WO2012126695A1 - Composition thiol-ène durcissable stable - Google Patents

Composition thiol-ène durcissable stable Download PDF

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Publication number
WO2012126695A1
WO2012126695A1 PCT/EP2012/053045 EP2012053045W WO2012126695A1 WO 2012126695 A1 WO2012126695 A1 WO 2012126695A1 EP 2012053045 W EP2012053045 W EP 2012053045W WO 2012126695 A1 WO2012126695 A1 WO 2012126695A1
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Prior art keywords
component
weight
curable composition
thiol
composition according
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PCT/EP2012/053045
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English (en)
Inventor
Zubair CHERKAOUI
Parichehr ESFANDIARI
Richard Frantz
Jean-Jacques Lagref
Robert Liska
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Huntsman Advanced Materials (Switzerland) Gmbh
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Publication of WO2012126695A1 publication Critical patent/WO2012126695A1/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
    • G03F7/0037—Production of three-dimensional images
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds

Definitions

  • the present invention relates to curable or photocurable thiol-ene or thiol-yne compositions.
  • Thiol- ene compositions comprise a thiol-component and an ene component, which is an ethylenically or acetylenically unsaturated monomer and are suited to be used in coating applications, adhesives, additive manufacturing technologies (AMT) and rapid prototyping (RP), in particular, suited for the production of three dimensional (3D) objects with the technique of stereolithography (SLA) and digital light processing (DLP).
  • AMT additive manufacturing technologies
  • RP rapid prototyping
  • the term Thiol-ene compositions includes also Thiol-yne compositions.
  • stereolithography One of the best-known rapid prototyping processes, stereolithography (SLA), is widely spread and is often used in a broad field of technical applications nowadays, mainly within the aerospace, automotive and mechanical engineering industries.
  • SLA stereolithography
  • the technique of stereolithography uses a liquid photopolymer that is locally cured by a UV coherent or incoherent light source, like a laser or a UV lamp (see patent applications WO 2010/043559 and WO 2010/043275).
  • the today standard stereolithographic resins are based on (meth)acrylate or epoxy photopolymers. (Meth)acrylate photopolymers exhibit relatively high shrinkage and oxygen inhibition whereas in epoxy
  • Formulations which have long term shelf stability can be for example defined as those which do not double their viscosity in six month at room temperature. An increase in viscosity indicates that a spontaneous oligomerization reaction occurs between the polyene and polythiol. In extreme cases the unstable formulation will result in intractable insoluble gels.
  • thiol-ene system show a limited shelf-life stability. All thiol-ene reactions exhibit spontaneous dark reactions, yielding polymers (oligomers) in the absence of initiator. The dark reaction takes place in the radiation curable formulations, in closed containers, usually resulting in premature polymerization.
  • the storage stability of the thiol-ene system is affected by dark reaction at different extents, based on the activity of unsaturated enes and thiols.
  • Thiol-ene polymerization exhibits a number of advantages over conventional UV-curable resins, including inherently rapid reaction rate, reduced oxygen inhibition and reduced shrinkage due to the thiol-ene step growth reaction. However, poor shelf-life stability restricts thiol-ene application.
  • the object of the present invention is solved according to the features of the following independent claims.
  • a curable, preferably photocurable, composition comprising:
  • At least one ethylenically or acetylenically unsaturated monomer preferably one acrylate or methacrylate or allylether or alkyne or allylazine or a mixture thereof;
  • the composition can be curable by heat, but is preferably photocurable, being curable by actinic radiation or ultraviolet light (UV).
  • component E exhibits the following structure (1):
  • n is an integer from 2 to 6
  • m is an integer from 0 to (6-n)
  • R m are independently from each other organic radicals, preferably a C 1 -C6 alkyl.
  • n 2, 3 or 4 and m is 0 or 1 in the structure (1) of component E
  • component A 25 - 98 %, preferably 50 - 95 % by weight of component A;
  • component B 1 - 70 %, preferably 3 - 40 % by weight of component B;
  • component C 0 - 10 %, preferably 1 - 7 % by weight of component C;
  • component D 0.01 - 10 %, preferably 0.5 - 5 % by weight of component D;
  • the curable composition comprises:
  • component A 60 - 90 % by weight of component A;
  • component B 5 - 40 % by weight of component B;
  • component C 1 - 5 % by weight of component C;
  • component D 1 - 4 % by weight of component D;
  • the photocurable composition comprises 25 - 98 %, preferably 50 - 95 % , most preferably 60 - 90 % by weight of component A, based on the total weight of the composition.
  • the photocurable composition comprises 1 - 70 %, preferably 3 - 40 % , most preferably 5 - 40 % by weight of component B, based on the total weight of the composition.
  • the photocurable composition comprises 0 - 10 %, preferably 1 - 7 % , most preferably 1 - 5 % by weight of component C, based on the total weight of the composition.
