WO2013172406A1 - Composition de résine pour stéréolithographie optique - Google Patents

Composition de résine pour stéréolithographie optique Download PDF

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Publication number
WO2013172406A1
WO2013172406A1 PCT/JP2013/063641 JP2013063641W WO2013172406A1 WO 2013172406 A1 WO2013172406 A1 WO 2013172406A1 JP 2013063641 W JP2013063641 W JP 2013063641W WO 2013172406 A1 WO2013172406 A1 WO 2013172406A1
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Prior art keywords
compound
group
cation
optical
resin composition
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PCT/JP2013/063641
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English (en)
Japanese (ja)
Inventor
信夫 大金
勇哉 大長
栄治 中本
千晴 本間
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シーメット株式会社
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Priority to JP2014515665A priority Critical patent/JP6096767B2/ja
Publication of WO2013172406A1 publication Critical patent/WO2013172406A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds

Definitions

  • the present invention relates to a resin composition for optical three-dimensional modeling and a method for producing an optical three-dimensional model using the composition. More specifically, the present invention relates to an optical three-dimensional modeling composition containing a non-antimony cationic polymerization initiator that is excellent in safety and free of environmental pollution, and the optical three-dimensional modeling resin of the present invention.
  • the composition By using the composition, with high curing sensitivity, while preventing pollution of the global environment, it has a low yellowness and a high total light transmittance and is colorless or transparent or close to it, and toughness, other An optical three-dimensional structure excellent in mechanical properties, water resistance, and the like can be produced safely and with high productivity at high modeling speed.
  • Resin composition for optical three-dimensional modeling containing a cationic polymerizable organic compound and a cationic polymerization initiator a resin composition for optical three-dimensional modeling containing a radical polymerizable organic compound and a radical polymerization initiator, a cationic polymerizable organic compound, Various types of resin compositions for optical three-dimensional modeling such as a resin composition for optical three-dimensional modeling containing a radical polymerizable organic compound, a cationic polymerization initiator, and a radical polymerization initiator have been conventionally proposed.
  • a cationic polymerization initiator existing in the system generates a cationic species (H + ) by light irradiation, which is chained.
  • the cation polymerizable organic compound is ring-opened due to the cation polymerizable organic compound such as an epoxy compound, and the reaction proceeds.
  • a photocurable resin composition based on a cationically polymerizable organic compound such as an epoxy compound it is generally obtained as compared with a case where a photocurable resin composition based on a radical polymerizable organic compound is used.
  • the shrinkage rate of the photocured product is small, and a shaped product with good dimensional accuracy is obtained.
  • Cationic polymerization initiators for photopolymerizing cationically polymerizable organic compounds include aromatic sulfonium salts of Group VIIa elements (see Patent Document 1) and aromatic onium salts of Group VIa elements (see Patent Document 2).
  • a cationic photopolymerization initiator made of an aromatic onium salt of a Group Va element is known.
  • a sulfonium salt containing antimony has been widely used as a photocationic polymerization initiator in a photocurable resin composition containing a cationically polymerizable organic compound.
  • Patent Literature a resin composition for optical three-dimensional modeling using a cationic polymerization initiator composed of a sulfonium salt containing phosphorus instead of the conventionally used antimony cationic polymerization initiator.
  • Patent Literature 4, 5, 6
  • cationic polymerization initiators made of sulfonium salts containing phosphorus have a lower acidity (cationic species) generated by light irradiation than antimony cationic polymerization initiators.
  • the catalyst activity as an initiator is low, and it is often impossible to obtain a three-dimensional structure with satisfactory physical properties.
  • the phosphoric cationic polymerization initiator composed of a phosphate having an anion moiety having a fluoroalkyl group is a conventional antimony-based cationic polymerization initiator. It is known to have the same photopolymerization initiating ability as that of an agent, but a resin composition for optical three-dimensional modeling is prepared using a phosphorous cationic polymerization initiator composed of a phosphate having an anion moiety having a fluoroalkyl group.
  • the color tone of the three-dimensional molded item obtained becomes light yellow, and the three-dimensional molded item which has a colorless and transparent or close color tone is not obtained.
  • the anion moiety is a cation of a phosphorus-based sulfonium salt, which is a trifluorotris (fluoroalkyl) phosphate ion represented by the formula: [PF 3 (Rf) 3 ⁇ ] (wherein Rf is a fluoroalkyl group).
  • the three-dimensional object obtained by optical modeling using the optical three-dimensional resin composition is a model for verifying the appearance design of various industrial products during the design, a model for checking the functionality of the parts, It is widely used as a resin mold for manufacturing molds, a base model for manufacturing molds, etc., and in recent years there is a model with high transparency and no yellowing like lenses of automobiles and motorcycles. Phosphorus cations that are highly safe because they are used in the arts and crafts field such as restoration of artworks, imitation and contemporary art, and design presentation models for glass-walled buildings. Optical three-dimensional modeling that gives a three-dimensional modeled article that has high transparency and is not colored yellow even for a resin composition for optical three-dimensional modeling containing a polymerization initiator The resin composition has been required.
  • the object of the present invention together with the above-mentioned properties of safety and colorless transparency, can produce a three-dimensional molded article that is excellent in toughness, is strong and is not easily damaged, and has high photocuring sensitivity,
  • 3D objects can be manufactured with high productivity in a shortened optical modeling time, and 3D objects with excellent dimensional accuracy, other mechanical properties, and heat resistance can be formed. It is to provide a resin composition.
  • the present inventors have made various studies to achieve the above-mentioned purpose.
  • a specific phosphorus-based aromatic as a cationic polymerization initiator
  • a sulfonium salt When combined with a sulfonium salt, a three-dimensional structure with a low yellowness, colorless transparency, or a color tone and appearance close to it, while exhibiting high catalytic activity equivalent to that obtained when an antimony cationic polymerization initiator is used. I found.
  • the present inventors further include at least one kind of dye selected from a purple dye and a blue dye in the resin composition for optical three-dimensional modeling
  • the yellowness is further reduced and colorless and transparent
  • the inventors of the present invention performed stereolithography when diglycidyl ether of a specific alicyclic diol is contained at a predetermined ratio as the cationic polymerizable organic compound. It discovered that the transparency of the three-dimensional molded article obtained improved further.
  • a resin composition for optical three-dimensional modeling comprising a cationically polymerizable organic compound (A), a radically polymerizable organic compound (B), a cationic polymerization initiator (C) and a radical polymerization initiator (D).
  • the cationic polymerization initiator (C) is represented by at least one aromatic sulfonium compound (C-1) represented by the following general formula (C-1) and the following general formula (C-2):
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are monovalent organic groups, Rf is a fluoroalkyl group, m is the same number as the cation valence of the “cation [S + (R 1 ) (R 2 ) (R 3 )]” in the general formula (C-1), n is an integer of 1 to 5 and p is the above In general formula (C-2), “the same number as the cation number of the cation [S + (R 4 ) (R 5 ) (R 6 )].”
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 in the above general formula (C-1) and (C-2) are each independently bonded to an aromatic ring.
