WO2024017926A1 - Composition de jet d'encre durcissable pour la fabrication de cartes de circuit imprimé - Google Patents

Composition de jet d'encre durcissable pour la fabrication de cartes de circuit imprimé Download PDF

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WO2024017926A1
WO2024017926A1 PCT/EP2023/069979 EP2023069979W WO2024017926A1 WO 2024017926 A1 WO2024017926 A1 WO 2024017926A1 EP 2023069979 W EP2023069979 W EP 2023069979W WO 2024017926 A1 WO2024017926 A1 WO 2024017926A1
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inkjet composition
curable inkjet
blocked isocyanate
compound
group
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PCT/EP2023/069979
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English (en)
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Marion Sauvageot
Jeannette MUNYESHYAKA
Mitch MATTHYS
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Agfa-Gevaert Nv
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Publication of WO2024017926A1 publication Critical patent/WO2024017926A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • the present invention relates to a curable composition for use as an ink jet composition in the manufacturing of electronic devices.
  • the invention also relates to a cured product of said composition.
  • PCBs Printed Circuit Boards
  • PCBs are traditionally manufactured in an extensive process including multiple photolithographic and etching steps, thereby generating a lot of waste.
  • PCB manufacturing workflow In order to reduce the amount of process steps, production costs, and waste, there is an increased interest in digitalizing the PCB manufacturing workflow.
  • Inkjet printing is a preferred digital manufacturing technology for several PCB production steps, such as the application of the etch resist and the solder mask, or printing of the legend.
  • the PCB solder mask acts as an insulator between the copper traces, and prevents the formation of solder bridges. Moreover, it plays an important role in protecting the board against oxidation triggered by outer influences, such as weather conditions, temperature variations, and humidity. When mechanical defects occur in the solder mask due to exposure to these external conditions, the protective and insulating function of the solder mask can be negatively affected. Therefore, the main objective for producing an effective solder mask is to provide a good resistance against the conditions to which it is exposed.
  • a first requirement is that the cured ink has a good adhesion on various substrates, such as copper and FR-4.
  • the adhesion on various substrates may be improved by adding adhesion promoters, as disclosed in WC2004/026977 and WC2004/105 (Avecia).
  • WC2018/087056 (Agfa-Gevaert /Electra Polymers) discloses a combination of an adhesion promoter with a compound including at least two phenolic groups.
  • adhesion promoters may result in a poor stability of the inkjet ink.
  • a second requirement is that the solder mask has to be able to withstand the severe conditions during typical finishing processes, such as soldering (solder resistance) and ENIG plating (ENIG plating resistance).
  • soldering solder resistance
  • ENIG plating ENIG plating resistance
  • EP-A 4032958 discloses a radiation curable inkjet ink to prepare a solder mask, wherein the ink comprises a polymerizable compound, a phenolic resin and a thermal cross-linking agent. The combination of these compounds ensures a good adhesion and a good ENIG plating resistance.
  • EP-A 1624001 discloses an inkjet ink for solder mask printing comprising a (meth)acrylate monomer including a thermosetting functional group.
  • WG2020/109769 discloses an inkjet ink for solder mask printing comprising a reactive monomer, an oligomer of prepolymer containing at least one epoxy or oxetane functional group, a free radical polymerizable compound, a thermal cross-linking agent and a radical initiator.
  • EP-A 3778793 discloses an inkjet ink for solder mask printing, comprising a photopolymerizable monomer with a cyclic skeleton and a shrinkage of less than 10%, which results in an improved heat resistance before ENIG plating.
  • the object of the invention is realized by the curable composition as defined in claim 1.
  • monofunctional in e.g. monofunctional polymerizable compound means that the polymerizable compound includes one polymerizable group.
  • difunctional in e.g. difunctional polymerizable compound means that the polymerizable compound includes two polymerizable groups.
  • polyfunctional or “multifunctional” in e.g. polyfunctional polymerizable compound means that the polymerizable compound includes more than two polymerizable groups.
  • alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. methyl, ethyl, for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethyl-propyl, 2,2-di methyl propyl and 2- methyl-butyl, etc.
  • a substituted or unsubstituted alkyl group is preferably a Cj to C 6 -al kyl group.
  • a substituted or unsubstituted alkenyl group is preferably a C 2 to C 6 -alkenyl group.
  • a substituted or unsubstituted alkynyl group is preferably a C 2 to C 6 -al kynyl group.
  • a substituted or unsubstituted alkaryl group is preferably a phenyl or naphthyl group including one, two, three or more Cj to C 6 -al kyl groups.
  • a substituted or unsubstituted aralkyl group is preferably a C 7 to C 20 -alkyl group including a phenyl group or naphthyl group.
  • a substituted or unsubstituted aryl group is preferably a phenyl group or naphthyl group.
  • a substituted or unsubstituted heteroaryl group is preferably a five- or six-membered ring substituted by one, two or three oxygen atoms, nitrogen atoms, sulphur atoms, selenium atoms or combinations thereof.
  • substituted in e.g. substituted alkyl group means that the alkyl group may be substituted by other atoms than the atoms normally present in such a group, i.e. carbon and hydrogen.
  • a substituted alkyl group may include a halogen atom or a thiol group.
  • An unsubstituted alkyl group contains only carbon and hydrogen atoms.
  • a substituted alkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted aralkyl group, a substituted alkaryl group, a substituted aryl and a substituted heteroaryl group are preferably substituted by one or more constituents selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tertiary- butyl, ester, amide, amine, ether, thioether, ketone, aldehyde, sulfoxide, sulfone, sulfonate ester, sulphonamide, -Cl, -Br, -I, -OH, -SH, -CN and -NO 2 .
  • an alkyl, a cycloalkyl or an aryl interrupted by a heteroatom means that a heteroatom in present in the carbon chain of said group, for example -C-O-C-C- or -C-S-C-C-.
