WO2004001507A1 - Compositions comprenant un photo-initiateur de benzophenone - Google Patents

Compositions comprenant un photo-initiateur de benzophenone Download PDF

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Publication number
WO2004001507A1
WO2004001507A1 PCT/NL2003/000457 NL0300457W WO2004001507A1 WO 2004001507 A1 WO2004001507 A1 WO 2004001507A1 NL 0300457 W NL0300457 W NL 0300457W WO 2004001507 A1 WO2004001507 A1 WO 2004001507A1
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Prior art keywords
composition
group
photoinitiator
ether
free radical
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PCT/NL2003/000457
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English (en)
Inventor
John Alan Lawton
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Dsm Ip Assets B.V.
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Priority claimed from PCT/NL2002/000408 external-priority patent/WO2003001295A1/fr
Application filed by Dsm Ip Assets B.V. filed Critical Dsm Ip Assets B.V.
Priority to AU2003247228A priority Critical patent/AU2003247228A1/en
Publication of WO2004001507A1 publication Critical patent/WO2004001507A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0037—Production of three-dimensional images

Definitions

  • the present invention relates to compositions comprising a benzophenone photoinitiator.
  • the present invention relates to applications for such compositions, such as their use in rapid prototyping processes.
  • aging stability is generally a relevant parameter.
  • a cured article may yellow over time, which is undesirable in a wide variety of applications, for instance because it may decrease the transparency of the article.
  • One of the objectives of the present invention is to decrease these undesirable effects.
  • curable compositions are set forth in, for instance, U.S. Patent 5,352,712; U.S. Patent 5,418,112; U.S. Patent 5,434,196; U.S. Patent 5,476,748; U.S. Patent 5,476,749; U.S. Patent 5,707,780; 5,849,459; U.S. Patent 5,972,563; U.S. Patent 6,136,497; U.S. Patent Application 09/379,781 ; U.S. Patent Application 10/091 ,119; and European Application 0360869; all of which are hereby incorporated in their entirety by reference.
  • the present invention provides, inter alia, compositions having a benzophenone photoinitiator.
  • the present invention provides a composition comprising, as pre-mixture ingredients, (i) at least one free radical curable component; (ii) at least one cationically curable component; (iii) at least one free radical photoinitiator (iii) selected from the group consisting of benzophenones.
  • the present invention provides a composition
  • a composition comprising, as pre-mixture ingredients, (i) at least one free radical curable component; and (ii) 0.01 to less than 0.50 wt% of a free radical photoinitiator selected from the group consisting of benzophenones.
  • Figure 1 depicts curves representing the transparency of a cured composition versus the benzophenone content of the composition.
  • Figure 2 depicts curves representing the color transparency of a composition versus the exposure time to radiation.
  • pre-mixture ingredients corresponds to the identity of components used for the present compositions prior to combining these components to form the present compositions. Accordingly, reactions that may occur between the several components after combining them are not taken into consideration.
  • (meth)acrylate is understood herein to include an acrylate and/or methacrylate.
  • the present compositions comprise one or more free radical polymerizable components.
  • the free radical polymerizable component may be monofunctional (i.e. comprise one free radical polymerizable group per molecule) or polyfunctional (i.e. comprise more than one free radical polymerizable group per molecule).
  • the compatible component comprises at least two free radical polymerizable groups, for instance 2, 3, 4, 5, or 6 free radical polymerizable groups.
  • the free radical polymerizable groups may be (meth)acrylate groups, for instance acrylate groups.
  • Suitable as the acrylic component are, for example, diacrylates of cycloaliphatic or aromatic diols, such as 1 ,4-dihydroxymethylcyclohexane, 2,2-bis(4- hydroxycyclohexyl)propane, 1 ,4-cyclohexanedimethanol, bis(4- hydroxycyclohexy
  • diacrylates of cycloaliphatic or aromatic diols such as 1 ,4-dihydroxymethylcyclohexane, 2,2-bis(4- hydroxycyclohexyl)propane, 1 ,4-cyclohexanedimethanol, bis(4- hydroxycyclohexy
  • compositions comprise a free radical polymerizable component having a functionality greater than 2 as the additional free radical polymerizable component.
  • a free radical polymerizable component having a functionality greater than 2 as the additional free radical polymerizable component.
  • These can be, for example, tri, tetra, penta, or hexafunctional monomeric or oligomeric aliphatic (meth)acrylates.
  • Suitable as aliphatic polyfunctional (meth)acrylates are, for example, the triacrylates and trimethacrylates of hexane-2,4,6-triol, glycerol, or 1,1 ,1 - trimethylolpropane, or 1,1 ,1 -trimethylolpropane and hydroxy group-containing tri(meth)acrylates which are obtained by, for instance, the reaction of triepoxy compounds with (meth)acrylic acid. It is also possible to use, for example,
  • (meth)acrylate-functional pentaerythritol derivates such as, for instance, pentaerythritol tri(meth)acrylate, dipentaerythritolpenta(meth)acrylate, or dipentaerythritolhexa(meth)acrylate.
  • (Meth)acrylate-functional neopentyl glycol derivatives e.g. alkoxylated neopentyl glycol di(meth)acrylates, are also suitable for use in the present compositions.
  • urethane (meth)acrylates are known to the person skilled in the art and can be prepared in known manner, for example by reacting a hydroxy-terminated polyurethane with acrylic acid or methacrylic acid, or by reacting an isocyanate-terminated prepolymer with hydroxyalkyl (meth)acrylates to form the urethane (meth)acrylate.
