WO2020246489A1 - Composition de résine durcissable, produit durci associé et procédé de fabrication d'article tridimensionnel - Google Patents

Composition de résine durcissable, produit durci associé et procédé de fabrication d'article tridimensionnel Download PDF

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Publication number
WO2020246489A1
WO2020246489A1 PCT/JP2020/021856 JP2020021856W WO2020246489A1 WO 2020246489 A1 WO2020246489 A1 WO 2020246489A1 JP 2020021856 W JP2020021856 W JP 2020021856W WO 2020246489 A1 WO2020246489 A1 WO 2020246489A1
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meth
acrylate
resin composition
curable resin
mass
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PCT/JP2020/021856
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English (en)
Japanese (ja)
Inventor
恭平 和田
卓之 平谷
涼 小川
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キヤノン株式会社
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Priority claimed from JP2020093207A external-priority patent/JP2020200450A/ja
Application filed by キヤノン株式会社 filed Critical キヤノン株式会社
Publication of WO2020246489A1 publication Critical patent/WO2020246489A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/264—Arrangements for irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/295—Heating elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/314—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G

Definitions

  • the present invention relates to a curable resin composition, a cured product thereof, and a method for producing a three-dimensional product.
  • the cured resin layer is integrally laminated.
  • stereolithography is known as an optical three-dimensional modeling method for producing the above.
  • the liquid surface of the liquid photocurable resin composition contained in the container is irradiated with light such as an ultraviolet laser to determine a predetermined value.
  • a cured resin layer having a desired pattern in thickness is formed.
  • a layer of the photocurable resin composition is supplied onto the cured resin layer, and by irradiating with light in the same manner, a new cured resin layer continuous with the previously formed cured resin layer is laminated.
  • a desired three-dimensional model can be obtained. According to such a stereolithography method, if there is three-dimensional shape data of a three-dimensional model, it is possible to easily produce a three-dimensional object having a complicated shape.
  • the stereolithography method is being applied to the modeling of prototypes for shape confirmation (rapid prototyping), the modeling of working models for functional verification, and the modeling of molds (rapid touring). Furthermore, in recent years, the use of stereolithography has begun to expand to the modeling of actual products (rapid manufacturing).
  • Patent Document 1 discloses a curable resin composition containing a urethane (meth) acrylate having a specific structure, a radically polymerizable compound, elastomer particles, and a radical polymerization initiator. Further, Patent Document 2 contains an oxetane compound, a compound having two or more epoxy groups other than an oxetanyl group, a photocationic polymerization initiator, a radical polymerizable compound, and a photoradical polymerization initiator. Curable resin compositions are disclosed.
  • Patent Document 1 Although the curable resin composition described in Patent Document 1 can be cured with good mechanical strength, it is not sufficient from the viewpoint of heat resistance and impact resistance. Further, in Patent Document 2, although high heat resistance and good toughness (snap fit) can be obtained, the impact resistance is not sufficient, and both high impact resistance and high heat resistance are insufficient. ..
  • An object of the present invention is to provide a curable resin composition capable of obtaining a cured product having excellent heat resistance and impact resistance.
  • the curable resin composition according to the present invention is A polyfunctional carbonate (meth) acrylate having at least two (meth) acryloyl groups and at least one carbonate group in the molecule and represented by the following general formula (1),
  • n represents a number of 1 or more.
  • R is an alkylene group having 4 or more carbon atoms and 18 or less carbon atoms, and the carbon atom constituting the alkylene group is an oxygen atom, a sulfur atom, a nitrogen atom or silicon. It may be replaced by an atom. R may be the same or different.
  • X represents a hydrogen atom or a methyl group.
  • the curable resin composition according to the present invention has at least two (meth) acryloyl groups and at least one carbonate group in the molecule, and has a polyfunctional carbonate (meth) represented by the following general formula (1). ) Contains acrylate.
  • n represents a number of 1 or more.
  • R is an alkylene group having 4 to 18 carbon atoms, and the carbon atom constituting the alkylene group may be replaced with an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. Examples of the group containing these atoms include a group containing an ether bond, an ester bond, a urea bond, a thiourea bond and a thiol bond. Rs may be the same or different.
  • X represents a hydrogen atom or a methyl group.
  • n is preferably a number of 2 or more. That is, the polyfunctional carbonate (meth) acrylate preferably contains two or more carbonate groups in the molecule.
  • the polyfunctional carbonate (meth) acrylate can be obtained by using a carbonate polyol such as a polycarbonate polyol.
  • a carbonate polyol such as a polycarbonate polyol.
  • Examples of the carbonate polyol include compounds represented by the following general formula (2).
  • N represents a number of 1 or more.