  • the photocurable composition comprises 0.01 - 10 %, preferably 0.5 - 5 % most preferably 1 - 4 % by weight of component D, based on the total weight of the composition.
  • the photocurable composition comprises 0.01 - 10 %, preferably 0.01 - 3 % , most preferably 0.05 - 2 % by weight of component E, based on the total weight of the composition.
  • component E exhibits at least one benzene ring or naphthalene ring with two, three or four hydroxyl substituents bonded directly to said benzene ring or naphthalene ring .
  • component E comprises an optionally substituted benzene diol, benzene triol or pyrogallol.
  • component D comprises phenylphosphonic acid, vinylphosphonic acid, octanedisphonic acid or 2-Propenoic acid, 2-[(2- phosphonoethoxy)methyl]-l -ethyl ester (also called Ethyl 2-[4-(dihydroxyphosphoryl)-2-oxa- butyl]acrylate).
  • component B is a polythiol exhibiting from 2 to 4 SH groups.
  • component B comprises pentaerythritol tetra (3-mercaptopropionate), glycol di-3-mercaptopropionate, trimethylolpropane Tri-3- mercaptopropionate or pentaerythritol tetra (3-mercaptobutylate).
  • component A comprises diacrylates or dimethacrylates, in particular, 1.6-Hexane diol diacrylate or Bisphenol A ethoxylated di(meth)acrylate.
  • the viscosity of the photocurable composition at 25°C after 76 or 110 days at 65°C remains lower than 3.5 times, preferably lower than 2.5 times, most preferably lower than 2 times, the initial viscosity of the composition at 25°C.
  • a process for producing a three- dimensional article in sequential cross-sectional layers in accordance with a model of the article comprising the following steps:
  • the actinic radiation is preferably incoherent and generated by an ultraviolet (UV) lamp.
  • UV ultraviolet
  • the curable composition comprises one component A, which can be for example one acrylate or methacrylate or allylether or alkyne or allylazine or a mixture thereof .
  • An acrylate component may refer to a single acrylate compound or to a mixture of different acrylate compounds.
  • Suitable acrylate components can be monofunctional, difunctional or of higher functionality.
  • Monofunctional acrylates may be used to modify resin properties.
  • Examples of monofunctional acrylates include such as isobornyl acrylate, tetrahydrofurfuryl acrylate, ethoxylated phenyl acrylates, lauryl acrylate, stearyl acrylate, octyl acrylate, isodecyl acrylate, tridecyl acrylate, caprolactone acrylate, nonyl phenol acrylate, cyclic trmethylolpropane formal acrylate, methoxy polyethyleneglycol acrylates, methoxy polypropyleneglycol acrylates, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate. This list is not exhaustive and in each case ethoxylation and / or propoxylation of those acrylates can be used to modify properties further.
  • acrylates are difunctional.
  • aliphatic or cycloaliphatic difunctional acrylates include tricyclodecane dimethanol diacrylate (Sartomer ® 833s), dioxane glycerol diacrylate (Sartomer ® CD 536), 1,6 hexanediol diacrylate (Sartomer ® 238), 3-methyl 1, 5-pentanediol diacrylate (Sartomer ® 341), tripropylene glycol diacrylate (Sartomer® 306), Neopentyl glycol diacrylate (Sartomer® 247),
  • dimethyloltricyclodecane diacrylate (Kayarad R-684), 1,4-dihydroxymethylcyclohexane diacrylate, 2,2-bis(4-hydroxy-cyclohexyl)propane diacrylate, bis(4-hydroxycyclohexyl)methane diacrylate.
  • acyclic aliphatic difunctional acrylates include compounds of the formulae (F-I) to (F-IV) of U.S. Patent No. 6,413,697, herein incorporated by reference. Further examples of possible difunctional acrylates are compounds of the formulae (F-V) to (F-VIII) of U.S. Patent No. 6,413,697.
  • aromatic difunctional acrylates include bisphenol A polyethylene glycol diether diacrylate (Kayarad R-551), 2,2'-methylenebis[p-phenylenepoly(oxyethylene)oxy]diethyl diacrylate (Kayarad R-712), hydroquinone diacrylate, 4,4'-dihydroxybiphenyl diacrylate, Bisphenol A diacrylate, Bisphenol F diacrylate, Bisphenol S diacrylate, ethoxylated or propoxylated Bisphenol A diacrylate, ethoxylated or propoxylated Bisphenol F diacrylate, ethoxylated or propoxylated Bisphenol S diacrylate, bisphenol-A epoxy diacrylate (Ebecryl ® 3700 UCB Surface Specialties).
  • polyethylenglycol difunctional acrylates used in resins according to the invention are tetraethyleneglycol diacrylate (Sartomer ® 268), polyethleneglycol(200) diacrylate (Sartomer ® 259), polyethleneglycol(400) diacrylate (Sartomer ® 344). This list is not exhaustive and in each case ethoxylation and / or propoxylation of those diacrylates can be used to modify properties further.
