CA2063982C - Photosensitive composition based on acrylates - Google Patents
Photosensitive composition based on acrylates Download PDFInfo
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- CA2063982C CA2063982C CA002063982A CA2063982A CA2063982C CA 2063982 C CA2063982 C CA 2063982C CA 002063982 A CA002063982 A CA 002063982A CA 2063982 A CA2063982 A CA 2063982A CA 2063982 C CA2063982 C CA 2063982C
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Classifications
-
- 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
- G03F7/04—Chromates
-
- 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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
- B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
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- 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
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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
Abstract
A liquid photosensitive composition comprising (1) 40 to 80 % by weight of a urethane (meth)acrylate having a functionality of 2 to 4 and a molecular weight (Mw) of 500 to 10 000, (2) 5 to 40 % by weight of a hydroxyl group containing aliphatic or cycloaliphatic di(meth)acrylate, (3) 0 to 40 % by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having a Mw of not more than 500, (4) 0.1 to 10 % by weight of a photoinitiator, (5) 0 to 30 % by weight of an aliphatic or cycloaliphatic: di(meth)acrylate which differs from (2), of an aliphatic tri(meth)acrylate or of an aromatic di- or tri(meth)acrylate, and (6) 0 to 5 % by weight of customary additives, such that the proportion of components (1) to (6) together is 100 % by weight.
The composition is a photosensitive composition which can be polymerised by irradiation with actinic light and which is suitable for the production preferably.of three-dimensional objects by the stereolithographic technique.
The composition is a photosensitive composition which can be polymerised by irradiation with actinic light and which is suitable for the production preferably.of three-dimensional objects by the stereolithographic technique.
Description
2~63~~~
I~-1 ~596/.~.
Photosensitive composition based on acr~htes The present invention relates to a liquid photosensitive composition, to a process for polymerising said composition by radiation with actinic light, to a process for the production of three-dimensional objects from said liquid compasidon and to the use of this composition for forming photopolyrnerisable layers, especially three-dimensional objects fabricated from a plurality of photopolymerisable layers.
It is known that radiation-sensitive liquid resins or resin compositions have versatile utilities, typically as coating compositions, adhesives or photoresists. In principle, liquid resins ar resin systems should quite generally also be suitable for forming three-dimensional objects by the stereolithographic technique disclosed in US patent 4 575 330. However, many resins prove to be too viscous, whereas others are too insufficiently light-sensitive or, during the cure, suffer too severe shrinkage. The strength properties of the moulded articles or objects fabricated from photocured resins are also often unsatisfactory.
That complicated three-dimensional objects can be formed from liquid light-sensitive resins by dhe stereolithographic technique is well-known. Such objects are formed from layers by bonding each new curable resin layer tenaciously to the previously prehardened layer by curing with UV/VIS light. It is common knowledge that the total assembly of the thxee-dimensional object can be accomplished by means of a computer-controlled process.
In recent years there has been no lack of efforts to develop resin systems suitable for the technique of stereolithography. In Rev. Sci. Instxum. 52 (11) 1170-1173 (1981), I-I. ICodama discloses under the registered trademark "Tevista" a liquid phatohardening resin composition comprising an unsaturated polyester, acrylate, styrene, a polymerisation initiator and a sensitiser. The daawback of this resin system fox use in stereolithogxaphy is that the photosensitivity is insufficient and the so-called "green strength"
of the objects hardened by laser beams is rather low.
The technique of stereolithagraphy is described in detail in US patent 4 575 330. The 2~~39~~
liquid resin used is a modified acrylate which is referred to in the description as "Potting Compound 363". Such resin compositions are disclosed in US patent 4 100 141.
They too have the drawback of being insufficiently light-sensitive and of requiring lengthy times for the fabrication of three-dimensional objects by the stereolithographic technique.
It is therefore understandable that the demands made of resins for use in stereolithography are high. For example, they must have a viscosity suitable for processing in the intended apparatus. The photosensitivity of the resin system must be such that the ratio of the radiation energy applied and the depth of penetration into the liquid photosensitive resin composition so as to effect solidification of the parts is within reasonable limits. This means that, when using a resin suitable for use in stereolithography, the aim shall be to achieve the greatest possible curing depth with little radiation energy, simultaneously coupled with a high degree of polymerisation and high green strength.
Tn the technique employed in stereolithography of successively polymerising thin layers, none of the layers is fully cured. The partially cured object is called a green object, and the module of elasticity and the tensile strength of this green object is called the green strength. Normally the green object is cured with UV/VIS light, conveniently with a mercury or xenon arc lamp. The green strength of an object is therefore an important parameter, as objects having a Inw green strength may become deformed under their own weight or, in the course of the cure, they may sag or collapse.
It has now been found that a liquid resin composition comprising several (meth)acrylates which differ from another, and which additionally comprises a hydxoxyl group containing aliphatic or cycloaliphatic di(meth)acrylate, may be used for stereolithography and is able to forth green objects when precured with laser beams, which objects have high green strength. 3'he objects formed by curing the green objects have excellent flexibility and, in addition, are distinguished by excellent teax growth resistance.
Accordingly, the invention relates to a liquid photosensitive composition comprising (1) 40 to 80 % by weight of a urethane (meth)acrylate having a functionality of 2 to 4 and a molecular weight (Mw) of 500 to 10 000, (2) 5 to 40 % by weight of a hydroxyl group containing aliphade or cycloaliphatic di(meth)acrylate, (3) 0 to 40 % by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having ~~6~~~~
a Mw of not more than 500, (4) 0.1 to 10 % by weight of a photoinitiator, (5) 0 to 30 % by weight of an aliphatic or cycloaliphatic di(meth)acrylate which differs from (2), of an aliphatic tri(meth)acrylate or of an aromatic di- or tri(meth)acrylate, and (b) 0 to 5 % by weight of customary additives, such that the proportion of components (1) to (6) together is 100 % by weight.
Preferably the composition of this invention comprises (1) 40 to 80 % by weight of a urethane (meth)acrylate having a functionality of 2 to 4 and a molecular weight (Mw) of 500 to 10 000, (2) 5 to 40 % by weight of a hydroxyl group containing aliphatic or cycloaliphatic di(meth)acrylate, (3) 5 to 40 % by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having a Mw of not more than 500, (4) 0.1 to 10 % by weight of a photoinitiator, (5) 0 to 30 % by weight of an aliphatic or cycloaliphatic di(meth)acrylate which differs from (2), of an aliphatic tri(meth)acrylate or of an aromatic di- or tri(meth)acrylate, and (6) 0 to 5 % by weight of customary additives.
More particularly the composition of the invention comprises (1) 50 to 70 % by weight of a urethane (meth)acrylate having a functionality of 2 to 4 and a molecular weight (Mw) of 1000 to 10 000, (2) 10 to 30 % by weight of a hydroxyl group containing aliphatic di(meth)acrylate, (3) 0 to 30 % by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having a Mw of not more than 500, (4) 0.5 to 7 % by weight of a photoinitiator, (5) 0 to 20 % by weight of an aliphatic or cycloaliphatic bis(meth)acrylate which differs from (2), of an aliphatic tris(meth)acrylate or of an aromatic di- or tris(meth)acrylate, and (6) 0 to 3 % by weight of an additive.
In the particularly preferred embodiment of the invention, component (3) comprises preferably 10 to 30 % by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having a Mw of not more than 500.
The urethane acrylates used as component (1) of the novel compositions are known to those skilled in the art and can be prepared in known manner, conveniently by reacting a hydroxyl-terminated 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. Appropriate processes are disclosed in published EP patent applications 114 982 and 133 908. The molecular weight of such acrylates is usuaily in the range from 400 to 10 000, preferably from 500 to 7000.