  • a monovalent aromatic group which may have a substituent, having one or more bonds represented by the formulas: —S—, —SO—, —O— and —CO—;
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 in the general formula (C-1) and the general formula (C-2) are each independently represented by the following general formula ⁇ 1> to ⁇ 11 >>, which is any group represented by any one of the above (1) to (4); It is.
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently have a substituent.
  • An alkyl group or an aryl group which may be X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 19 , X 20 , X 21 and X 22 are each independently an alkyl group, aryl group, alkoxy group, aryloxy group, hydroxy ( A group selected from a poly) alkyleneoxy group, a hydroxyl group, a cyano group, a nitro group and a halogen atom, and Z 1 , Z 2
  • the present invention also provides: (6) As the cationically polymerizable organic compound (A), the following general formula (A-1):
  • R 19 is hydrogenated bisphenol A residue, hydrogenated bisphenol E residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue or trimethyl Cyclodecane dimethanol residue is shown.
  • the alicyclic diglycidyl ether compound (A-1) represented by the formula (1) to (5) is contained in a proportion of 50 to 100% by mass based on the total mass of the cationically polymerizable organic compound (A). Any one of the resin composition for optical three-dimensional modeling.
  • Three-dimensional modeling resin composition and (9)
  • the content of the cationic polymerizable organic compound (A): radical polymerizable organic compound (B) is 30:70 to 90:10 (mass ratio), and the cationic polymerization initiator (C) is used as the cationic polymerizable organic.
  • 0.1 to 10% by mass of the radical polymerization initiator (D) based on the mass of the radical polymerizable organic compound (B).
  • the resin composition for optical three-dimensional modeling according to any one of (1) to (8), which is contained in the ratio of: It is.
  • the present invention provides (10) The following general formula (E); Q—O— (R 20 —O—) q— (R 21 —O—) rQ ′ (E) [Wherein R 20 and R 21 are linear or branched alkylene groups having 2 to 5 carbon atoms, and Q and Q ′ are each independently a hydrogen atom, an alkyl group, a phenyl group, an acetyl group or a benzoyl group. And q and r each independently represent 0 or an integer of 1 or more (provided that both q and r cannot be 0 at the same time). ]
  • the present invention also provides: (11) The above (1) further containing at least one dye (F) selected from a purple dye and a blue dye in an amount of 0.01 to 10 ppm based on the total mass of the resin composition for optical three-dimensional modeling.
  • the present invention provides (12) A method for producing a three-dimensional model by performing optical three-dimensional modeling using the resin composition for optical three-dimensional modeling according to any one of (1) to (11).
  • the resin composition for optical three-dimensional modeling of the present invention does not contain a toxic antimony-based cationic polymerization initiator, and as a cationic polymerization initiator (C), an aromatic sulfonium compound that is a phosphorus-based aromatic sulfonium salt ( Since C-1) and the aromatic sulfonium compound (C-2) are contained, it is excellent in safety and handling.
  • the aromatic sulfonium compound (C-1) and the aromatic sulfonium compound (C-2) are used in combination as the cationic polymerization initiator (C).
  • the three-dimensional modeled object obtained by optical modeling has a low yellowness and a high light transmittance, and is colorless and transparent or has a favorable color tone and appearance.
  • the resin composition for optical three-dimensional modeling of the present invention which contains at least one dye (F) selected from a purple dye and a blue dye together with the aromatic sulfonium compound (C-1) and the aromatic sulfonium compound (C-2)
  • the resin composition has better curing sensitivity to light and sufficient photocuring compared to the resin composition for optical three-dimensional modeling containing the aromatic sulfonium compound (C-1) alone as a cationic polymerization initiator. Therefore, it is possible to manufacture a three-dimensional structure that is excellent in mechanical properties such as strength, elastic properties, and impact resistance.
  • the resin composition for optical three-dimensional modeling of the present invention contains an alicyclic diglycidyl ether compound (A-1) represented by the above general formula (A-1) as the cationically polymerizable organic compound (A).
  • A-1 alicyclic diglycidyl ether compound represented by the above general formula (A-1) as the cationically polymerizable organic compound (A).
  • the resin composition for optical three-dimensional modeling of the present invention By optical modeling using the resin composition for optical three-dimensional modeling of the present invention, it has a low yellowness and a high light transmittance and is colorless and transparent or has a good color tone and appearance close to it, and has strength and elastic properties. Since the three-dimensional molded article having excellent mechanical properties such as impact resistance and toughness can be produced, the resin composition for optical three-dimensional modeling of the present invention has high transparency and has no yellow color appearance and color tone.
  • Model for checking functionality resin mold for making molds, base model for making molds, automobile and motorcycle lenses, restoration of works of art, imitation and modern art, glazed
  • Effectively used in various applications such as arts and crafts fields such as building design presentation models, precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, etc. can do.
  • the resin composition for optical three-dimensional modeling of this invention is a resin composition used in order to manufacture a three-dimensional molded item by performing three-dimensional modeling by irradiating active energy rays, such as light.
  • the resin composition for optical three-dimensional modeling of the present invention comprises a cationic polymerizable organic compound (A) and a radical polymerizable organic compound (B) as an active energy ray polymerizable compound that is polymerized by irradiation with active energy rays such as light. contains.
  • active energy rays refers to energy rays that can cure the resin composition for optical three-dimensional modeling, such as ultraviolet rays, electron beams, X-rays, radiation, and high frequencies.
  • the cationic polymerization initiation comprising the aromatic sulfonium compound (C-1) and the aromatic sulfonium compound (C-2) as the cationic polymerizable organic compound (A) is started.
  • Any compound can be used as long as it is an organic compound that undergoes a cationic polymerization reaction and / or a cationic crosslinking reaction when irradiated with active energy rays in the presence of the agent (C).
  • cationically polymerizable organic compound (A) that can be used in the present invention include epoxy compounds, oxetane compounds and other cyclic ether compounds, cyclic acetal compounds, cyclic lactone compounds, spiro orthoester compounds, vinyl ether compounds, and the like. These cationically polymerizable organic compounds may be used alone or in combination of two or more. Among these, in the present invention, an epoxy compound and an oxetane compound are preferably used as the cationically polymerizable organic compound (A).
  • Examples of the epoxy compound that can be used as the cationically polymerizable organic compound (A) in the present invention include epoxy compounds such as alicyclic epoxy compounds, aliphatic epoxy compounds, and aromatic epoxy compounds.
  • alicyclic epoxy compounds examples include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, cyclohexene ring-containing compounds, or cyclopentene ring-containing compounds such as hydrogen peroxide and peracid. Examples thereof include a cyclohexene oxide structure-containing compound or a cyclopentene oxide structure-containing compound obtained by epoxidation with an agent. More specifically, as an alicyclic epoxy compound, for example, The following general formula (A-1);
  • R 19 is hydrogenated bisphenol A residue, hydrogenated bisphenol E residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue or trimethyl Cyclodecane dimethanol residue is shown.)
