[go: up one dir, main page]

WO2003095506A1 - Compositions durcissables par rayonnement - Google Patents

Compositions durcissables par rayonnement Download PDF

Info

Publication number
WO2003095506A1
WO2003095506A1 PCT/EP2003/004849 EP0304849W WO03095506A1 WO 2003095506 A1 WO2003095506 A1 WO 2003095506A1 EP 0304849 W EP0304849 W EP 0304849W WO 03095506 A1 WO03095506 A1 WO 03095506A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrocarbo
ether
poly
ester
acrylate
Prior art date
Application number
PCT/EP2003/004849
Other languages
English (en)
Inventor
Kong Chin Chew
Norazmi Alias
Original Assignee
Ucb, S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ucb, S.A. filed Critical Ucb, S.A.
Priority to AU2003227739A priority Critical patent/AU2003227739A1/en
Publication of WO2003095506A1 publication Critical patent/WO2003095506A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines

Definitions

  • This invention relates to radiation curable compositions, which can be diluted/ dispersed in water, and may be used as liquid photo-resist compositions or additives for the fabrication of articles such as printed circuit boards.
  • the radiation curable compositions are removable when they are not cured by an aqueous alkaline water.
  • the circuitry images are defined by the cured composition area that remains after the alkaline removal of the uncured areas.
  • printed circuit boards are fabricated by applying a radiation curable coating to the copper surface of the board.
  • a negative film of the desired circuit image is then applied to the curable coating and the film is exposed to a UV light source.
  • the printed circuit board is washed in an aqueous alkaline solution to remove the coating areas that were not exposed to the UV light source.
  • the board is then etched to remove the uncoated copper regions.
  • Other imaging techniques may be used. In addition to this use for forming printed circuit boards, these techniques can be used to form other surfaces such as printing plate surfaces.
  • radiation curable compositions are termed photo-resist compositions.
  • Photo-imageable compositions useful as photo-resists in forming printed circuit boards are taught in US Patent 3,953,309.
  • the photo-imageable composition contains photo-polymerisable material to render it curable by irradiation, a photo-initiator system, and acid functional binder to allow for developing in alkaline solution.
  • acid groups such as carboxylic acid in the photo-polymerisable material is necessary to make the photo-resist compositions developable in alkaline solution.
  • the presence of the acid groups also allows the removal of the photo-cured composition, if required, by immersion in a second bath that is more alkaline than the developing bath solution.
  • this requirement is a disadvantage if it is desired that the cured coating remains and the subsequent processing solutions are alkaline.
  • the photo-polymerised portions would be subjected to degradation in the highly alkaline solution like the ammoniacal etchants or metal plating solutions. Under these conditions, such photo-resist would be subjected to delainination and stripping.
  • US Patent 4,943,516 teaches a photosensitive thermosetting composition containing a photosensitive polymer based on acid functional epoxy (meth.aciylates and a finely powdered epoxy compound useful in liquid photo-imageable solder mask.
  • the composition described in this patent is excellent in chemical and thermal resistance but lacks fast drying. Typically a long drying time is required to produce a tack-free surface prior to contact copying to image the circuit pattern onto the photo-resist coating. Attempts to speed the tack-free time by using ovens is usually unsatisfactory. Long residence times in an oven make the photo-resist susceptible to picking up dust particles and this can produce micro-defects during the subsequent photo-imaging step.
  • FR 2,253,772 teaches a photo-polymerisable composition for lithographic plates or a photo-resist and it comprises an addition copolymer of maleic anhydride with vinyl or styrene monomers. This copolymer is then esterifled with an ethylenically unsaturated alcohol or a polyol which itself is partially esterifled with an unsaturated aliphatic acid.
  • the unsaturated alcohol or polyol may contain alkoxy groups.
  • alkoxy (ethoxy or methoxy) groups may improve the alkaline developability of the unpolymerised region of the photo-resist but also degrades the acid and alkaline resistance of the cured photo-resist in the subsequent acidic or alkaline etching solution.
  • the incomplete opening of the anhydride (60-80% reacted) will subsequently reduce the alkaline developability of the photo-resist.
  • US Patent 5,296,334 teaches a polymerisable composition for use as a solder mask.
  • This composition contains a binder polymer made from the esterification product of a styrene maleic anhydride copolymer with less than 15% free anhydride, with at least 50% of the available anhydride groups esterifled with a hydroxy alkyl (meth.acrylate, and at least 0.1% of available anhydride groups being esterifled with monohydric alcohols. It also contains a multifunctional (meth)acrylate monomer and a multifunctional epoxide.
  • the use of high concentrations of (meth.acrylate monomers such as TMPTA, TPGDA or DPHA, increases the UV reactivity of the photo-resist. However, this generally adds to the tackiness of the photo-resist composition.
  • US Patent 4,370,403 teaches a polymerisable composition based on (a) reaction product of styrene maleic anhydride copolymer and 2-hydroxyethyl acrylate, (b) other ethylenically unsaturated compounds and (c) photo-initiator.
  • US Patent 4,722,947 describes a radiation curable polymer based on reaction of styrene/maleic anhydride copolymer with hydroxy alkyl acrylate and another alcohol, such as an arylalkyl monohydric alcohol.
