[go: up one dir, main page]

WO2018074517A1 - Composition de résine époxydique pour former une carte de circuit imprimé - Google Patents

Composition de résine époxydique pour former une carte de circuit imprimé Download PDF

Info

Publication number
WO2018074517A1
WO2018074517A1 PCT/JP2017/037708 JP2017037708W WO2018074517A1 WO 2018074517 A1 WO2018074517 A1 WO 2018074517A1 JP 2017037708 W JP2017037708 W JP 2017037708W WO 2018074517 A1 WO2018074517 A1 WO 2018074517A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
resin composition
epoxy resin
epoxy
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/037708
Other languages
English (en)
Japanese (ja)
Inventor
一樹 平佐田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Priority to KR1020197011435A priority Critical patent/KR102398796B1/ko
Priority to CN201780064085.1A priority patent/CN109843965B/zh
Priority to JP2018546382A priority patent/JP7004181B2/ja
Publication of WO2018074517A1 publication Critical patent/WO2018074517A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3236—Heterocylic compounds
    • C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
    • 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
    • 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
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • 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
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N

Definitions

  • the present invention relates to an invention of an epoxy resin composition for forming a printed wiring board containing a mixture of epoxy compounds. More specifically, the present invention relates to an epoxy resin composition for obtaining an epoxy resin having a low dielectric loss tangent and a low dielectric constant.
  • an epoxy resin is an epoxy resin composition combined with a curing agent or a curing catalyst, such as an adhesive, a high refractive index layer of an antireflection film (such as an antireflection film for a liquid crystal display), an optical thin film (such as a reflection plate), Widely used in applications such as sealing materials for electronic parts, printed wiring boards, and interlayer insulating film materials (such as interlayer insulating film materials for build-up printed boards).
  • a curing agent or a curing catalyst such as an adhesive, a high refractive index layer of an antireflection film (such as an antireflection film for a liquid crystal display), an optical thin film (such as a reflection plate), Widely used in applications such as sealing materials for electronic parts, printed wiring boards, and interlayer insulating film materials (such as interlayer insulating film materials for build-up printed boards).
  • a curing agent or a curing catalyst such as an adhesive, a high refractive index layer of an antireflection film (such as an antire
  • Patent Document 2 a method of adding a dielectric ceramic powder having a low dielectric loss tangent to the epoxy resin composition is known (for example, Patent Document 2).
  • Patent Document 3 discloses an epoxy resin composition in which triglycidyl isocyanurate, which is a crystalline epoxy resin, is modified so that it is liquid or solid and has improved cured properties such as excellent water absorption prevention and mechanical properties. It is described that it is obtained.
  • a cured product obtained from an epoxy resin composition containing a mixture of epoxy compounds having a specific structure has a low dielectric loss tangent and a low dielectric constant. It was expressed and found to be applicable to printed wiring board formation, and the present invention was completed.
  • the present invention provides, as a first aspect, a mixture comprising (a) an epoxy compound A represented by the formula [1] and a compound B optionally having an epoxy group represented by the formula [2], And (b) an epoxy resin composition for forming a printed wiring board, comprising a curing agent, (Wherein R 1 to R 3 each independently represents a hydrogen atom or a methyl group, and L 1 to L 3 each independently represents an alkylene group having 1 to 10 carbon atoms).
  • R 4 and R 5 are each independently an optionally substituted alkyl having 1 to 20 carbon atoms.
  • Group represents an optionally substituted aryl group having 6 to 10 carbon atoms, and a black dot represents a bond).
  • the epoxy resin composition according to the first aspect wherein the L 1 to L 3 are an alkylene group selected from the group consisting of a methylene group, a trimethylene group, and a hexamethylene group
  • the epoxy resin composition according to the first aspect or the second aspect wherein R 4 and R 5 are an optionally substituted alkyl group having 1 to 10 carbon atoms
  • R 4 and R 5 are an alkyl group having 2 to 10 carbon atoms
  • the epoxy resin composition according to the first aspect or the second aspect, wherein R 4 and R 5 are optionally substituted phenyl groups
  • the epoxy resin composition according to any one of the first aspect to the fifth aspect including 0.2 to 20 moles of the compound B with respect to 1 mole of the epoxy compound A
  • the (b) curing agent is at least one selected from the
  • any one of the first aspect to the seventh aspect includes 0.5 to 1.5 equivalents of the (b) curing agent with respect to 1 equivalent of the epoxy group of the (a) epoxy resin.
  • the cured product of the epoxy resin composition of the present invention has a low dielectric loss tangent and a low dielectric constant while maintaining a high glass transition temperature (Tg), and also has a low water absorption. Therefore, the epoxy resin composition of the present invention can be suitably used as an epoxy resin composition for forming a printed wiring board.
  • the epoxy resin composition for forming a printed wiring board of the present invention comprises (a) an epoxy compound A represented by the formula [1] and a compound B optionally having an epoxy group represented by the formula [2]. A mixture comprising, and (b) a curing agent.
