KR100461688B1 - Photo-curable resin composition - Google Patents

Abstract

The present invention relates to a photo-curable resin composition,

The resin composition can provide a three-dimensional object having excellent mechanical strength and high dimensional accuracy,

The resin composition may provide a three-dimensional object having excellent stability in form and properties by using an optical secondary processing method,

The composition has (A) a cationic polymerization compound, (B) a cationic photo-initiator, (C) an ethylenically unsaturated monomer, (D) a radical photo-initiator, (E) an average of about 3 or more hydroxyl groups Polyether polyols,

At least 60% by weight of the ethylenically unsaturated monomer is characterized in that it is a multifunctional monomer having three or more ethylenically unsaturated bonds in one molecule.

Description

Photo-curable resin composition {PHOTO-CURABLE RESIN COMPOSITION}

The present invention relates to liquid photo-curable resin compositions suitable as photo-curable resin compositions, in particular materials used in photo-secondary processing processes.

Recently, there has been proposed a light-secondary processing method for producing a three-dimensional object composed of an integrally laminated cured resin layer prepared by repeating the step of forming a cured resin layer by selectively irradiating light onto a liquid photo-curable material ( See Japanese Patent Publication No. 247515/1985, US Patent No. 4,575,330 (Japanese Patent Publication No. 35966/1987), Japanese Patent Publication No. 101408/1987, and Japanese Patent Publication No. 24119/1993.

A typical example of the photo-secondary processing method is to form a curable resin layer having a specific pattern by selectively irradiating light, for example using an ultraviolet laser, on the surface of a liquid photo-curable material (photo-curable resin composition), An equal amount of photo-curable resin composition is injected into one layer to form another thin layer of the composition on the cured resin layer, and light is applied to the thin layer to form a new cured resin layer integrated on the already formed cured resin layer. Consists of selectively investigating. The above steps are repeated many times with or without modifying the type of light irradiation to form a three-dimensional object composed of a multi-layered resin layer integrally laminated. The optical-secondary processing method requires considerable attention because the desired three-dimensional object can be easily manufactured in a short period of time even if the desired three-dimensional object has a complicated shape.

The following resin compositions (A) to (D) have been reported as photo-curable resin compositions used in the photo-secondary processing method.

(A) Resin composition containing radically polymerizable organic compounds such as urethane (meth) acrylate, oligoester (meth) acrylate, epoxy (meth) acrylate, thiol-ene compound, photosensitive polyimide, etc. (Japanese Patent Laid-Open 204915/1989, 208305/1990 and 160013/1991).

(B) Resin compositions containing cationic polymerizable organic compounds such as epoxy compounds, cyclic ether compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro-orthoester compounds, vinyl ether compounds and the like (Japan See Patent Publication No. 213304/1989)

(C) Resin compositions containing radically polymerizable organic compounds and cationically polymerizable organic compounds (see Japanese Patent Laid-Open Nos. 28261/1990 and 75618/1990)

(D) A resin composition containing a radically polymerizable organic compound, a cationically polymerizable organic compound and at least one trifunctional OH-terminated polycaprolactone (see Japanese Patent Laid-Open No. 228413/1994)

A required feature of the photo-curable resin composition used in the photo-secondary processing method includes a low viscosity for forming a flat liquid level and the ability to rapidly cure by irradiation of light. In addition, a required feature of the photo-curable resin composition is that of minimal deformation and cured product causing shrinkage during curing with light, such as the creation of bent, jagged (sink), or straight (opening) portions. Minimal swelling.

Three-dimensional objects manufactured by the photo-secondary processing method have conventionally been used in design models and test machine parts. In particular, for the test part, heat resistance sufficient to withstand high dimensions, mechanical strength, and use conditions according to a design model in a micro process is required. However, the conventional resin composition cannot satisfy the above requirements. The resulting three-dimensional objects exhibit deformation problems over time, such as the creation of bent, jagged, or straight parts (elongations) due to residual strain due to shrinkage during curing. The above problems of deformation over time can be partially solved by modifying input data in the CAD. However, this modification corresponds to recent progress in detail and complexity in form, and is insufficient for environmentally changing uses.

The mechanical properties of three-dimensional objects produced by photo-secondary processing using conventional resin compositions containing epoxy compounds are lost over time, depending on environmental conditions such as temperature and humidity. Therefore, the use of the three-dimensional object is unsuitable for applying those requiring mechanical strength for an extended period of time.

In addition, there is no three-dimensional object manufactured using a conventional resin composition provided with mechanical strength, dimensional accuracy, heat resistance and the like.

The present invention has been made in view of the above situation, and an object thereof is to provide a photo-curable resin composition.

Another object of the present invention is to provide a photo-curable resin composition having mechanical strength and high dimensional accuracy and providing a three-dimensional object suitable for a test machine part.

It is another object of the present invention to provide a photo-curable resin composition that can be secondary processed to produce a three-dimensional object that lasts minimal deformation properties.

It is another object of the present invention to provide a photo-curable resin composition which can be secondary processed to produce a three-dimensional object that lasts minimal sensitivity in mechanical properties.

