CA2088031A1 - Novel diacrylates and dimethacrylates - Google Patents
Novel diacrylates and dimethacrylatesInfo
- Publication number
- CA2088031A1 CA2088031A1 CA002088031A CA2088031A CA2088031A1 CA 2088031 A1 CA2088031 A1 CA 2088031A1 CA 002088031 A CA002088031 A CA 002088031A CA 2088031 A CA2088031 A CA 2088031A CA 2088031 A1 CA2088031 A1 CA 2088031A1
- Authority
- CA
- Canada
- Prior art keywords
- group
- formula
- phenyl
- substituent selected
- unsubstituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- 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
- B33Y10/00—Processes of additive manufacturing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/922—Polyepoxide polymer having been reacted to yield terminal ethylenic unsaturation
Abstract
Novel diacrylates and dimethacrylates Abstract of the Disclosure Compounds of formulae (Ia) and (Ib) (Ia), (Ib), wherein the substituents R1 are each independently of the other hydrogen or methyl, R2 is an unsubstituted C1-C20alkyl group or a C1-C20alkyl group which is substituted by one or more than one substituent selected from the group consisting of hydroxy, C6-C14aryl and halogen, an unsubstituted phenyl group or a phenyl group which issubstituted by one or more than one substituent selected from the group consisting of C1-C6alkyl, hydroxy or halogen, or is a radical of formula -CH2-OR3, wherein R3 is an unsubstituted C1-C20alkyl group or a C1-C20alkyl group which is substituted by one or more than one substituent selected from the group consisting of hydroxy, C6-C14aryl and halogen, an unsubstituted phenyl group or a phenyl group which is substituted by one or more than one substituent selected from the group consisting of C1-C6alkyl, hydroxy and halogen, or is a C2-C6alkenyl group, a C2-C20acyl group or an unsubstituted cyclohexyl-carbonyl group or a cyclohexylcarbonyl group which is substituted by one or more than one substituent selected from the group consisting of C1-C6alkyl, hydroxy and halogen, Z is a group of formulae (IIa)-(IIe) (IIa), (IIb), (IIc), (IId),
Description
Novel diacrvlates and dimethacrYlates The present invention relates to novel acrylates and methacrylates, to photosensitive compositdons containing these compounds and to a process for the preparadon of d~ree-dimensional objects from said photosensitive composidons.
Radiation-sensitive liquid resins or resin systems can be used for a variety of utilitdes, typically as coating compositdons, adhesives or photoresists. Quite generaUy, liquid resins or resin systems should also be suitable for fabricating three~imensional objects by the stereolithographic technique described in US-A 1 575 330; but many resins prove to be too viscous, whereas others are insufficiendy light sensi~ive or suffer too severe shrinkage during the cure. The strength propeIties of the moulded articles or objects made from photocured resins are also often unsatisfactory.
Liquid resin systems for stereolithography comprising different mono- and diacrylates and mono- and dimethacrylates as well as a urethane acrylate or methacrylate and a monomeric or oligomeric diacrylate or methacrylate derived from bisphenol A or bisphenol F are disclosed in l~P-A 425 441. When precured with laser light, these systems give green stages of superior green strength and, after the full cure, rigid-elastic objects whose flexibility is, however, insufficient for certain udlides.
EP-A 506 616 discloses liquid resin composidons of several acrylates andlor methacrylates which contain further hydroxyl group containing aliphadc or cycloaliphadc acrylates and/or methacrylates. The cured moulded ardcles made from these composidons by stereolithography have superior flexibility and tear propagadon strength. A drawback of these composidons for processing in mechanical apparatus, however, is their rather high viscosity.
It has now been found possible to prepare novel hydroxyl group containing acrylates and methacrylates which, in conjuncdon with other acrylates or me~acrylates, form low viscosity photocurable composidons which, when fully cured, give moulded ar~cles of excellent flexibility.
Radiation-sensitive liquid resins or resin systems can be used for a variety of utilitdes, typically as coating compositdons, adhesives or photoresists. Quite generaUy, liquid resins or resin systems should also be suitable for fabricating three~imensional objects by the stereolithographic technique described in US-A 1 575 330; but many resins prove to be too viscous, whereas others are insufficiendy light sensi~ive or suffer too severe shrinkage during the cure. The strength propeIties of the moulded articles or objects made from photocured resins are also often unsatisfactory.
Liquid resin systems for stereolithography comprising different mono- and diacrylates and mono- and dimethacrylates as well as a urethane acrylate or methacrylate and a monomeric or oligomeric diacrylate or methacrylate derived from bisphenol A or bisphenol F are disclosed in l~P-A 425 441. When precured with laser light, these systems give green stages of superior green strength and, after the full cure, rigid-elastic objects whose flexibility is, however, insufficient for certain udlides.
EP-A 506 616 discloses liquid resin composidons of several acrylates andlor methacrylates which contain further hydroxyl group containing aliphadc or cycloaliphadc acrylates and/or methacrylates. The cured moulded ardcles made from these composidons by stereolithography have superior flexibility and tear propagadon strength. A drawback of these composidons for processing in mechanical apparatus, however, is their rather high viscosity.
It has now been found possible to prepare novel hydroxyl group containing acrylates and methacrylates which, in conjuncdon with other acrylates or me~acrylates, form low viscosity photocurable composidons which, when fully cured, give moulded ar~cles of excellent flexibility.
Accordingly, dhe invention relates to compounds of formulae (Ia) and (Ib) qJ~O~ol~ J~o~oJ~ (Ia) R1 OH OH Rl ~ ~o~ ~o~~
OH HO
wherein the substituents Rl are each independendy of ~e other hydrogen or methyl, R2 is an unsubstituted Cl-C20al~yl group or a Cl-C20alkyl group which is substituted by one or more dhan one substituent selected from the group consisting of hydroxy, C6-Cl4aryl and halogen, an unsubstituted phenyl group or a phenyl group which issubstituted by one ~ more than one substituent selected from the group consisting of Cl-C6aL~yl, hydroxy or halogen, or is a radical of formula -CH2-OR3, wherein R3 is an unsubsdtuted Cl-C20alkyl group or a Cl-C20alkyl group which is substituted by one or more dhan one subsdtuent selected from the group consisdng of hydroxy, C6-Cl4aryl and halogen, an unsubsdtuted phenyl group or a phenyl group which is subsdtuted by one or more than one subsdtuent selected from the group consisting of Cl-C6allyl, hydroxy and halogen, or is a C2-C6alkenyl group, a C2-C20acyl group or an unsubstituted cyclohexyl-carbonyl group or a cyclohexylcarbonyl group which is subsdtuted by one or more than one subsdtuent selected from the group consisdng of Cl-C6alkyl, hydroxy and halogen, Z is a group of formulae (I[a)-(IIe) (IIa), ~ (lIb), ~3Y~3 (IIc), ~3 Y ~3} Y ~3 ~Id), ~088031 Rl r\ I r~
~ C ~ (IIe), wherein Y is a direct bond, Cl-C6aLI~ylene, -S-, -O-, -SO-, -SO2- or -CO-, and Rl is hydrogen or methyl, and wherein the aromatic and cycloaliphatic rings of formulae (Ila)-aIe) are unsubstituted or substituted by one or more than one substituent selected from the group consisting of Cl-C6aLkyl, chloro and bromo.
R2 or R3 as Cl-C20aL~yl may be branched or, preferably, straight-chain alkyl. Typical examples of such aLIcyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neo-pentyl, n-hexyl, octyl, decyl, dodecyl and icosyl.
The alkyl groups may also be subsdtuted by one or more than one subsdtuent selected from the group consisdng of hydroxy, C6-CI4aryl and halogen. Typical examples ofsubs~tuted alkyl groups are hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-chloropropyl, 2,3~ichlorobutyl, 2-phenylethyl and 2,3-diphenylbutyl.
R3 as C2-C6aL~cenyl may be branched or, preferably, straight-chain alkenyl. Typical examples of aLt~enyl groups are vinyl, prop-l-enyl, prop-2~nyl, 2-methylprop-2-enyl, n-but-3-enyl, n-pent-4-enyl and n-hex-5-enyl. ALkenyl groups containing two or three carbon atoms are preferred, and vinyl, prop-l-enyl and prop-2-enyl are especially preferred.
Typical examples of C2-C20acyl groups are acetyl, propionyl, n-butyryl, isobutyryl, pivaloyl, hexyloyl, octyloyl, tetradecyloyl, hexadecyloyl and octadecyloyl.
R3 as phenyl or cyclohexylcarbonyl rnay be unsubstituted or subsdtuted by one or more than one substituent selected from the group consisting of Cl-C6alkyl, hydroxy and halogen. Typical examples of such groups are tolyl, xylyl, mesityl, 2-hydroxyphenyl, 4 hydroxyphenyl, 2-chlorophenyl, 4-chlorophenyl, 3,5-dichlorophenyl, 2,~dichlorophenyl, 2,6 dimethylcyclohexylcarbonyl, 4-hydroxycyclohexylcarbonyl, p-hydroxybenzyl, p-chlorobenzyl and o-ethylbenzyl.
The aromadc and cycloaliphadc rings in formulae (IIa)-(lIe) are preferably unsubstitute~
2~88031 In the compounds of formulae (Ia) and (Ib) R2 is preferably Cl-C20aL~cyl, phenyl, Cl-C20aL~coxymethyl, phenoxymethyl or cyclohexylcarbonyloxymethyl.
Especially preferred compounds of formulae (Ia) and (Ib) are those wherein R2 is n-butyl, phenyl, n-butoxymethyl, phenoxymethyl or cyclohexylcarbonyloxyrnethyl.
The most preferred meaning of R2 is n-butoxymethyl.
Z in formulae (Ia) and (Ib) is preferably a group of formula (IIc) or aIe).
Compounds of formulae (~a) and ab) are especially preferred wherein Z is ~3 C ~3 or ~
The compounds of formulae (Ia) and ab) can be prepared by per se known processes. A
further object of the invention is a process for the preparadon of compounds of formulae (Ia) and ab), which comprises reacting a diglycidyl ether of formula (III) ~ 0 ~ --Z--~0~ ~ (m), wherein R2 and Z have the above meanings, in a manner known per se, with acrylic or methacrylic acid.
The diglycidyl compounds of formula ~lII) are known and disclosed, inter alia, in EP-A 22 073.
The reacdon of the diglycidyl compounds of formula (III) with acrylic or methacrylic acid normally gives a mixture of compounds (Ia) and (Ib), compound (Ia) being the main product and compound (Ib) being obtained in comparatively minor amounls (c. 10-20 %).