  • the curable inkjet composition according to the present invention comprises at least one photopolymerizable compound, at least one blocked isocyanate compound and at least one triazine compound, characterized in that a. the total amount of blocked isocyanate compounds and triazine compounds is at least 3 wt% relative to the total weight of the inkjet composition; and b. the amount of triazine compounds is at least 0.6 wt% relative to the total weight of the inkjet composition.
  • the composition is preferably a radiation-curable composition. Any type of radiation may be applied, but preferred radiation types are UV-light and UV- LED light. Therefore, the curable composition according to the present invention is preferably a UV-curable composition.
  • the curable composition according to the present invention is preferably also a thermally curable composition. Any type of heat source may be used for the thermal curing step, but preferably the thermal curing is performed in an oven.
  • the combination of a blocked isocyanate compound and a triazine compound is believed to be contributing to both the ENIG resistance and solder resistance by combining the reactivity of the blocked isocyanate compound and the rigidity and hardness of the triazine compound. By combining both, a good balance can be obtained between adhesion, hardness, resistance to soldering heat, resistance to chemicals, and electrical insulating properties.
  • the sum of the amount of blocked isocyanate compound and triazine compound is at least 3 wt%, more preferably at least 4 wt%, most preferably at least 5 wt% relative to the total weight of the curable composition. It is possible that below 3 wt%, the sum of the amount of blocked isocyanate and triazine is not sufficient to obtain a good ENIG resistance and solder resistance.
  • the sum of the amount of blocked isocyanate and triazine compound is less than 7.5 wt%, more preferably less than 7 wt%, most preferably less than 6.5 wt%. Above 7.5 wt%, it is possible that more cracks will occur especially during thermal stress tests.
  • the curable composition according to the invention is preferably applied as an inkjet ink.
  • the viscosity of the curable inkjet ink is preferably no more than 20 mPa.s at 45 ° C, more preferably from 1 tol8 mPa.s at 45 ° C, and most preferably from 4 to 14 mPa.s at 45 ° C, all at a shear rate of 1000 s’ 1 .
  • a preferred jetting temperature is from 10 to 70 ° C, more preferably from 20 to 55 ° C, and most preferably from 25 to 50 ° C.
  • the surface tension of the curable inkjet ink is preferably from 18 to 70 mN/m at 25 ° C, more preferably from 20 to 40 mN/m at 25 ° C.
  • the curable composition of the present invention contains at least one blocked isocyanate compound.
  • a blocked isocyanate can be obtained by reacting an isocyanate with a blocking agent of choice.
  • a blocking agent is a protective group, which is cleaved off at elevated temperatures, for example during a thermal curing process.
  • the isocyanate compound can become available for reaction after de-blocking.
  • the isocyanate compound may be monofunctional, difunctional or multifunctional.
  • the isocyanate compound may be an aliphatic, an alicyclic or an aromatic isocyanate.
  • the isocyanate compound is a multifunctional isocyanate, it may comprise a combination of aliphatic, alicyclic or aromatic isocyanate functionalities.
  • aliphatic isocyanates include, without limitation, 1,6- hexamethylene diisocyanate (HDI or HMDI), isophorone diisocyanate (IPDI), l,3-(isocyanatomethyl)cyclohexane (hydrogenated XDI) , lysine diisocyanate (LDI), 2,2,4-tri methyl hexamethylene diisocyanate (TMDI), and dimeryl diisocyanate (DDI).
  • HDI or HMDI 1,6- hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • hydroxDI lysine diisocyanate
  • TMDI 2,2,4-tri methyl hexamethylene diisocyanate
  • DDI dimeryl diisocyanate
  • alicyclic isocyanates include, without limitation, isophorone diisocyanate (IPDI), methylcyclohexane 2,4-(2,6)-diisocyanate (hydrogenated TDI), and 4,4'-methylenebis(cyclohexylisocyanate) (hydrogenated MDI).
  • IPDI isophorone diisocyanate
  • TDI methylcyclohexane 2,4-(2,6)-diisocyanate
  • MDI 4,4'-methylenebis(cyclohexylisocyanate)
  • aromatic isocyanates include, without limitation, toluene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), 4,4' -d i - ph eny I - methanediisocyanate (MDI) and xylylene diisocyanate (XDI).
  • TDI toluene diisocyanate
  • NDI 1,5-naphthalene diisocyanate
  • MDI 4,4' -d i - ph eny I - methanediisocyanate
  • XDI xylylene diisocyanate
  • Examples also include adducts (e.g. trimethylol propane adducts), uretdiones, biurets, and isocyanurates of the isocyanates listed above.
  • adducts e.g. trimethylol propane adducts
  • uretdiones e.g. uretdiones
  • biurets e.g. uretdiones
  • Isocyanate compounds are preferably used in combination with a compound comprising active hydrogen functionalities, including, without limitation, alcohols, thiols, amines, water, or combinations thereof. Atmospheric moisture may also cause isocyanate cross-linking. When atmospheric moisture is reacting with an isocyanate, it may not be necessary to include a compound comprising active hydrogen functionalities in the curable composition.
  • the blocking agent can be chosen such that it will cleave off at a certain temperature, the so-called de-blocking temperature. Using a blocked isocyanate typically improves the storage stability of the inkjet ink.
  • Examples of the blocking agent include alcohols such as ethanol, n-propanol, isopropanol, t-butanol, and isobutanol; phenols such as phenol, chlorophenol, cresol, xylenol, and p-nitrophenol; alkylphenols such as p-t- butyl phenol , p- sec-butylphenol, p-sec-amylphenol, p-octylphenol, and p-nonylphenol; basic nitrogen-containing compounds such as 3-hydroxypyridine, 8- hydroxyquinoline, and 8-hydroxyquinaldine; active methylene compounds such as diethyl malonate, ethyl acetoacetate, and acetylacetone; acid amides such as acetamide, acrylamide, and acetanilide; acid imides such as succinimide and maleic imide; imidazoles such as 2-ethylimidazole and 2-
  • Especially preferred blocking agents are £ -caprolactam, 3,5-dimethylpyrazole (DMP), and methyl ethyl ketone oxime (MEKO).