  • R 19 is hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD
  • Diglycidyl ether, hydrogenated bisphenol Z diglycidyl ether, cyclohexane dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether diglycidyl ether
  • Examples of the cyclohexene oxide structure-containing compound or the cyclopentene oxide structure-containing compound include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3, 4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3, 4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl- , 5-spiro-3,4-epoxy) cyclohexane-metadioxane, bis
  • the above-mentioned aliphatic epoxy compound that can be used as the cationically polymerizable organic compound (A) is not particularly limited, and examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, Mention may be made of polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, copolymers synthesized by vinyl polymerization of glycidyl acrylate and / or glycidyl methacrylate and other vinyl monomers, etc. it can.
  • Representative compounds include, for example, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl ether of higher alcohols, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, neopentyl glycol Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ethers of polyhydric alcohols such as diglycidyl ether of polytetramethylene glycol Mention may be made of the ether.
  • polyglycidyl ether of a polyether polyol obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol such as propylene, trimethylolpropane, glycerin, and diglycidyl of an aliphatic long chain dibasic acid examples include esters.
  • Epoxy alkanes include 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxycetane, 1,2-epoxyoctadecane, and 1,2-epoxyicosane. Can be mentioned.
  • the aromatic epoxy compound is not particularly limited, and examples thereof include polyglycidyl ethers and polyglycidyl esters of polyhydric phenols or alkylene oxide adducts thereof.
  • polyglycidyl ethers and polyglycidyl esters of polyhydric phenols or alkylene oxide adducts thereof include polyglycidyl ethers and polyglycidyl esters of polyhydric phenols or alkylene oxide adducts thereof.
  • bisphenol A, Bisphenol E, bisphenol F, bisphenol AD, bisphenol Z, or glycidyl ether, phenyl glycidyl ether, tert-butylphenyl glycidyl ether, resorcinol diglycidyl ether, or tetraphenol which is a compound obtained by further adding an alkylene oxide such as ethylene oxide or propylene oxide.
  • diglycidyl ether of biphenol diglycidyl ether of tetramethylbiphenol
  • VG3101L represented by the following chemical formula and other other aromatic epoxy compounds sold by Printec Co., Ltd. it can.
  • the resin composition for optical three-dimensional modeling of the present invention includes the alicyclic diglycidyl ether compound (A-1) represented by the general formula (A-1) described above as a resin composition for optical three-dimensional modeling.
  • It is particularly preferably contained in a proportion of 10 to 100% by mass, more preferably 30 to 90% by mass, especially 50 to 80% by mass, based on the total mass of the cationically polymerizable organic compound (A) contained therein.
  • the alicyclic diglycidyl ether compound (A-1) in an amount within the above range, the transparency of the three-dimensional structure obtained by stereolithography is further improved, and the time-dependent dimension of the three-dimensional structure is obtained. Stability, water resistance, moisture resistance, and heat resistance are excellent.
  • the oxetane compound (A-2) includes one or more of a monooxetane compound having one oxetane group in one molecule and a polyoxetane compound having two or more oxentane groups in one molecule. Can be used.
  • any monooxetane compound (A-2a) can be used as long as it is a compound having one oxetane group in one molecule.
  • it has one oxetane group in one molecule and is alcoholic.
  • a monooxetane monoalcohol compound having one hydroxyl group is preferably used.
  • At least one of the represented monooxetane monoalcohol compounds (A-2a 2 ) is more preferably used as a monooxetane compound from the viewpoints of availability, high reactivity, and low viscosity.
  • R 22 and R 23 represent an alkyl group having 1 to 5 carbon atoms
  • R 24 represents an alkylene group having 2 to 10 carbon atoms which may have an ether bond.
  • examples of R 22 include methyl, ethyl, propyl, butyl and pentyl.
  • Specific examples of monooxetane alcohol (A-2a 1 ) include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl- Examples thereof include 3-normal butyl oxetane and 3-hydroxymethyl-3-propyl oxetane, and one or more of these can be used. Among these, 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane are more preferably used from the viewpoint of availability and reactivity.
  • R 23 examples include methyl, ethyl, propyl, butyl and pentyl.
  • R 24 may be either a chain alkylene group or a branched alkylene group as long as it is an alkylene group having 2 to 10 carbon atoms, or an alkylene group. It may be a chain or branched alkylene group having 2 to 10 carbon atoms having an ether bond (ether oxygen atom) in the middle of the (alkylene chain).
  • R 24 examples include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, and 3-oxypentylene group.
  • R 24 is preferably a trimethylene group, a tetramethylene group, a pentamethylene group or a heptamethylene group from the viewpoints of easiness of synthesis and easy handling since the compound is liquid at normal temperature.
  • any of a compound having 2 oxetane groups, a compound having 3 or more oxetane groups, and a compound having 4 or more oxetane groups can be used.
  • the dioxetane compound having one is preferably used, and among them, the following general formula (A-2b 0 );
  • R 25 are the same or different alkyl groups having 1 to 5 carbon atoms
  • R 26 is a divalent organic group having or not having an aromatic ring
  • s is 0 or 1 Is shown.
  • the dioxetane compound (A-2b 0 ) represented by the formula is preferably used from the viewpoints of availability, reactivity, low hygroscopicity, and mechanical properties of the cured product.
  • examples of R 25 include methyl, ethyl, propyl, butyl and pentyl.
  • R 26 examples include linear or branched alkylene groups having 1 to 12 carbon atoms (eg, ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc. ), A divalent group represented by the formula: —CH 2 —Ph—CH 2 — or —CH 2 —Ph—Ph—CH 2 —, hydrogenated bisphenol A residue, hydrogenated bisphenol F residue, hydrogenated Examples thereof include bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue, tricyclodecanedimethanol residue, terephthalic acid residue, isophthalic acid residue, o-phthalic acid residue and the like.
  • dioxetane compound (A-2b 0 ) examples include dioxetane compounds represented by the following formula (A-2b 1 ) or formula (A-2b 2 ).
  • R 27 are the same or different alkyl groups having 1 to 5 carbon atoms, and R 28 is a divalent organic group having or not having an aromatic ring.
  • dioxetane compound represented by the above formula (A-2b 1 ) include bis (3-methyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) ether, bis (3 -Propyl-3-oxetanylmethyl) ether, bis (3-butyl-3-oxetanylmethyl) ether and the like.
  • specific examples of the dioxetane compound represented by the above formula (A-2b 2 ) include, in the above formula (A-2b 2 ), two R 27 s are both methyl, ethyl, propyl, butyl or pentyl groups.
  • R 28 is ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc.), formula: —CH 2 —Ph—CH 2 — or —CH 2 —Ph—Ph A divalent group represented by —CH 2 —, hydrogenated bisphenol A residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue, tricyclode Examples thereof include a dioxetane compound which is a candimethanol residue, a terephthalic acid residue, an isophthalic acid residue or an o-phthalic acid residue.
  • polyoxetane compound (A-2b 0 ) bis (3-methyl-3-oxetanylmethyl) in which two R 27 s are both a methyl group or an ethyl group in the above formula (A-2b 1 ).
  • Ether and / or bis (3-ethyl-3-oxetanylmethyl) ether are preferably used in view of availability, low hygroscopicity, mechanical properties of the cured product, and the like.
