CA1277070C - Photocurable epoxy resin compositions which contain fillers, and the use thereof - Google Patents
Photocurable epoxy resin compositions which contain fillers, and the use thereofInfo
- Publication number
- CA1277070C CA1277070C CA000495135A CA495135A CA1277070C CA 1277070 C CA1277070 C CA 1277070C CA 000495135 A CA000495135 A CA 000495135A CA 495135 A CA495135 A CA 495135A CA 1277070 C CA1277070 C CA 1277070C
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- Canada
- Prior art keywords
- composition according
- weight
- metal
- filler
- fillers
- 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.)
- Expired - Lifetime
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- 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
- C08G59/68—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 catalysts used
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
Abstract
Photocurable epoxy resin compositions which contain fillers, and the use thereof Abstract of the Disclosure The invention relates to epoxy resin compositions which contain fillers, said compositions comprising (a) 5-90% by weight of an epoxy resin or mixture of epoxy resins, which resin or resins do not contain olefinically unsaturated C=C
double bonds, (b) 0.1 to 15% by weight of at least one photoinitiator of formula I
[(R1)(R2M)a]+an [LQm]-q (I), wherein a is 1 or 2 and each of n and q independently of the other is an integer from 1 to 3, H is the cation of a monovalent to trivalent metal of Periodic Groups IVb to VIIb, VIII or Ib, m is an integer corresponding to the valency of L + q and Q is a halogen atom, L is a divalent to heptavalent metal or non-metal R1 is a .pi.-arene and R2 is a .pi.-arena or the anion of a .pi.-arene, and (c) 10 -90% by weight of at least one finely particulate filler selected from the group consisting of carbon black, graphite, metal-containing fillers and fillers with semi-conductor properties, and, optionally (d) flux materials and/or (e) further additives, the sum of all components being 100% by weight.
These compositions are suitable for the production of relief structures, images or bonds.
double bonds, (b) 0.1 to 15% by weight of at least one photoinitiator of formula I
[(R1)(R2M)a]+an [LQm]-q (I), wherein a is 1 or 2 and each of n and q independently of the other is an integer from 1 to 3, H is the cation of a monovalent to trivalent metal of Periodic Groups IVb to VIIb, VIII or Ib, m is an integer corresponding to the valency of L + q and Q is a halogen atom, L is a divalent to heptavalent metal or non-metal R1 is a .pi.-arene and R2 is a .pi.-arena or the anion of a .pi.-arene, and (c) 10 -90% by weight of at least one finely particulate filler selected from the group consisting of carbon black, graphite, metal-containing fillers and fillers with semi-conductor properties, and, optionally (d) flux materials and/or (e) further additives, the sum of all components being 100% by weight.
These compositions are suitable for the production of relief structures, images or bonds.
Description
~77~7~
~ 1 --3-15l55/~
hotocurabl_ epoxy resln composltions which contain ~illerfl~ ~nd the use thereof The present invention relates to photocurable epoxy reflin composit-ions which contains fillers, and to the use thereof, in particular for the production of relief structure~, images or bond~.
EuropeaD patent appllcations 094 915 A2 and 109 851 A2 disclose curable (polymerisable) compo~ition~ whlch contain a cationically polymerisable orgaDic materlal and organo~etalllc initiator~ ~uch as metallocene complexes. These patsnt applications i.a. generically mention fillers as further possible additives, but epoxy resin systems which contain fillers ~re not spQcifically disclosed.
Further, US patent specifications 3 9$8 Q56 and 3 989 644 discloae radiation curable, especially W curable, composition~ for msking conductive coatings, which compositions ~ay contain electrically conductive metals such as silver co~ted glass spheres ~8 flller~ and e.g. epoxy re~ins as organic resin binder. These co~positions may al80 contain VV photosensitisers such as ketones, ben~oin and benzoln derivative~ or aromatic onium salts of elements of Periodic Group V a.
The present invention relates to novel photocurable epoxy resin compositions which contain fillers said, co~positions comprising (a) 5-90% by weight of an epoxy resin or mixture of epoxy resins, which resin or resins do not contain ole~inically un~aturated C~C
double bonds, .-7t707(~
(b) 0.1 to 15~ by weight of at least one photoinitiator of formula I
[(Rl)(R2M) ]~an ~ [LQm] q (I), wherein a is 1 or 2 and each of n and ~ independently of the othe~
is an integer from 1 to 3, M is the cation of a monovalent to trivalent metal of Periodic Groups IVb to VIIb, VIII or Ib, m is an integer corresponding to the valency of L + q and Q is a halogen atom, L is a divalent to heptavalent metal or non-metal, R1 is a ~-arene and R is a ~-arene or the anion of a ~-arene, and (c) 10-90% by weight of at least one finely particulate filler selected from the group consisting of electrically conductive or semiconductive fillers, thermally conductive or dielectric fillers, fillers which influence the ferroelectric, ferromagnetic, piezo-electric or electrochromic properties and fillers with luminescent properties, the sum of all compounds being 100% by weight.
Surprisingly, the compositions of this invention can be cured with visible as well as with UV light, even when they contain high concentrations of fi.nely particulate filler. Further, -they make it possible to produce coatings which can be fully cured even if the layer thicknesses are substantial, although coating compo-sitions containing electrically conductive fillers such as metal powders, carbon black or graphite are usually only insufficiently cured under UV light, because the light on the surface of the metal , . .
~77~)t7~) powders is strongly reflected or strongly absorbed by the carbon - black or graphite.
2a -~,~7~0t7~
.
Suitable epoxy re~in~ (a) are pre~erably tho~e containlng on average more than one group of the formula II
~0\
-~H-~ ~ H (II) wherein each of Q' and Q~ i8 a hydrogen atom and Q~ i~ a hydrogen atom or a methyl group, or Q' and Q~ together ars -CH2CH2~ or -CH2CH2CH2- 8nd ~ iB a hydrogen stom, which group iR attached to hetero atom, e.g. a sulfur atom and, preferably, to an oxygen or nitrogen atom.
Typical examples of ~uch resin~ are polyglycidyl esters and poly-(~-methylglycidyl) esters which are derived from aliphatic, cyclo-aliphatic or ~romatic poly~arboxylic acids. Examples o~ 6~itable polycarboxylic acids are: 3uccinic acid, glutsric acid, adipic acid, plmelic acld, ~beric scid, azelaic scid, sebsclc acid, dimerised or trimeri~ed linoleic acid, tetrahydr3phthslic acid, 4-methyltetrahy-drophthalic acid, hexahydrophthalic acid, 4-mathylhexahydrophthalic acid, phthalic acid, isophthalic acid and tcrephthalic acid.
Furth~r examples are polyglycidyl ethers and poly(~-methylglycldyl) ethsrs which are obtained by reaoting a compound containing at le~t two alcoholic and/or phenollc hydroxyl groups per molecule with epichlorohydrin or with allyl chloride, and then epoxidi~ing the reactioD product with a peracid.
Example~ of suitable polyol9 are: ethylene glycol, diethylene glycol, poly(Qxyethylene) glycols, propane-1,2-diol, poly(oxypropyl-ene) glycol B, propane-1,3-diol, butane-1,4-diol, poly(oxytetramcth-ylene) glycol~, pentane-1,5-diol, hexane-2,4,6-triol, glycerol, 1,1,1-~rimethylolpropane, pentaerythritol and sorbitol; 1,3- and 1,4-cyclohexanediol, bis(4~hydroxycycloh~xyl)methane, 292-bis(4-hydroxycyclohexyl)propane and l,1-bisthydroxym~thyl~ryolohex~3~ene;
N,N-bi~t2-hydroxyethyl)aniline and 4,4'-bi~(2-hydroxyethylamino)-~L~7707() diphenylmethane; re~orcinol, hydroquinone, bi~(4-hydroxyphenyl)-methane (bi~phenol F), 2,2-bi~(4-hydroxyphenyl)propane (bi~phenol A), 2,2-bis(4-hydroxy-315-dlbromophenyl)propane (tetrabromobl~p~enol A), 1,1,2,2-tetrakis(4-hydroxyphenyl)ethune, 4,4'-dlhydrnxyblphcnyl, bi~(4-hydroxyphenyl)~ulfone, a~ well aR novolak~ of formaldehyde or acetaldehyde ~nd phenol, chlorophenol or alkylphsnol~ containing up to 9 carbon atoma in the alkyl moiety, preferably cre~ol and phenol novolak~.
Suitable poly~N-glycidyl) compo~nds are products obtained by dehydrochlorination of reaction products o~ epichlorohydrin and amines containing at least two active hydrogen atoms bonded to amino nitrogen atoms. Examples o$ suitable amines are: aniline, n-butyl-amine, bis(4-amlnophenyl)methane, 1,3- and 1,4-xylylenediamine, 1,3-and 1,4-bi~(aminomethyl)cyclohexane snd bis(4-methylaminophe-nyl)methane. Purther s~itable compounds are: triglycidyl isocyanu-rate, N,N'-diglycidyl der~vatives of cyclic alkylene ureas ~uch Ra e~hylene urea and 1,3-propylene urea, or hydantoins such as 5,5-dimethylhydantoin.
Examples of poly(S-glycidyl) compounds ~re the di-S-glycidyl derivati~es of dithiols such a~ ethane-1,2-dithiol and bia(4-mer-captomethylphenyl) ether.
Examples of epoxy resins containing one or more group~ of the formula I}, wherein Q' and Q~ together sre a -cH2cH2- or -CHzCH2CH2-group are bi~(2,3-epoxycyclopentyl) ether, 2,3-epo~ycyclopentyl glycidyl ether, 1,2 bi~(2,3-epoxycyclopentyloxy)ethane, 394-epoxy-6-methylcyclohexylmethyl-3',4'-epoxy-6'-methylcyclohexane carboxyl-ate and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3',4'-epoxy~cyclohexane dioxane.
Al~o eligible are epoxy re~in~ in which the epoxy group~ ar~
attached to hetero atoms of different kind, or ln which s30me or all of the epoxy group~ are centr~l, for example the N,N,0 trlglyc~dyl ~ 5 -derlvative of 4-aminophenol, N-glycidyl-N'-(2-glycidyloxypropyl)-S,S dimethylhydantoin, vinylcyclohexene dioxide, limonene dioxide and dicyclopentadiene dioxide.
The epoxy re~in~ (a) may be solid or liquid. Preferred epoxy re~ln~
are tho~e having an epoxide content of 1.0 to 5.5.
As component (8~ it i8 preferred to use diglycidyl ether~ or advanced diglycidyl ethern of dihydric phenol~ or dlhydric aliphatic C2-C4alcohols, in particular diglycidyl ethers or advanced diglyci-dyl ether~ of 2,2-bls(4-hydroxyphenyl)propane, 2,2-bi~(3,5~dibromo-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, bls(4-hydroxy-cyclohexyl~methane or 2,2-bis(4-hydroxycyclohexyl)propane; polygly-cidyl ethers of novolaks 7 or tetraglycidylated 4,4'-diaminodiphenyl-methane. Most preferred are diglycidyl Qthers or advanccd diglycidyl ethers of bisphenol A, tetrabromo-bisphenol A or bisphenol F, and, in particular, polyglycidyl ethers of phenol/formaldehyds or cresol/formaldehyde novolaks, or mixtures thereof.
Pos3ible ~-arenes Rl and R2 are, in particular, aromatic groups of 6 to 24 carbon atoms or heteroaromatic groups of 3 to 30 carbon atoms, which groups may be unsubstituted or ~ub~tituted by one or more identical or dif~erent monovalent radicals such as halogen atoms, preferably chlorine or bromine atoms, or Cl-Cgalkyl, Cl-Cg-alkoxy, cyano, C1-Cgalkylthio, C2-C6monocarboxylic acid alkyl ester, phenyl, C2-Cs~lkanoyl or benzoyl groups. These ~-arene groups may be mononuclear, condensed polynuclear or non-condensed polynuclear systems, in which last~mentioned systems the nuclel may be linked togeth0r direct or through bridge members such as -S- or -0-.