  • the (a) mixture of this invention contains the epoxy compound A represented by the said Formula [1].
  • R 1 to R 3 each independently represents a hydrogen atom or a methyl group
  • L 1 to L 3 each independently represent an alkylene group having 1 to 10 carbon atoms.
  • alkylene group having 1 to 10 carbon atoms represented by L 1 to L 3 examples include methylene group, ethylene group, trimethylene group, 1-methylethylene group, tetramethylene group, 1-methyltrimethylene group, 1,1 -Dimethylethylene group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-ethyltrimethylene group, hexamethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1-ethyltetramethylene group, 1,1,2-trimethyltrimethyle Group, 1,2,2-trimethyltrimethylene group, 1-ethyl-1-methyltrimethylene group, 1-ethyl-2-methyltrimethylene
  • the epoxy compound represented by Formula [1] can use a commercially available epoxy compound, or can use the isocyanurate ring containing epoxy compound manufactured by the well-known method.
  • TEPIC registered trademark
  • triglycidyl isocyanurate tris (3,4-epoxybutyl) isocyanurate
  • TEIC-VL registered trademark
  • Tris (4,5-epoxypentyl) isocyanurate Tris (5,6-epoxyhexyl) isocyanurate
  • TEIC-FL registered trademark
  • an isocyanurate ring-containing epoxy compound an epoxy resin excellent in light resistance, weather resistance, heat resistance, transparency and
  • the (a) mixture of this invention contains the compound B which may have the epoxy group represented by the said Formula [2].
  • L 1 to L 3 represent the same meaning as described above
  • X 1 to X 3 each independently represent a group represented by the above formula [2a] or the above formula [2b].
  • at least one of X 1 to X 3 represents a group represented by the formula [2b].
  • R 1 represents the same meaning as described above
  • the black dot represents a bond.
  • R 1 and black dots are as defined above, R 4 and R 5 are alkyl groups which do having 1 to carbon atoms which may be 20 substituted, or an optionally substituted carbon atoms Represents an aryl group of formula 6 to 10;
  • Examples of the optionally substituted alkyl group represented by R 4 and R 5 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • Linear alkyl groups such as nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group, isohexyl group, texyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, Heptane-3-yl group, heptane-4-yl group, 4-methylhexane 2-yl group, 3-methylhexane-3-yl group, 2,3
  • alkyl groups having 1 to 10 carbon atoms, more preferably an alkyl group having 2 to 10 carbon atoms.
  • alkyl groups may be substituted with a substituent such as a cyano group, an amino group, a nitro group, or a halogen atom.
  • a substituent such as a cyano group, an amino group, a nitro group, or a halogen atom.
  • the halogen atom include a fluoro group, a chloro group, a bromo group, and an iodo group.
  • Examples of the optionally substituted aryl group having 6 to 10 carbon atoms represented by R 4 and R 5 include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Preferably, each is a phenyl group.
  • These aryl groups may be substituted with a substituent such as an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group or a propyl group, a cyano group, an amino group, a nitro group or a halogen atom. .
  • the compound represented by Formula [2] can use a commercially available epoxy compound, or what was manufactured by the well-known method can be used.
  • a product obtained by reacting part or all of the epoxy group of the epoxy compound A represented by the formula [1] with an acid anhydride and replacing it with a group represented by the formula [2b] can be preferably used.
  • the compound B has the formula [3] on the epoxy group of the epoxy compound A.
  • the acid anhydride represented by the above formula [3] is an acid anhydride obtained from a so-called bimolecular monocarboxylic acid, and is different from an acid anhydride obtained from a dicarboxylic acid used as a curing agent for an epoxy resin.
  • the epoxy resin does not function as a curing agent.
  • compound B obtained by reacting an epoxy compound and an acid anhydride has no hydroxyl group, it has high storage stability without gelation even if unreacted acid anhydride is present.
  • the acid anhydride is not particularly limited, for example, acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, hexanoic anhydride, octanoic anhydride, trifluoroacetic anhydride, benzoic anhydride Etc.
  • the mixture (a) of the present invention comprises epoxy compound A: acid anhydride in a molar ratio of (epoxy group of epoxy compound A) :( acid anhydride) of 1: 0.1 to 1: 1, preferably 1. : 0.4 to 1: 0.8.
  • the reaction product is obtained by HPLC analysis, etc., from an unreacted epoxy compound A, a compound in which one acid anhydride represented by the formula [3] is added to the epoxy group of the epoxy compound A, a compound in which two are added, and The molar ratio of the three added compounds (compound B) can be determined.
  • the solvent used for the reaction only needs to be inert to the reaction.
  • these solvents include ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate; aromatic hydrocarbons such as chlorobenzene and toluene; chloroform and dichloroethane. And halogenated hydrocarbons.
  • the epoxy compound A such as triglycidyl isocyanurate is dissolved alone or as a mixed solvent.
  • tertiary amines such as triethylamine, tripropylamine, 1,8-diazabicyclo [5.4.0] undecan-7-ene, ethyltriphenylphosphonium bromide, tetraphenylphosphonium bromide
  • Quaternary phosphonium salts such as monoalkyltriphenylphosphonium halides, imidazole compounds such as 2-ethyl-4-methylimidazole, quaternary ammonium salts such as tetraethylammonium bromide, triphenylphosphine, etc. Phosphorus compounds and the like can be used.