  • R is an alkylene group having 4 to 18 carbon atoms, and the carbon atom constituting the alkylene group may be replaced with an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. Examples of the group containing these atoms include a group containing an ether bond, an ester bond, a urea bond, a thiourea bond and a thiol bond. Rs may be the same or different.
  • Examples of the alkylene group represented by R include a linear alkylene group, an alicyclic alkylene group, an unsaturated alkylene group, and an unsaturated alicyclic alkylene group.
  • -Diols without side chains such as -octanediol, 1,9-nonanodiol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,8-octanediol, 2-Ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4- Diol-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, etc.
  • compounds having 3 or more hydroxyl groups in one molecule for example, trimethylolethane, trimethylolpropane, hexanetriol, tris isocyanurate (2-hydroxyethyl), as long as the performance of the polyfunctional carbonate (meth) acrylate is not impaired.
  • Pentaerythritol, dipentaerythritol and the like can be used as raw materials for carbonate polyols.
  • Dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate and dibutyl carbonate, diaryl carbonates such as diphenyl carbonate, ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1 and 2 are used as raw materials for carbonate polyols.
  • Examples thereof include alkylene carbonates such as -butylene carbonate, 1,3-butylene carbonate and 1,2-pentylene carbonate. Of these, one or more carbonates can be used as raw materials.
  • dialkyl carbonate and / or diaryl carbonate a polycarbonate diol having a primary OH group at a specific ratio can be easily obtained by adjusting conditions such as the charging ratio of the diol and the carbonate. preferable. Further, it is more preferable to use ethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate and dibutyl carbonate from the viewpoint of easy availability and easy setting of conditions for the polymerization reaction.
  • a commercially available product can also be used as a polycarbonate diol suitable as a raw material for the carbonate polyol.
  • Commercially available polycarbonate diols include Duranol (trademark) (manufactured by Asahi Kasei Corporation), Beneviol (trademark) (manufactured by Mitsubishi Chemical Corporation), Eternacol (trademark) (manufactured by Ube Industries, Ltd.), and Nippon (manufactured by Tosoh Corporation). ), Kuraray polyol (manufactured by Kuraray Co., Ltd.) and the like.
  • the polyfunctional carbonate (meth) acrylate is obtained by condensing a carbonate polyol such as a polycarbonate polyol with (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid halide and the like.
  • the polyfunctional carbonate (meth) acrylate can also be obtained by reacting a carbonate polyol such as a polycarbonate polyol with a compound having a group that reacts with the carbonate polyol.
  • the weight average molecular weight (Mw) of the polyfunctional carbonate (meth) acrylate is preferably 500 or more and 60,000 or less, more preferably 600 or more and 50,000 or less, and further preferably 700 or more and 50,000 or less.
  • Mw weight average molecular weight
  • the weight average molecular weight is 500 or more, the impact resistance of the cured product tends to increase as the crosslink density decreases, which is preferable.
  • the weight average molecular weight is 60,000 or less, the viscosity of the curable composition tends to be appropriate and handling tends to be easy.
  • the weight average molecular weight (Mw) of the polyfunctional carbonate (meth) acrylate is the weight average molecular weight converted to the standard polystyrene molecular weight, and is used for high performance liquid chromatography (for example, high performance GPC apparatus "HLC-8220 GPC” manufactured by Tosoh Corporation). , column (e.g., "Shodex GPCLF-804" manufactured by Showa Denko KK (exclusion limit molecular weight: 2 ⁇ 10 6, separation range: 300 to 2 ⁇ 10 6)) is determined by using. In this case, two or more columns may be used in series.
  • the content of the polyfunctional carbonate (meth) acrylate is preferably 1 part by mass or more and 70 parts by mass or less, more preferably, with respect to 100 parts by mass in total of the polyfunctional carbonate (meth) acrylate and the radically polymerizable compound described later. Is 2 parts by mass or more and 60 parts by mass or less.
  • the content of the polyfunctional carbonate (meth) acrylate is within this range, it is possible to achieve both high impact resistance and heat resistance.
  • the content of the polyfunctional carbonate (meth) acrylate is 1 part by mass or more, sufficient impact resistance can be obtained.
  • the content of the polyfunctional carbonate (meth) acrylate is 70 parts by mass or less, sufficient heat resistance is obtained and the viscosity of the resin composition becomes appropriate.
  • the curable resin composition according to the present invention is a radically polymerizable compound having one or more radically polymerizable functional groups in the molecule, and contains a compound different from the polyfunctional carbonate (meth) acrylate.
  • the radically polymerizable functional group include ethylenically unsaturated groups.
  • examples of the ethylenically unsaturated group include a (meth) acryloyl group and a vinyl group.
  • a (meth) acryloyl group means an acryloyl group or a methacryloyl group.