R2 as the anion of a ~-arene may be an anion of 8 ~-arene o f the aforementioned kind, e.g. ths lndenyl anion, ~nd, in par~icular, ~he cyclopentadienyl anion, which anions may al80 be unsubstitutQd or substituted by one or more identical or differeDt monovalent radicals such as Cl-Cgalkyl, C2-C6monocsrboxylic acld alkyl ester, cyano, C2-Csalkanoyl or benzoyl group~.
~277~t~0 - h -Alkyl, alkoxy, alkylthio, ~onocarb~xylic acid alkyl e~ter and alkanoyl substituent~ may be ~traight chain or branched. Typical alkyl, alkoxy, alkylthio, ~onocarboxylic acld alkyl eAter or alkanoyl substituents are: methyl, ethyl, n-propyl, i~opropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, methoxy, ethoxy, n-p~opoxy, iaopropoxy, n-butoxy, n-hexyloxy, n-octylo~y, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, n-pentylthio and n-hexylthio, carboxylic acid methyl e~ter, ethyl ester, n-propyl e~ter, isopropyl e~ter, n-butyl e~ter and n-pentyl e~ter, acetyl, propionyl, butyryl, and valeroyl. Alkyl, alkoxy, alkylthio and monoc~rboxylic acid alkyl ester group~ containing 1 to 4 and especially 1 or 2 carbon ato~s in the alkyl moieties snd alkanoyl groups containing 2 or 3 carbon ato~s are preferred.
Preferred substituted ~-arene~ or anions of substituted ~-arenes are those containing one or two of the above-mentioned subs~ituents, in particular chlorine or bromine atoms, methyl, ethyl, methoxy, ethoxy, cyano~ carboxylic acid methyl or ethyl ester groups and acetyl groups.
Rl and R2 may be identical or different ~-arenes. Suitable hetero-aromatic ~-arenes are systems containlng S-, N- and/or 0-atoms.
Heteroaromatic ~-arene~ contsining S- and/or 0-atoms are preferred.
Examples of suitable $-srene3 are: benzene, toluene, xylenes, ethylbenzene, cumene (i~opropylbenzene), methoxybenzene, ethoxy-benzene, dimethoxybenzene, p-chlorotoluene, chlorobenzene, bromo-benzene, dichlorobenzene, acetylbenzene, trimethylbenzene, trime-thoxybenzene, naphthalens, 1,2-dihydronaphthalene, 1,2,3,4-tetra~
hydronaphthalene, methylnaphthalenes, meehoxynaphthalenes, ethoxy-naphthalenes, chloronaphthalene~, bromonaphthalene~, biphenyl, indene, fluorene, phenanthrene, anthracene, 9,10-dihydroanthracene, triphenylene, pyrene, naphthacene, coronene, thiophene, chromene 9 xanthene, thioxanthene, benzothiophene, naphthothiophene~ thi-anthrene, diphenylene oxide, diphenylene sulfide, acridine and carbazole.
~77070 If a i~ 2, then each R2 i8 preferably the anion of a n-arens, snd each M i9 sn identical metal atom. Examples of anions of subs~ituted ~-arenes are: the anions of met~hyl-, ethyl-, n-propyl- and n-butyl-cyclopentadiene, the ~nion~ of dimethylcyclopentadiene, oP cyclo-pentadiene c~rboxylic acid me~hyl ~nd e~hyl ester, and o~ acety~
cyclopentadlene, propionylcyclopentadiene, cyanocyclopents~diene and benzoylcyclopentsdiene. Preferred anions are the anion o unsubsti-tuted in~ene and especially the anion o~ unsubstituted cyclopenta-diene.
The preferred value of a i8 1, Rl i8 benzene, toluene, xylene, cumene, methoxybenzene, chlorobenzene, p-chlorotoluene, naphthalene, methylnaphthalene, chloronaphthalene, methoxynaphthalene, biphenyl, indene, pyrene or diphenylene sulfide, and R~ i8 the anion of cyclopentadisne, scetylcyclopentadiene OT 1ndene, or benzene, toluene, xylene, trimethylbenzene, naphthalene or ~ethylnaphthalene.
i~ T~2+ Ti3~ Zr~, Zr2+, Zr3+, Hf , Hf , Hf , Nb , Nb , Nb , Cr , Mo , Mo2 , ~ , W , Mn , Mn2 , Ra , Fe2+, Co3+, Ni2 or Cu2 . Preferably, M i~ a chromium, cobalt, mangsnese, tungsten or molybdenum cation, especially an iron catioD, most preferably Fe Psrticularly preferred complexss of for~uls I are those wherein a i8 1, Rl i9 n6-cumene or n6-2-methylnaphthalene and R2 ~3 the Inion of nS-cyclopentadiene, n iB preferably 1 or 2, preferably 1 t and q is preferably 1.
Examplès of suitable metals or non-metals L are Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn and Cu; lanthsnides such a~ Ce~ Pr and Nd, or actinide3, such as Th, Pa, V or Np. Suitable non-~e~als sre especially B, P and As. Prefarably L is P, As, B or Sb, with P bsing ~ost preferred.
Example~ of complex snions ~LQ~ q are BF4 , PF6 , AsF6 , SbF6 , FeCl4 , SnCl62 , SbCl6 , BiCl6 ~ The mos~ preferred complex anion~
are SbF6 ~ BF4 1 AsF6 and 9 in particular PF6 -~, .
7C)7~3 Examples of compounds of formula I are: (n6~toluene)(nS-lndenyl)-iron(II) hexafluorophosphate, (n6-Pyrene)(nS-cYclopontadienyl)-iron(II) hexaEluoroantimonate, (n6-toluene)(nS-cyclopentadlenyl)-iron(II) hexafluorophosphate, (n6-naphthalene)(~5-cyclopent2dien-yl)iron(II) hexafluoroarsenate, ~n6-2-methylnaphthalene)("S~cyclo--pentadienyl)iron(II) hexafluorophosphate, (n6-cumene)(nS-cyclopenta-d1enyl)iron(II) hexafluorophosphate and (n6-benzene)(nS-cyclopenta-dienyl)cobalt(III) bis(tetrafluoroborate).Such metallocene salts and the preparation thereof are de~cribed e.g. in European patent application 094 915 A2. Preferred compounds of formula I sre (n6-2-methylnaphthalene)(ns-cyclopentadienyl)iron(II) hexafluoro-phosphate and (n6-cumene)(n5-cyclopentadienyl)iron(II) hexafluoro-phosphate.
By appropriate choice of fillers it is possiblQ to influence the electrical, thermal and/or optical properties of the epoxy rs~in sy~tems, for example the electrically or thermally conductive or insulating properties, the ferroQlectric or ferromagnetic proper-ties, the piezoelectric, electrochromic or luminiscent propertles.
Photocursble resin compositions are thereby obtained which, after curing and development, give relief structures or image~ which find utility especislly in the fields of high-frequency engineering, electronics, microelectronics and optoelectronics, for example a~
active components in resistors, capacitors, transformer~, inductors~
magnets, memory and display materials, as passive cDmponents in ~lectricsl and thermsl insulators, heat extraction systems or electromagnetic shields, or also as so-called interconnec~ions, e.g.
in printed conductors or in chip contacting, as well ~B in mounting chips on the baDe plste~ of their assembly frames.
Suitable metal-con~sining fillers or fillers wi~h ~emiconductor propertie~ are, in particular~ metals, metal compound~ and alloyD in which the ~etal is one of Periodic Groups IIa, IlIa, IVa, Ib, Vb9 ~'77070 g VIb and/or VIII. Depending on the desired propertie3 or on the field of u~e of the epoxy resin compositions of this lnventlon, the following fillers may for example be used:
1. Electrically conductive fillers of organic or inorganic nature, e.g. carbon black snd graphite or metal~ of Periodic Group~ Vb, V~b, VIII and Ib, ~lloys and ~alts thereo~ ~uch 8~ hnlide~, ~xide~ and ~ulfides.
Examples of suitable metals and metal compounds are: vanadium, niobium, tantalum, molybdenum, tungsten, copper, noble metals auch as Pt, Pd, Ag snd Au, AgPd alloy3, ~ilver oxide, silver iodide, copper(II) sulfidet copper(I) iodide, copper(II) o~ide, gold(III) bromide, iodide and nxide, molybdenum(IV~ ~ulfide, niobium(IV) chloride and niobium(IV) oxide, palladium iodide, pallsdium oxlde, platinum(IV) bomide and platinum(IV) chloride, vanadium(III) chloride, vanadium(IV) oxide, tungsten(VI) chloride and tungsten(VI) oxide. Preferred metals are silver, copper, silver/palladium alloys, palladium, platinum, gold, ~ungsten and molybdenum. Particularly preferred metals are Au, Pt, AgPd, with Ag and Cu powder being most preferred.
~ 1 --3-15l55/~
hotocurabl_ epoxy resln composltions which contain ~illerfl~ ~nd the use thereof The present invention relates to photocurable epoxy reflin composit-ions which contains fillers, and to the use thereof, in particular for the production of relief structure~, images or bond~.
EuropeaD patent appllcations 094 915 A2 and 109 851 A2 disclose curable (polymerisable) compo~ition~ whlch contain a cationically polymerisable orgaDic materlal and organo~etalllc initiator~ ~uch as metallocene complexes. These patsnt applications i.a. generically mention fillers as further possible additives, but epoxy resin systems which contain fillers ~re not spQcifically disclosed.
Further, US patent specifications 3 9$8 Q56 and 3 989 644 discloae radiation curable, especially W curable, composition~ for msking conductive coatings, which compositions ~ay contain electrically conductive metals such as silver co~ted glass spheres ~8 flller~ and e.g. epoxy re~ins as organic resin binder. These co~positions may al80 contain VV photosensitisers such as ketones, ben~oin and benzoln derivative~ or aromatic onium salts of elements of Periodic Group V a.
The present invention relates to novel photocurable epoxy resin compositions which contain fillers said, co~positions comprising (a) 5-90% by weight of an epoxy resin or mixture of epoxy resins, which resin or resins do not contain ole~inically un~aturated C~C
double bonds, .-7t707(~
(b) 0.1 to 15~ by weight of at least one photoinitiator of formula I
[(Rl)(R2M) ]~an ~ [LQm] q (I), wherein a is 1 or 2 and each of n and ~ independently of the othe~
is an integer from 1 to 3, M is the cation of a monovalent to trivalent metal of Periodic Groups IVb to VIIb, VIII or Ib, m is an integer corresponding to the valency of L + q and Q is a halogen atom, L is a divalent to heptavalent metal or non-metal, R1 is a ~-arene and R is a ~-arene or the anion of a ~-arene, and (c) 10-90% by weight of at least one finely particulate filler selected from the group consisting of electrically conductive or semiconductive fillers, thermally conductive or dielectric fillers, fillers which influence the ferroelectric, ferromagnetic, piezo-electric or electrochromic properties and fillers with luminescent properties, the sum of all compounds being 100% by weight.
Surprisingly, the compositions of this invention can be cured with visible as well as with UV light, even when they contain high concentrations of fi.nely particulate filler. Further, -they make it possible to produce coatings which can be fully cured even if the layer thicknesses are substantial, although coating compo-sitions containing electrically conductive fillers such as metal powders, carbon black or graphite are usually only insufficiently cured under UV light, because the light on the surface of the metal , . .
~77~)t7~) powders is strongly reflected or strongly absorbed by the carbon - black or graphite.
2a -~,~7~0t7~
.