  • the reaction temperature is, for example, carried out at the reflux temperature of the solvent until the epoxy group content titrated with a 0.1N perchloric acid / acetic acid solution reaches a theoretical value (a value at which the added acid anhydride disappears by the reaction). Is called. After completion of the reaction, the solvent can be distilled off to obtain (a) a mixture.
  • the content of the epoxy compound A represented by the formula [1] and the compound B represented by the formula [2] is not particularly limited, but for example, with respect to 1 mol of the epoxy compound A Compound B is contained in an amount of 0.2 to 20 mol, preferably 0.7 to 4 mol.
  • the sum total of the epoxy groups of compound A and the epoxy groups of compound B is preferably 2 or more on average (converted to the total number of epoxy groups). If it is less than 2, the physical properties of the cured product, particularly the heat resistance, is lowered, which is not preferable.
  • the mixture of the present invention is a combination of the epoxy compound A represented by the formula [1] and the compound B represented by the formula [2] and other epoxy compounds within the range not impairing the effects of the present invention. can do.
  • the epoxy compound A represented by the formula [1] and the compound B represented by the formula [2] and the other epoxy compounds are in a molar ratio of epoxy groups, for example, in the range of 1: 0 to 1:20. Can be used.
  • the various polyfunctional epoxy compound marketed can be used without being specifically limited.
  • Examples of the epoxy compound that can be used in the present invention include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, (poly) ethylene glycol diglycidyl ether, and (poly) propylene glycol diglycidyl ether.
  • liquid epoxy compound examples include TEPIC (registered trademark) -UC (manufactured by Nissan Chemical Industries, Ltd.), jER (registered trademark) 828, YX8000 (both manufactured by Mitsubishi Chemical Corporation), Guatemala Resin (registered trademark) DME100 [ New Nippon Rika Co., Ltd.], Celoxide 2021P [manufactured by Daicel Corporation], and the like.
  • the epoxy resin composition for forming a printed wiring board of the present invention contains (b) a curing agent.
  • curing agent for example, an acid anhydride, an amine, a phenol resin, a polyamide resin, imidazoles, polymercaptan, or a mixture thereof can be used. Among these, acid anhydrides and amines are particularly preferable. Even if these hardening
  • the curing agent itself is preferably liquid at normal temperature and normal pressure.
  • the curing agent can be contained in a proportion of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, relative to 1 equivalent of the epoxy group of the epoxy compound.
  • the equivalent of the curing agent to the epoxy compound is represented by an equivalent ratio of the curable group of the curing agent to the epoxy group.
  • the epoxy group of all these epoxy compounds The equivalent to is in the above range.
  • the acid anhydride is preferably an anhydride of a compound having a plurality of carboxyl groups in one molecule.
  • These acid anhydrides include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol trislimitate, maleic anhydride, tetrahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride Methylcyclohexene dicarboxylic acid anhydride, chlorendic acid anhydr
  • methyltetrahydrophthalic anhydride methyl-5-norbornene-2,3-dicarboxylic acid anhydride (methyl nadic acid anhydride, methyl hymic anhydride), hydrogenated methyl nadic acid which is liquid at normal temperature and normal pressure
  • anhydrides methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, methylhexahydrophthalic anhydride, a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride.
  • These liquid acid anhydrides have a viscosity of about 10 to 1,000 mPa ⁇ s as measured at 25 ° C. In an acid anhydride group, one acid anhydride group is calculated as one equivalent.
  • amines examples include piperidine, N, N′-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, diethylenetriamine, and triethylene.
  • Tetramine Tetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di (1-methyl-2-aminocyclohexyl) methane, menthanediamine, isophoronediamine, diaminodicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane Xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and the like.
  • liquid diethylenetriamine triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, bis (1-methyl-2-aminocyclohexyl) methane, menthanediamine, isophoronediamine, diaminodicyclohexylmethane Etc.
  • liquid diethylenetriamine triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, bis (1-methyl-2-aminocyclohexyl) methane, menthanediamine, isophoronediamine, diaminodicyclohexylmethane Etc.
  • phenol resin examples include phenol novolac resin and cresol novolac resin.
  • the polyamide resin is produced by condensation of dimer acid and polyamine, and is a polyamide amine having a primary amine and a secondary amine in the molecule.
  • imidazoles examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, epoxy imidazole adduct, and the like.
  • Polymercaptan is, for example, one having a mercaptan group at the end of a polypropylene glycol chain or one having a mercaptan group at the end of a polyethylene glycol chain, and is preferably in a liquid form.
  • a hardening accelerator (it is also called a hardening adjuvant) may be used together.
  • Curing accelerators include organophosphorus compounds such as triphenylphosphine and tributylphosphine; quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and tetrabutylphosphonium O, O-diethylphosphorodithioate; 1,8-diazabicyclo [ 5.4.0] Undec-7-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene and octyl acid, quaternary ammonium such as zinc octylate, tetrabutylammonium bromide Examples include salt.