  • the (meth) acrylate-based compound means a compound having an acrylate group or a compound having a methacrylate group
  • the (meth) acrylamide-based compound is a compound having an acrylamide group or a compound having a methacrylicamide group.
  • Examples of the monofunctional radically polymerizable compound having a (meth) acryloyl group include a monofunctional (meth) acrylamide compound and a monofunctional (meth) acrylate compound.
  • Examples of the monofunctional (meth) acrylamide compound include (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, and N-phenyl (meth).
  • Acrylamide N-methylol (meth) acrylamide, N, N-diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, Examples thereof include N, N-dibutyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpiperidin, and N- [3- (dimethylamino) propyl] acrylamide.
  • Examples of the monofunctional (meth) acrylate-based compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) ) Acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-
  • Examples of the monofunctional radically polymerizable compound having an ethylenically unsaturated group other than the (meth) acryloyl group include styrene derivatives such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof.
  • Maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, vinyl acetate, vinyl propionate, vinyl pivalate, benzoic acid
  • Vinyl esters such as vinyl and vinyl laurate, vinyl cyanide compounds such as (meth) acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide and the like. -Examples include vinyl compounds.
  • These monofunctional radically polymerizable compounds may be used alone or in combination of two or more.
  • polyfunctional (meth) acrylate-based compound examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and nonaethylene glycol di.
  • Examples of the vinyl ether group-containing (meth) acrylate compound include 2-vinyloxyethyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, and 2- (vinyloxyethoxy) ethyl (meth). ) Acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate and the like.
  • Examples of the polyfunctional (meth) acryloyl group-containing isocyanurate compound include tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, and ⁇ -caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate. And so on.
  • polyfunctional (meth) acrylamide compound examples include N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, N, N'-(1,2-dihydroxyethylene) bisacrylamide, N, N'-. Methylenebismethacrylamide, N, N', N''-triacryloyl diethylenetriamine, 2,2-bis [(acryloyloxy) methyl] propan-1,3-diyl-diacrylate, 2-[(acryloyloxy) methyl]- 2- (Hydroxymethyl) Propane-1,3-diyl-diacryloyl, pentaerythritol triacrylate, trimethylolpropanetriacrylate, ditrimethylolpropanetetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, Examples thereof include trimethylolpropan trimethacrylate and N-
  • polyfunctional maleimide-based compound examples include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, and 3,3'-dimethyl-5,5'-diethyl-4,4'-.
  • examples thereof include diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, and 1,6-bismaleimide- (2,2,4-trimethyl) hexane.
  • polyfunctional vinyl ether-based compound examples include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol Falkylene oxide.
  • Examples thereof include divinyl ether, trimethylol propane trivinyl ether, ditrimethylol propane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether and dipentaerythritol hexavinyl ether.
  • polyfunctional aromatic vinyl compound examples include divinylbenzene.
  • polyfunctional radically polymerizable compounds may be used alone or in combination of two or more.
  • the radically polymerizable compound preferably contains at least a (meth) acrylamide compound or a (meth) acrylate compound. Further, the radically polymerizable compound more preferably contains at least a monofunctional (meth) acrylamide compound or a monofunctional (meth) acrylate compound. In particular, the radically polymerizable compound preferably contains a (meth) acrylamide compound. When the radically polymerizable compound contains a (meth) acrylamide compound or a (meth) acrylate compound, the curing rate can be improved.
  • the radically polymerizable compound contains a (meth) acrylamide compound or a (meth) acrylate compound
  • the mixed resin composition composed of the polyfunctional carbonate (meth) acrylate and the radically polymerizable compound permeates into the rubber particles described later and appropriately swells the rubber particles.
  • the impact resistance of the cured product is significantly improved.
  • the content of the radically polymerizable compound is preferably 30 parts by mass or more and 99 parts by mass or less, and more preferably 40 parts by mass or more and 98 parts by mass with respect to 100 parts by mass of the total of the polyfunctional carbonate (meth) acrylate and the radically polymerizable compound. It is less than a part by mass.
  • the content of the radically polymerizable compound is within this range, it is possible to achieve both high impact resistance and heat resistance.
  • the content of the radically polymerizable compound is 99 parts by mass or less, sufficient impact resistance can be obtained.
  • the content of the radically polymerizable compound is 30 parts by mass or more, sufficient heat resistance is obtained and the viscosity of the resin composition is appropriate.
  • the curable resin composition according to the present invention contains rubber particles.
  • the impact resistance of the cured product can be significantly improved.
  • the type of rubber particles is not particularly limited.
  • Preferred polymers constituting the rubber particles include, for example, butadiene rubber, styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, saturated rubber obtained by hydrogenating or partially hydrogenating these diene rubbers, crosslinked butadiene rubber, isoprene rubber, and the like. Examples thereof include chloroprene rubber, natural rubber, silicon rubber, ethylene / propylene / diene monomer ternary copolymer rubber, acrylic rubber, silicone / acrylic composite rubber, and urethane rubber. These polymers may be used alone or in combination of two or more.