Suitable epoxy re~in~ (a) are pre~erably tho~e containlng on average more than one group of the formula II
~0\
-~H-~ ~ H (II) wherein each of Q' and Q~ i8 a hydrogen atom and Q~ i~ a hydrogen atom or a methyl group, or Q' and Q~ together ars -CH2CH2~ or -CH2CH2CH2- 8nd ~ iB a hydrogen stom, which group iR attached to hetero atom, e.g. a sulfur atom and, preferably, to an oxygen or nitrogen atom.
Typical examples of ~uch resin~ are polyglycidyl esters and poly-(~-methylglycidyl) esters which are derived from aliphatic, cyclo-aliphatic or ~romatic poly~arboxylic acids. Examples o~ 6~itable polycarboxylic acids are: 3uccinic acid, glutsric acid, adipic acid, plmelic acld, ~beric scid, azelaic scid, sebsclc acid, dimerised or trimeri~ed linoleic acid, tetrahydr3phthslic acid, 4-methyltetrahy-drophthalic acid, hexahydrophthalic acid, 4-mathylhexahydrophthalic acid, phthalic acid, isophthalic acid and tcrephthalic acid.
Furth~r examples are polyglycidyl ethers and poly(~-methylglycldyl) ethsrs which are obtained by reaoting a compound containing at le~t two alcoholic and/or phenollc hydroxyl groups per molecule with epichlorohydrin or with allyl chloride, and then epoxidi~ing the reactioD product with a peracid.
Example~ of suitable polyol9 are: ethylene glycol, diethylene glycol, poly(Qxyethylene) glycols, propane-1,2-diol, poly(oxypropyl-ene) glycol B, propane-1,3-diol, butane-1,4-diol, poly(oxytetramcth-ylene) glycol~, pentane-1,5-diol, hexane-2,4,6-triol, glycerol, 1,1,1-~rimethylolpropane, pentaerythritol and sorbitol; 1,3- and 1,4-cyclohexanediol, bis(4~hydroxycycloh~xyl)methane, 292-bis(4-hydroxycyclohexyl)propane and l,1-bisthydroxym~thyl~ryolohex~3~ene;
N,N-bi~t2-hydroxyethyl)aniline and 4,4'-bi~(2-hydroxyethylamino)-~L~7707() diphenylmethane; re~orcinol, hydroquinone, bi~(4-hydroxyphenyl)-methane (bi~phenol F), 2,2-bi~(4-hydroxyphenyl)propane (bi~phenol A), 2,2-bis(4-hydroxy-315-dlbromophenyl)propane (tetrabromobl~p~enol A), 1,1,2,2-tetrakis(4-hydroxyphenyl)ethune, 4,4'-dlhydrnxyblphcnyl, bi~(4-hydroxyphenyl)~ulfone, a~ well aR novolak~ of formaldehyde or acetaldehyde ~nd phenol, chlorophenol or alkylphsnol~ containing up to 9 carbon atoma in the alkyl moiety, preferably cre~ol and phenol novolak~.
Suitable poly~N-glycidyl) compo~nds are products obtained by dehydrochlorination of reaction products o~ epichlorohydrin and amines containing at least two active hydrogen atoms bonded to amino nitrogen atoms. Examples o$ suitable amines are: aniline, n-butyl-amine, bis(4-amlnophenyl)methane, 1,3- and 1,4-xylylenediamine, 1,3-and 1,4-bi~(aminomethyl)cyclohexane snd bis(4-methylaminophe-nyl)methane. Purther s~itable compounds are: triglycidyl isocyanu-rate, N,N'-diglycidyl der~vatives of cyclic alkylene ureas ~uch Ra e~hylene urea and 1,3-propylene urea, or hydantoins such as 5,5-dimethylhydantoin.
Examples of poly(S-glycidyl) compounds ~re the di-S-glycidyl derivati~es of dithiols such a~ ethane-1,2-dithiol and bia(4-mer-captomethylphenyl) ether.
Examples of epoxy resins containing one or more group~ of the formula I}, wherein Q' and Q~ together sre a -cH2cH2- or -CHzCH2CH2-group are bi~(2,3-epoxycyclopentyl) ether, 2,3-epo~ycyclopentyl glycidyl ether, 1,2 bi~(2,3-epoxycyclopentyloxy)ethane, 394-epoxy-6-methylcyclohexylmethyl-3',4'-epoxy-6'-methylcyclohexane carboxyl-ate and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3',4'-epoxy~cyclohexane dioxane.
Al~o eligible are epoxy re~in~ in which the epoxy group~ ar~
attached to hetero atoms of different kind, or ln which s30me or all of the epoxy group~ are centr~l, for example the N,N,0 trlglyc~dyl ~ 5 -derlvative of 4-aminophenol, N-glycidyl-N'-(2-glycidyloxypropyl)-S,S dimethylhydantoin, vinylcyclohexene dioxide, limonene dioxide and dicyclopentadiene dioxide.
The epoxy re~in~ (a) may be solid or liquid. Preferred epoxy re~ln~
are tho~e having an epoxide content of 1.0 to 5.5.
As component (8~ it i8 preferred to use diglycidyl ether~ or advanced diglycidyl ethern of dihydric phenol~ or dlhydric aliphatic C2-C4alcohols, in particular diglycidyl ethers or advanced diglyci-dyl ether~ of 2,2-bls(4-hydroxyphenyl)propane, 2,2-bi~(3,5~dibromo-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, bls(4-hydroxy-cyclohexyl~methane or 2,2-bis(4-hydroxycyclohexyl)propane; polygly-cidyl ethers of novolaks 7 or tetraglycidylated 4,4'-diaminodiphenyl-methane. Most preferred are diglycidyl Qthers or advanccd diglycidyl ethers of bisphenol A, tetrabromo-bisphenol A or bisphenol F, and, in particular, polyglycidyl ethers of phenol/formaldehyds or cresol/formaldehyde novolaks, or mixtures thereof.
Pos3ible ~-arenes Rl and R2 are, in particular, aromatic groups of 6 to 24 carbon atoms or heteroaromatic groups of 3 to 30 carbon atoms, which groups may be unsubstituted or ~ub~tituted by one or more identical or dif~erent monovalent radicals such as halogen atoms, preferably chlorine or bromine atoms, or Cl-Cgalkyl, Cl-Cg-alkoxy, cyano, C1-Cgalkylthio, C2-C6monocarboxylic acid alkyl ester, phenyl, C2-Cs~lkanoyl or benzoyl groups. These ~-arene groups may be mononuclear, condensed polynuclear or non-condensed polynuclear systems, in which last~mentioned systems the nuclel may be linked togeth0r direct or through bridge members such as -S- or -0-.
R2 as the anion of a ~-arene may be an anion of 8 ~-arene o f the aforementioned kind, e.g. ths lndenyl anion, ~nd, in par~icular, ~he cyclopentadienyl anion, which anions may al80 be unsubstitutQd or substituted by one or more identical or differeDt monovalent radicals such as Cl-Cgalkyl, C2-C6monocsrboxylic acld alkyl ester, cyano, C2-Csalkanoyl or benzoyl group~.
~277~t~0 - h -Alkyl, alkoxy, alkylthio, ~onocarb~xylic acid alkyl e~ter and alkanoyl substituent~ may be ~traight chain or branched. Typical alkyl, alkoxy, alkylthio, ~onocarboxylic acld alkyl eAter or alkanoyl substituents are: methyl, ethyl, n-propyl, i~opropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, methoxy, ethoxy, n-p~opoxy, iaopropoxy, n-butoxy, n-hexyloxy, n-octylo~y, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, n-pentylthio and n-hexylthio, carboxylic acid methyl e~ter, ethyl ester, n-propyl e~ter, isopropyl e~ter, n-butyl e~ter and n-pentyl e~ter, acetyl, propionyl, butyryl, and valeroyl. Alkyl, alkoxy, alkylthio and monoc~rboxylic acid alkyl ester group~ containing 1 to 4 and especially 1 or 2 carbon ato~s in the alkyl moieties snd alkanoyl groups containing 2 or 3 carbon ato~s are preferred.
Preferred substituted ~-arene~ or anions of substituted ~-arenes are those containing one or two of the above-mentioned subs~ituents, in particular chlorine or bromine atoms, methyl, ethyl, methoxy, ethoxy, cyano~ carboxylic acid methyl or ethyl ester groups and acetyl groups.
Rl and R2 may be identical or different ~-arenes. Suitable hetero-aromatic ~-arenes are systems containlng S-, N- and/or 0-atoms.
Heteroaromatic ~-arene~ contsining S- and/or 0-atoms are preferred.
Examples of suitable $-srene3 are: benzene, toluene, xylenes, ethylbenzene, cumene (i~opropylbenzene), methoxybenzene, ethoxy-benzene, dimethoxybenzene, p-chlorotoluene, chlorobenzene, bromo-benzene, dichlorobenzene, acetylbenzene, trimethylbenzene, trime-thoxybenzene, naphthalens, 1,2-dihydronaphthalene, 1,2,3,4-tetra~
hydronaphthalene, methylnaphthalenes, meehoxynaphthalenes, ethoxy-naphthalenes, chloronaphthalene~, bromonaphthalene~, biphenyl, indene, fluorene, phenanthrene, anthracene, 9,10-dihydroanthracene, triphenylene, pyrene, naphthacene, coronene, thiophene, chromene 9 xanthene, thioxanthene, benzothiophene, naphthothiophene~ thi-anthrene, diphenylene oxide, diphenylene sulfide, acridine and carbazole.
~77070 If a i~ 2, then each R2 i8 preferably the anion of a n-arens, snd each M i9 sn identical metal atom. Examples of anions of subs~ituted ~-arenes are: the anions of met~hyl-, ethyl-, n-propyl- and n-butyl-cyclopentadiene, the ~nion~ of dimethylcyclopentadiene, oP cyclo-pentadiene c~rboxylic acid me~hyl ~nd e~hyl ester, and o~ acety~
cyclopentadlene, propionylcyclopentadiene, cyanocyclopents~diene and benzoylcyclopentsdiene. Preferred anions are the anion o unsubsti-tuted in~ene and especially the anion o~ unsubstituted cyclopenta-diene.
The preferred value of a i8 1, Rl i8 benzene, toluene, xylene, cumene, methoxybenzene, chlorobenzene, p-chlorotoluene, naphthalene, methylnaphthalene, chloronaphthalene, methoxynaphthalene, biphenyl, indene, pyrene or diphenylene sulfide, and R~ i8 the anion of cyclopentadisne, scetylcyclopentadiene OT 1ndene, or benzene, toluene, xylene, trimethylbenzene, naphthalene or ~ethylnaphthalene.
i~ T~2+ Ti3~ Zr~, Zr2+, Zr3+, Hf , Hf , Hf , Nb , Nb , Nb , Cr , Mo , Mo2 , ~ , W , Mn , Mn2 , Ra , Fe2+, Co3+, Ni2 or Cu2 . Preferably, M i~ a chromium, cobalt, mangsnese, tungsten or molybdenum cation, especially an iron catioD, most preferably Fe Psrticularly preferred complexss of for~uls I are those wherein a i8 1, Rl i9 n6-cumene or n6-2-methylnaphthalene and R2 ~3 the Inion of nS-cyclopentadiene, n iB preferably 1 or 2, preferably 1 t and q is preferably 1.
Examplès of suitable metals or non-metals L are Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn and Cu; lanthsnides such a~ Ce~ Pr and Nd, or actinide3, such as Th, Pa, V or Np. Suitable non-~e~als sre especially B, P and As. Prefarably L is P, As, B or Sb, with P bsing ~ost preferred.