  • a less preferred blocking agent is diethyl malonate.
  • Hindered secondary amines may be used as blocking agents for toxicology reasons.
  • Preferred hindered secondary amines are selected form the group consisting of ethyl-tert-butyl amine, diisopropyl amine, 2,6-dimethyl- piperidine, ethyl-isopropyl amine, di-tert-butyl amine and diisobutyl amine.
  • a preferred blocked isocyanate compound is a blocked HDI oligomer or a blocked IPDI oligomer.
  • Such an oligomer can be for example a trimethylol propane adduct, a biuret, or an isocyanurate.
  • IPDI and HDI oligomers are aliphatic multi-functional blocked isocyanates having some flexibility or mobility in their structure, which could contribute to the good adhesion during the ENIG plating process.
  • Particularly preferred blocked isocyanate compounds are Trixene Bl 7960, a HDI biuret blocked with 3,5-dimethylpyrazole, commercially available from Lanxess and Trixene BI7982, a HDI trimer blocked with 3,5-dimethylpyrazole, commercially available from Lanxess.
  • the inkjet composition may comprise a mixture of different blocked isocyanate compounds.
  • the amount of blocked isocyanate is preferably at least 1.5 wt%; more preferably at least 3 wt%, most preferably at least 4 wt% relative to the total weight of the inkjet composition.
  • the blocked isocyanate compound in the curable inkjet composition may improve the adhesion of the obtained cured film after soldering or ENIG plating.
  • the curable composition of the present invention comprises at least one triazine compound.
  • Triazines are a class of aromatic nitrogen-containing heterocycles having a planar six-membered benzene-like ring but with three carbons replaced with nitrogen atoms.
  • the presence of a triazine compound may improve the ENIG resistance because of the properties related to the rigidity and aromaticity of the triazine ring.
  • the triazine moiety is therefore believed to contribute to the mechanical properties and heat resistance of the cured film.
  • Any triazine compound may be used, for example guanamine, acetoguanamine, benzoguanamine, melamine and melamine-derivatives.
  • melamine-derivatives examples include CYMEL 303 LF (hexamethoxymethyl melamine) and CYMEL 1116 LF (methoxymethyl ethoxymethyl melamine).
  • Preferred triazine compounds are triazine compounds containing an unsaturated double bond, such as 2,4-diamino-6-vinyl-s-triazine; 2,4- dia mi no-6- methacryloyl oxyethyl -s-triazine; and 2,4-diamino-6-vinyl-s-triazine isocyanuric acid adduct.
  • a particularly preferred triazine compound has a chemical structure according to General Formula I,
  • Rl, R2 and R3 independently from each other represent a substituted or unsubstituted alkyl group
  • X preferably represents O or C, most preferably O.
  • Rl, R2 and R3 independently from each other represent a substituted or unsubstituted C1-C8 alkyl group. More preferably, Rl, R2 and R3 independently from each other represent a group selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, n-octyl, 2-ethyl hexyl.
  • Preferred triazine compounds according to General Formula I are commercially available from Allnex under the name Cymel® NF 2000A and from BASF under the name Larotact® 150.
  • Triazine compounds according to General Formula I have a unique crosslinking mechanism, different from other melamine-type thermal crosslinkers and blocked isocyanates. They can be used as the sole crosslinker or in combination with other crosslinkers such as amino resins or isocyanates.
  • the amount of the triazine compound is preferably at least 0.6 wt%, more preferably at least 0.8 wt%, most preferably at least 1 wt%, all relative to the total weight of the inkjet composition.
  • the curable inkjet composition according to the present invention contains one or more photopolymerizable compound.
  • Photopolymerizable compounds are preferably free radical polymerizable compounds.
  • the free radical polymerizable compounds may be monomers, oligomers and/or prepolymers. These monomers, oligomers and/or prepolymers may possess different degrees of functionality, i.e. a different amount of free radical polymerizable groups.
  • a mixture including combinations of mono-, di-, tri-and higher functional monomers, oligomers and/or prepolymers may be used.
  • the viscosity of the curable inkjet ink may be adjusted by varying the ratio between the monomers and oligomers.
  • the photopolymerizable compounds may also comprise functional groups, such as thiols, hydroxyls, amines, sulfonic acids, phosphoric acids, and carboxylic acids.
  • functional groups such as thiols, hydroxyls, amines, sulfonic acids, phosphoric acids, and carboxylic acids. Examples of hydroxyl-functionalized polymerizable compounds are those listed in paragraphs [0028] to [0029] in US2015/0090482A.
  • Preferred photopolymerizable compounds are those listed in paragraphs [0106] to [0115] in EP-A 1911814.
  • Especially preferred photopolymerizable compounds are selected from the group consisting of 2-ethyl hexyl acrylate, lauryl acrylate, stearyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, isobornyl acrylate, hexanediol diacrylate, trimethylolpropane triacrylate, polyethyleneglycol diacrylate, 2-phenoxyethyl acrylate, n-butyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, 2- ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, 3,3,5- trimethylcyclohexyl methacrylate, isobornyl methacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, polyethyleneglycol dimethacrylate and acryloyl morpholine
  • the curable inkjet composition preferably contains a photopolymerizable compound containing a vinyl group. More preferably, the vinyl group is a vinylether group, an N-vinyl amide group or an N-vinyl carbamate group. [0073] Preferred examples of photopolymerizable compounds containing a vinylether group or an N-vinylamide group are those listed in paragraphs [0047] to [0056] in EP-A 3686251.
  • a particularly preferred vinylether containing photopolymerizable compound is 2-(2-vinyloxyethoxy)ethyl acrylate, as it is advantageous in providing a good balance between the curability and the viscosity of the curable inkjet composition, especially when it is used in an amount of 5 wt%, preferably at least 7.5 wt% and most preferably at least 10 wt% based on the total weight of the curable inkjet composition.