  • At least one selected from butadiene rubber, crosslinked butadiene rubber, styrene / butadiene copolymer rubber, acrylic rubber, silicone / acrylic composite rubber, and urethane rubber is particularly preferable from the viewpoint of flexibility.
  • the rubber particles are preferably rubber particles having a core structure and a shell structure that covers the outside of the core structure (hereinafter, may be referred to as "core-shell rubber particles").
  • the polymer constituting the core structure of the rubber particles include the polymers exemplified as the preferable polymers constituting the rubber particles described above.
  • styrene / butadiene copolymer rubber as the core structure and changing the ratio of styrene and butadiene, physical properties such as the particle size of the core structure, the glass transition temperature of the copolymer rubber, the breaking stress, and the breaking elongation It is possible to control the value, which is preferable.
  • Examples of commercially available styrene / butadiene copolymer rubber include latex manufactured by JSR Corporation.
  • the shell structure consists of a polymer of a compound having radical polymerizable properties, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 3-methyl-3-.
  • Polymers such as (meth) acrylic acid esters such as oxetanyl-methyl (meth) acrylate and isobornyl (meth) acrylate, maleimide, styrene, and ⁇ -allyloxymethylacrylic acid ester can be used, but are limited thereto. It's not a thing.
  • the shell structure has two or more reactivity in molecules such as divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, and butylene glycol diacrylate. It may contain a polymer of a reactive cross-linking monomer having a functional group. It is preferable that the polymers constituting the core structure and the shell structure are different polymers.
  • the rubber particles having such a core structure and a shell structure it is possible to improve the dispersibility of the rubber particles in the mixed resin composition of the polyfunctional carbonate (meth) acrylate and the radically polymerizable compound. As a result, a cured product in which the rubber particles are dispersed can be obtained, and the rubber particles can effectively function in the cured product to remarkably improve the impact resistance.
  • the polymer of the radically polymerizable compound that forms the shell structure is preferably graft-polymerized on the surface of the core structure via a chemical bond and has a form that covers a part or the whole of the core structure.
  • Rubber particles having a core structure and a shell structure in which the shell structure is graft-polymerized into a core structure are formed by graft-polymerizing a compound having radical polymerization by a known method in the presence of particles having a core structure. be able to.
  • a radically polymerizable compound which is a component of a shell structure
  • latex particles dispersed in water which can be prepared by emulsion polymerization, miniemulsion polymerization, suspension polymerization, etc. can do.
  • the intermediate layer containing the reactive sites becomes the core structure.
  • the shell structure may be graft-polymerized after being provided on the surface of the above. That is, the form of the rubber particles having the core structure and the shell structure includes a form in which the shell structure is provided in the core structure via the intermediate layer.
  • the compound described as the radically polymerizable compound can be preferably used.
  • the compound used as the radically polymerizable compound in the composition and the radically polymerizable compound used in the shell structure need not be the same.
  • the polymer of the radically polymerizable compound used for the shell structure was appropriately selected from the viewpoint of compatibility with the core structure and dispersibility between the polyfunctional carbonate (meth) acrylate in the composition and the radically polymerizable compound. It is preferable to use one kind or two or more kinds of compounds.
  • the compound described as the polyfunctional carbonate (meth) acrylate may be used in combination.
  • the compound used as the polyfunctional carbonate (meth) acrylate in the composition and the compound having radical polymerization properties used in the shell structure need not be the same.
  • the polyfunctional radically polymerizable compound used for forming the shell structure is preferably 0 parts by mass or more and 40 parts by mass or less, more preferably 0 parts by mass or more, with respect to 100 parts by mass of the radically polymerizable compound for forming the shell structure. It is 30 parts by mass or less, more preferably 0 parts by mass or more and 25 parts by mass or less.
  • the content of the polyfunctional radical polymerizable compound is 40 parts by mass or less, the effect of improving the impact resistance can be easily obtained by adding the rubber particles having the core structure and the shell structure.
  • the polyfunctional radical-polymerizable compound used for shell formation can be appropriately selected from the viewpoint of compatibility with the core structure and dispersibility in the resin composition.
  • the polyfunctional radical contained in the radical-polymerizable compound can be selected appropriately.
  • From the polymerizable compounds one kind or a combination of two or more kinds may be used.
  • rubber particles commercially available rubber particles can be used.
  • Metabrene trademark
  • Kaneace trademark
  • Kaneka Corporation Japanese Industrial Corporation
  • the shell structure is preferably 1 part by mass or more and 200 parts by mass or less, more preferably 2 parts by mass with respect to 100 parts by mass of the core structure. It is 180 parts by mass or less.