  • trifunctional acrylates or acrylate with even higher functionality examples include hexane-2,4,6- triol triacrylate, glycerol triacrylate, 1,1,1-trimethylolpropane triacrylate, ethoxylated or propoxylated glycerol triacrylate, ethoxylated or propoxylated 1,1,1 -trimethylolpropane triacrylate.
  • pentaerythritol tetraacrylate bistrimethylolpropane tetraacrylate, pentaerythritol monohydroxytriacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol pentaacrylate (Sartomer® 399), pentaerythritol triacrylate (Sartomer® 444), pentaerythritol tetracrylate (Sartomer ® 295), trimethylolpropane triacrylate (Sartomer® 351), tris(2-acryloxy ethyl) isocyanurate triacrylate (Sartomer® 368), ethoxylated (3) trimethylolpropane triacrylate (Sartomer® 454), dipentaerythritol pentaacrylate ester (Sartomer® 9041),
  • suitable aromatic triacrylates are the reaction products of triglycidyl ethers of tri
  • a polyacrylate may also be a polyfunctional urethane acrylate.
  • Urethane acrylates may be prepared by, e.g., reacting a hydroxyl-terminated polyurethane with acrylic acid, or by reacting an isocyanate-terminated prepolymer with hydroxyalkyl acrylates to give the urethane acrylate.
  • Preferred are urethane acrylates made from polyester diols, aliphatic isocyanates and
  • hydroxyalkyl acrylates are also preferred.
  • those having polyfunctionality of acrylates or mixed acrylic and methacrylic functionality are also preferred.
  • acrylates including hyberbranched polyester types, may also be used for resin modification.
  • Commercially available examples include such as CN2301, CN2302, CN2303, CN2304 from Sartomer.
  • acrylates can be used in the formulation include such as D-310, D-330, DPHA-2H, DPHA-2C, DPHA-21, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN- 2475, T-2020, T-2040, TPA-320, TPA-330 T-1420, PET-30, THE-330 and RP-1040 from Kayarad, R-526, R-604, R-011, R-300 and R-205 from Nippon Kayaku Co.
  • a methacrylate component may refer to a single methacrylate compound or to a mixture of different methacrylate compounds.
  • Suitable methacrylate components can be monofunctional, difunctional or of higher functionality.
  • Monofunctional methacrylates may be used to modify resin properties.
  • Examples of monofunctional methacrylate include isobornyl methacrylate, tetrahydrofurfuryl methacrylate, ethoxylated phenyl methacrylate, lauryl methacrylate, stearyl methacrylate, octyl methacrylate, isodecyl methacrylate, tridecyl methacrylate, caprolactone methacrylate, nonyl phenol methacrylate, cyclic trmethylolpropane formal methacrylate, methoxy polyethyleneglycol methacrylates, methoxy polypropyleneglycol methacrylates, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate. This list is not exhaustive and in each case ethoxylation and / or propoxylation of those methacrylates can be used to modify properties further
  • aliphatic or cycloaliphatic difunctional methacrylates examples include 1,4- dihydroxymethylcyclohexane dimethacrylate, 2,2-bis(4-hydroxy-cyclohexyl)propane
  • dimethacrylate bis(4-hydroxycyclohexyl)methane dimethacrylate.
  • Examples of acyclic aliphatic difunctional methacrylates include compounds of the formulae (F-I) to (F-IV) of U.S. Patent No. 6,413,697, herein incorporated by reference. Further examples of possible dimethacrylates are compounds of the formulae (F-V) to (F-VIII) of U.S. Patent No. 6,413,697. Their preparation is also described in EP-A-0 646 580, herein incorporated by reference. Some compounds of the formulae (F-I) to (F-VIII) are commercially available. This list is not exhaustive and in each case ethoxylation and / or propoxylation of those
  • dimethacrylates can be used to modify properties further
  • Examples of preferred aromatic difunctional methacrylates used in resins according to the invention include ethoxylated (2) bisphenol A dimethacrylate (Sartomer ® 10 IK), ethoxylated (2) bisphenol A dimethacrylate (Sartomer ® 348L), ethoxylated (3) bisphenol A dimethacrylate (Sartomer ® 348C), ethoxylated (4) bisphenol A dimethacrylate (Sartomer ® 150), ethoxylated (4) bisphenol A dimethacrylate (Sartomer ® 540), ethoxylated (10) bisphenol A dimethacrylate (Sartomer ® 480), hydroquinone dimethacrylate, 4,4'-dihydroxybiphenyl dimethacrylate, Bisphenol A dimethacrylate, Bisphenol F dimethacrylate, Bisphenol S dimethacrylate, ethoxylated or propoxylated Bisphenol A dimethacrylate, ethoxyl
  • trifunctional methacrylates or a methacrylate with even higher functionality examples include such as tricyclodecane dimethanol dimethacrylate (Sartomer ® 834), trimethylolpropane trimethacrylate (Sartomer® 350), tetramethylolmethane tetramethacrylate (Sartomer ® 367), hexane-2,4,6-triol trimethacrylate, glycerol trimethacrylate, 1,1,1 -trimethylolpropane trimethacrylate, ethoxylated or propoxylated glycerol trimethacrylate, ethoxylated or propoxylated 1,1,1 -trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, bistrimethylolpropane tetramethacrylate, pentaerythritol monohydroxytrmethiacrylate, dipentaerythritol monohydroxy
  • Suitable aromatic trimethacrylates are the reaction products of triglycidyl ethers of trihydric phenols, and phenol or cresol novolaks containing three hydroxyl groups, with methacrylic acid.
  • Polymethacrylates may be used.
  • a polymethacrylate may be a polyfunctional urethane methacrylate.
  • Urethane methacrylates may be prepared by, e.g., reacting a hydroxyl-terminated polyurethane with methacrylic acid, or by reacting an isocyanate-terminated prepolymer with hydroxyalkyl methacrylates to give the urethane methacrylate.
  • Examples of preferred aliphatic urethane methacrylates used in resins according to the invention include Genomer® 4205, Genomer® 4256 and Genomer® 4297.
  • methacrylates including hyberbranched polyester types, may also be used for resin modification.
  • allylethers which could be used as component A in the curable composition according the present invention, are monomers containing one or more allyl ether groups, which typically are bonded to a core structural group which can be based on a wide variety of polyhydric alcohols.
  • Non-limiting examples of suitable polyhydric alcohols include neopentyl glycol, trimethylolpropane, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, trimethylene glycol, Methylene glycol, trimethylolethane, pentaerythritol, glycerol, diglycerol, 1 ,4-butanediol, 1,6- hexanediol, 1,4-cyclohexanedimethanol.
  • exemplary allyl ether monomers include hydroxyethyl allyl ether, hydroxypropyl allyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, triraethylolethane monoallyl ether, trimethylolethane diallyl ether, glycerol monoallyl ether, glycerol diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, 1,2,6-hexanetriol monoallyl ether, 1,2,6- hexanetriol diallyl ether, and the like.
  • a preferred allylether is pentaerythritolallyether.
  • alkynes which could be used as component A in the curable composition according the present invention, include phenylacetylene, 1-hexyne, 1-octyne, 1-decyne, 1,5-hexadiyne, 1 ,7- octadiyne, 3, 3 -dimethyl- 1-butyne, propargyl chloride, propargyl bromide, propargyl alcohol. 3-butyn- l -ol.
  • tripropargylamine 3-butyne-2-one.
  • propiolic acid 1-ethynyl-i-cyclohexanol, methyl propiolate, and trimeihylsilylacetyiene, 2-pentyne, 4-octyne, 2-butyne-l .4-diol.
  • a preferred alkyne is 1 .7-octadiyne.
  • component A in the curable composition according the present invention are compounds of the type cyanuric acid triallyl ester, triallyl tria/ine trione and the like.
  • a preferred compound is triallyltriazine trione (TATATO).
  • TATATO triallyltriazine trione
  • the curable composition comprises at least one thiol component B.
  • the resin composition comprises at least a monofunctional or multifunctional thiol.
  • Multifunctional thiol means a thiol with two or more thiol groups.
  • a multifunctional thiol may be a mixture of different multifunctional thiols.
  • a multifunctional thiol component of the inventive compositions may be any compound having two or more thiol groups per molecule. Suitable multifunctional thiols are described in U.S. Pat. No. 3,661,744 at Col. 8, line 76-Col. 9, line 46; in U.S. Pat. No. 4,119,617, Col. 7, lines 40-57; U.S. Pat. Nos. 3,445,419; and 4,289,867. Especially preferred are multifunctional thiols obtained by esterification of a polyol with an .alpha, or ⁇ -mercaptocarboxylic acid such as thioglycolic acid, or ⁇ -mercaptopropionic acid.
  • Examples of preferred thiols used in compositions according to the present invention include pentaerythritol tetra-(3-mercaptopropionate) (PETMP), pentaerythritol tetrakis(3- mercaptobutylate) (PETMB), trimethylolpropane tri-(3-mercaptopropionate) (TMPMP), glycol di-(3-mercaptopropionate) (GDMP), pentaerythritol tetramercaptoacetate (PETMA), trimethylolpropane trimercaptoacetate (TMPMA), glycol dimercaptoacetate (GDMA), ethoxylated trimethylpropane tri(3-mercapto-propionate) 700 (ETTMP 700), ethoxylated trimethylpropane tri(3-mercapto-propionate) 1300 (ETTMP 1300), propylene glycol 3- mercaptopropionate 800 (PPGMP 800
  • the curable composition is preferably photocurable and comprises preferably at least a radical photo initiator.
  • the radical photo initiator can be a photo initiating system comprising a combination of different photo initiators and/or sensitizers.
  • the photo initiating system can, however, be also a system comprising a combination of different compounds, which do not exhibit any photo initiating property when taken alone, but which do exhibit photo initiating properties when combined together.
  • the photo initiator may be chosen from those commonly used to initiate radical photo polymerization.
  • free radical photo initiators include benzoins, e.g., benzoin, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether, and benzoin acetate; acetophenones, e.g., acetophenone, 2,2-dimethoxyacetophenone, and 1,1- dichloroacetophenone; benzil ketals, e.g., benzil dimethylketal and benzil diethyl ketal; anthraquinones, e.g., 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertbutylanthraquinone, 1- chloroanthraquinone and 2-amylanthraquinone; triphenylphosphine; benzoylphosphine oxides, e.g., 2,4,6-trimethyl
  • the radical photo initiators are preferably selected and their concentrations are preferably adjusted to achieve an absorption capacity such that the depth of cure is from about 0.05 to about 2.5 mm.
  • the curable composition comprises at least one phosphonic acid D.
  • phosphonic acids are alkylphosphonic acid, benzylphospohnic acid, arylphosphonic acid or phosphonic acid bearing a polymerizable substituent.
  • preferred phosphonic acids are vinylphosphonic acid (VP), phenylphosphonic acid (PPA), 2- Propenoic acid, 2-[(2-phosphonoethoxy)methyl]-l-ethyl ester also called Ethyl 2-[4- (dihydroxyphosphoryl)-2-oxa-butyl]acrylate (MA or MA154).
  • E Component E
  • the curable composition comprises at least one component E, which is a component of the benzene or naphthalene series exhibiting at least one benzene ring or naphthalene ring containing at least two hydroxyl substituents.
  • the at least two hydroxyl substituents are preferably directly attached to the benzene ring or naphthalene ring.
  • Component E exhibits preferably the following structure (1):
  • n is an integer from 2 to 6
  • m is an integer from 0 to (6-n)
  • R m are, independently from each other, organic radicals, preferably a C1-C6 alkyl.
  • n 2, 3 or 4 and m is 0 or 1 in the structure (1) of component E.
  • Component E exhibits preferably at least one benzene ring or naphthalene ring with two, three or four hydroxyl substituents bonded directly to said benzene ring or naphthalene ring.
  • Component E comprises preferably an optionally substituted benzene diol, benzene triol or pyrogallol.
  • component E examples of specific possible compounds used as component E are: pyrogallol (PRA), 4-tert- butyl-l,2-dihydroxybenzene (BDB).
  • PRA pyrogallol
  • BDB 4-tert- butyl-l,2-dihydroxybenzene
  • composition can contain additional ingredients.
  • additional ingredients include, but are not limited to, light stabilizers; sensitizers; antioxidants; fillers, such as reinforcing fillers, extending fillers, and conductive fillers; adhesion promoters; and fluorescent dyes.
  • Table I shows the trade name, the supplier and the chemical name of each component used to produce examples of curable compositions according to the invention and comparative examples (see Table II A to Table II F).
  • Table 11 A describes examples 1 to 14, which arc photocurable thiol-ene compositions comprisin a radical photoiiiitiator and different phenols in combinatio or not with a phosphonic acid.
  • Tabic 11 B describes examples 15 to 18, which are photocurable thiol -cue compositions comprising a radical photoiiiitiator. pyrogallol in combination with phosphonic and not phosphonic acids.
  • Table 11 C describes examples 19 to 23, which are photocurable thiol -cue compositions comprising a radical photoiiiitiator. pyrogallol, a phosphonic acid, and different concentrations of Pentaerythritol tetrakis(3 -mcrcaptopropionatc).
  • Table 11 D describes examples 24 to 26, which are photocurable thiol -cue compositions comprising a radical photoiiiitiator. pyrogallol. a phosphonic acid, and different thiols.
  • Table 11 E describes examples 27 to 28, which are photocurable thiol -cue compositions comprising different (meih)acrylates. different radical photoinitiators. pyrogallol , and different phosphonic acids.
  • Table 11 F describes examples 29 to 32, which are photocurable thiol -cue compositions comprising a radical photoiiiitiator. pyrogallol (except example 32), a phosphonic acid, and pentaerythritol allylcthcr or 1.7-octadiyne or Triallyltria/incti ione.