Separation of the two structurally isomeric compounds for use in photosensidve compositions is not necessary.
s Illustratative specific examples of the diglycidyl compounds of formula (III) are:
2,2-bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis[p-(3-methoxy-2-glycidyloxypropoxy)phenyl~propane, 2,2-bis~p-(3-ethoxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis[p-(3-dodecyloxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis~p-(3-tetradecyloxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis[p-(3-benzyloxy-2-glycidyloxypropoxy)phenyl]propane, bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]methane, 1,3-bisLp-(3-phenoxy-2-glycidyloxypropoxy]benzene, bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]sulfone, 2,2-bis[p-(3-cyclohexoxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis[4-(3-butoxy-2-glycidyloxypropoxy)-3,5-dibromophenyl]propane, 2,2-bis[p-(3-allyloxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis[p-(3-phenoxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis~4-(3-butoxy-2-glycidyloxypropoxy)cyclohexyl]propane, 2,2-bis[p-(3-cyclohexylcarbonyloxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis[p-(2-glycidyloxyhexoxy)phenyl]propane, and 2,2-bis[p-(2-phenyl-2-glycidyloxyethoxy)phenyl]propane.
A further object of the invention is a photosensitive composition comprising (a) 5-65 % by weight of a compound of formula ~Ia) or (Ib) according to claim 1,(b) 15-70 % by weight of one or more than one bifunctional acrylate or methacrylate having a molecular weight in the range from 150 to 450 and differing from compound of formula (Ia) or (Ib), (c) 0-40 % by weight of one or more than one monomeric polyfunctional acrylate or methacrylate having a functionality of not less than 3 and a molecular weight of not more than 600, (d) 0-10 % by weight of at least one monofunctional acrylate or methacrylate, (e) 0-10 % by weight of N-vinylpyrrolidone or N-vinylcaprolactam, (f) 2-10 % by weight of at least one photoinitiator, and (g) 0-60 % by weight of at least one ure~hane acrylate or methacrylate having a functionality of 2-4 and a molecular weight in d~e range from 500 10 000, such that the sum of the amounts of components (a) to (g) together is 100 % by weight.
Compounds useful as component (b) include the diacrylate and dimethacrylate esters of aliphadc, cycloaliphadc or aromatic diols, including 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, tripropylene glycol, ethoxylated or propoxylated neopentyl glycol, 1,4-dihydroxymethylcyclohexane, 2,2-bis(4hydroxycyclohexyl)propane, bis(4-hydroxycyclohexyl)methane, hydroquinone, 4,4' dihydroxybiphenyl, bisphenol A, bisphenol P, bisphenol S, ethoxylated or propoxylated bisphenol A, ethoxylated or propoxylated bisphenol P or ethoxylated or propoxylated bisphenol S.
Such diacrylates and dimethacrylates are known and some are comrnercially available, typically those sold by the SARTOMER Company under the product names SR 348 for the dimethacrylate of ethoxylated bisphenol A, SR 349 for the diacrylate of ethoxylated bisphenol A, SR 247 for neopentyl glycol diacrylate and SR 344 for polyethylene glycol 400 diacrylate.
It is preferred to use a diacrylate or dimethacrylate of ethoxylated bisphenol A as component (b).
Compounds useful as component (c) are typically triacrylates or trimethacrylates of formula (IV) or (V~
R4--CH2--C~CH2--Rs)3 (IV), R5 {~ 2--R5)2 (V)~
wherein R4 is hydrogen, methyl or hydroxyl, and R5 is a radical of formula (VI) --O~il--CH2{~C~=CH2 (VI), wherein n is O or a number from 1-3 and R6 and R7 are each independendy of the other hydrogen or methyl.
Among the compounds of formulae (IV) and (V), those compounds of formula (IV) are especially preferred in which R4 is methyl and R5 is a radical of formula (VI), wherein n is 0.
Illustradve examples of compounds which may be used as component (c) are:
l,1,1-trimethylolprQpane triacrylate or methacrylate, ethoxylated or propoxylated l,l,l-trimethylolpropanetriacrylate or methacrylate, ethoxylated or propoxylated glycerol triacrylate, pentaerythritol monohydroxy triacrylate or methacrylate; and also higher funcdonal ac~ylates or methacrylates such as dipentaerythritol monohydroxy pentaacrylate or bis(trimethylolpropane) tetraacrylate. Such compounds are known to the skilled person and some are commercially available.
Preferably the compounds useful as component (c) have a molecular weight in the range from 250 to 700.
It is esperially prefelTed to use trimethylolpropanetriacrylate and trimethylolpropane trimethacrylate as component (c).
Component (d) of the novel composidons may be selected from the following compounds:
allyl acryiate, allyl methacrylate, methyl (meth~acrylate, ethyl (rneth)acrylate, n-propyl , n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate and n-dodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- and 3-hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth~acrylate and 2- or 3-ethoxypropyl (meth)acrylate, tetrahydrofu~furylmethacrylate, 2-(2-ethoxyethoxykthylacrylate, cyclohexyl methacrylate, 2-phenoxyethyl acrylate, glycidyl acrylate and isodecyl acrylate.
Such products are also known and some are commercially available, as from SARTOMER.
2-Phenoxyethylacrylate is especially prefe~
The novel composidons may contain up to 10 % by weight of N-vinylpy~rolidone o~
N-vinylcaprolactam or a mixture thereof as component (e). It is preferred to useN-vinylpyrrolidone.
8- `~088031 Any type of photoinidator which, when irradiated suitably, forms free radicals can be employed as component (f) in tho novel compositions. Typical known photoinidators are benzoins, benzoin ethers, including benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, benzoin phenyl ether and benzoin acetate; acetophenones, including acetophenone, 2,2-dimethoxyacetophenone and l,l-dichloroacetophcnone;
benzil, benzil ketals such as benzil dimethyl ketal and benzil diethyl ketal; anthraquinones, including 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, l~hloroanthraquinone and 2-amylanthraquinone; triphenylphosphine; benzoylphosphine oxides, for example 2,4,~trimethylbenzoyldiphenylphosphine oxide (Luzinn TPO);
benzophenones such as benzophenone and 4,A'-bis(N,N'-dimethylamino)benzophenone;thioxanthones and xanthones; acridine derivadves; phenazine derivadves; quinoxaline derivadves or l-phenyl-1,2-propanedione; 2-~benzoyl oxime; l-aminophenyl ketones or l-hydroxyphenyl ketones such as l-hydroxycyclohexyl phenyl ketone, phenyl l-hydroxyisopropyl ketone and 4-isopropylphenyl l-hydroxyisopropyl ketone.
Suitable initiators are also are electron transfer inidators of the xanthone type, for example 2,4,5,7-tetraiodo-~hydroxy-9-cyano-3H-xanthen-3-one which, together with suitable electron donors, have a high reactivity in the visible range of the spectrum.
Another class of suitable photoinitiators (f) comprises the ionic dye-counter ion compounds which are capable of absorbing acdnic radiadon and generadng free radicals which inidate the polymerisadon of the acrylates (a) to (d) and optionally (g). The compositdons of the invendon containing ionic dye-counter ion compounds can be cured more vaAably in this way with visible light within the adjustable wavelength range of 400 700 nm. Ionic dye-counter ion compounds and their mode of acdon are known, for example from EP-A-0 223 587 and US patents 4 751 102; 4 772 530 and 4 772 541.
Typical examples of suitable ionic dye-counter ion compounds are the anionic dye-iodonium ion complexes, the anionic dye-pyrylium ion complexes and, especially, the cadonic dye-borate anion compounds of formula R8 Rg /B\ X+, Rlo Rll 2~88031 g wherein X~ is a cationic dye and R8, Rg, Rlo and Rll are each independent1y of one another an alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl or alkynyl group, or an alicyclic or saturated or unsaturated heterocyclic group.
Particularly suitable photoinidators which are norrnally used in conjunction with a HeCd laser as source of irradiation are acetophenones such as 2,2-dialkoxybenzophenones, and a-hydroxyphenylketones, typically l-hydroxycyclohexylphenyl ketone or (2-hydroxyisopropyl)phenyl ketone (= 2-hydroxy-2,2-dimethylacetophenone).
A particularly preferred photoinitiator is l-hydroxycyclohexylphenyl ketone.
The novel compositions may also contain other photoinitiators of different sensidvity to radiadon of emission lines of different wavelengths. The inclusion of such photoinitiators effects the better udlisation of a UV/VIS light source which radiates emission lines of different wavelength. It is advantageous to choose these other photoinitdators and to use them in such a concentration that a uniform optical absoIpdon is produced with respect to the emission lines used.
The urethane acrylates used in the novel compositions as component (g) are known to those skilled in the art and can be prepared in known manner, typically by reacdng a hydroxyl-terlninated polyurethane with acrylic acid or methacrylic acid to the corresponding urethane acrylate, or by reacting an isocyanate-terminated prepolymer with hydroxyaLkyl acrylates or methacrylates to the urethane acrylate. Suitable processes are disclosed, inter alia, in EP-A 114 982 and EP-A 133 908. The molecular weight of such acrylates is generally in the range from 4Q0 to 10 000, preferably from 500 to 7000.
Urethane acrylates are also commercially available and are sold by UCB under theregistered trademark EBECRYL~, by Morton Thiokol under the registered trademark Uvithane~9 or by the SARTOMER Company under the product names SR 9504, SR 9600, SR 9610, SR 9620, SR 9630, SR 9640 and SR 9650.
It is preferred to use those urethane acrylates with have a molecular weight from 500 7000 and which are prepared preferably from aliphatic educts.
The novel photosensitive compositions can be polymerised by irradiation with actinic light, typically with electron beams, X-rays, UV or VIS light, i.e. with radiation in the `~88031 wavelength range from 280-650 nm. Particularly sui~able light sources are HeCd, argon or nitrogen laser light as well as metal vapour and NdYAG lasers with multiplc fiequency.
Those skilled in the art will know that the appropriate photoinitiator for each selected light source must be chosen and, if necessary, sensidsed. It has been found that the depth of penetradon of the radiatdon into the polymeIised composition and the processing rate are directly related to the absorpdon coefficient and the concentratdon of the photoinidator. In stereolithography it is preferred to use those photoinitiators which generate the highest number of resulting free radicals and make possible the greatest depth of penentradon into the compositions to be polymerised.
The invendon further relates to a process for the producdon of three-dimensional objects frDm the novel liquid compositions by lithographic methods, especially by stereolithography, in wh*h a layer of novel liquid composition is irradiated over the entire surface or in a predetermined pattern with a W/VIS light source, such that within the irradiated areas a layer solidifes in a desired layer thickness, then a new layer of novel composition is formed on the solidified layer, which is likewise irradiated over the entire surface or in a predetermined pattern, and such that three-dimensional objects are formed from a plurality of solidified layers which adhere to one another by repeated coating and irradiation.
In this process it is preferred to use a laser light which is preferably computer-controlled.
The novel compositions are distinguished by low viscosity and hence good processing properties. The green models obtained by precuring with laser light and the fully cured objects have good mechanical properdes, especially superior flexibility.
The novel compositions can be used typically as adhesive or coating compositions or as formulations for stereolithography or other methods of model construcdon with photopoplymers .
If the novel compositions are used as coating compos;dons, clear and hard coats are obtained on wood, paper, metal, ceramic or other surfaces. The coating thickness can vary over a very wide range and be from c. 1 ~,lm to c. 1 mm. ~elief images for printed circuit boards or printing plates can be produced from the novel compositions, conveniendy by computer-controlled laser light of appropriate wavelength or using a photomask and a suitable light source.
11 .
It is preferred to use the novel composidons for the producdon of photopolymerised layers, especially in the form of three-dimensional objects which are formed from a plurality of solidified layers which adhere to one another.
Examples:
I. Preparadon of the novd acrYlates and methacrYlates .l. Acrvlato A: Diacrylate of 2,2-bis(p-(3-butoxy-2-glycidyloxy-propoxy)phenyl]propane Method I: 100 g of 2,2-bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]propane (prepared according to EP-A 22 073) having an epoxy value of 2.9 eqkg are dissolved in 250 rnl of toluene. Then 1 g of tetraethylammonium bromide and 0.2 g of hydroquinone monomethyl ether are added and the mixture is heated to 80 C. A mixture of 22.98 g (0.32 mol) of acrylic acid and 0.17 g of hydroquinone monomethyl ether is then slowly added dropwise.
The reacdon mixture is kept at 80 C undl the epoxy value is less than 0.1 eqkg (c. 14 h).
The reaction mixture is then cooled to room temperature and extracted with a 5 % aqucous soludon of NaHCO3 and then with water. The organic phase is dried and concentrated first on a rotary evaporator and then under a high vacuum~
Yield: 106.94 g (88.5 %).
Method II: 0.2 g of di-tert-butyl p-cresol are added to 343.9 g of 2,2-bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]propane (prepared according to EP-A 22 073~ having an epoxy value of 2.9 eq/lcg, and the mixture is heated to 110 C With stirring, a mixture of 72.06 g (1 mol) of acrylic acid, 0.56 g of Nuosyn Chromium~ 5 % (fatty acid chromium salt in hydrocarbons, Durharn Chemicals, GB) and 0.42 g of di-tert-butyl p-cresol is added dropwise. The rnixture is kept at 110 C undl the epoxy value is less than 0.1 eq/kg (c. 4 h). A brownish viscous resin having a double bond value of 2.38 ea~kg is obtained (88.5 % of theory).
I.2. Methacrvlate B: Dimethacrylate of 2,2-bistp-(3-butoxy-2-glycidyloxy-propoxy)phenyllpropane 343.9 g of 2,2-bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]propane (prepared according to EP-A 22 073) having an epoxy value of 2.9 eq~g are reacted with 86.09 g (1 mol) of methacrylic acid by method II described above. The mixture is stirred at c. 110 C until the epoxy value is less than 0.1 eq/kg (c. 4 h). A brownish viscous resin hanng a double bond content of 2.26 eq/kg is obtained (87.2 96 of theory).
.3. Acrv!ate C: DiacIylate of 2,2-bist4-(3-butoxy-2-glycidyloxy-propoxy)cyclohexyl]propane 100 g of 2,2-bis~4-(3-butoxy-2-glycidyloxypropoxy)cyclohexyl]propane (prepared according to EP-A 22 073) having an epoxy value of 2.48 eq/kg are reacted with 19.67 g (0.273 mol) of acrylic acid by method I described above. The solution is sdrred for 4 h at 80 C. The epoxy value is then 0.12 ealkg. After extracdon with a 5 % aqueous solution of NaHCO3 and then with water, the organic phase is concentrated under a high vacuum.
Yield: 87.8 g (74.5 %) Double bond value: 1.91 eqQcg (71.8 % of theory).
.4. Methacrvlate D: Dirnethacrylate of 2,2-bis[4-(3-butoxy-2-g}ycidyloxy-propoxy)cyclohexyl]propane 82 g of 2,2-bis[4-(3-butoxy-2-glycidyloxypropoxy)cyclohexyl]propane ~prepared according to EP-A 22 073) having an epoxy value of 2.48 eq/kg are reacted with 19.2 g (0.223 mol) of methacrylic acid by method I described above. The soludon is sdrred for c. 32 h at 80 C. The epoxy value is then 0.17 eq~g. After extracdon with a 5 % aqueous soludon of NaHCO3 and then with water, the organic phase is concentrated under a high vacuum.
Yield: 84.33 g (84.7 %) Double bond value: 1.90 eq/~g (74.5 % of theory).
I.S. AcrYlate E: Diacrylate of 2,2-bislp-(3-phenoxy-2-glycidyloxy-propoxy)phenyl]propane 50 g of 2,2-bis[p-(3-phenoxy-2-glycidyloxypropoxy)phenyl]propane (prepared according to EP-A 22 073) having an epoxy value of 2 7 ea~g are reacted with 9.76 g (0.135 mol) acrylic acid by method II described above to give a viscous resin having a double bond value of 2.28 eq/kg (85.8 % of theory).
2asgo3l I.6. Acrvlate F: Diacrylate of 2,2-bis[p-(3-cyclohexylcarbonyloxy-2-glycidyloxy-propoxy)phenyl]propane a) Preparation of 2,2-bis[p-(3-cyclohexylcarbonyloxy-2-glycidyloxypropoxy)-phenyl]propane (according to EP-A 22 073):
With stirring, 50 g (0.27 mol) of glycidyl cyclohexanoate, 30 g (0.135 mol) of bisphenol A
and 0.8 g of benzyltrimethylamrnonium bromide are heated to 110 C. When the exothermic reacdon has subsided (rise in temperature to 140 C), the reacdon mixture is further sdrred at 10 C undl the epoxy value is less than 0.1 eq/lcg (2 h).
35 g (0.059 mol) of the resultant reacdon product are reacted with 87 g (0.94 mol) of epichlorohydrin and 0.77 g of tetramethylammonium bromide by the method described in EP-A 22 073. After addidon of 9.6 g (0.12 mol) of 50 % aqueous sodium hydroxide and removal of the water under vacuum, the product is isolated and dried.
Yield: 15.5 g (37 ~o) Epoxy value: 1.90 eq~cg (74.5 % of theory) b) Preparatdon of the diacrylate:
12.97 g (0.27 mol) of 2,2-bis[p-(3-cyclohexylcarbonyloxy-2-glycidyloxypropoxy)phen-yl]propane prepared acco~ding to a) are reacted with 1.8 g (0.025 mol) of acrylic acid by method II described above to give a viscous resin having a double bond value of 1.84 eq/kg t78.3 % of theory).
I.7. Acrvlate G: Diacrylate of 2,2-bis[p-(2-glycidyloxyhexoxy)phenyl]propanea) Preparadon of 2,2-bis[p-(2-glycidyloxyhexoxy)phenyl]propane (according to EP-A æ 073):
With stirring, 100.2 g (1 mol) of butyl oxirane, 114 g (0.5 mol) of bisphenol A and 2.14 g of benzyltrimethylammonium bromide are heated to 110 C. When the exothermic reacdon has subsided (rise in temperature to 115 C), the reacdon is further stirred at 110 C undl the epoxy value is less than 0.1 e~g (16 h).
85.52 g (0.2 mol) of the resultant reacdon product are reacted with 296 g (3.2 mol) of epichlorohydrin and 1.32 g of tetramethylammonium bromide according to the method described in EP-A 22 073. After addition of 33.6 g (Q.42 mol) of 50 % aqueous sodium hydroxide and removal of the water under vacuum, the product is isolated and dried.
Yield: 87.2 g (80.6 %) Epoxy value: 2.51 eq~cg (67.9% of theory).
~088031 b) Preparadon of the diacrylate:
100 g (0.11 mol) of 2,2-bislp-(2-glycidyloxyhexoxy)phenyl]propane prepared according to a) are reacted with 15.85 g (0.22 mol) of acrylic acid by method II described above to give a viscous resin having a double bond value of 1.87 eq,~cg (64 % of theory).
.8. Acrvlate H: Diacrylate of 2,2-bis[p-(2-phenyl-2-glycidyloxy-ethoxy)phenyl]propane a) Preparadon of 2,2-bis[p-(2-phenyl-2-glycidyloxyethoxy)phenyl]propane (according to EP-A 22 073):
With stirring, 100 g (0.83 mol) of phenylethylene oxide, 94.7 g (0.415 mol) of bisphenol A
and 1.95 g of benzyltrimethylammonium bromide are heated to 110 C When the exothermic reacdon has subsided (rise in temperature to 115 C), the reactdon mixture is further sdrred at 110 C undl the epoxy value is less than 0.1 eq/lcg (5 h).
80 g (0.17 mol) of the resultant reacdon product are reacted with 251.6 g (2.72 mol) of epichlorohydrin and 0.9 g of tetramethylammonium bromide according to the methoddescribed in EP-A 22 073. After addidon of 28.8 g (0.36 mol) of 50 % aqueous sodium hydroxide and removal of the water under vacuum, the product is isolated and dried.
Yield: 60.5 g (58.5 %) Epoxy value: 2.56 eq/kg (78 % of theory~.
b~ Preparadon of the diacrylate:
25 g (0.032 mol) of 2,2-bis[p-(2-phenyl-2-glycidyloxyethoxy)phenyl]propane prepared according to a) are reacted with 4.6 g (0.064 mol) of acrylic acid by method II described above to give a viscous resin having a double bond value of 2.12 eqlkg (76.8 % of theory).