  • Particularly preferred vinylamide containing photopolymerizable compounds are N-vinyl-2-pyrrolidone and N-vinylcaprolactam as they combine a high Tg with a good ink curability and a good adhesion of a cured ink layer to a recording medium.
  • the photopolymerizable compound containing an N-vinyl carbamate group is preferably a cyclic compound represented by General Formula II,
  • R4, R5, R6 and R7 independently from each other represent hydrogen, alkyl, cycloalkyl, or aryl and combinations thereof, any of which may be interrupted by heteroatoms. Any of R4 to R7 may represent the necessary atoms for forming a five-or six-membered ring.
  • R4, R5, R6 and R7 independently from each other represent hydrogen or a substituted or unsubstituted Cj to C 10 alkyl group.
  • Cyclic compounds according to General Formula II are often referred to as oxazolidinones.
  • a particularly preferred oxazolidinone is N - vi ny I -5- m ethy I -2 - oxazolidinone, also referred to as vinyl methyl oxazolidinone, or VMOX.
  • VMOX vinyl methyl oxazolidinone
  • Including VMOX improves the hardness of the cured ink layer, especially when it is used in an amount from 1 to 50 wt%, preferably from 2.5 to 40 wt%, and most preferably from 5 to 30 wt% based on the total weight of the curable inkjet composition.
  • VMOX has a low viscosity compared to other N- vinyl compounds, which makes it especially suitable for ink jet printing.
  • the photopolymerizable compound including a vinylether, an N-vinylamide or an N-vinyl carbamate may be used singly or in a combination of one or more polymerizable compounds including a vinylether, an N-vinylamide or an N- vinyl carbamate.
  • the curable inkjet composition preferably includes a photoinitiator, preferably a free radical photoinitiator.
  • a free radical photoinitiator is a chemical compound that initiates polymerization of monomers and oligomers when exposed to actinic radiation by the formation of a free radical.
  • a Norrish Type I initiator is an initiator which cleaves after excitation, yielding the initiating radical immediately.
  • a Norrish type 11 -initiator is a photoinitiator which is activated by actinic radiation and forms free radicals by hydrogen abstraction from a second compound that becomes the actual initiating free radical. This second compound is called a polymerization synergist or co-initiator. Both type I and type II photoinitiators can be used in the present invention, alone or in combination.
  • Suitable photoinitiators are disclosed in CRIVELLO, J.V., et al. Photoinitiators for Free Radical, Cationic and Anionic Photopolymerization. 2nd edition. Edited by BRADLEY, G. London, UK: John Wiley and Sons Ltd, 1998. p.276- 293.
  • free radical photoinitiators may include, but are not limited to, the following compounds or combinations thereof: benzophenone and substituted benzophenones; 1-hydroxycyclohexyl phenyl ketone; thioxanthones such as isopropylthioxanthone; 2-hydroxy-2-methyl-l- phenyl propan -1-one; 2- benzyl -2-di methylamino- (4- morpholinophenyl) butan-l-one; benzyl dimethylketal; 2-methyl-l- [4- (methylthio) phenyl] -2- morpholinopropan-l-one; 2,2-dimethoxy-l, 2-diphenylethan-l-one or 5,7- diiodo-3- butoxy-6-fluorone.
  • a preferred photoinitiator is a thioxanthone compound, such as Darocur ITX, an isomeric mixture of 2- and 4-isopropylthioxanthone.
  • acylphosphine oxide compound is an acylphosphine oxide compound.
  • the acylphosphine oxide compound may be selected from the group consisting of a mono-acylphosphine oxide and a di-acylphosphine oxide.
  • Preferred acylphosphine oxide photoinitiators are diphenyl (2,4,6- trimethylbenzoyl)phosphine oxide (TPO), ethyl (2,4,6-tri methyl benzoyl) phenyl phosphinate (TPO-L), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide) (BAPO), bis (2,6- dimethyl-benzoyl)-2,4,4-trimethylpentylphosphine oxide and 2,4,6-tri meth oxy benzoyl -di phenyl phosphine oxide.
  • TPO diphenyl (2,4,6- trimethylbenzoyl)phosphine oxide
  • TPO-L ethyl (2,4,6-tri methyl benzoyl) phenyl phosphinate
  • BAPO phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide
  • Photoinitiators are a -hydroxy-ketone Type I photoinitiators such as for example o I igo [2 - hyd roxy-2- methy I - 1 - [4- (1 - methy I vi ny I - phenyl]propanone] available as Esacure® KIP IT from IGM resins.
  • Type I photoinitiators such as for example o I igo [2 - hyd roxy-2- methy I - 1 - [4- (1 - methy I vi ny I - phenyl]propanone
  • a preferred amount of photoinitiator is from 0.2 to 20 wt%, more preferably from 0.5 to 10 wt%, most preferably from 1 to 8 wt%, particularly preferred from 1.5 to 6 wt%, all relative to the total weight of the curable inkjet composition.
  • the curable inkjet composition may additionally contain co-initiators.
  • co-initiators Suitable examples of coinitiators can be categorized in three groups:
  • tertiary aliphatic amines such as methyldiethanolamine, dimethylethanolamine, triethanolamine, triethylamine and N- methylmorpholine;
  • aromatic amines such as amylparadimethyl-aminobenzoate, 2-n- butoxyethyl-4-(dimethylamino) benzoate, 2- (di methylamino) -ethyl benzoate, ethyl-4-(dimethyl-amino)benzoate, and 2-ethylhexyl-4- (dimethylamino)benzoate; and
  • (meth)acrylated amines such as dialkylamino alkyl(meth)acrylates (e.g., diethyl-aminoethylacrylate) or N-morpholinoalkyl-(meth)acrylates (e.g., N- morpholi noethyl -acrylate).
  • dialkylamino alkyl(meth)acrylates e.g., diethyl-aminoethylacrylate
  • N-morpholinoalkyl-(meth)acrylates e.g., N- morpholi noethyl -acrylate
  • Preferred co-initiators are aminobenzoates.