Urethane acrylates are commercially available and are sold, inter alia, by UCB
under the registered trademark EBECRYL~, by Morton Thiokol under the registered trademark Uvithane~, 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 which have a Mw of 500-700 and which have preferably been prepared from aliphatic educts.
Compounds useful as component (2) include reaction products of aliphatic epoxy resins, such as alkanediol diglycidyl ethers, including the diglycidyl ether of 1,4-butanediol, the diglycidyl ether of polyethylene glycol or polybutylene glycol, or cycioaliphatic epoxy resins, such as the diglycidyl esters of cycloaliphatic dicarboxylic acids, for example the diglycidyl ester of hexahydrophthalic acid, or hydrogenated diglycidyl ethers of bisphenols, typically the diglycidyl ether of hydrogenated bisphenol A, or epoxy resins having an epoxy group attached direct to the cycloaliphatic ring, such as bis-(3,4-epoxycyclohexylmethyl) adipate, which cited compounds with (meth)acrylic acid may lead to reaction products of the following formulae R OH
O U.~.O
~O O , O OH R
R OH O
O O
O
/ ~ R
n 2~~3~~2 R OH O
O O
O~O , O OfH R
n OH O ,/
O O
O -"' R
O
O
OH O R
R O
y~~ O O
II p R or O O
OH
HO
O
R OH
O O~O
OH R
O
wherein R is a hydrogen atom or methyl and n is a number greater 1, and also reaction prcxlucts of epoxidised fatty acid dvith (meth)acrylic acid, or caprolactone-modified reaction products of aliphatic or cycloaliphatic epoxy resins, for example the diglycidyl ether of 1,4-butanedial, with (meth)acrylic acid to give a pznduct of formula 2fl~~9~~
_g_ OH
O
R O O
O~O O O
R
O
OI-I
wherein R is a hydrogen atom or methyl. These reaction products of aliphatic or cycloaliphatic epoxy resins and (meth)acrylic acid are known, inter alia from JP
ICokai 50-059487 or from Urg. Coat. Plast. Ch.°,m. 40, pages 104-109, 1979, where processes for their preparation are also described.
The caprolactone-modilaed reaction product of aliphatic or cycloaliphatic resins and (meth)acxylic acid is also known and can be prepared by reacting 1 mol of a reaction product of the aliphatic or cycloaliphatic epoxy resin and (meth)acrylic acid with 2 mol of caprolactone in an organic solvent at elevated temperature and in the presence or absence of a catalyst.
Representative examples of further aliphatic or cycloaliphatic resins which may be used for preparing the above mentioned reaction products are: the diglycidyl and bis(ø-methylglycidyl) esters of aliphatic dicarboxylic acids, including oxalic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, arelaic acid, sebacic acid or dimerised linolic acid, the diglycidyl esters of cycloaliphatic dicarboxylic acids, including tetra-hydrophthalic acid, 4-methyltetrahydrophthalic acid or 4-methylhexahydrophthalic acid, the diglycidyl ethers of higher aliphatic alcohols, such as 1,5-pentanediol, 1,6-hexanediol _7_ or 1,8-octanediol, the diglycidyl ethers of cycloaliphatic diols, such as resorcitol, quinitol, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane and 1,1-bis-(hydroxymethyl)3-cyclohexene.
The novel compositions preferably contain a xeaction product of the diglycidyl ether of 1,4-butanediol and acrylic acid as hydroxyl group containing aliphatic diacrylate (2).
Component (2) of the novel compositions is preferably a hydroxyl group containing cycloaliphatic bis(meth)acrylate, more particularly a reaction product of the diglycidyl ester of hexahydrophthalic acid or bis(3,4-epoxycyclohexylmethyl)adipate and (meth)acrylic acid Component (3) of the novel compositions may be selected from the following compounds:
allyl acrylate, allyl methacrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, 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 (nneth)acrylate, 2-hydroxyethyl (rneth)acrylate, 2- and :3-hydmxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)ac;rylate and 2- or 3-ethoxypropyl (meth)acrylate, tetrahydrofurfurylmethacrylate, 2-(2-ethoxyethoxy)ethylacrylate, cyclohexyl methacrylate, 2-phenoxyethyl acrylate, glycidyl acrylate and isodecyl acrylate;
and the mono-N-vinyl compound is N-vinylpyrrolidone or N-vinylcaprolactam.
Such products are also known and some are commercially available, as from SARTOMER.
The compounds suitable for use as component (3) preferably have a Mw von SO-300.
Component (3) of the novel compositions is preferably a mono-N-vinyl compound, mere particularly N-vinylpyrrolidone.
Any type of photoinitiator which, when izradiated suitably, forms frEe radicals can be employed as component (4) in the novel compositions. Typical known photoinitiators are benzoins, benzoin ethers, including benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, benzain phenyl ether and benzoin acetate, acetophenones, including acetophenone, 2,2-dimethoxyacetophenone and 1,1-dichloroacetophenone, benzil, benzil ketals, such as benzil dimethyl ketal and benzil diethyl ketal, anthraquinones, including 2-mefhylanthraquinone, 2-ethylanthraquinone, 2-tort-butyl-anthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone, triphenylphosphine, ~4~39~2 _g_ benzoylphosphine oxides, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide (I,uzirin TPO), benzophenones, such as benzophenone and 4,4'-his(N,N'-dimethyl-amino)benzophenone, thioxanthones and xanthones, acridine derivatives, phenazine derivatives, quinoxaline derivatives or 1-phenyl-1,2-propanedione, 2-O-benzoyl oxime, 1-aminophenyl ketones or 1-hydroxyphenyl ketones, such as 1-hydroxycyclohexyl phenyl ketone, phenyl 1-hydroxyisopropyl ketone and 4-isopropylphenyl 1-hydroxyisopropyl ketone, all of which are known compounds.
Particularly suitable photoinitiators which are normally used in combination with a HeCd laser as radiation source are acetophenones, conveniently 2,2-dialkoxybenzophenones, and a-hydroxyphenyl ketones, for example 1-hydroxycyclohexyl phenyl ketone or 2-hydroxy-isopropyl phenyl ketone (= 2-hydroxy-2,2-dimethylaceiophenone).
Another class of photoinitiators (4) which are normally employed when irradiating with argon ion lasers are the benzil ketals, typically benzil dimethyl ketal.
Preferably the photoinitiator is an a-hydroxyphenyl ketone, benzil dimethyl ketal ox 2,4,6-trimethyl-benzoyldiphenylphosphine oxide or a mixture of these: initiators.
Another class of suitable photoinitiators (4) comprise<; the ionic dye-counter ion compounds which are capable of absorbing actinic radiation and generating free radicals which initiate the polymerisation of the acrylates (1) to (3) and optionally (5). The compositions of the invention containing ionic dye-counter ion compounds can be cured more variably in this way with visible light within the adjustable wavelength range of 400-700 nm. Ionic dye-counter ion compounds and their mode of action are known, for example from EP-A-0 223 587 and US patents 4 751 i02; 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 cationic dye-borate anion compounds of formula R5~ ~R7 +
X , R6 Ra wherein X~' is a cationic dye and R$, R6, R~ and Rs are each independently of one another 2~~3~~~
an alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl or alkinyl group, an alicyclic group or a saturated or unsaturated heterocyclic group.
It is common practice to add the photoinitiators in effective amounts, i.e. in amounts of c. 0.1 to 10 °lo by weight, based on the total amount of the composition. If the novel compositions are used for stereolithographic methods in which laser beams are normally used, it is essential to adjust the absorption capacity of the mixtures by the type and concentration of the photoinitiator such that the depth of cure at normal laser speed is about 0.1 to 2.5 mm.