  • the mass ratio of the core structure and the shell structure is within this range, the effect of improving the impact resistance by containing the rubber particles is large.
  • the shell structure is 1 part by mass or more, the dispersibility in the curable resin composition is sufficient, and the effect of improving the impact resistance can be easily obtained.
  • the shell structure is 200 parts by mass or less, a sufficient effect of improving impact resistance can be obtained without adding a large amount of rubber particles, so that the curable resin composition has an appropriate viscosity and is handled. Becomes easier.
  • the average particle size of the rubber particles is preferably 0.10 ⁇ m or more and 2.0 ⁇ m or less, and more preferably 0.15 ⁇ m or more and 1.0 ⁇ m or less.
  • the average particle size is 0.10 ⁇ m or more, the viscosity increase due to the addition and the interaction between the rubber particles due to the increase in the specific surface area of the rubber particles are unlikely to occur, and the heat resistance and impact resistance of the cured product can be sufficiently obtained. Be done.
  • the average particle size is 2.0 ⁇ m or less, the dispersibility of the rubber particles in the curable resin composition can be sufficiently obtained, and the effect of improving the impact resistance by adding the rubber particles can be sufficiently obtained.
  • the average particle size of the rubber particles an arithmetic (number) average particle size is used, and a value measured by a dynamic light scattering method is used.
  • the rubber particles can be dispersed in a suitable organic solvent and measured using a particle size distribution meter.
  • the average particle size of the rubber particles is in the range of 0.15 ⁇ m or more and 1.0 ⁇ m or less, the dispersibility of the rubber particles in the curable resin composition is more stable, and high impact resistance of the cured product can be obtained.
  • the content of the rubber particles is preferably 2 parts by mass or more and 65 parts by mass or less, and more preferably 5 parts by mass or more and 60 parts by mass with respect to 100 parts by mass of the total of the polyfunctional carbonate (meth) acrylate and the radically polymerizable compound. It is as follows. When the content of the rubber particles is within this range, a cured product having both high impact resistance and heat resistance can be obtained. When the content of the rubber particles is 2 parts by mass or more, the effect of improving the impact resistance by adding the rubber particles can be sufficiently obtained. Further, when the content of the rubber particles is 65% by mass or less, the heat resistance of the obtained cured product is sufficient, and the viscosity of the curable resin composition is appropriate, so that the curable resin composition is easy to handle.
  • the curable resin composition according to the present invention contains a radical polymerization initiator.
  • a radical polymerization initiator a photoradical polymerization initiator or a thermal radical polymerization initiator can be used.
  • Photoradical polymerization initiators are mainly classified into intramolecular cleavage type and hydrogen abstraction type.
  • intramolecular cleavage type photoradical polymerization initiator by absorbing light of a specific wavelength, the bond at a specific site is cleaved, and a radical is generated at the cleaved site, which becomes a polymerization initiator and is polyfunctional. Polymerization of carbonate (meth) acrylate and radically polymerizable compound begins.
  • the hydrogen abstraction type it absorbs light of a specific wavelength and becomes excited, and the excited species causes a hydrogen abstraction reaction from the surrounding hydrogen donor, and radicals are generated, which becomes a polymerization initiator and is often used. Polymerization of the functional carbonate (meth) acrylate and the radically polymerizable compound begins.
  • an alkylphenone-based photoradical polymerization initiator As the intramolecular cleavage type photoradical polymerization initiator, an alkylphenone-based photoradical polymerization initiator, an acylphosphine oxide-based photoradical polymerization initiator, and an oxime ester-based photoradical polymerization initiator are known. These are of the type in which the bond adjacent to the carbonyl group is alpha-cleaved to produce a radical species.
  • the alkylphenone-based photoradical polymerization initiator include a benzylmethylketal-based photoradical polymerization initiator, an ⁇ -hydroxyalkylphenone-based photoradical polymerization initiator, and an aminoalkylphenone-based photoradical polymerization initiator.
  • Specific compounds include, for example, 2,2'-dimethoxy-1,2-diphenylethane-1-one (Irgacure TM 651, manufactured by BASF) and the like as a benzylmethyl ketal-based photoradical polymerization initiator.
  • Irgacure TM 651, manufactured by BASF 2,2'-dimethoxy-1,2-diphenylethane-1-one
  • ⁇ -hydroxyalkylphenone-based photoradical polymerization initiators 2-hydroxy-2-methyl-1-phenylpropan-1-one (DaroCure 1173, manufactured by BASF) and 1-hydroxycyclohexylphenylketone (Irgacure 184) are available.
  • oxime ester-based photoradical polymerization initiator examples include (2E) -2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] octane-1-one (Irgacure OXE-01, manufactured by BASF) and the like. However, it is not limited to this.