  • a preferred low molecular aminobenzoate is Genocure® EPD from RAHN.
  • Particularly preferred aminobenzoate co-initiators are selected from the group consisting of polymerisable, oligomeric and polymeric aminobenzoate coinitiators.
  • the aminobenzoate co-initiators are oligomeric aminobenzoate derivatives.
  • Particularly preferred aminobenzoates are polyether derivatives of aminobenzoates, wherein the polyether is selected from the group consisting of poly(ethylene oxide), polypropylene oxide), copolymers thereof, and poly(tetrahydrofuran), ethoxylated or propoxylated neopentyl glycol, ethoxylated or propoxylated trimethylpropane and ethoxylated or propoxylated pentaerythritol.
  • the polyether is selected from the group consisting of poly(ethylene oxide), polypropylene oxide), copolymers thereof, and poly(tetrahydrofuran), ethoxylated or propoxylated neopentyl glycol, ethoxylated or propoxylated trimethylpropane and ethoxylated or propoxylated pentaerythritol.
  • oligomeric aminobenzoates are disclosed in W01996/33157 (Lambson Fine Chemicals Ltd.) and W02011/030089 (Sun Chemicals B.V.).
  • Typical examples of polyethylene glycol bis p-dimethylaminobenzoate are OMNIPOL ASA, commercially available from IGM Resins and Speedcure 7040, commercially available from Lambson Fine Chemicals.
  • oligomeric or polymeric co-initiators are for example ESACURE A198, a polyfunctional amine from IGM and SARTOMER® CN3755, an acrylated amine co-initiator from ARKEMA.
  • the curable inkjet composition may contain at least one inhibitor for improving the thermal stability of the ink.
  • Suitable commercial inhibitors are, for example, SumilizerTM GA-80, SumilizerTM GM and SumilizerTM GS produced by Sumitomo Chemical Co. Ltd.; GenoradTM 16, GenoradTM18 and GenoradTM 20 from Rahn AG; lrgastabTMUV10 and IrgastabTM UV22, TinuvinTM 460 and CGS20 from Ciba Specialty Chemicals; FloorstabTM UV range (UV-1, UV-2, UV-5 and UV-8) from Kromachem Ltd, AdditolTM S range (S100, S110, S120 and S130) from Cytec Surface Specialties.
  • the amount capable of preventing polymerization is determined prior to blending.
  • the amount of a polymerization inhibitor is preferably lower than 5 wt%, more preferably lower than 3 wt% of the total curable inkjet composition.
  • the curable inkjet composition may include an adhesion promoter to further optimize the adhesion of the cured composition to various surfaces, in particular a copper surface.
  • Any adhesion promoter may be used, for example those disclosed in W02004/026977 and W02004/105 both from AVECIA; W02017/009097 and W02020/104302 both from Agfa-Gevaert; and W02018/087059, W02018087052 W02018087056 and W02018087055, all from Agfa- Gevaert/Electra Polymers.
  • the curable inkjet composition may include one adhesion promoter or a combination of two, three or more different adhesion promoters.
  • the total amount of adhesion promoters is preferably from 0.1 to 20 wt%, more preferably from 0.5 to 15 wt%, most preferably from 1 to 10 wt%, all relative to the total weight of the inkjet composition.
  • an inkjet composition according to the present invention may have a sufficient adhesion, even after soldering, gold or ENIG plating, in the absence of an adhesion promoter.
  • the curable inkjet composition according to the present invention preferably does not contain an adhesion promoter.
  • the amount of adhesion promotor is preferably less than 2.5 wt%, more preferably less than 1 wt%, most preferably less than 0.5 wt %, relative to the total weight of the composition.
  • the curable inkjet composition preferably comprises a flame retardant.
  • Preferred flame retardants are inorganic flame retardants, such as Alumina Trihydrate and Boehmite; organo-phosphor compounds, such as organophosphates (e.g. triphenyl phosphate (TPP), resorcinol bis (diphenylphosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP)); organo-phosphonates (e.g. dimethyl methylphosphonate (DMMP)); and organophosphinates (e.g. aluminium di methyl phosph inate).
  • organophosphates e.g. triphenyl phosphate (TPP), resorcinol bis (diphenylphosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP)
  • organo-phosphonates e.g. dimethyl methylphosphonate (DMMP)
  • organophosphinates
  • Preferred flame retardants are disclosed in WG2019/121098.
  • the curable inkjet composition may be a substantially colourless inkjet ink or may include at least one colorant.
  • the colorant makes the temporary mask clearly visible to the manufacturer of conductive patterns, allowing a visual inspection of quality.
  • the inkjet ink is used to apply a solder mask it typically contains a colorant.
  • a preferred colour for a solder mask is green, however other colours such as black or red may also be used.
  • the colorant may be a pigment or a dye.
  • a colour pigment may be chosen from those disclosed by HERBST, Willy, et al. Industrial Organic Pigments, Production, Properties, Applications. 3rd edition. Wiley - VCH, 2004. ISBN 3527305769. Suitable pigments are disclosed in paragraphs [0128] to [0138] of W02008/074548.
  • Pigment particles in inkjet inks should be sufficiently small to permit free flow of the ink through the inkjet-printing device, especially at the ejecting nozzles. It is also desirable to use small particles for maximum colour strength and to slow down sedimentation. Most preferably, the average pigment particle size is not larger than 150 nm. The average particle size of pigment particles is preferably determined with a Brookhaven Instruments Particle Sizer BI90plus based upon the principle of dynamic light scattering.
  • the colorant in the curable inkjet ink is an anthraquinone dye, such as MacrolexTM Blue 3R (CASRN 325781-98- 4) from LANXESS.
  • Other preferred dyes include crystal violet and a copper phthalocyanine dye.
  • a preferred combination of colorants to obtain a green solder mask is a combination of a blue and a yellow colorant.
  • a combination of pigment yellow 150 and pigment blue 15:4 is used.
  • the colorant is present in an amount of 0.5 to 6.0 wt%, more preferably 0.75 to 2.5 wt%, based on the total weight of the curable inkjet ink.
  • the curable inkjet ink preferably contains a dispersant, more preferably a polymeric dispersant, for dispersing the pigment.
  • Suitable polymeric dispersants are copolymers of two monomers but they may contain three, four, five or even more monomers. The properties of polymeric dispersants depend on both the nature of the monomers and their distribution in the polymer. Copolymeric dispersants preferably have the following polymer compositions:
  • alternating polymerized monomers e.g. monomers A and B polymerized into ABABABAB
  • block copolymers e.g. monomers A and B polymerized into AAAAABBBBBB wherein the block length of each of the blocks (2, 3, 4, 5 or even more) is important for the dispersion capability of the polymeric dispersant;
  • graft copolymers consist of a polymeric backbone with polymeric side chains attached to the backbone
  • Suitable polymeric dispersants are listed in the section on “Dispersants”, more specifically [0064] to [0070] and [0074] to [0077], in EP-A 1911814.
  • polymeric dispersants are the following:
  • the curable inkjet composition may contain at least one surfactant, which may act as wetting agent, dispersant or emulsifier.
  • the surfactant can be anionic, cationic, non-ionic, or zwitter-ionic.
  • Suitable surfactants include fluorinated surfactants, fatty acid salts, ester salts of a higher alcohol, alkylbenzene sulfonate salts, sulfosuccinate ester salts and phosphate ester salts of a higher alcohol (for example, sodium dodecylbenzenesulfonate and sodium dioctylsulfosuccinate), ethylene oxide adducts of a higher alcohol, ethylene oxide adducts of an alkylphenol, ethylene oxide adducts of a polyhydric alcohol fatty acid ester, and acetylene glycol and ethylene oxide adducts thereof (for example, polyoxyethylene nonylphenyl ether, and SURFYNOLTM 104, 104H, 440, 465 and TG available from AIR PRODUCTS & CHEMICALS INC.).
  • Preferred surfactants are selected from fluorinated surfactants (such as fluorinated hydrocarbons) and silicone surfactants.
  • the silicone surfactants are preferably siloxanes and can be alkoxylated, polyether modified, polyether modified hydroxy functional, amine modified, epoxy modified and other modifications or combinations thereof.
  • Preferred siloxanes are polymeric, for example polydimethylsiloxanes.
  • Preferred commercial silicone surfactants include BYK TM 333, BYK TM 347 and BYK TM UV3510 from BYK Chemie.
  • the surfactant is a polymerizable compound.
  • Preferred polymerizable silicone surfactants include a (meth)acrylated silicone surfactant.
  • the (meth)acrylated silicone surfactant is an acrylated silicone surfactant, because acrylates are more reactive than methacrylates.
  • a preferred commercial acrylated surfactant is Ebecryl 1360 from Allnex.
  • the (meth)acrylated silicone surfactant is a polyether modified (meth)acrylated polydimethylsiloxane or a polyester modified (meth)acrylated polydimethylsiloxane.
  • the surfactant is present in the curable inkjet composition in an amount of 0 to 3 wt% based on the total weight of the curable inkjet composition.
  • the method of manufacturing an electronic device according to the present invention includes at least one step wherein a curable inkjet composition as described above is jetted and cured on a substrate.
  • the electronic device is a Printed Circuit Board (PCB).
  • the method of manufacturing a PCB includes a step wherein the solder mask composition is applied on the substrate via an inkjet printing step, followed with a UV-curing step and a heat treatment step.
  • the substrate is preferably a dielectric substrate containing an electrically conductive pattern, which typically comprises conductive pads electrically connected with each other using traces.
  • the dielectric substrate of the electronic device may be any non-conductive material.
  • the substrate is typically a paper/resin composite or a resin/fibre glass composite, a ceramic substrate, a polyester or a polyimide.
  • FR-4 is an example of a material frequently used as dielectric substrate.
  • the electrically conductive pattern is typically made from any metal or alloy which is conventionally used for preparing electronic devices such as gold, silver, palladium, nickel/gold, nickel, tin, tin/lead, aluminium, tin/aluminium and copper.
  • the electrically conductive pattern is preferably made from copper.
  • the substrate Before applying the solder mask composition, the substrate is preferably subjected to one or more pre-treatment processes. These processes can be mechanical or chemical, or a combination thereof.
  • a preferred pre-treatment process is chemical micro-etching, which typically results in micro-roughness on the substrate.
  • a so-called anti-bleeding treatment can be additionally applied to the micro-etched surface to prevent bleeding of the ink into the micro-pores and to improve print quality.
  • This anti-bleeding treatment typically comprises applying a coating layer on the substrate in order to adjust its surface energy, resulting in sharper contact angles and minimal bleeding of ink into micro-pores. Anti-bleeding treatments are preferably used when printing low-viscous compositions.
  • the process of inkjet printing the solder mask layer on a dielectric substrate with an electrically conductive pattern preferably comprises one or more printing steps as listed below.
  • the printing of so-called “ramps” comprises printing lines next to the copper traces. This preparative printing step ensures a sufficient coverage of the Cu traces. If no ramps are printed next to the copper traces, the cured solder mask may be too thin on the edges (also called shoulders) of the copper traces.
  • the thickness of the printed ramps is related to the height of the plated Cu traces. For plated Cu traces having a large height, a higher ramp ink thickness is required in order to have sufficient coverage on the Cu edges. For plated Cu traces with a lower height, a lower ramp thickness may be used.
  • the ramps preferably have a thickness of 0 to 80 pm, more preferably from 10 to 60 pm, most preferably from 20 to 40 pm.
  • the printing of so-called “dams” is usually done to indicate the contours of the entire solder mask layer. These dams are usually cured with higher curing energies to provide precise features and lines.
  • the thickness of the dams is preferably at least the same as the thickness of the full solder mask layer.
  • the thickness of the dams is more preferably higher than the thickness of the full solder mask layer, in order to avoid possible ink flow towards the open pad.