Summary of the Invention

The first object of the present invention is (A) cationic polymerizable organic compound, (B) cationic photo-initiator, (C) ethylenically unsaturated monomer, (D) radical photo-initiator, and (E) three or A photo-curable resin composition composed of polyether polyols having more hydroxyl groups, wherein at least 60% by weight of the ethylenically unsaturated monomer (C) relative to the total composition is contained in one molecule. It is a multifunctional monomer having two or more ethylenically unsaturated bonds.

1 shows the configuration of a model for measuring strain over time, and is a schematic diagram illustrating a measuring method.

* Description of the main parts of the drawings

10: camber model

11, 12: foot part

20: flat

The invention will be explained in detail below.

<Cationically polymerizable organic compound>

The cationic polymerizable organic compound (hereinafter referred to as [component (A)]) contained in the photo-curable resin composition of the present invention can be polymerized or crosslinked by light-irradiation by irradiation with light in the presence of a cationic photoinitiator. Compound. Typical examples of component (A) include spiro, a reaction product of an epoxy compound, an oxetane compound, an oxolane compound, a cyclic acetal compound, a cyclic lactone compound, a thiirane compound, a titanium compound, a vinyl ether compound, an epoxy compound and a lactone Ortho ester compounds, ethylenically unsaturated compounds, cyclic ether compounds, cyclic thioether compounds and vinyl compounds.

For example, the following compounds may be described as epoxy compounds which can be used as component (A): bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol brominated 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'-epoxy-cyclohexane carboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4 -Epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxy-cyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinyl epoxycyclohexane, bis (3,4-epoxy-6-methyl Cyclohexylmethyl) adipate, 3,4-epoxy-6-methyl cycle Hexyl-3 ', 4'-epoxy-6'methyl-cyclohexane carboxylate, methylenebis (3,4-epoxy-cyclohexane), dicyclopentadiene diepoxide, di (3,4- of ethylene glycol Epoxy-cyclohexylmethyl) ether, ethylene-bis (3,4-epoxycyclohexanecarboxylate), epoxyhexahydrodioctyl phthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglyci Dill ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether; Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol or glycerol; Mono glycidyl esters of aliphatic long chain dibasic acids; Mono glycidyl ethers of aliphatic higher alcohols; Polyether alcohols obtained by adding alkylene oxide to phenol, cresol or butylphenol or mono glycidyl ethers of phenol, cresol and butylphenol; Glycidyl esters of higher fatty acids; Epoxidized soybean oil, butyl epoxystearate, octyl epoxystearate, epoxidized linseed oil and epoxidized polybutadiene.

Other compounds that can be used as component (A) include trimethylene oxide, 3,3-dimethyl oxetane, 3,3-dichloromethyl oxetane, 3-ethyl-3-phenoxymethyl oxetane and bis (3-ethyl Oxetane, such as 3-methyloxy) butane; Oxolanes such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; Cyclic acetals such as trioxane, 1,3-dioxolane and 1,3,6-trioxane cyclooctane; cyclic lactones such as β-propiolactone and ε-caprolactone; Thiiranes such as ethylene sulfide, 1,2-propylene sulfide and tyroepichlorohydrin; Ethane such as 3,3-dimethyl diethan; Vinyl ethers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether and trimethylolpropane trivinyl ether; Spiro-ortho esters obtained by the reaction of an epoxy compound and a lactone; Ethylenically unsaturated compounds such as vinylcyclohexane, isobutylene and polybutadiene; And derivatives thereof.

Preferred compounds among the cationically polymerizable compounds are bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 3,4-epoxy-cyclo Hexylmethyl-3 ', 4'-epoxycyclohexane carboxylate, bis- (3,4-epoxycyclohexylmethyl) adipate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol digly Cydyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.

Particularly preferred cationically polymerizable compounds as component (A) include 3,4-epoxy-cyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate or bis- (3,4-epoxycyclohexylmethyl) adipate. Likewise, it is a compound containing two or more aliphatic epoxy groups in one molecule. When the epoxy compound of this kind is contained in the component (A) in an amount of 50% by weight or more, the resin composition obtained has a large cation polymerization rate (cure rate), which not only reduces the molding time but also cures shrinkage. Can be reduced. This proves that the three-dimensional object shows only small deformations over time.

The following commercially useful products are preferred as cationically polymerizable organic compounds used as component (A): UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, UVR-6216 from Union Carbide Corp. Manufactured by), Celoxide 2021, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 2000, Celloxide 3000, Glycidole, AOEX24, Cyclomer A200, Cyclomer M100, Epolead GT-300, Epoid GT-301, Epoid GT-302, Epoid GT-400, Epoid 401, Epoid 403 (Diesel ( Daicel) manufactured by Chemical Industries Co., Ltd.), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (manufactured by Yuka Shell Campus Limited), KRM- 2100, KRM-2110, KRM-2199, KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2200, KRM-2720, KRM-2750 (Asahi Denka Kogyo) Manufactured by DE), Rapi-Cure DVE-3, CHVE, PEPC (manufactured by ISP Company Limited) and VECTOMER 2010, 2020, 4010, 4020 (manufactured by Allied Signal Corporation) ).

The cationically polymerizable compounds may be used individually or in combination of two or more.

The proportion of component (A) in the photo-curable resin composition of the present invention is about 30-85% by weight, preferably about 40-80% by weight and more preferably about 50-75% by weight. If the ratio of component (A) is too low, the dimensional accuracy of the three-dimensional object from the resin composition is reduced, and the three-dimensional object tends to deform with time. On the other hand, if the proportion in component (A) is too high, the photo-curing properties of the obtained resin composition are reduced, and the secondary processing effect is reduced.