  • An example of the product name is also shown in parentheses.
  • hydrogen abstraction type radical polymerization initiator examples include anthraquinone derivatives such as 2-ethyl-9,10-anthraquinone and 2-t-butyl-9,10-anthraquinone, and thioxanthone derivatives such as isopropylthioxanthone and 2,4-diethylthioxanthone. However, it is not limited to this.
  • photoradical polymerization initiators may be used alone or in combination of two or more. In addition, it may be used in combination with a thermal radical polymerization initiator described later.
  • the amount of the photoradical polymerization initiator added is preferably 0.1 part by mass or more and 15 parts by mass or less, more preferably 0, based on 100 parts by mass of the total of the polyfunctional carbonate (meth) acrylate and the radically polymerizable compound. . 1 part by mass or more and 10 parts by mass or less.
  • the amount of the photoradical polymerization initiator is 0.1 parts by mass or more, the polymerization is sufficient.
  • the amount of the photoradical polymerization initiator is 15 parts by mass or less, the molecular weight is sufficiently increased, and heat resistance or impact resistance can be sufficiently obtained.
  • the thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used.
  • azo compounds, peroxides, persulfates and the like can be used.
  • azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-.
  • examples thereof include azobis (1-acetoxy-1-phenylethane).
  • peroxide examples include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate and di (4-t-butylcyclohexyl) peroxydicarbonate.
  • persulfate examples include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.
  • the amount of the thermal radical polymerization initiator added is preferably 0.1 part by mass or more and 15 parts by mass or less, more preferably 0, based on 100 parts by mass of the total of the polyfunctional carbonate (meth) acrylate and the radically polymerizable compound. . 1 part by mass or more and 10 parts by mass or less.
  • the amount of the thermal radical polymerization initiator is 0.1 parts by mass or more, the polymerization is sufficient.
  • the amount of the thermal radical polymerization initiator is 15 parts by mass or less, the molecular weight is sufficiently increased, and heat resistance or impact resistance can be sufficiently obtained.
  • the curable resin composition of the present invention may contain various additives as other optional components as long as the object and effect of the present invention are not impaired.
  • the amount of the additive added is preferably 0.05 parts by mass or more and 25 parts by mass or less, more preferably 0.1 parts by mass, based on 100 parts by mass of the total of the polyfunctional carbonate (meth) acrylate and the radically polymerizable compound. It is 20 parts by mass or less.
  • a resin such as epoxy resin, polyurethane, polychloroprene, polyester, polysiloxane, petroleum resin, xylene resin, ketone resin, cellulose resin, or polycarbonate
  • Engineering plastics such as polytrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, fluorine-based oligomers, silicone-based oligomers, polysulfide-based oligomers, soft metals such as gold, silver, and lead, graph
  • Layered crystal structure substances such as tungsten, boron nitride, graphite fluoride, calcium fluoride, barium fluoride, lithium fluoride, silicon nitride, and molybdenum selenium may be added.
  • photosensitizers polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, and tertiary compounds.
  • An amine compound, a xanthone compound and the like may be added.
  • additives include polymerization initiators, leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, silane coupling agents, inorganic fillers, pigments, dyes, antioxidants, flame retardants. , Thickener, antifoaming agent and the like.
  • the composition of the present invention is usually prepared by charging an appropriate amount of a polyfunctional carbonate (meth) acrylate, a radically polymerizable compound, rubber particles, and a radical polymerization initiator, and if necessary, other optional components into a stirring vessel. Stir at 0 ° C. or higher and 120 ° C. or lower, preferably 20 ° C. or higher and 100 ° C. or lower. Then, it can be produced by removing a volatile solvent or the like as needed.
  • the curable resin composition according to the present invention can be suitably used as a modeling material used in the stereolithography method. That is, it is desired by selectively irradiating the curable resin composition of the present invention with active energy rays such as ultraviolet / visible light, electron beam, X-ray, and radiation to supply the energy required for curing. It is possible to manufacture a modeled object having the shape of.
  • the viscosity at 25 ° C. is preferably 10 mPa ⁇ s or more and 10,000 mPa ⁇ s or less, and more preferably 10 mPa ⁇ s or more and 5,000 mPa. ⁇ It is s or less.
  • the cured resin product of the present invention can be obtained by curing the above-mentioned curable resin composition by using a known method such as activation energy ray irradiation or heat irradiation.
  • the active energy ray include ultraviolet / visible light, electron beam, X-ray, and radiation.
  • ultraviolet / visible light having a wavelength of 300 nm or more and 450 nm or less can be preferably used in terms of easy availability and compatibility with a photoradical polymerization initiator.
  • an ultraviolet / visible light laser for example, Ar laser, He-Cd laser, etc.