  • -Oxetanylmethyl) ether is more preferably used.
  • molding of this invention is contained in the resin composition for optical three-dimensional model
  • the oxetane compound (A-2) is preferably contained in a proportion of 1 to 35% by mass, and more preferably in a proportion of 5 to 30% by mass. The content is preferably 7 to 25% by mass.
  • radical polymerizable organic compound (B) include compounds having a (meth) acrylate group, unsaturated polyester compounds, allyl urethane compounds, polythiol compounds, and the like. 1 type (s) or 2 or more types can be used. Among them, a compound having at least one (meth) acryloyloxy group in one molecule is preferably used. Specific examples include a reaction product of an epoxy compound and (meth) acrylic acid, and a (meth) alcohol (meth) An acrylic ester, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, etc. can be mentioned.
  • reaction product of the above-mentioned epoxy compound and (meth) acrylic acid it can be obtained by reaction of an aromatic epoxy compound, an alicyclic epoxy compound and / or an aliphatic epoxy compound with (meth) acrylic acid (meta) )
  • Acrylate-based reaction products and specific examples thereof include bisphenol compounds such as bisphenol A and bisphenol S, bisphenol compounds such as bisphenol A and bisphenol S in which the benzene ring is substituted with an alkoxy group, etc.
  • (Meth) acrylate obtained by reacting a glycidyl ether obtained by reaction of an alkylene oxide adduct of a bisphenol compound or a substituted bisphenol compound with an epoxidizing agent such as epichlorohydrin with (meth) acrylic acid, Pokishinoborakku resin and (meth) reacting the acrylic acid and the like are (meth) acrylate reaction product obtained.
  • Examples of the (meth) acrylic acid esters of the alcohols described above include aromatic alcohols, aliphatic alcohols, alicyclic alcohols and / or their alkylene oxide adducts having at least one hydroxyl group in the molecule; Mention may be made of (meth) acrylates obtained by reaction with (meth) acrylic acid.
  • bisphenol compounds such as bisphenol A and bisphenol S, or di (meth) acrylates of bisphenol compounds such as bisphenol A and bisphenol S in which the benzene ring is substituted with an alkoxy group
  • 2-ethylhexyl (meta ) Acrylate 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) ) Acrylate
  • Poly (meth) acrylates of polyhydric alcohols having at least one hydroxyl group polyhydric alcohols such as diols, triols, tetraols, hexaols, etc. , And the like (meth) acrylates of alkylene oxide adducts of Lumpur.
  • examples of the urethane (meth) acrylate described above include (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid ester with an isocyanate compound.
  • the hydroxyl group-containing (meth) acrylic acid ester is preferably a hydroxyl group-containing (meth) acrylic acid ester obtained by an esterification reaction of an aliphatic dihydric alcohol and (meth) acrylic acid.
  • 2-hydroxy Examples thereof include ethyl (meth) acrylate.
  • the polyisocyanate compound which has a 2 or more isocyanate group in 1 molecule like tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. is preferable.
  • polyester (meth) acrylate examples include polyester (meth) acrylate obtained by a reaction between a hydroxyl group-containing polyester and (meth) acrylic acid.
  • polyether (meth) acrylate the polyether acrylate obtained by reaction of a hydroxyl-containing polyether and acrylic acid can be mentioned.
  • the resin composition for optical three-dimensional modeling as part of the radical polymerizable organic compound (B), based on the mass of the radical polymerizable organic compound (B), polytetramethylene glycol di (meth) acrylate, polypropylene glycol
  • polyalkylene glycol di (meth) acrylate such as di (meth) acrylate and polyethylene glycol di (meth) acrylate is contained in an amount of 1 to 20% by mass, further 2 to 15% by mass, particularly 3 to 10% by mass.
  • the toughness of the three-dimensional model obtained from the optical three-dimensional model resin composition is improved.
  • polyalkylene glycol di (meth) acrylate a poly (alkylene glycol) di (meth) acrylate having a number average molecular weight of 300 to 1500, particularly 600 to 900 is preferably used.
  • the heat-deformation temperature of the three-dimensional molded item obtained will become low, and heat resistance will fall.
  • the resin composition for optical three-dimensional modeling of the present invention includes at least one aromatic sulfonium compound (C-1) represented by the following general formula (C-1) as the cationic polymerization initiator (C) and the following: And at least one aromatic sulfonium compound (C-2) represented by the general formula (C-2).
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are monovalent organic groups, Rf is a fluoroalkyl group, m is the same number as the cation valence of the “cation [S + (R 1 ) (R 2 ) (R 3 )]” in the general formula (C-1), n is an integer of 1 to 5 and p is the above In general formula (C-2), “the same number as the cation number of the cation [S + (R 4 ) (R 5 ) (R 6 )].”
  • the aromatic sulfonium compound (C-1) includes a cation represented by the formula: [S + (R 1 ) (R 2 ) (R 3 )] and a formula: [P ⁇ F 6-n (Rf) n ]. Is an ion-bonded salt.
  • the aromatic sulfonium compound (C-2) has a cation represented by the formula: [S + (R 4 ) (R 5 ) (R 6 )] and an anion represented by the formula: [P ⁇ F 6 ]. , An ion-bonded salt.
  • R 1 , R 2 and R 3 which are monovalent organic groups are each independently R 4 , R 5 and R 6.
  • bonds selected from —S— (thioether bond), —SO— (sulfoxide bond), —O— (ether bond) and —CO— (carbonyl bond) It is a monovalent aromatic group having or not having a catalytic activity, easy to obtain From the viewpoints of properties and handling properties, it is preferable.
  • Rf is a fluoroalkyl group, preferably a fluoroalkyl group having 1 to 10 carbon atoms, more preferably a fluoroalkyl group having 1 to 8 carbon atoms, More preferred is a fluoroalkyl group having 1 to 4 carbon atoms.
  • the catalytic activity of the aromatic sulfonium compound (C-1) is such that Rf is a fluoroalkyl group in which 80% or more, more preferably 90% or more, particularly 100% of the hydrogen atoms in the alkyl group are substituted with fluorine atoms. From the point of view, it is preferable.
  • Rf examples include, but are not limited to, CF 3 —, C 2 F 5 —, CF 3 CF 2 CF 2 —, (CF 3 ) 2 CF—, C 4 F 9 —, C 5.
  • F 11- , C 6 F 13- , C 7 F 15- , C 8 F 17- and the like can be mentioned, in particular CF 3- , C 2 F 5- , CF 3 CF 2 CF 2- , (CF 3 2 CF-, C 4 F 9 -is preferred.
  • n is preferably an integer of 1 to 5 from the viewpoint of fast curing of the composition and good physical properties of the three-dimensional structure obtained by photocuring.
  • m is the same number as the cation number of the cation [S + (R 1 ) (R 2 ) (R 3 )].
  • p is the same number as the cation number of the cation [S + (R 4 ) (R 5 ) (R 6 )].
  • R 1 , R 2 and R 3 in the above general formula (C-1) and general formula (C-2) are representative examples of R 4 , R 5 and R 6 .
  • Examples include groups represented by the following formulas ⁇ 1 >> to ⁇ 11 >>.