<Cationic photo-initiator>

Cationic photo-initiators (hereinafter referred to as [component (B)]) contained in the photo-curable resin composition of the present invention can generate molecules that initiate cation polymerization of component (A) by receiving radiation such as light. Compound. Particularly preferred examples of cationic photo-initiators are provided with onium salts according to formula 1, which are compounds which emit Lewis acids while receiving light:

[R ¹ _a R ² _b R ³ _c R ⁴ _d Z] ^{+ m} [MX _{n + m} ] ^-m

(In Formula 1, the cation is onium; Z is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or N≡N; R ¹ , R ² , R ³ and R ⁴ represents the same or different organic group, respectively; a, b, c and d are each an integer of 0 to 3, and the sum of a, b, c and d (= a + b + c + d) is equal to the valence of Z same)

M represents the metalloid or metal which comprises the central atom of the halide complex. Typical examples of M include B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn and Co. X represents a halogen atom. m is the actual charge and n is the number of atoms in the halide complex ion.

Formula 1 in the anion with tetrafluoroborate as a specific example of the (MX _{n + m)} borate (BF ₄ ^-), phosphate (PF ₆ ^-) hexafluoropropane, antimonate hexafluorophosphate (SbF ₆ ^-), hexafluorophosphate Arsenate (AsF ₆ ⁻ ) and hexachloroantimonate (SbCl ₆ ⁻ ) are provided.

Onium salts represented by the general formula [MX _n (OH)] can also be used. And perchloric acid ion (ClO ₄ ^-), sulfonate ion trifluoroacetate (CF ₃ SO ₃ ^-), sulfonate ion fluoro (FSO ₃ ^-), toluene sulfonate ion, trinitrotoluene sulfonate negative ion, and trinitrotoluene sulfonate Onium salts containing anions such as anions are suitable.

Among the onium salts, particularly effective onium salts are aromatic onium salts in which the following compounds are preferable: the aromatic halonium salts described in Japanese Patent Laid-Open Nos. 151996/1975 and 158680/1975; VIA aromatic onium salts described in Japanese Patent Laid-Open Nos. 151997/1975, 30899/1977, 55420/1981 and 125105/1980; VA aromatic onium salts described in Japanese Patent Laid-Open No. 158698/1975; Oxosulfonium salts described in Japanese Patent Application Laid-Open Nos. 8428/1981, 149402/1981 and 192429/1982; Aromatic diazonium salts described in Japanese Patent Laid-Open No. 1170/1974; And thiobilylium salts described in US Pat. No. 4,139,655. Iron / allen composites and aluminum composite / photodegradable silica compound initiators are also provided as examples of onium salts.

Preferred examples of commercially useful products of cationic photo-initiators that can be used as component (B) include UVI-6950, UVI-6970, UVI-6974, UVI-6990 (manufactured by Union Carbide Corporation), AdekaOpto Adekaoptomer SP-150, SP-151, SP-170, SP-171 (manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (manufactured by Shiba gauge), CI-2481, CI -2624, CI-2639, CI-2064 (manufactured by Nippon Soda Company Limited), CD-1010, CD-1011, CD-1012 (manufactured by Sartomer Company Limited), DTS-102, DTS-103, NAT -103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (manufactured by Midori Chemical Co., Ltd.) are provided. Among them, UVI-6970, UVI-6974, adekaoptomer SP-170, SP-171, CD-1012, and MPI-103 are particularly preferable for developing high curing sensitivity of the resin composition containing the compound.

The cationic photo-initiators can be used as component (B) individually or in combination of two or more.

The proportion of component (B) in the photo-curable resin composition is about 0.1-10% by weight, preferably about 0.2-5% by weight, more preferably about 0.3-3% by weight. If the proportion of component (B) is too low, the photo-curing characteristics of the obtained resin composition are insufficient. Three-dimensional objects with sufficient mechanical strength cannot be produced from the resin composition. On the other hand, if the proportion of component (B) is too high, an appropriate light capacity (curing depth) cannot be obtained when the obtained resin composition is used in the photo-secondary processing process. Mechanical strength such as toughness of the tertiary material prepared from the resin composition tends to be reduced.

<Ethylenically unsaturated monomer>

An ethylenically unsaturated monomer (henceforth [component (C)]) is a compound which has an ethylenically unsaturated group (C = C) in a molecule | numerator. Typical examples of component (C) are monofunctional monomers having one ethylenically unsaturated bond in one molecule and polyfunctional monomers having two or more ethylenically unsaturated bonds in one molecule. Examples of monofunctional monomers used as component (C) include acrylamide, (meth) acryloyl morpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, iso Boryloxyethyl (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, dicyclopentenyloxyethyl ( Meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydro Lefuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl ( Meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinyl caprolactam, N-vinyl pyrroli Don, Phenoxyethyl (meth) acrylate, Butoxyethyl (meth) acrylate, Pentachlorophenyl (meth) acrylate, Pentabromophenyl (meth) acrylate, Polyethylene glycol mono- (meth) acrylate, Poly Propylene glycol mono- (meth) acrylate, bornyl (meth) acrylate, methyltriethylene diglycol (meth) acrylate and the compounds represented by the following formula (2) or (3) are provided.

(In Formulas 2 and 3, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an alkylene group containing 2-6, preferably 2-4 carbon atoms, R ⁷ is 1-20, preferably Or an alkyl group or hydrogen atom containing 1-12 carbon atoms, wherein R ⁷ may consist of an ether group or the like in a dioxane or tetrahydrofuran group; or R ⁷ is C ₁ -C ₁₂ , an alkyl group, preferably And an aromatic group optionally substituted with a C _8-9 alkyl group, R ₈ represents an alkylene group containing 2-8, preferably 2-5 carbon atoms, r is 0-12, preferably 1-8 Is an integer, q represents an integer of 1-8, preferably 1-4)

Of these monofunctional monomers, isobornyl (meth) acrylate, lauryl (meth) acrylate and phenoxyethyl (meth) acrylate are particularly preferred. Examples of commercially available monofunctional monomer products include Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (Toagosei Chemical Industries, Ltd.). Manufactured by Limited), KAYARAD TC-110S, R-564, R-128H (manufactured by Nippon Kayaku Co., Ltd.), Viscoat 192, Viscoat 220, Viscoat 2311HP, Viscoat 2000, Viscoat 2100, Viscoat 2150, Viscoat 8F, Viscoat 17F (manufactured by Osaka Organic Chemical Industry Co., Ltd.) is provided.

Preferred examples of the polyfunctional monomer used as component (C) are ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate , Tricyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylic Latex, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as [EO]) modified trimethylolpropane tree (Meth) acrylate, propylene oxide (hereinafter sometimes referred to as [PO]) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) arc Latex, neopentyl glycol di (meth) acrylate, two terminal (meth) acrylic acid adducts of bisphenol A diglycidyl ether, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) Acrylate, ditrimethylolpropane tetra (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, EO modified A hydrogenated bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, and phenol novolac polyglycidyl ether is provided.

Commercially useful products of the multifunctional monomers include SA1002 (manufactured by Mitsubishi Chemical Company Limited), Viscoat 195, Viscoat 230, Viscoat 260, Viscoat 215, Viscoat 310, Viscoat 214HP, Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT , Viscoat 400, Viscoat 700, Viscoat 540, Viscoat 3000, Viscoat 3700 (manufactured by OSAKA ORGANIC COMPOUND CHEMICAL INDUSTRY LIMITED), KAYARAD R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R-712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-21, D-310, D-330, DPCA-20, DPCA- 30, DPCA-60, DPCA-120, DPCA-0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA-330, RP-1040, RP-2040, R-011, R-300, R-205 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M-309, M- 310, M-315, M-325, M-400, M-6200, M-6400 (manufactured by Toagosei Chemical Industries, Ltd.), Light Acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (manufactured by Gioaisa Chemical Industries, Ltd.), New Frontier BPE-4, TEICA, BR-42M, GX-8345 (Manufactured by Daiichi Kogyo Seiyaku Chemical Company Limited), ASF-400 (manufactured by Nippon Steel Chemical Company Limited), Ripoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP -4060 (manufactured by Suwa High Polymer Company Limited) and NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Industries Co., Ltd.).

Component (C), which is a constituent of the photo-curable resin composition of the present invention, contains at least about 60% by weight of a multifunctional monomer having three or more ethylenically unsaturated bonds in one molecule. The proportion of multifunctional monomers having three or more functional groups is preferably at least about 70% by weight, more preferably at least about 80% by weight. An especially preferred proportion of the polyfunctional monomer is substantially 100% by weight. If the proportion of the multifunctional monomer having three or more functional groups is less than about 60% by weight, the photo-curing properties of the obtained resin composition are insufficient, and the secondary processed three-dimensional object tends to deform with time.

The polyfunctional monomer having three or more polyfunctionals may be selected from the above tri (meth) acrylate compound, tetra (meth) acrylate compound, penta (meth) acrylate compound and hexa (meth) acrylate compound. . Among the above, trimethylol propane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and ditrimethylol Propane tetra (meth) acrylate is particularly preferred. The monofunctional and polyfunctional monomers can be used individually or in combination of two or more as component (C).

The ratio of monofunctional and polyfunctional monomers in the photo-curable resin composition of the present invention is generally about 5-30% by weight, preferably about 7-25% by weight and more preferably about 10-20% by weight. If the proportion of component (C) is too low, the photo-curing properties of the resin composition are insufficient. Three-dimensional objects with sufficient mechanical strength cannot be secondary processed from the resin composition. On the other hand, if the ratio of component (C) is too high, the obtained resin composition easily contracts during photo-curing, and mechanical strength such as toughness of the three-dimensional object tends to be decreased.

<Radical light-initiator>

Radical photo-initiator (hereinafter referred to as component (D)), which is a constituent of the photo-curable resin composition of the present invention, is a compound that decomposes and generates radicals by receiving radiation such as light. The radical polymerization reaction of C) is started.

Specific examples of radical photo-initiators that can be used as component (D) include acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropa-1 -Non, carbazole, xanthone, 4-chlorobenzo-phenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone , Thioxanthone compound, 2-methyl-1-4- (methylthio) phenyl-2-morpholino-propano-2-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butan-1-non, triphenylamine, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-tri-methylpentyl- Phosphine oxide, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropa-1-non, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, Benzoin propyl ether, benzophenone, Michler's ketone, 3-methylacetophenone, 3,3 ', 4,4'- Tetra (t-butyl peroxycarbonyl) benzophenone (BTTB) and a combination of xanthene, thioxanthene, coumarin, ketocoumarin or other colorant photosensitizer with BTTB are provided. Among the above, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Buta-1-non etc. are particularly preferable.

The radical photo-initiators can be used as component (D) individually or in combination of two or more.

The proportion of component (D) in the photo-curable resin composition of the present invention is usually about 0.01-10% by weight, preferably about 0.1-8% by weight. If the proportion of component (D) is too low, the radical polymerization rate (curing rate) is reduced too much, so that the secondary processing time can be prolonged, and the resolution tends to be low. On the other hand, if the ratio of component (D) is too high, excess photo-initiator sometimes adversely affects the resin composition and the curing properties, heat resistance, and three-dimensional objects obtained from the resin composition of the specific examples.

<Polyether polyol>

The polyether polyol (hereinafter referred to as [component (E)]) is an essential component for developing the photo-curability of the resin composition and the morphological stability (resistance to deformation with time) of the three-dimensional object obtained from the resin composition. The polyether polyols used as component (E) have an average of about three or more, preferably about 3 to 6, hydroxyl groups in the molecule. If polyether polyols having less than three hydroxyl groups (eg, polyether diols) are used, the objective of developing photo-curing properties cannot be achieved, and three-dimensional objects having sufficient mechanical strength can be produced. none. On the other hand, when polyether polyols having an average of seven or more hydroxyl groups are used, the elongation and toughness of the three-dimensional object obtained from the resin composition tends to be low.

Specific examples of component (E) include trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose with cyclic ether compounds such as ethylene oxide (EO), propylene oxide (PO), butylene oxide, tetrahydrofuran and the like. There is provided a polyether polyol prepared by modifying a trivalent or higher polyhydric alcohol such as polyether polyol and the like. Specific examples of the polyether polyol include EO modified trimethylolpropane, PO modified trimethylolpropane, tetrahydrofuran modified trimethylolpropane, EO modified glycerol, PO modified glycerol, tetrahydrofuran modified glycerol, EO modified pentaerythritol, PO Modified pentaerythritol, tetrahydrofuran modified pentaerythritol, EO modified sorbitol, PO modified sorbitol, EO modified sucrose, PO modified sucrose, EO modified quodor. Among the above, EO-modified trimethylolpropane, PO-modified trimethylolpropane, PO-modified glycerol and PO-modified sorbitol are preferable.

The preferred molecular weight of the polyether polyol is about 100 to about 2,000, more preferably about 160 to 1,000. If polyether polyols having too little molecular weight are used as component (E), it is difficult to produce three-dimensional objects that are stable in form and properties. If a polyether polyol having a too large molecular weight is used as component (E), the viscosity of the obtained resin composition becomes too high, and the mechanical strength of the three-dimensional object obtained by the photo-secondary processing method is low.

Specific examples of the polyether polyols that can be used as component (E) include Sunnix TP-400, Sunnix GP-600, Sunnix GP-1000, Sunnix SP-750, Sunnix GP-250, Sunnix GP-400, Sunnix GP-600 (Sanyo). Manufactured by Chemical Company Limited), TMP-3 glycol, PNT-4 glycol, EDA-P-4, EDA-P-8 (manufactured by Nippon Niyukazai Company Limited) and G-300, G-400, G -700, T-400, EDP-450, SP-600, SC-800 (manufactured by Denka Kogyo Co., Ltd.) are provided.

The polyether polyols can be used individually or in combination of two or more as component (E).

The proportion of component (E) in the photo-curable resin composition of the present invention is usually about 5-30% by weight, preferably about 7-25% by weight, more preferably about 10-20% by weight. If the proportion of component (E) is too low, the purpose of developing the photo-curing properties cannot be achieved, and a case arises in which a three-dimensional object having sufficient stability in shape and properties cannot be produced from the resin composition. On the other hand, when the ratio of component (E) is too high, there exists a tendency for the photo-curing characteristic of a resin composition to disappear, and the mechanical strength of the three-dimensional object obtained from a resin composition will fall.

<Optional ingredient>

In addition to the components (A) to (E), other various components may also be incorporated into the photo-curable resin composition to such an extent that it does not adversely affect the curability of the photo-curable resin composition of the present invention. The optional component may be a photosensitive agent (polymerization accelerator) of an amine compound such as triethanolamine, methyl diethanolamine, triethylamine, diethylamine; Photosensitizers including thioxanthone or derivatives thereof, anthraquinone or derivatives thereof, anthracene or derivatives thereof, perylenes and derivatives thereof, benzophenone, benzoin isopropyl ether and the like; Reactive diluents such as vinyl ether, vinyl sulfide, vinyl urethane or vinyl urea. Various additives may also be incorporated into the photo-curable resin composition. The additive is epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, Polymers or oligomers such as fluorine oligomers, silicone oligomers and polysulfide oligomers; Polymerization initiators such as phenothiazine or 2,6-di-t-butyl-4-methyl phenol, polymerization initiation aids, homogenizers, wettability enhancers, surfactants, plasticizers, UV absorbers, silane coupling agents, inorganic fillers, resin particles, Pigments, dyes and the like. The photo-curable resin composition of the present invention can be prepared by uniformly mixing the components (A) to (E), optional components, and various additives.