  • Hydroxyfunctional free radical polymerizable ester components have also been found to be useful in certain embodiments.
  • An example is, for instance, caprolactone acrylate.
  • the present compositions comprise 0-8wt% of caprolactone acrylate.
  • the present compositions comprise 0-
  • caprolactone acrylate 3 wt% of caprolactone acrylate.
  • the present compositions are absent caprolactone acrylate.
  • compositions comprise at least one free radical polymerizable component having a certain quantity of ether groups.
  • An ether group according to the present invention is a group represented by the following formula (1 ):
  • R represents a branched or unbranched, cyclic or non-cyclic aliphatic group comprising from 1 -10 carbon atoms, preferably 2-6 carbon atoms, more preferably 2-4 carbon atoms, and most preferably 2-3 carbon atoms.
  • R consists of carbon atoms and hydrogen atoms, but in certain embodiments some or all of these hydrogen atoms may be replaced with other atoms, preferably monovalent atoms, such as for instance halogen atoms.
  • R is non-cyclic.
  • the oxygen in formula (1 ) is bonded, besides to "R", to a cyclic or non-cyclic aliphatic hydrocarbon group or • an aromatic ring.
  • the free radical polymerizable component comprises at least one G t -C 10 ether group, for instance at least one C 2 -C 8 ether group or at least one C 2 -C ether group.
  • Free radical polymerizable components that are absent an aromatic ring-structure and that comprise at least one, for instance at least two, ether groups are also suitable for use in the present compositions.
  • the non-aromatic component comprising at least two ether groups comprises at least one ether group per free radical polymerizable group.
  • Monofunctional components that may be used as the non-aromatic component include, for instance alkoxylated isodecyl acrylate, alkoxylated isobornyl acrylate, and alkoxylated lauryl acrylate.
  • suitable non-aromatic compatible polyfunctional components include, for instance, tripropyleneglycol diacrylate, polypropyleneglycol dimethacrylate, alkoxylated neopentylglycol diacrylate, alkoxylated alkanediol diacrylates (e.g. ethoxylated or propoxylated hexanediol diacrylate), and alkoxylated trimethylolpropane triacrylate.
  • oligomeric components may be used, such as, for instance, polytetrahydrofuran poly(meth)acrylates, poly(oxyethylene- oxypropylene) random or block copolymer poly(meth)acrylates, and poly(oxyethylene- oxybutylene) random or block copolymer poly(meth)acrylates.
  • the number average molecular weight M n of the oligomeric components is preferably between 250-5000 g/mol, more preferably between 250-2000 g/mol, and most preferably between 250- 1250 g/mol.
  • non-aromatic free radical polymerizable components are not only absent aromatic ring structures but are also absent aliphatic ring structures.
  • Non-aromatic free radical polymerizable components include those represented by the following formula (2):
  • X represents a branched or unbranched aliphatic group comprising 1-10 carbon atoms, preferably 1 -6 carbon atoms, more preferably 3-5 carbon atoms; n represent an integer from 1 to 6, preferably 2-4, more preferably 2-3; each R independently represents a branched or unbranched, cyclic or non-cyclic aliphatic group comprising from 1 -10 carbon atoms, preferably 2-6 carbon atoms, more preferably 2-4 carbon atoms, and most preferably 2-3 carbon atoms.
  • R consists of carbon atoms and hydrogen atoms, but in certain embodiments some or all of these hydrogen atoms may be replaced with other atoms, preferably monovalent atoms, such as for instance halogen atoms.
  • R is non-cyclic; each m independently represents an integer from 0-10, preferably 1 -5, more preferably 1 -3; at least one m represents an integer of at least 1 , preferably at least 2; each A independently represents a free radical polymerizable group, preferably a (meth)acrylate group, more preferably an acrylate group.
  • formula (2) comprises components represented by the following formula (3):
  • n 2 is, for instance, propoxylated (1 +1 ) neopentylglycol diacrylate:
  • Aromatic components comprising one or more ether groups may be used in the present compostions. In one embodiment, it is preferred that the aromatic components comprise at least four ether groups. In a further embodiment, the aromatic component comprises more than two ether groups per free radical curable group, more preferably at least 4 ether groups per free radical curable group.
  • Monofunctional aromatic compatible components that may be used include, for instance, alkoxylated alkyl phenol acrylates (e.g. ethoxylated or propoxylated nonylphenol acrylate).
  • Polyfunctional aromatic compatible components may also be used, for instance components represented by the following formula (5):
  • Ai and A 2 independently represent a free radical polymerizable group, preferably a
  • (meth)acrylate group more preferably an acrylate group
  • R is the same as defined above; p represents an integer from 0 to 30, for instance 2 to 15 or 4 to 15. q represents an integer from 0 to 30, for instance 2 to 15 or 4 to 15. p+q is preferably at least 5, for instance at least 8 or at least 12; and
  • Y represents a branched or unbranched aliphatic group comprising 1-10 carbon atoms, for instance 1 -6 carbon atoms, 3-5 carbon atoms, or 3 carbon atoms.
  • An example of a compound represented by formula (5) is, for instance, ethoxylated (4+4) bisphenol A diacrylate:
  • the present compositions generally comprise, relative to the total weight of the composition, more than 2 wt% of free radical polymerizable component having one or more ether groups, e.g. at least 3 wt% or at least 5 wt%.