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently have a substituent.
  • An alkyl group or an aryl group which may be X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 19 , X 20 , X 21 and X 22 are each independently an alkyl group, aryl group, alkoxy group, aryloxy group, hydroxy ( A group selected from a poly) alkyleneoxy group, a hydroxyl group, a cyano group, a nitro group and a halogen atom, and Z 1 , Z 2
  • the group represented by the formula ⁇ 1 >> is not particularly limited, and examples thereof include a phenyl group substituted with a halogen atom such as a phenyl group, a chlorophenyl group, and a bromophenyl group, methyl Examples thereof include a phenyl group substituted with an alkyl group such as a phenyl group and an ethylphenyl group, and a hydroxyphenyl group.
  • Examples of the group represented by the formula ⁇ 2 >> include a naphthyl group, a halogen-substituted naphthyl group, an alkyl group-substituted naphthyl group, and a hydroxyl group-substituted naphthyl group.
  • Examples of the group represented by the formula ⁇ 3 >> include a biphenylyl group, a halogen-substituted biphenylyl group, an alkyl group-substituted biphenylyl group, and a hydroxyl group-substituted biphenylyl group.
  • Examples of the group represented by the formula ⁇ 4 >> include, for example, a methylcarbonylphenyl group, a benzoylphenyl group, a hydrogen atom of a benzene ring in these groups is a halogen atom such as chlorine or bromine, an alkyl group such as a methyl group or an ethyl group And a group substituted with a hydroxyl group.
  • Examples of the group represented by the formula ⁇ 5 >> include a methylcarbonylphenylthiophenyl group, a benzoylphenylthiophenyl group, a hydrogen atom of a benzene ring in these groups being a halogen atom such as chlorine or bromine, a methyl group or an ethyl group. And a group substituted with an alkyl group, a hydroxyl group, and the like.
  • Examples of the group represented by the formula ⁇ 6 >> include a methylthiophenyl group, a phenylthiophenyl group, a naphthylthiophenyl group, a methoxyphenyl group, a phenoxyphenyl group, and a naphthoxyphenyl group.
  • R 9 is a phenyl group.
  • Examples of the group represented by the formula ⁇ 7 >> include a methylthiophenylthiophenyl group, a phenylthiophenylthiophenyl group, a naphthylthiophenylthiophenyl group, a methoxyphenylthiophenyl group, a phenoxyphenylthiophenyl group, and a naphthoxyphenylthio group.
  • Examples of the group represented by the formula ⁇ 8 >> include a diphenylthiobiphenylyl group, a dinaphthylthiobiphenylyl group, a dimethylthiobiphenylyl group, and a hydrogen atom of an aromatic ring in these groups is a halogen atom such as chlorine or bromine. And a group substituted with an alkyl group such as a methyl group or an ethyl group, or a hydroxyl group.
  • Examples of the group represented by the formula ⁇ 9 >> include a group in which Z 3 and Z 4 are —S— in the formula ⁇ 9 >>, a group in which Z 3 and Z 4 are --SO— in the formula ⁇ 9 >>, Examples thereof include a group in which a hydrogen atom of a benzene ring in these groups is substituted by a halogen atom such as chlorine or bromine, an alkyl group such as a methyl group or an ethyl group, or a hydroxyl group.
  • Examples of the group represented by the formula ⁇ 10 >> include trialkylsilylphenyl groups such as trimethylsilylphenyl group and triethylsilylphenyl group, dialkylphenylsilylphenyl groups such as triphenylsilylphenyl group and dimethylphenylsilylphenyl group, and methyl.
  • Examples include alkyldiphenylsilylphenyl groups such as diphenylsilylphenyl groups, groups in which the hydrogen atoms of the benzene ring in these groups are substituted by halogen atoms such as chlorine and bromine, alkyl groups such as methyl and ethyl groups, and hydroxyl groups. be able to.
  • Examples of the group represented by the formula ⁇ 11 >> include trialkylsilylphenylthiophenyl groups such as trimethylsilylphenylthiophenyl group and triethylsilylphenylthiophenyl group, triphenylsilylphenylthiophenyl group, dimethylphenylsilylphenylthiophenyl group, and the like.
  • Dialkylphenylsilylphenylthiophenyl groups such as alkyldiphenylsilylphenylthiophenyl groups such as methyldiphenylsilylphenylthiophenyl groups
  • hydrogen atoms of the benzene ring in these groups are halogen atoms such as chlorine and bromine, methyl groups and ethyl Examples thereof include an alkyl group such as a group, a group substituted with a hydroxyl group, and the like.
  • All of the six groups R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be different from each other, or two of the 6 groups are the same and the remaining 4 One group may be different from each other, three of the six groups may be the same and the remaining three groups may be different from each other, or four of the six groups may be the same And the remaining two groups may be different from each other, five of the six groups may be the same and the remaining one group may be different from each other, or all of the six groups may be The same group may be sufficient.
  • the cation [S + (R 1 ) (R 2 ) (R 3 )] in the aromatic sulfonium compound (C-1) and the cation [S + in the aromatic sulfonium compound (C-2) are not limited thereto.
  • Examples of (R 4 ) (R 5 ) (R 6 )] include the following cations ⁇ a-1> to (a-20).
  • hal is a chlorine atom or a fluorine atom
  • f is 0 or 1
  • the number f of each substituent in a plurality of substituents (hal) f described in one cationic group is each substituent ( hal) 0 or 1 independently for each f .
  • hal is a chlorine atom or a fluorine atom
  • f is 0 or 1
  • the number f of each substituent in a plurality of substituents (hal) f described in one cationic group is each substituent ( hal) 0 or 1 independently for each f .
  • aromatic sulfonium compound (C-1) only one kind of the above-mentioned compounds may be used, or two or more kinds may be used in combination.
  • the cation [S + (R 4 ) (R 5 ) (R 6 )] in the aromatic sulfonium compound (C-2) is not limited in any way.
  • the aromatic sulfonium compound (C-2) that can be used in the present invention is not limited.
  • any one of the above-mentioned cations (a-1) to (a-20) and a positive Examples include compounds in which one or two anions represented by the formula [P ⁇ F 6 ] are ion-bonded according to the ion value (cation value) of the ion (cation).
  • aromatic sulfonium compound (C-2) only one type of compound included in the category of the compound represented by the general formula (C-2) may be used, or two or more types may be used. You may use together.
  • aromatic sulfonium compound (C-1) a cation (sulfonium ion) represented by the formula: [S + (R 1 ) (R 2 ) (R 3 )] and a formula: [PF 3 (Rf) 3 ] is used, and an aromatic sulfonium compound represented by the above general formula (C-2) is used as a compound having an ionic bond with an anion [trifluorotris (fluoroalkyl) phosphate ion] represented by
  • (C-2) is used in combination, a three-dimensional molded article having a high activity as a cationic polymerization initiator and a lower yellowness can be obtained.
  • the cation in the aromatic sulfonium compound (C-2) at that time include cations (a-4), (a-5), (a-11) and the like.
  • the resin composition for optical three-dimensional modeling of the present invention comprises an aromatic sulfonium compound (C-1) and an aromatic sulfonium compound (C-2) as a cationic polymerization initiator, and an aromatic sulfonium compound (C-1):
  • the aromatic sulfonium compound (C-2) is preferably contained in a mass ratio of 90:10 to 60:40, more preferably 85:15 to 70:30.
  • the production method of the aromatic sulfonium compound (C-1) and the aromatic sulfonium compound (C-2) used in the present invention is not particularly limited, and can be produced by, for example, the methods described in Patent Documents 4 and 5 and the like. it can.
  • the aromatic sulfonium compound (C-1) and the aromatic sulfonium compound (C-2) are both commercially available.
  • the aromatic sulfonium compound (C-1) is available from San Apro Co., Ltd. as CPI-200K and CPI.
  • the aromatic sulfonium compound (C-2) is available as CPI-100P, CPI-110P, CPI-500P, etc. from San Apro Co., Ltd.
  • CPI-500K is preferably used as the aromatic sulfonium compound (C-1)
  • CPI-500P is preferably used as the aromatic sulfonium compound (C-2).
  • molding of this invention is a polymerization start which can start radical polymerization of a radically polymerizable organic compound (B) when active energy rays, such as light, are irradiated as a radical polymerization initiator (D).
  • Any of the agents can be used, and examples thereof include benzyl or its dialkyl acetal compound, phenyl ketone compound, acetophenone compound, benzoin or its alkyl ether compound, benzophenone compound, and thioxanthone compound.
  • examples of benzyl or a dialkyl acetal compound thereof include benzyl dimethyl ketal and benzyl- ⁇ -methoxyethyl acetal.
  • examples of phenyl ketone compounds include 1-hydroxy-cyclohexyl phenyl ketone.
  • acetophenone compounds include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 2-hydroxy-2 -Methyl-propiophenone, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone and the like.
  • benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, and benzoin isobutyl ether.
  • benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, and the like.
  • thioxanthone compound examples include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.
  • radical polymerization initiator (D) 1 type, or 2 or more types can be mix
  • the radical polymerization initiator (D) 1-hydroxycyclohexyl phenyl ketone is excellent in the strength and heat resistance of the three-dimensional structure obtained by optical modeling, and has good reactivity. It is preferably used from the viewpoint that the hue of the three-dimensional model to be formed is good (eg, the yellowness is small).
  • molding of this invention is cation polymerizable organic compound (A) and radical polymerizable organic compound (B) from points, such as photocuring performance, modeling speed, and the dimensional stability of the three-dimensional model
  • a cationically polymerizable organic compound (A): a radically polymerizable organic compound (B) 30: 70 to 90:10, more preferably 50:50 to 85:15, particularly 60:40 to 80:20. It is preferable to contain.
  • the cationic polymerization initiator (C) is 0.1 to 10% by mass, particularly 0.5 to 5%, based on the mass of the cationic polymerizable organic compound (A).
  • the radical polymerization initiator (D) is contained in an amount of 0.1 to 10% by mass, particularly 0.5 to 5% by mass, based on the mass of the radical polymerizable organic compound (B). It is preferable.
  • molding of this invention can contain the polyalkylene ether type compound depending on the case, and when it contains the polyalkylene ether type compound, the toughness of the three-dimensional modeled article obtained is improved. It is strong and difficult to break.
  • the polyalkylene ether compound a polyalkylene ether compound represented by the following general formula (E) is particularly preferably used.
  • R 20 and R 21 are linear or branched alkylene groups having 2 to 5 carbon atoms, and Q and Q ′ are each independently a hydrogen atom, an alkyl group, a phenyl group, an acetyl group or a benzoyl group. And q and r each independently represent 0 or an integer of 1 or more (provided that both q and r cannot be 0 at the same time). ]
  • polyalkylene ether compound (E) represented by the above general formula (E) [hereinafter sometimes referred to as “polyalkylene ether compound (E)”]
  • q and r are both integers of 1 or more, and q and r Are 3 or more
  • the oxyalkylene unit (alkylene ether unit): —R 20 —O— and the oxyalkyne unit (alkylene ether unit): —R 21 —O— are bonded in a random manner. Alternatively, they may be combined in a block shape, or random bonds and block bonds may be mixed.
  • R 20 and R 21 include ethylene group, n-propylene group, isopropylene group, n-butylene group (tetramethylene group), isobutylene group, tert- Butylene group, linear or branched pentylene group [for example, —CH 2 CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH (CH 3 ) CH 2 — etc.], etc.] .
  • R 20 and R 21 are ethylene group, n-propylene group, isopropylene group, n-butylene group (tetramethylene group), n-pentylene group, formula: —CH 2 CH 2 CH (CH 3 ) CH It is preferably any one of branched pentylene groups represented by 2- .
  • Q and Q ′ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, an acetyl group, and a benzoyl group. Among them, it is preferable that at least one of Q and Q ′, particularly both are hydrogen atoms.
  • q and r which indicate the number of repeating oxyalkylene units, are such that the number average molecular weight of the polyalkylene ether compound is in the range of 500 to 10,000, particularly 500 to 5,000.
  • Suitable examples of the above polyalkylene ether compound (E) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene oxide-polypropylene oxide block copolymer, random copolymer of ethylene oxide and propylene oxide, formula : Having an alkyl substituent represented by —CH 2 CH 2 CH (R 29 ) CH 2 O— (wherein R 29 is a lower alkyl group having 1 to 4 carbon atoms, preferably a methyl or ethyl group).
  • a polyether having an oxytetramethylene unit (tetramethylene ether unit having an alkyl substituent) bonded thereto, the oxytetramethylene unit and the above formula: —CH 2 CH 2 CH (R 29 ) CH 2 O— (wherein R 29 Is a lower alkyl group having 1 to 4 carbon atoms) Oxytetramethylene units having a substituent and the like polyethers randomly bonded.
  • the island portion can be composed of one or more of the polyalkylene ether compounds described above.
  • a polytetramethylene glycol and / or tetramethylene ether unit having a number average molecular weight in the range of 500 to 10,000 described above and a formula: —CH 2 CH 2 CH (R 29 ) CH 2 O— (wherein R 29 is preferably a polyether in which tetramethylene ether units having an alkyl substituent represented by a lower alkyl group are randomly bonded.
  • R 29 is preferably a polyether in which tetramethylene ether units having an alkyl substituent represented by a lower alkyl group are randomly bonded.
  • the hygroscopic property is low and the dimensional stability and physical property stability are reduced.
  • An excellent stereolithography can be obtained.
  • molding of this invention contains a polyalkylene ether type compound
  • content of a polyalkylene ether type compound is 0.5 with respect to the total mass of the resin composition for optical three-dimensional model
  • molding of this invention can further contain the at least 1 sort (s) of dye (F) chosen from a purple dye and a blue dye.
  • the resin composition for optical three-dimensional modeling of the present invention may or may not contain at least one dye (F) selected from a purple dye and a blue dye, but is selected from a purple dye and a blue dye.
  • yellowness can be further reduced while maintaining high transparency of the three-dimensional structure obtained by stereolithography, and thereby colorless transparency. Can be obtained.
  • the dye (F) selected from a purple dye and a blue dye, a purple dye and / or a blue dye that does not reduce the photocuring sensitivity of the resin composition for optical three-dimensional modeling and does not impair the transparency of the three-dimensional modeled product to be obtained.
  • Any dye can be used, such as methyl violet 10B, methyl violet 2B (crystal violet), purple dye I [1,3-dioxoindan-2-ylidene) (carboxymethyl) (hydroxyoxylatophosphinylmethyl) iminium ] Purple No. 401, Blue No. 1 (Brilliant Blue FCF), Blue No. 2 (Indigo Carmine), Patent Blue VI and the like.
  • the resin composition for optical three-dimensional modeling of the present invention may contain only a purple dye, may contain only a blue dye, or contains both a purple dye and a blue dye. Also good.
  • the content in the case of containing at least one dye (F) selected from a violet dye and a blue dye in the optical three-dimensional modeling resin composition is 0. 0 based on the mass of the optical three-dimensional modeling resin composition. It is preferably 01 to 5 ppm, more preferably 0.05 to 3 ppm, and still more preferably 0.1 to 1 ppm.
  • dye (F) selected from a violet dye and a blue dye is 0. 0 based on the mass of the optical three-dimensional modeling resin composition. It is preferably 01 to 5 ppm, more preferably 0.05 to 3 ppm, and still more preferably 0.1 to 1 ppm.
  • the color tone of the three-dimensional molded item obtained by optical modeling will become purple and it will become difficult to become colorless and transparent.
  • a violet pigment and / or a blue pigment
  • the resin composition for optical modeling according to the present invention includes an antifoaming agent, a leveling agent, a thickener, a flame retardant, an antioxidant, a modifying resin, and the like.
  • an antifoaming agent e.g., a leveling agent, a thickener, a flame retardant, an antioxidant, a modifying resin, and the like.
  • One or two or more kinds may be contained in appropriate amounts.
  • any of the conventionally known optical three-dimensional modeling methods and apparatuses can be used for optical three-dimensional modeling using the optical modeling resin composition of the present invention.
  • the active energy ray is selectively irradiated so that a cured layer having a desired pattern is obtained in the liquid resin composition for optical modeling of the present invention.
  • a cured layer is formed, and then an uncured liquid optical modeling resin composition is supplied to the cured layer, and similarly, a cured layer continuous with the cured layer is formed by irradiating active energy rays.
  • the method of finally obtaining the target three-dimensional molded item can be mentioned by repeating lamination
  • Examples of the active energy rays at that time include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies as described above. Among them, ultraviolet rays having a wavelength of 300 to 400 nm are preferably used from an economical viewpoint.
  • an ultraviolet laser for example, a semiconductor-excited solid laser, an Ar laser, a He—Cd laser
  • a high-pressure mercury lamp is used as a light source at that time.
  • Ultra high pressure mercury lamps, low pressure mercury lamps, xenon lamps, halogen lamps, metal halide lamps, ultraviolet LEDs (light emitting diodes), ultraviolet fluorescent lamps, and the like can be used.
  • a cured resin layer having a predetermined shape pattern by irradiating an active energy ray on a modeling surface made of a resin composition for optical three-dimensional modeling the active energy is reduced to a point such as a laser beam.
  • a planar drawing mask in which a hardened resin layer may be formed by a line drawing method using a line or a plurality of micro light shutters such as a liquid crystal shutter or a digital micromirror shutter (DMD).
  • a modeling method may be employed in which a cured resin layer is formed by irradiating the modeling surface with active energy rays through the surface.
  • the resin composition for optical modeling of the present invention can be widely used in the field of optical three-dimensional modeling, and is not limited at all. However, as a typical application field, the appearance design is verified during the design. Shape confirmation model, functional test model for checking the functionality of parts, master model for producing mold, master model for producing mold, direct mold for prototype mold, automobile and motorcycle Lenses, restoration of art, imitation and contemporary art, art and craft fields such as design presentation models for glass-walled buildings, precision parts, electrical and electronic parts, furniture, building structures, automotive parts, various containers, It can be effectively used for various applications such as casting models.
  • the viscosity of the resin composition for optical three-dimensional modeling the mechanical properties of the optical molding obtained by optical molding using the resin composition for optical modeling [tensile characteristics (tensile strength (tensile breaking strength, tensile breaking elongation) Degree, tensile elastic modulus), bending properties (bending strength, bending elastic modulus), impact strength], heat distortion temperature, yellowness and total light transmittance were measured as follows.
  • Viscosity of resin composition for optical modeling The resin composition for optical modeling was placed in a thermostatic bath at 25 ° C. and the temperature of the photocurable resin composition was adjusted to 25 ° C., and then measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.).
  • Bending characteristics (bending strength, bending elastic modulus) of the optically shaped object The bending strength and the flexural modulus of the test piece were measured according to JIS K-7171 using the optically shaped article (bar-shaped test piece conforming to JIS K-7171) produced in the following examples or comparative examples. .
  • Example 1 3,4-Epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“Cel-2021P” manufactured by Daicel Corporation) 5.5 parts by weight, hydrogenated bisphenol A diglycidyl ether (Shin Nippon Rika Co., Ltd.) 60 parts by mass of “HBE-100” manufactured by the company, 7.5 parts by mass of 3-ethyl-3-hydroxymethyloxetane (“OXT101” manufactured by Toagosei Co., Ltd.), bis (3-ethyl-3-oxetanylmethyl) ether ( 12.5 parts by mass of “OXT221” manufactured by Toagosei Co., Ltd., 13 parts by mass of dipentaerythritol pentaacrylate (“A-9550W” manufactured by Shin-Nakamura Chemical Co., Ltd.), “NK” manufactured by Shin-Nakamura Chemical Co., Ltd.
  • A-9550W manufactured by Shin-N
  • Ester-LA 10 parts by weight, bisphenol A diglycidyl ether 3 parts by mass of 2-moleic acid adduct (“VR-77” manufactured by Showa Denko KK), polytetramethylene glycol diacrylate (number average molecular weight 650) (“A-PTMG-65” manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.5 parts by mass, 1.5 parts by mass of polytetramethylene ether glycol (“PTG-850SN” manufactured by Hodogaya Chemical Co., Ltd., number average molecular weight 801 to 890), “CPI-500K” [aromatic sulfonium manufactured by San Apro Co., Ltd.
  • Solution] 1.5 parts by mass and 2.5 parts by mass of 1-hydroxy-cyclohexyl phenyl ketone (“Irgacure-184” manufactured by BASF, radical polymerization initiator) are mixed well to prepare a resin composition for optical three-dimensional modeling. did. It was 232 mPa * s when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
  • Example 2 (1) In Example 1 (1), methyl violet 10B (“Crystal Violet” manufactured by Wako Pure Chemical Industries, Ltd.) 3.0 ⁇ 10 ⁇ 5 parts by mass (based on the mass of the resin composition for optical three-dimensional modeling) In addition, a resin composition for optical three-dimensional modeling was prepared in the same manner as (1) of Example 1 except that 0.25 ppm) was further added. It was 226 mPa * s when the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-mentioned method. (2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared and post-cured in the same manner as (2) of Example 1. The mechanical properties, heat distortion temperature, yellowness and total light transmittance of the test piece after post-curing were measured by the methods described above. The results are shown in Table 1 below.
  • Example 3 (1) In (1) of Example 1, instead of 1.5 parts by mass of “CPI-500K”, “CPI-200K” manufactured by Sun Apro Co., Ltd. [phosphorus represented by the following formula (C-1 ⁇ 2 ) Cationic polymerization initiator solution containing 50% by mass of aromatic aromatic sulfonium compound] Resin composition for optical three-dimensional modeling in the same manner as (1) of Example 1 except that 1.5 parts by mass was mixed. Was prepared. It was 240 mPa * s when the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-mentioned method.
  • Comparative Example 3 >> (1) Instead of “CPI-500K” and “CPI-500P” in (1) of Example 1, “CPI-200K” manufactured by San Apro Co., Ltd. used in Example 3 [the above formula (C-1 ⁇ 2 ) Cationic polymerization initiator solution containing a phosphorus-based aromatic sulfonium compound represented by 50) in a concentration of 50% by mass], except that 2.0 parts by mass was mixed. A three-dimensional modeling resin composition was prepared. It was 242 mPa * s when the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-mentioned method.
  • the optical three-dimensional modeling of Examples 1 to 3 containing both the aromatic sulfonium compound (C-1) and the aromatic sulfonium compound (C-2) as the cationic polymerization initiator The three-dimensional structure obtained using the resin composition for optical use has a low yellowness, a high total light transmittance, excellent colorless transparency, and in particular, a resin for optical three-dimensional structure of Example 2 further containing a purple dye
  • the three-dimensional structure obtained by using the composition has a very low yellowness of 1 while maintaining a high total light transmittance of 86%, and is extremely excellent in colorless transparency.
  • the three-dimensional model obtained from the optical three-dimensional model resin compositions of Comparative Examples 1 and 3 containing the aromatic sulfonium compound (C-1) alone as the cationic polymerization initiator, 3 is significantly higher in yellowness than the three-dimensional modeled product obtained by using the optical three-dimensional modeled resin composition. Further, the three-dimensional model obtained from the resin composition for optical three-dimensional modeling of Comparative Example 2 containing the aromatic sulfonium compound (C-2) alone is the same as the resin composition for optical three-dimensional modeling of Example 1.
  • the breaking strength, bending strength, and bending elastic modulus of the three-dimensional structure are Compared to the three-dimensional modeled object obtained by using the three-dimensional model, it is too soft and soft, and when manufacturing a three-dimensional modeled object having a complicated shape, it is easy to hang from the support and deform, and the three-dimensional model of the target shape and structure It is difficult to manufacture things.
  • the resin composition for optical three-dimensional modeling of the present invention is excellent in safety and handleability, and gives a three-dimensional modeled article having excellent transparency and colorless transparency. It is extremely useful as a resin composition.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

Le problème décrit par la présente invention est de produire une composition de résine pour stéréolithographie optique qui ne renferme pas d'initiateur de polymérisation cationique à base d'antimoine toxique, qui ne soit pas dangereuse et qui possède d'excellentes propriétés de traitement, et qui permette d'obtenir des produits stéréolithographiques dotés d'une excellente apparence externe et d'excellentes couleurs ne jaunissant pas, et possédant une translucidité incolore. Pour ce faire, la présente invention concerne une composition de résine pour stéréolithographie optique comprenant un composé organique polymérisable par voie cationique, un composé organique polymérisable par voie radicalaire, un initiateur de polymérisation cationique et un initiateur de polymérisation par voie radicalaire. Cette composition de résine pour stéréolithographie optique comprend, comme initiateur de polymérisation cationique, un composé aromatique du sulfonium représenté par la formule générale (C-1) et un composé aromatique du sulfonium représenté par la formule générale (C-2) (dans la formule générale (C-1) et dans la formule générale (C-2) : R1, R2, R3, R4, R5, et R6 représentent chacun un groupe organique monovalent ; Rf représente un groupe fluoroalkyle ; m représente le même nombre que la charge cationique du « cation (S+(R1)(R2)(R3)) » dans la formule générale (C-1) ; n représente un nombre entier situé dans la plage allant de 1 à 5 ; et p représente le même nombre que la charge cationique du « cation (S+(R4)(R5)(R6)) » dans la formule générale (C-2)).
PCT/JP2013/063641 2012-05-18 2013-05-16 Composition de résine pour stéréolithographie optique WO2013172406A1 (fr)

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JP2016188308A (ja) * 2015-03-30 2016-11-04 シーメット株式会社 光学的立体造形用樹脂組成物
JP2018087291A (ja) * 2016-11-29 2018-06-07 マクセルホールディングス株式会社 サポート材組成物
JP2018172698A (ja) * 2018-07-31 2018-11-08 マクセルホールディングス株式会社 サポート材組成物
JP2019099666A (ja) * 2017-12-01 2019-06-24 サンアプロ株式会社 光学的立体造形用樹脂組成物
JP7489612B2 (ja) 2019-06-10 2024-05-24 パナソニックＩｐマネジメント株式会社 紫外線硬化性樹脂組成物、発光装置の製造方法及び発光装置

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JPH09194540A (ja) * 1996-01-22 1997-07-29 Mitsubishi Rayon Co Ltd 光学的立体造形用樹脂組成物
JP2005015739A (ja) * 2003-06-24 2005-01-20 Cmet Inc 靱性に優れた光学的立体造形用樹脂組成物
JP2007284550A (ja) * 2006-04-17 2007-11-01 Cmet Inc 光学的立体造形用樹脂組成物

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JPH09194540A (ja) * 1996-01-22 1997-07-29 Mitsubishi Rayon Co Ltd 光学的立体造形用樹脂組成物
JP2005015739A (ja) * 2003-06-24 2005-01-20 Cmet Inc 靱性に優れた光学的立体造形用樹脂組成物
JP2007284550A (ja) * 2006-04-17 2007-11-01 Cmet Inc 光学的立体造形用樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016188308A (ja) * 2015-03-30 2016-11-04 シーメット株式会社 光学的立体造形用樹脂組成物
JP2018087291A (ja) * 2016-11-29 2018-06-07 マクセルホールディングス株式会社 サポート材組成物
CN109715370A (zh) * 2016-11-29 2019-05-03 麦克赛尔控股株式会社 支撑材用组合物和光造形用油墨组
US10557032B2 (en) 2016-11-29 2020-02-11 Maxell Holdings, Ltd. Composition for support material and ink set for stereolithography
JP2019099666A (ja) * 2017-12-01 2019-06-24 サンアプロ株式会社 光学的立体造形用樹脂組成物
JP2018172698A (ja) * 2018-07-31 2018-11-08 マクセルホールディングス株式会社 サポート材組成物
JP7489612B2 (ja) 2019-06-10 2024-05-24 パナソニックＩｐマネジメント株式会社 紫外線硬化性樹脂組成物、発光装置の製造方法及び発光装置

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