II. Use Exam~les Use of the novel diacrylates and dimethacrylates in formuladons for stereolithography.
Exam~le 1:
49.85 g of acrylate A, 26 g of the dimethacrylate of ethoxylated bisphenol A (SR 348, Sartomer), 14 g of trimethylolpropane trimethacrylate (SR 350, Sartomer) and 6 g of phenoxyethyl acrylate (SR 339, Sartomer) are mixed at c. 60 C with 0.15 g of hydroquinone monomethyl ether and 4 g of l-hydroxycyclohexyl phenyl ketone. The resultant homogeneous liquid formuladon has a viscosity of 631 mPa-s at 30 C. Amoulded ardcle (green model) cured from this formuladon using a HelCd laser () 3 ~
(40 mJ/cm3 has a modulus of elasticity (DIN 53 371; green strength) of 16.2 N/mm2, a tensile strength ~ma~ (DIN 53 455) of 1.31 N/mm2 and a flexural elongadon (DIN 53 455) of 10.2 %.
The green model is fully cured by irradiation for 30 minutes with UV/VIS light. The moulded article then has the following properdes:
modulus of elasticity: 1610 N/mm2 tensile strength ~max 32.8 N/mm2 flexural elongation ~: 7.2 %
Examples 2-10: Formulations of the components listed in Tables 1 and 2 are prepared and processed to three-dimensional objects as described in Example 1. The properties of the liquid formulations, of the green models and of the fully cured moulded articles are indicated in Table 2.
Table 1:
Example _ 2 3 4 acrylate A [g] 49.85 36.85 methacrylate B [g] 49.85 methacrylate D [g] 48.85 dimethacrylate of ethoxylated bisphenol A [g] 26.0 26.0 6.0 (SR 348, Sartomer) diacrylate of ethoxylated bisphenol A [g] 26.0 25.0 (SR 349, Sartomer) trimethylolpropane trimethacrylate (SR 350, Sartomer) [g] 14.0 14.0 6.0 trimethylolpropane triacrylate (SR 351, Sartomer) [g] 14.0 12.0 phenoxyethyl acrylate (SR 339, Sartomer) [g] 6.0 6.0 6.0 5.0 l-hydroxycyclohexyl phenyl ketone [g] 4.0 4.0 5~0 4.0 N-vinylpy~rolidone [g] 5.0 hydroquinone monomethyl ether [g] 0.15 0.15 0.15 0.15 _ Viscosity Tl of the liquid formuladon at 30 C [mPa- s] 631 578 451 302 Properties of the green models modulus of elasdcity lN/mm2] 16.2 20.4 35.8 tensile strength ~ma~ [N/mm2] 1.31 1.56 2.70 flexural elongation ~ [~o] 10.2 20.4 12.5 _ Properties of the fully cured moulded ardcles modulus of elasticity [N/mm2] 1610 1734 1660 251.3 tensile strength ~ma~ [N/mm2] 32.8 35.0 32.0 9.8 flexural elongation ~ [%] 7.2 4.1 5.0 11.0 _ - 17- 208803~
Table 2:
_ Example 5 6 7 8 9 10 _ acrylate A [g] 9.0 30.0 19.0 methacrylate B [g] 9.0 30.0 19.0 dimethacrylate of ethoxylated bisphenol A 29.0 29.0 5.0 5.0 29.0 29.0 (SR 348, Sartomer) tg]
diacrylate of ethoxylated bisphenol A 20.0 20.0 (SR 349, Sartomer) polyethylene glycol 400 diacrylate [g]14.0 14.0 14.0 14.0 (SR 344, Sartomer) neopentylglycol diacrylate 7.0 7.0 7.0 7.0 tnmethylolpropane triacrylate [g] 12.0 12.0 (SR 351, Sartomer) phenoxyethyl acrylate [g] 1.0 1.0 5.0 5.0 1.0 1.0 l-hydroxycyclohexyl phenyl ketone [g] 5.0 5.0 5.0 5.0 5.0 5.0 aliphatic urethane acrylate [g] 35.0 35.0 23.0 23.0 25.0 25.0 (SR 9640, Sartomer, MG: 1300, viscosity at 60 C: 18000 mPa s) _ viscosity ~ of the liquid formulation 1490 1600 2250 2120 1010 925 at 30 C [mPa s]
. _ . _ Properties of the green models modulus of elasticity [N/mm2] 23.9 59.4 52.2 36A 19.6 27.3 tensile strength ~m8~ [N/mm2] 3.7 3.8 3.7 3.9 29 3.3 flexural elongation ~ [%] 22.8 17.4 13.6 20.0 19.9 18.8 _ Properiies of the fully curred moulded articles modulus of elasticity [N/mm2] 729 948 772 1340 941 1102 tensile streng~h ~ma~ [Nlmm2] 26.6 27.8 18.7 24.8 25.8 3Q0 flexural elongation ~ [%] 21.0 17A 7 5 6.3 13.5 16.0
OH HO
wherein the substituents Rl are each independendy of ~e other hydrogen or methyl, R2 is an unsubstituted Cl-C20al~yl group or a Cl-C20alkyl group which is substituted by one or more dhan one substituent selected from the group consisting of hydroxy, C6-Cl4aryl and halogen, an unsubstituted phenyl group or a phenyl group which issubstituted by one ~ more than one substituent selected from the group consisting of Cl-C6aL~yl, hydroxy or halogen, or is a radical of formula -CH2-OR3, wherein R3 is an unsubsdtuted Cl-C20alkyl group or a Cl-C20alkyl group which is substituted by one or more dhan one subsdtuent selected from the group consisdng of hydroxy, C6-Cl4aryl and halogen, an unsubsdtuted phenyl group or a phenyl group which is subsdtuted by one or more than one subsdtuent selected from the group consisting of Cl-C6allyl, hydroxy and halogen, or is a C2-C6alkenyl group, a C2-C20acyl group or an unsubstituted cyclohexyl-carbonyl group or a cyclohexylcarbonyl group which is subsdtuted by one or more than one subsdtuent selected from the group consisdng of Cl-C6alkyl, hydroxy and halogen, Z is a group of formulae (I[a)-(IIe) (IIa), ~ (lIb), ~3Y~3 (IIc), ~3 Y ~3} Y ~3 ~Id), ~088031 Rl r\ I r~
~ C ~ (IIe), wherein Y is a direct bond, Cl-C6aLI~ylene, -S-, -O-, -SO-, -SO2- or -CO-, and Rl is hydrogen or methyl, and wherein the aromatic and cycloaliphatic rings of formulae (Ila)-aIe) are unsubstituted or substituted by one or more than one substituent selected from the group consisting of Cl-C6aLkyl, chloro and bromo.
R2 or R3 as Cl-C20aL~yl may be branched or, preferably, straight-chain alkyl. Typical examples of such aLIcyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neo-pentyl, n-hexyl, octyl, decyl, dodecyl and icosyl.
The alkyl groups may also be subsdtuted by one or more than one subsdtuent selected from the group consisdng of hydroxy, C6-CI4aryl and halogen. Typical examples ofsubs~tuted alkyl groups are hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-chloropropyl, 2,3~ichlorobutyl, 2-phenylethyl and 2,3-diphenylbutyl.
R3 as C2-C6aL~cenyl may be branched or, preferably, straight-chain alkenyl. Typical examples of aLt~enyl groups are vinyl, prop-l-enyl, prop-2~nyl, 2-methylprop-2-enyl, n-but-3-enyl, n-pent-4-enyl and n-hex-5-enyl. ALkenyl groups containing two or three carbon atoms are preferred, and vinyl, prop-l-enyl and prop-2-enyl are especially preferred.
Typical examples of C2-C20acyl groups are acetyl, propionyl, n-butyryl, isobutyryl, pivaloyl, hexyloyl, octyloyl, tetradecyloyl, hexadecyloyl and octadecyloyl.
R3 as phenyl or cyclohexylcarbonyl rnay be unsubstituted or subsdtuted by one or more than one substituent selected from the group consisting of Cl-C6alkyl, hydroxy and halogen. Typical examples of such groups are tolyl, xylyl, mesityl, 2-hydroxyphenyl, 4 hydroxyphenyl, 2-chlorophenyl, 4-chlorophenyl, 3,5-dichlorophenyl, 2,~dichlorophenyl, 2,6 dimethylcyclohexylcarbonyl, 4-hydroxycyclohexylcarbonyl, p-hydroxybenzyl, p-chlorobenzyl and o-ethylbenzyl.
The aromadc and cycloaliphadc rings in formulae (IIa)-(lIe) are preferably unsubstitute~
2~88031 In the compounds of formulae (Ia) and (Ib) R2 is preferably Cl-C20aL~cyl, phenyl, Cl-C20aL~coxymethyl, phenoxymethyl or cyclohexylcarbonyloxymethyl.
Especially preferred compounds of formulae (Ia) and (Ib) are those wherein R2 is n-butyl, phenyl, n-butoxymethyl, phenoxymethyl or cyclohexylcarbonyloxyrnethyl.
The most preferred meaning of R2 is n-butoxymethyl.
Z in formulae (Ia) and (Ib) is preferably a group of formula (IIc) or aIe).
Compounds of formulae (~a) and ab) are especially preferred wherein Z is ~3 C ~3 or ~
The compounds of formulae (Ia) and ab) can be prepared by per se known processes. A
further object of the invention is a process for the preparadon of compounds of formulae (Ia) and ab), which comprises reacting a diglycidyl ether of formula (III) ~ 0 ~ --Z--~0~ ~ (m), wherein R2 and Z have the above meanings, in a manner known per se, with acrylic or methacrylic acid.
The diglycidyl compounds of formula ~lII) are known and disclosed, inter alia, in EP-A 22 073.
The reacdon of the diglycidyl compounds of formula (III) with acrylic or methacrylic acid normally gives a mixture of compounds (Ia) and (Ib), compound (Ia) being the main product and compound (Ib) being obtained in comparatively minor amounls (c. 10-20 %).
Separation of the two structurally isomeric compounds for use in photosensidve compositions is not necessary.
s Illustratative specific examples of the diglycidyl compounds of formula (III) are:
2,2-bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis[p-(3-methoxy-2-glycidyloxypropoxy)phenyl~propane, 2,2-bis~p-(3-ethoxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis[p-(3-dodecyloxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis~p-(3-tetradecyloxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis[p-(3-benzyloxy-2-glycidyloxypropoxy)phenyl]propane, bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]methane, 1,3-bisLp-(3-phenoxy-2-glycidyloxypropoxy]benzene, bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]sulfone, 2,2-bis[p-(3-cyclohexoxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis[4-(3-butoxy-2-glycidyloxypropoxy)-3,5-dibromophenyl]propane, 2,2-bis[p-(3-allyloxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis[p-(3-phenoxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis~4-(3-butoxy-2-glycidyloxypropoxy)cyclohexyl]propane, 2,2-bis[p-(3-cyclohexylcarbonyloxy-2-glycidyloxypropoxy)phenyl]propane, 2,2-bis[p-(2-glycidyloxyhexoxy)phenyl]propane, and 2,2-bis[p-(2-phenyl-2-glycidyloxyethoxy)phenyl]propane.