Example~ of complex snions ~LQ~ q are BF4 , PF6 , AsF6 , SbF6 , FeCl4 , SnCl62 , SbCl6 , BiCl6 ~ The mos~ preferred complex anion~
are SbF6 ~ BF4 1 AsF6 and 9 in particular PF6 -~, .
7C)7~3 Examples of compounds of formula I are: (n6~toluene)(nS-lndenyl)-iron(II) hexafluorophosphate, (n6-Pyrene)(nS-cYclopontadienyl)-iron(II) hexaEluoroantimonate, (n6-toluene)(nS-cyclopentadlenyl)-iron(II) hexafluorophosphate, (n6-naphthalene)(~5-cyclopent2dien-yl)iron(II) hexafluoroarsenate, ~n6-2-methylnaphthalene)("S~cyclo--pentadienyl)iron(II) hexafluorophosphate, (n6-cumene)(nS-cyclopenta-d1enyl)iron(II) hexafluorophosphate and (n6-benzene)(nS-cyclopenta-dienyl)cobalt(III) bis(tetrafluoroborate).Such metallocene salts and the preparation thereof are de~cribed e.g. in European patent application 094 915 A2. Preferred compounds of formula I sre (n6-2-methylnaphthalene)(ns-cyclopentadienyl)iron(II) hexafluoro-phosphate and (n6-cumene)(n5-cyclopentadienyl)iron(II) hexafluoro-phosphate.
By appropriate choice of fillers it is possiblQ to influence the electrical, thermal and/or optical properties of the epoxy rs~in sy~tems, for example the electrically or thermally conductive or insulating properties, the ferroQlectric or ferromagnetic proper-ties, the piezoelectric, electrochromic or luminiscent propertles.
Photocursble resin compositions are thereby obtained which, after curing and development, give relief structures or image~ which find utility especislly in the fields of high-frequency engineering, electronics, microelectronics and optoelectronics, for example a~
active components in resistors, capacitors, transformer~, inductors~
magnets, memory and display materials, as passive cDmponents in ~lectricsl and thermsl insulators, heat extraction systems or electromagnetic shields, or also as so-called interconnec~ions, e.g.
in printed conductors or in chip contacting, as well ~B in mounting chips on the baDe plste~ of their assembly frames.
Suitable metal-con~sining fillers or fillers wi~h ~emiconductor propertie~ are, in particular~ metals, metal compound~ and alloyD in which the ~etal is one of Periodic Groups IIa, IlIa, IVa, Ib, Vb9 ~'77070 g VIb and/or VIII. Depending on the desired propertie3 or on the field of u~e of the epoxy resin compositions of this lnventlon, the following fillers may for example be used:
1. Electrically conductive fillers of organic or inorganic nature, e.g. carbon black snd graphite or metal~ of Periodic Group~ Vb, V~b, VIII and Ib, ~lloys and ~alts thereo~ ~uch 8~ hnlide~, ~xide~ and ~ulfides.
Examples of suitable metals and metal compounds are: vanadium, niobium, tantalum, molybdenum, tungsten, copper, noble metals auch as Pt, Pd, Ag snd Au, AgPd alloy3, ~ilver oxide, silver iodide, copper(II) sulfidet copper(I) iodide, copper(II) o~ide, gold(III) bromide, iodide and nxide, molybdenum(IV~ ~ulfide, niobium(IV) chloride and niobium(IV) oxide, palladium iodide, pallsdium oxlde, platinum(IV) bomide and platinum(IV) chloride, vanadium(III) chloride, vanadium(IV) oxide, tungsten(VI) chloride and tungsten(VI) oxide. Preferred metals are silver, copper, silver/palladium alloys, palladium, platinum, gold, ~ungsten and molybdenum. Particularly preferred metals are Au, Pt, AgPd, with Ag and Cu powder being most preferred.
2. Thermally conductive fillers or dielectric substances such as alumini~m oxide, beryllium oxide, lithium aluminium oxide and si~icon carbide.
3. Fillers which influence the ferroelectric, $erromagnetic, piezoèlectric, electrochromic and/or optical properties of the epoxy resin compositions, for example:
- Ferroelectric substances, e.g. barium titanate, lead titanate, lead zirconate, NaNbO3, KNbO3, AgNb03 and W03, ~hich are used, inter alia, for semiconductor~, condenser~ and in display and data memories in optoeIectronics. Barlum titanate, lead titanate snd lead zirconate csn al80 be u~ed for imparting piezoelectric propertie~, e.g. in high-frequency engineering. Tung~t-n, however, also ha~3 ~77~7() electrochromlc properties and i9 therefore used e.g. in dlgltal di~plays and in electrography. Preferred ferroelectric ~ubstances or electrochromic fillers are barium titsnate, lead titanate, lead circonate and W03.
- Ferromagnetic substQnces ~nd ferrltes of th~ general compo~ltion MI FezIIIO4 or MIIO~Fe203, whereln MII is a divalent metal ~uch as Zn, Cd, Co, Ni, Hn, Fe, Cu, Ba, Sr or Mg. Representatlve examples of preferred ferromagnetic substance~ and ferrites are Fe304, NlFe204, CoFe20l, and the manganese~zinc ferrites known under the registeret trademark Ferroxcube~ such as Ferroxcube 4C49 3D3, 3B9, 3B7 and 3C8.
Ferromagnetic substances and ferrites are used e.g. as pe~manent magnets (MII ~ e.g. Ba or Sr) for transformer~, inductors, insu-lators, sound recording systems, farrite aerials, magnetic ampli~
fiers or in ferrite cores, e.g. for core memories in elactronlc data processing systems.
- Phosphore3cent fillers and phosphor3 with luminescent proper~ies, for exampla CdS, GdZnSI SrS, MgS, CaS and, in particular, ZnS. Such materisls are used in particular for electro-optical displays.
To achieve the desired, preferably isotropic, physical effect, the filler~ muBt be u3ed in finely partieulate For~. They are preferably in very finely particulate form, in particular as 6pherlcal or rod-shaped, e.g. dendritic or la~ellar, particles. The flverage particle size of spherical particles i9 advantageously from 0.1 to 20 ~m ~micrometers), preferably from about 0.2 to 5 ~m. Rod-shapad particies, e~pecially dendritic amd lamellar particles, are preferab-ly ~.3 to 20 ~m in length and have a layer thickness of 0.1 to 1 ~m.
Compositions of this invention intended for applicstlon to ceramic substrates additionally contain a flux material (d), preferably in an amount of 5-5G% by weight, preferably of 10-40% by weight, ba~ed on the total weight of the compo~ition. Suitable $1ux ~ateri~l ara s.g. quartz powder~ and, in particulsr, glass powders, ~uch as ~'77~70 lead/borosilicate powder, borosilicate powder and blsmuth/lead silicate powder. Preferred glsss powders sre those having a refrac-tlve index below 1.8 and A particle ~ize ln the range from 2-50 ~m.
Component (a) ifi preEerably used in sn amount of 5-40% by weight, whereas the photoinitiator (b) is preferably u~ed ln an amount o~
0.3-4% by weight. The filler (c) ia convenien~ly u~ed in an amount o~ 30-85% by weight, but the amount of filler lc) and flux material ~d) should normally not exceed 95% by weigh~, based on the total weight of the composition.
Particularly preferred comnpositions are those contalning:
i) a polyglycidyl ether of a phenol/formaldehyde or cresol/formalde hyde novolak, silver powder, glsss powder and (n~-2-methylnaphthal-ene)(ns-cyclopentadienyl~iron(II~ hexafluorophosphate or ("6-cu-Mene)(ns-cyclopentadienyl~iron(II) hexafluorophosphate as photoinit-iator;
ii) a polyglyridyl ether of a phenol/formaldehyde or cresol/formalde-hyda novolak, copper powder, glas3 powder and (n6-2-~ethylnaphtha-lene)(nS cyclopentadienyl)iron(II) hexafluorophosphate, or iii~ a liquid bisphenol A epoxy resin, silver powder and (n6-2-methylnaphthalene)(ns-cyclopentadienyl)iron(II~ hexafluoropho~
phate or (n6-cumene)(ns-cyclopentadienyl)iron(II) hexsfluorophos-phate as photoinitiator.
The compositlons of the present invention may sl~o contain other known additiver (e~ conventionally employed in the art of photocur-able ~sterials. Examples of such additives are: pigments, dye~
reinforcing materials such as glass fibres, other fibre materlals, flame retardants, reactive diluent~ for the epo~y resins, e.g.
phenyl or cresyl glycidyl ethers, butanediol diglycidyl ethers and hexahydrophthalic acid glycidyl ethers, antistatic agent~, levelling ~X77C)70 agents, mould release agents, adhe~ion promoters, antioxidants, light stabilisers snd sensitisers for component (b) such as thioxan-thones, phthalimlde~, coumarins and anthracenes.
If the compositions contain the flux material (d) or fur~her conventional additive~ (e), then the sum of component~ ~a), (b~, (c), (d) and/or (e) iB 100 % by weight.
The compositions of this inventlon csn be prepared in a manner known per 8e by ~ixing the individual components. The are normally applied in the form of solutions in organic solvent~ to suitable supports such as plastic aheets, e.g. polyester sheets, metals, metal alloys, semi metals, semiconductors,, glass plates, ceramlcs, laminates such 8B copper-coated epoxy laminates, sio2 or Si3N14. Examples of suitable organic solvents are polar solvents, preferably polar aprotic organic solvents which may be used singly or in mixtures.
Examples of such suitable solvents are: slcohols such as ~ethanol, ethanol and diacetone alcohol amides of sliphatic monocarboxylic acids such as N,N-dimethylfor~Amide and N,N-di~ethylscstamide;
ethers such as diethyl ether, di-n-butyl ether, tetrahydrofuran, dioxane, 2-methoxyethanol, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol dimethyl ether; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetra-chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,l,2,2~tetra-chloroethane; carboxylates and lactones such as propylene carbonate, ethyl acetate, methyl propionate, ethyl benzoate, l-acetoxy-2-ethoxyethane, l-acetoxy-2-methoxyethane t r-butyrolac~one and r-valerolactone sulfoxides such as dlmethylsuloxide and trimethyl-sulfoxide, sulfone3 such as dimethyl sulfone, diethyl sulfone, tri~ethylene sulfone snd tetramethylene ~ulfone; ketone~ ~uch as di~ethyl ketone, methyl ethyl ketone, methyl lsobutyl ketone nnd cyclohexanone; ~ubstituted benzenee such a~ chlorobenzene and nitrobenzene. Preferred solvents are carboxylates and ketone~ such as 2-acetDxy-2-ethoxyethane and cyclohexanone.
~t77~)7~
The ~olutions sre applied by conventlonal methods to the support, for example by dipping, coating, spraying, padding, centrifuging or by roller coating.
The compositiona of this invention can al80 be applied in the dry state, e.g. by powder coating. Depending on the utility, the dry layer thicknesses sre generally in the range from about 0.5 to 200 ~m, preferably from 5 to 100 ~m. After coating, any residual solvent is removed in conventional manner, e.g. by heating and, lf desired, additionally under vscuum.
It i~ al80 po~sible to apply films obtained with the composition~ of this invention to other substrates before further treatment. Thus, for example, films obtained on pl~tic sheets can be applied, after drying, with a roll laminator to other ~ubstrates such aR glas~ or ceramic plstes, Monel~ ~3ubstrates (nickel/copper alloys~ and Tombak substraees (copper/zinc alloys), e.g. silver-coated or gold-coated Tombak and Monel substrates.
Curing of the composition~ and the coatings obtained there~ith can be carried out in one step by photocuring, preferably at ~levated temperature, e.g. in the range from 80 to 130C. Howe~er, curing i~
conveniently carried out in two steps, i.e. by photocuring followed by a thermal postcuring. Photocusing can be carried out with visible l~ght as well as with U~ light having a wavelength of 200~600 nm and at an intensity of 150-8000 watt~, preferably of 1000-5000 watts.