The photo-curable resin composition of the present invention preferably has a viscosity at 25 ° C. in the range of about 50-1,000 mPa.s (cps), preferably about 70-500 mPa.s (cps).

<Optical-secondary processing method>

The photo-curable resin composition of the present invention prepared in the above method is suitable as a photo-curable (liquid) material used in the photo-secondary processing method. In particular, a three-dimensional object having a preferred shape is a light-secondary processing method comprising selectively irradiating visible light, ultraviolet light or infrared light onto the photo-curable resin composition of the present invention, and injecting the energy required to cure the resin composition Can be obtained using

Various methods can be used to selectively irradiate light to the photo-curable resin composition without particular limitation. The light irradiation method is, for example, irradiating the composition with a laser beam, light collected by a lens, a mirror, etc. during scanning, irradiating the composition with light that is not collected through a mask having a fixed pattern through which light is transmitted. And a method of irradiating the composition with light through a plurality of optical fibers bundled in a light conducting member corresponding to the fixing pattern. In the method of using the mask, the mask electro-optically forms a mask image composed of a region where light is not transmitted and a region where light is transmitted, according to the pattern according to a theory such as that of a liquid crystal display device. When the obtained three-dimensional object has a minute portion or when high-dimensional accuracy is required to form the three-dimensional object, a method using a scanning laser beam having a small spot size is preferable to selectively irradiate light onto the resin composition.

In this method, the irradiated side (e.g., the side scanned by light) of the resin composition placed in the container is the side when the liquid comes into contact with the transparent container wall or the liquid surface of the resin composition. When the irradiated surface is the liquid surface or the contact surface of the vessel wall, light can shine directly out of the vessel or through the vessel.

In the above light-secondary processing method, a preferred solid form can be produced by curing a fixed portion of the resin composition and moving the light spot continuously or gradually to stack the cured portion from the cured portion to the uncured portion. Can be. Various methods for moving the light spot include, for example, moving any one of a light source, a resin composition container, or a cured portion of the resin composition. There is also a method in which the new resin composition is added to the cured resin composition in the container.

In a typical photo-secondary process, the surface of the support stage, which can be raised in the vessel, is significantly lowered from the liquid surface to form a thin layer 1 of the resin composition, the thin layer 1 being a solid curable resin layer 1 '. Light is optionally irradiated to form a. A resin composition is applied on the thin layer 1 'to form a second thin layer 2, and the thin layer 2 is light to stack a new solid cured resin layer 2' on the thin layer 1 '. This is optionally examined. The step is repeated a predetermined number of times without deforming or deforming the pattern to which light is irradiated to produce a three-dimensional object composed of a plurality of laminated resin layers n '.

In this method, the secondary processed three-dimensional object is processed to remove unreacted photo-curable resin composition which is discharged from the container and remains on the surface, and washed with a solvent as necessary. Examples of solvents include alcohols such as isopropyl alcohol or ethyl alcohol, organic solvents such as acetone, ethyl acetate, methylethyl ketone, aliphatic organic solvents such as terpenes, or organics typified by low viscosity liquid thermoplastic or photo-curing resins. Solvent is provided.

When forming a three-dimensional object with a smooth surface, the cured material is preferably washed using a thermoplastic or photo-curable resin. In this case, it is necessary to postcure the product by heat radiation or light irradiation depending on the type of solvent used in the washing step. The post curing treatment is effective not only for curing the resin remaining uncured on the surface of the laminate but also for curing the resin composition remaining uncured in the laminate. Thus, the post-curing treatment is also effective when the secondary processed three-dimensional object is washed with an organic solvent.

The three-dimensional object obtained in the above method has high mechanical strength, high dimensional accuracy and excellent heat resistance. In addition, the three-dimensional object maintains a fixed shape and exhibits high stability in maintaining stable characteristics. Therefore, three-dimensional objects made from resin compositions are preferably used as test products for mechanical parts.

In order to improve the strength and heat resistance of the surface, it is preferable to cover the surface of the three-dimensional object with a heat-curable or photo-curable hard coating material. Depending on the hard coating material, an organic coating material or an inorganic coating material such as an acrylic resin, an epoxy resin, a silicone resin, or the like may be used. The hard coatings can be used individually or in combination of two or more.

The invention will be explained in more detail by way of examples, which do not limit the invention. In the examples, unless stated otherwise the weight percent value is for the total weight of the composition.

<Example 1>

48% by weight of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carbolate (UVR-6110, manufactured by Union Carbide), butanediol diglycidyl, according to the formulation shown in Table 1 16% by weight of ether (KRM-2720, manufactured by Asahi Denka Kogyo), 5% by weight of trimethylolpropane triacrylate (Viscoat 295, manufactured by Osaka Organic Chemicals), dipentaerythritol hexaacrylate (KAYARAD DPHA) , 5% by weight of Nippon Kayaku, 5% by weight of bisphenol A diglycidyl ether diacrylate (Novacure 3700, manufactured by Radcure), triallylsulfonium hexafluoro antimonate (UVI -6974, 2% by weight of Union Carbide, 0.2% by weight of diethylthioxanthone (DETX-S, manufactured by Nippon Kayaku), 1-hydroxycyclohexylphenylketone (Irgacure 184, Ciba Gauge) 2 wt% of PO and modified glycerol (Sunnix GP-250, Put the 17% by weight of the production by the yaw Chemical) in a vessel equipped with a stirrer, and the mixture was reacted with stirring at 60 ℃ for 1 hour to prepare a transparent liquid composition (the resin composition of the present invention). The viscosity of the obtained liquid composition was measured with a type B viscometer at 25 ° C. The viscosity of the composition was 150 mPa · s (cps).

<Example 2-9>

A transparent liquid composition (photo-curable resin composition of the present invention) was prepared in the same manner as in Example 1 according to the formulation shown in Table 1 except that other components were used. The viscosity (at 25 ° C.) of the prepared liquid composition was measured with a B-type viscometer, respectively. The results are shown in Table 1.

<Comparative Example A-D>

A transparent liquid composition (comparative photo-curable resin composition) was prepared in the same manner as in Example 1 according to the formulation shown in Table 1 except that other ingredients and optional ingredients were used. The viscosity (25 degreeC) of the prepared liquid composition was measured with the B-type viscometer, respectively. The results are shown in Table 1.

Amount (wt.% Of total composition) Example Comparative Example One 2 3 4 5 6 7 8 9 A B C D Component A-3,4-Epoxycyclohexyl-methyl-3 ', 4'-epoxy-cyclohexanecarboxylate-butanediol diglycidyl ether 4816 4818 4818 4818 4818 4816 4818 4816 4818 4818 4818 4818 4818 Component B triarylsulfonium hexafluoroantimonate-UVI-6974 ^{* 1} -UVI-6970 ^{* 1} -SP-171 ^{* 2} 2-- 2-- -2- --2 2-- 2-- One-- 2-- 2-- 2-- One-- 2-- 2-- Component C-trimethylolpropane triacrylate-dipentaerythritol hexaacrylate-bisphenol A diglycidyl ether diacrylate 555 85- 85- 85- 85- 85- 85- 555 85- 85- -48 -48 85- Component (D) 1-hydroxycyclohexyl phenyl ketone 2 2 2 2 2 2 One 2 2 2 One 2 2 Component (E) -PO-modified glycerin-PO-modified trimethylol-propane ^{* 3} -EO-modified trimethylol-propane ^{* 4} -PO-modified sorbitol ^{* 5} -polyether polyol ^{* 6} 17 ---- 17 ---- 17 ---- 17 ---- -12 --- --17-- --- 19- 17 ---- ---- 17 ----- ----- 17 ---- ----- Optional Components-Diethyl Thioxanthone ^{* 7} -1,4-butenediol adipic acid ester ^{* 8} 0.2- - - - -5 - - - - - - - -17 Caprolactone Triol ^{＊ 9} - - - - - - - - - 17 20 - - Viscosity (25 ° C) (mPa.s (cps)) 150 110 110 110 150 100 250 150 170 160 220 160 220

^* 1) [UVI-6974], [UVI-6970] (manufactured by Union Carbide Corporation)

^＊ 2) [SP-171] (manufactured by Asahi Denka Industries Co., Ltd.)

^＊ 3) [Sunnix GP-400] (manufactured by Sanyo Chemical Company Limited)

^＊ 4) [TMP-30U] (manufactured by Nippon New Kazai Kogyo Co., Ltd.)

^＊ 5) [Sunnix SP-750] (manufactured by Sanyo Chemical Company Limited)

^* 6) [Desmophenon 1915] (manufactured by Bayer)

^＊ 7) Photosensitizer

^＊ 8) [Nipporan 4009] (manufactured by Nippon Polyurethane Industry Co., Ltd.)

^＊ 9) [TONE-0301] (manufactured by Union Carbide Corporation)

As shown in Table 1, all the compositions prepared in Examples 1 to 9 had the optimum viscosity as the resin composition used in the photo-secondary processing method.

<Evaluation of Photo-Curable Resin Composition>

The photo-curable resin compositions prepared in Examples 1-9 and Comparative Examples A-D were evaluated by measuring Young's modulus and strain over time of the cured product. The results are shown in Table 2.

〈Change of Young's modulus over time〉

(1) Preparation of test specimen

The composition was added to the glass plate using an applicator to prepare a coating film having a thickness of 200 μm. Ultraviolet light was irradiated to the surface of the film at a dose of 0.5 J / cm 2 using a conveyor curing mechanism equipped with a metal halide lamp to produce a semi-cured resin film. The semi-cured resin film was then peeled off the glass plate and placed on a paper that could be released. The opposite side to the first cured by irradiation was irradiated with ultraviolet light at a dose of 0.5 J / cm 2 to produce a fully cured resin film.

Three test specimens (1) to (3) were prepared by placing the cured resin film under the atmospheric conditions described below.

Specimen (1) was prepared at a temperature of 23 ° C. under 50% humidity and placed in a thermo-hygrostat for 24 hours.

Specimen 2 was prepared at a temperature of 23 ° C. under 50% humidity and placed in a thermo-hygrostat for 30 days.

Specimen (3) was prepared at a temperature of 23 ° C. under a humidity of 80% and placed in a thermo-hygrostat for 30 days.