A further object of the invention is a photosensitive composition comprising (a) 5-65 % by weight of a compound of formula ~Ia) or (Ib) according to claim 1,(b) 15-70 % by weight of one or more than one bifunctional acrylate or methacrylate having a molecular weight in the range from 150 to 450 and differing from compound of formula (Ia) or (Ib), (c) 0-40 % by weight of one or more than one monomeric polyfunctional acrylate or methacrylate having a functionality of not less than 3 and a molecular weight of not more than 600, (d) 0-10 % by weight of at least one monofunctional acrylate or methacrylate, (e) 0-10 % by weight of N-vinylpyrrolidone or N-vinylcaprolactam, (f) 2-10 % by weight of at least one photoinitiator, and (g) 0-60 % by weight of at least one ure~hane acrylate or methacrylate having a functionality of 2-4 and a molecular weight in d~e range from 500 10 000, such that the sum of the amounts of components (a) to (g) together is 100 % by weight.
Compounds useful as component (b) include the diacrylate and dimethacrylate esters of aliphadc, cycloaliphadc or aromatic diols, including 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, tripropylene glycol, ethoxylated or propoxylated neopentyl glycol, 1,4-dihydroxymethylcyclohexane, 2,2-bis(4hydroxycyclohexyl)propane, bis(4-hydroxycyclohexyl)methane, hydroquinone, 4,4' dihydroxybiphenyl, bisphenol A, bisphenol P, bisphenol S, ethoxylated or propoxylated bisphenol A, ethoxylated or propoxylated bisphenol P or ethoxylated or propoxylated bisphenol S.
Such diacrylates and dimethacrylates are known and some are comrnercially available, typically those sold by the SARTOMER Company under the product names SR 348 for the dimethacrylate of ethoxylated bisphenol A, SR 349 for the diacrylate of ethoxylated bisphenol A, SR 247 for neopentyl glycol diacrylate and SR 344 for polyethylene glycol 400 diacrylate.
It is preferred to use a diacrylate or dimethacrylate of ethoxylated bisphenol A as component (b).
Compounds useful as component (c) are typically triacrylates or trimethacrylates of formula (IV) or (V~
R4--CH2--C~CH2--Rs)3 (IV), R5 {~ 2--R5)2 (V)~
wherein R4 is hydrogen, methyl or hydroxyl, and R5 is a radical of formula (VI) --O~il--CH2{~C~=CH2 (VI), wherein n is O or a number from 1-3 and R6 and R7 are each independendy of the other hydrogen or methyl.
Among the compounds of formulae (IV) and (V), those compounds of formula (IV) are especially preferred in which R4 is methyl and R5 is a radical of formula (VI), wherein n is 0.
Illustradve examples of compounds which may be used as component (c) are:
l,1,1-trimethylolprQpane triacrylate or methacrylate, ethoxylated or propoxylated l,l,l-trimethylolpropanetriacrylate or methacrylate, ethoxylated or propoxylated glycerol triacrylate, pentaerythritol monohydroxy triacrylate or methacrylate; and also higher funcdonal ac~ylates or methacrylates such as dipentaerythritol monohydroxy pentaacrylate or bis(trimethylolpropane) tetraacrylate. Such compounds are known to the skilled person and some are commercially available.
Preferably the compounds useful as component (c) have a molecular weight in the range from 250 to 700.
It is esperially prefelTed to use trimethylolpropanetriacrylate and trimethylolpropane trimethacrylate as component (c).
Component (d) of the novel composidons may be selected from the following compounds:
allyl acryiate, allyl methacrylate, methyl (meth~acrylate, ethyl (rneth)acrylate, n-propyl , n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate and n-dodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- and 3-hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth~acrylate and 2- or 3-ethoxypropyl (meth)acrylate, tetrahydrofu~furylmethacrylate, 2-(2-ethoxyethoxykthylacrylate, cyclohexyl methacrylate, 2-phenoxyethyl acrylate, glycidyl acrylate and isodecyl acrylate.
Such products are also known and some are commercially available, as from SARTOMER.
2-Phenoxyethylacrylate is especially prefe~
The novel composidons may contain up to 10 % by weight of N-vinylpy~rolidone o~
N-vinylcaprolactam or a mixture thereof as component (e). It is preferred to useN-vinylpyrrolidone.
8- `~088031 Any type of photoinidator which, when irradiated suitably, forms free radicals can be employed as component (f) in tho novel compositions. Typical known photoinidators are benzoins, benzoin ethers, including benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, benzoin phenyl ether and benzoin acetate; acetophenones, including acetophenone, 2,2-dimethoxyacetophenone and l,l-dichloroacetophcnone;
benzil, benzil ketals such as benzil dimethyl ketal and benzil diethyl ketal; anthraquinones, including 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, l~hloroanthraquinone and 2-amylanthraquinone; triphenylphosphine; benzoylphosphine oxides, for example 2,4,~trimethylbenzoyldiphenylphosphine oxide (Luzinn TPO);
benzophenones such as benzophenone and 4,A'-bis(N,N'-dimethylamino)benzophenone;thioxanthones and xanthones; acridine derivadves; phenazine derivadves; quinoxaline derivadves or l-phenyl-1,2-propanedione; 2-~benzoyl oxime; l-aminophenyl ketones or l-hydroxyphenyl ketones such as l-hydroxycyclohexyl phenyl ketone, phenyl l-hydroxyisopropyl ketone and 4-isopropylphenyl l-hydroxyisopropyl ketone.
Suitable initiators are also are electron transfer inidators of the xanthone type, for example 2,4,5,7-tetraiodo-~hydroxy-9-cyano-3H-xanthen-3-one which, together with suitable electron donors, have a high reactivity in the visible range of the spectrum.
Another class of suitable photoinitiators (f) comprises the ionic dye-counter ion compounds which are capable of absorbing acdnic radiadon and generadng free radicals which inidate the polymerisadon of the acrylates (a) to (d) and optionally (g). The compositdons of the invendon containing ionic dye-counter ion compounds can be cured more vaAably in this way with visible light within the adjustable wavelength range of 400 700 nm. Ionic dye-counter ion compounds and their mode of acdon are known, for example from EP-A-0 223 587 and US patents 4 751 102; 4 772 530 and 4 772 541.
Typical examples of suitable ionic dye-counter ion compounds are the anionic dye-iodonium ion complexes, the anionic dye-pyrylium ion complexes and, especially, the cadonic dye-borate anion compounds of formula R8 Rg /B\ X+, Rlo Rll 2~88031 g wherein X~ is a cationic dye and R8, Rg, Rlo and Rll are each independent1y of one another an alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl or alkynyl group, or an alicyclic or saturated or unsaturated heterocyclic group.
Particularly suitable photoinidators which are norrnally used in conjunction with a HeCd laser as source of irradiation are acetophenones such as 2,2-dialkoxybenzophenones, and a-hydroxyphenylketones, typically l-hydroxycyclohexylphenyl ketone or (2-hydroxyisopropyl)phenyl ketone (= 2-hydroxy-2,2-dimethylacetophenone).
A particularly preferred photoinitiator is l-hydroxycyclohexylphenyl ketone.
The novel compositions may also contain other photoinitiators of different sensidvity to radiadon of emission lines of different wavelengths. The inclusion of such photoinitiators effects the better udlisation of a UV/VIS light source which radiates emission lines of different wavelength. It is advantageous to choose these other photoinitdators and to use them in such a concentration that a uniform optical absoIpdon is produced with respect to the emission lines used.
The urethane acrylates used in the novel compositions as component (g) are known to those skilled in the art and can be prepared in known manner, typically by reacdng a hydroxyl-terlninated polyurethane with acrylic acid or methacrylic acid to the corresponding urethane acrylate, or by reacting an isocyanate-terminated prepolymer with hydroxyaLkyl acrylates or methacrylates to the urethane acrylate. Suitable processes are disclosed, inter alia, in EP-A 114 982 and EP-A 133 908. The molecular weight of such acrylates is generally in the range from 4Q0 to 10 000, preferably from 500 to 7000.
Urethane acrylates are also commercially available and are sold by UCB under theregistered trademark EBECRYL~, by Morton Thiokol under the registered trademark Uvithane~9 or by the SARTOMER Company under the product names SR 9504, SR 9600, SR 9610, SR 9620, SR 9630, SR 9640 and SR 9650.
It is preferred to use those urethane acrylates with have a molecular weight from 500 7000 and which are prepared preferably from aliphatic educts.
The novel photosensitive compositions can be polymerised by irradiation with actinic light, typically with electron beams, X-rays, UV or VIS light, i.e. with radiation in the `~88031 wavelength range from 280-650 nm. Particularly sui~able light sources are HeCd, argon or nitrogen laser light as well as metal vapour and NdYAG lasers with multiplc fiequency.
Those skilled in the art will know that the appropriate photoinitiator for each selected light source must be chosen and, if necessary, sensidsed. It has been found that the depth of penetradon of the radiatdon into the polymeIised composition and the processing rate are directly related to the absorpdon coefficient and the concentratdon of the photoinidator. In stereolithography it is preferred to use those photoinitiators which generate the highest number of resulting free radicals and make possible the greatest depth of penentradon into the compositions to be polymerised.
The invendon further relates to a process for the producdon of three-dimensional objects frDm the novel liquid compositions by lithographic methods, especially by stereolithography, in wh*h a layer of novel liquid composition is irradiated over the entire surface or in a predetermined pattern with a W/VIS light source, such that within the irradiated areas a layer solidifes in a desired layer thickness, then a new layer of novel composition is formed on the solidified layer, which is likewise irradiated over the entire surface or in a predetermined pattern, and such that three-dimensional objects are formed from a plurality of solidified layers which adhere to one another by repeated coating and irradiation.
In this process it is preferred to use a laser light which is preferably computer-controlled.
The novel compositions are distinguished by low viscosity and hence good processing properties. The green models obtained by precuring with laser light and the fully cured objects have good mechanical properdes, especially superior flexibility.
The novel compositions can be used typically as adhesive or coating compositions or as formulations for stereolithography or other methods of model construcdon with photopoplymers .
If the novel compositions are used as coating compos;dons, clear and hard coats are obtained on wood, paper, metal, ceramic or other surfaces. The coating thickness can vary over a very wide range and be from c. 1 ~,lm to c. 1 mm. ~elief images for printed circuit boards or printing plates can be produced from the novel compositions, conveniendy by computer-controlled laser light of appropriate wavelength or using a photomask and a suitable light source.
11 .
It is preferred to use the novel composidons for the producdon of photopolymerised layers, especially in the form of three-dimensional objects which are formed from a plurality of solidified layers which adhere to one another.
Examples:
I. Preparadon of the novd acrYlates and methacrYlates .l. Acrvlato A: Diacrylate of 2,2-bis(p-(3-butoxy-2-glycidyloxy-propoxy)phenyl]propane Method I: 100 g of 2,2-bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]propane (prepared according to EP-A 22 073) having an epoxy value of 2.9 eqkg are dissolved in 250 rnl of toluene. Then 1 g of tetraethylammonium bromide and 0.2 g of hydroquinone monomethyl ether are added and the mixture is heated to 80 C. A mixture of 22.98 g (0.32 mol) of acrylic acid and 0.17 g of hydroquinone monomethyl ether is then slowly added dropwise.
The reacdon mixture is kept at 80 C undl the epoxy value is less than 0.1 eqkg (c. 14 h).
The reaction mixture is then cooled to room temperature and extracted with a 5 % aqucous soludon of NaHCO3 and then with water. The organic phase is dried and concentrated first on a rotary evaporator and then under a high vacuum~
Yield: 106.94 g (88.5 %).
Method II: 0.2 g of di-tert-butyl p-cresol are added to 343.9 g of 2,2-bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]propane (prepared according to EP-A 22 073~ having an epoxy value of 2.9 eq/lcg, and the mixture is heated to 110 C With stirring, a mixture of 72.06 g (1 mol) of acrylic acid, 0.56 g of Nuosyn Chromium~ 5 % (fatty acid chromium salt in hydrocarbons, Durharn Chemicals, GB) and 0.42 g of di-tert-butyl p-cresol is added dropwise. The rnixture is kept at 110 C undl the epoxy value is less than 0.1 eq/kg (c. 4 h). A brownish viscous resin having a double bond value of 2.38 ea~kg is obtained (88.5 % of theory).
I.2. Methacrvlate B: Dimethacrylate of 2,2-bistp-(3-butoxy-2-glycidyloxy-propoxy)phenyllpropane 343.9 g of 2,2-bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]propane (prepared according to EP-A 22 073) having an epoxy value of 2.9 eq~g are reacted with 86.09 g (1 mol) of methacrylic acid by method II described above. The mixture is stirred at c. 110 C until the epoxy value is less than 0.1 eq/kg (c. 4 h). A brownish viscous resin hanng a double bond content of 2.26 eq/kg is obtained (87.2 96 of theory).
.3. Acrv!ate C: DiacIylate of 2,2-bist4-(3-butoxy-2-glycidyloxy-propoxy)cyclohexyl]propane 100 g of 2,2-bis~4-(3-butoxy-2-glycidyloxypropoxy)cyclohexyl]propane (prepared according to EP-A 22 073) having an epoxy value of 2.48 eq/kg are reacted with 19.67 g (0.273 mol) of acrylic acid by method I described above. The solution is sdrred for 4 h at 80 C. The epoxy value is then 0.12 ealkg. After extracdon with a 5 % aqueous solution of NaHCO3 and then with water, the organic phase is concentrated under a high vacuum.
Yield: 87.8 g (74.5 %) Double bond value: 1.91 eqQcg (71.8 % of theory).
.4. Methacrvlate D: Dirnethacrylate of 2,2-bis[4-(3-butoxy-2-g}ycidyloxy-propoxy)cyclohexyl]propane 82 g of 2,2-bis[4-(3-butoxy-2-glycidyloxypropoxy)cyclohexyl]propane ~prepared according to EP-A 22 073) having an epoxy value of 2.48 eq/kg are reacted with 19.2 g (0.223 mol) of methacrylic acid by method I described above. The soludon is sdrred for c. 32 h at 80 C. The epoxy value is then 0.17 eq~g. After extracdon with a 5 % aqueous soludon of NaHCO3 and then with water, the organic phase is concentrated under a high vacuum.
Yield: 84.33 g (84.7 %) Double bond value: 1.90 eq/~g (74.5 % of theory).
I.S. AcrYlate E: Diacrylate of 2,2-bislp-(3-phenoxy-2-glycidyloxy-propoxy)phenyl]propane 50 g of 2,2-bis[p-(3-phenoxy-2-glycidyloxypropoxy)phenyl]propane (prepared according to EP-A 22 073) having an epoxy value of 2 7 ea~g are reacted with 9.76 g (0.135 mol) acrylic acid by method II described above to give a viscous resin having a double bond value of 2.28 eq/kg (85.8 % of theory).
2asgo3l I.6. Acrvlate F: Diacrylate of 2,2-bis[p-(3-cyclohexylcarbonyloxy-2-glycidyloxy-propoxy)phenyl]propane a) Preparation of 2,2-bis[p-(3-cyclohexylcarbonyloxy-2-glycidyloxypropoxy)-phenyl]propane (according to EP-A 22 073):
With stirring, 50 g (0.27 mol) of glycidyl cyclohexanoate, 30 g (0.135 mol) of bisphenol A
and 0.8 g of benzyltrimethylamrnonium bromide are heated to 110 C. When the exothermic reacdon has subsided (rise in temperature to 140 C), the reacdon mixture is further sdrred at 10 C undl the epoxy value is less than 0.1 eq/lcg (2 h).
35 g (0.059 mol) of the resultant reacdon product are reacted with 87 g (0.94 mol) of epichlorohydrin and 0.77 g of tetramethylammonium bromide by the method described in EP-A 22 073. After addidon of 9.6 g (0.12 mol) of 50 % aqueous sodium hydroxide and removal of the water under vacuum, the product is isolated and dried.
Yield: 15.5 g (37 ~o) Epoxy value: 1.90 eq~cg (74.5 % of theory) b) Preparatdon of the diacrylate:
12.97 g (0.27 mol) of 2,2-bis[p-(3-cyclohexylcarbonyloxy-2-glycidyloxypropoxy)phen-yl]propane prepared acco~ding to a) are reacted with 1.8 g (0.025 mol) of acrylic acid by method II described above to give a viscous resin having a double bond value of 1.84 eq/kg t78.3 % of theory).
I.7. Acrvlate G: Diacrylate of 2,2-bis[p-(2-glycidyloxyhexoxy)phenyl]propanea) Preparadon of 2,2-bis[p-(2-glycidyloxyhexoxy)phenyl]propane (according to EP-A æ 073):
With stirring, 100.2 g (1 mol) of butyl oxirane, 114 g (0.5 mol) of bisphenol A and 2.14 g of benzyltrimethylammonium bromide are heated to 110 C. When the exothermic reacdon has subsided (rise in temperature to 115 C), the reacdon is further stirred at 110 C undl the epoxy value is less than 0.1 e~g (16 h).
85.52 g (0.2 mol) of the resultant reacdon product are reacted with 296 g (3.2 mol) of epichlorohydrin and 1.32 g of tetramethylammonium bromide according to the method described in EP-A 22 073. After addition of 33.6 g (Q.42 mol) of 50 % aqueous sodium hydroxide and removal of the water under vacuum, the product is isolated and dried.
Yield: 87.2 g (80.6 %) Epoxy value: 2.51 eq~cg (67.9% of theory).
~088031 b) Preparadon of the diacrylate:
100 g (0.11 mol) of 2,2-bislp-(2-glycidyloxyhexoxy)phenyl]propane prepared according to a) are reacted with 15.85 g (0.22 mol) of acrylic acid by method II described above to give a viscous resin having a double bond value of 1.87 eq,~cg (64 % of theory).
.8. Acrvlate H: Diacrylate of 2,2-bis[p-(2-phenyl-2-glycidyloxy-ethoxy)phenyl]propane a) Preparadon of 2,2-bis[p-(2-phenyl-2-glycidyloxyethoxy)phenyl]propane (according to EP-A 22 073):
With stirring, 100 g (0.83 mol) of phenylethylene oxide, 94.7 g (0.415 mol) of bisphenol A
and 1.95 g of benzyltrimethylammonium bromide are heated to 110 C When the exothermic reacdon has subsided (rise in temperature to 115 C), the reactdon mixture is further sdrred at 110 C undl the epoxy value is less than 0.1 eq/lcg (5 h).
80 g (0.17 mol) of the resultant reacdon product are reacted with 251.6 g (2.72 mol) of epichlorohydrin and 0.9 g of tetramethylammonium bromide according to the methoddescribed in EP-A 22 073. After addidon of 28.8 g (0.36 mol) of 50 % aqueous sodium hydroxide and removal of the water under vacuum, the product is isolated and dried.
Yield: 60.5 g (58.5 %) Epoxy value: 2.56 eq/kg (78 % of theory~.
b~ Preparadon of the diacrylate:
25 g (0.032 mol) of 2,2-bis[p-(2-phenyl-2-glycidyloxyethoxy)phenyl]propane prepared according to a) are reacted with 4.6 g (0.064 mol) of acrylic acid by method II described above to give a viscous resin having a double bond value of 2.12 eqlkg (76.8 % of theory).
II. Use Exam~les Use of the novel diacrylates and dimethacrylates in formuladons for stereolithography.
Exam~le 1:
49.85 g of acrylate A, 26 g of the dimethacrylate of ethoxylated bisphenol A (SR 348, Sartomer), 14 g of trimethylolpropane trimethacrylate (SR 350, Sartomer) and 6 g of phenoxyethyl acrylate (SR 339, Sartomer) are mixed at c. 60 C with 0.15 g of hydroquinone monomethyl ether and 4 g of l-hydroxycyclohexyl phenyl ketone. The resultant homogeneous liquid formuladon has a viscosity of 631 mPa-s at 30 C. Amoulded ardcle (green model) cured from this formuladon using a HelCd laser () 3 ~
(40 mJ/cm3 has a modulus of elasticity (DIN 53 371; green strength) of 16.2 N/mm2, a tensile strength ~ma~ (DIN 53 455) of 1.31 N/mm2 and a flexural elongadon (DIN 53 455) of 10.2 %.
The green model is fully cured by irradiation for 30 minutes with UV/VIS light. The moulded article then has the following properdes:
modulus of elasticity: 1610 N/mm2 tensile strength ~max 32.8 N/mm2 flexural elongation ~: 7.2 %
Examples 2-10: Formulations of the components listed in Tables 1 and 2 are prepared and processed to three-dimensional objects as described in Example 1. The properties of the liquid formulations, of the green models and of the fully cured moulded articles are indicated in Table 2.