The novel compositions may also contain other photoinitiators of different sensitivity to radiation of emission lines of different wavelengths. The inclusion of such photoinitiatoxs effects the better utilisation of a UV/VIS light source which radiates emission Lines of different wavelength. It is advantageous to choose these other photoinitiators and to use them such that a uniform optical absorption is produced with respect to the emission lines used.
The photoinitiator (4) in the novel compositions is preferably a 1-hydroxyphenyl ketone, moxe particularly 1-hydroxycyclohexyl phenyl ketone.
The novel compasitions may contain as component (5) further acrylates which differ from component (2).
Suitable aliphatic or cycloaliphatic di(meth)acrylates which differ from component (2) are typically the diacrylaee and dimethacrylate esters of aliphatic or cycloaliphatic diols, including 1,3-butylene glycol,1,4-butanediol, neopentyl glycol,1,6-hexanediol, di-ethylene glycol, triethyleneglycol, tetraethylene glycol, polyethylene glycol 400, poly-ethylene glycol b00, tripropylene glycol, ethoxylated or propoxylated neopentyl glycol, 1,4-dimethylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane or bis(4-hydroxycyclo-hexyl)methane.
Tri(meth)acrylates useful as component (5) are typically the non-hydroxylated triacrylate and trimethacrylate esters of 2,4,6-hexanetriol, glycerol or 1,1,1-trimethylolpropane, ethoxylated or propoxylated glycerol or 1,1,1-trimethylolpropane and the hydroxyl group containing tri(meth)acrylates which are obtained by reaction of triepoxy compounds such as the triglycidyl ethexs of the cited triols with (meth)acrylic acid 2~~3~~2 - lo-Aromatic bis- and tris(meth)acrylates useful as component (5) are typically the reaction products of bis- or trisglycidyl ethers of dihydric or trihydric phenols, including resorcinol, hydroquinone, bis(4-hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl, bis(4-hydroxy-phenyl)sulfone, 1,1,2,2-tetrakis(4-hydroxyphenyl~thane, 2,2-bis(4-hydroxyphenyl)-propane, ethoxylated or propoxylated 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)propane and trihydroxylated phenol or cresol novolaks with (meth)acrylic acid.
The acrylates useful as component (5) are also known compounds.
Preferably component (5) of the photosensitive compositions is a reaction product of a diglycidyl ether of a bisphenol and acrylic acid, more particularly of a diglycidyl ether of bisphenol A and acrylic acid.
If desired, customary additives can be added to the compositions of this invention, typically stabilisers such as UV stabilisers, polymerisation inhibitors, slip agents, wetting agents, flow control agents, sensitisers, antiprecipitants, surfactants, dyes, pigments or fillers.
The compositions can be prepared in known manner, conveniently by premixing individual components and subsequently blending these premixes, or by blending all components in conventional apparatus, such as stirred vessels, excluding light and at slightly elevated temperature.
The novel photosensitive compositions can be polymerised by irradiation with actinic light, typically with electron beams, X-rays, UV ox VIS light, i.e. with radiation in the wavelength range from 280-6SO nm. Particularly suitable light sources are HeCd, argon or nitrogen laser light as well as metal vapour and NdYAG lasers with multiple frequency.
Those skilled in the art will know that the appropriate photoinitiator for each selected light source must be chosen and, if necessary, sensitised. It has been found that the depth of penetration of the radiation into the polymerised composition and the processing rate are directly related to the absorprion coefficient and the concentration of the photoinitiator. In stereolithography it is preferred to use those photoinitiators which generate the highest numbex of resulting free radicals and make possible the greatest depth of penentration into the compositions to be polymerised.
2~~~~~2 Accordingly, the invention also relates to a process for polymerising the novel compositions by irradiating said compositions with actinic Light.
The novel compositions are liquids having a viscosity of c. 150 to c. 10 000 mPa~s at 30°C, preferably of 300 to 10 000 mPa~s, more particularly of 500 to 5000 mPa~s and, most preferably, of 500 to 2500 mPa~s. Surprisingly, the novel compositions have a low curl factor coupled with high light sensitivity and a high dimensional stability after precuring with laser light (green strength) - an important factor in sterealithography. After full cure, the shaped objects formed from the novel compositions have high mechanical strength coupled with adequate elasticity. They are therefore rigid-elastic and have excellent tear growth resistance.
The invention further relates to a process for the production of three-dimensional objects from the novel liquid compositions by lithographic methods, especially by stereolithography, :in which a layer of novel liquid 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 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 predetea~nined 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.
If the novel compositions are used as coating compositions, clear and hard coats are obtained an wood, paper, metal, ceramic or other surfaces. The coating thickness can vary over a very wide range and be from c, 1 ltm to c. 1 mm. Relief images for printed circuit boards ar printing plates can be produced from the navel compositions, conveniently by computer-controlled laser light of appropriate wavelength or using a photornask and a suitable light source.
It is preferred to use the novel compositions for the production of photopolymerised layers, especially in the form of three-dimensional objects which are formed from a pluxality of solidified layers which adhere to one another.
2~~~9~2 1 he following urethane acrylates and hydroxyl group containing bis(meth)acrylates are used in the Examples:
Uvithane~892: Urethane acrylate supplied by Morton Thiokol Inc., double bond equivalent =1800, viscosity=410 Pa-s at 49°C.
SR-9504: Urethane acrylate supplied by Sartomex, Mw=1700, viscosity c. 167 Pa-s at 25°C.
Diacrylate I: Reaction product of a diglycidyl ether of bisphenol A and acrylic acid, commercially available under the registered trademark Novacure~ 3700.
Diacrylate II: Reaction product of butanediol diglycidyl ether and acrylic acid, commercially available under the registered trademark Laxomer ~LR 8765.
Diac , lanl to III: Reaction product of the diglycidyl ester of hexahydrophthalic acid and methacrylic acid having a double bond value of 4.06 equivalents/kg, obtained by reacting 100 g of the diglycidyl ester of hexahydrophthalic acid having an epoxy value of 4,06 equivalents/kg with 66.2 g (0,77 mol) of methacrylic acid and 1 % by weight of tetra-ammonium bromide as catalyst in toluene as solvent.
Diacrylate IV: Reaction product of sorbitol diglycidyl ether and acrylic acid having a double bond value of 3.3 equivalentslkg, obtained by reacting 100 g of sorbitol diglycidyl ether having an epoxy value of 4.90 equivalents/kg with 38.84 g (0.54 mol) of acrylic acid by the method disclosed in JP Kokai 63-132 916.
Diacrylate V: Reaction product of polypropylene glycol diglycidyl ether and acrylic acid having a double bond value of 2:27 equivalents/kg, obtained by reacting 100 g of polypropylene glycol diglycidyl ether having an epoxy value of 2.71 equivalents/kg with 21.4 g (0.3 mol) of acrylic acid by the process disclosed in JP Kokai 63-132 916.
Diac lr~ate VI: Reaction product of bis(3,4-epoxycyclohexylmethyl)adipate and acrylic acid having a double bond value of 3.18 equivalents/kg, obtained by reacting 100 g of bis-(3,4-epoxycyclohexylmethyl)adipate having an epoxy value of 5.0 equivalents/kg with 39.6 g (0.55 mol) of acrylic acid by the process disclosed in JP Kokai 63-132 916, 2~~~~~2 Diacrylate VII: Reaction product of the diglycidyl ester of hexahydrophthalic acid and acrylic acid having a double bond value of 4.06 equivalents/kg, obtained by reacting 100 g of the diglycidyl ester of hexahydrophthalic acid having an epoxy value of 7.0 equivalents/kg with 55.4 g (0.77 mol) of acrylic acid and 1 % by weight of tetraethyl-ammonium bromide as catalyst.
Diacrvlate VIII: Reaction product of sorbitol diglycidyl ether and methacrylic acid having a double bond value of 2.9 equivalents/kg, obtained by reacting 100 g of sorbitol diglycidyl ether having an epoxy value of 4.90 equivalents/kg with 46.4 g (0.54 mol) of methacrylic acid and 1 % by weight of tetraethylammonium bromide as catalyst.
Example 1: 60 g of urethane acrylate SR 9504 are mixed with 20 g of N-vinylpyrrolidone, g of 1-hydroxycyclohexyl phenyl ketone and 15 g of hexahydrophthalic acid diglycidyl ester dimethacrylate at 40°C. The resultant homogenous liquid composition has a viscosity of 1390 rnPa~s at 35°C. A shaped object produced from this composition using a He-Cd laser (40 mJ/cm2) has a modulus of elasticity (DIN 53 371; green strength) of 3 N/mm2, a tensile strength a mar (DIN 53455) of 1 N/mm2 and an elongation at break a (DIN 35 455) of 32 ~Io.
After curing the green object fox 30 minutes with UV/VIS light, the modulus of elasticity is 479 N/mm2, the tensile strength 28 N/mm2 and the s;longation at break 37 %.
To measure the Shore hardness and the tear growth resistance, 2 mm sheets are cast from the liquid composition and cured for 60 minutes with UV/VIS light. The cured composition has a Shore D hardness of 72 and a tear growth resistance of 3.1 N/mm2 (DIN 53 356A).
Examples 2-7: Formulations of the components listed in Tables 1 and 2 are prepared as in Example 1 and processed to three-dimensional shaped objects and to sheets under the conditions described in Example 1. The properties of the shaped objects are also shown in Tables 1 and 2.
2~~~~~2 3'able 1 Example 2 3 4 Uvithane 892 [g] 53.95 59.425 60.0 N-vinylpyraolidone17.575?4.265 20.0 [g]
diacrylate I [g] 6.350 diacrylate II [g] 17.12311.309 diacrylate all 15.0 [g]
1-hydroxycyclohexyl5.0 5.0 5.0 phenyl ketone [g]
r~ (35C) [mPa~s] 2990 1970 2940 * modulus of elasticity12 2.4 1.4 [N/mm2]
[N/mrn2] 3.3 1 1.2 * ~
m~
'' a (%] 44 41 68 **modulus of elasticity60 25 :136 (N/mm2]
** cr 14 15 27 [N/mrn2]
m~
** a [%] 64 96 90 ** tear growth 5 ~ 10.0 resistance (N/mm]
** Shore D-hardness55 47 53 * values after lasex cure (40 mJ/cm2) ** values after full cure Table 2 Example 5 6 7 SIt 9504 [g] 60 60 60 N-vinylpyrrolidone20 20 20 [g]
1-hydroxycyclohexyl5 5 5 phenyl ketone [g]
diacrylate IV
[g]
diacrylate V 15 [g]
diacrylate II
[g]
diacrylate III I5 [g]
diacrylate VI 15 (g]
~ (35C) [mpa~s] 1220 1550 1670 * modules of 9 72 72 elasticity [N/mm2l [N/mm2] 2 6 7 ~~
max *e [%] 22 ~ 29 31 ** modules of 118 458 425 elasticity IN/mm2]
(N/mm2] 14 29 26 **a m~
** a [/'o] 39 36 38 tear growth resistance1.7 4.2 3.1 (DIN 533560 [N/mm]
Shore D-hardness47 68 69 * values after laser cure (40 mJ/cm2) ** values after full cure Examples 8 and 9: Formulations of the components listed in Table 3 are prepared as in Example 1 and processed to three-dimensional shaped objects and to sheets under the conditions described in Example 1. The properties of the shaped objects are also shown in Table 3.
Table 3 Example 8 9 Uvithane 892 60 60 N-vinylpyrrolidone20 20 diacrylate VII 15 diacrylate VIII 15 1-hydroxycyclohexyl5 5 phenyl ketone ~ (35C) (mPas] 4990 5110 * modules of elasticity14.9 12.3 [N/mm2]
*a 2.7 4.8 (N/mm2]
m~
*E (~o] 39.6 so.2 ** modules of 70.4 124.8 elasticity (N/mm2]
*'~crm~ [N/mm2] 10.9 12.5 ** a (%] 43.5 41.8 tear gxowth resistance9.8 10.6 [N/mrn]
Shore D-hardness * values after laser cure (40 mJ/cm2) ** values after full cure
I~-1 ~596/.~.
Photosensitive composition based on acr~htes The present invention relates to a liquid photosensitive composition, to a process for polymerising said composition by radiation with actinic light, to a process for the production of three-dimensional objects from said liquid compasidon and to the use of this composition for forming photopolyrnerisable layers, especially three-dimensional objects fabricated from a plurality of photopolymerisable layers.
It is known that radiation-sensitive liquid resins or resin compositions have versatile utilities, typically as coating compositions, adhesives or photoresists. In principle, liquid resins ar resin systems should quite generally also be suitable for forming three-dimensional objects by the stereolithographic technique disclosed in US patent 4 575 330. However, many resins prove to be too viscous, whereas others are too insufficiently light-sensitive or, during the cure, suffer too severe shrinkage. The strength properties of the moulded articles or objects fabricated from photocured resins are also often unsatisfactory.
That complicated three-dimensional objects can be formed from liquid light-sensitive resins by dhe stereolithographic technique is well-known. Such objects are formed from layers by bonding each new curable resin layer tenaciously to the previously prehardened layer by curing with UV/VIS light. It is common knowledge that the total assembly of the thxee-dimensional object can be accomplished by means of a computer-controlled process.
In recent years there has been no lack of efforts to develop resin systems suitable for the technique of stereolithography. In Rev. Sci. Instxum. 52 (11) 1170-1173 (1981), I-I. ICodama discloses under the registered trademark "Tevista" a liquid phatohardening resin composition comprising an unsaturated polyester, acrylate, styrene, a polymerisation initiator and a sensitiser. The daawback of this resin system fox use in stereolithogxaphy is that the photosensitivity is insufficient and the so-called "green strength"
of the objects hardened by laser beams is rather low.
The technique of stereolithagraphy is described in detail in US patent 4 575 330. The 2~~39~~
liquid resin used is a modified acrylate which is referred to in the description as "Potting Compound 363". Such resin compositions are disclosed in US patent 4 100 141.
They too have the drawback of being insufficiently light-sensitive and of requiring lengthy times for the fabrication of three-dimensional objects by the stereolithographic technique.
It is therefore understandable that the demands made of resins for use in stereolithography are high. For example, they must have a viscosity suitable for processing in the intended apparatus. The photosensitivity of the resin system must be such that the ratio of the radiation energy applied and the depth of penetration into the liquid photosensitive resin composition so as to effect solidification of the parts is within reasonable limits. This means that, when using a resin suitable for use in stereolithography, the aim shall be to achieve the greatest possible curing depth with little radiation energy, simultaneously coupled with a high degree of polymerisation and high green strength.
Tn the technique employed in stereolithography of successively polymerising thin layers, none of the layers is fully cured. The partially cured object is called a green object, and the module of elasticity and the tensile strength of this green object is called the green strength. Normally the green object is cured with UV/VIS light, conveniently with a mercury or xenon arc lamp. The green strength of an object is therefore an important parameter, as objects having a Inw green strength may become deformed under their own weight or, in the course of the cure, they may sag or collapse.
It has now been found that a liquid resin composition comprising several (meth)acrylates which differ from another, and which additionally comprises a hydxoxyl group containing aliphatic or cycloaliphatic di(meth)acrylate, may be used for stereolithography and is able to forth green objects when precured with laser beams, which objects have high green strength. 3'he objects formed by curing the green objects have excellent flexibility and, in addition, are distinguished by excellent teax growth resistance.
Accordingly, the invention relates to a liquid photosensitive composition comprising (1) 40 to 80 % by weight of a urethane (meth)acrylate having a functionality of 2 to 4 and a molecular weight (Mw) of 500 to 10 000, (2) 5 to 40 % by weight of a hydroxyl group containing aliphade or cycloaliphatic di(meth)acrylate, (3) 0 to 40 % by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having ~~6~~~~
a Mw of not more than 500, (4) 0.1 to 10 % by weight of a photoinitiator, (5) 0 to 30 % by weight of an aliphatic or cycloaliphatic di(meth)acrylate which differs from (2), of an aliphatic tri(meth)acrylate or of an aromatic di- or tri(meth)acrylate, and (b) 0 to 5 % by weight of customary additives, such that the proportion of components (1) to (6) together is 100 % by weight.
Preferably the composition of this invention comprises (1) 40 to 80 % by weight of a urethane (meth)acrylate having a functionality of 2 to 4 and a molecular weight (Mw) of 500 to 10 000, (2) 5 to 40 % by weight of a hydroxyl group containing aliphatic or cycloaliphatic di(meth)acrylate, (3) 5 to 40 % by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having a Mw of not more than 500, (4) 0.1 to 10 % by weight of a photoinitiator, (5) 0 to 30 % by weight of an aliphatic or cycloaliphatic di(meth)acrylate which differs from (2), of an aliphatic tri(meth)acrylate or of an aromatic di- or tri(meth)acrylate, and (6) 0 to 5 % by weight of customary additives.
More particularly the composition of the invention comprises (1) 50 to 70 % by weight of a urethane (meth)acrylate having a functionality of 2 to 4 and a molecular weight (Mw) of 1000 to 10 000, (2) 10 to 30 % by weight of a hydroxyl group containing aliphatic di(meth)acrylate, (3) 0 to 30 % by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having a Mw of not more than 500, (4) 0.5 to 7 % by weight of a photoinitiator, (5) 0 to 20 % by weight of an aliphatic or cycloaliphatic bis(meth)acrylate which differs from (2), of an aliphatic tris(meth)acrylate or of an aromatic di- or tris(meth)acrylate, and (6) 0 to 3 % by weight of an additive.
In the particularly preferred embodiment of the invention, component (3) comprises preferably 10 to 30 % by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having a Mw of not more than 500.
The urethane acrylates used as component (1) of the novel compositions are known to those skilled in the art and can be prepared in known manner, conveniently by reacting a hydroxyl-terminated 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. Appropriate processes are disclosed in published EP patent applications 114 982 and 133 908. The molecular weight of such acrylates is usuaily in the range from 400 to 10 000, preferably from 500 to 7000.
Urethane acrylates are commercially available and are sold, inter alia, by UCB
under the registered trademark EBECRYL~, by Morton Thiokol under the registered trademark Uvithane~, 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 which have a Mw of 500-700 and which have preferably been prepared from aliphatic educts.
Compounds useful as component (2) include reaction products of aliphatic epoxy resins, such as alkanediol diglycidyl ethers, including the diglycidyl ether of 1,4-butanediol, the diglycidyl ether of polyethylene glycol or polybutylene glycol, or cycioaliphatic epoxy resins, such as the diglycidyl esters of cycloaliphatic dicarboxylic acids, for example the diglycidyl ester of hexahydrophthalic acid, or hydrogenated diglycidyl ethers of bisphenols, typically the diglycidyl ether of hydrogenated bisphenol A, or epoxy resins having an epoxy group attached direct to the cycloaliphatic ring, such as bis-(3,4-epoxycyclohexylmethyl) adipate, which cited compounds with (meth)acrylic acid may lead to reaction products of the following formulae R OH
O U.~.O
~O O , O OH R
R OH O
O O
O
/ ~ R
n 2~~3~~2 R OH O
O O
O~O , O OfH R
n OH O ,/
O O
O -"' R
O
O
OH O R
R O
y~~ O O
II p R or O O
OH
HO
O
R OH
O O~O
OH R
O
wherein R is a hydrogen atom or methyl and n is a number greater 1, and also reaction prcxlucts of epoxidised fatty acid dvith (meth)acrylic acid, or caprolactone-modified reaction products of aliphatic or cycloaliphatic epoxy resins, for example the diglycidyl ether of 1,4-butanedial, with (meth)acrylic acid to give a pznduct of formula 2fl~~9~~
_g_ OH
O
R O O
O~O O O
R
O
OI-I
wherein R is a hydrogen atom or methyl. These reaction products of aliphatic or cycloaliphatic epoxy resins and (meth)acrylic acid are known, inter alia from JP
ICokai 50-059487 or from Urg. Coat. Plast. Ch.°,m. 40, pages 104-109, 1979, where processes for their preparation are also described.
The caprolactone-modilaed reaction product of aliphatic or cycloaliphatic resins and (meth)acxylic acid is also known and can be prepared by reacting 1 mol of a reaction product of the aliphatic or cycloaliphatic epoxy resin and (meth)acrylic acid with 2 mol of caprolactone in an organic solvent at elevated temperature and in the presence or absence of a catalyst.
Representative examples of further aliphatic or cycloaliphatic resins which may be used for preparing the above mentioned reaction products are: the diglycidyl and bis(ø-methylglycidyl) esters of aliphatic dicarboxylic acids, including oxalic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, arelaic acid, sebacic acid or dimerised linolic acid, the diglycidyl esters of cycloaliphatic dicarboxylic acids, including tetra-hydrophthalic acid, 4-methyltetrahydrophthalic acid or 4-methylhexahydrophthalic acid, the diglycidyl ethers of higher aliphatic alcohols, such as 1,5-pentanediol, 1,6-hexanediol _7_ or 1,8-octanediol, the diglycidyl ethers of cycloaliphatic diols, such as resorcitol, quinitol, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane and 1,1-bis-(hydroxymethyl)3-cyclohexene.
The novel compositions preferably contain a xeaction product of the diglycidyl ether of 1,4-butanediol and acrylic acid as hydroxyl group containing aliphatic diacrylate (2).
Component (2) of the novel compositions is preferably a hydroxyl group containing cycloaliphatic bis(meth)acrylate, more particularly a reaction product of the diglycidyl ester of hexahydrophthalic acid or bis(3,4-epoxycyclohexylmethyl)adipate and (meth)acrylic acid Component (3) of the novel compositions may be selected from the following compounds:
allyl acrylate, allyl methacrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, 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 (nneth)acrylate, 2-hydroxyethyl (rneth)acrylate, 2- and :3-hydmxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)ac;rylate and 2- or 3-ethoxypropyl (meth)acrylate, tetrahydrofurfurylmethacrylate, 2-(2-ethoxyethoxy)ethylacrylate, cyclohexyl methacrylate, 2-phenoxyethyl acrylate, glycidyl acrylate and isodecyl acrylate;
and the mono-N-vinyl compound is N-vinylpyrrolidone or N-vinylcaprolactam.
Such products are also known and some are commercially available, as from SARTOMER.
The compounds suitable for use as component (3) preferably have a Mw von SO-300.
Component (3) of the novel compositions is preferably a mono-N-vinyl compound, mere particularly N-vinylpyrrolidone.
Any type of photoinitiator which, when izradiated suitably, forms frEe radicals can be employed as component (4) in the novel compositions. Typical known photoinitiators are benzoins, benzoin ethers, including benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, benzain phenyl ether and benzoin acetate, acetophenones, including acetophenone, 2,2-dimethoxyacetophenone and 1,1-dichloroacetophenone, benzil, benzil ketals, such as benzil dimethyl ketal and benzil diethyl ketal, anthraquinones, including 2-mefhylanthraquinone, 2-ethylanthraquinone, 2-tort-butyl-anthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone, triphenylphosphine, ~4~39~2 _g_ benzoylphosphine oxides, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide (I,uzirin TPO), benzophenones, such as benzophenone and 4,4'-his(N,N'-dimethyl-amino)benzophenone, thioxanthones and xanthones, acridine derivatives, phenazine derivatives, quinoxaline derivatives or 1-phenyl-1,2-propanedione, 2-O-benzoyl oxime, 1-aminophenyl ketones or 1-hydroxyphenyl ketones, such as 1-hydroxycyclohexyl phenyl ketone, phenyl 1-hydroxyisopropyl ketone and 4-isopropylphenyl 1-hydroxyisopropyl ketone, all of which are known compounds.
Particularly suitable photoinitiators which are normally used in combination with a HeCd laser as radiation source are acetophenones, conveniently 2,2-dialkoxybenzophenones, and a-hydroxyphenyl ketones, for example 1-hydroxycyclohexyl phenyl ketone or 2-hydroxy-isopropyl phenyl ketone (= 2-hydroxy-2,2-dimethylaceiophenone).
Another class of photoinitiators (4) which are normally employed when irradiating with argon ion lasers are the benzil ketals, typically benzil dimethyl ketal.
Preferably the photoinitiator is an a-hydroxyphenyl ketone, benzil dimethyl ketal ox 2,4,6-trimethyl-benzoyldiphenylphosphine oxide or a mixture of these: initiators.
Another class of suitable photoinitiators (4) comprise<; the ionic dye-counter ion compounds which are capable of absorbing actinic radiation and generating free radicals which initiate the polymerisation of the acrylates (1) to (3) and optionally (5). The compositions of the invention containing ionic dye-counter ion compounds can be cured more variably in this way with visible light within the adjustable wavelength range of 400-700 nm. Ionic dye-counter ion compounds and their mode of action are known, for example from EP-A-0 223 587 and US patents 4 751 i02; 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 cationic dye-borate anion compounds of formula R5~ ~R7 +
X , R6 Ra wherein X~' is a cationic dye and R$, R6, R~ and Rs are each independently of one another 2~~3~~~
an alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl or alkinyl group, an alicyclic group or a saturated or unsaturated heterocyclic group.
It is common practice to add the photoinitiators in effective amounts, i.e. in amounts of c. 0.1 to 10 °lo by weight, based on the total amount of the composition. If the novel compositions are used for stereolithographic methods in which laser beams are normally used, it is essential to adjust the absorption capacity of the mixtures by the type and concentration of the photoinitiator such that the depth of cure at normal laser speed is about 0.1 to 2.5 mm.
The novel compositions may also contain other photoinitiators of different sensitivity to radiation of emission lines of different wavelengths. The inclusion of such photoinitiatoxs effects the better utilisation of a UV/VIS light source which radiates emission Lines of different wavelength. It is advantageous to choose these other photoinitiators and to use them such that a uniform optical absorption is produced with respect to the emission lines used.
The photoinitiator (4) in the novel compositions is preferably a 1-hydroxyphenyl ketone, moxe particularly 1-hydroxycyclohexyl phenyl ketone.
The novel compasitions may contain as component (5) further acrylates which differ from component (2).
Suitable aliphatic or cycloaliphatic di(meth)acrylates which differ from component (2) are typically the diacrylaee and dimethacrylate esters of aliphatic or cycloaliphatic diols, including 1,3-butylene glycol,1,4-butanediol, neopentyl glycol,1,6-hexanediol, di-ethylene glycol, triethyleneglycol, tetraethylene glycol, polyethylene glycol 400, poly-ethylene glycol b00, tripropylene glycol, ethoxylated or propoxylated neopentyl glycol, 1,4-dimethylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane or bis(4-hydroxycyclo-hexyl)methane.
Tri(meth)acrylates useful as component (5) are typically the non-hydroxylated triacrylate and trimethacrylate esters of 2,4,6-hexanetriol, glycerol or 1,1,1-trimethylolpropane, ethoxylated or propoxylated glycerol or 1,1,1-trimethylolpropane and the hydroxyl group containing tri(meth)acrylates which are obtained by reaction of triepoxy compounds such as the triglycidyl ethexs of the cited triols with (meth)acrylic acid 2~~3~~2 - lo-Aromatic bis- and tris(meth)acrylates useful as component (5) are typically the reaction products of bis- or trisglycidyl ethers of dihydric or trihydric phenols, including resorcinol, hydroquinone, bis(4-hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl, bis(4-hydroxy-phenyl)sulfone, 1,1,2,2-tetrakis(4-hydroxyphenyl~thane, 2,2-bis(4-hydroxyphenyl)-propane, ethoxylated or propoxylated 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)propane and trihydroxylated phenol or cresol novolaks with (meth)acrylic acid.
The acrylates useful as component (5) are also known compounds.
Preferably component (5) of the photosensitive compositions is a reaction product of a diglycidyl ether of a bisphenol and acrylic acid, more particularly of a diglycidyl ether of bisphenol A and acrylic acid.
If desired, customary additives can be added to the compositions of this invention, typically stabilisers such as UV stabilisers, polymerisation inhibitors, slip agents, wetting agents, flow control agents, sensitisers, antiprecipitants, surfactants, dyes, pigments or fillers.
The compositions can be prepared in known manner, conveniently by premixing individual components and subsequently blending these premixes, or by blending all components in conventional apparatus, such as stirred vessels, excluding light and at slightly elevated temperature.
The novel photosensitive compositions can be polymerised by irradiation with actinic light, typically with electron beams, X-rays, UV ox VIS light, i.e. with radiation in the wavelength range from 280-6SO nm. Particularly suitable light sources are HeCd, argon or nitrogen laser light as well as metal vapour and NdYAG lasers with multiple frequency.
Those skilled in the art will know that the appropriate photoinitiator for each selected light source must be chosen and, if necessary, sensitised. It has been found that the depth of penetration of the radiation into the polymerised composition and the processing rate are directly related to the absorprion coefficient and the concentration of the photoinitiator. In stereolithography it is preferred to use those photoinitiators which generate the highest numbex of resulting free radicals and make possible the greatest depth of penentration into the compositions to be polymerised.
2~~~~~2 Accordingly, the invention also relates to a process for polymerising the novel compositions by irradiating said compositions with actinic Light.
The novel compositions are liquids having a viscosity of c. 150 to c. 10 000 mPa~s at 30°C, preferably of 300 to 10 000 mPa~s, more particularly of 500 to 5000 mPa~s and, most preferably, of 500 to 2500 mPa~s. Surprisingly, the novel compositions have a low curl factor coupled with high light sensitivity and a high dimensional stability after precuring with laser light (green strength) - an important factor in sterealithography. After full cure, the shaped objects formed from the novel compositions have high mechanical strength coupled with adequate elasticity. They are therefore rigid-elastic and have excellent tear growth resistance.
The invention further relates to a process for the production of three-dimensional objects from the novel liquid compositions by lithographic methods, especially by stereolithography, :in which a layer of novel liquid 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 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 predetea~nined 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.
If the novel compositions are used as coating compositions, clear and hard coats are obtained an wood, paper, metal, ceramic or other surfaces. The coating thickness can vary over a very wide range and be from c, 1 ltm to c. 1 mm. Relief images for printed circuit boards ar printing plates can be produced from the navel compositions, conveniently by computer-controlled laser light of appropriate wavelength or using a photornask and a suitable light source.
It is preferred to use the novel compositions for the production of photopolymerised layers, especially in the form of three-dimensional objects which are formed from a pluxality of solidified layers which adhere to one another.
2~~~9~2 1 he following urethane acrylates and hydroxyl group containing bis(meth)acrylates are used in the Examples:
Uvithane~892: Urethane acrylate supplied by Morton Thiokol Inc., double bond equivalent =1800, viscosity=410 Pa-s at 49°C.
SR-9504: Urethane acrylate supplied by Sartomex, Mw=1700, viscosity c. 167 Pa-s at 25°C.
Diacrylate I: Reaction product of a diglycidyl ether of bisphenol A and acrylic acid, commercially available under the registered trademark Novacure~ 3700.
Diacrylate II: Reaction product of butanediol diglycidyl ether and acrylic acid, commercially available under the registered trademark Laxomer ~LR 8765.
Diac , lanl to III: Reaction product of the diglycidyl ester of hexahydrophthalic acid and methacrylic acid having a double bond value of 4.06 equivalents/kg, obtained by reacting 100 g of the diglycidyl ester of hexahydrophthalic acid having an epoxy value of 4,06 equivalents/kg with 66.2 g (0,77 mol) of methacrylic acid and 1 % by weight of tetra-ammonium bromide as catalyst in toluene as solvent.
Diacrylate IV: Reaction product of sorbitol diglycidyl ether and acrylic acid having a double bond value of 3.3 equivalentslkg, obtained by reacting 100 g of sorbitol diglycidyl ether having an epoxy value of 4.90 equivalents/kg with 38.84 g (0.54 mol) of acrylic acid by the method disclosed in JP Kokai 63-132 916.
Diacrylate V: Reaction product of polypropylene glycol diglycidyl ether and acrylic acid having a double bond value of 2:27 equivalents/kg, obtained by reacting 100 g of polypropylene glycol diglycidyl ether having an epoxy value of 2.71 equivalents/kg with 21.4 g (0.3 mol) of acrylic acid by the process disclosed in JP Kokai 63-132 916.
Diac lr~ate VI: Reaction product of bis(3,4-epoxycyclohexylmethyl)adipate and acrylic acid having a double bond value of 3.18 equivalents/kg, obtained by reacting 100 g of bis-(3,4-epoxycyclohexylmethyl)adipate having an epoxy value of 5.0 equivalents/kg with 39.6 g (0.55 mol) of acrylic acid by the process disclosed in JP Kokai 63-132 916, 2~~~~~2 Diacrylate VII: Reaction product of the diglycidyl ester of hexahydrophthalic acid and acrylic acid having a double bond value of 4.06 equivalents/kg, obtained by reacting 100 g of the diglycidyl ester of hexahydrophthalic acid having an epoxy value of 7.0 equivalents/kg with 55.4 g (0.77 mol) of acrylic acid and 1 % by weight of tetraethyl-ammonium bromide as catalyst.
Diacrvlate VIII: Reaction product of sorbitol diglycidyl ether and methacrylic acid having a double bond value of 2.9 equivalents/kg, obtained by reacting 100 g of sorbitol diglycidyl ether having an epoxy value of 4.90 equivalents/kg with 46.4 g (0.54 mol) of methacrylic acid and 1 % by weight of tetraethylammonium bromide as catalyst.
Example 1: 60 g of urethane acrylate SR 9504 are mixed with 20 g of N-vinylpyrrolidone, g of 1-hydroxycyclohexyl phenyl ketone and 15 g of hexahydrophthalic acid diglycidyl ester dimethacrylate at 40°C. The resultant homogenous liquid composition has a viscosity of 1390 rnPa~s at 35°C. A shaped object produced from this composition using a He-Cd laser (40 mJ/cm2) has a modulus of elasticity (DIN 53 371; green strength) of 3 N/mm2, a tensile strength a mar (DIN 53455) of 1 N/mm2 and an elongation at break a (DIN 35 455) of 32 ~Io.
After curing the green object fox 30 minutes with UV/VIS light, the modulus of elasticity is 479 N/mm2, the tensile strength 28 N/mm2 and the s;longation at break 37 %.
To measure the Shore hardness and the tear growth resistance, 2 mm sheets are cast from the liquid composition and cured for 60 minutes with UV/VIS light. The cured composition has a Shore D hardness of 72 and a tear growth resistance of 3.1 N/mm2 (DIN 53 356A).
Examples 2-7: Formulations of the components listed in Tables 1 and 2 are prepared as in Example 1 and processed to three-dimensional shaped objects and to sheets under the conditions described in Example 1. The properties of the shaped objects are also shown in Tables 1 and 2.
2~~~~~2 3'able 1 Example 2 3 4 Uvithane 892 [g] 53.95 59.425 60.0 N-vinylpyraolidone17.575?4.265 20.0 [g]
diacrylate I [g] 6.350 diacrylate II [g] 17.12311.309 diacrylate all 15.0 [g]
1-hydroxycyclohexyl5.0 5.0 5.0 phenyl ketone [g]
r~ (35C) [mPa~s] 2990 1970 2940 * modulus of elasticity12 2.4 1.4 [N/mm2]
[N/mrn2] 3.3 1 1.2 * ~
m~
'' a (%] 44 41 68 **modulus of elasticity60 25 :136 (N/mm2]
** cr 14 15 27 [N/mrn2]
m~
** a [%] 64 96 90 ** tear growth 5 ~ 10.0 resistance (N/mm]
** Shore D-hardness55 47 53 * values after lasex cure (40 mJ/cm2) ** values after full cure Table 2 Example 5 6 7 SIt 9504 [g] 60 60 60 N-vinylpyrrolidone20 20 20 [g]
1-hydroxycyclohexyl5 5 5 phenyl ketone [g]
diacrylate IV
[g]
diacrylate V 15 [g]
diacrylate II
[g]
diacrylate III I5 [g]
diacrylate VI 15 (g]
~ (35C) [mpa~s] 1220 1550 1670 * modules of 9 72 72 elasticity [N/mm2l [N/mm2] 2 6 7 ~~
max *e [%] 22 ~ 29 31 ** modules of 118 458 425 elasticity IN/mm2]
(N/mm2] 14 29 26 **a m~
** a [/'o] 39 36 38 tear growth resistance1.7 4.2 3.1 (DIN 533560 [N/mm]
Shore D-hardness47 68 69 * values after laser cure (40 mJ/cm2) ** values after full cure Examples 8 and 9: Formulations of the components listed in Table 3 are prepared as in Example 1 and processed to three-dimensional shaped objects and to sheets under the conditions described in Example 1. The properties of the shaped objects are also shown in Table 3.