  • the photocurable compositions were prepared by addition of component D (phosphonic acid), E (phenolic component) and C (photoinitiator) to a 50 x 15 mm glass bottle. Next component A was added and the bottle was placed in an ultrasonic bath at 40°C. The bottle was occasionally removed from the ultrasonic bath and shaken for a few minutes until all the solids were completely dissolved. The mixture was cooled to room temperature and then component B was added and mixed for a few minutes. The glass bottles were then sealed and aged at room temperature (25 °C) or at 65°C. The whole process was carried out excluding actinic radiation and under a normal atmosphere. Viscosity measurements were performed at 25 °C just after preparation and periodically within the storage time. Viscosity measurements:
  • a Modular Compact Rheometer Physica MCR 300 was used for measuring the viscosity.
  • a cone-on-plate geometry was used with a cone angle of 1° and a cone diameter of 25 mm. The tests were always performed at a constant temperature of 25°C.
  • the viscosity was tested in decreasing shear rates from 150 s "1 to 10 s "1 , over a period of 75 s, taking measurement every 5 s. This resulted in 15 measurement points.
  • the viscosity was measured under shear rate of 100 s "1 .
  • the measurements were performed with 0.1 ml of samples and with accuracy of about ⁇ 3.5 %.
  • the prepared formulations were kept at ambient temperature in a room with yellow light. This should avoid the light-induced polymerization.
  • the viscosity measurements were performed at 25 °C at storage time zero just after the preparation, and within a number of days between 4 and 110 after a storage time at room temperature (25 °C) or at 65°C.
  • the definition of an acceptable viscosity increase of the thiol-ene photocurable compositions during the ageing time depends from the applications. Since ageing test at room temperature (25 °C) would take too long time, accelerated ageing tests at 65 °C are considered, in order to evaluate the stability of the photocurable composition as a function of the ageing time.
  • such photocurable composition can be defined as stable and can be considered suited for several stereolithography (SLA) applications, for example as photocurable resin for the stereolithography rapid prototyping equipments disclosed in WO 2010/043559 or WO 2010/043275.
  • SLA stereolithography
  • a inventive example 3 shows that the photocurable thiol-ene composition is surprisingly and unexpectedly stabilized by the synergetic effect of the combination of pyrogallol with phosphonic acid, and only a slight viscosity increase (from 0.99 to 1.64 Pa- s ) occurs after 76 days at 65 °C.
  • Example 3 must be compared with example 1 and 2, which are similar compositions, but do not exhibit the favourable stabilising combination of pyrogallol with phosphonic acid.
  • a inventive example 5 shows that the photocurable thiol-ene composition is surprisingly and unexpectedly stabilized by the synergetic effect of the combination of pyrogallol with phosphonic acid also if the amount of pyrogallol is only 0.1 wt%, and only a slight viscosity increase (from 0.90 to 1.46 Pa- s ) occurs after 76 days at 65°C.
  • Example 5 must be compared with example 1 and 4, which are similar compositions, but do not exhibit the favourable stabilising combination of pyrogallol with phosphonic acid.
  • a inventive example 8 shows that the photocurable thiol-ene composition is surprisingly and unexpectedly stabilized by the synergetic effect of the combination of 4-tert- butyl-l,2-dihydroxybenzene with phosphonic acid, and only a slight viscosity increase (from 0.93 to 2.12 Pa- s ) occurs after 76 days at 65°C.
  • Example 8 must be compared with example 1 and 7, which are similar compositions, but do not exhibit the favourable stabilising combination of 4-tert-butyl-l,2-dihydroxybenzene with phosphonic acid.
  • inventive examples 15 and 16 show that the photocurable thiol-ene composition is surprisingly and unexpectedly stabilized by the synergetic effect of the combination of pyrogallol with different types of phosphonic acids, and only a slight viscosity increase (respectively from 0.92 to 1.71 Pa- s and from 1.03 to 1.83 Pa- s) occurs after 76 days at 65°C.
  • Examples 15 and 16 must be compared with comparative examples 17 and 18, which are similar compositions, but exhibit the combination of pyrogallol with non phosphonic acids.
  • inventive examples 19 to 23 show that the photocurable thiol-ene composition is surprisingly and unexpectedly stabilized by the synergetic effect of the combination of pyrogallol with phosphonic acid, when the content of Pentaerythritol tetrakis(3-mercaptopropionate) is varied from 4 wt% to 34 wt%, and only a slight viscosity increase occurs after 79 days at 65 °C.
  • inventive examples 24 to 26 containing different types of thiols show that the photocurable thiol-ene composition is surprisingly and unexpectedly stabilized by the synergetic effect of the combination of pyrogallol with phosphonic acid for different types of thiols, and only a slight viscosity increase occurs after 79 days at 65°C.
  • inventive examples 29 to 31 containing different types of allylethers or alkynes or allylazines show that the photocurable thiol-ene composition is surprisingly and unexpectedly stabilized by the synergetic effect of the combination of pyrogallol with phosphonic acid for different types of allylethers or alkynes or allylazines, and only a slight viscosity increase occurs after 79 days at 65°C.