  • organophosphorus compounds such as triphenylphosphine and tributylphosphine
  • quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and tetrabutylphosphonium O, O-diethylphosphorodithioate
  • imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole mentioned above as curing agents
  • amines such as 2,4,6-tris (dimethylaminomethyl) phenol and benzyldimethylamine are also included. It can be used as a curing accelerator for these types of curing agents.
  • These curing accelerators can be used at a ratio of 0.001 to 0.1 parts by mass with respect to 1 part by mass of the curing agent.
  • Epoxy resin composition for forming printed wiring board >>
  • the epoxy compound A represented by the formula [1] and the compound B represented by the formula [2], the curing agent, and a curing accelerator, if desired, are mixed to form a printed wiring board.
  • An epoxy resin composition is obtained. It is preferable to stir and mix these mixtures under reduced pressure to degas them.
  • the cured product obtained from the epoxy resin composition is pre-cured at a temperature of, for example, 100 to 120 ° C. by applying the epoxy resin composition to a base plate or pouring it onto a casting plate coated with a release agent, and 120 It can be obtained by main curing (post-curing) at a temperature of ⁇ 200 ° C.
  • cured material obtained from the epoxy resin composition of this invention can be used suitably for a printed wiring board.
  • the heating time can be appropriately adjusted depending on the size and thickness of the epoxy resin.
  • both the pre-curing and the main curing are each 1 to 12 hours, for example, about 2 to 5 hours.
  • Examples of the method for applying the epoxy resin composition of the present invention on a substrate include a flow coating method, a spin coating method, a spray coating method, a screen printing method, a flexographic printing method, an ink jet printing method, a casting method, and a bar coating method. , Curtain coating method, roll coating method, gravure coating method, dipping method, slit method and the like.
  • a curing catalyst such as (c1) an acid generator and / or (c2) a base generator can be used. Thereby, even if the epoxy compound of the present invention and the curing catalyst are mixed, curing does not occur immediately, so that the storage stability is excellent and sufficient working time is obtained.
  • (C1) Acid generator As the acid generator, a photoacid generator or a thermal acid generator can be used.
  • the photo acid generator or thermal acid generator is not particularly limited as long as it generates an acid (Lewis acid or Bronsted acid) directly or indirectly by light irradiation or heating.
  • the epoxy resin composition containing the thermal acid generator can be cured in a short time by heating. Moreover, since the epoxy resin composition which mix
  • photoacid generators include onium salts such as iodonium salts, sulfonium salts, phosphonium salts, selenium salts, metallocene complex compounds, iron arene complex compounds, disulfone compounds, sulfonic acid derivative compounds, triazine compounds, acetophenone derivatives. Compounds, diazomethane compounds, and the like.
  • iodonium salt examples include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-di-tert-butyldiphenyliodonium, 4-methylphenyl (4- ( 2-methylpropyl) phenyl) iodonium, 3,3′-dinitrophenyliodonium, 4- (1-ethoxycarbonylethoxy) phenyl (2,4,6-trimethylphenyl) iodonium, 4-methoxyphenyl (phenyl) iodonium, etc.
  • Iodonium chloride, bromide, mesylate, tosylate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, hexafluorophosphate, hexafluoroarsene DOO, diaryliodonium salts such as hexafluoroantimonate, and the like.
  • sulfonium salt examples include triphenylsulfonium, diphenyl (4-tert-butylphenyl) sulfonium, tris (4-tert-butylphenyl) sulfonium, diphenyl (4-methoxyphenyl) sulfonium, tris (4-methylphenyl) Sulfonium chloride, bromide, sulfonium such as sulfonium, tris (4-methoxyphenyl) sulfonium, tris (4-ethoxyphenyl) sulfonium, diphenyl (4- (phenylthio) phenyl) sulfonium, tris (4- (phenylthio) phenyl) sulfonium, Triarylsulfonium such as trifluoromethanesulfonate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsen
  • Examples of the phosphonium salt include chloride, bromide, tetrafluoro of phosphonium such as tetraphenylphosphonium, ethyltriphenylphosphonium, tetra (p-methoxyphenyl) phosphonium, ethyltri (p-methoxyphenyl) phosphonium, benzyltriphenylphosphonium.
  • Examples thereof include arylphosphonium salts such as borate, hexafluorophosphate, and hexafluoroantimonate.
  • selenium salt examples include triaryl selenium salts such as triphenyl selenium hexafluorophosphate.
  • iron arene complex compound examples include bis ( ⁇ 5 -cyclopentadienyl) ( ⁇ 6 -isopropylbenzene) iron (II) hexafluorophosphate.
  • photoacid generators can be used alone or in combination of two or more.
  • thermal acid generator examples include sulfonium salts and phosphonium salts, and sulfonium salts are preferably used.
  • thermal acid generators examples include the compounds mentioned as examples of various onium salts in the above-mentioned photoacid generator. These thermal acid generators can be used alone or in combination of two or more.
  • the acid generator (c1) a sulfonium salt compound or an iodonium salt compound is preferable.
  • a compound having an anionic species such as hexafluorophosphate or hexafluoroantimonate showing strong acidity is preferable.
  • the content of the acid generator (c1) in the epoxy resin composition of the present invention is preferably 0.1 to 20 parts by mass, or 0.1 to 10 parts by mass, more preferably 100 parts by mass of the epoxy compound (a). May be 0.5 to 10 parts by mass.
  • content with respect to 100 mass parts of all those epoxy compounds becomes the said range.
  • (C2) Base generator (C2)