(2) Measurement of Young's modulus

The Young's modulus of the test specimens was measured at a temperature of 23 ° C. under a humidity of 50% under conditions of a tensile rate of 1 mm / min and a mark length of 25 mm.

[Strain over time]

(1) Preparation of test specimen

Measured on the irradiated surface (liquid surface) using an optical-secondary processing device (Solid Creator JSC-2000, manufactured by Sony Corporation) with a light source (wavelengths 351 nm and 365 nm) for applying an argon ion laser beam The photo-curable resin composition was selectively irradiated with a laser beam at a scanning speed of 400 mm / s under a laser power of 100 mW to form a cured resin film having a thickness of 0.15 mm. The secondary processing process was repeated several times to prepare a measurement model (called a camber model) as shown in FIG. 1. Then, the camber model was separated from the optical-secondary processing apparatus, the remaining resin composition attached to the outer surface of the camber model was removed, and the excess resin composition was removed using a terpene-type solvent.

(2) measurement

As shown in FIG. 1, the foot parts 11 of the camber model 10 are fixed to the plane 20, and the distance between the plane 20 and the bottom part 12 of the foot part (lift length). Δh (mm) was measured to determine the primary camber speed.

After the camber model 10 was placed in a constant temperature and humidity chamber at 23 ° C. under 50% humidity for 3 days, the camber speed was measured in the same manner as in the above procedure.

Young's modulus over time Change over time Psalms (1) Psalms (2) Psalms (3) Bending degree (mm) Withstanding temperature, humidity, time cycle Initial value 30 days later 23 ℃, 50%, 24 hours 23 ℃, 50%, 30 days 23 ℃, 80%, 30 days Example 123456789 150170170170155160185150130 145170170170140170190135110 140160160160140155170120100 0.000.000.000.000.020.000.000.010.04 0.100.020.020.020.090.040.050.150.12 Comparative Example 165140130120 110708085 70106035 0.020.000.020.10 0.420.580.220.22

As apparent from Table 2, all cured products from the photo-curable resin compositions of the invention prepared in Examples 1-9, in particular Examples 1-7, exhibit excellent mechanical properties of high Young's modulus and low sustaining Camber speed. Had

In contrast, the cured product formed from the composition prepared in Comparative Example A using caprolactone modified triol (polyester polyol) instead of component (E) showed a large change in Young's modulus and minimal strain over time.

Evaluation was made on the cured product formed from the following composition prepared in Comparative Example: Prepared in Comparative Example B using caprolactone modified triols instead of component (E), three or more of components (C) A composition containing less than 60% by weight of the multifunctional monomer having the above polyfunctionality; A composition prepared in Comparative Example C, containing component (E) but containing less than 60% by weight of a multifunctional monomer having three or more multifunctional monomers in component (C); And compositions prepared using adipic esters of 1,4 butanediol instead of component (E) in Comparative Example D. All of the above cured products from the compositions prepared from the comparative examples had a low mechanical strength with a small Young's modulus and a large change in Young's modulus and camber speed over time.

The photo-curable resin composition of the present invention can produce a cured product having a small change in mechanical properties and deformation rate with time, maintaining high dimensional accuracy and exhibiting excellent mechanical strength and heat resistance. Therefore, the hardened product can be suitably used as a three-dimensional object such as a test product for mechanical parts.

In addition, the photo-secondary processing method using the photo-curable resin composition of the present invention can provide a three-dimensional object having excellent primary characteristics and high durability.

Claims (8)

(A) a cationic polymer, (B) a cationic photo-initiator, (C) an ethylenically unsaturated monomer, (D) a radical photo-initiator, and (E) a poly with an average of about three or more hydroxyl groups Consisting of ether polyols, At least about 60% by weight of the ethylenically unsaturated monomer to the total composition is a multifunctional monomer having three or more ethylenically unsaturated bonds in one molecule. The method of claim 1, The composition comprises about 30-85 wt.% Of component (A), about 0.1-10 wt.% Of component (B), about 5-30 wt.% Of component (C), and about 0.1 of component (D) relative to the total composition. A photo-curable resin composition, characterized in that it is formulated from a component consisting of -10 wt.% And about 5-30 wt.% Of component (E). The method of claim 1, And the composition has a viscosity in the range of about 50-1000 mPa.s (cps) at 25 ° C. The method of claim 1, Component (A) is a photo-curable resin composition, characterized in that the compound consisting of at least one epoxy group. The method of claim 1, Component (C) is a photo-curable resin composition, characterized in that the compound consisting of at least one (meth) acrylate group. The method of claim 1, The component (E) has a photo-curable resin composition, characterized in that it has an average of about 3-6 hydroxyl groups. The method of claim 1, Component (E) is a light-curable resin composition, characterized in that having a molecular weight of about 100-2,000. In the secondary processing method of the three-dimensional object, In order to form another thin layer of the composition on the cured resin layer, an equivalent amount of photo-curable resin composition is injected into one layer to selectively irradiate light to form a cured resin layer having a specific pattern, and integrated on the already formed cured resin layer. Selectively irradiating the thin layer with light to form a new stacked resin layer, Repeating the above steps many times with or without modifying the pattern to which the light is irradiated to form a three-dimensional object composed of a multi-layered cured resin layer, The method according to any one of claims 1 to 7, characterized in that the resin composition is used.