Table 3 Example 8 9 Uvithane 892 60 60 N-vinylpyrrolidone20 20 diacrylate VII 15 diacrylate VIII 15 1-hydroxycyclohexyl5 5 phenyl ketone ~ (35C) (mPas] 4990 5110 * modules of elasticity14.9 12.3 [N/mm2]
*a 2.7 4.8 (N/mm2]
m~
*E (~o] 39.6 so.2 ** modules of 70.4 124.8 elasticity (N/mm2]
*'~crm~ [N/mm2] 10.9 12.5 ** a (%] 43.5 41.8 tear gxowth resistance9.8 10.6 [N/mrn]
Shore D-hardness * values after laser cure (40 mJ/cm2) ** values after full cure
Claims (18)
1. ~A liquid photosensitive composition comprising:
(1) 40 to 80% by weight of a urethane (meth)acrylate having a functionality of 2 to 4 and a molecular weight (Mw) of 500 to 10 000, (2) 5 to 40% by weight of a hydroxyl group containing aliphatic or cycloaliphatic di(meth)acrylate, (3) 0 to 40% by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having a Mw of not more than 500, (4) 0.1 to 10% by weight of a photoinitiator, (5) 0 to 30% by weight of an aliphatic or cycloaliphatic di(meth)acrylate which differs from (2), of an aliphatic tri(meth)acrylate or of an aromatic di- or tri(meth)acrylate, and (6) 0 to 5% by weight of customary additives, such that the proportion of components (1) to (6) together is 100%
by weight.
(1) 40 to 80% by weight of a urethane (meth)acrylate having a functionality of 2 to 4 and a molecular weight (Mw) of 500 to 10 000, (2) 5 to 40% by weight of a hydroxyl group containing aliphatic or cycloaliphatic di(meth)acrylate, (3) 0 to 40% by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having a Mw of not more than 500, (4) 0.1 to 10% by weight of a photoinitiator, (5) 0 to 30% by weight of an aliphatic or cycloaliphatic di(meth)acrylate which differs from (2), of an aliphatic tri(meth)acrylate or of an aromatic di- or tri(meth)acrylate, and (6) 0 to 5% by weight of customary additives, such that the proportion of components (1) to (6) together is 100%
by weight.
2. ~A composition according to claim 1, comprising:
(1) 40 to 80% by weight of a urethane (meth)acrylate having a functionality of 2 to 4 and a molecular weight (Mw) of 500 to 10 000, (2) 5 to 40% by weight of a hydroxyl group containing aliphatic or cycloaliphatic di(meth)acrylate, (3) 5 to 40% by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having a Mw of not more than 500, (4) 0.1 to 10% by weight of a photoinitiator, (5) 0 to 30% by weight of an aliphatic or cycloaliphatic di(meth)acrylate which differs from (2), of an aliphatic tri(meth)acrylate or of an aromatic di- or tri(meth)acrylate, and (6) 0 to 5% by weight of customary additives.
(1) 40 to 80% by weight of a urethane (meth)acrylate having a functionality of 2 to 4 and a molecular weight (Mw) of 500 to 10 000, (2) 5 to 40% by weight of a hydroxyl group containing aliphatic or cycloaliphatic di(meth)acrylate, (3) 5 to 40% by weight of a mono(meth)acrylate or of a mono-N-vinyl compound having a Mw of not more than 500, (4) 0.1 to 10% by weight of a photoinitiator, (5) 0 to 30% by weight of an aliphatic or cycloaliphatic di(meth)acrylate which differs from (2), of an aliphatic tri(meth)acrylate or of an aromatic di- or tri(meth)acrylate, and (6) 0 to 5% by weight of customary additives.
3. ~A composition according to claim 1 or 2, wherein component (1) is an aliphatic urethane acrylate.
4. ~A composition according to any one of claims 1 to 3, wherein the hydroxyl group containing diacrylate (2) is a reaction product of a diglycidyl ether of 1,4-butanediol and acrylic acid.
5. ~A composition according to any one of claims 1 to 3, wherein component (2) is a hydroxyl group containing cycloaliphatic di(meth)acrylate.
6. ~A composition according to claim 5, wherein component (2) is a reaction product of the diglycidyl ester of hexahydrophthalic acid or bis(3,4-epoxycyclohexylmethyl)adipate and (meth)acrylic acid.
7. ~A composition according to any one of claims 1 to 6, wherein component (3) is a mono-N-vinyl compound.
8. ~A composition according to claim 7, wherein component (3) is N-vinylpyrrolidone.
9. ~A composition according to any one of claims 1 to 8, wherein the photoinitiator (4) is a 1-hydroxyphenyl ketone.
10. ~A composition according to any one of claims 1 to 8 wherein the photoinitiator (4) is a 1-hydroxycyclohexyl phenyl ketone.
11. ~A composition according to any one of claims 1 to 10, wherein component (5) is a reaction product of a bisphenol diglycidyl ether and acrylic acid.
12. ~A composition according to any one of claims 1 to 10, wherein component (5) is a reaction product of a diglycidyl ether of bisphenol A and acrylic acid.
13. ~A process for polymerising a composition as claimed in any one of claims 1 to 12 by irradiation with actinic light.
14. ~A process for the production of three-dimensional objects from the liquid photosensitive compositions of any one of claims 1 to 12 by lithographic methods, wherein a layer of the liquid 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 the 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.
15. ~A process according to claim 14, wherein a laser beam is used as source of irradiation.
16. ~A process according to claim 15, wherein the laser beam is computer-controlled.
17. ~Use of a composition as claimed in any one of claims 1 to 12 for the production of photopolymerised layers.
18. ~Use according to claim 17, wherein the photopolymerised layers are in the form of a three-dimensional object which is formed from a plurality of solidified layers which adhere to one another.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH93691 | 1991-03-27 | ||
| CH19992 | 1992-01-23 | ||
| CH199/92-4 | 1992-01-23 | ||
| CH936/91-5 | 1992-01-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2063982A1 CA2063982A1 (en) | 1992-09-28 |
| CA2063982C true CA2063982C (en) | 2002-05-28 |
Family
ID=25683853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002063982A Expired - Fee Related CA2063982C (en) | 1991-03-27 | 1992-03-25 | Photosensitive composition based on acrylates |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5476749A (en) |
| EP (1) | EP0506616B1 (en) |
| JP (1) | JP3252331B2 (en) |
| KR (1) | KR100199479B1 (en) |
| CA (1) | CA2063982C (en) |
| DE (1) | DE59209143D1 (en) |
| HK (1) | HK1005630A1 (en) |
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| EP0378144B1 (en) * | 1989-01-10 | 1995-03-08 | Ciba-Geigy Ag | Photocurable compositions |
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-
1992
- 1992-03-19 EP EP92810201A patent/EP0506616B1/en not_active Expired - Lifetime
- 1992-03-19 DE DE59209143T patent/DE59209143D1/en not_active Expired - Fee Related
- 1992-03-25 CA CA002063982A patent/CA2063982C/en not_active Expired - Fee Related
- 1992-03-26 KR KR1019920005148A patent/KR100199479B1/en not_active IP Right Cessation
- 1992-03-27 JP JP11513692A patent/JP3252331B2/en not_active Expired - Fee Related
-
1994
- 1994-09-09 US US08/303,563 patent/US5476749A/en not_active Expired - Lifetime
-
1998
- 1998-06-02 HK HK98104761A patent/HK1005630A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0506616B1 (en) | 1998-01-21 |
| HK1005630A1 (en) | 1999-01-15 |
| KR100199479B1 (en) | 1999-06-15 |
| EP0506616A1 (en) | 1992-09-30 |
| US5476749A (en) | 1995-12-19 |
| KR920018522A (en) | 1992-10-22 |
| JPH05224412A (en) | 1993-09-03 |
| DE59209143D1 (en) | 1998-02-26 |
| CA2063982A1 (en) | 1992-09-28 |
| JP3252331B2 (en) | 2002-02-04 |
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