  • the photobase acid generator or the heat base generator is not particularly limited as long as it generates a base (Lewis base or Bronsted base) directly or indirectly by light irradiation or heating.
  • An epoxy resin composition containing a thermal base generator can be cured in a short time by heating.
  • blended the photobase generator hardens
  • photobase generators can be used singly or in combination of two or more.
  • the photobase generator is available as a commercial product.
  • the photobase generator WPBG series WPBG-018, 027, 082, 140, 266, manufactured by Wako Pure Chemical Industries, Ltd. 300
  • WPBG-018, 027, 082, 140, 266, manufactured by Wako Pure Chemical Industries, Ltd. 300 can be preferably used.
  • thermal base generator examples include carbamates such as 1-methyl-1- (4-biphenylyl) ethyl carbamate and 2-cyano-1,1-dimethylethyl carbamate; urea, N, N-dimethyl-N′— Ureas such as methylurea; guanidines such as guanidine trichloroacetate, guanidine phenylsulfonylacetate and guanidine phenylpropiolate; dihydropyridines such as 1,4-dihydronicotinamide; N- (isopropoxycarbonyl) -2,6-dimethyl Dimethylpiperidines such as piperidine, N- (tert-butoxycarbonyl) -2,6-dimethylpiperidine, N- (benzyloxycarbonyl) -2,6-dimethylpiperidine; tetramethylammonium phenylsulfonylacetate, tetramethylphenylpropiolate Ann
  • U-CAT registered trademark
  • SA810 SA831, SA841, and SA851 which are salts of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) [San Apro Corporation ) Made] and the like.
  • DBU 1,8-diazabicyclo [5.4.0] undec-7-ene
  • the content of the base generator (c2) in the epoxy resin composition of the present invention is preferably 0.1 to 20 parts by mass, or 0.1 to 10 parts by mass, more preferably 100 parts by mass of the (a) epoxy compound. May be 0.5 to 10 parts by mass.
  • 100 mass parts of all these epoxy compounds The content with respect to is in the above range.
  • an epoxy resin composition is obtained by mixing the mixture (a) and the curing catalyst.
  • the operating conditions for mixing to obtain the epoxy resin composition are as described above.
  • the epoxy resin composition containing the said (a) mixture and a photo-acid generator or a photobase generator can be apply
  • the epoxy resin composition containing the said (a) mixture and a thermal acid generator or a thermal base generator can be apply
  • the epoxy resin composition containing the mixture (a) and the thermal acid generator and the photoacid generator or the thermal base generator and the photobase generator can be applied on a substrate and cured by light irradiation after heating. .
  • the thickness of the coating film formed from the epoxy resin composition of the present invention can be selected from a range of about 0.01 ⁇ m to 10 mm depending on the use of the cured product. For example, when used for a photoresist, 0.05 to 10 ⁇ m. (Especially 0.1 to 5 ⁇ m), about 10 ⁇ m to 5 mm (particularly 100 ⁇ m to 1 mm) when used for a printed wiring board, and 0.1 to 100 ⁇ m (particularly when used for an optical thin film) In particular, it can be about 0.3 to 50 ⁇ m.
  • Examples of light to be irradiated or exposed in the case of using a photoacid generator or a photobase generator include gamma rays, X-rays, ultraviolet rays, and visible rays, and usually visible rays or ultraviolet rays, particularly ultraviolet rays are used. There are many cases.
  • the wavelength of light is, for example, about 150 to 800 nm, preferably about 150 to 600 nm, more preferably about 200 to 400 nm, and particularly about 300 to 400 nm.
  • Irradiation dose may vary depending on the thickness of the coating film, for example, 2 ⁇ 20,000mJ / cm 2, preferably to the 5 ⁇ 5,000mJ / cm 2 approximately.
  • the light source can be selected according to the type of light to be exposed.
  • a low-pressure mercury lamp for example, in the case of ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a deuterium lamp, a halogen lamp, laser light (helium-cadmium laser, excimer) Laser, etc.), UV-LED, etc. can be used. By such light irradiation, the curing reaction of the composition proceeds.
  • the coating film is heated after light irradiation using a photoacid generator or a photobase generator, for example, from room temperature (approximately 23 ° C.) to about 250 ° C. Done in The heating time can be selected from a range of 3 seconds or more (for example, about 3 seconds to 5 hours), for example, about 5 seconds to 2 hours.
  • the coating film formed on the base material may be subjected to pattern exposure.
  • This pattern exposure may be performed by scanning with a laser beam or by irradiating light through a photomask.
  • a pattern or an image can be formed by developing (or dissolving) a non-irradiated region (unexposed portion) generated by such pattern exposure with a developer.
  • an alkaline aqueous solution or an organic solvent can be used as the developer.
  • the alkaline aqueous solution include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate; quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline.
  • Aqueous solution An aqueous amine solution such as ethanolamine, propylamine, and ethylenediamine can be used.
  • the alkali developer is generally an aqueous solution of 10% by mass or less, and preferably an aqueous solution of 0.1 to 3% by mass is used. Further, alcohols and surfactants may be added to the developer and used, and the amount of these added is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the developer. Specifically, a 0.1 to 2.38 mass% tetramethylammonium hydroxide aqueous solution or the like can be used.
  • the organic solvent as a developing solution can use a common organic solvent, for example, aromatic hydrocarbons, such as toluene; ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl Esters such as ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; Amides such as N, N-dimethylformamide (DMF); Nitriles such as acetonitrile; Ketones such as acetone and cyclohexanone; Methanol, Ethanol, 2-propanol, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol And alcohols such as chromatography mono butyl ether.