  • a mercury lamp for example, a mercury lamp, a xenon lamp, a halogen lamp, a fluorescent lamp, or the like
  • the laser light source is preferably adopted because it can raise the energy level and shorten the molding time, and also has excellent light-collecting property and can obtain high molding accuracy.
  • the curing method can be appropriately selected according to the type of radical polymerization initiator contained in the curable resin composition. Further, the curing method may be used alone or in combination of two or more.
  • the curable resin composition of the present invention can be suitably used as a modeling material for a stereolithography method.
  • the three-dimensional model obtained by curing the curable resin composition of the present invention can be produced by using a known stereolithography method and apparatus.
  • a typical example of a preferable stereolithography method is a method having a step of photocuring a curable resin composition layer by layer based on slice data generated from three-dimensional shape data of a three-dimensional model to form a modeled object. is there.
  • the cured layer is formed by selectively irradiating the liquid curable resin composition with active energy rays based on the slice data so that a cured layer having a desired pattern can be obtained.
  • an uncured layer made of a liquid curable resin composition is supplied in contact with the cured layer, and similarly, an active energy ray is irradiated based on the slice data to newly form a cured layer continuous with the cured layer. To form.
  • a method of finally obtaining a desired three-dimensional model corresponding to the three-dimensional model can be mentioned.
  • the active energy rays focused in dots like laser light are used.
  • Pointillism or line drawing may be used.
  • a method of irradiating the uncured layer with active energy rays in a planar manner may be adopted through a planar drawing mask formed by arranging a plurality of micro light shutters such as a liquid crystal shutter or a digital micromirror shutter.
  • the free liquid level method is explained as a typical example of the stereolithography method as follows. First, in a container containing a liquid curable resin composition, a support stage provided so as to be able to move up and down is lowered (precipitated) by a predetermined amount from the liquid surface of the resin composition to be curable on the support stage. Supply the resin composition. Next, the curable resin composition on the support stage is selectively irradiated with light based on the slice data to form a solid-cured cured layer (1). Next, the support stage is lowered by a predetermined amount, the curable resin composition is supplied onto the cured layer (1), and the curable resin composition is selectively irradiated with light to obtain the cured layer (1).
  • a new cured layer (2) is formed so as to be continuously and integrally laminated on the layer.
  • a predetermined number of times without changing or changing the pattern of light irradiation of the curable resin composition for each layer based on the slice data, a plurality of cured layers (1, 2). , ... n) are integrally laminated to form a three-dimensional model.
  • it is also modeled by a ready-made liquid level method or an inkjet method.
  • the modeled product thus obtained is taken out of the container and washed if necessary to remove the unreacted curable resin composition remaining on the surface thereof.
  • the cleaning agent include alcohol-based organic solvents typified by alcohols such as isopropyl alcohol and ethyl alcohol; ketone-based organic solvents typified by acetone, ethyl acetate, methyl ethyl ketone and the like; aliphatic organic solvents typified by terpenes. Can be used. After removing the unreacted curable resin composition, post-cure with active energy rays or heat may be performed, if necessary.
  • the unreacted curable resin composition remaining on the surface and inside of the modeled object can be cured, the stickiness of the surface of the modeled object can be suppressed, and the initial strength of the modeled object can be improved. Can be improved.
  • B-1 Acryloyl morpholine (Product name: ACMO, manufactured by KJ Chemicals Co., Ltd.)
  • B-2 Bifunctional acrylic monomer (Product name: KAYARAD HX-220, manufactured by Nippon Kayaku Co., Ltd.)
  • B-3 N-Phenylmaleimide (Product name: imilex TM -P, manufactured by Nippon Shokubai Co., Ltd.)
  • ⁇ Rubber particles with core structure and shell structure> [Production of acetone dispersion of core-shell rubber particles (C-1) having an average particle size of 0.28 ⁇ m]
  • C-1 core-shell rubber particles having an average particle size of 0.28 ⁇ m
  • 185 parts by mass equivalent to 100 parts by mass of polybutadiene rubber particles
  • 315 parts by mass of deionized water product name: Nipol LX111A2, manufactured by Nippon Zeon Corporation
  • EDTA disodium ethylenediamine tetraacetate
  • radically polymerizable compounds 17.5 parts by mass of methyl methacrylate (MMA) and 17.5 parts by mass of 3-methyl-3-oxetanyl-methyl methacrylate (product name: ETERNCOLL TM OXMA, manufactured by Ube Kosan Co., Ltd.), and A radically polymerizable compound was graft-polymerized on the surface of the particles of the polybutadiene rubber by continuously adding a mixture of 0.1 parts by mass of formaldehyde hydroperoxide over 2 hours.
  • MMA methyl methacrylate
  • ETERNCOLL TM OXMA 3-methyl-3-oxetanyl-methyl methacrylate
  • the aqueous dispersion of rubber particles having the core structure and the shell structure obtained as described above was put into 450 parts by mass of acetone and mixed uniformly. After centrifuging at a rotation speed of 12,000 rpm and a temperature of 10 ° C. for 30 minutes using a centrifuge, the supernatant was removed. Acetone is added to the precipitated rubber particles of the core structure and the shell structure to redisperse them, and the core-shell rubber particles (C-1) are dispersed in acetone by repeating centrifugation and removing the supernatant liquid twice under the same conditions as above. I got the liquid. The average particle size of the core-shell rubber particles (C-1) measured by the method shown below was 0.28 ⁇ m.
  • Core-shell rubber particles (trade name: Kaneka Corporation, manufactured by Kaneka Corporation, grade B-564, average particle size 0.17 ⁇ m)
  • ⁇ Manufacturing of curable resin composition The polyfunctional carbonate (meth) acrylate, the radically polymerizable compound, and the radical polymerization initiator were blended in the blending ratios shown in Table 1 and mixed uniformly. Acetone dispersion of rubber particles was mixed with this formulation, and acetone, which was a volatile component, was removed using a rotary evaporator to obtain a curable resin composition.
  • a cured product was prepared by the following method. First, a mold having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was sandwiched between two pieces of quartz glass, and a curable resin composition was poured into the mold. The poured curable resin composition was alternately irradiated with ultraviolet rays of 5 mW / cm 2 from both sides of the mold four times for 180 seconds with an ultraviolet irradiator (trade name: LIGHT SOURCE EXECURE 3000, manufactured by HOYA CANDEO OPTRONICS Co., Ltd.). .. The obtained cured product was placed in a heating oven at 50 ° C. for 1 hour and heat-treated in a heating oven at 100 ° C. for 2 hours to obtain a test piece having a length of 80 mm, a width of 10 mm and a thickness of 4 mm. It was.
  • Deflection temperature under load For the test piece, use a deflection temperature tester under load (trade name: No. 533 HDT tester 3M-2, manufactured by Toyo Seiki Seisakusho Co., Ltd.) according to JIS K 7191-2, at a bending stress of 1.80 MPa, and at room temperature. The temperature was raised at 2 ° C. every minute. The temperature at which the amount of deflection of the test piece reached 0.34 mm was defined as the deflection temperature under load, and was used as an index of heat resistance. The results obtained are shown in Table 1. The heat resistance was evaluated as A (very good) when the load deflection temperature was 70 ° C. or higher, B (good) when the load deflection temperature was 60 ° C. or higher and lower than 70 ° C., and C (defective) when the load deflection temperature was lower than 60 ° C.
  • the results obtained are shown in Table 1.
  • the impact resistance was evaluated as A (very good) for Charpy impact strength of 10 kJ / m 2 or more, B (good) for 8 kJ / m 2 or more and less than 10 kJ / m 2, and less than 8 kJ / m 2.
  • C defective
  • Comparative Example 1 is a system that does not contain polyfunctional carbonate (meth) acrylate.
  • the load deflection temperature is 90 ° C., but the Charpy impact strength is 3.4 kJ / m 2 , and it cannot be said that heat resistance and toughness are well balanced.
  • the toughness is excellent and the heat resistance is also excellent, and physical properties exceeding the range normally expected are given.
  • the curable resin composition of the present invention has an effect of achieving both high toughness and heat resistance, contrary to expectations.
  • the curable resin composition of the present invention has an excellent effect of achieving both impact resistance and heat resistance, and can be suitably used for optical three-dimensional modeling.

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Abstract

La présente invention concerne une composition de résine durcissable à partir de laquelle peut être obtenu un produit durci présentant une excellente résistance à la chaleur et une excellente résistance aux chocs. La composition de résine durcissable contient : au moins deux groupes (méth)acryloyle dans une molécule ; un (méth)acrylate de carbonate multifonctionnel qui comprend au moins un groupe carbonate et est représenté par la formule générale (1) ; un composé polymérisable par voie radicalaire comprenant au moins un groupe fonctionnel polymérisable par voie radicalaire dans une molécule ; des particules de caoutchouc ayant un diamètre moyen de particules de 0,10 à 2,0 µm ; et un initiateur de polymérisation radicalaire.
PCT/JP2020/021856 2019-06-07 2020-06-03 Composition de résine durcissable, produit durci associé et procédé de fabrication d'article tridimensionnel WO2020246489A1 (fr)

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WO2021215407A1 (fr) * 2020-04-21 2021-10-28 キヤノン株式会社 Composition de résine durcissable et procédé de fabrication d'un objet tridimensionnel au moyen de cette composition
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