Suitable light source3 are e.g. xenon lamps, argon lamps, tung~ten lamps, carbon src3, metal halide and metal arc lamps ~uch a8 low-pressure, medium-pressure and high-prsssure mercury lsmps, argon ion lasers, frequency d~ubled Nd-YAG lasers (yttrium/aluminlum garnet) ~nd W lasers. It i~ preferred to effect irradiation with vi~ible light (VIS) or VIS lasers.
* ~lrQ ~ kt~k~
~L2~07C~
Tha irr~diation time depend~ on a number oE factors, e.g. on the thickness of the composltion, the nature of the llght Dource and its dlstance from the layer to be irrsdiated. The irradiatlon time is normally from 1 second to 600 ~econds.
The thermal aftertreatment (po~tcurlng? i~ conveniently 0Ef0cted in the temperature range from 50 to 150C, preferably from 60 to 130C.
After exposure and the optional additlonal thQrmal curi~g, the unexposed image srea~ are developed with a solvent or mixture of solvents. Sui~able ~olvents are for example tho~e of the kind cited above. Preferred solvents for developing are cyclohexanone and mixtures of propylene carbonate, diethylene glycol mono-n-butyl ether and r-butyrolactone.
Coating~ obtained wlth compositions containing electrically conduct-ive or dielectric fillers and flux materials are particularly Auitable for applications to ceramic, e.g. for thick-layer circuit~
on ceramic substrates or contacts on cera~ic substrates for lnte-grat~d circuits (chips).
After curing, the coatings are conveniently baked at elevated teMperature, preferably in the range from 250 to 1000C, most prefer~bly from 400 to 900C, to give conductive or dielectric relief structures or images. Baking iB advantageously effected in air, in an atmosphere of 2, N2 and/or H2. When uslng silver powder as filler or silver-containing fillers, baking iB preferably effected in an atmo~phere of 02. If copper powdar or A copper compound iB UBed aB filler, baking is advantageously carried out first in 2 and then in Nz or H2 or in A mixture of botb gases.
AB already mentioned, the compositionq of this invention are suitable for use in various fields of technology, especially in electronics, microelectronic~ and optoelectronics. Accordingly, th~
707~
invention al80 relates to the u~e of the composition~ for producing relief structures, iMages or bnnds by photocuring ~nd optional additional postcuring. Preferred utilities are:
When using electrically conductive filler~:
- for printed conductors on ceramic, enamelled steel plates, poly~er printed circuit boards or flexible plastic sheets;
- the production of electrodP patterns on aluminium and gla~s for liquid crystal displays and the like;
- for touch contact3 on flexible plaYtic sheets for keyboards;
- for contact bonds between chips and their supports;
- for bonding acti~e and passlve microelectronic componcnts to printed circuit boards (made of ceramlc, enamelled steel or plas~ics);
- for improving dsmaged tracks and contact~ in electronic systems, components and modules.
When using dielectric fillers:
- for insulating ad~acent or converging tracks on ceramic, enamelled steel and plastic ~ubstrates;
- for protecting layers as coverings for electronic and m~croel~
ectronic circuit components, contacts and tracks.
When using thermally conductive fillers:
- for heat extraction sy~tems in high-performance and high-frequency electronics.
When using ferroelectric fillers:
- for producing pressure-sensitive and sound-sensitive sensors Dn the basis of pie20electric effect~;
- for making optoelectronic display element~.
When using electrochromlc filler~:
- for making electrochromic display element~.
~77C~70 When uaing phosphoresc~nt fillers or phosphor~:
- for making flnely structured cathode ray tube display~
- for applying luminescent markings to masks for photographic or lithographlc purposes and to variou~ articles, shield~ and surfaces for informatlon, safety and decorative purpose~, A particulsrly preferred utility of the compo~itions of thi~
invention (with flux material~ i9 the productlon of thick layer circuit~.
In the following Examples, parts and percentages are by weight unless otherwise indicated.
Example l: To ~ parts of a 45% solution of an epoxy/cresol/novolak resin (mol wt c. 1270, epoxide eq. wt. 238 g/eq., epoxide content 4.2 eq./kg) in cyclohexanone are added lO parts of silver powder ~precipitated, average particle size 10 ~m, ex Fluka), S parts o a TiO2 gla~ powder ~hcmogeneou~ white powdes mix 20-6000, ex Draken-feld) and 0.18 part of (n6-2-methYlnaphthalene)(nS-cYclopenta-dienyl)iron(II) hexAfluorophosphate. The mixture i8 dispersed for 10 minutes in an ultrasonic3 bath and applied with a 50 ~m doctor knife to a 3 mm Pyrex~ glass plate. Through a photomask which reproduces a typical pattern of a printed circuit, a conductive pattern of a printed circuit that still has slight conductivity (<10 6 oh~ l-cml) i8 obtained by exposure for 5 minute3 to the rAdiation of a 1000 watt halogen lamp, curlng for 20 minutes at 80C and sub~equent development in ~yclohexanone in an ultrasonics bath. Tracks with a specific conductivity of 4.9 x 104 ohm l~cm 1 are obtained by subJecting the printed circuit so obtained to a heat treatment for 5 minutes at 650C in air.
Example 2: To 6.75 parta of a 60% solution of the epoxyJnovolak resin described in Exa~ple 1 in l-acetoxy 2-ethoxyethane are added 10 part~ of silver powder (average particle aize 2-3.5 ~, ex Ventron) and 5 part~ of a glass powder tLow Expansion Glsas Frit E
;~ , ~E ~ ARtc ~,2770~o 1980~, ex Drakenfeld). The mixture is dil~ted wi~h 1.25 partn of 1-acetoxy-2-ethoxyethane and ground for 15 hours in a ball mill with 4 mm glass beads. Then a solution of 0.18 part of (~6-2-methylnsphthal-ne)(ns-cyclopentadienyl)iron(II) hexafluoropho3phate di~solved in 0.5 part of N,N-dimethylformamide and 0.5 part of 1-acetoxy-Z-ethoxyethane is added. A film of the composition ao obtained is applied wlth a 50 ~m doctor knife to a polyethylene terephthslate sheet and dried for 10 minutes at 80C. This film is then trans-ferred at 130C with a roll laminator to an Al203/ceramic plate (Rubalith~ substrate for thick film coatings, ex Rosenthal Techn~k AG).
Through a photomask which reproduces a typical pattern of a prlnted circuit, a 12-~tep Stouffer wedge and an ITEK bar pattern mask for determining the resolution, the film i~ exposed for 5 minutes to the radiation of a 1000 watt halogen lamp, cured for 5 minutes at 110C
and developed in a devPloping bath consisting of 50 partæ of propylene carbonate, 30 parts of diethylene glycol mono-n-butyl ether and 210 parts of ~-butyrolsctone, to give the conducti~e pattern of the printed circuit as well as cl~arly resolved lines of the bar pattern havlng a width of 50 ~m. The conductive image is baked for 80 minute~ at 800C in a retort furnace. The track~
subsequently have a surface resi~tance of 20 mohm ~thickness o~ the layer: 8 ~m). Last completely reproduced step on the 12-step Stouffer wedge after baking: step 8 (known to be a referencQ
standard for the light-3ensitivity).
Conductive psttern~ with comparably good properties are obtained by using corre~ponding amount~ of (n6-cumene)(nS-cyclopentadienyl)-iron(II) hexafluorophosphate instead of (n6 2-methylnaphthal-ene)(n~-cyclopentadienyl~iron(II) hexsfluorophoæphate in E~ample~ 1 and 2.
Example 3: A copper-coated epoxy laminate (gla3~-reinforced epoxy printed circuit board) is coated with the composition descrlbed in Example 1 with the aid of a 50 ~m doctor knife and the coating i~
RA~E~A~CS
~L2~7070 dried for 15 ~inutes at 80C~ On exposure to radiation ~i~h the 514 nm line oE an argon ion laser (Innova 90~, ex Coherent), an energy of 270 mJ/cm2 suffices to develop a conductive pattern after a 5 minute cure at 110C.
Examnple 4: 3 parts oE a 45% solution in cyclohexanone of the epoxy/novolak resin described in Example 1 and 12 parts of copper powder (spherical, 325 mesh, ex Ventron), 2 g o~ a TiO2/glass powder (Homogeneous White Powder Mix 20-6000, ex Drakenfeld) and 0.06 part oE (~6-2-methylnaphthalene)(ns-cyclopentadienyl)iron(II) hexafluoro-phosphate are processed as described in Example 1. Likewise as described in Example l, Pyrex~ plates are coated with this mixture and the coating is irradiated and developed. The conductive patterns are su'osequently treated with air for lO minutes at 500C in a retort furnace, heated for 5 minutes under nitrogen to 750C and exposed for 10 minutes at 750C to a flow of hydrogen (10 ml/min).
The tracks have a surface resistance of 6 m-ohm (layer thickness:
8 ~m~.
Example 5: 25 parts of copper powder (avera~e particle size 10 ~m, ex Ventron, washed for 10 minutes in a 2N HNO3 solution, filtered and dried for 1 hour at 80C/13332 Pa) and 0.6 part of (~6-2-methyl-naphthalne)(n5-cyclopentadienyl)iron(II~ hexafluorophosphate are added to 30 parts of a 45% solution in cyclohexanone of the epoxy novolak resin described in Example 1. The ~ixture is dispersed for 10 minutes in an ultrasonics bath and applied with a 150 ~m doctor knife to a polyester sheet (MELINE~, ex ICI). The film is dried for 20 minutes at 75C to give a dry film of 60 ~m. This film is exposed for 3 minutes to the radiation of a 1000 watt halogen lamp at 20~C
through a photomask representing the pattern of a four-point measurement for conductivity measuring 5 x 0.5 mm. The film is then cured for 20 minutes at 80C and subsequently developed with cyclohexanone for 30 seconds in an ultrasonics bath, affording a pattern for the 4-point measurement of conductivity with a specific conductivity of 43 ohm cm 1.
.,,. ~
~77~
Exsmple 6: The proced~re of Ex~mple 5 is rep~ated, u~ing 40 g of a zinc ~ulfide phosphor ~LInMINEX G~, luminescent mlxture ex Riedel-D~
Haen) in~tesd of copper powder. Images which luminesc~ in the dark sfter 10 minutes are obtained.
Exampls 7: 1.5 parta of silvsr powdsr (average particle size 2-3.5 ~m, ex Ventron) and 0.06 part of (~6-2-methylnaphthalene)(~5-cyclo-pentadienyl)iron(II) hexafluorophosphats are addsd to 3 part~ of a 45% solution in cyclohexanone of the epoxylnovolak rssin described in Example 1. Ths mixture is di~persed for 10 minutes in an ultrason ic~ bath and a film of thi~ mixturs is applied with a 100 ~m doctor knifs to a polysthylsne terephthalats ~heet and then dried Por 10 minute~ at 80C. A piece of this film msssuring 0.2 x 0.3 cm i8 transferred at 130C to the silvsred base plats of a DIL (Dual-in-Line) a~ssmbly frams, exposed for 60 seconds to ths radistion of a 5000 watt halogen lamp and thsn bondsd to a 0.2 x 0.3 cm ~ilicon crystal at 120C over 2 minutes by fixing ths ~andwich coDsisting of assembly frame/silver-containing epoxy resin film/~ilicon cry~tal with clips betesn two plates. Ths ~ilicon crystal ~ub3equently ha~ a bonding strength of 10 N/~m2 on the ~ilvered a3sembly frame ldet~r-mined by the bonding ~trength test of E. Ludsr: ~8U hybridsr Mikro~chaltungen, page 42, Springsr Verlag, Berlin (1977)1.
