WO2014158015A1 - Composition de résine liquide durcissable par un rayonnement destinée à un façonnage tridimensionnel optique et objet façonné optiquement obtenu par photodurcissement de celle-ci - Google Patents

Composition de résine liquide durcissable par un rayonnement destinée à un façonnage tridimensionnel optique et objet façonné optiquement obtenu par photodurcissement de celle-ci Download PDF

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Publication number
WO2014158015A1
WO2014158015A1 PCT/NL2014/050126 NL2014050126W WO2014158015A1 WO 2014158015 A1 WO2014158015 A1 WO 2014158015A1 NL 2014050126 W NL2014050126 W NL 2014050126W WO 2014158015 A1 WO2014158015 A1 WO 2014158015A1
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Prior art keywords
component
meth
compound
resin composition
radiation
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PCT/NL2014/050126
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English (en)
Inventor
Katsuyuki Takase
Keisuke Satou
Yusuke Amano
Daigou MOCHIZUKI
Takahiko Kurosawa
Original Assignee
Dsm Ip Assets B.V.
Jsr Corporation
Japan Fine Coatings Co., Ltd.
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Application filed by Dsm Ip Assets B.V., Jsr Corporation, Japan Fine Coatings Co., Ltd. filed Critical Dsm Ip Assets B.V.
Publication of WO2014158015A1 publication Critical patent/WO2014158015A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0037—Production of three-dimensional images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to a radiation-curable liquid resin composition for optical three-dimensional shaping, and an optically shaped article obtained by photo-curing the same.
  • a cured resin layer having a predetermined pattern is formed by selectively irradiating the liquid surface of a radiation-curable liquid resin composition received by a container with light such as
  • a new cured resin layer is integrally laminated on the previously formed cured resin layer by supplying the radiation-curable liquid resin composition in an amount corresponding to one layer on the cured resin and selectively irradiating the liquid surface of the radiation- curable liquid resin composition with light, so that the new cured resin layer may be continuous with the previously formed cured resin layer. Then, a three-dimensional article in which a plurality of cured resin layers are integrally laminated is formed by repeating the above steps a
  • This optical three-dimensional shaping method can provide a target three-dimensional article easily and in a short time even when the shape thereof is complicated. This technique is extremely useful in the trial production process in the new product development in motor vehicle or household appliance industry, and is becoming an indispensable means for the shortening of development period of time and the cost reduction.
  • a radiation-curable liquid resin composition which comprises a cationically polymerizable compound having an oxetane structure and is used for an optical three-dimensional shaping method is also disclosed (refer to Patent Literatures 2 to 5).
  • the resulting optically shaped article has a disadvantage of being brittle and susceptible to breakage when mechanical stress is applied.
  • heat resistance is insufficient. Therefore, it is difficult to obtain an optically shaped article excellent in both the toughness and heat resistance.
  • Patent Literature 6 a specific radiation-curable liquid resin composition comprising a dendrimer is not disclosed.
  • Patent Literature 1 Japanese Patent Application Laid-Open No.
  • Patent Literature 2 Japanese Patent Application Laid-Open No.
  • Patent Literature 3 Japanese Patent Application Laid-Open No.
  • Patent Literature 4 Japanese Patent Application Laid-Open No.
  • Patent Literature 5 Japanese Patent Application Laid-Open No.
  • Patent Literature 6 Japanese Patent Application Laid-Open No.
  • An object of the present invention is to provide a radiation-curable liquid resin composition for optical three-dimensional shaping capable of obtaining an optically shaped article excellent in toughness and heat resistance.
  • the present inventor has found that it is possible to obtain an optically shaped article excellent in toughness and heat resistance by using a radiation-curable liquid resin composition for optical three-dimensional shaping comprising a compound which has a carbonate group and two or more (meth)acryloyl groups and does not have a urethane bond, and has completed the present invention.
  • the present invention provides the following (1) to (6).
  • dimensional shaping comprising: (A) a compound which has a carbonate group and two or more (meth)acryloyl groups and does not have a urethane bond; (B) a cationically polymerizable compound; (C) a photo cationic polymerization initiator; (D) a radically polymerizable compound; and (E) a photo-radical polymerization initiator.
  • R 1 and R 2 are each independently a monovalent organic group having an aliphatic, alicyclic or aromatic structure
  • R 3 and R 4 are each independently a monovalent organic group having an aliphatic, alicyclic or aromatic structure
  • R 5 and R 6 are each independently an alkylene group
  • nl and n2 are each independently an integer of 2 or more
  • ml and m3 are each independently an integer of 3 or more
  • m2 is an integer of 1 to 3, provided that at least one of R 1 and R 3 or R 2 and R 4 constituting one compound has an aromatic structure.
  • (6) An optically shaped article obtained by irradiating the radiation- curable liquid resin composition according to any one of the above (1) to (5) with light.