  • the present compositions generally comprise, relative to the total weight of the composition, at most 60 wt% of free radical polymerizable component having one or more ether groups, e.g at most 30 wt%, at most 15 wt%, or at most 10 wt%.
  • the composition comprises at least one polyfunctional ethylenically unsaturated component selected from the group consisting of ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, tricyclodecanediyldimethylene di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, tripropyiene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, both-terminal (meth)acrylic acid adduct of bisphenol A diglycidyl ether, 1 ,4-butanediol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, poly
  • compositions generally comprise, relative to the total weight of the composition, at least 5 wt% of at least one free radical polymerizable component, e.g. at least 10 wt% or at least 15 wt%. Overall, the compositions generally comprise, relative to the total weight of the composition, less than 70 wt% of at least one free radical polymerizable component, e.g. less than 50 wt%, less than 30 wt%, or less than 20 wt%.
  • the present invention may comprise a suitable cationically polymerizable component, such as, for instance, an epoxide-containing compound.
  • Epoxide-containing materials are cationically curable, by which is meant that polymerization and/or crosslinking and other reactions of the epoxy group can be initiated by cations.
  • These materials may be monomers, oligomers or polymers and are sometimes referred to as "resins.”
  • Such materials may have an aliphatic, aromatic, cycloaliphatic, arylaliphatic or heterocyclic structure; they can comprise epoxide groups as side groups or groups that form part of an alicyclic or heterocyclic ring system.
  • Epoxy resins of those types include those that are generally known and are commercially available.
  • the composition may contain one or more epoxy resins.
  • the composition will comprise at least one liquid (at room temperature, 23°C) component such that the combination of materials is a liquid.
  • the epoxide- containing material is preferably a single liquid epoxy material, a combination of liquid epoxy materials, or a combination of liquid epoxy material(s) and solid epoxy material(s) which is soluble in the liquid.
  • the epoxide material may be comprised only of materials that are solid at room temperature. When solid compositions are used, the compositions may be thinned or liquefied by applying shear and/or heat prior to or during use.
  • suitable epoxy materials include polyglycidyl and poly(methylglycidyl) esters of polycarboxylic acids, or poly(oxiranyl) ethers of polyethers.
  • the polycarboxylic acid can be aliphatic, such as, for example, glutaric acid, adipic acid and the like; cycloaliphatic, such as, for example, tetrahydrophthalic acid; or aromatic, such as, for example, phthalic acid, isophthalic acid, trimellitic acid, or pyromellitic acid.
  • the polyether can be poly(tetramethylene oxide).
  • Suitable epoxy materials also include polyglycidyl or poly(- methylglycidyl) ethers obtainable by the reaction of a compound having at least one free alcoholic hydroxy group and/or phenolic hydroxy group and a suitably substituted epichlorohydrin.
  • the alcohols can be acyclic alcohols, such as, for example, ethylene glycol, diethylene glycol, and higher poly(oxyethylene) glycols; cycloaliphatic, such as, for example, 1 ,3- or 1 ,4-dihydroxycyclohexane, bis(4-hydroxycyclohexyl)methane, 2,2- bis(4-hydroxycyclohexyl)propane, or 1 ,1-bis(hydroxymethyl)cyclohex-3-ene; or contain aromatic nuclei, such as N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2- hydroxyethylamino)diphenylmethane.
  • cyclic alcohols such as, for example, ethylene glycol, diethylene glycol, and higher poly(oxyethylene) glycols
  • cycloaliphatic such as, for example, 1 ,3- or 1 ,4-dihydroxycyclohexane, bis(4-hydroxycyclohe
  • Suitable epoxy compounds include those which may be derived from mono nuclear phenols, such as, for example, resorcinol or hydroquinone, or they may be based on polynuclear phenols, such as, for example, bis(4- hydroxyphenyl)methane (bisphenol F), 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), or on condensation products, obtained under acidic conditions, of phenols or cresols with formaldehyde, such as phenol novolacs and cresol novolacs.
  • mono nuclear phenols such as, for example, resorcinol or hydroquinone
  • polynuclear phenols such as, for example, bis(4- hydroxyphenyl)methane (bisphenol F), 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), or on condensation products, obtained under acidic conditions, of phenols or cresols with formaldehyde, such as phenol novolacs and cresol novolac
  • Suitable epoxy materials also include poly(N-glycidyl) compounds, which are, for example, obtainable by dehydrochlorination of the reaction products of epichlorohydrin with amines that comprise at least two amine hydrogen atoms, such as, for example, n-butylamine, aniline, toluidine, m-xylylene diamine, bis(4- aminophenyl)methane or bis(4-methylaminophenyl)methane.
  • poly(N-glycidyl) compounds which are, for example, obtainable by dehydrochlorination of the reaction products of epichlorohydrin with amines that comprise at least two amine hydrogen atoms, such as, for example, n-butylamine, aniline, toluidine, m-xylylene diamine, bis(4- aminophenyl)methane or bis(4-methylaminophenyl)methane.
  • Suitable poly(N-glycidyl) compounds also include N,N'-diglycidyl derivatives of cycloalkyleneureas, such as ethyleneurea or 1 ,3-propyleneurea, and N,N'-diglycidyl derivatives of hydantoins, such as of 5,5-dimethylhydantoin.
  • suitable epoxy materials include poly(S-glycidyl) compounds which are di-S-glycidyl derivatives which are derived from dithiols, such as, for example, ethane-1 ,2-dithiol or bis(4-mercaptomethylphenyl) ether.
  • Preferred epoxide-containing materials include those selected from the group consisting of bis(2,3-epoxycyclopentyl)ether, 2,3-epoxy cyclopentyl glycidyl ether, 1 ,2-bis(2,3-epoxycyclopentyloxy)ethane, bis(4-hydroxycyclohexyl)methane diglycidyl ether, 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, 3,4- epoxycyclohexylmethyl-3,4-epoxycyclohexane, 3,4-epoxy-6-methylcyclohexylmethyl- 3,4-epoxy-6-methylcyclohexanecaboxylate, di(3,4- epoxycyclohexylmethyl)hexanedioate, di(3,4-epoxy-6- methylcyclohexylmethyl)hexanedioate, ethylenebis(3,4-epoxycyclohex
  • epoxy resins in which the 1 ,2- epoxy groups are bonded to different heteroatoms or functional groups.
  • Those compounds include, for example, the N,N,O-triglycidyl derivative of 4-aminophenol, the glycidyl ether glycidyl ester of salicylic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-5,5- dimethylhydantoin, or 2-glycidyloxy-1 ,3-bis(5,5-dimethyl-1 -glycidylhydantoin-3- yl)propane.
  • liquid prereacted adducts of such epoxy resins with hardeners are suitable for epoxy resins.
  • the composition comprises at least one cycloaliphatic epoxide, for instance a cycloaliphatic diepoxide.
  • the compositions may comprise an epoxy component having at least one cyclohexeneoxide structure, for instance at least 2 cyclohexeneoxide structures.
  • the epoxy materials can have molecular weights which vary over a wide range.
  • the epoxy equivalent weight i.e., the number average molecular weight divided by the number of reactive epoxy groups, is preferably in the range of 60 to 1000.
  • Other cationically polymerizable components that may be used in the composition of the present invention include, for instance, cyclic ether compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds, and oxetane compounds.
  • oxetane compounds include compounds represented by the following formula (8):
  • Q ⁇ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (such as a methyl, ethyl, propyl, or butyl group), a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group, or a thienyl group;
  • Q 2 represents an alkylene group having 1 to 6 carbon atoms (such as a methylene, ethylene, propylene, or butylene group), or an alkylene group containing an ether linkage, for example, an oxyalkylene group, such as an oxyethylene, oxypropylene, or oxybutylene group
  • Z represents an oxygen atom or a sulphur atom
  • R 2 represents a hydrogen atom, an alkyl group having 1-6 carbon atoms (e.g. a methyl group, ethyl group, propyl group, or butyl group), an alkenyl group having 2-6 carbon atoms (e.g. a 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2- methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, or 3-butenyl group), an aryl group having 6-18 carbon atoms (e.g.
  • a phenyl group, naphthyl group, anthranyl group, or phenanthryl group a substituted or unsubstituted aralkyl group having 7-18 carbon atoms
  • a substituted or unsubstituted aralkyl group having 7-18 carbon atoms e.g. a benzyl group, fluorobenzyl group, methoxy benzyl group, phenethyl group, styryl group, cynnamyl group, ethoxybenzyl group
  • an aryloxyalkyl group e.g. a phenoxymethyl group or phenoxyethyl group
  • an alkylcarbonyl group having 2-6 carbon atoms e.g.
  • an ethylcarbonyl group, propylcarbonyl group, or butylcarbonyl group an alkoxy carbonyl group having 2-6 carbon atoms (e.g. an ethoxycarbonyl group, propoxycarbonyl group, or butoxycarbonyl group), an N-alkylcarbamoyl group having 2-6 carbon atoms (e.g. an ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, or pentylcarbamoyl group), or a polyethergroup having 2-1000 carbon atoms.
  • an alkoxy carbonyl group having 2-6 carbon atoms e.g. an ethoxycarbonyl group, propoxycarbonyl group, or butoxycarbonyl group
  • an N-alkylcarbamoyl group having 2-6 carbon atoms e.g. an ethylcarbamoyl group, propylcarbamo
  • Preferred oxetanes include those wherein Q ⁇ represents a C ⁇ -C 4 alkyl group (e.g. an ethyl group), Z represents an oxygen atom, Q 2 represents a methylene group, and/or R 2 represents a hydrogen atome, a CrC 8 alkyl group, a phenylgroup, 3- ethyl-3-hydroxymethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, (3-ethyl-3- oxetanylmethoxy)benzene, 2-ethylhexyl (3-ethyl-3-oxetanyl methyl) ether, 1 ,4-bis[(3- ethyl-3-oxetanylmethoxy)methyl]benzene, 1 ,2-bis[(3-ethyl-3- oxetanylmethoxy)methyl]benzene, 1 ,3-bis[(3-
  • Oxetane compounds containing one oxetane ring in the molecule include, for instance, 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3- oxetanylmethoxy)methylbenzene, (3-ethyl-3-oxetanylmethoxy)benzene, 4-fluoro-[1 -(3- ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1 -(3-ethyl-3- oxetanylmethoxy)methyl]benzene, [1 -(3-ethyl-3-oxetanylmethoxy)ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobutoxymethyl (3-ethyl-3-oxe
  • Oxetane compounds containing two or more oxetane rings in the molecule include, for instance, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3'-(1 ,3-(2- methylenyl)propanediylbis(oxymethylene))bis-(3-ethyloxetane), 1 ,4-bis[(3-ethyl-3- oxetanylmethoxy)methyl]benzene, 1 ,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1 ,3-bis[(3-ethyl-3-oxetanylmethoxy)methy]propane, ethylene glycol bis(3-ethyl-3- oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol
  • the composition of the present invention comprises, relative to the total weight of the composition, preferably at least 10wt%, e.g. at least 20wt%, at least 30wt%, or at least 45wt% of cationically curable components.
  • the composition of the invention comprises, relative to the total weight of the composition, less than 95 wt%, e.g. less than 85wt% or less than less than 70wt% of cationically curable components.
  • the present compositions comprise at least one free radical photoinitiator selected from the group consisting of benzophenones.
  • benzophenones include, for instance, benzophenone, alkyl-substituted benzophenone (e.g. 2-methylbenzophenone, 3-methylbenzophenone, or 4-methylbenzophenone), alkoxy-substituted benzophenone (e.g. 4-methoxybenzophenone), 4- morpholinobenzophenone, and 4,4'-bis(N,N'-dimethylamino)-benzophenone.
  • benzophenones include benzophenone derivatives of the formula (7)
  • R 5 , R 6 and R 7 independently are C C 12 -alkyl, C r C 4 -alkylthio, CrC -alkoxy, halogen or C 2 -C 6 -alkoxycarbonyl and R 8 , R 9 and R 10 are hydrogen, CrC 12 -alkyl, C C 4 - alkoxy, halogen or C 2 -C 6 -alkoxycarbonyl or C C -alkylthio; benzophenone derivatives of the formula 8:
  • R 11 , R 12 , R 13 and R 14 independently are hydrogen, d -C 12 -alkyl, d -C 4 -alkoxy, C ⁇ -C 4 -alkylthio, halogen or C 2 -C 6 -alkoxycarbonyl;
  • R 11 , R 12 , R 13 and R 14 independently are hydrogen or Ci -C 12 -alkyl, especially Ci -C 4 -alkyl, or methyl.
  • at least 2 of the radicals R 11 , R 12 , R 13 and R 14 are hydrogen and the others are hydrogen or the above alkyl.
  • benzophenone derivatives are the ones having the formula (8), wherein R 11 is hydrogen, R 2 is hydrogen, chloro, methoxycarbonyl, methyl, t-butyl; and R 13 and R 14 are the same or different and each is -CH 2 X, CHX 2 , or CX 3 wherein X is chloro or bromo.
  • benzophenone derivatives are 3,4- bis(chloromethyl)benzophenone, 3,4-bis(chloromethyl)-4'-carbomethoxy benzophenone, 3,4-bis(chloromethyl)-4'-chlorobenzophenone, 3,4-bis- (bromomethyl)benzophenone, 3,4-bis(dichloromethyl)benzophenone.
  • the benzophenone photoinitiators are preferably absent a hydroxy group.
  • the at least one free radical photoinitiator selected from the group consisting of benzophenones is generally present in the compositions in an amount of, relative to the total weight of the composition, less than 5 wt%, e.g. less than 2.5wt%, less than 1.5wt%, less than 0.5 wt%, less than 0.3 wt%, less than 0.1 wt%, or less than 0.08 wt%.
  • the amount will generally be above 0.01 wt%, e.g. above 0.03 wt%.
  • compositions may, in addition, employ one or more other free radical photoinitiators (i.e. photoinitiators not selected from the group consisting of benzophenones).
  • photoinitiators i.e. photoinitiators not selected from the group consisting of benzophenones.
  • Typical compounds of such other photoinitiators are benzoins, e.g.
  • benzoin benzoin ethers, such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, benzoin phenyl ether, and benzoin acetate; acetophenones, such as acetophenone, 2,2-dimethoxyacetophenone, 4-(phenylthio)acetophenone, and 1 ,1-dichloroacetophenone; benzil, benzil ketals, such as benzil dimethyl ketal, and benzil diethyl ketal; anthraquinones, such as 2-methylanthraquinone, 2- ethylanthraquinone, 2-tertbutylanthraquinone, 1-chloroanthraquinone, and 2- amylanthraquinone; triphenylphosphine, benzoylphosphine oxides, such as, for example, 2,4,6-trimethylbenzoyl
  • ionic dye-counter ion compounds which are capable of absorbing actinic rays and producing free radicals, which can initiate the polymerization of the acrylates.
  • the compositions according to the invention that comprise ionic dye-counter ion compounds can thus be cured in a more variable manner using visible light in an adjustable wavelength range of 400 to 700 nanometers.
  • Ionic dye-counter ion compounds and their mode of action are known, for example from published European patent application EP 223587 and U.S. Patents 4,751 ,102, 4,772,530 and 4,772,541.
  • ionic dye-counter ion compounds the anionic dye-iodonium ion complexes, the anionic dye-pyryllium ion complexes and, especially, the cationic dye-borate anion compounds of the following formula (9)
  • D + is a cationic dye and R 22 , R 23 , R 24 , and R 25 are each independently of the others alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, an alicyclic or saturated or unsaturated heterocyclic group.
  • R 22 , R 23 , R 24 , and R 25 are each independently of the others alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, an alicyclic or saturated or unsaturated heterocyclic group.
  • Preferred definitions for the radicals R 22 to R 25 can be found, for example, in published European patent application EP 223587.
  • the weight ratio of the at least one photoinitiator selected from the group of benzophenones to the at least one other photoinitiator is preferably less than 0.50, for instance less than 0.35, less than 0.25, less than 0.15, less than 0.10, or less than 0.05.
  • the weight ratio will generally be greater than 0.01.
  • the present compositions may comprise suitable hydroxy-functional compounds.
  • the hydroxy-functional components may be absent free radical polymerizable groups, epoxy groups, and/or oxetane groups.
  • the hydroxyl-containing material which can be used in the present invention may be any suitable organic material having a hydroxyl functionality of at least 1 ("monol"), and' preferably at least 2 ("polyol").
  • the material is preferably substantially free of any groups which interfere with the curing reactions or which are thermally or photolytically unstable.
  • the hydroxyl-containing material contains two or more primary or secondary aliphatic hydroxyl groups.
  • the hydroxyl group may be internal in the molecule or terminal.
  • the hydroxyl equivalent weight i.e., the number average molecular weight divided by the number of hydroxyl groups, may vary and may be, for instance, in the range of 31 to 5000.
  • Representative examples of hydroxyl-containing materials having a hydroxyl functionality of 1 include alkanols, monoalkyl ethers of polyoxyalkyleneglycols, monoalkyl ethers of alkyleneglycols, and others, and combinations thereof.
  • useful polyhydroxy organic materials include alkylene and arylalkylene glycols, such as 1 ,2,4-butanetriol, 1 ,2,6-hexanetriol, 1 ,2,3-heptanetriol, 2,6-dimethyl-1 ,2,6-hexanetriol, (2R,3R)-(-)-2-benzyloxy-1 ,3,4- butanetriol, 1 ,2,3-hexanetriol, 1 ,2,3-butanetriol, 3-methyl-1 ,3,5-pentanetriol, 1 ,2,3- cyclohexanetriol, 1 ,3,5-cyclohexanetriol, 3,7,11 ,15-tetramethyl-1 ,2,3-hexadecanetriol, 2-hydroxymethyltetrahydropyran-3,4,5-triol, 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 1 ,3-cyclopentanediol, trans-1
  • useful oligomeric and polymeric hydroxyl-containing materials include polyoxyethylene and polyoxypropylene glycols and triols of molecular weights from about 200 to about 10,000; polytetramethylene glycols of varying molecular weight; poly(oxyethylene-oxybutylene) random or block • copolymers; copolymers containing pendant hydroxy groups formed by hydrolysis or partial hydrolysis of vinyl acetate copolymers, poly inylacetal resins containing pendant hydroxyl groups; hydroxy-functional (e.g. hydroxy-terminated) polyesters and hydroxy- functional (e.g.
  • hydroxy-terminated) polylactones hydroxy-functionalized polyalkadienes, such as polybutadiene; aliphatic polycarbonate polyols, such as an aliphatic polycarbonate diol; and hydroxy-functional (e.g. hydroxy-terminated) polyethers (e.g. polytetrahydrofuran polyols in the range of 150-4000 g/mol, 150- 1500g/mol, or 150-750 g/mol), and combinations thereof.
  • hydroxy-functionalized polyalkadienes such as polybutadiene
  • aliphatic polycarbonate polyols such as an aliphatic polycarbonate diol
  • hydroxy-functional (e.g. hydroxy-terminated) polyethers e.g. polytetrahydrofuran polyols in the range of 150-4000 g/mol, 150- 1500g/mol, or 150-750 g/mol
  • the composition preferably comprises, relative to the total weight of the composition, at least 1 wt% of hydroxy-functional compounds, e.g. at least 5 wt%, at least 10 wt%, or at least 15 wt%. Furthermore, the composition generally comprises, relative to the total weight of the composition, at most 75 wt% of one or more non-free radical polymerizable hydroxy-functional compounds, e.g. at most 50 wt%, at most 30wt%, or at most 20wt%.
  • any suitable type of photoinitiator that, upon exposure to actinic radiation, forms cations that initiate the reactions of the cationically polymerizable compounds, such as epoxy material(s), can be used.
  • cationic photoinitiators include, for example, onium salts with anions of weak nucleophilicity.
  • halonium salts such as are described in published European patent application EP 153904 and WO 98/28663, sulfoxonium salts, such as described, for example, in published European patent applications EP 35969, 44274, 54509, and 164314, or diazonium salts, such as described, for example, in U.S. Patents 3,708,296 and 5,002,856. All eight of these disclosures are hereby incorporated in their entirety by reference.
  • Other cationic photoinitiators are metallocene salts, such as described, for example, in published European applications EP 94914 and 94915, which applications are both hereby incorporated in their entirety by reference.
  • Preferred initiators include diaryl iodonium salts, triaryl sulfonium salts, or the like.
  • Typical photo-polymerization initiators include those represented by the following formulae (10) and (11):
  • Q 3 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms;
  • M represents a metal atom, preferably antimony;
  • HAL represents a halogen atom, preferably fluorine; and
  • t is the valent number of the metal, for example 6 in the case of antimony.
  • Preferred cationic photoinitiators include iodonium photoinitiators, e.g. iodonium tetrakis (pentafluorophenyl) borate, because they tend to be less yellowing, especially when used in combination with photosensitizers such as, for instance, n- ethyl carbazole.
  • sensitizers In order to increase the light efficiency, or to sensitize the cationic photoinitiator to specific wavelengths, such as for example specific laser wavelengths or a specific series of laser wavelengths, it is also possible, depending on the type of initiator, to use sensitizers. Examples are polycyclic aromatic hydrocarbons or aromatic keto compounds. Specific examples of preferred sensitizers are mentioned in published European patent application EP I53904. Other preferred sensitizers are benzoperylene, 1 ,8-diphenyl-1 ,3,5,7-octatetraene, and 1 ,6-diphenyl-1 ,3,5-hexatriene as described in U.S. Patent 5,667,937, which is hereby incorporated in its entirety by reference. It will be recognized that an additional factor in the choice of sensitizer is the nature and primary wavelength of the source of actinic radiation.
  • the present composition comprises, relative to the total • weight of the composition, 0.1-15 wt% of one or more cationic photoinitiators, more preferably 1 -10 wt%.
  • Additives may also be present in the composition of the invention.
  • Stabilizers are often added to the compositions in order to prevent a viscosity build-up, for instance a viscosity build-up during usage in a solid imaging process.
  • Preferred stabilizers include those described in U.S. Patent 5,665,792, the entire disclosure of which is hereby incorporated by reference.
  • Such stabilizers are usually hydrocarbon carboxylic acid salts of group I A and IIA metals. Most preferred examples of these salts are sodium bicarbonate, potassium bicarbonate, and rubidium carbonate. Rubidium carbonate is preferred for formulations of this invention with recommended amounts varying between 0.0015 to 0.005% by weight of composition.
  • Alternative stabilizers are polyvinylpyrrolidones and polyacrylonitriles.
  • Other possible additives include dyes, pigments, fillers, antioxidants, wetting agents, photosensitizers for the free-radical photoinitiator, leveling agents, surfactants, and the like.
  • antioxidants such as, for example, Longnox 10 (Longchem Int.) and Irganox 1035 (Ciba Geigy) in ranges of 0.01-2% levels have been found to be effective in conjunction with the compounds of the instant invention.
  • a filler can be any substance without special limitation and be for example organic or inorganic.
  • inorganic filler is preferred from the point of view of the water-resisting capabilities and mechanical properties of the parts made of the resin composition of the invention.
  • inorganic fillers are silica, glass powder, alumina, alumina hydrate, magnesium oxide, magnesium hydroxide, barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, silicate mineral, diatomaceous earth, silica sand, silica powder, titanium oxide, aluminum powder, bronze, zinc powder, copper powder, lead powder, gold powder, silver dust, glass fiber, glass beads, talc, titanic acid potassium whiskers, carbon whiskers, sapphire whiskers, boron carbide whiskers, silicon carbide whiskers, and silicon nitride whiskers.
  • the present compositions are suitable for a wide variety of applications.
  • the present compositions may be used as coating compositions (e.g. for optical fibers or displays), as adhesives (e.g. as adhesives for - digital versatile discs), or as compositions for preparing a three dimensional object by rapid prototyping.
  • the compositions may be cured by heat or any suitable form of radiation, e.g. electron beam radiation or actinic radiation, or mixtures thereof.
  • the composition may first be cured to a certain extent by radiation and subsequently be post-cured by heat. Rapid prototyping, sometimes also referred to as "solid imaging" or
  • stereolithography is a process wherein a photoformable liquid is coated into a thin layer upon a surface and exposed imagewise to actinic radiation such that the liquid solidifies imagewise. See, e.g., U.S. Patents 5,476,748 and 5,707,780. This coating is most conveniently done if the composition is a liquid at room temperature, but a solid composition may also be melted to form a layer. It is also possible to work with viscosity reducible or thixotropic formulations, like disclosed in U.S. Patent 5,474,719.
  • step (3) (4) exposing said thin layer from step (3) imagewise to actinic radiation to form an additional imaged cross-section, wherein the radiation is of sufficient intensity to cause substantial curing of the thin layer in the exposed areas and to cause adhesion to the previously exposed imaged cross-section;
  • the present invention also provides a process for improving the color stability of an article formed at least in part by curing a composition, wherein the process comprises including a benzophenone- type photoinitiator, and optionally at least one other photoinitiator, in the composition prior to cure.
  • a spectrophotometer (Cary UV 500) such that the bottom of an empty polystyrene dish was substantially vertical and normal to the sample beam of the spectrophotometer.
  • the reference beam was against air.
  • a baseline from 800 to 400 nm was run with the empty dish in this manner in order to eliminate surface reflection dispersion anomalies and absorption effects from the polystyrene dish over this wavelength range. In effect therefore the petri dish is a normalized control sample having 100% transparency over the wavelength range for the purposes of this evaluation.
  • the samples were placed in the sample beam of the spectrophotometer with the flat of the dish vertical and substantially normal to the beam. A spectrum was measured for each
  • the El 0 mJ/cm 2 value is a measure of photospeed (See also test methods below). The lower the E10 number in general the faster the photospeed.
  • Both Examples 1 and 8 have only benzophenone as a free-radical intiator source but Example 1 has a slow photospeed of 113 mj/cm 2 while Example 8 has a relatively fast photospeed of 57.6 mJ/cm 2 . While not wishing to be limited by any particular theory, it is believed that the presence of the polyether polyol component provides a suitable hydrogen abstraction source for the benzophenone, thereby enhancing the photospeed of Example 8 relative to Example 1 which does not have a polyether polyol component in the liquid.
  • the Photoproperties Ec (mJ/cm 2 ), Dp (mm), and E10 (mJ/cm 2 ) represent the photoresponse (in this case thickness of layer formed) of a particular formulation to exposure by a single wavelength or range of wavelengths.
  • at least 20 grams of composition was poured into a 100 mm diameter petri-dish and allowed to equilibrate to approximately 30°C and 30% RH.
  • the samples were then scanned in a line-by-line fashion using a focused laser beam of approximately 100-140 mW.
  • the laser a frequency tripled YAG laser, had an output wavelength of 354.7 nm and was pulsed at 80 KHz.
  • the exposures were made in a square pattern approximately 20 mm by 20 mm. Six individual exposures were made at near constant laser power but at various scan speeds. The parallel scan lines making up each exposure were drawn approximately 50 um apart. Based upon knowledge of the diameter of the focused beam at the liquid surface, the scan speed, the laser power, and the scan spacing, the summation of exposure mJ/cm 2 was calculated. Each square was allowed to float on the surface of the petri-dish for approximately 15 minutes. Then the squares were blotted and a thickness measurement was taken using Mitutoyo NTO25-8"C spring loaded Absolute Digimatic calipers. When the natural log of the exposures is plotted against the measured thickness a least squares fit line can be drawn.
  • the Dp (mm) is the slope of the least squares fit line.
  • the E10 is the energy necessary to produce a layer approximately 10 mils (254 um) thick. In general the lower the E10 number, the faster the photospeed of the composition (especially when producing a 10 mil exposure).
  • the present compositions have an E10 number of less than 150 mJ/cm 2 , for instance less than 100 mJ/cm 2 , less than 75 mJ/cm 2 , less than 60 mJ/cm 2 , or less than 50 mJ/cm 2 .

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Abstract

La présente invention porte sur des compositions comprenant, comme ingrédients prémélangés, au moins un composant durcissable à radical libre, au moins un composant durcissable cationiquement et au moins un photo-initiateur à radical libre (iii) sélectionné dans le groupe comprenant des benzophénones. Cette invention porte, de plus, sur des applications de ces compositions, par exemple, dans un procédé de prototypage rapide permettant de former un article tridimensionnel.
PCT/NL2003/000457 2002-06-20 2003-06-20 Compositions comprenant un photo-initiateur de benzophenone WO2004001507A1 (fr)

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NLPCT/NL02/00408 2002-06-20
PCT/NL2002/000408 WO2003001295A1 (fr) 2001-06-21 2002-06-20 Composition de resine durcissable par rayonnement et procede de prototypage rapide utilisant cette composition
US41551402P 2002-10-03 2002-10-03
US60/415,514 2002-10-03

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005045523A1 (fr) * 2003-11-06 2005-05-19 Huntsman Advanced Materials (Switzerland) Gmbh Composition photodurcissable destinee a la production d'articles polymerises possedant des proprietes mecaniques ameliorees et une transparence elevee
WO2006082103A2 (fr) * 2005-02-02 2006-08-10 Dsm Ip Assets B.V. Nouvelles compositions cationiques et procedes de fabrication et d'utilisation afferents

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4623676A (en) * 1985-01-18 1986-11-18 Minnesota Mining And Manufacturing Company Protective coating for phototools
EP0509512A1 (fr) * 1991-04-17 1992-10-21 Nippon Paint Co., Ltd. Composition photosensible pour l'enregistrement d'hologrammes volumiques
EP0697631A1 (fr) * 1994-07-29 1996-02-21 Toppan Printing Co., Ltd. Matériau d'enregistrement photosensible, support d'enregistrement photosensible et procédé de fabrication d'hologrammes utilisant ce support
JPH0873771A (ja) * 1994-09-12 1996-03-19 Asahi Denka Kogyo Kk 光硬化性ハードコート組成物およびその塗布物品
EP0831127A1 (fr) * 1995-05-12 1998-03-25 Asahi Denka Kogyo Kabushiki Kaisha Composition a base de resines stereolithographiques et procede de stereolithographie
EP0938026A1 (fr) * 1998-02-18 1999-08-25 Dsm N.V. Composition liquide à base de résine photodurcissable

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4623676A (en) * 1985-01-18 1986-11-18 Minnesota Mining And Manufacturing Company Protective coating for phototools
EP0509512A1 (fr) * 1991-04-17 1992-10-21 Nippon Paint Co., Ltd. Composition photosensible pour l'enregistrement d'hologrammes volumiques
EP0697631A1 (fr) * 1994-07-29 1996-02-21 Toppan Printing Co., Ltd. Matériau d'enregistrement photosensible, support d'enregistrement photosensible et procédé de fabrication d'hologrammes utilisant ce support
JPH0873771A (ja) * 1994-09-12 1996-03-19 Asahi Denka Kogyo Kk 光硬化性ハードコート組成物およびその塗布物品
EP0831127A1 (fr) * 1995-05-12 1998-03-25 Asahi Denka Kogyo Kabushiki Kaisha Composition a base de resines stereolithographiques et procede de stereolithographie
EP0938026A1 (fr) * 1998-02-18 1999-08-25 Dsm N.V. Composition liquide à base de résine photodurcissable

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005045523A1 (fr) * 2003-11-06 2005-05-19 Huntsman Advanced Materials (Switzerland) Gmbh Composition photodurcissable destinee a la production d'articles polymerises possedant des proprietes mecaniques ameliorees et une transparence elevee
US7820275B2 (en) 2003-11-06 2010-10-26 Huntsman Advanced Materials Americas Llc Photocurable composition for producing cured articles having high clarity and improved mechanical properties
WO2006082103A2 (fr) * 2005-02-02 2006-08-10 Dsm Ip Assets B.V. Nouvelles compositions cationiques et procedes de fabrication et d'utilisation afferents
WO2006082103A3 (fr) * 2005-02-02 2008-05-02 Dsm Ip Assets Bv Nouvelles compositions cationiques et procedes de fabrication et d'utilisation afferents

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