Claim 21]

 The method of claim 18,

 A dry film solder resist, having a thickness of 10 urn to 150 and a thermal conductivity of at least 1.10 W / mK. [Claim 22]

 The method of claim 21,

Dry film solder resist having an insulation resistance of 10.0 * 10 ^η Ω or less. [Claim 23]

 A circuit board comprising the dry film solder resist of claim 18.