Example 8: 1 part of 3ilver powdsr (~ilvsr flakes havlng an average psrt~cle si~e of 3 x 10 ~m, sx Ventron~ snd 0.06 part of (n6-2-~e-thylnaphthalsne)(ns-cyclopsntsdisnyl)iron(II) hexa~luorophohosphate srs added to 2 parts of a liquid bisphenol A spoxy resin lbi~phenol A diglycidl ether mixed with 2 % by weight o~ cresyl glycidyl ether;
epoxids content 5.31 eqlkg~ and the mlxture i8 di~per~ed for 10 minutss in sn ultrssonlc~ bsth. Thsn 0.2 part of thi~ mixtura i~
applied to the silvsred ba~e plsts of a DIL assembly frame. The mixture i~ sxposed or 300 ~scond~ to the rsdiation of a 5000 watt hslogen lamp and ths assembly fr~me i~ bonded to a 0.2 x 0.3 silicon cry~tal by h~ating for 5 minutes to 130C. According to the bonding strength test described in Exampls 7~ the 8ilicon cry~tal ha~ a bonding strsngth of 10 N/~m2. To dst~rmins the ~olum~ resi~tivity 7~0~70 an analogou6 formulation iB prepared with a 0.06 cm copper plate measurlng 0.2 x 0.3 cm. A ~imple two-point measurement gives a volume resistlvity of 70 m-ohm (thickness of the adhesiva layer c.
10 ~m). Compar~bly good re~ults are obtained by using a corre~pond-ing amount of (n~-cumene)~ns-cyclopentadienyl)iron(II) hexafluoro-pho~phate in thi~ Example instead of (n6-2-methylnaphthalane)(nS-cyclopentadienyl)iron(II) hexafluoropho~pha~e.
- Ferroelectric substances, e.g. barium titanate, lead titanate, lead zirconate, NaNbO3, KNbO3, AgNb03 and W03, ~hich are used, inter alia, for semiconductor~, condenser~ and in display and data memories in optoeIectronics. Barlum titanate, lead titanate snd lead zirconate csn al80 be u~ed for imparting piezoelectric propertie~, e.g. in high-frequency engineering. Tung~t-n, however, also ha~3 ~77~7() electrochromlc properties and i9 therefore used e.g. in dlgltal di~plays and in electrography. Preferred ferroelectric ~ubstances or electrochromic fillers are barium titsnate, lead titanate, lead circonate and W03.
- Ferromagnetic substQnces ~nd ferrltes of th~ general compo~ltion MI FezIIIO4 or MIIO~Fe203, whereln MII is a divalent metal ~uch as Zn, Cd, Co, Ni, Hn, Fe, Cu, Ba, Sr or Mg. Representatlve examples of preferred ferromagnetic substance~ and ferrites are Fe304, NlFe204, CoFe20l, and the manganese~zinc ferrites known under the registeret trademark Ferroxcube~ such as Ferroxcube 4C49 3D3, 3B9, 3B7 and 3C8.
Ferromagnetic substances and ferrites are used e.g. as pe~manent magnets (MII ~ e.g. Ba or Sr) for transformer~, inductors, insu-lators, sound recording systems, farrite aerials, magnetic ampli~
fiers or in ferrite cores, e.g. for core memories in elactronlc data processing systems.
- Phosphore3cent fillers and phosphor3 with luminescent proper~ies, for exampla CdS, GdZnSI SrS, MgS, CaS and, in particular, ZnS. Such materisls are used in particular for electro-optical displays.
To achieve the desired, preferably isotropic, physical effect, the filler~ muBt be u3ed in finely partieulate For~. They are preferably in very finely particulate form, in particular as 6pherlcal or rod-shaped, e.g. dendritic or la~ellar, particles. The flverage particle size of spherical particles i9 advantageously from 0.1 to 20 ~m ~micrometers), preferably from about 0.2 to 5 ~m. Rod-shapad particies, e~pecially dendritic amd lamellar particles, are preferab-ly ~.3 to 20 ~m in length and have a layer thickness of 0.1 to 1 ~m.
Compositions of this invention intended for applicstlon to ceramic substrates additionally contain a flux material (d), preferably in an amount of 5-5G% by weight, preferably of 10-40% by weight, ba~ed on the total weight of the compo~ition. Suitable $1ux ~ateri~l ara s.g. quartz powder~ and, in particulsr, glass powders, ~uch as ~'77~70 lead/borosilicate powder, borosilicate powder and blsmuth/lead silicate powder. Preferred glsss powders sre those having a refrac-tlve index below 1.8 and A particle ~ize ln the range from 2-50 ~m.
Component (a) ifi preEerably used in sn amount of 5-40% by weight, whereas the photoinitiator (b) is preferably u~ed ln an amount o~
0.3-4% by weight. The filler (c) ia convenien~ly u~ed in an amount o~ 30-85% by weight, but the amount of filler lc) and flux material ~d) should normally not exceed 95% by weigh~, based on the total weight of the composition.
Particularly preferred comnpositions are those contalning:
i) a polyglycidyl ether of a phenol/formaldehyde or cresol/formalde hyde novolak, silver powder, glsss powder and (n~-2-methylnaphthal-ene)(ns-cyclopentadienyl~iron(II~ hexafluorophosphate or ("6-cu-Mene)(ns-cyclopentadienyl~iron(II) hexafluorophosphate as photoinit-iator;
ii) a polyglyridyl ether of a phenol/formaldehyde or cresol/formalde-hyda novolak, copper powder, glas3 powder and (n6-2-~ethylnaphtha-lene)(nS cyclopentadienyl)iron(II) hexafluorophosphate, or iii~ a liquid bisphenol A epoxy resin, silver powder and (n6-2-methylnaphthalene)(ns-cyclopentadienyl)iron(II~ hexafluoropho~
phate or (n6-cumene)(ns-cyclopentadienyl)iron(II) hexsfluorophos-phate as photoinitiator.
The compositlons of the present invention may sl~o contain other known additiver (e~ conventionally employed in the art of photocur-able ~sterials. Examples of such additives are: pigments, dye~
reinforcing materials such as glass fibres, other fibre materlals, flame retardants, reactive diluent~ for the epo~y resins, e.g.
phenyl or cresyl glycidyl ethers, butanediol diglycidyl ethers and hexahydrophthalic acid glycidyl ethers, antistatic agent~, levelling ~X77C)70 agents, mould release agents, adhe~ion promoters, antioxidants, light stabilisers snd sensitisers for component (b) such as thioxan-thones, phthalimlde~, coumarins and anthracenes.
If the compositions contain the flux material (d) or fur~her conventional additive~ (e), then the sum of component~ ~a), (b~, (c), (d) and/or (e) iB 100 % by weight.
The compositions of this inventlon csn be prepared in a manner known per 8e by ~ixing the individual components. The are normally applied in the form of solutions in organic solvent~ to suitable supports such as plastic aheets, e.g. polyester sheets, metals, metal alloys, semi metals, semiconductors,, glass plates, ceramlcs, laminates such 8B copper-coated epoxy laminates, sio2 or Si3N14. Examples of suitable organic solvents are polar solvents, preferably polar aprotic organic solvents which may be used singly or in mixtures.
Examples of such suitable solvents are: slcohols such as ~ethanol, ethanol and diacetone alcohol amides of sliphatic monocarboxylic acids such as N,N-dimethylfor~Amide and N,N-di~ethylscstamide;
ethers such as diethyl ether, di-n-butyl ether, tetrahydrofuran, dioxane, 2-methoxyethanol, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol dimethyl ether; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetra-chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,l,2,2~tetra-chloroethane; carboxylates and lactones such as propylene carbonate, ethyl acetate, methyl propionate, ethyl benzoate, l-acetoxy-2-ethoxyethane, l-acetoxy-2-methoxyethane t r-butyrolac~one and r-valerolactone sulfoxides such as dlmethylsuloxide and trimethyl-sulfoxide, sulfone3 such as dimethyl sulfone, diethyl sulfone, tri~ethylene sulfone snd tetramethylene ~ulfone; ketone~ ~uch as di~ethyl ketone, methyl ethyl ketone, methyl lsobutyl ketone nnd cyclohexanone; ~ubstituted benzenee such a~ chlorobenzene and nitrobenzene. Preferred solvents are carboxylates and ketone~ such as 2-acetDxy-2-ethoxyethane and cyclohexanone.
~t77~)7~
The ~olutions sre applied by conventlonal methods to the support, for example by dipping, coating, spraying, padding, centrifuging or by roller coating.
The compositiona of this invention can al80 be applied in the dry state, e.g. by powder coating. Depending on the utility, the dry layer thicknesses sre generally in the range from about 0.5 to 200 ~m, preferably from 5 to 100 ~m. After coating, any residual solvent is removed in conventional manner, e.g. by heating and, lf desired, additionally under vscuum.
It i~ al80 po~sible to apply films obtained with the composition~ of this invention to other substrates before further treatment. Thus, for example, films obtained on pl~tic sheets can be applied, after drying, with a roll laminator to other ~ubstrates such aR glas~ or ceramic plstes, Monel~ ~3ubstrates (nickel/copper alloys~ and Tombak substraees (copper/zinc alloys), e.g. silver-coated or gold-coated Tombak and Monel substrates.
Curing of the composition~ and the coatings obtained there~ith can be carried out in one step by photocuring, preferably at ~levated temperature, e.g. in the range from 80 to 130C. Howe~er, curing i~
conveniently carried out in two steps, i.e. by photocuring followed by a thermal postcuring. Photocusing can be carried out with visible l~ght as well as with U~ light having a wavelength of 200~600 nm and at an intensity of 150-8000 watt~, preferably of 1000-5000 watts.
Suitable light source3 are e.g. xenon lamps, argon lamps, tung~ten lamps, carbon src3, metal halide and metal arc lamps ~uch a8 low-pressure, medium-pressure and high-prsssure mercury lsmps, argon ion lasers, frequency d~ubled Nd-YAG lasers (yttrium/aluminlum garnet) ~nd W lasers. It i~ preferred to effect irradiation with vi~ible light (VIS) or VIS lasers.
* ~lrQ ~ kt~k~
~L2~07C~
Tha irr~diation time depend~ on a number oE factors, e.g. on the thickness of the composltion, the nature of the llght Dource and its dlstance from the layer to be irrsdiated. The irradiatlon time is normally from 1 second to 600 ~econds.
The thermal aftertreatment (po~tcurlng? i~ conveniently 0Ef0cted in the temperature range from 50 to 150C, preferably from 60 to 130C.
After exposure and the optional additlonal thQrmal curi~g, the unexposed image srea~ are developed with a solvent or mixture of solvents. Sui~able ~olvents are for example tho~e of the kind cited above. Preferred solvents for developing are cyclohexanone and mixtures of propylene carbonate, diethylene glycol mono-n-butyl ether and r-butyrolactone.
Coating~ obtained wlth compositions containing electrically conduct-ive or dielectric fillers and flux materials are particularly Auitable for applications to ceramic, e.g. for thick-layer circuit~
on ceramic substrates or contacts on cera~ic substrates for lnte-grat~d circuits (chips).
After curing, the coatings are conveniently baked at elevated teMperature, preferably in the range from 250 to 1000C, most prefer~bly from 400 to 900C, to give conductive or dielectric relief structures or images. Baking iB advantageously effected in air, in an atmosphere of 2, N2 and/or H2. When uslng silver powder as filler or silver-containing fillers, baking iB preferably effected in an atmo~phere of 02. If copper powdar or A copper compound iB UBed aB filler, baking is advantageously carried out first in 2 and then in Nz or H2 or in A mixture of botb gases.