  • composition of the present invention According to the radiation-curable liquid resin composition for optical three-dimensional shaping of the present invention (hereinafter also referred to as the "composition of the present invention"), an optically shaped article excellent in toughness and heat resistance can be obtained.
  • Figure 1 is a view showing an optically shaped article produced using a composition described in Examples and Comparative Examples.
  • composition of the present invention comprises (A), (B), (C), (D), and (E) components to be described below as essential components. Further, the composition may also comprise (F), (G), and (H) components, and the like to be described below as optional components.
  • the (A) component used as a component of the composition of the present invention is a compound which has a carbonate group and two or more (meth)acryloyl groups and does not have a urethane bond.
  • the (A) component can provide an optically shaped article excellent in toughness since it has a carbonate group and can provide an optically shaped article excellent in heat resistance since it has two or more (meth)acryloyl groups.
  • the composition for the optical three-dimensional shaping of the invention of the present application is a combined use system of a radical polymerization system and a cationic polymerization system; and the composition has a feature capable of reducing the distortion of the optically shaped article due to the crosslinking shrinkage compared with the case of the radical polymerization system alone, and has an advantage of a higher cure rate compared with the case of the cationic polymerization system alone.
  • the content is preferably 10 mass% or less, more preferably 3 mass% or less, and most preferably 0 mass% relative to the total amount of the composition.
  • the (A) component preferably has two or more carbonate groups and three or more (meth)acryloyl groups. Since the (A) component has two or more carbonate groups, it is possible to improve the kinetic properties of an optical shaping.
  • the (A) component preferably has a branched structure.
  • An optically shaped article excellent in toughness can be obtained by having a branched structure.
  • the branched structure which the (A) component has is not particularly limited, but can be obtained, for example, by reacting a di- or higher-valent compound having a halogenated formyl group with a tri- or higher-hydric alcohol.
  • the (A) component preferably has an aromatic structure.
  • An optically shaped article excellent in stiffness can be formed by having an aromatic structure.
  • the number average molecular weight of the component (A) is preferably 500 to 50 000 g/mol, more preferably 2000 to 30 000 g/mol.
  • the number average molecular weight of the component (A) is in the range of 500 to 50 000 g/mol, the viscosity of the composition is suitable for use in an optical shaping apparatus, and an optically shaped article excellent in heat resistance and toughness can be obtained.
  • the number average molecular weight is a number average molecular weight in terms of polystyrene measured by a gel permeation chromatography method.
  • the (A) component can be obtained, for example, by introducing a (meth)acryloyl group into one or more compounds selected from the following [1] and [2].
  • a compound having three or more hydroxy groups obtained by reacting a compound represented by the following formula (1) with a compound represented by the following formula (3).
  • a compound having three or more hydroxy groups obtained by reacting a compound represented by the following formula (2) with a compound represented by following formula (4).
  • R 4 - ⁇ [R5-0-(C 0)-0] m2 -R 6 -OH ⁇ m3 (4)
  • R 1 and R 2 are each independently a monovalent organic group having an aliphatic, alicyclic or aromatic structure
  • R 3 and R 4 are each independently a monovalent organic group having an aliphatic, alicyclic or aromatic structure
  • R 5 and R 6 are each independently an alkylene group
  • nl and n2 are each independently an integer of 2 or more
  • ml is an integer of 3 or more
  • m3 is an integer of 2 or more
  • m2 is an integer of 1 to 3.
  • at least one of R 1 and R 3 or R 2 and R 4 constituting one compound has an aromatic structure.
  • m, n, p, q, and r are suitably selected so that the molecular weight of the compound represented by formula (8) may be 500 to 3000 g/mol.
  • HO-[R 7 -0-(C 0)-0-] s -R 7 -OH (9) wherein, R 7 is an alkylene group or a divalent organic group having an alicyclic structure, and s is suitably selected so that the molecular weight of the compound represented by formula (9) may be 500 to 3000 g/mol.
  • Specific examples of the compound represented by the above formula (9) include a hydrogenated polybutadiene diol, 1,9-nonanediol 1,4-cyclohexanedimethanol carbonate diol,
  • reaction product of the compound represented by the above formula (1) with the compound represented by the above formula (3) for the (A) component include a compound having a repeated structure represented by the following formula (10) as described in Japanese Patent Application Laid-Open No. 2008-274239.
  • reaction product of the compound represented by the above formula (2) with the compound represented by the above formula (4) for the (A) component include compounds having structures represented by the following formulas (11) and (12).
  • R 3 is a divalent organic group having an aromatic structure
  • R 4 is a trivalent aliphatic group
  • R 5 s are each independently an alkylene group
  • R 6 is a trivalent organic group having an aromatic structure
  • R 7 s are each independently a divalent organic group having an alkylene group or an alicyclic structure
  • n is suitably selected so that the compound represented by formula (11) or formula (12) may have a suitable molecular weight as the component (A).