  • styrene/maleic anhydride copolymer with hydroxy alkyl acrylate and another alcohol, such as an arylalkyl monohydric alcohol.
  • another alcohol such as an arylalkyl monohydric alcohol.
  • the presence of an alcohol with no acrylate unsaturation decreases the UV reactivity and the resultant UV cross-linking of the coating. This leads also to a reduction in the chemical resistance of the photo-resist in subsequent alkaline or acidic processing.
  • US Patent 4,723,857 describes the photo-imageable compositions containing styrene/maleic anhydride copolymer partially esterifled with methanol and isopropanol.
  • the resultant polymer is acidic in nature but contains no acrylate unsaturation to render it photo-polymerisable under ultraviolet irradiation.
  • photo-resist compositions have short tack-free times and relatively short times for dissolution in alkaline solution.
  • WO 98/457755 (Advanced Coatings International) describes certain waterborne dispersions of aliphatic urethane acrylate oligomers for use in making photo-resists.
  • the compositions require the addition of based such as ammonia, morpholine and potassium hydroxide to neutralize the acid groups to render the polymeric binder water soluble.
  • Ciba US Patents 5,691,006 and 5,501,942 and EP 493317 (Ciba) teaches the use of commercially available solid acid containing acrylic copolymers such as Carboset 525, XL37 and 531 which are neutralized with ammonia or amines before dispersion in water. Due to the high Tg of the binders, solvents are still required to dissolve the resins prior to neutralization.
  • US patent 5,045,435 describes waterborne and aqueous developable coating composition.
  • the examples describe usage of commercially available latex copolymer composition such as Neocryl CL-340, Acrysol 1-2074 and Neocryl BT-175 as the base polymer.
  • Neutralization is carried out with ammonia.
  • a tack free film is achieved after drying at 70 Celsius for 10 minutes.
  • US Patent 5,364,737 describes the use of an associative thickener based on a polyether polyurethane (such as Henkel's DSX-1514) to stabilize emulsions. This allows lesser neutralization with amines or ammonia, and increases the chemical resistance of the photoresist.
  • a polyether polyurethane such as Henkel's DSX-1514
  • the process for preparation of the waterborne photoresist contains two parts, one hydrophobic phase containing (meth) acrylate monomers, initiators, antoixidants and dyes, and another aqueous phase containing the acidic acrylic copolymer (Neocryl CL-340), antifoaming agent (Byk 033), neutralizers (DMAMP-90, and AMP-95) and associative thickener (DSX-1514) in water.
  • the hydrophobic phase and aqueous phase are blended to form a hydrophobic phase in water emulsion.
  • Surface tension modifier such as Fluorad FC170-C and up to 5% coalescing solvent such as methoxy propyl acetate are used.
  • Final composition has 20-40% solid, and typically 3-20% (meth) acrylate monomers mainly ethoxylated type like TMP(EO)TA.
  • PDMS polydimethoxysiloxane
  • amino acrylates for neutralization such as dimethylaminoethyl acrylate
  • tertiary aminoacrylates such as N.N- diethylaminoethyl acrylate, N,N-dimethylaminoetyhyl (meth)acrylate, and N,N- dimethylaminopropyl (meth) acrylate are also used. It is claimed that amino acrylates eliminate developing residue and etch retardation due to the higher solubility of the uncured resist in alkaline solution. It also gives a faster drying time and exposure time, and fewer pinholes, and finally faster stripping of the cured portion of the resist.
  • US Patent 5,942,371 describes an acid containing acrylate oligomer neutralized with ammonia, amine or an organic base to make the oligomer soluble or dispersible in water.
  • Epoxy acrylate further acidified with anhydride is the preferred oligomer.
  • the oligomer can contain up to 15% by weight of solvent.
  • Acid value of the COOH-containing oligomer prior to neutralization must be at least 25 mg KOH/gm but higher than 60 mg KOH/gm is preferred. This composition was tested for solder mask applications and was reported to give good results.
  • GB 878926A claims a composition based on reaction of a polymer containing a major proportion of anhydride units with:
  • X and Y are H or hydrocarbons of 1-20 C, and/ or:
  • EP 0365020A (Kanegafuchi Kagaky Kogyo) describes Michael addition of an amine (eg dodecylamine) with an urethane acrylate. This 'prepolymer' is then co- polymerised with other monomers (eg methyl methacrylate, methacrylic acid) to give final acrylic product. There is no Michael addition of an arninoalcohol to multifunctional (meth)acrylate.
  • EP 0731121A2 (BASF AG) describes urethane acrylates obtained by:
  • the present invention provides in one form a water-dilutable and/or dispersible radiation curable composition that is soluble in aqueous alkaline solution and which comprises the reaction product of a hydroxy functionalised amino (meth) acrylate with anhydride containing compounds.
  • the hydroxy functionalised amino (meth) acrylate is prepared from the Michael addition of a primary, or more preferably, a secondary amine to a multifunctional (methjacrylated monomer.
  • the amine compound shall be as described in Formula I,
  • Ri and R2 independently represent H or optionally substituted hydrocarbo, such as but not limited to, alkyl, aryl, cycloalkyl, arylalkyl, hydroxy alkyl, hydroxy aryl, hydroxy cycloalkyl and hydroxy cycloaryl.
  • R_ and Ra may also contain, within them, the organo linkages such as, but not limited to, (poly)amido, (poly)ester, (poly)urethane, (poly)urea, (poly)ether, and (poly)carbonate.
  • a further requirement is that Ri and R2 must not both represent H at the same time.
  • the multifunctional (meth)acrylated monomer can consist of material such as, but not limited to, trimethylolpropane tricarylate, pentaerithrytol tetraacrylate, tripropylene glycol diacrylate and dipentaerithrytol hexaacrylate.
  • the multifunctional (meth)acrylated monomer is represented in Formula II,
  • R a , R b and R c are independently H or methyl, preferably R a is methyl or H and R b and R c are both H;
  • Y is oxo (-0-), imino (-NH-) or hydrocarbo substituted imino (-NR 1 -, where R_ is hydrocarbo, preferably alkyl);
  • W represent a divalent optionally substituted organo linking moiety preferably selected from a group consisting of one or more optionally substituted hydrocarbo, hydrocarbo ether; poly(hydrocarbo ether); hydrocarbo ester, poly(hydrocarbo ester) and poly(hydrocarbo ether hydrocarbo ester); more preferably selected from the group consisting of: alkylene, alkylene ether, polyether, polyester, alkylene ester and polyether polyester; X represent a n-valent optionally substituted organo linking moiety preferably selected from a group consisting of one or more optionally substituted hydrocarbo, hydrocarbo ether; poly(hydrocarbo ether); hydrocarbo ester, poly(hydrocarbo ester) and poly(hydrocarbo ether hydrocarbo ester); more preferably selected from the group consisting of: alkylene, alkylene ether, polyether, polyester, alkylene ester and polyether polyester.
  • Formula II denotes a (meth) acrylate).
  • the anhydride containing compound is represented in Formula III.
  • n is 1 or greater; is 1 when p is 0.
  • m is 1 or greater, preferably 1 to 40.
  • Z represents an optionally substituted organo linking moiety selected from, but not limited to, a group consisting of one or more optionally substituted hydrocarbo, hydrocarbo ether; poly(hydrocarbo ether); hydrocarbo ester, poly(hydrocarbo ester) and poly(hydrocarbo ether hydrocarbo ester); alkylene, alkylene ether, polyether, polyester, alkylene ester and polyether polyester, oxo (-0-), or hydrocarbo substituted imino (-NRi-, where R_ is hydrocarbo, preferably alkyl).
  • R represents an optionally substituted organo linking moiety selected from, but not limited to, a group consisting of one or more optionally substituted hydrocarbo, hydrocarbo ether; poly(hydrocarbo ether); hydrocarbo ester, poly(hydrocarbo ester) and polyfhydrocarbo ether hydrocarbo ester); alkylene, alkylene ether, polyether, polyester, alkylene ester and polyether polyester, oxo (-0-), or hydrocarbo substituted imino (-NRi-, where R_ is hydrocarbo, preferably alkyl), such that each anhydride moiety forms a ring, the smallest, and most preferable of which is a flve-membered ring, with two atoms on R.
  • R is preferably selected from the group consisting of an optionally substituted alkyl, aryl, alkylene, alkynyl, and cycloalkyl, such that each anhydride moiety forms a ring, the smallest, and most preferable of which is a flve-membered ring, with two atoms on R.
  • R is preferably selected from a group consisting of one or more optionally substituted hydrocarbo, hydrocarbo ether; poly(hydrocarbo ether); hydrocarbo ester, poly(hydrocarbo ester) and poly (hydrocarbo ether hydrocarbo ester); alkylene, alkylene ether, aryl, polyether, polyester, alkylene ester and polyether polyester; such that the anhydride moieties form rings, the smallest, and most preferable of which is a flve-membered ring, with two atoms on R; more preferably R is an ethylene linkage combined with Z which is preferably a polyarylalkene such as polystyrene where the anhydride and the styrene exist as a copolymer; an example of which is the styrene-maleic anhydride copolymer shown in Formulae IIIA,
  • the anhydrides are preferred to be any cyclic (dfjcarboxylic anhydride such as, but not limited to, maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, bis(phenol)-A dianhydride, and benzophenone tetracarboxylic dianhydride.
  • High molecular weight, anhydride containing copolymers preferred is the styrene-maleic anhydride copolymer (SMA), at various ratios of styrene to maleic anhydride.
  • hydroxy containing compounds can also be used together with the hydroxy containing amino (methjacrylates.
  • the hydroxy containing compounds can be:
  • any optionally substituted monoalcohol or optionally substituted polyols such as, but not limited to, methanol, ethanol, (poly) ethylene glycol, methoxypropanol and trimethylolpropane.
  • R a , R b and R c are independently H or methyl, preferably R a is methyl or H and R b and R c are both H (i.e. Formula IV denotes a (meth)acrylate when Y is oxo);
  • W represents a divalent optionally substituted organo linking moiety preferably selected from a group consisting of one or more optionally substituted hydrocarbo, hydrocarbo ether; poly (hydrocarbo ether); hydrocarbo ester, poly (hydrocarbo ester) and poly (hydrocarbo ether hydrocarbo ester); more preferably selected from the group consisting of: alkylene, alkylene ether, polyether, polyester, alkylene ester and polyether polyester;
  • X represents a (n+l)valent optionally substituted organo linking moiety preferably selected from a group consisting of one or more optionally substituted hydrocarbo, hydrocarbo ether; poly(hydrocarbo ether); hydrocarbo ester, poly(hydrocarbo ester) and poly(hydrocarbo ether hydrocarbo ester); more preferably selected from the group consisting of: alkylene, alkylene ether, polyether, polyester, alkylene ester and polyether polyester;
  • Ra and Rs independently represent H or optionally substituted hydrocarbo, preferably optionally substituted alkyl, aryl, cycloalkyl, or arylalkyl Ri independently in each case represents a direct bond (i.e. where the OH is attached to the nitrogen or carbonyl) or a divalent optionally substituted organo linking moieiy, preferably optionally substituted hydrocarbo; more preferably optionally substituted alkylene, arylene, cycloalkylene, or arylalkylene; and m is 1 or greater.
  • the multifunctional (methjacrylated monomer of Formula II preferrably corresponds to the following:
  • a further step in this invention is the incorporation of (meth) acrylate unsaturation end or side groups of the N-containing Compound derived from reaction of compounds of Formulae I, II and III independently through the free carboxylic acid, COOH, with epoxy-containing compound bearing (meth) acrylate unsaturation.
  • This epoxy-containing compounds bearing (meth) acrylate unsaturation is shown as in Formula V and VI
  • R5 can be -CH2-, -O-alkyl-, etc, and Re is either H or CH3, and
  • R. can be -CH2-, -O-alkyl-, etc, and Rs is either H or CH3
  • the hydroxy containing amino compound of the present invention is prepared by the Michael addition of a primary or secondary amine to a (meth) acrylate group of a multifunctional monomer.
  • the reaction of the monomer with the amino alcohol is usually carried out in the presence of polymerisation inhibitors to prevent thermal polymerisation of the (meth) acrylate unsaturation.
  • Typical inhibitors used are hydroquinone and its derivatives, triphenyl antimony, and trisnonyl phenyl phosphite.
  • the inhibitors are usually added before the reaction is started.
  • the amine is added dropwise to the monomer (or vice versa), causing an exothermic temperature rise. The temperature is typically maintained below 50 Celsius during the addition. Upon completion of the exotherm, the reaction is maintained at 45 Celsius for about two hours before it is stopped.
  • Examples of the arnino alcohol include, but is not limited to, monomethylethanolamine, monoethylethanolamine, diethanolamine, ethanolamlne, butanolamine, and aminopolyethylene glycol monomethyl ether.
  • multifunctional monomer examples include, but not limited to, trimethylolpropane tricarylate, pentaerithrytol tetraacrylate, tripropylene glycol diacrylate and dipentaerithrytol hexaacrylate.
  • a similar reaction can also be carried out between an alkylamine and a hydroxy containing (meth) acrylate.
  • alkylamine include but not limited to, diethylamine, dibutylamlne, dipropylamine, and ethylene diamine.
  • hydroxy containing (meth) acrylates include, but not limited to, hydroxyethylacrylate, hydroxyethylmethacrylate, hydroxypropyl.
  • a further option is to perform a similar reaction between an amino alcohol and a hydroxy containing (meth)acrylate.
  • the reaction of the hydroxy containing amino acrylate and anhydrides is usually carried out without the presence of organic solvents in the case of low molecular weight mono- or dianhydrides and is usually carried out in the presence of solvents in the case of high molecular weight polymeric anhydrides.
  • Typical solvents used are propylene glycol mono methyl ether, propylene glycol mono methyl ether acetate, butyl ether glycol acetate, and butyl carbitol acetate.
  • the hydroxy containing amino acrylates is typically charged into a reaction vessel along with any polymerisation inhibitors to prevent thermal polymerisation of the (meth) acrylate unsaturation.
  • Typical inhibitors used are hydroquinone and its derivatives, triphenyl antimony, and trisnonyl phenyl phosphite.
  • other hydroxy containing compounds as outlined in Formula IV can also be added at this stage.
  • the temperature of the mixture is then raised to 70 or 80 Celsius.
  • the anhydride can then be added into the mixture, while maintaining the reaction temperature in the range of 100-110 Celsius. Complete reaction is established when the partial and total acid values are similar or when the total acid value remains constant over a period of time.
  • the solvent and preferably the hydroxy containing compounds of Formula IV are typically first charged into a glass vessel.
  • Polymerisation inhibitors are also added to prevent thermal polymerisation of the (meth) acrylate unsaturation.
  • Typical inhibitors used are hydroquinone and its derivatives, triphenyl antimony, and trisnonyl phenyl phosphite.
  • the mixture is heated to 100°C. At this temperature the polymeric anhydride may be added slowly.
  • the hydroxy containing amino (meth) acrylate may then be added into the solution in the vessel.
  • other non-(meth)acrylated hydroxy containing compounds can also be added at this stage.
  • the temperature is maintained at 100 to 110°C, and held until nearly all the anhydride groups are opened. Complete reaction can be established when the acid value of the reaction product nearly equals the acid value of the semi-ester.
  • a typical high molecular weight polymeric anhydride include the styrene- maleic anhydride copolymer.
  • Styrene maleic anhydride copolymers are commercially available resins such as SMA resins from Elf Atochem, and Leumal resins from Leuna Harze GmbH.
  • the preferred styrene maleic anhydride copolymer resins has molecular weight between 1000 and 100,000 and a mole ratio of styrene to maleic anhydride in the respective range of about (1 to 1) to about (3 to 1).
  • Suitable hydroxyl alkyl (meth)acrylates for partial esteriflcation with the styrene maleic anhydride copolymer are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, hydroxyl propyl methacrylate, n-methylol methaciylamide and n-methylol acrylamide.
  • Examples of hydroxyl monomers with more than one (meth)acrylate groups are ditrimethylopropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. (Meth)acrylate monomers with functionality greater than one are preferred when very high photosensitivity of the photo-resist composition is desired.
  • caproloactone containing hydroxyl (meth)acrylate examples are commercially available from Union Carbide Corporation under the trade names Tone M-100 and M-200.
  • alkoxy-containing hydroxyl (meth) acrylate examples include polyethyleneglycol monoacrylate, polyethyleneglycol monomethacrylate, polypropyleneglycol monoacrylate, polypropyleneglycol monomethacrylate, and mixtures of ethylene and propylene glycol such as polyalkyleneglycol monomethacrylate. Examples of these are available from Inspec under the trade names Bisomer PEM63P and PPM63E.
  • side chains may influence the overall solubility of the copolymer composition, especially in dilute alkaline solutions.
  • An example of a possible non (meth) acrylate side chain is methoxy polyethyleneglycol.
  • Another example is an alkanolamine of formula HONR 2 R 3 as well as an amido alcohol of formula HOR 3 (NHCO)m'R 2 ; where R 2 and/or R 3 may be independently alkyl, aryl, cycloalkyl, arylalkyl and m' is 1 or greater.
  • epoxy containing compound bearing (meth)acrylate unsaturation are but not limited to, glycidyl acrylate, glycidyl methacrylate, glycidyl methyl methacrylate, 4-hydroxybutylacrylate glycidyl ether, 3,4-epoxy-cyclohexyl methyl acrylate, and 3,4-epoxycyclohexyl methyl methacrylate.
  • Optional substituent' and/or Optionally substituted' as used herein signifies the one or more of following groups (or substitution by these groups): carboxy, sulpho, formyl, hydroxy, amino, imino, nitrilo, mercapto, cyano, nitro, methyl, methoxy and/or combinations thereof.
  • These optional groups include all chemically possible combinations in the same moiety of a plurality (preferably two) of the aforementioned groups (e.g. amino and sulphonyl if directly attached to each other represent a sulphamoyl group).
  • Preferred optional substituents comprise: carboxy, sulpho, hydroxy, amino, mercapto, cyano, methyl and/or methoxy.
  • Organic substituent' and "organic group” as used herein denote any univalent or multivalent moiety (optionally attached to one or more other moieties) which comprises one or more carbon atoms and optionally one or more other heteroatoms.
  • Organic groups may comprise organoheteryl groups (also known as organoelement groups) which comprise univalent groups containing carbon, which are thus organic, but which have their free valence at an atom other than carbon (for example organothio groups).
  • Organoheteryl groups also known as organoelement groups
  • Organic groups may alternatively or additionally comprise organyl groups which comprise any organic substituent group, regardless of functional type, having one free valence at a carbon atom.
  • Organic groups may also comprise heterocyclyl groups which comprise univalent groups formed by removing a hydrogen atom from any ring atom of a heterocyclic compound: (a cyclic compound having as ring members atoms of at least two different elements, in this case one being carbon).
  • the non carbon atoms in an organic group may be selected from: hydrogen, halo, phosphorus, nitrogen, oxygen and/or sulphur, more preferably from hydrogen, nitrogen, oxygen and/or sulphur.
  • hydrocarbo group' as used herein is a sub-set of a organic group and denotes any univalent or multivalent moiety (optionally attached to one or more other moieties) which consists of one or more hydrogen atoms and one or more carbon atoms.
  • Hydrocarbo groups may comprise one or more of the following groups.
  • Hydrocarbyl groups comprise univalent groups formed by removing a hydrogen atom from a hydrocarbon.
  • Hydrocarbylene groups comprise divalent groups formed by removing two hydrogen atoms from a hydrocarbon the free valencies of which are not engaged in a double bond.
  • organic groups comprise one or more of the following carbon containing moieties: alkyl, alkoxy, alkanoyl, carboxy, carbonyl, formyl and/or combinations thereof; optionally in combination with one or more of the following heteroatom containing moieties: oxy, thio, sulphinyl, sulphonyl, amino, imino, nitrilo and/or combinations thereof.
  • Organic groups include all chemically possible combinations in the same moiety of a plurality (preferably two) of the aforementioned carbon containing and/or heteroatom moieties (e.g. alkoxy and carbonyl if directly attached to each other represent an alkoxycarbonyl group):
  • any substituent, group or moiety mentioned herein refers to a monovalent species unless otherwise stated or the context clearly indicates otherwise (e.g. an alkylene moiety may comprise a bivalent group linked two other moieties).
  • a group which comprises a chain of three or more atoms signifies a group in which the chain wholly or in part may be linear, branched and/ or form a ring (including spiro and/or fused rings).
  • the total number of certain atoms may be specified for certain substituents for example C_- x organo, signifies an organic group having from 1 to x carbon atoms.
  • the substituent may replace any hydrogen atom attached to another atom and/ or may be located at any available position on the moiety which is chemically suitable and/ or where there is a free valence (which may be indicated in the formulae herein by an arrow).
  • organic groups such as hydrocarbo, alkyl etc listed herein do not have the number of carbon atoms specified in which case preferably such groups comprise from 1 to 36 carbon atoms, more preferably from 1 to 18 carbon atoms. It is particularly preferred that the number of carbon atoms in such groups is from 1 to 10 inclusive.
  • 'effective' (for example with reference to the process, uses, products, materials, compounds, monomers, oligomers, polymer precursors and/or polymers of the present invention) will be understood to refer to those ingredients which if used in the correct manner provide the required properties to the material, compound, composition, monomer, oligomer, polymer precursor and/or polymer to which they are added and/or incorporated in any one or more of the uses and/or applications described herein.
  • suitable denotes that a functional group is compatible with producing an effective product.
  • the substituents on the repeating unit may be selected to improve the compatibility of the materials with the polymers and/or resins in which they may be formulated and/or incorporated to form an effective material.
  • the size and length of the substituents may be selected to optimise the physical entanglement or interlocation with the resin or they may or may not comprise other reactive entities capable of chemically reacting and/or cross-linking with such other resins.
  • moieties, species, groups, repeat units, compounds, oligomers, polymers, materials, mixtures, compositions and/or formulations which comprise some or all of the invention as described herein may exist as one or more stereoisomers (such as enantiomers, diastereoisomers, geometric isomers, tautomers and/or conformers), salts, zwitterions, complexes (such as chelates, clathrates, crown compounds, cyptands / cryptades, inclusion compounds, intercalation compounds, interstitial compounds, ligand complexes, non-stoichiometric complexes, organometallic complexes, ⁇ -adducts, solvates and/or hydrates); isotopically substituted forms, polymeric configurations [such as homo or copolymers, random, graft or block polymers, linear or branched polymers (e.g.
  • star and/or side branched polymers such as those of the type described in WO 93/17060
  • hyperbranched polymers and/or dendritic macromolecules such as those of the type described in WO 93/17060
  • cross-linked and/or networked polymers polymers obtainable from di and/or tri-valent repeat units, dendrimers, polymers of different tacticity (e.g. isotactic, syndiotactic or atactic polymers)]; polymorphs [ such as interstitial forms, crystalline forms, amorphous forms, phases and/ or solid solutions] combinations thereof where possible and/or mixtures thereof.
  • the present invention comprises all such forms which are effective.
  • the multifunctional (mefh)acrylated monomer is represented as in Formula Ila:
  • n is an integer from 1 to 10;
  • R a , R b and R c are independently H or methyl, preferably R a is methyl or H and R b and R c are both H (i.e. Formula II denotes a (meth) acrylate);
  • X and W independently represent a divalent optionally substituted organo linking moiety preferably selected from a group consisting of one or more optionally substituted hydrocarbo, hydrocarbo ether; poly(hydrocarbo ether); hydrocarbo ester, polyChydrocarbo ester) and poly(hydrocarbo ether hydrocarbo ester); more preferably selected from the group consisting of: alkylene, alkylene ether, polyether, polyester, alkylene ester and polyether polyester;
  • Y is oxo (-0-), imino (-NH-) or hydrocarbo substituted imino (-NR_-, where R_ is hydrocarbo, preferably alkyl).
  • the hydroxy containing compounds can be compounds described by Formula IVa:
  • n is an integer from 1 to 7;
  • R a , R b and R° are independently H or methyl, preferably R a is methyl or H and R b and R c are both H (i.e. Formula I denotes a (meth) acrylate);
  • X and W independently represent a divalent optionally substituted organo linking moiety preferably selected from a group consisting of one or more optionally substituted hydrocarbo, hydrocarbo ether; poly (hydrocarbo ether); hydrocarbo ester, poly(hydrocarbo ester) and poly(hydrocarbo ether hydrocarbo ester); more preferably selected from the group consisting of: alkylene, alkylene ether, polyether, polyester, alkylene ester and polyether polyester;
  • Y is oxo (-0-), imino (-NH-) or hydrocarbo substituted imino (-NR_-, where R_ is hydrocarbo, preferably alkyl).
  • This Example illustrates the preparation of the hydroxy containing amino acrylates used in compositions according to the present invention.
  • TMPTA trimethylolpropane triacrylate
  • TNPP trisnonylphenylphosphite
  • TPS triphenyl stibine
  • MMEA monomethylethanolamine
  • oligomer B The amount of 600g TMPTA, 9.0g TNPP and 1.8g TPS was charged into a flask. To this mixture, 300g of MMEA was added over 60 minutes. The reaction temperature was maintained at below 50 Celsius during the exothermic reaction. Upon completion of the exotherm, the temperature was maintained at 45 Celsius for 2h to give a yellow liquid product. This oligomer was designated as oligomer B.
  • oligomer C The amount of 500g TMPTA, 9.7g TNPP and 1.9g TPS was charged into a flask. To this mixture, 412g of MMEA was added over 60 minutes. The reaction temperature was maintained at below 50 Celsius during the exothermic reaction. Upon completion of the exotherm, the temperature was maintained at 45 Celsius for 2h to give a yellow liquid product. This oligomer was designated as oligomer C.
  • This Example illustrates the preparation of low molecular weight amlno-acid (meth) acrylates according to the present invention.
  • oligomer D The amount of 380g of oligomer A was charged into a flask and to this was added l. lg of 4-ethylmorpholine, 0.3g of TPS, and 0.3g of hydroquinone (HQ). The mixture was heated to 75 Celsius before 150g phthalic anhydride (PA) was added over 20 minutes. An exothermic temperature rise was observed. The reaction was allowed to mature until all the anhydride was consumed. The final acid value was 112 mgKOH/g. This product was designated as oligomer D. The reaction is illustrated in Formulae VIB.
  • oligomer E The amount of 300g of oligomer B was charged into a flask and to this was added l.Og of 4-ethylmorpholine, 0.25g of TPS, and 0.25g of HQ. The mixture was heated to 65 Celsius before 197g PA was added over 20 minutes. An exothermic temperature rise was observed. The reaction was allowed to mature until all the anhydride was consumed. The final acid value was 163 mgKOH/g. This product was designated as oligomer E.
  • oligomer F The amount of 300g of oligomer B was charged into a flask and to this was added l.Og of 4-ethylmorpholine, 0.25g of TPS, and 0.25g of HQ. The mixture was heated to 87 Celsius before 203g tetrahydrophthalic anhydride (THPA) was added over 20 minutes. An exothermic temperature rise was observed. The reaction was allowed to mature until all the anhydride was consumed. The final acid value was 156 mgKOH/g. This product was designated as oligomer F.
  • THPA tetrahydrophthalic anhydride
  • This example illustrates the preparation of mixtures of low and high molecular weight amino acid acrylates.
  • This example illustrates the preparation of amino acid (methjacrylates based on pyromellitic dianhydride (PMDA).
  • This example illustrates the method of preparing high Tg and high molecular weight arnino-acid methacrylates based on styrene-maleic anhydride copolymer and a hydroxy containing amino acrylate.
  • the amount of 50.2g hydroxyethyl methacrylate (HEMA), 217g propylene glycol methyl ether acetate, 0.27g triphenyl stibine, and 0.27g hydroquinone are charged into a 1 litre glass vessel and the mixture was heated to 100 Celsius. 0.6g of 4-ethyl morpholine was then added into the mixture. The amount of 75.
  • SMA1000 Og styrene- maleic anhydride copolymer
  • This example evaluates the water dilutability of the resins D, E, F, G, H, J and K.
  • the evaluation was done by adding a certain amount of deionised water to a sample of each resin and to observe whether a homogeneous mixture was obtained or whether a separation into water and organic phases is observed.
  • heating was applied via a microwave oven or a conventional oven to shorten the dissolution time. The results are compiled in Table 1.
  • This example evaluates the ability of the amino-acid (meth)acrylates to impart water-dilutability/dispersibility property to usually water incompatible resins.
  • the amino-acid acrylates are first diluted in water. An amount of this diluted resin is then added into a water insoluble resin and the mixture is dispersed. The appearance of the mixture is checked for any signs of phase separation. More water can also be added to see if the mixture is able to absorb an extra amount of water.
  • Tack-free property is evaluated by applying a coating of the resin mixture onto a copper board and heating the board in an oven at 80 Celsius for 10 minutes or more. The film was rated as tack-free if no finger marks were left on the film surface.
  • the alkaline solubility of the copolymer (in 1% Na 2 C ⁇ 3 solution at 30°C) was dete ⁇ nined using a spraying unit containing the alkaline solution.
  • the amount of copolymer left on the board was checked after periodic spraying with the alkaline solution at intervals of 30 seconds.
  • ACA210P is methyl methacrylate / methacrylic resin acrylated with epoxy cyclohexyl acrylate, product of Daicel-UCB, Japan.
  • SRD1043 is an acid functionalised, rubber-modified epoxy novolac resin in 30% methoxy propyl acetate, product of UCB Chemicals.
  • SRD1074 is a styrene-maleic anhydride methacrylate half ester in 40% methoxy propyl acetate, product of UCB Chemicals.
  • This example evaluates the water dilutability, tack-free property and alkaline solubility of copolymer K.
  • copolymer K has allowed the incorporation of water into the resin, while retaining the tack-free property usually associated with SMA-(meth)acrylate half-esters.
  • the alkaline solubility is also remarkably good.
  • This example illustrates the process of low molecular weight product, finally capped with compound as described by Formula V.
  • TMPTA trimethylolpropane triacrylate
  • TNPP trisnonylphenylphosphite
  • TPS triphenyl stibine
  • MMEA monomethylethanolamine
  • This example illustrates the utility of Oligomer N in alkaline developable photoresist formulation.
  • Cyclomer-P ACA250 is unsaturated acrylic polymer commercially available from Daicel Chemicals. Pigment paste is prepared using 60 parts by weight of phthalocyanin blue pigment, in 40 parts dipentaerythritol hexaacrylate, which was milled to particle size of 5-10 um using triple rolled mill. Ebecryl 81 is an amino acrylate, commercially available from UCB Chemicals.
  • Formulations I, II and III are tested for alkaline developability, and sensitivity.
  • Each formulation is applied onto a pre-cleaned Cu board, using a wirebar coater, giving approximately 25-30 microns of wet film.
  • the coated board is placed in an oven at 80 Celsius for 2-5 minutes to flash off the solvent, and produced a tack-free surface of the coated board.
  • the coated board is exposed to a Fe-doped metal halide lamp, with power of 3 kilowatts, through a glass plate, and through a 21 -step Stouffer tablet.
  • the ultraviolet intensity at the coated surface is approximately 10 mW/cm2.
  • the exposure time is varied from 5 to 60 seconds.
  • the uncured portion of the coating is developed using 1% sodium carbonate solution at 35 Celsius for 1 minute. This leaves an image of the 21 -step Stouffer tablet on the coated board.
  • the number of steps remaining on the board is counted such that the highest number steps remain indicates the higher sensitivity of the formulation.
  • Table below indicates the last step remains on the board for the different formulation, and board exposed at different exposure time.
  • This example indicates formulation containing Oligomer N improves the sensitivity of photoresist, at lower exposure conditions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Selon un aspect, l'invention concerne une composition durcissable par rayonnement pouvant être diluée et/ou dispersée dans l'eau, qui est soluble dans une solution alcaline aqueuse et qui comprend le produit de réaction d'un (méth)acrylate amino fonctionnalisé hydroxy avec des composés contenant des anhydrides. Ledit (méth)acrylate amino fonctionnalisé hydroxy est préparé selon l'addition de Michael d'une amine primaire, ou idéalement secondaire à un monomère (méth)acrylaté multifonctionnel. Le composé amine est représenté par la formule générale (I), dans laquelle R1 et R2 représentent indépendamment H ou un hydrocarbure éventuellement substitué, de type, de façon non exhaustive, alkyle, aryle, cycloalkyle, arylalkyle, hydroxy alkyle, hydroxy aryle, hydroxy cycloalkyle et hydroxy cycloaryle. R1 et R2 peuvent également contenir, en eux, les liaisons organo de type, de façon non exhaustive, (poly)amide, (poly)ester, (poly)uréthane, (poly)urée, (poly)éther, et (poly)carbonate. En outre, R1 et R2 ne doivent pas représenter H en même temps.
PCT/EP2003/004849 2002-05-10 2003-05-09 Compositions durcissables par rayonnement WO2003095506A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003227739A AU2003227739A1 (en) 2002-05-10 2003-05-09 Radiation curable compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI20021704 2002-05-10
MYPI20021704 2002-05-10

Publications (1)

Publication Number Publication Date
WO2003095506A1 true WO2003095506A1 (fr) 2003-11-20

Family

ID=29417492

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/004849 WO2003095506A1 (fr) 2002-05-10 2003-05-09 Compositions durcissables par rayonnement

Country Status (3)

Country Link
AU (1) AU2003227739A1 (fr)
TW (1) TW200307696A (fr)
WO (1) WO2003095506A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008074759A1 (fr) * 2006-12-21 2008-06-26 Agfa Graphics Nv Nouvelles compositions durcissables par rayonnement
US8110610B2 (en) 2006-12-21 2012-02-07 Agfa Graphics N.V. Amine co-initiators for radiation curable compositions
US8338499B2 (en) 2006-12-21 2012-12-25 Agfa Graphics Nv Amine co-initiators for radiation curable compositions
CN115945445A (zh) * 2022-12-29 2023-04-11 常州银河世纪微电子股份有限公司 Dfn或qfn封装件切割残胶去除方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB878926A (en) * 1958-03-31 1961-10-04 Goodrich Co B F Improvements in and relating to polymers
FR2139090A1 (fr) * 1971-05-25 1973-01-05 Bayer Ag
EP0326723A1 (fr) * 1988-02-01 1989-08-09 Rohm And Haas Company Procédé de réaction de deux composants, compositions, compositions de revêtement et leur application
EP0365020A2 (fr) * 1988-10-21 1990-04-25 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Composition résineuse et son utilisation
EP0447845A2 (fr) * 1990-03-07 1991-09-25 BASF Aktiengesellschaft Composés uréthane acrylate durcissables par de l'irradiation contenant des groupes amine et urée
EP0687713A1 (fr) * 1994-06-13 1995-12-20 Dow Corning Corporation Composition de revêtement durcissable par irradiation et à base d'oligomères
DE19653631A1 (de) * 1996-12-20 1998-06-25 Basf Coatings Ag Verfahren zum Herstellen von durch Strahlung vernetzbaren polymeren Acryl- oder Methacrylsäureestern
EP1167395A1 (fr) * 2000-06-19 2002-01-02 Toagosei Co., Ltd. Compositions de résines réticulables

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB878926A (en) * 1958-03-31 1961-10-04 Goodrich Co B F Improvements in and relating to polymers
FR2139090A1 (fr) * 1971-05-25 1973-01-05 Bayer Ag
EP0326723A1 (fr) * 1988-02-01 1989-08-09 Rohm And Haas Company Procédé de réaction de deux composants, compositions, compositions de revêtement et leur application
EP0365020A2 (fr) * 1988-10-21 1990-04-25 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Composition résineuse et son utilisation
EP0447845A2 (fr) * 1990-03-07 1991-09-25 BASF Aktiengesellschaft Composés uréthane acrylate durcissables par de l'irradiation contenant des groupes amine et urée
EP0687713A1 (fr) * 1994-06-13 1995-12-20 Dow Corning Corporation Composition de revêtement durcissable par irradiation et à base d'oligomères
DE19653631A1 (de) * 1996-12-20 1998-06-25 Basf Coatings Ag Verfahren zum Herstellen von durch Strahlung vernetzbaren polymeren Acryl- oder Methacrylsäureestern
EP1167395A1 (fr) * 2000-06-19 2002-01-02 Toagosei Co., Ltd. Compositions de résines réticulables

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008074759A1 (fr) * 2006-12-21 2008-06-26 Agfa Graphics Nv Nouvelles compositions durcissables par rayonnement
US8110610B2 (en) 2006-12-21 2012-02-07 Agfa Graphics N.V. Amine co-initiators for radiation curable compositions
US8338499B2 (en) 2006-12-21 2012-12-25 Agfa Graphics Nv Amine co-initiators for radiation curable compositions
CN115945445A (zh) * 2022-12-29 2023-04-11 常州银河世纪微电子股份有限公司 Dfn或qfn封装件切割残胶去除方法

Also Published As

Publication number Publication date
TW200307696A (en) 2003-12-16
AU2003227739A1 (en) 2003-11-11

Similar Documents

Publication Publication Date Title
TWI778003B (zh) 負型光硬化性樹脂組成物、乾薄膜、硬化物及印刷配線板
CA2127238C (fr) Compositions photopolymerisables
WO2010117056A1 (fr) Résine photodurcissable et composition de résine photodurcissable
TW201732422A (zh) 硬化性樹脂組成物、乾膜、硬化物及印刷配線板
JP2008174515A (ja) 塩基増殖剤及び感光性樹脂組成物
WO2003078494A1 (fr) Resines durcissables et compositions de resines durcissables les contenant
JP4705311B2 (ja) 紫外線硬化性樹脂組成物および同組成物を含むフォトソルダーレジストインク
US4144283A (en) Curable coating compositions
EP0180466B1 (fr) Composition photopolymérisable utilisée comme mère pour l'obtention d'une réserve pour l'attaque chimique
JP2010077283A (ja) 多分岐ポリエステル（メタ）アクリレート化合物
CN107817652B (zh) 感光性树脂组合物和由其制造的光固化图案
WO2003095506A1 (fr) Compositions durcissables par rayonnement
US20040039100A1 (en) Radiation curable compositions
TW201942674A (zh) 光硬化性熱硬化性樹脂組成物及乾膜及硬化物以及印刷配線板
EP1629046A2 (fr) Compose polymere durcissant
JP3617398B2 (ja) 活性エネルギー線硬化型レジスト用組成物
EP0434098A2 (fr) Compositions photodurcissables aminées
WO2003095507A1 (fr) Compositions durcissables par rayonnement diluables/dispersibles dans l'eau
JP2001181355A (ja) 活性エネルギー線硬化型組成物
KR0180973B1 (ko) 감광성 열경화제로 치환된 공중합성 단량체를 포함하는 감광성 열경화성 조성물
JPH1017614A (ja) 光硬化性樹脂
JP4043884B2 (ja) 水性光重合性樹脂組成物の製造方法及び水性光重合性樹脂組成物
JP2009098455A (ja) 感光性樹脂組成物およびそれを用いて得られるカバー絶縁層を有するフレキシブルプリント配線回路基板
JP2002003563A (ja) カリックスアレーン誘導体及びそれを含有するアルカリ現像型光硬化性組成物
TWI841408B (zh) 感光性樹脂組成物、感光絕緣層、軟性電路板的乾膜光阻及油墨塗料

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP