WO2003095507A1 - Compositions durcissables par rayonnement diluables/dispersibles dans l'eau - Google Patents

Compositions durcissables par rayonnement diluables/dispersibles dans l'eau Download PDF

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WO2003095507A1
WO2003095507A1 PCT/EP2003/004865 EP0304865W WO03095507A1 WO 2003095507 A1 WO2003095507 A1 WO 2003095507A1 EP 0304865 W EP0304865 W EP 0304865W WO 03095507 A1 WO03095507 A1 WO 03095507A1
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hydrocarbo
optionally substituted
ether
poly
ester
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PCT/EP2003/004865
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English (en)
Inventor
Kong Chin Chew
Norazmi Alias
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Ucb, S.A.
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Priority to AU2003239855A priority Critical patent/AU2003239855A1/en
Publication of WO2003095507A1 publication Critical patent/WO2003095507A1/fr

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    • 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
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages

Definitions

  • This invention relates to radiation curable compositions which can be diluted with (and /or dispersed in) water, and may be used as liquid photo-resist compositions 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 imagining 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.
  • 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. 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. It is desirable that 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 carboxylic 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 5,741,621 and EP 747769/A2 describe process for using photoimageable films prepared for aqueous photoimageable liquid emulsions.
  • Polymer based on methyl methacrylate/ethyl acrylate/styrene/methacrylic acid prepared by emulsion polymerisation using persulfate initiator (based on NH 4 + or Na + salts) is preferred to give stable polymer emulsion. It is thought that the charged sulfate group introduced onto the surface of emulsion particles may serve to stabilise the resulting emulsion by raising the electrical potential of the emulsion particles.
  • US patent 5,045,435 describes waterbome and aqueous developable coating composition.
  • Neocryl CL-340 a commercially available latex copolymer composition
  • Acrysol 1-2074 a commercially available latex copolymer composition
  • Neocryl BT-175 a commercially available latex copolymer composition
  • 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 waterbome 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 acrylate for neutralization such as dimethylaminoethyl acrylate
  • acrylate 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.
  • the present invention provides in one form a water-dilutable and/or dispersible radiation curable composition that is developable in aqueous alkaline solution and which comprises the reaction product of a (meth)acrylated polymeric binder containing acid group with a primary, or more preferably, a secondary amine containing compound of Formula I,
  • Ri and R 2 independently represent H or optionally substituted hydrocarbo, such as alkyl, aryl, cycloalkyl, arylalkyl, hydroxy alkyl, hydroxy aryl, hydroxy cycloalkyl and hydroxy cycloaryl. Ri and R 2 may also contain, within them, the organo linkages such as (poly)amido, (poly)ester, (poly)urethane, (polyjurea, (poly)ether, and (poly)carbonate. A further requirement is that Ri and R 2 must not both represent H at the same time.
  • a radiation curable composition made from the reaction of the compounds of Formula I with an unsaturated carboxylic acid functionalised copolymer made via (meth)acrylic polymerisation of Formula IA:
  • Ri and R 2 independently represent optionally substituted hydrocarbo, hydrocarbo ether; poly(hydrocarbo ether); hydrocarbo ester, poly(hydrocarbo ester) and poly(hydrocarbo ether hydrocarbo ester); preferably optionally substituted alkyl, aryl, cycloalkyl, or arylalkyl and where the molecular weight of the copolymer is preferably 1000-100000, the acid value is preferably 50-300 mgKOH/g and the unsaturated functionality is 1-100; m and n are 1 or greater than 1.
  • the reaction of the amine-containing compound of formula I with the unsaturated carboxylic acid functionalised copolymer of formula IA is partial and provides a reaction product containing carboxylic group, (meth)acrylate functionality and amine functionality.
  • the acid containing (meth)acrylated polymeric binder can be a composition which comprises of:
  • 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 I denotes a (meth)acrylate);
  • 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+1) 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;
  • Y is oxo (-0-), imino (-NH-) or hydrocarbo substituted imino (-NRi-, where Ri is hydrocarbo, preferably alkyl); (b) optionally, a partial esterification product of a styrene maleic anhydride copolymer with one or more hydroxyl containing compounds of the following formulae:
  • R 2 and R3 independently represent H or optionally substituted hydrocarbo, preferably optionally substituted alkyl, aryl, cycloalkyl, or arylalkyl; 4 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 moiety, preferably optionally substituted hydrocarbo; more preferably optionally substituted alkylene, arylene, cycloalkylene, or arylalkylene; and m is 1 or greater.
  • the acid containing (meth) acrylate polymeric binder may also be of a composition which comprises of:
  • 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 H (i.e. Formula II denotes a (meth)acrylate) when Y is oxo;
  • X' represents a (n+1) 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;
  • 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;
  • Y" is oxo (-0-), imino (-NH-) or hydrocarbo substituted imino (-NR'i-, where R' ⁇ is hydrocarbo, preferably alkyl); (b) optionally a partial esteriflcation product of a styrene maleic anhydride copolymer with one or more hydroxyl containing compounds of the following formulae: HO
  • R'2 and R' 3 independently represent H or optionally substituted hydrocarbo, preferably optionally substituted alkyl, aryl, cycloalkyl, or arylalkyl
  • R' 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 moiety, preferably optionally substituted hydrocarbo; more preferably optionally substituted alkylene, arylene, cycloalkylene, or arylalkylene; and t is 1 or greater.
  • unsaturated carboxylic acid containing acrylic polymer derived from the reaction of (I) carboxylic acid containing acrylic polymer and unsaturation- containing epoxide, or (II) epoxide containing acrylic polymer and acrylic acid, or methacrylic acid or (meth)acrylic acid esters.
  • An example is the commercially available unsaturated carboxylic acid containing acrylic polymer, Cyclomer-P ACA series from Daicel Chemical, Japan.
  • the preferred molecular weight of such binders is 1000-100,000; the preferred acid value is 50-2000 mgKOH/g; the preferred functionality is between 5 and 50.
  • the copolymer of the present invention is prepared by the Michael addition of a primary or secondary amine to a (meth) acrylate group of a solvent-based acid containing (meth)acrylated polymeric binder.
  • acid containing (meth)ac ⁇ ylated polymeric binder examples include commercially available acrylic resins such as Cyclomer-P ACA250 (copolymer of methyl methacrylate/methacrylic acid, functionalized with 3, 4- epoxycyclohexylmethacrylate, product of Daicel Chemical, Japan).
  • the acid containing (meth)acrylated polymeric binder is the copolymer preferably prepared by esteriflcation of at least 50 mole % of the free anhydride groups in the styrene maleic anhydride copolymer with hydroxy alkyl (meth)acrylates, and less than 50 mole % of the free anhydride groups with caprolactone - or alkoxy - containing hydroxy (meth)acrylates.
  • the reaction is preferably carried out with an excess of hydroxyl groups.
  • the reaction of the anhydride and hydroxyl monomers is usually carried out in the presence of organic solvents.
  • TyP ica l solvents used for liquid photo-resist systems are propylene glycol mono methyl ether, propylene glycol mono methyl ether acetate, butyl ether glycol acetate, and butyl carbitol acetate.
  • the solvent is typically first charged into a glass vessel and heated slowly to 60°C. At this temperature a styrene maleic anhydride copolymer may be added along with polymerisation inhibitors to prevent thermal polymerisation of the (meth)acrylate unsaturation.
  • Typ ica l inhibitors used are hydroquinone and its derivatives triphenyl antimony, and trionyl phenyl phosphite.
  • the hydroxyl (meth)acrylate monomer may then be added into the copolymer solution in the vessel.
  • the temperature can then be increased to 90°C to 100°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.
  • the first is by reacting the styrene maleic anhydride copolymer separately with two different types of hydroxyl (meth)acrylates, and then blending these two different copolymers such that the mixture contains partial esteriflcation products of the styrene maleic anhydride with two different hydroxyl (meth) acrylates.
  • the second method is to react the styrene maleic anhydride copolymer simultaneously with two different hydroxyl (meth) acrylates.
  • a typical structure of a copolymer of the invention is:
  • R is a divalent alkyl ester, divalent alkyl ether moiety, and/or
  • R2 and R3 independently represent optionally substituted hydrocarbo, preferably optnioally substituted alkyl, aryl, cycloalkyl, or arylalkyl;
  • Ri independently in each case represents a direct bond or a divalent optionally substituted organo linking moiety, preferably optionally substituted hydrocarbo; more preferably optionally substituted alkylene, arylene, cycloalkylene, or arylalkylene e, f, g and/or h preferably independently represent 1 or greater, more preferably an integer from 1 to 7 (inclusive); and k and 1 independently represent 0 or an integer from 1 to 7 (inclusive).
  • m is 1 or greater, preferably 1 ;
  • R is
  • R2 and R3 independently represent H or optionally substituted hydrocarbo, preferably optionally substituted alkyl, aryl, cycloalkyl, or arylalkyl
  • Rt independently in each case represents a direct bond or a divalent optionally substituted organo linking moiety, preferably optionally substituted hydrocarbo; more preferably optionally substituted alkylene, arylene, cycloalkylene, or arylalkylene. More preferably when 1 is from 1 to 7 then R is a divalent alkyl ester or divalent alkyl ether moiety.
  • 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 30,000 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 methacrylamide 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.
  • caprolactone containing hydroxyl (meth) acrylate 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. It is not essential that all the maleic anhydride rings of the copolymer are reacted with (meth) acrylate monomers. For example, minor amounts of amine or hydroxyl containing moieties may be used to form non (meth)acrylate amide or ester side chains respectively.
  • 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 4 (NHCO) m R 2 ; where R 2 and/or R 3 may be independently alkyl, aryl, cycloalkyl, arylalkyl and m' is 1 or greater.
  • the reaction of the (meth)acrylated polymeric binder with the amine is usually carried out in the presence of polymerisation inhibitors to prevent thermal polymerisation of the (meth) acrylate unsaturation.
  • TyP ica l 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 polymeric binder, 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.
  • the amount of amine compound to be reacted to the (meth)acrylated polymeric binder is between 0.1 and 0.9 amine equivalent for each double bond equivalent of the (meth)acrylate functionality.
  • 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.
  • organo 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).
  • Organo 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.
  • Hydrocarbylidene groups comprise divalent groups (represented by formed by removing two hydrogen atoms from the same carbon atom of a hydrocarbon, the free valencies of which are engaged in a double bond; Hydrocarbylidyne groups comprise trivalent groups (represented by "RC ⁇ "), formed by removing three hydrogen atoms from the same carbon atom of a hydrocarbon the free valencies of which are engaged in a triple bond. Hydrocarbo groups may also comprise any saturated, unsaturated double and/or triple bonds (e.g. alkenyl, and/or alkynyl respectively) and/or aromatic groups (e.g. aryl) and where indicated may be substituted with other functional groups.
  • 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): The term 'alkyl' or its equivalent (e.g.
  • 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).
  • Parts of some chemical terms used herein are given in parentheses and unless the context dictates otherwise (e.g. parentheses in an IUAPC name), these denote that the parenthetic moiety is optional.
  • the term "(meth)acrylate” denotes both methacrylate and acrylate.
  • 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.
  • the term "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 acid containing (meth)acrylated polymeric binder can be a composition which comprises of:
  • n is an integer from 1 to 7;
  • R a , R b and R c are independently H or methyl, preferably R a is methyl or H and R 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 (-NRi-, where Ri is hydrocarbo, preferably alkyl);
  • This Example illustrates the preparation of copolymer used in compositions according to the present invention.
  • the amount of 195.4 grams of the styrene maleic anhydride copolymer, SMA 3000 (having a molecular weight of 10,000 and styrene to maleic anhydride mole ratio of 3 to 1 and available commercially from Elf Atochem under the SMA 3000 trade designation) and 180 grams of propylene glycol methyl ether acetate were charged to a stirred one litre three-neck glass vessel and heated to 85-90°C to dissolve the copolymer. To this solution 0.27 grams of hydroquinone and 0.27 grams of triphenyl stibene inhibitors were added.
  • This Example illustrates the preparation of copolymer compositions according to the present invention.
  • copolymer B The amount of 166 grams of copolymer A was charged into a 400ml beaker, followed by 20g monomethylethanolamine (MMEA). The mixture is stirred for 30 minutes where an exothermic temperature rise is observed. A soft material is formed, physically separated from the solvent. This amine adduct is designated copolymer B.
  • MMEA monomethylethanolamine
  • copolymer C The amount of 299 grams of copolymer A was charged into a 500ml vessel and is stirred continuously at room temperature. 39.9 g diethylamine (DEA) is then added slowly over 20 minutes. An exothermic temperature rise is observed, and controlled to below 50 Celsius. When the exo therm is over, the reaction temperature is maintained at 45 Celsius for 2h to give the amine-modified copolymer designated as copolymer C.
  • DEA diethylamine
  • This example illustrates the water dilutability of the copolymers B, C and D.
  • mixture E Into a 50 ml beaker, charge 20 g of copolymer B. Under continuous agitation, 6 g of deionised water was added. A homogeneous mixture was formed, designated as mixture E.
  • mixture F Into a 50 ml beaker was charged 20 g of copolymer C. Under continuous agitation, 5 g of deionised water was added to give a homogeneous mixture designated as mixture F.
  • mixture G Into a 50 ml beaker was charged 20 g of copolymer D. Under continuous agitation, add 13 g of deionised water. A homogeneous mixture was formed, designated as mixture G.
  • Example 4 This example evaluates the tack-free and alkaline developability of the water diluted mixtures E, F and G.
  • a copolymer was coated onto a cleaned copper board using a #16 wire drawdown bar to give an approximately 20-30 ⁇ m thick wet film.
  • the coated board was then placed in an 80°C oven. The tackiness was checked at 5 minute intervals commencing immediately after the board was removed from the oven.
  • the copolymer film was rated as tack-free if no finger marks were left on the film surface.
  • the solubility of the copolymer in 1% Na 2 C0 3 solution at 30°C was determined 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.
  • copolymers B, C and D are beneficial in conferring water dilutable properties, as shown in Example 3, in preparing the mixtures E, F and G.
  • copolymer A and the commercial resin Cyclomer-P ACA250 are not water dilutable by themselves.
  • a further advantage is that the present embodiment, as shown by mixtures E and F, has improved the tack free property and alkaline solubility of the parent copolymer A.

Abstract

Selon un aspect, l'invention concerne une composition durcissable par rayonnement diluable et/ou dispersible dans l'eau pouvant être développée dans une solution alcaline aqueuse, et qui comprend le produit de réaction d'un liant polymère (méth)acrylé contenant un groupe acide avec une amine primaire, et idéalement une amine secondaire qui contient un composé de formule (I), dans laquelle: R1 et R2 représentent indépendamment H ou un hydrocarbure éventuellement substitué de type 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 (poly)amido, (poly)ester, (poly)uréthanne, (poly)urée, (poly)éther, et (poly)carbonate. R1 et R2 doivent en outre ne pas représenter H en même temps.
PCT/EP2003/004865 2002-05-10 2003-05-09 Compositions durcissables par rayonnement diluables/dispersibles dans l'eau WO2003095507A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003239855A AU2003239855A1 (en) 2002-05-10 2003-05-09 Water-dilutable/dispersible radiation curable compositions

Applications Claiming Priority (2)

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MYPI20021687 2002-05-10
MYPI20021687 2002-05-10

Publications (1)

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WO2003095507A1 true WO2003095507A1 (fr) 2003-11-20

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006039013A1 (fr) * 2004-10-01 2006-04-13 Basf Corporation Polymères d’addition portant des fonctions carbamate et méthode de préparation desdits polymères
CN115397929A (zh) * 2020-04-14 2022-11-25 汉高股份有限及两合公司 消声材料组合物

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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
EP0035574A1 (fr) * 1979-08-28 1981-09-16 ARAI, Tokuji Composition de resine photo-polymerisable sensible a la lumiere et materiau en feuilles sensible a la lumiere
US4722947A (en) * 1985-08-05 1988-02-02 Pony Industries, Inc. Production of radiation curable partial esters of anhydride-containing copolymers
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
US5045435A (en) * 1988-11-25 1991-09-03 Armstrong World Industries, Inc. Water-borne, alkali-developable, photoresist coating compositions and their preparation
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 (11)

* 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
EP0035574A1 (fr) * 1979-08-28 1981-09-16 ARAI, Tokuji Composition de resine photo-polymerisable sensible a la lumiere et materiau en feuilles sensible a la lumiere
US4722947A (en) * 1985-08-05 1988-02-02 Pony Industries, Inc. Production of radiation curable partial esters of anhydride-containing copolymers
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
US5045435A (en) * 1988-11-25 1991-09-03 Armstrong World Industries, Inc. Water-borne, alkali-developable, photoresist coating compositions and their preparation
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7342075B2 (en) 2002-10-31 2008-03-11 Basf Corporation Carbamate functional addition polymers and method for their preparation
WO2006039013A1 (fr) * 2004-10-01 2006-04-13 Basf Corporation Polymères d’addition portant des fonctions carbamate et méthode de préparation desdits polymères
CN115397929A (zh) * 2020-04-14 2022-11-25 汉高股份有限及两合公司 消声材料组合物

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AU2003239855A1 (en) 2003-11-11

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