  • aromatic hydrocarbons such as toluene
  • PMEA propylene glycol monomethyl ether a
  • ethyl lactate propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) and the like can be preferably used.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether
  • the above epoxy resin composition can contain a solvent, if necessary.
  • the solvent include aromatic hydrocarbons such as toluene and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, and ethyl lactate Propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy- Hydroxy esters such as ethyl 2-methylpropionate and methyl 2-hydroxy-3-methylbutanoate; methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, e
  • a vinyl group-containing compound, an oxetanyl group-containing compound, or the like can be used as the cationic curable monomer for the purpose of adjusting the viscosity of the epoxy resin composition or improving the curability.
  • the vinyl group-containing compound is not particularly limited as long as it is a compound having a vinyl group.
  • HEVE 2-hydroxyethyl vinyl ether
  • DEGV diethylene glycol monovinyl ether
  • HBVE 2-hydroxybutyl vinyl ether
  • triethylene glycol And vinyl ether compounds such as divinyl ether.
  • a vinyl compound having a substituent such as an alkyl group or an allyl group at the ⁇ -position and / or ⁇ -position can be used.
  • a vinyl ether compound containing a cyclic ether group such as an epoxy group and / or an oxetanyl group can be used, and examples thereof include oxynorbornene divinyl ether and 3,3-dimethanol oxetane divinyl ether.
  • a compound having a vinyl group and a (meth) acryl group can be used, and examples thereof include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate.
  • the oxetanyl group-containing compound is not particularly limited as long as it is a compound having an oxetanyl group, and 3-ethyl-3- (hydroxymethyl) oxetane (OXA), 3-ethyl-3- (phenoxymethyl) oxetane (POX), Bis ((3-ethyl-3-oxetanyl) methyl) ether (DOX), 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene (XDO), 3-ethyl-3- ( 2-ethylhexyloxymethyl) oxetane (EHOX), 3-ethyl-3-((3-triethoxysilylpropoxy) methyl) oxetane (TESOX), oxetanylsilsesquioxane (OX-SQ), phenol novolac oxetane (PNOX- 100
  • a compound having an oxetanyl group and a (meth) acryl group can be used, and examples thereof include (meth) acrylic acid (3-ethyl-3-oxetanyl) methyl.
  • These oxetanyl group-containing compounds can be used alone or in combination of two or more.
  • the above composition may contain a conventional additive as required.
  • additives include thickeners, sensitizers, antifoaming agents, leveling agents, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), Examples include plasticizers, surfactants, dissolution accelerators, fillers, antistatic agents, and curing agents. These additives may be used alone or in combination of two or more.
  • a surfactant may be added to the epoxy resin composition of the present invention for the purpose of improving coating properties.
  • surfactants include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants, but are not particularly limited thereto.
  • the said surfactant can be used individually or in combination of 2 or more types.
  • a fluorosurfactant is preferable because of its high coating property improving effect.
  • fluorosurfactant examples include, for example, EFTOP (registered trademark) EF-301, EF-303, and EF-352 [all manufactured by Mitsubishi Materials & Chemicals Co., Ltd.], MegaFuck (registered trademark) ) F-171, F-173, F-482, R-08, R-30, R-90, BL-20 [all made by DIC Corporation], Florard FC-430, FC-431 [all manufactured by 3M Japan Co., Ltd.], Asahi Guard (registered trademark) AG-710 (manufactured by Asahi Glass Co., Ltd.), Surflon S-382, SC-101, SC-102, SC-103 SC-104, SC-105, SC-106 [all manufactured by AGC Seimi Chemical Co., Ltd.], etc., but are not limited thereto.
  • the addition amount of the surfactant in the epoxy resin composition of the present invention is 0.01 to 5% by mass, preferably 0.01 to 3% by mass, based on the solid content of the epoxy resin composition.
  • An adhesion promoter can be added to the epoxy resin composition of the present invention for the purpose of improving the adhesion to the substrate after development.
  • adhesion promoters include chlorosilanes such as chlorotrimethylsilane, trichloro (vinyl) silane, chloro (dimethyl) (vinyl) silane, chloro (methyl) (diphenyl) silane, and chloro (chloromethyl) (dimethyl) silane.
  • adhesion promoters can be used alone or in combination of two or more.
  • the addition amount of the adhesion promoter in the epoxy resin composition of the present invention is usually 20% by mass or less, preferably 0.01 to 10% by mass, more preferably based on the solid content of the epoxy resin composition. 0.05 to 5% by mass.
  • the epoxy resin composition of the present invention may contain a sensitizer.
  • sensitizers that can be used include anthracene, phenothiazene, perylene, thioxanthone, and benzophenone thioxanthone.
  • sensitizing dyes thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes And pyrylium salt pigments.
  • anthracene-based sensitizer when used in combination with a cationic curing catalyst (radiation sensitive cationic polymerization initiator), the sensitivity is drastically improved and also has a radical polymerization initiation function.
  • a cationic curing catalyst radiation sensitive cationic polymerization initiator
  • the catalyst species can be simplified.
  • anthracene compounds dibutoxyanthracene, dipropoxyanthraquinone and the like are effective.
  • Examples of the sensitizer when using a base generator as a curing catalyst include acetophenones, benzoins, benzophenones, anthraquinones, xanthones, thioxanthones, ketals, and tertiary amines. it can.
  • the addition amount of the sensitizer in the epoxy resin composition of the present invention is 0.01 to 20% by mass, preferably 0.01 to 10% by mass, based on the solid content of the epoxy resin composition. .
  • the epoxy resin composition containing the (a) mixture and (b) curing agent of the present invention has light and thermosetting properties, and has a high refractive index of an adhesive and an antireflection film (such as an antireflection film for a liquid crystal display). It can be widely used in the field of electronic materials such as layers, optical thin films (reflecting plates, etc.), encapsulants for electronic parts, printed wiring boards, interlayer insulating film materials (interlayer insulating film materials for build-up printed boards, etc.). In particular, it can be widely used as an electronic material required to have a low dielectric loss tangent and a low dielectric constant, such as a printed wiring board and an interlayer insulating film material.
  • GPC Gel permeation chromatography
  • Sample holder 12962 type room temperature sample holder, manufactured by Toyo Corporation (6) Glass transition temperature Tg Apparatus: Dynamic viscoelasticity measuring apparatus (DMA) Q800 manufactured by TA Instrument Deformation mode: Dual cantilever Frequency: 1Hz Strain: 0.05% Sweep temperature: 30-300 ° C Temperature increase rate: 5 ° C / min (7) Flexural modulus, deflection Device: Desktop precision universal testing machine Autograph AGS-5kNX, manufactured by Shimadzu Corporation (8) Oven device: Yamato Kagaku Co., Ltd. blown low temperature thermostat DNF400
  • BA Butyric anhydride [manufactured by Tokyo Chemical Industry Co., Ltd.]
  • BzA Benzoic anhydride [manufactured by Tokyo Chemical Industry Co., Ltd.]
  • iBA Isobutyric anhydride [manufactured by Tokyo Chemical Industry Co., Ltd.]
  • OA Octanoic anhydride [manufactured by Tokyo Chemical Industry Co., Ltd.]
  • PA propionic anhydride [APA made by Daicel Corporation]
  • P3EPB Ethyltriphenylphosphonium bromide [made by Hokuko Chemical Co., Ltd.]
  • P4PB Tetraphenylphosphonium bromide [Tokyo Chemical Industry Co., Ltd.]
  • BPA bisphenol A type epoxy resin [jER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation]
  • TGIC Triglycidyl isocyanurate [TEPIC (registered trademark) -S manufactured by Nissan Chemical Industries, Ltd
  • the epoxy equivalent of the obtained BA-TGIC was 192 (theoretical value 193).
  • TGIC non-adduct: 1 mol adduct: 2 mol adduct: 3 mol adduct (area ratio) was 33: 52: 14: 0.1.
  • TGIC octanoic anhydride modified product (OA-TGIC) TGIC octanoic anhydride modified product (OA-) was prepared in the same manner as in Production Example 2 except that BA was changed to 29.1 g (108 mmol) of OA. TGIC) was obtained as a liquid. The epoxy equivalent of the obtained OA-TGIC was 234 (theoretical value 234). In HPLC analysis, TGIC (non-adduct): 1 mol adduct: 2 mol adduct: 3 mol adduct (area ratio) was 29: 43: 24: 4.
  • TGIC benzoic anhydride modified product (BzA-TGIC) TGIC benzoic anhydride modified product (BzA-) was prepared in the same manner as in Production Example 2 except that BA was changed to 24.4 g (108 mmol) of BzA.
  • TGIC was obtained as a liquid.
  • the epoxy equivalent of the obtained BzA-TGIC was 217 (theoretical value 217).
  • TGIC (non-adduct): 1 mol adduct: 2 mol adduct: 3 mol adduct (area ratio) was 15: 43: 35: 7.
  • Tg Glass transition temperature
  • cured products (Examples 1 to 5) obtained using the epoxy resin composition of the present invention are BPA (Comparative Example 2), which is an epoxy compound that is widely used for printed wiring board formation. Compared with, it showed a very low dielectric loss tangent.
  • BPA Comparative Example 2
  • an epoxy resin composition containing an epoxy compound modified with an aromatic carboxylic acid anhydride achieves a low water absorption and a low dielectric constant while maintaining a high Tg, and is used as a resin for forming a printed wiring board. It was confirmed to be suitable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème décrit par la présente invention est de fournir une composition de résine époxydique qui a un faible facteur de dissipation et une faible constante diélectrique et qui est appropriée pour former des cartes de circuit imprimé. La solution selon l'invention porte sur une composition de résine époxydique pour former des cartes de circuit imprimé, contenant (a) un mélange contenant un composé époxydique A représenté par la formule [1] et un composé B éventuellement contenant un groupe époxydique représenté par la formule [2] et (b) un agent de durcissement. (Dans la formule, R1 à R3 représentent chacun indépendamment un atome d'hydrogène ou un groupe méthyle, et L1 à L3 représentent chacun indépendamment un groupe alkylène ayant de 1 à 10 atomes de carbone.) (Dans les formules, L1 à L3 et R1 sont définis comme ci-dessus ; X1 à X3 représentent chacun indépendamment un groupe représenté par la formule [2a] ou la formule [2b] (cependant, au moins l'un de X1 à X3 représente un groupe représenté par la formule [2b]) ; R4 et R5 représentent chacun indépendamment un groupe alkyle éventuellement substitué ayant de 1 à 20 atomes de carbone ou un groupe aryle éventuellement substitué ayant de 6 à 10 atomes de carbone ; et le point noir représente une liaison.)
PCT/JP2017/037708 2016-10-18 2017-10-18 Composition de résine époxydique pour former une carte de circuit imprimé Ceased WO2018074517A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020197011435A KR102398796B1 (ko) 2016-10-18 2017-10-18 프린트배선판 형성용 에폭시수지 조성물
CN201780064085.1A CN109843965B (zh) 2016-10-18 2017-10-18 印刷配线板形成用环氧树脂组合物
JP2018546382A JP7004181B2 (ja) 2016-10-18 2017-10-18 プリント配線板形成用エポキシ樹脂組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016204690 2016-10-18
JP2016-204690 2016-10-18

Publications (1)

Publication Number Publication Date
WO2018074517A1 true WO2018074517A1 (fr) 2018-04-26

Family

ID=62019235

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/037708 Ceased WO2018074517A1 (fr) 2016-10-18 2017-10-18 Composition de résine époxydique pour former une carte de circuit imprimé

Country Status (5)

Country Link
JP (1) JP7004181B2 (fr)
KR (1) KR102398796B1 (fr)
CN (1) CN109843965B (fr)
TW (1) TWI753959B (fr)
WO (1) WO2018074517A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3375804A4 (fr) * 2015-11-10 2019-07-31 Nissan Chemical Corporation Composition de résine époxy contenant un groupe alcylène à longue chaîne

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006035641A1 (fr) * 2004-09-29 2006-04-06 Nissan Chemical Industries, Ltd. Formulation de résine époxy modifiée
WO2009008509A1 (fr) * 2007-07-11 2009-01-15 Nissan Chemical Industries, Ltd. Préparation liquide formant une résine époxyde et contenant des particules inorganiques
WO2009069429A1 (fr) * 2007-11-29 2009-06-04 Nissan Chemical Industries, Ltd. Agent de durcissement époxy contenant de la silice et corps durci en résine époxy
WO2012124390A1 (fr) * 2011-03-17 2012-09-20 日産化学工業株式会社 Procédé pour la préparation d'agent durcisseur d'époxyde contenant de la silice

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR9810600A (pt) * 1997-07-16 2000-07-11 Ciba Sc Holding Ag Compostos espiro-poliglicidila e seu uso em resinas epóxi
JP2004221572A (ja) 2002-12-27 2004-08-05 Tdk Corp 電子部品及び多層基板
JP5423602B2 (ja) 2004-07-27 2014-02-19 日立化成株式会社 低誘電率絶縁性樹脂組成物
JP5282917B2 (ja) * 2008-11-12 2013-09-04 日産化学工業株式会社 レジスト下層膜形成組成物及びそれを用いたパターニング方法
EP2995633A4 (fr) * 2013-05-10 2016-10-26 Daicel Corp Composition de résine époxy durcissable et produit durci correspondant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006035641A1 (fr) * 2004-09-29 2006-04-06 Nissan Chemical Industries, Ltd. Formulation de résine époxy modifiée
WO2009008509A1 (fr) * 2007-07-11 2009-01-15 Nissan Chemical Industries, Ltd. Préparation liquide formant une résine époxyde et contenant des particules inorganiques
WO2009069429A1 (fr) * 2007-11-29 2009-06-04 Nissan Chemical Industries, Ltd. Agent de durcissement époxy contenant de la silice et corps durci en résine époxy
WO2012124390A1 (fr) * 2011-03-17 2012-09-20 日産化学工業株式会社 Procédé pour la préparation d'agent durcisseur d'époxyde contenant de la silice

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3375804A4 (fr) * 2015-11-10 2019-07-31 Nissan Chemical Corporation Composition de résine époxy contenant un groupe alcylène à longue chaîne
US10669369B2 (en) 2015-11-10 2020-06-02 Nissan Chemical Industries, Ltd. Long-chain alkylene group-containing epoxy resin composition

Also Published As

Publication number Publication date
CN109843965A (zh) 2019-06-04
CN109843965B (zh) 2021-07-27
JP7004181B2 (ja) 2022-01-21
KR102398796B1 (ko) 2022-05-17
TW201821527A (zh) 2018-06-16
KR20190070328A (ko) 2019-06-20
JPWO2018074517A1 (ja) 2019-08-08
TWI753959B (zh) 2022-02-01

Similar Documents

Publication Publication Date Title
CN108350252B (zh) 环氧系反应性稀释剂及含有其的环氧树脂组合物
JP6898596B2 (ja) 多官能エポキシ化合物及びそれを含む硬化性組成物
JP6931199B2 (ja) 長鎖アルキレン基含有エポキシ樹脂組成物
JP5867749B2 (ja) 多官能エポキシ化合物
JP6893921B2 (ja) エポキシ化合物、これを含む硬化性組成物および硬化性組成物を硬化させた硬化物
JP5849963B2 (ja) 多官能エポキシ化合物
JP7004181B2 (ja) プリント配線板形成用エポキシ樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17861467

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018546382

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20197011435

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17861467

Country of ref document: EP

Kind code of ref document: A1