AB already mentioned, the compositionq of this invention are suitable for use in various fields of technology, especially in electronics, microelectronic~ and optoelectronics. Accordingly, th~
707~
invention al80 relates to the u~e of the composition~ for producing relief structures, iMages or bnnds by photocuring ~nd optional additional postcuring. Preferred utilities are:
When using electrically conductive filler~:
- for printed conductors on ceramic, enamelled steel plates, poly~er printed circuit boards or flexible plastic sheets;
- the production of electrodP patterns on aluminium and gla~s for liquid crystal displays and the like;
- for touch contact3 on flexible plaYtic sheets for keyboards;
- for contact bonds between chips and their supports;
- for bonding acti~e and passlve microelectronic componcnts to printed circuit boards (made of ceramlc, enamelled steel or plas~ics);
- for improving dsmaged tracks and contact~ in electronic systems, components and modules.
When using dielectric fillers:
- for insulating ad~acent or converging tracks on ceramic, enamelled steel and plastic ~ubstrates;
- for protecting layers as coverings for electronic and m~croel~
ectronic circuit components, contacts and tracks.
When using thermally conductive fillers:
- for heat extraction sy~tems in high-performance and high-frequency electronics.
When using ferroelectric fillers:
- for producing pressure-sensitive and sound-sensitive sensors Dn the basis of pie20electric effect~;
- for making optoelectronic display element~.
When using electrochromlc filler~:
- for making electrochromic display element~.
~77C~70 When uaing phosphoresc~nt fillers or phosphor~:
- for making flnely structured cathode ray tube display~
- for applying luminescent markings to masks for photographic or lithographlc purposes and to variou~ articles, shield~ and surfaces for informatlon, safety and decorative purpose~, A particulsrly preferred utility of the compo~itions of thi~
invention (with flux material~ i9 the productlon of thick layer circuit~.
In the following Examples, parts and percentages are by weight unless otherwise indicated.
Example l: To ~ parts of a 45% solution of an epoxy/cresol/novolak resin (mol wt c. 1270, epoxide eq. wt. 238 g/eq., epoxide content 4.2 eq./kg) in cyclohexanone are added lO parts of silver powder ~precipitated, average particle size 10 ~m, ex Fluka), S parts o a TiO2 gla~ powder ~hcmogeneou~ white powdes mix 20-6000, ex Draken-feld) and 0.18 part of (n6-2-methYlnaphthalene)(nS-cYclopenta-dienyl)iron(II) hexAfluorophosphate. The mixture i8 dispersed for 10 minutes in an ultrasonic3 bath and applied with a 50 ~m doctor knife to a 3 mm Pyrex~ glass plate. Through a photomask which reproduces a typical pattern of a printed circuit, a conductive pattern of a printed circuit that still has slight conductivity (<10 6 oh~ l-cml) i8 obtained by exposure for 5 minute3 to the rAdiation of a 1000 watt halogen lamp, curlng for 20 minutes at 80C and sub~equent development in ~yclohexanone in an ultrasonics bath. Tracks with a specific conductivity of 4.9 x 104 ohm l~cm 1 are obtained by subJecting the printed circuit so obtained to a heat treatment for 5 minutes at 650C in air.
Example 2: To 6.75 parta of a 60% solution of the epoxyJnovolak resin described in Exa~ple 1 in l-acetoxy 2-ethoxyethane are added 10 part~ of silver powder (average particle aize 2-3.5 ~, ex Ventron) and 5 part~ of a glass powder tLow Expansion Glsas Frit E
;~ , ~E ~ ARtc ~,2770~o 1980~, ex Drakenfeld). The mixture is dil~ted wi~h 1.25 partn of 1-acetoxy-2-ethoxyethane and ground for 15 hours in a ball mill with 4 mm glass beads. Then a solution of 0.18 part of (~6-2-methylnsphthal-ne)(ns-cyclopentadienyl)iron(II) hexafluoropho3phate di~solved in 0.5 part of N,N-dimethylformamide and 0.5 part of 1-acetoxy-Z-ethoxyethane is added. A film of the composition ao obtained is applied wlth a 50 ~m doctor knife to a polyethylene terephthslate sheet and dried for 10 minutes at 80C. This film is then trans-ferred at 130C with a roll laminator to an Al203/ceramic plate (Rubalith~ substrate for thick film coatings, ex Rosenthal Techn~k AG).
Through a photomask which reproduces a typical pattern of a prlnted circuit, a 12-~tep Stouffer wedge and an ITEK bar pattern mask for determining the resolution, the film i~ exposed for 5 minutes to the radiation of a 1000 watt halogen lamp, cured for 5 minutes at 110C
and developed in a devPloping bath consisting of 50 partæ of propylene carbonate, 30 parts of diethylene glycol mono-n-butyl ether and 210 parts of ~-butyrolsctone, to give the conducti~e pattern of the printed circuit as well as cl~arly resolved lines of the bar pattern havlng a width of 50 ~m. The conductive image is baked for 80 minute~ at 800C in a retort furnace. The track~
subsequently have a surface resi~tance of 20 mohm ~thickness o~ the layer: 8 ~m). Last completely reproduced step on the 12-step Stouffer wedge after baking: step 8 (known to be a referencQ
standard for the light-3ensitivity).
Conductive psttern~ with comparably good properties are obtained by using corre~ponding amount~ of (n6-cumene)(nS-cyclopentadienyl)-iron(II) hexafluorophosphate instead of (n6 2-methylnaphthal-ene)(n~-cyclopentadienyl~iron(II) hexsfluorophoæphate in E~ample~ 1 and 2.
Example 3: A copper-coated epoxy laminate (gla3~-reinforced epoxy printed circuit board) is coated with the composition descrlbed in Example 1 with the aid of a 50 ~m doctor knife and the coating i~
RA~E~A~CS
~L2~7070 dried for 15 ~inutes at 80C~ On exposure to radiation ~i~h the 514 nm line oE an argon ion laser (Innova 90~, ex Coherent), an energy of 270 mJ/cm2 suffices to develop a conductive pattern after a 5 minute cure at 110C.
Examnple 4: 3 parts oE a 45% solution in cyclohexanone of the epoxy/novolak resin described in Example 1 and 12 parts of copper powder (spherical, 325 mesh, ex Ventron), 2 g o~ a TiO2/glass powder (Homogeneous White Powder Mix 20-6000, ex Drakenfeld) and 0.06 part oE (~6-2-methylnaphthalene)(ns-cyclopentadienyl)iron(II) hexafluoro-phosphate are processed as described in Example 1. Likewise as described in Example l, Pyrex~ plates are coated with this mixture and the coating is irradiated and developed. The conductive patterns are su'osequently treated with air for lO minutes at 500C in a retort furnace, heated for 5 minutes under nitrogen to 750C and exposed for 10 minutes at 750C to a flow of hydrogen (10 ml/min).
The tracks have a surface resistance of 6 m-ohm (layer thickness:
8 ~m~.
Example 5: 25 parts of copper powder (avera~e particle size 10 ~m, ex Ventron, washed for 10 minutes in a 2N HNO3 solution, filtered and dried for 1 hour at 80C/13332 Pa) and 0.6 part of (~6-2-methyl-naphthalne)(n5-cyclopentadienyl)iron(II~ hexafluorophosphate are added to 30 parts of a 45% solution in cyclohexanone of the epoxy novolak resin described in Example 1. The ~ixture is dispersed for 10 minutes in an ultrasonics bath and applied with a 150 ~m doctor knife to a polyester sheet (MELINE~, ex ICI). The film is dried for 20 minutes at 75C to give a dry film of 60 ~m. This film is exposed for 3 minutes to the radiation of a 1000 watt halogen lamp at 20~C
through a photomask representing the pattern of a four-point measurement for conductivity measuring 5 x 0.5 mm. The film is then cured for 20 minutes at 80C and subsequently developed with cyclohexanone for 30 seconds in an ultrasonics bath, affording a pattern for the 4-point measurement of conductivity with a specific conductivity of 43 ohm cm 1.
.,,. ~
~77~
Exsmple 6: The proced~re of Ex~mple 5 is rep~ated, u~ing 40 g of a zinc ~ulfide phosphor ~LInMINEX G~, luminescent mlxture ex Riedel-D~
Haen) in~tesd of copper powder. Images which luminesc~ in the dark sfter 10 minutes are obtained.
Exampls 7: 1.5 parta of silvsr powdsr (average particle size 2-3.5 ~m, ex Ventron) and 0.06 part of (~6-2-methylnaphthalene)(~5-cyclo-pentadienyl)iron(II) hexafluorophosphats are addsd to 3 part~ of a 45% solution in cyclohexanone of the epoxylnovolak rssin described in Example 1. Ths mixture is di~persed for 10 minutes in an ultrason ic~ bath and a film of thi~ mixturs is applied with a 100 ~m doctor knifs to a polysthylsne terephthalats ~heet and then dried Por 10 minute~ at 80C. A piece of this film msssuring 0.2 x 0.3 cm i8 transferred at 130C to the silvsred base plats of a DIL (Dual-in-Line) a~ssmbly frams, exposed for 60 seconds to ths radistion of a 5000 watt halogen lamp and thsn bondsd to a 0.2 x 0.3 cm ~ilicon crystal at 120C over 2 minutes by fixing ths ~andwich coDsisting of assembly frame/silver-containing epoxy resin film/~ilicon cry~tal with clips betesn two plates. Ths ~ilicon crystal ~ub3equently ha~ a bonding strength of 10 N/~m2 on the ~ilvered a3sembly frame ldet~r-mined by the bonding ~trength test of E. Ludsr: ~8U hybridsr Mikro~chaltungen, page 42, Springsr Verlag, Berlin (1977)1.
Example 8: 1 part of 3ilver powdsr (~ilvsr flakes havlng an average psrt~cle si~e of 3 x 10 ~m, sx Ventron~ snd 0.06 part of (n6-2-~e-thylnaphthalsne)(ns-cyclopsntsdisnyl)iron(II) hexa~luorophohosphate srs added to 2 parts of a liquid bisphenol A spoxy resin lbi~phenol A diglycidl ether mixed with 2 % by weight o~ cresyl glycidyl ether;
epoxids content 5.31 eqlkg~ and the mlxture i8 di~per~ed for 10 minutss in sn ultrssonlc~ bsth. Thsn 0.2 part of thi~ mixtura i~
applied to the silvsred ba~e plsts of a DIL assembly frame. The mixture i~ sxposed or 300 ~scond~ to the rsdiation of a 5000 watt hslogen lamp and ths assembly fr~me i~ bonded to a 0.2 x 0.3 silicon cry~tal by h~ating for 5 minutes to 130C. According to the bonding strength test described in Exampls 7~ the 8ilicon cry~tal ha~ a bonding strsngth of 10 N/~m2. To dst~rmins the ~olum~ resi~tivity 7~0~70 an analogou6 formulation iB prepared with a 0.06 cm copper plate measurlng 0.2 x 0.3 cm. A ~imple two-point measurement gives a volume resistlvity of 70 m-ohm (thickness of the adhesiva layer c.
10 ~m). Compar~bly good re~ults are obtained by using a corre~pond-ing amount of (n~-cumene)~ns-cyclopentadienyl)iron(II) hexafluoro-pho~phate in thi~ Example instead of (n6-2-methylnaphthalane)(nS-cyclopentadienyl)iron(II) hexafluoropho~pha~e.
Claims (22)
1. A photocurable epoxy resin composition which contains filler, said composition comprising (a) 5-90 % by weight of an epoxy resin or epoxy resin mixture, which resin or resins do not contain olefinically unsaturated C=C double bonds, (b) 0.1 to 15 % by weight of at least one photoinitiator of formula I
[(R1)(R2M)a]+an [LQm]-q (I), wherein a is 1 or 2 and each of n and q independently of the other is an integer from 1 to 3, M is the cation of a monovalent to trivalent metal of Periodic Groups IVb to VIIb, VIII or Ib, m is an integer corresponding to the valency of L + q and Q is a halogen atom, L is a divalent to heptavalent metal or non-metal, R1 is a .pi.-arene and R2 is a .pi.-arene or the anion of a .pi.-arene, and (c) 10 -90 % by weight of at least one finely particulate filler selected from the group consisting of electrically conductive or semiconductive fillers, thermally conductive or dielectric fillers, fillers which influence the ferroelectric, ferromagnetic, piezo-electric or electrochromic properties and fillers with luminescent properties, the sum of all compounds being 100 % by weight.
[(R1)(R2M)a]+an [LQm]-q (I), wherein a is 1 or 2 and each of n and q independently of the other is an integer from 1 to 3, M is the cation of a monovalent to trivalent metal of Periodic Groups IVb to VIIb, VIII or Ib, m is an integer corresponding to the valency of L + q and Q is a halogen atom, L is a divalent to heptavalent metal or non-metal, R1 is a .pi.-arene and R2 is a .pi.-arene or the anion of a .pi.-arene, and (c) 10 -90 % by weight of at least one finely particulate filler selected from the group consisting of electrically conductive or semiconductive fillers, thermally conductive or dielectric fillers, fillers which influence the ferroelectric, ferromagnetic, piezo-electric or electrochromic properties and fillers with luminescent properties, the sum of all compounds being 100 % by weight.
2. A composition according to claim 1, wherein component c) is selected from the group consisting of carbon black, graphite, metal-containing fillers and fillers with semi-conductor properties, the sum of all components being 100% by weight.
3. A composition according to claim 1, wherein the epoxy resin (a) is an epoxy resin containing on average more than one group of the formula II
(II) wherein each of Q' and Q2 is a hydrogen atom and Q1 is a hydrogen atom or a methyl group, or Q' and Q2 together are -CH2CH2- or -CH2CH2CH2- and Q1 is a hydrogen atom, which group is attached to an -O-, -S- or -N- atom.
(II) wherein each of Q' and Q2 is a hydrogen atom and Q1 is a hydrogen atom or a methyl group, or Q' and Q2 together are -CH2CH2- or -CH2CH2CH2- and Q1 is a hydrogen atom, which group is attached to an -O-, -S- or -N- atom.
4. A composition according to claim 1, wherein the epoxy resin (a) is a diglycidyl ether or an advanced diglycidyl ether of a dihydric phenol or of a dihydric aliphatic alcohol of 2 to 4 carbon atoms, a polyglycidyl ether of a novolak or a tetraglycidylated 4,4'-diamino-diphenylmethane.
5. A composition according to claim 1, wherein the epoxy resin (a) is a diglycidyl ether or an advanced diglycidyl ether of bis-phenol A, tetrabromo-bisphenol A or bisphenol F, a polyglycidyl ether of a phenol/formaldehyde or cresol/formaldehyde novolak or a mixture of such resins.
6. A composition according to claim 1 which contains a photoinit-iator of formula I, wherein a is 1, R1 is benzene, toluene, xylene, cumene, methoxybenzene, chlorobenzene, p-chlorotoluene, naphthalene, methylnaphthalene, chloronaphthalene, methoxynaphthalene, biphenyl, indene, pyrene or diphenylenesulfide, and R2 is the anion of cyclopentadiene, acetylcyclopentadiene or indene, or is benzene, toluene, xylene, trimethylbenzene, naphthalene or methylnaphthalene.
7. A composition according to claim 1 which contains a photoiniator of formula I, wherein a is 1, R1 is ?6-cumene or ?6-2-methylnaphtha-lene and R2 is the anion of ?5-cyclopentadiene, and n is 1 or 2 and q is 1.
8. A composition according to claim 1, wherein M is a chromium, cobalt, manganese, tungsten, molybdenum or iron cation, and [LQm]-q is SbF6-, BF4-, AsF6- or PF6-.
9. A composition according to claim 8, wherein M is Fe2+.
10. A composition according to claim 1, wherein the metal-containing filler or the filler with semiconductor properties is a metal, a metal compound or a metal alloy, in which the metal is a metal of Periodic Groups IIa, IIIa, IVa, Ib, Vb, VIb and/or VIII.
11. A composition according to claim 1, wherein the metal-containing filler is silver, copper, a silver/palladium alloy, palladium, platinum, gold, tungsten or molybdenum.
12. A composition according to claim 1, wherein the metal-containing filler is Au, Pt or AgPd.
13. A composition according to claim 1, wherein the filler is silver powder or copper powder.
14. A composition according to claim 1, wherein the filler is aluminium oxide, beryllium oxide, lithium aluminium oxide, silicon carbide, barium titanate, lead titanate, lead zirconate, WO3, Fe3O4, NiFe2O4, CoFe2O4, a manganese/zinc ferrite or ZnS.
15. A composition according to claim 1, wherein the filler is in the form of spherical or rod-shaped particles.
16. A composition according to claim 1, wherein the filler has a particle size of 0.1 to 20 micrometers.
17. A composition according to claim 1, which additionally contains 5-50 % by weight of a flux material (d), the sum total of components (a) to (d) being 100 % by weight.
18. A composition according to claim 1, which contains 5-40 % by weight of component (a), 0.3-4 % by weight of photoinitiator (b) and 30-85 % by weight of filler (c).
19. A composition according to claim 17, which contains together not more than 95 % by weight of filler (c) and flux material (d), based on the total weight of said composition.
20. A composition according to claim 17, wherein the flux material is glass powder.
21. A process for the production of relief structures, images or bonds, which comprises subjecting a composition as claimed in claim 1 to photocuring.
22. A process according to claim 21, which comprises carrying out a thermal postcuring.
FO 7.3 ACK/bg*
FO 7.3 ACK/bg*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH544784 | 1984-11-14 | ||
| CH5447/84-1 | 1984-11-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1277070C true CA1277070C (en) | 1990-11-27 |
Family
ID=4293733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000495135A Expired - Lifetime CA1277070C (en) | 1984-11-14 | 1985-11-12 | Photocurable epoxy resin compositions which contain fillers, and the use thereof |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0182744B1 (en) |
| JP (1) | JPS61120827A (en) |
| CA (1) | CA1277070C (en) |
| DE (1) | DE3586485D1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5494943A (en) * | 1993-06-16 | 1996-02-27 | Minnesota Mining And Manufacturing Company | Stabilized cationically-curable compositions |
| US5624976A (en) * | 1994-03-25 | 1997-04-29 | Dentsply Gmbh | Dental filling composition and method |
| US5876210A (en) | 1994-04-22 | 1999-03-02 | Dentsply G.M.B.H. | Dental polymer product |
| US5998499A (en) | 1994-03-25 | 1999-12-07 | Dentsply G.M.B.H. | Liquid crystalline (meth)acrylate compounds, composition and method |
| US6353061B1 (en) | 1993-05-26 | 2002-03-05 | Dentsply Gmbh | α, ω-methacrylate terminated macromonomer compounds |
| US6369164B1 (en) | 1993-05-26 | 2002-04-09 | Dentsply G.M.B.H. | Polymerizable compounds and compositions |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4963300A (en) * | 1987-12-15 | 1990-10-16 | Ciba-Geigy Corporation | Process for the preparation of laminates |
| US4920182A (en) * | 1987-12-18 | 1990-04-24 | Ciba-Geigy Corporation | Epoxy resin compositions containing polyester flexibilizer and metallocene complex initiator |
| US5434196A (en) * | 1988-02-19 | 1995-07-18 | Asahi Denka Kogyo K.K. | Resin composition for optical molding |
| JPH0826121B2 (en) * | 1988-02-19 | 1996-03-13 | 旭電化工業株式会社 | Resin composition for optical modeling |
| ATE161860T1 (en) * | 1988-02-19 | 1998-01-15 | Asahi Denka Kogyo Kk | PLASTIC COMPOSITION FOR OPTICAL MODELING |
| DE3806738C1 (en) * | 1988-03-02 | 1989-09-07 | Espe Stiftung & Co Produktions- Und Vertriebs Kg, 8031 Seefeld, De | |
| EP0386473B1 (en) * | 1989-03-08 | 1996-12-11 | Siemens Aktiengesellschaft | Drop-covering mass for electric and electronic devices |
| US5667934A (en) * | 1990-10-09 | 1997-09-16 | International Business Machines Corporation | Thermally stable photoimaging composition |
| US5362421A (en) * | 1993-06-16 | 1994-11-08 | Minnesota Mining And Manufacturing Company | Electrically conductive adhesive compositions |
| DE4324322B4 (en) * | 1993-07-20 | 2005-11-24 | Delo Industrieklebstoffe Gmbh & Co. Kg | Flexible, light-initiated curing epoxy resin compositions, their preparation and use |
| FR2876983B1 (en) * | 2004-10-22 | 2007-02-16 | Eads Space Transp Sa Sa | RIGIDIFICATION OF INFLATABLE DEPLOYMENT STRUCTURES ESPECIALLY FOR SPATIAL USE |
| JP4872443B2 (en) * | 2006-04-25 | 2012-02-08 | パナソニック電工株式会社 | Method for forming optical waveguide |
| DE102006057142A1 (en) * | 2006-12-01 | 2008-06-05 | Henkel Kgaa | Metal compounds as initiators |
| PT2609049E (en) | 2010-08-27 | 2015-01-14 | Diana Friedrich | Phosphorescent compositions and use thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3709861A (en) * | 1970-12-14 | 1973-01-09 | Shell Oil Co | Process for light-induced curing of epoxy resins in presence of cyclopentadienylmanganese tricarbonyl compounds |
| US3989644A (en) * | 1974-09-27 | 1976-11-02 | General Electric Company | Radiation curable inks |
| DE3369398D1 (en) * | 1982-05-19 | 1987-02-26 | Ciba Geigy Ag | Curable compositions containing metallocen complexes, activated primers obtained therefrom and their use |
-
1985
- 1985-11-08 DE DE8585810524T patent/DE3586485D1/en not_active Expired - Lifetime
- 1985-11-08 EP EP85810524A patent/EP0182744B1/en not_active Expired - Lifetime
- 1985-11-12 CA CA000495135A patent/CA1277070C/en not_active Expired - Lifetime
- 1985-11-14 JP JP60255808A patent/JPS61120827A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6339114B1 (en) | 1993-05-26 | 2002-01-15 | Dentsply Detrey Gmbh | Liquid crystalline (meth)acrylate compounds, composition and method |
| US6353061B1 (en) | 1993-05-26 | 2002-03-05 | Dentsply Gmbh | α, ω-methacrylate terminated macromonomer compounds |
| US6369164B1 (en) | 1993-05-26 | 2002-04-09 | Dentsply G.M.B.H. | Polymerizable compounds and compositions |
| US5494943A (en) * | 1993-06-16 | 1996-02-27 | Minnesota Mining And Manufacturing Company | Stabilized cationically-curable compositions |
| US5672637A (en) * | 1993-06-16 | 1997-09-30 | Minnesota Mining And Manufacturing Company | Stabilized cationically-curable compositions |
| US5624976A (en) * | 1994-03-25 | 1997-04-29 | Dentsply Gmbh | Dental filling composition and method |
| US5998499A (en) | 1994-03-25 | 1999-12-07 | Dentsply G.M.B.H. | Liquid crystalline (meth)acrylate compounds, composition and method |
| US5876210A (en) | 1994-04-22 | 1999-03-02 | Dentsply G.M.B.H. | Dental polymer product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61120827A (en) | 1986-06-07 |
| EP0182744A3 (en) | 1988-07-06 |
| EP0182744B1 (en) | 1992-08-12 |
| EP0182744A2 (en) | 1986-05-28 |
| DE3586485D1 (en) | 1992-09-17 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |