WO2023167267A1 - Curable resin composition, cured product, and printed wiring board - Google Patents

Curable resin composition, cured product, and printed wiring board Download PDF

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Publication number
WO2023167267A1
WO2023167267A1 PCT/JP2023/007717 JP2023007717W WO2023167267A1 WO 2023167267 A1 WO2023167267 A1 WO 2023167267A1 JP 2023007717 W JP2023007717 W JP 2023007717W WO 2023167267 A1 WO2023167267 A1 WO 2023167267A1
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Prior art keywords
resin composition
curable resin
epoxy resin
filler
mass
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PCT/JP2023/007717
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French (fr)
Japanese (ja)
Inventor
千夏 高橋
義和 大胡
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太陽ホールディングス株式会社
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Publication of WO2023167267A1 publication Critical patent/WO2023167267A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a curable resin composition, and more particularly to a curable resin composition suitably used for smoothing by filling holes in printed wiring boards and filling gaps between circuits. Furthermore, the present invention relates to a cured product of the curable resin composition and a printed wiring board comprising the cured product, particularly to a printed wiring board smoothed by the cured product.
  • a double-sided substrate provided with a through hole for forming an interlayer connection for electrically connecting different wiring layers, that is, a through hole, an insulating layer and a conductor circuit are sequentially formed on a core substrate, and a via hole or the like is formed.
  • a multi-layer printed wiring board such as a build-up wiring board in which the layers are connected and multi-layered is used. In such a printed wiring board, gaps (concavities) between conductor circuits on the surface, and holes such as through holes and via holes with wiring layers formed on the inner wall surfaces are filled with a curable resin filler.
  • Patent Documents 1 to 3 As a curable resin filler, a thermosetting resin composition containing an epoxy resin as a curable resin component, an epoxy resin curing agent and an inorganic filler is generally used (eg, Patent Document 4).
  • halogen-containing compounds including resin materials
  • resin materials are widely used in the manufacture of electronic devices. Since such halogen-containing compounds generate harmful gases when burned, various efforts including legal regulations have been made to suppress the generation of harmful gases.
  • Epoxy resin which is used as the main component of thermosetting resin compositions, generally contains a large amount of chlorine because epichlorohydrin, which is a raw material usually used in its synthesis, contains a large amount of chlorine.
  • epichlorohydrin which is a raw material usually used in its synthesis
  • chlorine a raw material usually used in its synthesis
  • epoxy resins are mostly used in a chlorine-containing state. Therefore, when burning a thermosetting resin filler containing such an epoxy resin, a large amount of chlorine is included. There is a problem that harmful gases are emitted and a large burden is placed on the environment. In order to solve such problems, it has been considered to reduce the chlorine content by washing (purifying) the epoxy resin or using an epoxy resin synthesized without using epichlorohydrin. , the time and economic costs were very high, and it was difficult to say that it was realistic.
  • Brominated epoxy resin is sometimes used as a thermosetting resin filler.
  • colorants, especially pigments, used in thermoset fillers may contain bromine.
  • harmful gases containing bromine are released, so the above-mentioned thermosetting resins containing chlorine-containing epoxy resins are not recommended.
  • the present inventors have found that in a curable resin composition containing an epoxy resin, an epoxy resin curing agent and a filler, the amount of halogen-containing substances emitted during combustion can be suppressed by using a specific component as the filler. I got the knowledge of The present invention is based on such findings. That is, the gist of the present invention is as follows.
  • a curable resin composition comprising an epoxy resin curing agent and a filler,
  • the filler contains at least one selected from the group consisting of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide,
  • a curable resin composition characterized by having a halogen content of 100 to 1000 ppm as measured by a quartz tube combustion method.
  • the curable resin composition according to [1], wherein the total content of the filler is 50 to 300 parts by mass with respect to 100 parts by mass of the epoxy resin.
  • the total content of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide is 10 to 250 parts by mass with respect to 100 parts by mass of the epoxy resin.
  • a curable resin composition is 10 to 250 parts by mass with respect to 100 parts by mass of the epoxy resin.
  • the present invention it is possible to realize a curable resin composition in which the amount of halogen-containing substances released during combustion is suppressed. Furthermore, by using the curable resin composition, it is possible to realize a cured product in which the amount of halogen-containing substances released during combustion is suppressed, and a printed wiring board provided with the cured product.
  • the curable resin composition of the present invention contains an epoxy resin, an epoxy resin curing agent and a filler as essential components.
  • the curable resin composition of the present invention can be used as a solder resist layer formation, an interlayer insulating material, and a hole-filling material for printed wiring boards. It can be suitably used as a filling material for filling gaps (recesses) and as a filling material for gaps between circuits on a printed wiring board.
  • the curable resin composition of the present invention can suppress the release of halogen-containing substances during combustion by using a specific component as a filler.
  • epoxy resins are mainly synthesized using epichlorohydrin, and since epichlorohydrin has chlorine atoms, the synthesized epoxy resin contains a large amount of chlorine derived from epichlorohydrin. Therefore, when such an epoxy resin is used in the production of a curable resin composition, a large amount of chlorine is inevitably contained in the curable resin composition unless the epoxy resin is washed (purified) or otherwise treated. become.
  • brominated epoxy resins may be used as epoxy resins, or components containing bromine may be used.
  • coloring agents such as pigments often contain bromine.
  • bromine is contained in the curable resin composition.
  • halogen-containing substances for example, simple halogens such as chlorine and bromine, hydrogen halides such as hydrogen chloride, organic halogen compounds such as dioxins and brominated dioxins (brominated dioxins).
  • Halogen-containing compounds such as Many of these halogen-containing substances are regulated as hazardous substances and pollutants in various environmental standards. Therefore, in a curable resin composition produced using a halogen-containing component as described above, there is an inseparable problem of a particularly large amount of halogen-containing substances being emitted by burning the curable resin composition.
  • the curable resin composition of the present invention has a halogen content of 100 to 1000 ppm, preferably 100 to 700 ppm, more preferably 100 to 650 ppm, as measured by the quartz tube combustion method.
  • halogen means chlorine and bromine.
  • the terms “amount” and “content” of halogen refer to the total amount and content of chlorine and bromine, respectively. That is, for example, “the amount of halogen is 100 to 1000 ppm” means that the total amount of chlorine and bromine is in the range of 100 to 1000 ppm.
  • halogen-free in environmental laws and regulations, but regarding copper-clad laminates used in electrical and electronic equipment, for example, the Japan Electronic Circuits Association (JPCA) and the International Electrotechnical Commission ( IEC) standards, "halogen-free” can be claimed if the respective chlorine and bromine contents are 900 ppm or less and the total chlorine and bromine content is 1500 ppm or less.
  • the total content of halogens (chlorine and bromine) measured by the quartz tube combustion method is 1000 ppm or less. can be used in the production of "halogen-free" cures and printed wiring boards.
  • the curable resin composition of the present invention preferably has a chlorine content of 900 ppm or less and a bromine content of 900 ppm or less.
  • the curable resin composition of the present invention can avoid such a problem because the amount of halogen measured by the quartz tube combustion method is 100 ppm or more.
  • the amount of halogen (the amount of chlorine and bromine) in the cured product of the curable resin composition by the quartz tube combustion method can be measured according to the standard IEC 62321-3-2 established by the International Electrotechnical Commission (IEC). Specifically, it can be measured according to the following procedure. First, 0.1 g of a curable resin composition to be measured is burned using an automatic sample burner AQF-2100H manufactured by Nitto Seiko Analyticc Co., Ltd. to collect gas components.
  • the collected gas components are absorbed into an absorption liquid (hydrogen peroxide solution), and the resulting absorption liquid is subjected to ion chromatography systems Thermo Scientific Dionex ICS-1100 and Thermo Scientific Dionex AERS 500 manufactured by Thermo Fisher Scientific. Chlorine and bromine are quantified by ion chromatography using a suppressor and a Dionex IonPac AS12A column.
  • the curable resin composition of the present invention contains an epoxy resin. Any known epoxy resin can be used. Epoxy resins may be monofunctional or polyfunctional.
  • an epoxy resin having a tertiary amine an epoxy resin having a bisphenol skeleton, or the like is preferably used.
  • an epoxy resin having a tertiary amine refers to an epoxy resin having two or more epoxy groups in one molecule and one or more tertiary amine groups.
  • Each of these epoxy resins may be an aliphatic epoxy resin or an aromatic epoxy resin. From the viewpoint of heat resistance, electrical insulation, water absorption, etc., aromatic epoxy resins are preferably used.
  • Liquid epoxy resins are used as these epoxy resins.
  • the term "liquid" refers to being in a fluid state at 20°C.
  • epoxy resins described above particularly an epoxy resin having a tertiary amine
  • the crosslink density when the curable resin composition is cured increases, so curing is sufficient and good heat resistance (high glass transition It has the advantage that a cured product having a temperature Tg) and a coefficient of linear expansion (low CTE) can be obtained.
  • epoxy resins with tertiary amines generally have a high chlorine content and are released during combustion, as many raw materials containing chlorine are used to impart functional groups to the molecules during the synthesis process. There is a problem in terms of the increase in chlorine-containing substances used.
  • an epoxy resin having a tertiary amine is preferably used because it is possible to enjoy the advantages described above while solving such problems by using a specific component as a filler.
  • epoxy resins having a tertiary amine examples include N,N,N',N'-tetraglycidylaminodiphenylmethane, N,N,N',N'-tetraglycidyl-m-xylylenediamine, triglycidyl-p -aminophenol, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine and the like.
  • Examples of commercially available epoxy resins having a tertiary amine include jER (registered trademark) 630 (para-aminophenol type epoxy resin) and jER (registered trademark) 604 (diaminodiphenylmethane type epoxy) manufactured by Mitsubishi Chemical Corporation, and Sumitomo Chemical.
  • ELM-100 para-aminophenol type epoxy resin manufactured by Co., Ltd., GAN (diglycidylaniline) manufactured by Nippon Kayaku Co., Ltd., GOT (diglycidyl orthotoluidine) manufactured by Nippon Kayaku Co., Ltd., manufactured by Sumitomo Chemical Co., Ltd.
  • Sumiepoxy (registered trademark) ELM-434, TETRAD (registered trademark)-X manufactured by Mitsubishi Gas Chemical Company, Inc., and the like can be mentioned.
  • examples of epoxy resins having a bisphenol skeleton include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol E (AD)-type epoxy resins, bisphenol S-type epoxy resins, and the like. From the viewpoint of the electrical insulation properties of the cured product of the curable resin composition and the adhesion to the conductive portion and the insulating portion, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol E (AD) type epoxy resin are preferable. Used. Moreover, the epoxy resin having a bisphenol-type skeleton is preferably liquid from the viewpoint of filling properties of the curable resin composition.
  • the liquid state of the epoxy resin having a bisphenol skeleton is as described in the explanation of the epoxy resin having a tertiary amine.
  • Examples of commercially available epoxy resins having a bisphenol skeleton include jER (registered trademark) 828, jER (registered trademark) 834, and jER (registered trademark) 1001 manufactured by Mitsubishi Chemical Corporation (all of which are bisphenol A type epoxy resins), jER (registered trademark) 807, jER (registered trademark) 4004P (both of which are bisphenol F type epoxy resins), R710 (bisphenol E type epoxy resin) manufactured by Air Water Inc., and the like.
  • Epoxy resins having a bisphenol skeleton may be used singly or in combination of two or more, but it is particularly preferred to use a combination of a bisphenol A epoxy resin and a bisphenol F epoxy resin. preferable.
  • the content of the epoxy resin in the curable resin composition is not particularly limited as long as the effect of the present invention is exhibited, but it is preferably 10 to 60 parts by mass in terms of solid content with respect to 100 parts by mass of the curable resin composition. , more preferably 25 to 50 parts by mass.
  • Epoxy resin curing agent The curable resin composition of the present invention contains an epoxy resin curing agent for curing the epoxy resin described above.
  • an epoxy resin curing agent a known curing agent generally used for curing epoxy resins can be used.
  • Epoxy resin curing agents include, for example, amines, imidazoles, polyfunctional phenols, acid anhydrides, isocyanates, and polymers containing these functional groups. Epoxy resin curing agents may be used alone or in combination of two or more.
  • amines and imidazoles are particularly preferably used from the viewpoint of adhesion to the conductive portion and the insulating portion, storage stability, heat resistance, and the like.
  • amines include aliphatic polyamine adduct compounds such as alkylenediamines having 2 to 6 carbon atoms, polyalkylenepolyamines having 2 to 6 carbon atoms, and aromatic ring-containing aliphatic polyamines having 8 to 15 carbon atoms, or isophorone.
  • a curing agent containing an adduct compound of xylylenediamine or isophoronediamine as a main component is preferably used.
  • aliphatic polyamine adduct compound those obtained by subjecting the aliphatic polyamine to addition reaction with aryl glycidyl ether (especially phenyl glycidyl ether or tolyl glycidyl ether) or alkyl glycidyl ether are preferably used.
  • aryl glycidyl ether especially phenyl glycidyl ether or tolyl glycidyl ether
  • alkyl glycidyl ether alkyl glycidyl ether
  • aliphatic polyamines examples include alkylenediamines having 2 to 6 carbon atoms such as ethylenediamine and propylenediamine, polyalkylenepolyamines having 2 to 6 carbon atoms such as diethylenetriamine and triethylenetriamine, and 8 to 15 carbon atoms such as xylylenediamine. and aromatic ring-containing aliphatic polyamines.
  • alkylenediamines having 2 to 6 carbon atoms such as ethylenediamine and propylenediamine
  • polyalkylenepolyamines having 2 to 6 carbon atoms such as diethylenetriamine and triethylenetriamine
  • 8 to 15 carbon atoms such as xylylenediamine.
  • aromatic ring-containing aliphatic polyamines examples include aromatic ring-containing aliphatic polyamines.