  • Comparative example 32 exhibits the same composition as example 30 without pyrogallol and gelled after 1 day at 65°C.
  • the photocurable compositions according to the invention have been cured by the use of incoherent actinic radiation and ultraviolet (UV) radiation to produce three dimensional (3D) objects.
  • UV radiation ultraviolet
  • the addition in the thiol-ene photocurable composition of the stabilizing system phosphonic acid/phenolic component changed neither the reactivity, the photosensitivity, the curing speed of the composition, nor the mechanical strength, the elastic modulus, the toughness of the produced 3D objects.
  • the specimens for notch impact strength test were produced using digital light processing (DLP).
  • the 3D-parts were produced using a stereolithography equipment EnvisionTec Perfactory® SXGA+W/ERM Mini MultiLens with a resolution of 1400 x 1050.
  • the specimens were built with an exposure time of 11 s for a layer thickness of 50 ⁇ , at a lamp power of 800 mW/dm 2 .
  • the prototype was rinsed with ethanol, followed by 20 minutes post-curing (10 minutes per each side) under the UV lamp (INTELLI-RAY 600 Watt UV flood curing system.).
  • the specimens were rectangular with a dimension of about 14/7/55 mm (width/ height /length) for notch impact strength.
  • Izod notched impact strength was evaluated using DLP -formed notched specimen. Tests were performed on a Zwick Model 5113.11 impact tester type machine, equipped with a hammer (Zwick Co., Germany), according to ISO 180 standards. Table IV shows the results of the notch impact strength measurements on the cured composition I (comparative example) and on the inventive composition 5, cured immediately or after a storage time of 30 days at 65°C. The notch impact strength measurements show that the addition of the stabilizing system phosphonic acid/phenolic component did not impair at all the impact strength of the cured composition. Furthermore, the impact strength of the cured stabilized composition is not affected at all by an ageing time of 30 days at 65 °C before curing.
  • Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 number (wi%) (wi%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (w
  • MAI 54 1.9 - 1.9 - 1.9 1.9 - 1.9 - 1.9 1.9 - 1.9 - 1.9 - 1.9
  • Tabic 11 A compositions with different phenolic components
  • Table 11 B compositions with phosphonic and non phosphonic acids
  • Table 11 C compositions with different PETMP concentrations
  • Table 11 D compositions with different thiols
  • Tabic 11 F compositions with allylether or alkyne or allyla/ine
  • Example Storage time at 25°C at 65°C Example Storage time at 25°C at 65°C Number (day) Viscosity (Pa -s) Number (day) Viscosity (Pa -s)
  • Example Storage time (day) Viscosity (Pa-s) Example Storage time (day) Viscosity (Pa-s) Number at 65°C Number at 65°C
  • Table I II B viscosity at 25 °C as a function of 26 1.59 ageing time at 65 °C for compositions in Table 79 1.67 11 B with phosphonic and non phosphonic
  • Table III C viscosity at 25 °C as a function of ageing time at 65 °C for compositions in Table 11 C with different PET M P concentrations
  • Table III F viscosity at 25°C as a function of ageing time at 65 °C for compositions in Tabic 11 F with allylether or alkyne or allylazine

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne une composition durcissable qui comprend : A) au moins un monomère éthylénique ou acétylénique insaturé, ou un mélange des deux ; B) au moins un thiol ; D) au moins un acide phosphonique ; E) un constituant de la série benzénique ou de la série naphtalénique présentant au moins un noyau benzénique ou un noyau naphtalénique qui contiennent au minimum deux substituants hydroxyles.
PCT/EP2012/053045 2011-03-23 2012-02-23 Composition thiol-ène durcissable stable WO2012126695A1 (fr)

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EP2878613A1 (fr) 2013-12-02 2015-06-03 Allnex Belgium, S.A. Stabilisateur pour compositions de thiol-ène
WO2016050398A1 (fr) 2014-10-01 2016-04-07 Basf Se Procédé pour faire durcir des compositions durcissables
WO2018077973A1 (fr) 2016-10-27 2018-05-03 Michael Malkoch Composition comprenant des composés contenant du thiol, de l'alcène et de l'acide phosphonique pour une utilisation en tant que primaire pour l'amélioration de l'adhérence
WO2018226654A1 (fr) * 2017-06-05 2018-12-13 Austin Smith Stabilisation d'acide de concentrés et prémélanges de résine à points quantiques
JPWO2017154428A1 (ja) * 2016-03-07 2018-12-27 昭和電工株式会社 活性エネルギー線硬化性組成物及びその硬化物
WO2019081641A1 (fr) 2017-10-25 2019-05-02 Biomedical Bonding Ab Composition comprenant des composés contenant du thiol, de l'alcène et de l'acide phosphonique destinée à être utilisée comme apprêt pour l'amélioration de l'adhérence
WO2019185697A1 (fr) * 2018-03-27 2019-10-03 Mercene Labs Ab Revêtement à base d'acrylate avec ajout de thiol
WO2020001835A1 (fr) * 2018-06-26 2020-01-02 Arkema France Compositions durcissables à base de polymères à plusieurs étages
WO2020016343A2 (fr) 2018-07-20 2020-01-23 Montanuniversität Leoben Composition de résine appropriée pour l'impression et procédés d'impression
WO2020243235A1 (fr) * 2019-05-31 2020-12-03 The Regents Of The University Of Colorado, A Body Corporate Élastomères mécanotropiques
EP3804990A1 (fr) * 2018-03-28 2021-04-14 Benjamin Lund Composition thiol-acrylates photopolymerisable
US11015114B2 (en) 2015-12-31 2021-05-25 3M Innovative Properties Company Article comprising particles with quantum dots
US11015115B2 (en) 2015-12-31 2021-05-25 3M Innovative Properties Company Curable quantum dot compositions and articles
DE102020124036A1 (de) 2020-09-15 2022-03-17 Bruno Bock Chemische Fabrik GmbH & Co. Kommanditgesellschaft Sulfidhaltiges Stabilisatorsystem für Thiol-En- und Thiol-In- Zusammensetzungen
WO2022072790A1 (fr) * 2020-10-01 2022-04-07 Facebook Technologies, Llc Élastomères électroconducteurs à revêtement de surface
CN114761204A (zh) * 2019-07-23 2022-07-15 适应3D技术公司 用于3d打印的硫醇-丙烯酸酯弹性体
WO2024039675A1 (fr) * 2022-08-15 2024-02-22 Align Technology, Inc. Encre pour jet d'encre à base d'éther vinylique photopolymérisée par chimie click thiol-ène utilisée pour le renforcement de photopolymères

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US10995270B2 (en) 2013-12-02 2021-05-04 Allnex Belgium S.A. Stabilizer for thiol-ene compositions
EP2878613A1 (fr) 2013-12-02 2015-06-03 Allnex Belgium, S.A. Stabilisateur pour compositions de thiol-ène
WO2015082244A1 (fr) 2013-12-02 2015-06-11 Allnex Belgium , S.A. Stabilisateur pour compositions thiol-ène
US10563125B2 (en) 2013-12-02 2020-02-18 Allnex Belgium S.A. Stabilizer for thiol-ene compositions
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JP2017508012A (ja) * 2013-12-02 2017-03-23 オルネクス ベルギー エス エー チオール−エン組成物用安定化剤
WO2016050398A1 (fr) 2014-10-01 2016-04-07 Basf Se Procédé pour faire durcir des compositions durcissables
US10577471B2 (en) 2014-10-01 2020-03-03 Basf Se Method for curing curable compositions
US11015114B2 (en) 2015-12-31 2021-05-25 3M Innovative Properties Company Article comprising particles with quantum dots
US11015115B2 (en) 2015-12-31 2021-05-25 3M Innovative Properties Company Curable quantum dot compositions and articles
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US11015007B2 (en) 2016-03-07 2021-05-25 Showa Denko K.K. Active energy ray-curable composition and cured product thereof
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CN110072564A (zh) * 2016-10-27 2019-07-30 生物医学键合有限公司 作为底涂剂用于粘合性改善的包含硫醇、烯烃和含膦酸化合物的组合物
US11684554B2 (en) 2016-10-27 2023-06-27 Biomedical Bonding Ab Composition comprising thiol, alkene and phosphonic acid containing compounds for use as a primer for adhesion improvement
US11612549B2 (en) 2016-10-27 2023-03-28 Biomedical Bonding Ab Composition comprising thiol, alkene and phosphonic acid containing compounds for use as a primer for adhesion improvement
CN111491674B (zh) * 2016-10-27 2022-08-23 生物医学键合有限公司 用作改善附着力的底涂剂的包含含硫醇、烯烃和膦酸的化合物的组合物
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WO2018077973A1 (fr) 2016-10-27 2018-05-03 Michael Malkoch Composition comprenant des composés contenant du thiol, de l'alcène et de l'acide phosphonique pour une utilisation en tant que primaire pour l'amélioration de l'adhérence
US10961448B2 (en) 2017-06-05 2021-03-30 Nanosys, Inc. Acid stabilization of quantum dot-resin concentrates and premixes
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WO2019185697A1 (fr) * 2018-03-27 2019-10-03 Mercene Labs Ab Revêtement à base d'acrylate avec ajout de thiol
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US20210317241A1 (en) * 2018-07-20 2021-10-14 Montanuniversität Leoben Resin composition suitable for printing and printing methods
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WO2020243235A1 (fr) * 2019-05-31 2020-12-03 The Regents Of The University Of Colorado, A Body Corporate Élastomères mécanotropiques
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