  • the dams preferably have a thickness of 5 to 75 pm, more preferably from 10 to 60 pm, most preferably from 20 to 40 pm.
  • the curable inkjet composition may be cured by exposing the composition to actinic radiation, such as electron beam or ultraviolet (UV) radiation.
  • actinic radiation such as electron beam or ultraviolet (UV) radiation.
  • UV radiation Preferably the curable inkjet composition is cured by UV radiation, more preferably using UV LED curing.
  • a UV pin curing step may be used immediately after printing. This UV pin curing may improve the print quality.
  • a heat treatment is preferably applied to the jetted and UV-cured curable inkjet composition.
  • the heat treatment is preferably carried out at a temperature between 80 ° C and 250 ° C.
  • the temperature is preferably not less than 100° C, more preferably not less than 120 ° C.
  • the temperature is preferably not higher than 200 ° C, more preferably not higher than 160 ° C.
  • the thermal treatment is typically carried out from 15 to 90 minutes.
  • the purpose of the thermal treatment is two-fold: curing thermal cross-linking agents present in the curable composition, and further polymerizing potentially non-reacted radiation curable compounds. A dense interpenetrating polymer network can thus be created.
  • the method of manufacturing a PCB may comprise two, three or more inkjet printing steps.
  • the method may comprise two inkjet printing steps wherein an etch resist is provided on a metal surface in one inkjet printing step and wherein a solder mask is provided on a dielectric substrate containing an electrically conductive pattern in another inkjet printing step.
  • a third inkjet printing step may be used for legend printing.
  • Inkjet printing devices
  • the curable inkjet composition may be jetted by one or more print heads ejecting small droplets in a controlled manner through nozzles onto a substrate, which is moving relative to the print head(s).
  • a preferred print head for the inkjet printing system is a piezoelectric head. Piezoelectric inkjet printing is based on the movement of a piezoelectric ceramic transducer when a voltage is applied thereto. The application of a voltage changes the shape of the piezoelectric ceramic transducer in the print head creating a void, which is then filled with ink. When the voltage is again removed, the ceramic expands to its original shape, ejecting a drop of ink from the print head.
  • the inkjet printing method according to the present invention is not restricted to piezoelectric inkjet printing. Other inkjet print heads can be used and include various types, such as a continuous type.
  • the inkjet print head normally scans back and forth in a transversal direction across the moving ink-receiving surface (substrate). Often the inkjet print head does not print on the way back. Bi-directional printing is preferred for obtaining a high areal throughput.
  • Another preferred printing method is by a “ single pass printing process”, which can be performed by using page wide inkjet print heads or multiple staggered inkjet print heads which cover the entire width of the ink-receiving surface. In a single pass printing process, the inkjet print heads usually remain stationary and the ink-receiving surface is transported under the inkjet print heads.
  • VEEA is 2-(vinylethoxy)ethyl acrylate available from NIPPON SHOKUBAI, Japan
  • PEA is 2-phenoxyethyl acrylate available as SartomerTM SR339 from ARKEMA.
  • ACMO is acryloyl morpholine available from RAHN.
  • VMOX is vinyl methyl oxazolidinone available from BASF.
  • EHMA is 2-ethyl hexyl methacrylate.
  • PEGDA is polyethyleneglycol diacrylate available as SartomerTM SR259 from ARKEMA.
  • DAROCUR ITX is an isomeric mixture of 2- and 4-isopropylthioxanthone from BASF.
  • BAPO is a bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide photoinitiator available as IrgacureTM 819 from BASF.
  • BISAPHOS is a flame retardant containing a mixture of aromatic polyphosphates available from ADEKA.
  • Trixene BI7960 is a 70 wt% solution in methoxypropanol of trifunctional DMP- blocked biuret cross-linking agent commercially available from LANXESS.
  • Trixene BI7982 is a 70 wt% solution in methoxypropanol of trifunctional DMP- blocked isocyanurate crosslinking agent commercially available from LANXESS.
  • Trixene Bl 7963 is a 70 wt% solution in methoxypropanol of malonate blocked HDI biuret crosslinking agent commercially available from LANXESS.
  • Cymel NF2000A is a 50 wt% solution in butanol of a triazine cross-linking agent according to General Formula I commercially available from ALLNEX.
  • CYMEL 303 LF is 2,4,6-tris[bis(methoxymethyl)amino]-l,3,5-triazine, a triazine compound commercially available from ALLNEX.
  • CYMEL 1116 LF is a methoxymethyl ethoxymethyl melamine, a triazine compound commercially available from ALLNEX.
  • Ebecryl 1360 is a silicone hexa-acrylate available from ALLNEX.
  • WET is a 1% solution of Ebecryl 1360 in VEEA.
  • Cyan is SUN FAST BLUE 15:4, a cyan pigment available from SUN CHEMICALS.
  • Yellow is CROMOPHTAL YELLOW D 1085J, a yellow pigment from BASF.
  • INHIB is a mixture forming a polymerization inhibitor having a composition according to Table 1.
  • CupferronTM AL is aluminium N-nitrosophenylhydroxylamine from WAKO CHEMICALS LTD.
  • PRECIP 162 is a dispersing agent and has been precipitated from Disperbyk 162, a dispersant solution available from BYK (ALTANA).
  • DISP is a solution of 30 wt% PRECIP 162 and 1 wt% INHIB in VEEA.
  • GD is a green dispersion prepared as follows:
  • a concentrated green dispersion, GD was prepared having a composition according to Table 2.
  • GD was prepared as follows: 138 g of VEEA, 2 g of INHIB, 30 g of DISP, 30 g of Cyan and 30 g of Yellow were mixed using a DISPERLUXTM dispenser. Stirring was continued for 30 minutes.
  • the vessel was connected to a NETZCH MiniZeta mill filled with 900 g of 0.4 mm yttrium stabilized zirconia beads (“high wear resistant zirconia grinding media” from TOSOH Co.). The mixture was circulated over the mill over 120 minutes (residence time of 45 minutes) and a rotation speed in the mill of about 10.4 m/s. During the complete milling procedure, the content in the mill was cooled to keep the temperature below 60° C. After milling, the dispersion was discharged into a vessel.