  • the component (A) has a structure represented by formulas (10) to (12)
  • the component (A) can have a polymer structure with a large number of branches (a polymer having such structure is also referred to as a dendrimer) by having branched structures in its repeated structures.
  • An optically shaped article which is more excellent in heat resistance and toughness can be obtained by having a polymer structure with a large number of branches.
  • the compound represented by the above formula (1), the compound represented by the above formula (3), and a basic catalyst such as pyridine are dissolved in an organic solvent and allowed to react, for example, at room temperature for 1 to 6 hours to obtain a compound having three or more hydroxy groups which is a precursor of the (A) component.
  • a basic catalyst such as pyridine
  • anhydrous (meth)acrylate or the like is allowed to react with a hydroxy group of the precursor compound to obtain a compound of the component (A).
  • a method comprising the steps of mixing the compound
  • a method comprising the steps of synthesizing a reaction product of the compound represented by the above formula (2) with the compound represented by the above formula (4) (a compound having three or more hydroxy groups which is a precursor of the (A) component), separately synthesizing a reaction product of the compound represented by the above formula (2) with a (meth)acryloyl ester having a hydroxy group (a compound for introducing a (meth)acryloyl group), and then allowing the compound for introducing a (meth)acryloyl group to react with the compound having three or more hydroxy groups which is a precursor of the (A) component.
  • the content of the (A) component in the composition of the present invention is preferably 1 to 40 mass%, more preferably 2 to 30 mass%, and particularly preferably 5 to 20 mass% relative to the total amount of the composition.
  • the toughness of the optically shaped article can be further increased.
  • the (B) component used as a component of the composition of the present invention is a cationically polymerizable compound.
  • the (B) component is preferably a compound having one or more epoxy groups.
  • an epoxy group means a group in which an oxygen atom is bonded to two carbon atoms in one molecule, and examples thereof include groups such as three-membered rings such as a glycidyl group, four-membered rings such as an oxetanyl group, and five-membered rings.
  • the epoxy group which the (B) component has is preferably a glycidyl group or an oxetanyl group.
  • Specific examples of the cationically polymerizable compound having a glycidyl group include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate,
  • trimethylolpropane triglycidyl ether polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ether;
  • polyglycidylethers of polyether polyol obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol, and glycerin; diglycidyl esters of aliphatic long-chain dibasic acid; monoglycidyl ethers of aliphatic higher alcohol; monoglycidyl ethers of polyether alcohol obtained by adding phenol, cresol, butylphenol, or alkylene oxide; glycidyl esters of higher fatty acid; epoxidized soybean oil; butyl epoxy stearate; octyl epoxy stearate; epoxidized linseed oil; and epoxidized polybutadiene. These can be used alone or in combination of two or more.
  • Examples of the commercially available products of the (B l) component include UVR-6100, UVR-6105, UVR-6110, UVR-6128,
  • UVR-6200, UVR-6216 (all manufactured by Union Carbide Corporation), CELLOXIDE 2021, CELLOXIDE 202 IP, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, EPOLEAD GT-300, EPOLEAD GT-301,
  • EPOLEAD GT-302, EPOLEAD GT-400, EPOLEAD 401, EPOLEAD 403 (aU manufactured by Daicel Chemical Industries, Ltd.), KRM-2100, KRM-2110, KRM-2199, KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2200, KRM-2720, KRM-2750 (all manufactured by Asahi Denka Kogyo K.K.), Rapi-cure DVE-3, CHVE, PEPC (all manufactured by ISP Inc.), Epikote 828, Epikote 812, Epikote 1031, Epikote 872, Epikote CT508 (all
  • Specific examples of the cationically polymerizable compound having an oxetanyl group include a compound having two or more oxetanyl groups such as
  • DOX di[2-(3-oxetanyl)butyl]ether
  • POX 3-ethyl-3-(phenoxymethyl)oxetane
  • the content of the (B) component in the composition of the present invention is 30 to 90 mass%, preferably 40 to 80 mass%, and more preferably 50 to 75 mass% relative to the total amount of the composition. When the content of the (B) component is 30 to 90 mass%, the mechanical and thermal properties of the optically shaped article is more improved.
  • the (C) component used as a component of the composition of the present invention is a photo-cationic polymerization initiator. The (C) component acts as a photo-cationic polymerization initiator in the
  • Examples of the (C) component include a salt of
  • diphenyl(phenylthiophenyl)sulfonium including a structure represented by he following formula (3).
  • the (C) component includes not only a salt containing an antimony atom such as
  • tris(pentafluoroethyl)trifluorophosphate a salt which does not contain an antimony atom is preferred from the point of view of safety.
  • Examples of the commercially available products of the (C) component include CPI-100A, CPI-101A, CPI- l lOA, and CPI-200K
  • the content of the (C) component in the composition of the present invention is 0.1 to 15 mass%, preferably 0.5 to 10 mass%, and more preferably 1 to 7 mass% relative to the total amount of the composition. If the content of the (C) component is less than 0.1 mass%, the
  • the content of the (C) component exceeds 15 mass%, it may be impossible to obtain a suitable optical transparency when a liquid resin composition is subjected to an optical three-dimensional shaping method, and as a result, it may be difficult to control the curing depth, and the shaping accuracy of the resulting three- dimensional article tends to be reduced.
  • Each of a monofunctional monomer and a polyfunction al monomer can be used alone or in combination of two or more. It is also possible to use at least one of the monofunctional monomers and at least one of the polyfunctional monomers in combination.
  • a polyfunctional monomer having a functionality of three or more that is, a polyfunctional monomer having three or more ethylenically unsaturated bonds in one molecule be contained at a proportion of 60 mass% or more relative to 100 mass% of the total amount of the (D) component.
  • the content of the polyfunctional monomer having a functionality of three or more is more preferably 70 mass% or more, further preferably 80 mass% or more, and most preferably 100 mass%. When the content is 60 mass% or more, the radiation-curability of the resulting resin composition is further improved, and the deformation with time of the three-dimensional article to be shaped tends to hardly occur.
  • monofunctional monomer as the (D) component examples include acrylamide, (meth)acryloyl morpholine,
  • (meth)acrylamide isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyldiethylene glycol (meth)acrylate, t-octyl (meth)acrylamide, diacetone (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, lauryl (meth)acrylate, dicyclopentadiene (meth)acrylate,
  • (meth)acrylate pentabromophenyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, bornyl (meth)acrylate, and methyltriethylene diglycol (meth)acrylate.
  • polyfunctional monomer as the (D) component examples include ethylene glycol di(meth)acrylate, dicy clop entenyl di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tricyclodecanediyldimethylene di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate,
  • EO trimethylolpropane tri(meth)acrylate
  • PO propylene oxide
  • EO trimethylolpropane tri(meth)acrylate
  • tripropylene glycol di(meth)acrylate tripropylene glycol di(meth)acrylate
  • neopentyl glycol di(meth)acrylate both-terminal (meth)acrylic acid adduct of bisphenol A diglycidyl ether, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate
  • polyester di(meth)acrylate polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythr
  • dipentaerythritolmonohydroxy penta(meth)acrylate dipentaerythritolmonohydroxy penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified
  • a tri(meth)acrylate compound a tetra(meth)acrylate compound, a penta(meth)acrylate compound, a hexa(meth)acrylate compound, or the like , which are exemplified above, corresponding to a polyfunction al monomer having a functionality of three or more. More preferred examples among them include tris(acryloyloxy ethyl) isocyanurate, trimethylolpropane
  • penta(meth)acrylate ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritolmonohydroxy penta(meth)acrylate.
  • Examples of the commercially available products of the monofunctional monomer as the (D) component include Aronix M- 101, M-102, M-l l l, M-113, M-117, M- 152, TO-1210 (all manufactured by Toagosei Co., Ltd.), KAYARAD TC- 110S, R-564, R-128H (aU manufactured by Nippon Kayaku Co., Ltd.), Biscoat 192, Biscoat 220, Biscoat 23 HHP, Biscoat 2000, Biscoat 2100, Biscoat 2150, Biscoat 8F, Biscoat 17F (all manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY, LTD.).
  • Examples of the commercially available products of the polyfunctional monomer as the (D) component include SA1002 (manufactured by Mitsubishi Chemical Corporation), Biscoat 195, Biscoat 230, Biscoat 260, Biscoat 215, Biscoat 310, Biscoat 214HP, Biscoat 295, Biscoat 300, Biscoat 360, Biscoat GPT, Biscoat 400, Biscoat 700, Biscoat 540, Biscoat 3000, Biscoat 3700 (all manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY, LTD.), KAYARAD R-526, HDDA, NPGDA,
  • the content of the (D) component in the composition of the present invention is 1 to 50 mass%, preferably 5 to 40 mass%, and more preferably 10 to 30 mass% relative to the total amount of the composition.
  • the (E) component used as a component of the composition of the present invention is a photo-radical polymerization initiator.
  • the (E) component is a compound which decomposes by receiving radiation such as light and initiates the radical polymerization reaction of the (E) component by the radicals generated.
  • Specific examples of the (E) component include acetophenone, acetophenone benzyl ketal, anthraquinone,
  • triphenylamine 2,4,6-trimethylbenzoyl diphenylphosphine oxide
  • BTTB 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone
  • BTTB a dye sensitizer such as xanthene, thioxanthene, coumarin, and ketocoumarin.
  • the above photo-radical polymerization initiator can be used alone or in combination of two or more.
  • the content of the (E) component in the composition of the present invention is 0.01 to 10 mass%, preferably 0.1 to 5 mass%, and more preferably 1 to 4 mass% relative to the total amount of the composition. If the content of the (E) component is less than 0.01 mass%, there is a tendency that the radical polymerization reaction rate (cure rate) of a liquid resin composition is reduced, and that as a result, the time required for shaping is increased or the resolution is reduced. On the other hand, if the content of the (E) component exceeds 10 mass%, excessive amount of the polymerization initiator may reduce the curing characteristics of a liquid resin composition, or may have a bad influence on the moisture resistance and heat resistance of a three-dimensional article.
  • composition of the present invention may comprise elastomer particles as a (F) component in a range that does not inhibit the effect of the present invention.
  • the (F) component include elastomer particles using, as a base component, polybutadiene, polyisoprene, butadiene/acrylonitrile copolymer, a styrene/butadiene copolymer, a styrene/isoprene copolymer, an ethylene/propylene copolymer, an
  • ethylene/oc-olefin copolymer an ethylene/ -olefin/polyene copolymer, acrylic rubber, a butadiene/(meth)acrylate copolymer, a styrene/butadiene block copolymer, a styrene/isoprene block copolymer, and the like.
  • the (F) component include core/shell-type particles in which these elastomer particles are covered with a methyl methacrylate polymer, a methyl methacrylate/glycidyl
  • the ratio of the radius of the core to the thickness of the shell is generally 1/2 to 1000/1, preferably 1/1 to 200/1.
  • the ratio of the radius of the core to the thickness of the shell is 35/1.
  • elastomer particles in which a core obtained by partially crosslinking polybutadiene, polyisoprene, a styrene/butadiene copolymer, a styrene/isoprene copolymer, a
  • butadiene/(meth)acrylate copolymer, a styrene/butadiene block copolymer, a styrene/isoprene block copolymer, or the like is covered with a methyl methacrylate polymer or covered with a methyl methacrylate/glycidyl methacrylate copolymer.
  • the (F) component may have a crosslinking structure in the inner part of the particles, and can be crosslinked by generally used means.
  • the crosslinking agent used in this case include divinylbenzene, ethylene glycol di(meth)acrylate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, trimethylolpropane triacrylate, and allyl methacrylate.
  • These elastomer particles can be produced by a generally used method.
  • the generally used method include an emulsion polymerization method.
  • the emulsion polymerization method which can be adopted include a method wherein the whole amount of monomer components is charged in one lot, a method wherein a part of monomer components are polymerized, followed by continuously or intermittently adding the remaining part, a method wherein monomer components are continuously added from the start of polymerization, and a method wherein seed particles are used.
  • the number average particle size of the elastomer particles obtained by these methods is preferably 10 to 1000 nm, more preferably 10 to 700 nm. If the number average particle size is less than 10 nm, the impact resistance and fracture toughness of the resulting three-dimensional article may be reduced and the viscosity of the resin liquid may be increased, thereby affecting the productivity and shaping accuracy of the three-dimensional article. On the other hand, if the number average particle size exceeds 1000 nm, a three-dimensional article in which the surface is sufficiently smooth may not be obtained, or the shaping accuracy may be reduced.
  • the number average particle size of the elastomer particles is measured as a number average particle size in terms of polystyrene particles based on a light scattering method or a dynamic light scattering method.
  • Examples of the commercially available products of the above core/shell-type elastomer particles include Resinous Bond RKB
  • These elastomer particles as the (F) component can be used alone or in combination of two or more.
  • the content of the (F) component in the composition of the present invention is preferably 1 to 35 mass%, more preferably 3 to 30 mass%, and particularly preferably 5 to 20 mass% relative to the total amount of the composition. If the content is less than 1 mass%, the impact resistance and fracture toughness may be reduced. On the other hand, if the content exceeds 35 mass%, there is a tendency for the shaping accuracy of the resulting three-dimensional article to be reduced.
  • composition of the present invention may comprise, as a (G) component, a compound having a phenolic hydroxy! group and/or a phosphite group, in a range that does not inhibit the effect of the present invention.
  • Examples of the (G) component include a known antioxidant. Among them, a hindered phenol-based compound or a phosphorus-based compound is preferred. Adding the (G) component can effectively reduce the discoloration (yellowing) of a three-dimensional shaped article with time to maintain high transparency of the three-dimensional shaped article over a long period of time after shaping.
  • (G) component examples include the following compounds. Note that those written in parentheses after the following compounds each are an example of a trade name.
  • Examples of the hindered phenol-based compound include pent aery thritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (Irganox 1010),
  • Irganox is a registered trademark of Ciba Specialty Chemicals Corp.
  • Sumilizer is a registered trademark of Sumitomo Chemical Co., Ltd.
  • Examples of the phosphorus-based compound include
  • Irgafos is a registered trademark of Ciba
  • examples of the commercially available products of the hindered phenol-based (G) component include Irganox 1010, 1035FF, 245, 1076, 1330, 3114, 1520L, 3125 (all manufactured by Ciba Specialty Chemicals Corp.), Sumilizer BHT, GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), and Cyanox 1790 (manufactured by Cytech, Inc.).
  • examples of the commercially available products of the phosphorus-based (G) component include Irgafos 168, 12, 38 (all manufactured by Ciba Specialty Chemicals Corp.), ADK STAB 329K, PEP36, PEP-8 (all manufactured by Asahi Denka Kogyo K.K.), Sandstab P-EPQ (manufactured by Clariant, Corp.), Weston 618, 619G, Ultranox 626 (all manufactured by General Electric Company), and Sumilizer GP
  • the content of the (G) component in the composition of the present invention is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and particularly preferably 1 to 4 mass% relative to the total amount of the composition. If the content of the (G) component is less than 0.01 mass% or if it exceeds 10 mass%, a problem in which the transparency of an optically shaped article is reduced with time or the like may occur. Therefore, such a content is not preferred.
  • composition of the present invention may comprise water as a (H) component in a range that does not inhibit the effect of the present invention.
  • the radiation-curability of a liquid resin composition can be improved. Further, adding water can improve the mechanical properties, particularly elastic modulus, of a cured product obtained by irradiating a liquid resin composition with light to suppress the change with time of the shape and mechanical properties of a three- dimensional shaped article obtained by optical shaping.
  • the content of water in the composition of the present invention is preferably 0.1 to 2 mass%, more preferably 0.2 to 1 mass% relative to the total amount of the composition.
  • additives may be contained as other optional components in a range that does not impair the purpose and effect of the present invention.
  • additives include polymers or oligomers such as epoxy resins, polyamides, polyamideimides, polyurethanes, polybutadienes, polychloroprenes, polyethers, polyesters, styrene-butadiene block copolymers, petroleum resins, xylene resins, ketone resins, cellulosic resins, fluorine-based oligomers, silicone-based oligomers, and polysulfide-based oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methyl phenol; polymerization initiation aids; leveling agents; wettabihty improving agents; surfactants; plasticizers; ultraviolet absorbers; silane coupling agents; inorganic fillers;
  • composition of the present invention can be produced by charging a suitable amount of the above essential components (A), (B), (C), (D), and (E) and other optional components if needed to an agitation vessel and stirring these components at a temperature of generally 30 to 70 °C, preferably 50 to 60 °C for generally 1 to 6 hours, preferably 1 to 2 hours.
  • the viscosity at 25 °C of the composition of the present invention is preferably 50 to 2000 mPa s, more preferably 70 to 1500 mPa s.
  • composition of the present invention obtainable as described above is suitably used as a radiation-curable liquid resin composition in an optical three-dimensional shaping method. That is, a three-dimensional article (optically shaped article) having a desired shape can be produced by an optical three-dimensional shaping method in which the radiation-curable liquid resin composition of the present invention is selectively irradiated with light such as visible light, ultraviolet light, and infrared light to supply energy necessary for curing.
  • light such as visible light, ultraviolet light, and infrared light
  • optically shaped article of the present invention can be obtained by irradiating the composition of the present invention with radiation such as hght.
  • a means to selectively irradiate the composition of the present invention with light is not particularly limited, and various means can be adopted.
  • the means that can be adopted include a means of irradiating a composition with light such as a laser beam or convergent light obtained using a lens, a mirror, or the hke while scanning the hght; a means of using a mask having a light transmission part of a predetermined pattern and irradiating a composition with non-convergent light through the mask; and a means of using a light guide member prepared by bundling a large number of optical fibers and irradiating a composition with light through the optical fibers corresponding to a predetermined pattern in the light guide member.
  • a mask in which a mask image consisting of a light-transmitting region and a light non-transmitting region is electrooptically formed in a predetermined pattern by the same principle as in a liquid crystal display.
  • a target three-dimensional article has a fine part or is required for high dimensional accuracy, it is preferred to adopt a means to scan a laser beam having a small spot diameter as a means to selectively irradiate a composition with light.
  • a light irradiation surface for example, scanning plane of convergent light
  • a light irradiation surface of a resin composition received in a container may be any of a liquid surface of the resin composition and a contact surface with a container wall of a translucent container.
  • the liquid surface of the resin composition or the contact surface with a container wall is used as the light irradiation surface, it can be irradiated with light directly from the outside of the container or through the container wall.
  • the light irradiation position (irradiation surface) is moved continuously or stepwise from a cured part to an uncured part to thereby laminate the curing part to form a desired three-dimensional shape.
  • the transfer of the irradiation position can be performed by various methods, and examples thereof include a method of moving any of a light source, a receiving container of a resin composition, and a cured part of a resin composition, and a method of additionally supplying a resin composition to the container.
  • a method of moving any of a light source, a receiving container of a resin composition, and a cured part of a resin composition and a method of additionally supplying a resin composition to the container.
  • a supporting stage which is freely vertically movably provided in a receiving container is lowered (settled) by a fine amount from the liquid surface of a resin composition to thereby supply the resin composition on the supporting stage to form a thin layer (1) thereof.
  • the thin layer (1) is selectively irradiated with light to thereby form a solid cured resin layer (1).
  • a radiation-curable liquid resin composition is supplied on the cured resin layer (1) to form a thin layer (2) thereof, and the thin layer
  • a three-dimensional article in which a plurality of cured resin layers (1, 2, ... n) are integrally laminated is shaped by repeating these steps a predetermined number of times while changing or without changing the pattern which is irradiated with light.
  • the three-dimensional article obtained in this way is taken out from the receiving container, and an unreacted resin composition remaining on the surface thereof is removed, and then the article is washed if needed.
  • the washing agent include an alcohol-based organic solvent typified by alcohols such as isopropyl alcohol and ethyl alcohol; a ketone-based organic solvent typified by acetone, ethyl acetate, methyl ethyl ketone, and the like; an ahphatic organic solvent typified by terpenes; and a thermosetting resin and a radiation-curable resin each having a low viscosity.
  • postcuring by heat irradiation or light irradiation may be performed if needed.
  • the postcuring can cure an unreacted resin composition which may remain on the surface and in the inner part of a three-dimensional article to suppress the stickiness of the surface of a shaped article, and can improve the initial strength of a shaped article.
  • the optically shaped article of the present invention is excellent in toughness and heat resistance.
  • the reaction liquid was separated into a gel part and a chloroform -soluble part by adding 160 ml of chloroform to the reaction liquid to dilute it and washing it with chloroform using a Kiriyama funnel.
  • the chloroform -soluble part was concentrated using an evaporator, and then subjected to reprecipitation purification by using chloroform as a good solvent and methanol as a poor solvent, followed by reduced pressure drying to obtain 4.63 g of a polymer having a hydroxy group of a white powder at a yield of 80%.
  • HEMA 2 -hydroxy ethyl methacrylate
  • PCTL manufactured by Kuraray Co., Ltd. (CF-1000)
  • CF-1000 polycarbonate triol
  • 5.62 g (0.07 mol) of pyridine as a base in 30 ml of ethyl acetate was allowed to react for 1 hour.
  • Synthesis Example 3 Synthesis of a compound having three or more hydroxy groups to be obtained by reacting the compound represented by the above formula (2) with the compound represented by the above formula (4), which is a precursor of the component (A)
  • PCTL solution 2 obtained by dissolving 9.60 g (0.0096 mol) of polycarbonate triol (PCTL) and 0.78 g (0.0098 mol) of pyridine as a base in 100 ml of ethyl acetate, and the mixture was allowed to react for 1 hour to obtain a precursor of the component (A) having three or more hydroxy groups.
  • Synthesis Example 4 Synthesis of a compound for introducing a
  • OPC p-phthalic acid chloride
  • HEMA 2 -hydroxy ethyl methacrylate
  • Synthesis Example 3 were dropwise added the compound solution obtained in Synthesis Example 4 and 1.94 g (0.0242 mol) of pyridine over 30 minutes, and the mixture was allowed to react for 1 hour.
  • reaction mother liquor was filtered, separated, dehydrated, and then concentrated using an evaporator. Subsequently, the concentrated liquor was subjected to reprecipitation purification by using ethyl acetate as a good solvent and methanol as a poor solvent, followed by reduced pressure drying to obtain a polymer (component (A)) of viscous liquid at a yield of 44%.
  • a liquid resin composition was applied to a glass plate in a thickness of 200 ⁇ and irradiated with 1 J/cm 2 using a metal-halide lamp to obtain a cured film. Subsequently, it was allowed to stand in a constant temperature and humidity chamber at a temperature of 23 °C and a humidity of 50% for 24 hours.
  • test piece having a dimension of 8 cm x 0.6 cm was cut out from the cured film prepared according to the above described procedure.
  • the Young's modulus of the test piece was measured according to JIS K7127 using a tensile tester AGS-50G manufactured by Shimadzu Corp. At this time, the measurement was performed with a gauge length of 2.5 cm (grips at both ends of 2.75 cm) at a tension speed of 1 mm/min.
  • a cured film was prepared under the same conditions as in the preparation of the test piece of the Young's modulus of a cured film.
  • a test piece prepared according to the above described procedure was allowed to stand in a constant temperature and humidity chamber at a temperature of 23 °C and a humidity of 50% for 24 hours, and then a test piece having a dimension of 10 cm x 10 cm was cut out.
  • the film impact value was measured using a film impact tester manufactured by Yasuda Seiki Seisakusho, Ltd.
  • a plastic ball having a diameter of 12 mm was used as an impact ball.
  • a radiation-curable resin composition was applied to a glass plate using a 15-mil (corresponding to a coating film thickness of about 200 mm) applicator bar, and the coating film was irradiated with ultraviolet rays with energy of 1000 mJ/cm 2 in the air to cure the composition to obtain a film for measurement.
  • a test piece having a size of 3 mm x 35 mm was cut out from this film for measurement and measured for the dynamic viscoelasticity using RHEOVIBRON DDV-01FP manufactured by
  • the temperature showing the maximum value of a loss tangent (tan ⁇ ) at an oscillation frequency of 3.5 Hz was defined as glass transition temperature, and the glass transition temperature was obtained.
  • a pair of shaped articles having a fitting shape shown in Figure 1 (the size of the convex article is 62 x 34 x 11 mm, and the size of the concave article is 52 x 34 x 11 mm) was produced by repeating the step of selectively irradiating each liquid resin composition with a laser beam to form a cured resin layer (0.10 mm in thickness) under conditions of a laser power at the irradiation surface (liquid surface) of 100 mW and a scanning rate at which curing depth is 0.2 mm in each composition, using a Solid Creator SCS-300P (manufactured by Sony Manufacturing Systems Co., Ltd.).
  • EXA850CRP bisphenol A type diglycidyl ether (manufactured by Dainippon Ink & Chemicals, Inc.)
  • EXA830CRP bisphenol F type diglycidyl ether (manufactured by Dainippon Ink & Chemicals, Inc.)
  • OXIPA isophthalic acid bis[(3-ethyl-3-oxetanyl)methyl]ester
  • OXA 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co.,
  • DPHA dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
  • Irgacure 184 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Corp.)
  • Elastomer particles RKB5610CP-60 (manufactured by Resinous Kasei Co., Ltd.)
  • Irganox 1010 hindered phenol-type antioxidant (manufactured by Ciba Japan, K.K.)
  • DOX bis[l-ethyl(3-oxetanyl)]methyl ether (manufactured by Toagosei Co., Ltd.)
  • Hydroxy group-terminated reactive polycarbonate-based dendrimer a reaction product obtained by reacting bisphenol A bis (chloroform ate) (BABC) with 1, 1, l-tris(4-hydroxyphenyl ethane)ethane (THE)
  • Comparative Example 1 in which the component (A) was not blended.
  • Comparative Examples 2 to 4 using polycarbonatediol or a dendrimer not corresponding to the component (A) instead of the component (A) Young's modulus and T g are poor in Comparative Example 2; Young's modulus and a film impact value are poor in Comparative Example 3; and Young's modulus and Tg are poor in Comparative Example 4.

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  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne une composition de résine liquide durcissable par un rayonnement destinée à un façonnage tridimensionnel optique permettant d'obtenir un objet façonné optiquement présentant d'excellentes propriétés de solidité et de résistance à la chaleur. La composition de résine liquide durcissable par un rayonnement destinée à un façonnage tridimensionnel optique comprend : (A) un composé qui présente un groupe carbonate et deux groupes (méth)acryloyle ou plus et qui ne présente pas de liaison uréthane ; (B) un composé polymérisable par voie cationique ; (C) un initiateur de polymérisation photocationique ; (D) un composé polymérisable par voie radicalaire ; et (E) un initiateur de polymérisation à photoradicaux. Un exemple préféré du constituant (A) est un composé présentant deux groupes carbonate ou plus et trois groupes (méth)acryloyle ou plus. Des exemples de la partie structurale préférée comprise dans la structure chimique du constituant (A) comprennent une structure ramifiée et une structure aromatique.
PCT/NL2014/050126 2013-03-29 2014-03-03 Composition de résine liquide durcissable par un rayonnement destinée à un façonnage tridimensionnel optique et objet façonné optiquement obtenu par photodurcissement de celle-ci WO2014158015A1 (fr)

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EP2842980B1 (fr) * 2013-08-09 2021-05-05 DSM IP Assets B.V. Compositions de résine pour moule aligneur dentaire durcissable par rayonnement liquide de faible viscosité de fabrication additive
JP7385983B2 (ja) * 2016-10-06 2023-11-24 株式会社ダイセル 硬化性樹脂組成物及びその硬化物、プリプレグ、並びに繊維強化複合材料
WO2020246489A1 (fr) * 2019-06-07 2020-12-10 キヤノン株式会社 Composition de résine durcissable, produit durci associé et procédé de fabrication d'article tridimensionnel

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