  • examples of commercially available modified aliphatic polyamines include FXE-1000, FXR-1020, Fujicure FXR-1030, Fujicure FXR-1080
  • Alicyclic polyamines include, for example, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, and lalomine.
  • modified alicyclic polyamines include Ancamine 1618, Ancamine 2074, Ancamine 2596, Ancamine 2199, Sunmide IM-544, Sunmide I-544, Ancamine 2075, Ancamine 2280, and Ancamine 1934 manufactured by Evonik Japan Co., Ltd. Ancamine 2228, Daito Sangyo Co., Ltd.
  • Daito Kuraru F-5197, Daito Kuraru B-1616, T&K TOKA Corporation Fuji Cure FXD-821, Fuji Cure 4233, Mitsubishi Chemical Corporation JER (registered trademark) Cure 113, BASF Laromin C-260 manufactured by Japan Co., Ltd. and the like can be mentioned.
  • imidazole compounds include 2-methylimidazole, 4-methyl-2-ethylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-ethylimidazole, 2 -isopropylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole and the like.
  • imidazole compounds include, for example, imidazoles such as 2E4MZ, C11Z, C17Z, and 2PZ manufactured by Shikoku Kasei Co., Ltd., imidazole AZINE compounds such as 2MZ-A and 2E4MZ-A, and 2MZ-OK. , isocyanurate of imidazole such as 2PZ-OK, and hydroxymethyl imidazole such as 2PHZ and 2P4MHZ.
  • imidazole-type latent curing agents include Cure Duct P-0505 manufactured by Shikoku Kasei Co., Ltd., for example.
  • the content of the epoxy resin curing agent in the curable resin composition is not particularly limited as long as the effect of the present invention is exhibited, but it is preferably 1 to 30 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin described above. can be 4 to 20 parts by mass.
  • the content ratio of imidazoles, polyamines and imidazole-type latent curing agents is 1:99 on a mass basis. ⁇ 99:1, more preferably 10:90 to 90:10.
  • the curable resin composition of the present invention contains a filler.
  • the filler contains at least one selected from the group consisting of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide.
  • hydrotalcite is a concept that also includes so-called hydrotalcite-like compounds.
  • Hydrotalcite is a kind of naturally or artificially obtained clay mineral, and includes a positively charged base layer composed mainly of [Mg 1-X Al x (OH) 2 ] X+ and a negatively charged [(CO 3 ) X/2 ⁇ mH 2 O] is a general term for layered inorganic compounds represented by the following general formula, having an intermediate layer containing X- as a main component:
  • M 1 represents a divalent metal cation such as Mg 2+ , Fe 2+ , Zn 2+ , Ca 2+ , Li 2+ , Ni 2+ , Co 2+ , Cu 2+
  • M2 represents a trivalent metal cation such as Al3 + , Fe3 + , Mn3 +
  • a n- represents an n-valent anion such as CO 3 2- , Cl ⁇ , NO 3-
  • X represents any number that satisfies 0 ⁇ X ⁇ 0.33
  • m represents any number that satisfies 0 ⁇ m. ].
  • hydrotalcite examples include Indigirite Mg 2 Al 2 [(CO 3 ) 4 (OH) 2 ] ⁇ 15H 2 O, Fe 2+ 4 Al 2 [(OH) 12 CO 3 ] ⁇ 3H 2 O, and Quintinite Mg.
  • hydrotalcite Commercial products of hydrotalcite include, for example, Alkamizer (registered trademark) manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4A (registered trademark), Kyoward (registered trademark) 500, Kyoward (registered trademark) 1000, Sakai HT-1, HT-7, HT-P, etc. of the STABIACE (registered trademark) series manufactured by Kagaku Kogyo Co., Ltd. can be mentioned.
  • the hydrotalcite one containing magnesium and aluminum as main components, that is, a hydrotalcite in which M 1 is Mg 2+ and M 2 is Al 3+ is preferably used.
  • magnesium carbonate Commercial products of magnesium carbonate include, for example, GP-30 manufactured by Kajima Chemical Co., Ltd.
  • Examples of commercial products of magnesium oxide include SMO series manufactured by Sakai Chemical Industry Co., Ltd., RF-50-FC manufactured by Ube Material Industries, Ltd., and the like.
  • Examples of commercial products of aluminum hydroxide include C-305 manufactured by Hayashi Kasei Co., Ltd., C-310 manufactured by Sumitomo Chemical Co., Ltd., BF-013 manufactured by Nippon Light Metal Co., Ltd., and the like.
  • Each filler containing hydrotalcite is not limited to the above-mentioned commercially available products, and other commercially available products may be used, and those appropriately adjusted may be used.
  • the filler may contain other known fillers, particularly inorganic fillers, used in ordinary resin compositions.
  • inorganic fillers include nonmetallic fillers such as silica, barium sulfate, calcium carbonate, silicon nitride, aluminum nitride, boron nitride, alumina, magnesium hydroxide, titanium oxide, mica, talc, and organic bentonite.
  • silica and calcium carbonate are preferably used.
  • Other fillers may be used singly or in combination of two or more.
  • the shape of the filler is not particularly limited. From the point of view, it is preferably spherical.
  • the average particle diameter of the filler is preferably 0.1 ⁇ m to 25 ⁇ m, more preferably 0.1 ⁇ m to 25 ⁇ m, more preferably 0.1 ⁇ m to 25 ⁇ m in consideration of the dispersibility of the filler, the ability to fill holes, and the smoothness when forming a wiring layer in the filled portion. 1 ⁇ m to 15 ⁇ m, more preferably 1 ⁇ m to 10 ⁇ m.
  • the "average particle size" of the filler means the average primary particle size, and the average particle size (D50) can be measured by a laser diffraction/scattering method.
  • the content of the filler in the curable resin composition is not particularly limited as long as the effect of the present invention is exhibited, but the total content of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide with respect to 100 parts by mass of the epoxy resin
  • the content of is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 10 to 250 parts by mass, more preferably 10 to 150 parts by mass, and still more preferably 20 to 250 parts by mass with respect to 100 parts by mass of the epoxy resin. It is adjusted to 100 parts by mass.
  • the amount of halogen-containing substances released when the cured product of the curable resin composition is burned can be sufficiently reduced. while the viscosity of the curable resin composition can be in a range suitable for use (for example, application to a substrate, etc.).
  • the content of the filler in the curable resin composition is the above range of the total amount of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide, and all is adjusted to preferably 50 to 300 parts by mass, more preferably 100 to 250 parts by mass with respect to 100 parts by mass of the epoxy resin.
  • filler content means the total content of magnesium carbonate, magnesium oxide, hydrotalcite, aluminum hydroxide and other fillers.
  • the total content of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide is not particularly limited as long as the effect of the present invention is exhibited, but is preferably is 4 to 100% by mass, more preferably 10 to 100% by mass, still more preferably 20 to 100% by mass.
  • the ratio of the total content of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide to the total content of the filler within the range described above, the amount of halogen-containing substances released during combustion of the curable resin composition can be suppressed to be within the range as described above.
  • the curable resin composition of the present invention preferably contains no solvent.
  • most of the solvents (diluting solvents) used to adjust the viscosity of the curable resin composition volatilize during curing of the curable resin composition, but the volatilized solvent is used to cure the curable resin composition. It can cause voids to form in the material.
  • voids present in the cured product of the curable resin composition may impair the properties required of the filler. From the viewpoint of avoiding deterioration of the properties of the cured product of such a curable resin composition, it is preferred that the curable resin composition does not contain a solvent.
  • the curable resin composition of the present invention may optionally further contain a coloring agent, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion promoter, a block copolymer, a chain transfer agent, a polymerization inhibitor, copper damage inhibitor, antioxidant, rust inhibitor, organic bentonite, thickener such as montmorillonite, at least one of silicone-based, fluorine-based, polymer-based defoaming agent and leveling agent, imidazole-based, Components such as a thiazole-based or triazole-based silane coupling agent, a phosphinate, a phosphoric acid ester derivative, a phosphorus compound such as a phosphazene compound, and other flame retardants can be blended.
  • a coloring agent an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion
  • the viscosity of the curable resin composition is not particularly limited as long as the effect of the present invention is exhibited, but the viscosity measured by a rotary viscometer, that is, the viscosity when rotated at 25 ° C. at a rotation speed of 5 rpm for 30 seconds , preferably 200 to 1000 dPa ⁇ s, more preferably 200 to 800 dPa ⁇ s.
  • the curable resin composition can have good shape retention (suppression of liquid dripping) and good embedding properties.
  • the viscosity of the curable resin composition can be measured using a cone-plate viscometer consisting of a cone rotor (cone rotor) and a plate described in JIS Z 8803 (for example, model TV-30 manufactured by Toki Sangyo Co., Ltd., rotor 3° ⁇ R9.7).
  • the curable resin composition of the present invention can be formed by using a known patterning method such as a screen printing method or a vacuum printing method. ) can be filled.
  • the curable resin composition of the present invention is filled evenly (having a uniform height) when filling the holes of the through-holes and the gaps between circuits.
  • a cured product having a smooth surface can be formed on the printed wiring board after curing the curable resin composition.
  • the filling is completed so as to protrude slightly from the hole or recess.
  • the curable resin composition is cured to form a cured product.
  • the curable resin composition may be pre-cured at a lower temperature and then main-cured (finish-cured). Heating at 80 to 110° C. for about 30 to 90 minutes is preferable as the condition for pre-curing. Since the hardness of the pre-cured cured product is relatively low, unnecessary portions protruding from the substrate surface can be easily removed by physical polishing, and a smooth surface can be obtained. After that, it is heated to be fully cured. Heating at 130 to 160° C. for about 30 to 180 minutes is preferable as the condition for main curing. The hardness of the pre-cured product can be controlled by changing the heating time and heating temperature for pre-curing.
  • the curable resin composition As described above, if necessary, unnecessary portions of the cured product of the printed wiring board are removed by a known physical polishing method, and after smoothing, the wiring layer on the surface is removed. A predetermined circuit pattern is formed by patterning. If necessary, the surface of the cured product may be roughened with an aqueous solution of potassium permanganate or the like, and then a wiring layer may be formed on the cured product by electroless plating or the like.
  • Epoxy resin 1 (epoxy resin having a tertiary amine): p-aminophenol type liquid epoxy resin (jER (registered trademark) 630, manufactured by Mitsubishi Chemical Corporation)
  • Epoxy resin 2 (epoxy resin having a tertiary amine): N, N, N', N'-tetraglycidyl-m-xylenediamine
  • Epoxy resin 3 (epoxy resin having a tertiary amine): p-aminophenol type liquid epoxy Resin (jER (registered trademark) 604, manufactured by Mitsubishi Chemical Corporation)
  • Epoxy resin 4 (epoxy resin having a bisphenol skeleton): bisphenol A type epoxy resin (jER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation)
  • Epoxy resin 5 (epoxy resin having a bisphenol skeleton): bisphenol F type epoxy resin (jER (registered trademark) 806H, manufactured by Mitsubishi Chemical Corporation)
  • Epoxy resin curing agent 2,4-d
  • Chlorine and bromine were quantified by ion chromatography using a suppressor and a Dionex IonPac AS12A column, respectively.
  • the amount of halogen in each curable resin composition of Examples and Comparative Examples was evaluated according to the following criteria. Table 1 shows the measurement results and evaluation results of the amount of halogen (total amount of chlorine and bromine).
  • A The amount of halogen is 500 ppm or less, and the amount of released halogen-containing substances is extremely well suppressed.
  • ⁇ The amount of halogen is more than 500 ppm and not more than 1000 ppm, and the release amount of halogen-containing substances is well suppressed.
  • x The amount of halogen exceeds 1000 ppm, and the release amount of halogen-containing substances is not sufficiently suppressed.
  • soldering heat resistance of each curable resin composition of Examples and Comparative Examples was evaluated according to the following procedure. First, the same substrates for evaluation as those used for evaluating the polishing property were prepared. The surface of each substrate for evaluation on which the curable resin composition was applied was physically polished using a polishing machine with a buff for resin polishing equivalent to #320. Then, each substrate for evaluation after physical polishing was immersed in a solder solution at 288° C. for 10 seconds three times, and then allowed to cool to room temperature. Next, each evaluation substrate was cut at the through-hole portion, the cross section was observed with an optical microscope, and the number of cracks in 100 through-holes was counted.
  • each curable resin composition of Examples the amount of halogen measured by the quartz tube combustion method is as low as 1000 ppm or less.
  • the amount of halogen measured by the quartz tube combustion method is considered to be the amount of halogen derived from various halogen-containing substances released during combustion. Therefore, it can be said that the curable resin compositions of the examples suppress the release of halogen-containing substances during combustion.
  • each curable resin composition of Examples exhibits good printability that can be suitably used for smoothing by filling holes in printed wiring boards and filling gaps between circuits, and good solder heat resistance. I understand.
  • the curable resin compositions of the comparative examples release a large amount of halogen during combustion, exceeding 1000 ppm. Therefore, it can be said that the curable resin compositions of the comparative examples do not sufficiently suppress the emission of halogen-containing substances during combustion.

Abstract

[Problem] To provide a curable resin composition from which a cured product having excellent insulation reliability can be formed and which has a suppressed amount of emission of halogen-containing substances during combustion. [Solution] This curable resin composition comprises an epoxy resin, an epoxy resin curing agent, and a filler, wherein a filler containing at least one selected from the group consisting of magnesium carbonate, magnesium oxide, hydrotalcite, and aluminum hydroxide is used as the filler.

Description

硬化性樹脂組成物、硬化物およびプリント配線板Curable resin composition, cured product and printed wiring board
　本発明は硬化性樹脂組成物に関し、特にプリント配線板の穴埋めや回路間の隙間を埋めることによる平滑化に好適に用いられる硬化性樹脂組成物に関する。さらに、本発明は、該硬化性樹脂組成物の硬化物および該硬化物を備えるプリント配線板、特に硬化物によって平滑化されたプリント配線板に関する。 The present invention relates to a curable resin composition, and more particularly to a curable resin composition suitably used for smoothing by filling holes in printed wiring boards and filling gaps between circuits. Furthermore, the present invention relates to a cured product of the curable resin composition and a printed wiring board comprising the cured product, particularly to a printed wiring board smoothed by the cured product.
　近年の電子機器の小型化、高機能化に伴い、プリント配線板のパターンの微細化、実装面積の縮小化、部品実装の高密度化の必要性が増している。そのため、異なる配線層同士を電気的に接続するための層間接続を形成する貫通孔、すなわちスルーホールが設けられた両面基板や、コア基材上に絶縁層、導体回路が順次形成され、ビアホール等で層間接続されて多層化されたビルドアップ配線板等の多層のプリント配線板が用いられる。このようなプリント配線板において、表面の導体回路間の隙間（凹部）や、内壁面に配線層が形成されたスルーホール、ビアホール等の穴部は、硬化性樹脂充填材により穴埋め加工処理して平滑化するのが一般的である（例えば、特許文献１～３）。硬化性樹脂充填材としては、一般に、硬化性樹脂成分としてのエポキシ樹脂、エポキシ樹脂硬化剤および無機フィラーを含有する熱硬化性樹脂組成物が用いられている（例えば、特許文献４）。 With the recent miniaturization and sophistication of electronic devices, there is an increasing need for finer printed wiring board patterns, smaller mounting areas, and higher density component mounting. Therefore, a double-sided substrate provided with a through hole for forming an interlayer connection for electrically connecting different wiring layers, that is, a through hole, an insulating layer and a conductor circuit are sequentially formed on a core substrate, and a via hole or the like is formed. A multi-layer printed wiring board such as a build-up wiring board in which the layers are connected and multi-layered is used. In such a printed wiring board, gaps (concavities) between conductor circuits on the surface, and holes such as through holes and via holes with wiring layers formed on the inner wall surfaces are filled with a curable resin filler. Smoothing is common (for example, Patent Documents 1 to 3). As a curable resin filler, a thermosetting resin composition containing an epoxy resin as a curable resin component, an epoxy resin curing agent and an inorganic filler is generally used (eg, Patent Document 4).
　ところで、電子機器の製造においては、樹脂材料をはじめとしてハロゲン含有化合物が広く用いられている。このようなハロゲン含有化合物は燃焼時に有害なガスを発生することから、有害なガスの発生を抑制するために、法的な規制をはじめとした様々な取り組みがなされている。 By the way, halogen-containing compounds, including resin materials, are widely used in the manufacture of electronic devices. Since such halogen-containing compounds generate harmful gases when burned, various efforts including legal regulations have been made to suppress the generation of harmful gases.
　熱硬化性樹脂組成物の主成分として用いられるエポキシ樹脂は、その合成に通常用いられる原料であるエピクロルヒドリンが多量の塩素を含むため、エポキシ樹脂には一般的に多量の塩素が含まれる。電子機器の製造においては、エポキシ樹脂は塩素を含んだ状態で用いられることがほとんどであり、したがって、そのようなエポキシ樹脂を含む熱硬化性樹脂充填材を燃焼する場合には塩素を多量に含む有害なガスが放出され、環境に大きな負荷がかかるという問題があった。そのような問題を解決するために、エポキシ樹脂を洗浄（精製）したり、エピクロルヒドリンを用いないで合成されたエポキシ樹脂を用いたりして塩素の含有量を低減することも考えられてはいたが、その時間的、経済的コストが非常に大きく、現実的とは言い難かった。 Epoxy resin, which is used as the main component of thermosetting resin compositions, generally contains a large amount of chlorine because epichlorohydrin, which is a raw material usually used in its synthesis, contains a large amount of chlorine. In the manufacture of electronic devices, epoxy resins are mostly used in a chlorine-containing state. Therefore, when burning a thermosetting resin filler containing such an epoxy resin, a large amount of chlorine is included. There is a problem that harmful gases are emitted and a large burden is placed on the environment. In order to solve such problems, it has been considered to reduce the chlorine content by washing (purifying) the epoxy resin or using an epoxy resin synthesized without using epichlorohydrin. , the time and economic costs were very high, and it was difficult to say that it was realistic.
　また、熱硬化性樹脂充填材としては臭素化エポキシ樹脂が用いられる場合がある。さらに、熱硬化性樹脂充填材に用いられる着色剤、特に顔料には臭素が含まれる場合がある。そのような臭素化エポキシ樹脂や臭素を含む着色剤を含む熱硬化性樹脂充填材を燃焼する場合には臭素を含む有害なガスが放出されるため、上述した塩素を含むエポキシ樹脂を含む熱硬化性樹脂充填材と同様に、環境に大きな負荷がかかるという問題があった。 Brominated epoxy resin is sometimes used as a thermosetting resin filler. Additionally, colorants, especially pigments, used in thermoset fillers may contain bromine. When burning such brominated epoxy resins and thermosetting resin fillers containing bromine-containing colorants, harmful gases containing bromine are released, so the above-mentioned thermosetting resins containing chlorine-containing epoxy resins are not recommended. There is also the problem of placing a heavy burden on the environment, as is the case with the flexible resin filler.
特開２００１－１５９０９号公報Japanese Unexamined Patent Application Publication No. 2001-15909 特開２００７－４９１０６号公報Japanese Patent Application Laid-Open No. 2007-49106 特開２００４－７５９６７号公報JP 2004-75967 A 特開２０１３－７６００２号公報Japanese Unexamined Patent Application Publication No. 2013-76002
　したがって、本発明の目的は、燃焼時のハロゲン含有物質の放出量が抑制された硬化性樹脂組成物を提供することである。また、本発明の別の目的は、上記硬化性樹脂組成物を硬化させた硬化物、該硬化物を備えるプリント配線板を提供することである。 Therefore, an object of the present invention is to provide a curable resin composition in which the amount of halogen-containing substances released during combustion is suppressed. Another object of the present invention is to provide a cured product obtained by curing the curable resin composition, and a printed wiring board comprising the cured product.
　本発明者らは、エポキシ樹脂、エポキシ樹脂硬化剤およびフィラーを含む硬化性樹脂組成物において、フィラーとして特定の成分を用いることにより、燃焼時のハロゲン含有物質の放出量を抑制することができるとの知見を得た。本発明はかかる知見に基づくものである。すなわち、本発明の要旨は以下の通りである。 The present inventors have found that in a curable resin composition containing an epoxy resin, an epoxy resin curing agent and a filler, the amount of halogen-containing substances emitted during combustion can be suppressed by using a specific component as the filler. I got the knowledge of The present invention is based on such findings. That is, the gist of the present invention is as follows.
［１］エポキシ樹脂、
　エポキシ樹脂硬化剤、および
　フィラー
を含む硬化性樹脂組成物であって、
　前記フィラーが炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムからなる群から選択される少なくとも１種を含み、
　石英管燃焼法により測定されるハロゲンの量が１００～１０００ｐｐｍであることを特徴とする、硬化性樹脂組成物。
［２］前記フィラーの総含有量が、前記エポキシ樹脂１００質量部に対して５０～３００質量部である、［１］に記載の硬化性樹脂組成物。
［３］前記炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムの総含有量が、前記エポキシ樹脂１００質量部に対して１０～２５０質量部である、［１］または［２］に記載の硬化性樹脂組成物。
［４］前記炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムの総含有量が、前記フィラーの総含有量に対して４～１００質量％の割合で含まれる、［１］～［３］のいずれかに記載の硬化性樹脂組成物。
［５］前記エポキシ樹脂が３級アミンを有するエポキシ樹脂を含む、［１］～［４］のいずれかに記載の硬化性樹脂組成物。
［６］前記エポキシ樹脂の含有量が、前記硬化性樹脂組成物１００質量部に対して１０～６０質量部である、［１］～［５］のいずれかに記載の硬化性樹脂組成物。
［７］２５℃で５ｒｐｍの回転速度で３０秒間回転させた場合の粘度が２００～１０００ｄＰａ・ｓである、［１］～［６］のいずれかに記載の硬化性樹脂組成物。
［８］プリント配線板の穴埋めまたはプリント配線板の回路間の間隙の充填に用いられる、［１］～［７］のいずれかに記載の硬化性樹脂組成物。
［９］［１］～［８］のいずれかに記載の硬化性樹脂組成物の硬化物。
［１０］［９］に記載の硬化物を備える、プリント配線板。 [1] epoxy resin,
A curable resin composition comprising an epoxy resin curing agent and a filler,
The filler contains at least one selected from the group consisting of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide,
A curable resin composition characterized by having a halogen content of 100 to 1000 ppm as measured by a quartz tube combustion method.
[2] The curable resin composition according to [1], wherein the total content of the filler is 50 to 300 parts by mass with respect to 100 parts by mass of the epoxy resin.
[3] According to [1] or [2], the total content of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide is 10 to 250 parts by mass with respect to 100 parts by mass of the epoxy resin. A curable resin composition.
[4] The total content of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide is contained at a rate of 4 to 100% by mass with respect to the total content of the filler, [1] to [3] Curable resin composition according to any one of.
[5] The curable resin composition according to any one of [1] to [4], wherein the epoxy resin contains an epoxy resin having a tertiary amine.
[6] The curable resin composition according to any one of [1] to [5], wherein the content of the epoxy resin is 10 to 60 parts by mass with respect to 100 parts by mass of the curable resin composition.
[7] The curable resin composition according to any one of [1] to [6], which has a viscosity of 200 to 1000 dPa·s when rotated at 25° C. and a rotation speed of 5 rpm for 30 seconds.
[8] The curable resin composition according to any one of [1] to [7], which is used for filling holes in printed wiring boards or filling gaps between circuits on printed wiring boards.
[9] A cured product of the curable resin composition according to any one of [1] to [8].
[10] A printed wiring board comprising the cured product of [9].
　本発明によれば、燃焼時のハロゲン含有物質の放出量が抑制された硬化性樹脂組成物を実現することができる。さらに、前記硬化性樹脂組成物を用いて、燃焼時のハロゲン含有物質の放出量が抑制された硬化物、および該硬化物を備えるプリント配線板を実現できる。 According to the present invention, it is possible to realize a curable resin composition in which the amount of halogen-containing substances released during combustion is suppressed. Furthermore, by using the curable resin composition, it is possible to realize a cured product in which the amount of halogen-containing substances released during combustion is suppressed, and a printed wiring board provided with the cured product.
［硬化性樹脂組成物］
　本発明の硬化性樹脂組成物は、エポキシ樹脂、エポキシ樹脂硬化剤およびフィラーを必須成分として含む。本発明の硬化性樹脂組成物は、プリント配線板のソルダーレジスト層の形成、層間絶縁材および穴埋め材として用いることができ、特にプリント配線板上のスルーホール、ビアホール等の穴部や回路間の隙間（凹部）を埋めるための穴埋め材、プリント配線板の回路間の間隙の充填材として好適に用いることができる。本発明の硬化性樹脂組成物は、フィラーとして特定の成分を用いることにより燃焼時のハロゲン含有物質の放出量を抑制することができる。 [Curable resin composition]
The curable resin composition of the present invention contains an epoxy resin, an epoxy resin curing agent and a filler as essential components. The curable resin composition of the present invention can be used as a solder resist layer formation, an interlayer insulating material, and a hole-filling material for printed wiring boards. It can be suitably used as a filling material for filling gaps (recesses) and as a filling material for gaps between circuits on a printed wiring board. The curable resin composition of the present invention can suppress the release of halogen-containing substances during combustion by using a specific component as a filler.
　従来、エポキシ樹脂は、エピクロルヒドリンを用いて合成されるのが主流であり、エピクロルヒドリンは塩素原子を有していることから、合成されるエポキシ樹脂にはエピクロルヒドリンに由来する塩素が多量に含まれる。したがって、硬化性樹脂組成物の製造においてそのようなエポキシ樹脂を用いる場合、エポキシ樹脂の洗浄（精製）等の処理を行わない限り、必然的に多量の塩素が硬化性樹脂組成物に含まれることになる。 Conventionally, epoxy resins are mainly synthesized using epichlorohydrin, and since epichlorohydrin has chlorine atoms, the synthesized epoxy resin contains a large amount of chlorine derived from epichlorohydrin. Therefore, when such an epoxy resin is used in the production of a curable resin composition, a large amount of chlorine is inevitably contained in the curable resin composition unless the epoxy resin is washed (purified) or otherwise treated. become.
　また、硬化性樹脂組成物の製造においては、エポキシ樹脂として臭素化エポキシ樹脂が用いられたり、臭素を含む成分が用いられたりする場合がある。特に、顔料等の着色剤には臭素が含まれる場合が多くある。そして、硬化性樹脂組成物の製造においてそのような臭素化エポキシ樹脂や臭素を含む成分を用いる場合、臭素が硬化性樹脂組成物に含まれることになる。 In addition, in the production of curable resin compositions, brominated epoxy resins may be used as epoxy resins, or components containing bromine may be used. In particular, coloring agents such as pigments often contain bromine. And when using such a brominated epoxy resin or a component containing bromine in the production of the curable resin composition, bromine is contained in the curable resin composition.
　したがって、そのようなハロゲンを含む硬化性樹脂組成物の硬化物を燃焼する場合、それらのハロゲンを含む化合物、すなわちハロゲン含有物質が、硬化物の燃焼により発生するガスの成分として放出される。ハロゲン含有物質としては有害なものが多く存在し、例えば、塩素および臭素等の単体ハロゲン、ならびに塩化水素等のハロゲン化水素、ダイオキシン類および臭素化ダイオキシン類（臭素系ダイオキシン類）等の有機ハロゲン化合物等のハロゲン含有化合物が挙げられる。そして、これらのハロゲン含有物質は、その多くが様々な環境基準において有害物質や汚染物質として規定されている。したがって、上述したようなハロゲン含有成分を用いて製造される硬化性樹脂組成物においては、硬化性樹脂組成物を燃焼する特に放出される多量のハロゲン含有物質が不可分の問題として存在する。 Therefore, when a cured product of a curable resin composition containing such halogens is burned, compounds containing those halogens, that is, halogen-containing substances are released as components of gas generated by combustion of the cured product. There are many harmful halogen-containing substances, for example, simple halogens such as chlorine and bromine, hydrogen halides such as hydrogen chloride, organic halogen compounds such as dioxins and brominated dioxins (brominated dioxins). Halogen-containing compounds such as Many of these halogen-containing substances are regulated as hazardous substances and pollutants in various environmental standards. Therefore, in a curable resin composition produced using a halogen-containing component as described above, there is an inseparable problem of a particularly large amount of halogen-containing substances being emitted by burning the curable resin composition.
　ハロゲン含有成分を用いて製造される硬化性樹脂組成物においてフィラーとして特定の成分を用いることにより、上述したような硬化物の燃焼時のハロゲン含有物質の放出量が抑制される理由は定かではないが、以下のように推論できる。すなわち、本発明で用いられる特定のフィラーは、当該フィラー中に遊離可能な陰イオンを保持していると考えられる。したがって、硬化性樹脂組成物に含まれるハロゲン含有成分中のハロゲンが遊離してハロゲン化物イオンとなり、そのハロゲン化物イオンとフィラーに保持される陰イオンとが交換または置換されることによって、ハロゲンとフィラー（例えば、フィラーを構成する金属種）とが化学的または物理的な結合を形成すると考えられる。これによりハロゲン化物イオンがフィラーに保持され、結果として、硬化性樹脂組成物の硬化物の燃焼時に放出されるハロゲン含有物質の量が抑制されると考えられる。 It is not clear why the use of a specific component as a filler in a curable resin composition produced using a halogen-containing component suppresses the amount of halogen-containing substances released during combustion of the cured product as described above. can be inferred as follows. That is, it is believed that certain fillers used in the present invention retain releasable anions within the filler. Therefore, the halogen in the halogen-containing component contained in the curable resin composition is liberated to become halide ions, and the halide ions and the anions retained in the filler are exchanged or substituted to obtain halogen and filler. (for example, metal species constituting the filler) are thought to form a chemical or physical bond. It is believed that this causes halide ions to be retained in the filler, and as a result, the amount of halogen-containing substances released during combustion of the cured product of the curable resin composition is suppressed.
　本発明の硬化性樹脂組成物は、石英管燃焼法により測定した場合のハロゲンの量が１００～１０００ｐｐｍであり、好ましくは１００～７００ｐｐｍ、より好ましくは１００～６５０ｐｐｍである。なお、本明細書においてハロゲンは塩素および臭素を意味するものである。また、本明細書において、ハロゲンについて「量」や「含有量」という場合、それぞれ塩素および臭素の合計の量や含有量を意味する。すなわち、例えば「ハロゲンの量が１００～１０００ｐｐｍ」とは、塩素および臭素の量の合計が１００～１０００ｐｐｍの範囲にあることを意味する。現在、環境法規制等において「ハロゲンフリー」についての規定はないものの、電気、電子機器に用いられる銅張積層板に関しては、例えば、社団法人日本電子回路工業会（ＪＰＣＡ）や国際電気標準会議（ＩＥＣ）の規格では、塩素および臭素のそれぞれの含有量が９００ｐｐｍ以下であり、かつ塩素および臭素の総含有量が１５００ｐｐｍ以下である場合に「ハロゲンフリー」を謳うことができる。本発明の硬化性樹脂組成物は、石英管燃焼法により測定されるハロゲン（塩素および臭素）の総含有量が１０００ｐｐｍ以下であるから、塩素および臭素の含有量がいずれも９００ｐｐｍ以下である場合には、「ハロゲンフリー」の硬化物やプリント配線板の製造に用いられ得る。したがって、本発明の硬化性樹脂組成物は、塩素および臭素の含有量がいずれも９００ｐｐｍ以下であることが好ましい。一方で、硬化性樹脂組成物中のハロゲンの量が少ないほど硬化性樹脂組成物の反応性が増大することから、硬化性樹脂組成物中のハロゲンの量が少なすぎると硬化性樹脂組成物の粘度が過度に高くなる傾向があり、その使用時に問題を生じる。したがって、本発明の硬化性樹脂組成物は、石英管燃焼法により測定されるハロゲンの量が１００ｐｐｍ以上であることにより、そのような問題を回避することができる。 The curable resin composition of the present invention has a halogen content of 100 to 1000 ppm, preferably 100 to 700 ppm, more preferably 100 to 650 ppm, as measured by the quartz tube combustion method. In this specification, halogen means chlorine and bromine. Further, in the present specification, the terms "amount" and "content" of halogen refer to the total amount and content of chlorine and bromine, respectively. That is, for example, "the amount of halogen is 100 to 1000 ppm" means that the total amount of chlorine and bromine is in the range of 100 to 1000 ppm. At present, there is no provision for "halogen-free" in environmental laws and regulations, but regarding copper-clad laminates used in electrical and electronic equipment, for example, the Japan Electronic Circuits Association (JPCA) and the International Electrotechnical Commission ( IEC) standards, "halogen-free" can be claimed if the respective chlorine and bromine contents are 900 ppm or less and the total chlorine and bromine content is 1500 ppm or less. In the curable resin composition of the present invention, the total content of halogens (chlorine and bromine) measured by the quartz tube combustion method is 1000 ppm or less. can be used in the production of "halogen-free" cures and printed wiring boards. Therefore, the curable resin composition of the present invention preferably has a chlorine content of 900 ppm or less and a bromine content of 900 ppm or less. On the other hand, since the reactivity of the curable resin composition increases as the amount of halogen in the curable resin composition decreases, if the amount of halogen in the curable resin composition is too small, the curable resin composition It tends to be too viscous, creating problems during its use. Therefore, the curable resin composition of the present invention can avoid such a problem because the amount of halogen measured by the quartz tube combustion method is 100 ppm or more.
　石英管燃焼法による硬化性樹脂組成物の硬化物中のハロゲンの量（塩素および臭素の量）は、国際電気標準会議（ＩＥＣ）が定める規格ＩＥＣ　６２３２１－３－２に従って測定することができる。具体的には、以下の手順に従って測定することができる。まず、日東精工アナリテック株式会社製の自動試料燃焼装置ＡＱＦ－２１００Ｈを用いて測定対象の硬化性樹脂組成物０．１ｇを燃焼させてガス成分を捕集する。次いで、捕集されたガス成分を吸収液（過酸化水素水）に吸収し、得られた吸収液をについてＴｈｅｒｍｏ　Ｆｉｓｈｅｒ　Ｓｃｉｅｎｔｉｆｉｃ社製のイオンクロマトグラフシステムＴｈｅｒｍｏ　Ｓｃｉｅｎｔｉｆｉｃ　Ｄｉｏｎｅｘ　ＩＣＳ－１１００、Ｔｈｅｒｍｏ　Ｓｃｉｅｎｔｉｆｉｃ　Ｄｉｏｎｅｘ　ＡＥＲＳ　５００サプレッサーおよびＤｉｏｎｅｘ　ＩｏｎＰａｃ　ＡＳ１２Ａカラムを用いたイオンクロマトグラフ法により塩素および臭素を定量する。 The amount of halogen (the amount of chlorine and bromine) in the cured product of the curable resin composition by the quartz tube combustion method can be measured according to the standard IEC 62321-3-2 established by the International Electrotechnical Commission (IEC). Specifically, it can be measured according to the following procedure. First, 0.1 g of a curable resin composition to be measured is burned using an automatic sample burner AQF-2100H manufactured by Nitto Seiko Analyticc Co., Ltd. to collect gas components. Next, the collected gas components are absorbed into an absorption liquid (hydrogen peroxide solution), and the resulting absorption liquid is subjected to ion chromatography systems Thermo Scientific Dionex ICS-1100 and Thermo Scientific Dionex AERS 500 manufactured by Thermo Fisher Scientific. Chlorine and bromine are quantified by ion chromatography using a suppressor and a Dionex IonPac AS12A column.
　以下、本発明の硬化性樹脂組成物の各成分について詳細に説明する。
（エポキシ樹脂）
　本発明の硬化性樹脂組成物は、エポキシ樹脂を含む。エポキシ樹脂としては、公知のものをいずれも用いることができる。エポキシ樹脂は、単官能であってもよく、多官能であってもよい。 Each component of the curable resin composition of the present invention will be described in detail below.
(Epoxy resin)
The curable resin composition of the present invention contains an epoxy resin. Any known epoxy resin can be used. Epoxy resins may be monofunctional or polyfunctional.
　エポキシ樹脂としては、エポキシ化植物油；ビスフェノールＡ型エポキシ樹脂；ハイドロキノン型エポキシ樹脂；ビスフェノール型エポキシ樹脂；チオエーテル型エポキシ樹脂；ブロム化エポキシ樹脂；ノボラック型エポキシ樹脂；フェノールノボラック型エポキシ樹脂；ビフェノールノボラック型エポキシ樹脂；ビスフェノールＦ型エポキシ樹脂；水添ビスフェノールＡ型エポキシ樹脂；グリシジルアミン型エポキシ樹脂；ヒダントイン型エポキシ樹脂；脂環式エポキシ樹脂；トリヒドロキシフェニルメタン型エポキシ樹脂；ビキシレノール型もしくはビフェノール型エポキシ樹脂またはそれらの混合物；ビスフェノールＳ型エポキシ樹脂；ビスフェノールＡノボラック型エポキシ樹脂；テトラフェニロールエタン型エポキシ樹脂；複素環式エポキシ樹脂；ジグリシジルフタレート樹脂；テトラグリシジルキシレノイルエタン樹脂；ナフタレン基含有エポキシ樹脂；ジシクロペンタジエン骨格を有するエポキシ樹脂；グリシジルメタアクリレート共重合系エポキシ樹脂；シクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂；エポキシ変性のポリブタジエンゴム誘導体；ＣＴＢＮ変性エポキシ樹脂；臭素化エポキシ樹脂等が挙げられるが、これらに限られるものではない。これらのエポキシ樹脂は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Epoxidized vegetable oil; bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; thioether type epoxy resin; brominated epoxy resin; Resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; bisphenol A novolak epoxy resin; tetraphenylolethane epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl xylenoyl ethane resin; epoxy resin having a dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivative; CTBN-modified epoxy resin; However, it is not limited to these. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.
　エポキシ樹脂としては、好ましくは３級アミンを有するエポキシ樹脂、ビスフェノール骨格を有するエポキシ樹脂等が用いられる。本明細書において、３級アミンを有するエポキシ樹脂とは、１分子中に２個以上のエポキシ基を有し、かつ１個以上の３級アミン基を有するエポキシ樹脂をいう。これらの各エポキシ樹脂は、脂肪族系エポキシ樹脂であっても芳香族エポキシ樹脂であってもよい。耐熱性、電気絶縁性、吸水性等の観点から、好ましくは芳香族系エポキシ樹脂が用いられる。また、これらの各エポキシ樹脂としては、液状のものが用いられる。なお、本発明において液状とは、２０℃で流動性を有する液状状態にあることをいう。上述した各エポキシ樹脂、特に３級アミンを有するエポキシ樹脂を用いる場合、硬化性樹脂組成物を硬化させた場合の架橋密度が高くなるため、硬化が十分であり、良好な耐熱性（高いガラス転移温度Ｔｇ）および線膨張係数（低いＣＴＥ）を有する硬化物を得ることができるという利点を有する。一方で、３級アミンを有するエポキシ樹脂は、その合成過程で分子中に官能基を付与するために塩素を含む原料が多く用いられるため、一般的には塩素の含有量が高く、燃焼時に放出される塩素含有物質の増大という観点から問題がある。本発明では、フィラーとして特定の成分を用いることによりこのような問題を解消しつつ、上述したような利点を享受することができることから、３級アミンを有するエポキシ樹脂が好ましく用いられる。 As the epoxy resin, an epoxy resin having a tertiary amine, an epoxy resin having a bisphenol skeleton, or the like is preferably used. As used herein, an epoxy resin having a tertiary amine refers to an epoxy resin having two or more epoxy groups in one molecule and one or more tertiary amine groups. Each of these epoxy resins may be an aliphatic epoxy resin or an aromatic epoxy resin. From the viewpoint of heat resistance, electrical insulation, water absorption, etc., aromatic epoxy resins are preferably used. Liquid epoxy resins are used as these epoxy resins. In the present invention, the term "liquid" refers to being in a fluid state at 20°C. When using each of the epoxy resins described above, particularly an epoxy resin having a tertiary amine, the crosslink density when the curable resin composition is cured increases, so curing is sufficient and good heat resistance (high glass transition It has the advantage that a cured product having a temperature Tg) and a coefficient of linear expansion (low CTE) can be obtained. On the other hand, epoxy resins with tertiary amines generally have a high chlorine content and are released during combustion, as many raw materials containing chlorine are used to impart functional groups to the molecules during the synthesis process. There is a problem in terms of the increase in chlorine-containing substances used. In the present invention, an epoxy resin having a tertiary amine is preferably used because it is possible to enjoy the advantages described above while solving such problems by using a specific component as a filler.
　３級アミンを有するエポキシ樹脂としては、例えば、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジルアミノジフェニルメタン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシリレンジアミン、トリグリシジル－ｐ－アミノフェノール、Ｎ，Ｎ－ジグリシジルアニリン、Ｎ，Ｎ－ジグリシジル－ｏ－トルイジン等が挙げられる。３級アミンを有するエポキシ樹脂の市販品としては、例えば、三菱ケミカル株式会社製のｊＥＲ（登録商標）６３０（パラアミノフェノール型エポキシ樹脂）、ｊＥＲ（登録商標）６０４（ジアミノジフェニルメタン型エポキシ）、住友化学株式会社製のＥＬＭ－１００（パラアミノフェノール型エポキシ樹脂）、日本化薬株式会社製のＧＡＮ（ジグリシジルアニリン）、日本化薬株式会社製のＧＯＴ（ジグリシジルオルトトルイジン）、住友化学株式会社製のスミエポキシ（登録商標）ＥＬＭ－４３４、三菱ガス化学株式会社製のＴＥＴＲＡＤ（登録商標）－Ｘ等が挙げられる。 Examples of epoxy resins having a tertiary amine include N,N,N',N'-tetraglycidylaminodiphenylmethane, N,N,N',N'-tetraglycidyl-m-xylylenediamine, triglycidyl-p -aminophenol, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine and the like. Examples of commercially available epoxy resins having a tertiary amine include jER (registered trademark) 630 (para-aminophenol type epoxy resin) and jER (registered trademark) 604 (diaminodiphenylmethane type epoxy) manufactured by Mitsubishi Chemical Corporation, and Sumitomo Chemical. ELM-100 (para-aminophenol type epoxy resin) manufactured by Co., Ltd., GAN (diglycidylaniline) manufactured by Nippon Kayaku Co., Ltd., GOT (diglycidyl orthotoluidine) manufactured by Nippon Kayaku Co., Ltd., manufactured by Sumitomo Chemical Co., Ltd. Sumiepoxy (registered trademark) ELM-434, TETRAD (registered trademark)-X manufactured by Mitsubishi Gas Chemical Company, Inc., and the like can be mentioned.
　また、ビスフェノール骨格を有するエポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＥ（ＡＤ）型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂等が挙げられる。硬化性樹脂組成物の硬化物の電気絶縁性、導電部および絶縁部への密着性の観点からは、好ましくはビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＥ（ＡＤ）型エポキシ樹脂が用いられる。また、ビスフェノール型骨格を有するエポキシ樹脂は、硬化性樹脂組成物の充填性の観点から、液状であることが好ましい。なお、ビスフェノール骨格を有するエポキシ樹脂について液状とは、３級アミンを有するエポキシ樹脂の説明で述べたとおりである。ビスフェノール骨格を有するエポキシ樹脂の市販品としては、例えば、三菱ケミカル株式会社製のｊＥＲ（登録商標）８２８、ｊＥＲ（登録商標）８３４、ｊＥＲ（登録商標）１００１（いずれもビスフェノールＡ型エポキシ樹脂）、ｊＥＲ（登録商標）８０７、ｊＥＲ（登録商標）４００４Ｐ（いずれもビスフェノールＦ型エポキシ樹脂）、エア・ウォーター株式会社製のＲ７１０（ビスフェノールＥ型エポキシ樹脂）等が挙げられる。ビスフェノール型骨格を有するエポキシ樹脂は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよいが、ビスフェノールＡ型エポキシ樹脂とビスフェノールＦ型エポキシ樹脂とを組み合わせて用いることが特に好ましい。 In addition, examples of epoxy resins having a bisphenol skeleton include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol E (AD)-type epoxy resins, bisphenol S-type epoxy resins, and the like. From the viewpoint of the electrical insulation properties of the cured product of the curable resin composition and the adhesion to the conductive portion and the insulating portion, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol E (AD) type epoxy resin are preferable. Used. Moreover, the epoxy resin having a bisphenol-type skeleton is preferably liquid from the viewpoint of filling properties of the curable resin composition. The liquid state of the epoxy resin having a bisphenol skeleton is as described in the explanation of the epoxy resin having a tertiary amine. Examples of commercially available epoxy resins having a bisphenol skeleton include jER (registered trademark) 828, jER (registered trademark) 834, and jER (registered trademark) 1001 manufactured by Mitsubishi Chemical Corporation (all of which are bisphenol A type epoxy resins), jER (registered trademark) 807, jER (registered trademark) 4004P (both of which are bisphenol F type epoxy resins), R710 (bisphenol E type epoxy resin) manufactured by Air Water Inc., and the like. Epoxy resins having a bisphenol skeleton may be used singly or in combination of two or more, but it is particularly preferred to use a combination of a bisphenol A epoxy resin and a bisphenol F epoxy resin. preferable.
　硬化性樹脂組成物におけるエポキシ樹脂の含有量は、本発明の効果が奏される限り特に限定されないが、硬化性樹脂組成物１００質量部に対し、固形分換算で、好ましくは１０～６０質量部、より好ましくは２５～５０質量部とすることができる。 The content of the epoxy resin in the curable resin composition is not particularly limited as long as the effect of the present invention is exhibited, but it is preferably 10 to 60 parts by mass in terms of solid content with respect to 100 parts by mass of the curable resin composition. , more preferably 25 to 50 parts by mass.
（エポキシ樹脂硬化剤）
　本発明の硬化性樹脂組成物は、上述したエポキシ樹脂を硬化させるためのエポキシ樹脂硬化剤を含む。エポキシ樹脂硬化剤としては、エポキシ樹脂を硬化させるために一般的に用いられる公知の硬化剤を用いることができる。エポキシ樹脂硬化剤としては、例えば、アミン類、イミダゾール類、多官能フェノール類、酸無水物、イソシアネート類およびこれらの官能基を含むポリマー類が挙げられる。エポキシ樹脂硬化剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 (epoxy resin curing agent)
The curable resin composition of the present invention contains an epoxy resin curing agent for curing the epoxy resin described above. As the epoxy resin curing agent, a known curing agent generally used for curing epoxy resins can be used. Epoxy resin curing agents include, for example, amines, imidazoles, polyfunctional phenols, acid anhydrides, isocyanates, and polymers containing these functional groups. Epoxy resin curing agents may be used alone or in combination of two or more.
　上述したエポキシ樹脂硬化剤の中でも、導電部および絶縁部との密着性、保存安定性、耐熱性等の観点から、特に、アミン類およびイミダゾール類が好適に用いられる。アミン類としては、例えば、炭素数２～６のアルキレンジアミン、炭素数２～６のポリアルキレンポリアミン、炭素数８～１５である芳香環含有脂肪族ポリアミン等の脂肪族ポリアミンのアダクト化合物、またはイソホロンジアミン、１，３－ビス（アミノメチル）シクロヘキサン等の脂環式ポリアミンのアダクト化合物、または上記脂肪族ポリアミンのアダクト化合物と上記脂環式ポリアミンのアダクト化合物との混合物を主成分とするものが挙げられる。特に、キシリレンジアミンまたはイソホロンジアミンのアダクト化合物を主成分とする硬化剤が好適に用いられる。 Among the epoxy resin curing agents described above, amines and imidazoles are particularly preferably used from the viewpoint of adhesion to the conductive portion and the insulating portion, storage stability, heat resistance, and the like. Examples of amines include aliphatic polyamine adduct compounds such as alkylenediamines having 2 to 6 carbon atoms, polyalkylenepolyamines having 2 to 6 carbon atoms, and aromatic ring-containing aliphatic polyamines having 8 to 15 carbon atoms, or isophorone. Diamine, alicyclic polyamine adduct compounds such as 1,3-bis(aminomethyl)cyclohexane, or mixtures of the above-mentioned aliphatic polyamine adduct compounds and the above-mentioned alicyclic polyamine adduct compounds as main components. be done. In particular, a curing agent containing an adduct compound of xylylenediamine or isophoronediamine as a main component is preferably used.
　上記脂肪族ポリアミンのアダクト化合物としては、当該脂肪族ポリアミンにアリールグリシジルエーテル（特にフェニルグリシジルエーテルまたはトリルグリシジルエーテル）またはアルキルグリシジルエーテルを付加反応させて得られるものが好適に用いられる。また、上記脂環式ポリアミンのアダクト化合物としては、当該脂環式ポリアミンにｎ－ブチルグリシジルエーテル、ビスフェノールＡジグリシジルエーテル等を付加反応させて得られるものが好適に用いられる。 As the above aliphatic polyamine adduct compound, those obtained by subjecting the aliphatic polyamine to addition reaction with aryl glycidyl ether (especially phenyl glycidyl ether or tolyl glycidyl ether) or alkyl glycidyl ether are preferably used. As the adduct compound of the alicyclic polyamine, those obtained by subjecting the alicyclic polyamine to addition reaction with n-butyl glycidyl ether, bisphenol A diglycidyl ether or the like are preferably used.
　脂肪族ポリアミンとしては、例えば、エチレンジアミン、プロピレンジアミン等の炭素数２～６のアルキレンジアミン、ジエチレントリアミン、トリエチレントリアミン等の炭素数２～６のポリアルキレンポリアミン、キシリレンジアミン等の炭素数８～１５の芳香環含有脂肪族ポリアミン等が挙げられる。変性脂肪族ポリアミンの市販品の例としては、例えば、株式会社Ｔ＆Ｋ　ＴＯＫＡ製のＦＸＥ－１０００、ＦＸＲ－１０２０、フジキュアーＦＸＲ－１０３０、フジキュアーＦＸＲ－１０８０、ＦＸＲ－１０９０Ｍ２、エボニックジャパン株式会社製のアンカミン２０８９Ｋ、サンマイドＰ－１１７、サンマイドＸ－４１５０、アンカミン２４２２、サーウェットＲ、サンマイドＴＸ－３０００、サンマイドＡ－１００等が挙げられる。 Examples of aliphatic polyamines include alkylenediamines having 2 to 6 carbon atoms such as ethylenediamine and propylenediamine, polyalkylenepolyamines having 2 to 6 carbon atoms such as diethylenetriamine and triethylenetriamine, and 8 to 15 carbon atoms such as xylylenediamine. and aromatic ring-containing aliphatic polyamines. Examples of commercially available modified aliphatic polyamines include FXE-1000, FXR-1020, Fujicure FXR-1030, Fujicure FXR-1080, FXR-1090M2 manufactured by T&K TOKA Co., Ltd., and Ankamin 2089K manufactured by Evonik Japan. , Sunmide P-117, Sunmide X-4150, Ancamine 2422, Serwet R, Sunmide TX-3000, Sunmide A-100 and the like.
　脂環式ポリアミンとしては、例えば、イソホロンジアミン、１，３－ビス（アミノメチル）シクロヘキサン、ビス（４－アミノシクロヘキシル）メタン、ノルボルネンジアミン、１，２－ジアミノシクロヘキサン、ラロミン等が挙げられる。変性脂環式ポリアミンの市販品としては、例えば、エボニックジャパン株式会社製のアンカミン１６１８、アンカミン２０７４、アンカミン２５９６、アンカミン２１９９、サンマイドＩＭ－５４４、サンマイドＩ－５４４、アンカミン２０７５、アンカミン２２８０、アンカミン１９３４、アンカミン２２２８、大都産業株式会社製のダイトクラールＦ－５１９７、ダイトクラールＢ－１６１６、株式会社Ｔ＆Ｋ　ＴＯＫＡ製のフジキュアーＦＸＤ－８２１、フジキュアー４２３３、三菱ケミカル株式会社製のｊＥＲ（登録商標）キュア１１３、ＢＡＳＦジャパン株式会社製のラロミンＣ－２６０等が挙げられる。 Alicyclic polyamines include, for example, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, and lalomine. Examples of commercially available modified alicyclic polyamines include Ancamine 1618, Ancamine 2074, Ancamine 2596, Ancamine 2199, Sunmide IM-544, Sunmide I-544, Ancamine 2075, Ancamine 2280, and Ancamine 1934 manufactured by Evonik Japan Co., Ltd. Ancamine 2228, Daito Sangyo Co., Ltd. Daito Kuraru F-5197, Daito Kuraru B-1616, T&K TOKA Corporation Fuji Cure FXD-821, Fuji Cure 4233, Mitsubishi Chemical Corporation JER (registered trademark) Cure 113, BASF Laromin C-260 manufactured by Japan Co., Ltd. and the like can be mentioned.
　イミダゾール化合物としては、例えば、２－メチルイミダゾール、４－メチル－２－エチルイミダゾール、２－フェニルイミダゾール、４－メチル－２－フェニルイミダゾール、１－ベンジル－２－メチルイミダゾール、２－エチルイミダゾール、２－イソプロピルイミダゾール、１－シアノエチル－２－メチルイミダゾール、１－シアノエチル－２－エチル－４－メチルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾール等が挙げられる。イミダゾール化合物の市販品としては、例えば、四国化成工業株式会社製の２Ｅ４ＭＺ、Ｃ１１Ｚ、Ｃ１７Ｚ、２ＰＺ等のイミダゾール類や、２ＭＺ－Ａ、２Ｅ４ＭＺ－Ａ等のイミダゾールのＡＺＩＮＥ（アジン）化合物、２ＭＺ－ＯＫ、２ＰＺ－ＯＫ等のイミダゾールのイソシアヌル酸塩、２ＰＨＺ、２Ｐ４ＭＨＺ等のイミダゾールヒドロキシメチル体等が挙げられる。また、イミダゾール型潜在性硬化剤の市販品としては、例えば、四国化成工業株式会社製のキュアダクトＰ－０５０５等が挙げられる。 Examples of imidazole compounds include 2-methylimidazole, 4-methyl-2-ethylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-ethylimidazole, 2 -isopropylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole and the like. Commercially available imidazole compounds include, for example, imidazoles such as 2E4MZ, C11Z, C17Z, and 2PZ manufactured by Shikoku Kasei Co., Ltd., imidazole AZINE compounds such as 2MZ-A and 2E4MZ-A, and 2MZ-OK. , isocyanurate of imidazole such as 2PZ-OK, and hydroxymethyl imidazole such as 2PHZ and 2P4MHZ. Commercially available imidazole-type latent curing agents include Cure Duct P-0505 manufactured by Shikoku Kasei Co., Ltd., for example.
　硬化性樹脂組成物におけるエポキシ樹脂硬化剤の含有量は、本発明の効果が奏される限り特に限定されないが、上述したエポキシ樹脂１００質量部に対して、好ましくは１～３０質量部、より好ましくは４～２０質量部とすることができる。 The content of the epoxy resin curing agent in the curable resin composition is not particularly limited as long as the effect of the present invention is exhibited, but it is preferably 1 to 30 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin described above. can be 4 to 20 parts by mass.
　また、イミダゾール類とポリアミン類およびイミダゾール型潜在性硬化剤の少なくとも１種とを併用する場合には、イミダゾール類とポリアミン類およびイミダゾール型潜在性硬化剤との含有割合は、質量基準において１：９９～９９：１であることが好ましく、より好ましくは１０：９０～９０：１０である。 In addition, when imidazoles and at least one of polyamines and imidazole-type latent curing agents are used in combination, the content ratio of imidazoles, polyamines and imidazole-type latent curing agents is 1:99 on a mass basis. ~99:1, more preferably 10:90 to 90:10.
（フィラー）
　本発明の硬化性樹脂組成物は、フィラーを含む。フィラーは、炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムからなる群から選択される少なくとも１種を含む。なお、本発明において、ハイドロタルサイトとは、いわゆるハイドロタルサイト様化合物も包含する概念である。 (filler)
The curable resin composition of the present invention contains a filler. The filler contains at least one selected from the group consisting of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide. In the present invention, hydrotalcite is a concept that also includes so-called hydrotalcite-like compounds.
　ハイドロタルサイトとは、天然または人工的に得られる粘土鉱物の一種であり、正に帯電する［Ｍｇ１－ＸＡｌＸ（ＯＨ）２］Ｘ＋を主成分とする基本層と、負に帯電する［（ＣＯ３）Ｘ／２・ｍＨ２Ｏ］Ｘ－を主成分とする中間層とを有する、下記の一般式で表される層状の無機化合物の総称である：
Figure JPOXMLDOC01-appb-C000001
 ［式中、
　Ｍ１はＭｇ２＋、Ｆｅ２＋、Ｚｎ２＋、Ｃａ２＋、Ｌｉ２＋、Ｎｉ２＋、Ｃｏ２＋、Ｃｕ２＋等の２価の金属カチオンを表し、
　Ｍ２はＡｌ３＋、Ｆｅ３＋、Ｍｎ３＋等の３価の金属カチオンを表し、
　Ａｎ－はＣＯ３ ２－、Ｃｌ－、ＮＯ３－等のｎ価のアニオンを表し、
　Ｘは０＜Ｘ≦０．３３を満たす任意の数を表し、
　ｍは０≦ｍを満たす任意の数を表す。］。 Hydrotalcite is a kind of naturally or artificially obtained clay mineral, and includes a positively charged base layer composed mainly of [Mg 1-X Al x (OH) 2 ] X+ and a negatively charged [(CO 3 ) X/2 ·mH 2 O] is a general term for layered inorganic compounds represented by the following general formula, having an intermediate layer containing X- as a main component:
Figure JPOXMLDOC01-appb-C000001
 [In the formula,
M 1 represents a divalent metal cation such as Mg 2+ , Fe 2+ , Zn 2+ , Ca 2+ , Li 2+ , Ni 2+ , Co 2+ , Cu 2+ ,
M2 represents a trivalent metal cation such as Al3 + , Fe3 + , Mn3 + ,
A n- represents an n-valent anion such as CO 3 2- , Cl − , NO 3- ,
X represents any number that satisfies 0<X≦0.33;
m represents any number that satisfies 0≦m. ].
　ハイドロタルサイトの具体例としては、Ｉｎｄｉｇｉｒｉｔｅ　Ｍｇ２Ａｌ２［（ＣＯ３）４（ＯＨ）２］・１５Ｈ２Ｏ、Ｆｅ２＋ ４Ａｌ２［（ＯＨ）１２ＣＯ３］・３Ｈ２Ｏ、Ｑｕｉｎｔｉｎｉｔｅ　Ｍｇ４Ａｌ２（ＯＨ）１２ＣＯ３・Ｈ２Ｏ、Ｍａｎａｓｓｅｉｔｅ　Ｍｇ６Ａｌ２［（ＯＨ）１６ＣＯ３］・４Ｈ２Ｏ、ＳｊＯｅｇｒｅｎｉｔｅ　Ｍｇ６Ｆｅ３＋ ２［（ＯＨ）１６ＣＯ３］・４Ｈ２Ｏ、Ｚａｃｃａｇｎａｉｔｅ　Ｚｎ４Ａｌ２（ＣＯ３）（ＯＨ）１２・３Ｈ２Ｏ、Ｄｅｓａｕｔｅｌｓｉｔｅ　Ｍｇ６Ｍｎ３＋ ２［（ＯＨ）１６ＣＯ３］・４Ｈ２Ｏ、Ｈｙｄｒｏｔａｌｃｉｔｅ　Ｍｇ６Ａｌ２［（ＯＨ）１６ＣＯ３］・４Ｈ２Ｏ、Ｐｙｒｏａｕｒｉｔｅ　Ｍｇ６Ｆｅ３＋ ２［（ＯＨ）１６ＣＯ３］・４Ｈ２Ｏ、Ｒｅｅｖｅｓｉｔｅ　Ｎｉ６Ｆｅ３＋ ２［（ＯＨ）１６ＣＯ３］・４Ｈ２Ｏ、Ｓｔｉｃｈｔｉｔｅ　Ｍｇ６Ｃｒ２［（ＯＨ）１６ＣＯ３］・４Ｈ２Ｏ、Ｔａｋｏｖｉｔｅ　Ｎｉ６Ａｌ２［（ＯＨ）１６ＣＯ３］・４Ｈ２Ｏ等が挙げられる。ハイドロタルサイトの市販品としては、例えば、協和化学工業株式会社製のアルカマイザー（登録商標）、ＤＨＴ－４Ａ（登録商標）、キョーワード（登録商標）５００、キョーワード（登録商標）１０００、堺化学工業株式会社製のＳＴＡＢＩＡＣＥ（登録商標）シリーズのＨＴ－１、ＨＴ－７、ＨＴ－Ｐ等が挙げられる。ハイドロタルサイトとしては、マグネシウムおよびアルミニウムを主成分として含むもの、すなわち上述したＭ１がＭｇ２＋であり、Ｍ２がＡｌ３＋であるハイドロタルサイトが好ましく用いられる。 Specific examples of hydrotalcite include Indigirite Mg 2 Al 2 [(CO 3 ) 4 (OH) 2 ]·15H 2 O, Fe 2+ 4 Al 2 [(OH) 12 CO 3 ]·3H 2 O, and Quintinite Mg. 4Al2 ( OH ) 12CO3.H2O , Manasseite Mg6Al2 [ ( OH) 16CO3 ] .4H2O , SjOegrenite Mg6Fe3 + 2 [(OH) 16CO3 ] .4H2O , Zaccagnaite Zn4Al2 ( CO3 )(OH) 12.3H2O , Desautelsite Mg6Mn3 + 2 [( OH ) 16CO3 ] .4H2O, Hydrotalcite Mg6Al2 [(OH) 16CO3 ] .4H2O , Pyroaurite Mg6Fe3 + 2 [(OH) 16CO3 ] .4H2O , Reevesite Ni6Fe3 + 2 [(OH ) 16CO3 ] .4H2O, Stichtite Mg6Cr2 [ (OH) 16 CO 3 ].4H 2 O, Takovite Ni 6 Al 2 [(OH) 16 CO 3 ].4H 2 O and the like. Commercial products of hydrotalcite include, for example, Alkamizer (registered trademark) manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4A (registered trademark), Kyoward (registered trademark) 500, Kyoward (registered trademark) 1000, Sakai HT-1, HT-7, HT-P, etc. of the STABIACE (registered trademark) series manufactured by Kagaku Kogyo Co., Ltd. can be mentioned. As the hydrotalcite, one containing magnesium and aluminum as main components, that is, a hydrotalcite in which M 1 is Mg 2+ and M 2 is Al 3+ is preferably used.
　炭酸マグネシウムの市販品としては、例えば、神島化学工業株式会社製のＧＰ－３０等が挙げられる。また、酸化マグネシウムの市販品としては、例えば、堺化学工業株式会社製のＳＭＯシリーズ、宇部マテリアルズ株式会社製のＲＦ－５０－ＦＣ等が挙げられる。また、水酸化アルミニウムの市販品としては、例えば、林化成株式会社製のＣ－３０５、住友化学株式会社製のＣ－３１０、日本軽金属株式会社製のＢＦ－０１３等が挙げられる。ハイドロタルサイトを含む各フィラーは、上述した市販品に限定されるものではなく、その他の市販品を用いてもよく、適宜調整したものを用いてもよい。 Commercial products of magnesium carbonate include, for example, GP-30 manufactured by Kajima Chemical Co., Ltd. Examples of commercial products of magnesium oxide include SMO series manufactured by Sakai Chemical Industry Co., Ltd., RF-50-FC manufactured by Ube Material Industries, Ltd., and the like. Examples of commercial products of aluminum hydroxide include C-305 manufactured by Hayashi Kasei Co., Ltd., C-310 manufactured by Sumitomo Chemical Co., Ltd., BF-013 manufactured by Nippon Light Metal Co., Ltd., and the like. Each filler containing hydrotalcite is not limited to the above-mentioned commercially available products, and other commercially available products may be used, and those appropriately adjusted may be used.
　フィラーは、上述した炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウム以外にも、通常の樹脂組成物に用いられる公知のその他のフィラー、特に無機フィラーを含んでもよい。そのような無機フィラーとしては、例えば、シリカ、硫酸バリウム、炭酸カルシウム、窒化ケイ素、窒化アルミニウム、窒化ホウ素、アルミナ、水酸化マグネシウム、酸化チタン、マイカ、タルク、有機ベントナイト等の非金属フィラーが挙げられるが、シリカおよび炭酸カルシウムが好適に使用できる。その他のフィラーは、１種類を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 In addition to the magnesium carbonate, magnesium oxide, hydrotalcite, and aluminum hydroxide described above, the filler may contain other known fillers, particularly inorganic fillers, used in ordinary resin compositions. Examples of such inorganic fillers include nonmetallic fillers such as silica, barium sulfate, calcium carbonate, silicon nitride, aluminum nitride, boron nitride, alumina, magnesium hydroxide, titanium oxide, mica, talc, and organic bentonite. However, silica and calcium carbonate are preferably used. Other fillers may be used singly or in combination of two or more.
　フィラーの形状は、特に制限されるものではなく、球状、針状、板状、鱗片状、中空状、不定形状、六角状、キュービック状、薄片状等が挙げられるが、フィラーの含有量を高める観点から球状であることが好ましい。 The shape of the filler is not particularly limited. From the point of view, it is preferably spherical.
　フィラーの平均粒径は、フィラーの分散性、穴部への充填性、穴埋めした部分に配線層を形成する際の平滑性等を考慮すると、好ましくは０．１μｍ～２５μｍ、より好ましくは０．１μｍ～１５μｍ、さらに好ましくは１μｍ～１０μｍである。なお、フィラーの「平均粒径」とは平均一次粒径を意味し、平均粒径（Ｄ５０）は、レーザー回折／散乱法により測定することができる。 The average particle diameter of the filler is preferably 0.1 μm to 25 μm, more preferably 0.1 μm to 25 μm, more preferably 0.1 μm to 25 μm in consideration of the dispersibility of the filler, the ability to fill holes, and the smoothness when forming a wiring layer in the filled portion. 1 μm to 15 μm, more preferably 1 μm to 10 μm. The "average particle size" of the filler means the average primary particle size, and the average particle size (D50) can be measured by a laser diffraction/scattering method.
　硬化性樹脂組成物におけるフィラーの含有量は、本発明の効果が奏される限り特に限定されないが、エポキシ樹脂１００質量部に対して、炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムの合計の含有量は、本発明の効果が奏される限り特に限定されないが、エポキシ樹脂１００質量部に対して、好ましくは１０～２５０質量部、より好ましくは１０～１５０質量部、さらに好ましくは２０～１００質量部となるように調整される。エポキシ樹脂に対する炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムの合計量を上述した範囲に調整することにより、硬化性樹脂組成物の硬化物の燃焼時に放出されるハロゲン含有物質の量を十分に抑制することができ、一方で、硬化性樹脂組成物の粘度を、使用（例えば、基板への塗布等）に適した範囲にすることができる。また、フィラーが上述したその他のフィラーを含む場合、硬化性樹脂組成物におけるフィラーの含有量は、炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムの合計量が上述した範囲であり、かつすべてのフィラーの合計量が、エポキシ樹脂１００質量部に対して、好ましくは５０～３００質量部、より好ましくは１００～２５０質量部となるように調整される。エポキシ樹脂に対するフィラーの含有量を上述した範囲に調整することにより、プリント配線板の穴埋めや回路間の間隙の充填に適し印刷性が良好な組成物を得ることができ、また硬化物に求められる良好なはんだ耐熱性を得ることができる。なお、本明細書において「フィラーの含有量」とは、いずれも上述した炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムとその他のフィラーとの総含有量を意味する。 The content of the filler in the curable resin composition is not particularly limited as long as the effect of the present invention is exhibited, but the total content of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide with respect to 100 parts by mass of the epoxy resin The content of is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 10 to 250 parts by mass, more preferably 10 to 150 parts by mass, and still more preferably 20 to 250 parts by mass with respect to 100 parts by mass of the epoxy resin. It is adjusted to 100 parts by mass. By adjusting the total amount of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide to the epoxy resin within the range described above, the amount of halogen-containing substances released when the cured product of the curable resin composition is burned can be sufficiently reduced. while the viscosity of the curable resin composition can be in a range suitable for use (for example, application to a substrate, etc.). In addition, when the filler contains other fillers described above, the content of the filler in the curable resin composition is the above range of the total amount of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide, and all is adjusted to preferably 50 to 300 parts by mass, more preferably 100 to 250 parts by mass with respect to 100 parts by mass of the epoxy resin. By adjusting the content of the filler to the epoxy resin within the range described above, it is possible to obtain a composition suitable for filling holes in printed wiring boards and filling gaps between circuits and having good printability. Good solder heat resistance can be obtained. As used herein, the term "filler content" means the total content of magnesium carbonate, magnesium oxide, hydrotalcite, aluminum hydroxide and other fillers.
　硬化性樹脂組成物において、炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムの総含有量は、本発明の効果が奏される限り特に限定されないが、フィラーの総含有量に対して、好ましくは４～１００質量％、より好ましくは１０～１００質量％、さらに好ましくは２０～１００質量％の割合である。フィラーの総含有量に対する炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムの総含有量の割合を上述した範囲に調整することにより、硬化性樹脂組成物の燃焼時のハロゲン含有物質の放出量を抑制して上述したような範囲内とすることができる。 In the curable resin composition, the total content of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide is not particularly limited as long as the effect of the present invention is exhibited, but is preferably is 4 to 100% by mass, more preferably 10 to 100% by mass, still more preferably 20 to 100% by mass. By adjusting the ratio of the total content of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide to the total content of the filler within the range described above, the amount of halogen-containing substances released during combustion of the curable resin composition can be suppressed to be within the range as described above.
（溶剤）
　本発明の硬化性樹脂組成物は、溶剤を含まないことが好ましい。一般的に、硬化性樹脂組成物の粘度調整等に用いられる溶剤（希釈溶剤）は、そのほとんどが硬化性樹脂組成物の硬化時に揮発するが、揮発した溶剤は、硬化性樹脂組成物の硬化物中にボイド（空隙）が形成される原因となり得る。例えば、本発明の硬化性樹脂組成物が充填材として用いられる場合、硬化性樹脂組成物の硬化物内にボイドが存在すると、充填材に求められる特性を損ねる可能性がある。そのような硬化性樹脂組成物の硬化物の特性を損ねるのを避ける観点から、硬化性樹脂組成物は溶剤を含まないことが好ましい。 (solvent)
The curable resin composition of the present invention preferably contains no solvent. In general, most of the solvents (diluting solvents) used to adjust the viscosity of the curable resin composition volatilize during curing of the curable resin composition, but the volatilized solvent is used to cure the curable resin composition. It can cause voids to form in the material. For example, when the curable resin composition of the present invention is used as a filler, voids present in the cured product of the curable resin composition may impair the properties required of the filler. From the viewpoint of avoiding deterioration of the properties of the cured product of such a curable resin composition, it is preferred that the curable resin composition does not contain a solvent.
（その他の成分）
　本発明の硬化性樹脂組成物には、必要に応じてさらに、着色剤、エラストマー、メルカプト化合物、ウレタン化触媒、チキソ化剤、密着促進剤、ブロック共重合体、連鎖移動剤、重合禁止剤、銅害防止剤、酸化防止剤、防錆剤、有機ベントナイト、モンモリロナイト等の増粘剤、シリコーン系、フッ素系、高分子系等の消泡剤およびレベリング剤の少なくともいずれか１種、イミダゾール系、チアゾール系、トリアゾール系等のシランカップリング剤、フォスフィン酸塩、燐酸エステル誘導体、フォスファゼン化合物等のリン化合物等の難燃剤等の成分を配合することができる。これらは、電子材料の分野において公知の物を使用することができる。 (other ingredients)
The curable resin composition of the present invention may optionally further contain a coloring agent, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion promoter, a block copolymer, a chain transfer agent, a polymerization inhibitor, copper damage inhibitor, antioxidant, rust inhibitor, organic bentonite, thickener such as montmorillonite, at least one of silicone-based, fluorine-based, polymer-based defoaming agent and leveling agent, imidazole-based, Components such as a thiazole-based or triazole-based silane coupling agent, a phosphinate, a phosphoric acid ester derivative, a phosphorus compound such as a phosphazene compound, and other flame retardants can be blended. As these, those known in the field of electronic materials can be used.
　硬化性樹脂組成物の粘度は、本発明の効果が奏される限り特に限定されないが、回転式粘度計により測定される粘度、すなわち２５℃で５ｒｐｍの回転速度で３０秒間回転させた場合の粘度として、好ましくは２００～１０００ｄＰａ・ｓ、より好ましくは２００～８００ｄＰａ・ｓである。硬化性樹脂組成物の粘度が上述した範囲であることにより、硬化性樹脂組成物の形状保持性（液ダレ抑制）および埋め込み性を良好なものとすることができる。なお、硬化性樹脂組成物の粘度は、ＪＩＳ　Ｚ　８８０３に記載されているコーンローター（円錐ロータ）とプレートからなるコーンプレート型粘度計（例えば、東機産業株式会社製のＴＶ－３０型、ロータ３°×Ｒ９．７）を用いて測定することができる。 The viscosity of the curable resin composition is not particularly limited as long as the effect of the present invention is exhibited, but the viscosity measured by a rotary viscometer, that is, the viscosity when rotated at 25 ° C. at a rotation speed of 5 rpm for 30 seconds , preferably 200 to 1000 dPa·s, more preferably 200 to 800 dPa·s. When the viscosity of the curable resin composition is within the range described above, the curable resin composition can have good shape retention (suppression of liquid dripping) and good embedding properties. The viscosity of the curable resin composition can be measured using a cone-plate viscometer consisting of a cone rotor (cone rotor) and a plate described in JIS Z 8803 (for example, model TV-30 manufactured by Toki Sangyo Co., Ltd., rotor 3°×R9.7).
　本発明の硬化性樹脂組成物は、スクリーン印刷法、真空印刷法等の公知のパターニング方法を用いて、例えば、多層プリント配線板の貫通孔の穴部や、回路間の隙間（底部を有する凹部）に充填することができる。好ましくは、貫通孔の穴部や回路間の隙間を埋める際に、本発明の硬化性樹脂組成物が平坦になる（均一な高さを有する）ように充填する。そのように硬化性樹脂組成物を充填することによって、硬化性樹脂組成物を硬化させた後に、プリント配線板上に平滑な表面を有する硬化物を形成することができる。硬化性樹脂組成物の充填にあたっては、好ましくは穴部や凹部から少しはみ出るように完全に充填される。穴部や凹部が硬化性樹脂組成物で充填された多層プリント配線板を、例えば８０～１６０℃で３０～１８０分程度加熱することにより、硬化性樹脂組成物が硬化して、硬化物が形成される。印刷時に発生する泡を抑制する観点から２段階で硬化させてもよい。すなわち、より低い温度で硬化性樹脂組成物を予備硬化させておき、その後に本硬化（仕上げ硬化）させてもよい。予備硬化としての条件は、８０～１１０℃で３０～９０分程度の加熱が好ましい。予備硬化した硬化物の硬度は比較的に低いため、基板表面からはみ出している不必要部分を物理研磨により容易に除去でき、平滑面とすることができる。その後、加熱して本硬化させる。本硬化としての条件は、１３０～１６０℃で３０～１８０分程度の加熱が好ましい。なお、予備硬化物の硬度は、予備硬化の加熱時間、加熱温度を変えることによってコントロールすることができる。 The curable resin composition of the present invention can be formed by using a known patterning method such as a screen printing method or a vacuum printing method. ) can be filled. Preferably, the curable resin composition of the present invention is filled evenly (having a uniform height) when filling the holes of the through-holes and the gaps between circuits. By filling the curable resin composition in such a manner, a cured product having a smooth surface can be formed on the printed wiring board after curing the curable resin composition. When filling the curable resin composition, it is preferable that the filling is completed so as to protrude slightly from the hole or recess. By heating the multilayer printed wiring board in which the holes and recesses are filled with the curable resin composition, for example, at 80 to 160 ° C. for about 30 to 180 minutes, the curable resin composition is cured to form a cured product. be done. It may be cured in two steps from the viewpoint of suppressing bubbles generated during printing. That is, the curable resin composition may be pre-cured at a lower temperature and then main-cured (finish-cured). Heating at 80 to 110° C. for about 30 to 90 minutes is preferable as the condition for pre-curing. Since the hardness of the pre-cured cured product is relatively low, unnecessary portions protruding from the substrate surface can be easily removed by physical polishing, and a smooth surface can be obtained. After that, it is heated to be fully cured. Heating at 130 to 160° C. for about 30 to 180 minutes is preferable as the condition for main curing. The hardness of the pre-cured product can be controlled by changing the heating time and heating temperature for pre-curing.
　上記のようにして硬化性樹脂組成物を硬化させた後、必要に応じてプリント配線板の硬化物の不要部分を公知の物理研磨方法により除去し、平滑化した後、表面の配線層を所定パターンにパターニングして、所定の回路パターンが形成される。なお、必要に応じて過マンガン酸カリウム水溶液等により硬化物の表面粗化を行った後、無電解めっきなどにより硬化物上に配線層を形成してもよい。 After curing the curable resin composition as described above, if necessary, unnecessary portions of the cured product of the printed wiring board are removed by a known physical polishing method, and after smoothing, the wiring layer on the surface is removed. A predetermined circuit pattern is formed by patterning. If necessary, the surface of the cured product may be roughened with an aqueous solution of potassium permanganate or the like, and then a wiring layer may be formed on the cured product by electroless plating or the like.
　以下、実施例を挙げて、本発明をさらに詳細に説明するが、本発明は、これらの実施例に限定されるものではない。なお、実施例において、「部」および「％」の記載は、特に断りのない限りいずれも質量基準である。 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, "parts" and "%" are based on mass unless otherwise specified.
［硬化性樹脂組成物の調製］
　下記表１に示す各成分を、同表に示す量で混合し、撹拌機を用いて予備撹拌した後、３本ロールミルを用いて混錬し、実施例１～１１および比較例１～４の各硬化性樹脂組成物を調製した。なお、表１中の各成分の詳細は以下の通りである。なお、表１中、単位を記載していない数値は、いずれも質量部を表す。
　エポキシ樹脂１（３級アミンを有するエポキシ樹脂）：ｐ－アミノフェノール型液状エポキシ樹脂（ｊＥＲ（登録商標）６３０、三菱ケミカル株式会社製）
　エポキシ樹脂２（３級アミンを有するエポキシ樹脂）：Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン
　エポキシ樹脂３（３級アミンを有するエポキシ樹脂）：ｐ－アミノフェノール型液状エポキシ樹脂（ｊＥＲ（登録商標）６０４、三菱ケミカル株式会社製）
　エポキシ樹脂４（ビスフェノール骨格を有するエポキシ樹脂）：ビスフェノールＡ型エポキシ樹脂（ｊＥＲ（登録商標）８２８、三菱ケミカル株式会社製）
　エポキシ樹脂５（ビスフェノール骨格を有するエポキシ樹脂）：ビスフェノールＦ型エポキシ樹脂（ｊＥＲ（登録商標）８０６Ｈ、三菱ケミカル株式会社製）
　エポキシ樹脂硬化剤：２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン（キュアゾール２ＭＺＡ－ＰＷ、四国化成工業株式会社製）
　フィラー１：炭酸カルシウム
　フィラー２：シリカ
　フィラー３：合成ハイドロタルサイト
　フィラー４：水酸化アルミニウム
　フィラー５：酸化マグネシウム
　フィラー６：炭酸マグネシウム
　消泡剤：シリコーン樹脂（ＫＳ－６６、信越化学工業株式会社製） [Preparation of curable resin composition]
Each component shown in Table 1 below was mixed in the amount shown in the same table, pre-stirred using a stirrer, and then kneaded using a three-roll mill to obtain Examples 1-11 and Comparative Examples 1-4. Each curable resin composition was prepared. The details of each component in Table 1 are as follows. In Table 1, all numerical values without units represent parts by mass.
Epoxy resin 1 (epoxy resin having a tertiary amine): p-aminophenol type liquid epoxy resin (jER (registered trademark) 630, manufactured by Mitsubishi Chemical Corporation)
Epoxy resin 2 (epoxy resin having a tertiary amine): N, N, N', N'-tetraglycidyl-m-xylenediamine Epoxy resin 3 (epoxy resin having a tertiary amine): p-aminophenol type liquid epoxy Resin (jER (registered trademark) 604, manufactured by Mitsubishi Chemical Corporation)
Epoxy resin 4 (epoxy resin having a bisphenol skeleton): bisphenol A type epoxy resin (jER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation)
Epoxy resin 5 (epoxy resin having a bisphenol skeleton): bisphenol F type epoxy resin (jER (registered trademark) 806H, manufactured by Mitsubishi Chemical Corporation)
Epoxy resin curing agent: 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (Curesol 2MZA-PW, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Filler 1: Calcium carbonate Filler 2: Silica Filler 3: Synthetic hydrotalcite Filler 4: Aluminum hydroxide Filler 5: Magnesium oxide Filler 6: Magnesium carbonate Defoamer: Silicone resin (KS-66, manufactured by Shin-Etsu Chemical Co., Ltd.)
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［石英管燃焼法によるハロゲン量の測定］
　実施例および比較例の各硬化性樹脂組成物を燃焼させた場合に放出される塩素および臭素の量を以下の手順に従って測定した。
　まず、日東精工アナリテック株式会社製の自動試料燃焼装置ＡＱＦ－２１００Ｈを用いて各硬化性樹脂組成物０．１ｇを燃焼させてガス成分を捕集した。次いで、捕集されたガス成分を吸収液（過酸化水素水）に吸収し、得られた吸収液をについてＴｈｅｒｍｏ　Ｆｉｓｈｅｒ　Ｓｃｉｅｎｔｉｆｉｃ社製のイオンクロマトグラフシステムＴｈｅｒｍｏ　Ｓｃｉｅｎｔｉｆｉｃ　Ｄｉｏｎｅｘ　ＩＣＳ－１１００、Ｔｈｅｒｍｏ　Ｓｃｉｅｎｔｉｆｉｃ　Ｄｉｏｎｅｘ　ＡＥＲＳ　５００サプレッサーおよびＤｉｏｎｅｘ　ＩｏｎＰａｃ　ＡＳ１２Ａカラムを用いたイオンクロマトグラフ法により塩素および臭素をそれぞれ定量した。実施例および比較例の各硬化性樹脂組成物のハロゲン量を以下の基準に従って評価した。ハロゲンの量（塩素および臭素の合計量）の測定結果および評価結果を表１に示す。
　◎：ハロゲン量が５００ｐｐｍ以下であり、ハロゲン含有物質の放出量が極めて良好に抑制されている。
　○：ハロゲン量が５００ｐｐｍ超１０００ｐｐｍ以下であり、ハロゲン含有物質の放出量が良好に抑制されている。
　×：ハロゲン量が１０００ｐｐｍ超であり、ハロゲン含有物質の放出量が十分に抑制されていない。 [Measurement of Halogen Amount by Quartz Tube Combustion Method]
The amounts of chlorine and bromine released when the curable resin compositions of Examples and Comparative Examples were burned were measured according to the following procedure.
First, 0.1 g of each curable resin composition was burned using an automatic sample burner AQF-2100H manufactured by Nitto Seiko Analyticc Co., Ltd. to collect gas components. Next, the collected gas components are absorbed in an absorbent (hydrogen peroxide solution), and the obtained absorbent is subjected to ion chromatography systems Thermo Scientific Dionex ICS-1100 and Thermo Scientific Dionex AERS 500 manufactured by Thermo Fisher Scientific. Chlorine and bromine were quantified by ion chromatography using a suppressor and a Dionex IonPac AS12A column, respectively. The amount of halogen in each curable resin composition of Examples and Comparative Examples was evaluated according to the following criteria. Table 1 shows the measurement results and evaluation results of the amount of halogen (total amount of chlorine and bromine).
A: The amount of halogen is 500 ppm or less, and the amount of released halogen-containing substances is extremely well suppressed.
◯: The amount of halogen is more than 500 ppm and not more than 1000 ppm, and the release amount of halogen-containing substances is well suppressed.
x: The amount of halogen exceeds 1000 ppm, and the release amount of halogen-containing substances is not sufficiently suppressed.
［印刷性の評価］
　実施例および比較例の各硬化性樹脂組成物の印刷性を、以下の手順に従って評価した。
　予めパネルめっきにより直径５００μｍのスルーホールを形成した厚さ１ｍｍのガラスエポキシ基板に、実施例および比較例の各硬化性樹脂組成物をスクリーン印刷法により下記の印刷条件でスルーホール内に充填した。各硬化性樹脂組成物を充填したガラスエポキシ基板を熱風循環式乾燥炉に入れ、１８０℃で１時間水平状態に保持して各硬化性樹脂組成物を硬化させて、各評価用基板を得た。
（印刷条件）
　スキージ：スキージ厚２０ｍｍ、硬度７０°、斜め研磨：２３°
　版：ＰＥＴ１００メッシュバイアス版
　印圧：６０ｋｇｆ／ｃｍ２
　スキージスピード：５ｃｍ／秒
　スキージ角度：８０° [Evaluation of printability]
The printability of each curable resin composition of Examples and Comparative Examples was evaluated according to the following procedure.
A glass epoxy substrate having a thickness of 1 mm and a through hole having a diameter of 500 μm formed in advance by panel plating was filled with each of the curable resin compositions of Examples and Comparative Examples by screen printing under the following printing conditions. The glass epoxy substrate filled with each curable resin composition was placed in a hot air circulating drying oven and held horizontally at 180° C. for 1 hour to cure each curable resin composition to obtain each evaluation substrate. .
(Printing conditions)
Squeegee: Squeegee thickness 20 mm, hardness 70°, oblique polishing: 23°
Plate: PET100 mesh bias plate Printing pressure: 60 kgf/cm 2
Squeegee speed: 5 cm/sec Squeegee angle: 80°
　各評価用基板について、スルーホール内に充填された硬化性樹脂組成物の硬化物の充填度合いを目視により観察し、実施例および比較例の各硬化性樹脂組成物の印刷性を以下の基準に従って評価した。評価結果を表１に示す。
　◎：完全に充填されており、硬化もされている。
　○：完全ではないが十分に充填されており、硬化もされている。
　×：充填が困難である。 For each substrate for evaluation, the degree of filling of the cured product of the curable resin composition filled in the through holes was visually observed, and the printability of each curable resin composition of Examples and Comparative Examples was evaluated according to the following criteria. evaluated. Table 1 shows the evaluation results.
A: Completely filled and cured.
◯: Not completely, but sufficiently filled and cured.
x: Filling is difficult.
［はんだ耐熱性の評価］
　実施例および比較例の各硬化性樹脂組成物のはんだ耐熱性を、以下の手順に従って評価した。
　まず、上述した研磨性の評価に用いたのと同じ各評価用基板を準備した。各評価用基板における硬化性樹脂組成物を塗布した側の表面を、研磨機を用いて＃３２０相当の樹脂研磨用バフ１軸により物理研磨した。次いで、物理研磨後の各評価用基板を２８８℃のはんだ液中に１０秒間、３回浸漬した後、室温まで放冷した。次いで、各評価用基板をスルーホール部で切断し、断面を光学顕微鏡にて観察して、１００個のスルーホールにおけるクラックの数を数えた。クラックの数に基づいて、実施例および比較例の各硬化性樹脂組成物のはんだ耐熱性を以下の基準に従って評価した。評価結果を表１に示す。
　○：クラックが０個である。
　△：クラックが１～５個である。
　×：クラックが６個以上である。 [Evaluation of solder heat resistance]
Soldering heat resistance of each curable resin composition of Examples and Comparative Examples was evaluated according to the following procedure.
First, the same substrates for evaluation as those used for evaluating the polishing property were prepared. The surface of each substrate for evaluation on which the curable resin composition was applied was physically polished using a polishing machine with a buff for resin polishing equivalent to #320. Then, each substrate for evaluation after physical polishing was immersed in a solder solution at 288° C. for 10 seconds three times, and then allowed to cool to room temperature. Next, each evaluation substrate was cut at the through-hole portion, the cross section was observed with an optical microscope, and the number of cracks in 100 through-holes was counted. Based on the number of cracks, the soldering heat resistance of each curable resin composition of Examples and Comparative Examples was evaluated according to the following criteria. Table 1 shows the evaluation results.
○: 0 cracks.
Δ: 1 to 5 cracks.
x: 6 or more cracks.
　表１に示す評価結果から、実施例の各硬化性樹脂組成物では、石英管燃焼法により測定されるハロゲン量が１０００ｐｐｍ以下と低いことが分かる。石英管燃焼法により測定されるハロゲン量は、燃焼時に放出される様々なハロゲン含有物質に由来するハロゲンの量と考えられる。したがって、実施例の各硬化性樹脂組成物では、燃焼時のハロゲン含有物質の放出量が抑制されていると言える。また、実施例の各硬化性樹脂組成物では、プリント配線板の穴埋めや回路間の隙間を埋めることによる平滑化に好適に用いられ得る良好な印刷性、および良好なはんだ耐熱性が奏されることが分かる。一方、比較例の各硬化性樹脂組成物では、燃焼時のハロゲンの放出量が１０００ｐｐｍ超と高いことが分かる。したがって、比較例の各硬化性樹脂組成物では、燃焼時のハロゲン含有物質の放出量が十分に抑制されていないと言える。 From the evaluation results shown in Table 1, it can be seen that in each curable resin composition of Examples, the amount of halogen measured by the quartz tube combustion method is as low as 1000 ppm or less. The amount of halogen measured by the quartz tube combustion method is considered to be the amount of halogen derived from various halogen-containing substances released during combustion. Therefore, it can be said that the curable resin compositions of the examples suppress the release of halogen-containing substances during combustion. In addition, each curable resin composition of Examples exhibits good printability that can be suitably used for smoothing by filling holes in printed wiring boards and filling gaps between circuits, and good solder heat resistance. I understand. On the other hand, it can be seen that the curable resin compositions of the comparative examples release a large amount of halogen during combustion, exceeding 1000 ppm. Therefore, it can be said that the curable resin compositions of the comparative examples do not sufficiently suppress the emission of halogen-containing substances during combustion.

Claims (10)

  1. 　エポキシ樹脂、
    　エポキシ樹脂硬化剤、および
    　フィラー
    を含む硬化性樹脂組成物であって、
    　前記フィラーが炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムからなる群から選択される少なくとも１種を含み、
    　石英管燃焼法により測定されるハロゲンの量が１００～１０００ｐｐｍであることを特徴とする、硬化性樹脂組成物。     Epoxy resin,
    A curable resin composition comprising an epoxy resin curing agent and a filler,
    The filler contains at least one selected from the group consisting of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide,
    A curable resin composition characterized by having a halogen content of 100 to 1000 ppm as measured by a quartz tube combustion method.
  2. 　前記フィラーの総含有量が、前記エポキシ樹脂１００質量部に対して５０～３００質量部である、請求項１に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the total content of said filler is 50 to 300 parts by mass with respect to 100 parts by mass of said epoxy resin.
  3. 　前記炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムの総含有量が、前記エポキシ樹脂１００質量部に対して１０～２５０質量部である、請求項１または２に記載の硬化性樹脂組成物。 3. The curable resin composition according to claim 1, wherein the total content of said magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide is 10 to 250 parts by mass with respect to 100 parts by mass of said epoxy resin. .
  4. 　前記炭酸マグネシウム、酸化マグネシウム、ハイドロタルサイトおよび水酸化アルミニウムの総含有量が、前記フィラーの総含有量に対して４～１００質量％の割合で含まれる、請求項１または２に記載の硬化性樹脂組成物。 Curability according to claim 1 or 2, wherein the total content of magnesium carbonate, magnesium oxide, hydrotalcite and aluminum hydroxide is contained in a proportion of 4 to 100% by mass with respect to the total content of the filler. Resin composition.
  5. 　前記エポキシ樹脂が３級アミンを有するエポキシ樹脂を含む、請求項１または２に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1 or 2, wherein the epoxy resin contains an epoxy resin having a tertiary amine.
  6. 　前記エポキシ樹脂の含有量が、前記硬化性樹脂組成物１００質量部に対して１０～６０質量部である、請求項１または２に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1 or 2, wherein the content of the epoxy resin is 10 to 60 parts by mass with respect to 100 parts by mass of the curable resin composition.
  7. 　２５℃で５ｒｐｍの回転速度で３０秒間回転させた場合の粘度が２００～１０００ｄＰａ・ｓである、請求項１または２に記載の硬化性樹脂組成物。 3. The curable resin composition according to claim 1, which has a viscosity of 200 to 1000 dPa·s when rotated at 25° C. and a rotation speed of 5 rpm for 30 seconds.
  8. 　プリント配線板の穴埋めまたはプリント配線板の回路間の間隙の充填に用いられる、請求項１または２に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1 or 2, which is used for filling holes in printed wiring boards or filling gaps between circuits on printed wiring boards.
  9. 　請求項１または２に記載の硬化性樹脂組成物の硬化物。 A cured product of the curable resin composition according to claim 1 or 2.
  10. 　請求項９に記載の硬化物を備える、プリント配線板。 A printed wiring board comprising the cured product according to claim 9.
PCT/JP2023/007717 2022-03-02 2023-03-02 Curable resin composition, cured product, and printed wiring board WO2023167267A1 (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6119625A (en) * 1984-07-05 1986-01-28 Toshiba Corp Epoxy resin composition for sealing semiconductor
JPH06148388A (en) * 1992-11-10 1994-05-27 Mitsubishi Gas Chem Co Inc Composition for neutron shield material
JPH09118810A (en) * 1996-09-12 1997-05-06 Nitto Denko Corp Semiconductor device
JP2007049106A (en) * 2005-08-11 2007-02-22 Sanei Kagaku Kk Planarized resin-coated printed wiring board
JP2013076002A (en) * 2011-09-30 2013-04-25 Taiyo Ink Mfg Ltd Thermosetting resin filler, and printed wiring board
JP2015054940A (en) * 2013-09-13 2015-03-23 スリーボンドファインケミカル株式会社 Flame-retardant epoxy resin composition
JP2018059041A (en) * 2016-10-03 2018-04-12 東洋スチレン株式会社 Flame-retardant resin composition and flame-retardant resin molded body
JP2021167422A (en) * 2017-03-31 2021-10-21 昭和電工マテリアルズ株式会社 Epoxy resin composition, epoxy resin cured product, and electronic component device

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6119625A (en) * 1984-07-05 1986-01-28 Toshiba Corp Epoxy resin composition for sealing semiconductor
JPH06148388A (en) * 1992-11-10 1994-05-27 Mitsubishi Gas Chem Co Inc Composition for neutron shield material
JPH09118810A (en) * 1996-09-12 1997-05-06 Nitto Denko Corp Semiconductor device
JP2007049106A (en) * 2005-08-11 2007-02-22 Sanei Kagaku Kk Planarized resin-coated printed wiring board
JP2013076002A (en) * 2011-09-30 2013-04-25 Taiyo Ink Mfg Ltd Thermosetting resin filler, and printed wiring board
JP2015054940A (en) * 2013-09-13 2015-03-23 スリーボンドファインケミカル株式会社 Flame-retardant epoxy resin composition
JP2018059041A (en) * 2016-10-03 2018-04-12 東洋スチレン株式会社 Flame-retardant resin composition and flame-retardant resin molded body
JP2021167422A (en) * 2017-03-31 2021-10-21 昭和電工マテリアルズ株式会社 Epoxy resin composition, epoxy resin cured product, and electronic component device

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