  • the viscosity at 45 ° C and at a shear rate of 1000 s’ 1 is preferably from 5.0 to 15 mPa.s. More preferably the viscosity at 45° C and at a shear rate of 1 000 s’ 1 is less than 15 mPa.s.
  • the boards were dipped in a bath of acid cleaner (Umicore cleaner 865) at 40 ° C during 4 min. The boards were then removed and dipped in a rinsing bath of deionized water (DW) at room temperature (RT) during 90 seconds.
  • acid cleaner Umicore cleaner 865
  • DW deionized water
  • the boards were dipped in a microetching bath comprising 8.5 wt% Na 2 S 2 0 8 and ⁇ 3.2 wt% H 2 SO 4 (98 %) in water at a temperature between 26-33 ° C for 100 s. The boards were then removed and rinsed in respectively DW, a 2.5 wt% aqueous H 2 SO 4 solution and DW, all at RT during 90 seconds.
  • the boards were dipped in 2.5 wt% aqueous H 2 SO 4 solution at RT during 30 seconds after which they were removed and rinsed in DW at RT during 90 seconds. They were then dipped again in the same solution during 60 seconds.
  • the boards were dipped in a palladium activator bath (Accemulta MKN 4) at a temperature around 30 ° C for 90 s followed by dipping in a 5 wt% aqueous H 2 SO 4 solution at RT during 75 seconds. The boards were then removed and dipped in a rinsing bath of DW at RT during 90 seconds.
  • a palladium activator bath Accelemulta MKN 4
  • solder resistance of the inkjet inks was evaluated using a SPL600240 Digital Dynamic Solder Pot available from L&M PRODUCTS filled with a TSC puralloy SN100C solder alloy available from SOLDER CONNECTION.
  • the temperature of the solder was set at 290 ° C.
  • solder flux SC7560A from SOLDER CONNECTION was applied on the surface of the samples to clean the surface.
  • the solder flux was dried by placing the samples for 1 minute on each side above the solder pot. The remaining flux was wiped off with a soft tissue.
  • the curable inkjet composition Ex-1 to Ex-4 and the comparative curable inkjet composition Comp-1 to Comp-4 were prepared according to Table 3. The weight percentages are based on the total weight of the curable inkjet composition.
  • the inkjet inks were printed using a MicroCraft CPS2013D (Printhead Konica Minolta KM1024iS, UV LED 395 12 W total output of the lamp) on a checkerboard (copper plated on FR4) substrate from Eurocircuits to obtain a soldermask layer having a final thickness of +/- 22 pm.
  • the checkerboards include a 35 pm copper layer that was roughened by chemical etching.
  • the substrate was transported through a Bungard Sprint 3000 Conveyorized Spray Etch machine at a speed of 0.4 m/min while spraying with the chemical etchant CZ2001 (available from MEC) heated at 30° C.
  • Print-1 An image having a resolution 1440 dpi in the x-direction and 1440 dpi in the y-direction was printed and cured.
  • the UV energy applied corresponded to 10 % of the total power of the 12 W lamp.
  • a final cure was applied to further cure the printed solder mask layer (4 passes at full energy of the 12 W lamp).
  • Print-2 (P2): Compared to Print 1, the image was printed and cured in two passes to achieve a certain thickness and the UV energy applied corresponded to 100 % of the total power of the 12 W lamp. A final cure was then carried out as described for Print-1. [0192] The ENIG resistance was tested as described above. The results are shown in Table 4.
  • curable inks comprising a polymerizable compound, a blocked isocyanate and a triazine compound have a good stability and an improved ENIG resistance, when the triazine compound is present in an amount of at least 0.6 wt% (i.e. at least 1.2 wt% Cymel NF2000A) relative to the total ink composition.
  • the curable inkjet composition Ex-5 to Ex-7 and the comparative curable inkjet composition Comp-5 to Comp-6 were prepared according to Table 5. The weight percentages are based on the total weight of the curable inkjet composition.
  • curable inks comprising a polymerizable compound, a blocked isocyanate and a triazine compound have a good stability and an improved ENIG resistance when the sum of the amount of blocked isocyanate and triazine is at least 3 wt% (considering the actual concentration of blocked isocyanate and triazine in Cymel NF2000A and Trixene BI7960).
  • the sum of the amount of blocked isocyanate and triazine is at least 3 wt%, blistering and HALO effect start to reduce.
  • solder resistance was evaluated as described above. All inks had a perfect solder resistance after ENIG plating (not shown in the table).
  • the ENIG resistance is good.
  • the blocking agent is DMP or £ -caprolactam
  • the ENIG resistance is improved compared to a diethyl malonate blocking agent.
  • solder resistance was evaluated as described above. All inks had a good solder resistance after ENIG plating (not shown in the table).
  • solder resistance was evaluated as described above. All inks had a good solder resistance after ENIG plating (not shown in the table).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention concerne une composition de jet d'encre durcissable pour une carte de circuit imprimé, comprenant au moins un composé photopolymérisable, au moins un composé isocyanate bloqué et au moins un composé triazine, caractérisée en ce que a. la quantité totale de composés isocyanate bloqué et de composés triazine est d'au moins 3 % en poids par rapport au poids total de la composition de jet d'encre ; et b. la quantité de composés triazine est d'au moins 0,6 % en poids par rapport au poids total de la composition de jet d'encre.
PCT/EP2023/069979 2022-07-19 2023-07-19 Composition de jet d'encre durcissable pour la fabrication de cartes de circuit imprimé WO2024017926A1 (fr)

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WO2017009097A1 (fr) 2015-07-14 2017-01-19 Agfa-Gevaert Fabrication de cartes de circuit imprimé au moyen d'encre pour jet d'encre durcissable par radicaux libres induits par rayonnement uv
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