Table 1:
Example _ 2 3 4 acrylate A [g] 49.85 36.85 methacrylate B [g] 49.85 methacrylate D [g] 48.85 dimethacrylate of ethoxylated bisphenol A [g] 26.0 26.0 6.0 (SR 348, Sartomer) diacrylate of ethoxylated bisphenol A [g] 26.0 25.0 (SR 349, Sartomer) trimethylolpropane trimethacrylate (SR 350, Sartomer) [g] 14.0 14.0 6.0 trimethylolpropane triacrylate (SR 351, Sartomer) [g] 14.0 12.0 phenoxyethyl acrylate (SR 339, Sartomer) [g] 6.0 6.0 6.0 5.0 l-hydroxycyclohexyl phenyl ketone [g] 4.0 4.0 5~0 4.0 N-vinylpy~rolidone [g] 5.0 hydroquinone monomethyl ether [g] 0.15 0.15 0.15 0.15 _ Viscosity Tl of the liquid formuladon at 30 C [mPa- s] 631 578 451 302 Properties of the green models modulus of elasdcity lN/mm2] 16.2 20.4 35.8 tensile strength ~ma~ [N/mm2] 1.31 1.56 2.70 flexural elongation ~ [~o] 10.2 20.4 12.5 _ Properties of the fully cured moulded ardcles modulus of elasticity [N/mm2] 1610 1734 1660 251.3 tensile strength ~ma~ [N/mm2] 32.8 35.0 32.0 9.8 flexural elongation ~ [%] 7.2 4.1 5.0 11.0 _ - 17- 208803~
Table 2:
_ Example 5 6 7 8 9 10 _ acrylate A [g] 9.0 30.0 19.0 methacrylate B [g] 9.0 30.0 19.0 dimethacrylate of ethoxylated bisphenol A 29.0 29.0 5.0 5.0 29.0 29.0 (SR 348, Sartomer) tg]
diacrylate of ethoxylated bisphenol A 20.0 20.0 (SR 349, Sartomer) polyethylene glycol 400 diacrylate [g]14.0 14.0 14.0 14.0 (SR 344, Sartomer) neopentylglycol diacrylate 7.0 7.0 7.0 7.0 tnmethylolpropane triacrylate [g] 12.0 12.0 (SR 351, Sartomer) phenoxyethyl acrylate [g] 1.0 1.0 5.0 5.0 1.0 1.0 l-hydroxycyclohexyl phenyl ketone [g] 5.0 5.0 5.0 5.0 5.0 5.0 aliphatic urethane acrylate [g] 35.0 35.0 23.0 23.0 25.0 25.0 (SR 9640, Sartomer, MG: 1300, viscosity at 60 C: 18000 mPa s) _ viscosity ~ of the liquid formulation 1490 1600 2250 2120 1010 925 at 30 C [mPa s]
. _ . _ Properties of the green models modulus of elasticity [N/mm2] 23.9 59.4 52.2 36A 19.6 27.3 tensile strength ~m8~ [N/mm2] 3.7 3.8 3.7 3.9 29 3.3 flexural elongation ~ [%] 22.8 17.4 13.6 20.0 19.9 18.8 _ Properiies of the fully curred moulded articles modulus of elasticity [N/mm2] 729 948 772 1340 941 1102 tensile streng~h ~ma~ [Nlmm2] 26.6 27.8 18.7 24.8 25.8 3Q0 flexural elongation ~ [%] 21.0 17A 7 5 6.3 13.5 16.0
Claims (13)
1. A compound of formula (Ia) or (Ib) (Ia), (Ib), wherein the substituents R1 are each independently of the other hydrogen or methyl, R2 is an unsubstituted C1-C20alkyl group or a C1-C20alkyl group which is substituted by one or more than one substituent selected from the group consisting of hydroxy, C6-C14aryl and halogen, an unsubstituted phenyl group or a phenyl group which issubstituted by one or more than one substituent selected from the group consisting of C1-C6alkyl, hydroxy or halogen, or is a radical of formula -CH2-OR3, wherein R3 is an unsubstituted C1-C20alkyl group or a C1-C20alkyl group which is substituted by one or more than one substituent selected from the group consisting of hydroxy, C6-C14aryl and halogen, an unsubstituted phenyl group or a phenyl group which is substituted by one or more than one substituent selected from the group consisting of C1-C6alkyl, hydroxy and halogen, or is a C2-C6alkenyl group, a C2-C20acyl group or an unsubstituted cyclohexyl-carbonyl group or a cyclohexylcarbonyl group which is substituted by one or more than one substituent selected from the group consisting of C1-C6alkyl, hydroxy and halogen, Z is a group of formulae (IIa)-(IIe) (IIa). (IIb), (IIc), (IId), (IIe), wherein Y is a direct bond, C1-C6alkylene, -S-, -O-, -SO-, -SO2- or -CO-, and R1 is hydrogen or methyl, and wherein the aromadc and cycloaliphatic rings of formulae(IIa)-(IIe) are unsubstituted or substituted by one or more than one substituent selected from the group consisting of C1-C6alkyl, chloro and bromo.
2. A compound of formula (Ia) or (Ib) according to claim 1, wherein R2 is preferably C1-C20aLkyl, phenyl, C1-C20alkoxymethyl, phenoxymethyl or cyclohexylcarbonyloxy-methyl.
3. A compound of formula (Ia) or (Ib) according to claim 1, wherein R2 is n-butyl, phenyl, n-butoxymethyl, phenoxymethyl or cyclohexylcarbonyloxymethyl.
4. A compound of formula (Ia) or (Ib) according to claim 1, wherein R2 is n-butoxymethyl.
5. A compound of formula (Ia) or (Ib) according to claim 1, wherein Z is a group of formula (IIc) or (IIe).
6. A compound of formula (Ia) or (Ib), wherein Z is .
7. A process for the preparation of a compound of formula (Ia) or (Ib), which comprises reacting a diglycidyl ether of formula (III) (III), wherein R2 and Z have the above meanings, in a manner known per se, with acrylic or methacrylic acid.
8. A photosensitive composition comprising (a) 5-65 % by weight of a compound of formula (Ia) or (Ib) according to claim 1,(b) 15-70 % by weight of one or more than one bifunctional acrylate or methacrylate having a molecular weight in the range from 150 to 450 and differing from the compound of formula (Ia) or (Ib), (c) 0-40 % by weight of one or more than one monomeric polyfunctional acrylate or methacrylate having a functionality of not less than 3 and a molecular weight of not more than 600, (d) 0-10 % by weight of at least one monofunctional acrylate or methacrylate, (e) 0-10 % by weight of N-vinylpyrrolidone or N-vinylcaprolactam, (f) 2-10 % by weight of at least one photoinitiator, and (g) 0-60 % by weight of at least one urethane acrylate or methacrylate having a functionality of 2-4 and a molecular weight in the range from 500-10 000, such that the sum of the amounts of components (a) to (g) together is 100 % by weight.
9. A composition according to claim 8, wherein component (b) is a diacrylate or dimethacrylate of ethoxylated bisphenol A.
10. A composition according to claim 8, wherein component (c) is trimethylpropane triacrylate or trimethylolpropane trimethacrylate.
11. A composition according to claim 8, wherein component (d) is phenoxyethyl acrylate.
12. A composidon according to claim 8, wherein component (f) is 1-hydroxycyclohexyl phenyl ketone.
13. A process for the production of three-dimensional objects from a photosensitive composition according to claim 8 by stereolithography, wherein a layer of novel composition is irradiated over the entire surface or in a predetermined pattern with a UV/VIS light source, such that within the irradiated areas a layer solidifies in a desired layer thickness, then a new layer of novel composition is formed on the solidified layer, which is likewise irradiated over the entire surface or in a predetermined pattern, and such that three-dimensional objects are formed from a plurality of solidified layers which adhere to one another by repeated coating and irradiation.
FD 4.3/SP/CW
FD 4.3/SP/CW
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH216/92-0 | 1992-01-27 | ||
| CH21692 | 1992-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2088031A1 true CA2088031A1 (en) | 1993-07-28 |
Family
ID=4181922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002088031A Abandoned CA2088031A1 (en) | 1992-01-27 | 1993-01-25 | Novel diacrylates and dimethacrylates |
Country Status (7)
| Country | Link |
|---|---|
| US (3) | US6043323A (en) |
| EP (1) | EP0554215B1 (en) |
| JP (2) | JPH05286897A (en) |
| KR (1) | KR100263033B1 (en) |
| CA (1) | CA2088031A1 (en) |
| DE (1) | DE59304927D1 (en) |
| TW (1) | TW311923B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW311923B (en) * | 1992-01-27 | 1997-08-01 | Ciba Sc Holding Ag | |
| US5854313A (en) * | 1994-09-28 | 1998-12-29 | Takeda Chemical Industries, Ltd. | Fine particles of high heat resistant polymer and epoxy esters |
| JPH08269146A (en) * | 1994-09-28 | 1996-10-15 | Takeda Chem Ind Ltd | Highly heat-resistant high-molecular polymer fine particle and epoxy ester |
| GB9504995D0 (en) * | 1995-03-11 | 1995-04-26 | Zeneca Ltd | Compositions |
| GB9504996D0 (en) * | 1995-03-11 | 1995-04-26 | Zeneca Ltd | Compositions |
| US6476122B1 (en) * | 1998-08-20 | 2002-11-05 | Vantico Inc. | Selective deposition modeling material |
| JP4572431B2 (en) * | 1999-08-19 | 2010-11-04 | 日本化成株式会社 | (Meth) acrylate derivative and method for producing the same |
| KR20030013879A (en) * | 2001-08-09 | 2003-02-15 | 최동훈 | Photo-reactive di(meth)acrylate derivative and its preparation method thereof |
| US7235195B2 (en) * | 2002-09-06 | 2007-06-26 | Novartis Ag | Method for making opthalmic devices |
| US20040115561A1 (en) * | 2002-12-13 | 2004-06-17 | Mikhail Laksin | Energy curable, water washable printing inks suitable for waterless lithographic printing |
| EP1727663B1 (en) * | 2004-03-22 | 2011-10-05 | Huntsman Advanced Materials (Switzerland) GmbH | Photocurable compositions |
| DE102004056398A1 (en) * | 2004-11-23 | 2006-05-24 | Bayer Materialscience Ag | Hydrolysis stable, hydrophobic, solvent-free polyols |
| JP4642076B2 (en) * | 2005-07-22 | 2011-03-02 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition and laminate |
| US8474153B2 (en) * | 2005-09-15 | 2013-07-02 | Alfred Cloutier Ltée | Adaptable shoe cover |
| JP4749305B2 (en) * | 2005-10-05 | 2011-08-17 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition and laminate |
| EP2270108B1 (en) * | 2006-02-24 | 2012-01-04 | Teikoku Printing Inks Mfg. Co., Ltd | Process for producing ink and relevant to the process, ink, printed matter and molding |
| US8635214B2 (en) * | 2006-07-26 | 2014-01-21 | International Business Machines Corporation | Improving results from search providers using a browsing-time relevancy factor |
| CN105524525A (en) * | 2011-01-21 | 2016-04-27 | 精工爱普生株式会社 | Radiation-curable ink for ink jet recording, record made using the same, and ink jet recording method using the same |
| JP6736051B2 (en) * | 2016-05-30 | 2020-08-05 | 協立化学産業株式会社 | Epoxy resin, completely modified epoxy resin and curable composition containing them |
| JP6943950B2 (en) * | 2017-03-29 | 2021-10-06 | 三井化学株式会社 | Photocurable composition, denture base and denture with floor |
Family Cites Families (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056453A (en) * | 1973-11-27 | 1977-11-01 | Basf Aktiengesellschaft | Uv-curing printing inks |
| US4097994A (en) * | 1975-11-24 | 1978-07-04 | Monsanto Company | Dental restorative composition containing oligomeric BIS-GMA resin and Michler's ketone |
| US4169732A (en) * | 1978-01-09 | 1979-10-02 | International Business Machines Corporation | Photosensitive coating composition and use thereof |
| US4284574A (en) * | 1979-06-15 | 1981-08-18 | Ciba-Geigy Corporation | Diglycidyl ethers of di-secondary alcohols, their preparation, and curable compositions containing them |
| US5015701A (en) * | 1981-07-01 | 1991-05-14 | Union Carbide Chemicals And Plastics Company Inc. | Composition of vinyl ester resin, hydroxyalkyl (meth)acrylate and a styrene |
| JPS58213009A (en) | 1982-06-04 | 1983-12-10 | Kanegafuchi Chem Ind Co Ltd | Crosslinked vinyl chloride resin |
| JPS60118710A (en) * | 1983-11-29 | 1985-06-26 | Osaka Soda Co Ltd | Air-drying allyl epoxy polyacrylate resin composition |
| JPS60135931A (en) * | 1983-12-24 | 1985-07-19 | Asahi Chem Ind Co Ltd | Novel photopolymerizable composition |
| JPH0762123B2 (en) | 1985-01-08 | 1995-07-05 | 武田薬品工業株式会社 | Adhesion method |
| US4575330A (en) * | 1984-08-08 | 1986-03-11 | Uvp, Inc. | Apparatus for production of three-dimensional objects by stereolithography |
| DE3446910A1 (en) | 1984-12-21 | 1986-07-03 | Siemens AG, 1000 Berlin und 8000 München | Stiffening device for an electronics cabinet |
| JPS61285201A (en) | 1985-06-13 | 1986-12-16 | Canon Inc | Active energy ray curing type resin composition |
| JPS6366279A (en) | 1986-04-11 | 1988-03-24 | Takeda Chem Ind Ltd | Bonding |
| US4836832A (en) * | 1986-08-11 | 1989-06-06 | Minnesota Mining And Manufacturing Company | Method of preparing coated abrasive having radiation curable binder |
| EP0292219A3 (en) * | 1987-05-21 | 1989-10-11 | AT&T Corp. | Printed circuit board fabrication |
| JPS6436615A (en) | 1987-07-31 | 1989-02-07 | Desoto Inc | Ultraviolet ray curable resin composition for information recording carrier |
| JP2535030B2 (en) | 1987-08-05 | 1996-09-18 | ディーエスエム ナムローゼ フェンノートシャップ | Radiation curable paint |
| JPH0195105A (en) | 1987-10-06 | 1989-04-13 | Takemoto Oil & Fat Co Ltd | Photocurable resin composition |
| US5180757A (en) * | 1987-12-16 | 1993-01-19 | Michael Lucey | Photopolymerizable compositions used in electronics |
| US5215863A (en) * | 1987-12-18 | 1993-06-01 | Nippon Kayaku Kabushiki Kaisha | Resin composition and solder resist composition |
| JP2525216B2 (en) | 1988-01-27 | 1996-08-14 | ディーエスエム・エヌヴィ | Resin composition for optical three-dimensional modeling |
| JPH01204973A (en) | 1988-02-01 | 1989-08-17 | Desoto Inc | Radiation curable paint |
| JP2582600B2 (en) | 1988-02-01 | 1997-02-19 | 日本合成ゴム株式会社 | Radiation curable paint |
| JP2610468B2 (en) | 1988-02-24 | 1997-05-14 | 日本合成ゴム株式会社 | Method for producing radiation-curable polyurethane |
| JPH0241380A (en) | 1988-07-11 | 1990-02-09 | Dent Inc | Radiation-curable paint |
| EP0378144B1 (en) * | 1989-01-10 | 1995-03-08 | Ciba-Geigy Ag | Photocurable compositions |
| JPH02265477A (en) * | 1989-04-04 | 1990-10-30 | Hitachi Chem Co Ltd | Controlling element of growing direction of nerve fiber and production thereof |
| US5084353A (en) * | 1989-05-12 | 1992-01-28 | Gencorp Inc. | Thermosetting in-mold coating compositions |
| US5229252A (en) * | 1989-06-09 | 1993-07-20 | Morton International, Inc. | Photoimageable compositions |
| EP0425440B1 (en) * | 1989-10-27 | 1994-11-17 | Ciba-Geigy Ag | Method of adjusting the photosensitivity of photopolymerizable compositions |
| EP0425441B1 (en) * | 1989-10-27 | 1995-12-27 | Ciba-Geigy Ag | Photosensitive mixture |
| JPH03199227A (en) | 1989-12-25 | 1991-08-30 | Desoto Inc | Manufacture of curable resin |
| JP3160013B2 (en) | 1991-06-21 | 2001-04-23 | 三菱化学株式会社 | New peptide |
| TW311923B (en) * | 1992-01-27 | 1997-08-01 | Ciba Sc Holding Ag | |
| TW269017B (en) * | 1992-12-21 | 1996-01-21 | Ciba Geigy Ag | |
| TW418215B (en) * | 1995-03-13 | 2001-01-11 | Ciba Sc Holding Ag | A process for the production of three-dimensional articles in a stereolithography bath comprising the step of sequentially irradiating a plurality of layers of a liquid radiation-curable composition |
| US6379866B2 (en) * | 2000-03-31 | 2002-04-30 | Dsm Desotech Inc | Solid imaging compositions for preparing polypropylene-like articles |
-
1993
- 1993-01-18 TW TW082100278A patent/TW311923B/zh active
- 1993-01-19 DE DE59304927T patent/DE59304927D1/en not_active Expired - Fee Related
- 1993-01-19 EP EP93810029A patent/EP0554215B1/en not_active Expired - Lifetime
- 1993-01-25 CA CA002088031A patent/CA2088031A1/en not_active Abandoned
- 1993-01-26 JP JP5029726A patent/JPH05286897A/en active Pending
- 1993-01-26 KR KR1019930000958A patent/KR100263033B1/en not_active IP Right Cessation
-
1994
- 1994-11-21 US US08/342,955 patent/US6043323A/en not_active Expired - Fee Related
-
2000
- 2000-01-13 US US09/483,057 patent/US6316552B1/en not_active Expired - Lifetime
-
2001
- 2001-09-17 US US09/953,250 patent/US6783809B2/en not_active Expired - Fee Related
-
2002
- 2002-05-20 JP JP2002145184A patent/JP2003073337A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0554215B1 (en) | 1997-01-02 |
| US6043323A (en) | 2000-03-28 |
| US6316552B1 (en) | 2001-11-13 |
| DE59304927D1 (en) | 1997-02-13 |
| US20020068801A1 (en) | 2002-06-06 |
| KR100263033B1 (en) | 2000-08-01 |
| US6783809B2 (en) | 2004-08-31 |
| EP0554215A2 (en) | 1993-08-04 |
| JPH05286897A (en) | 1993-11-02 |
| TW311923B (en) | 1997-08-01 |
| KR930016385A (en) | 1993-08-26 |
| EP0554215A3 (en) | 1993-09-01 |
| JP2003073337A (en) | 2003-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2088031A1 (en) | Novel diacrylates and dimethacrylates | |
| US5461088A (en) | Liquid radiation-curable formulation, in particular for use in stereolithography | |
| JP3252331B2 (en) | Acrylate-based photosensitive composition | |
| KR100355949B1 (en) | (Meth) acrylate containing urethane group | |
| US5783712A (en) | Vinyl ether compounds having additional functional groups other than vinyl ether groups and the use thereof in the formulation of curable compositions | |
| US5468886A (en) | (Cyclo)aliphatic epoxy compounds | |
| JP3787788B2 (en) | Composition | |
| US5472992A (en) | Photopolymerizable compositions containing an alkylbisacylphosphine oxide | |
| US5085974A (en) | Photopolymerizable mixture, and a recording material produced therefrom | |
| US5221595A (en) | Photopolymerizable mixture and recording material prepared therefrom | |
| EP0614122B1 (en) | Tetra-acrylates containing polymerizable mixtures | |
| JPH01102455A (en) | Photopolymerizable recording material for plate body and relief plate in particular | |
| CA2007295C (en) | Photocurable compositions | |
| CA2028541C (en) | Photosensitive mixture | |
| JPS62254141A (en) | Photopolymerizable mixture, photosensitive recording elementcontaining the same and manufacture of lithographic plate using the same | |
| CA1304372C (en) | Oligomeric benzil ketals and their use as photoinitiators | |
| CA2076727A1 (en) | Alkaline-etch resistant dry film photoresist | |
| JP2990398B2 (en) | Photosensitive composition | |
| CA2032919A1 (en) | Process for obtaining textured coatings from photo-curable urea-containing compositions | |
| US4590147A (en) | Dry film resists containing unsaturated oligomer | |
| JPS58103519A (en) | Curable resin composition | |
| KR100310329B1 (en) | Liquid radiation-curable blends for use in stereolithography | |
| JPH06128342A (en) | Resin composition for optical three-dimensional shaping |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |