WO2020241501A1 - 硬化性樹脂組成物およびその硬化物 - Google Patents

硬化性樹脂組成物およびその硬化物 Download PDF

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WO2020241501A1
WO2020241501A1 PCT/JP2020/020310 JP2020020310W WO2020241501A1 WO 2020241501 A1 WO2020241501 A1 WO 2020241501A1 JP 2020020310 W JP2020020310 W JP 2020020310W WO 2020241501 A1 WO2020241501 A1 WO 2020241501A1
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mass
meth
resin composition
parts
acrylate
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English (en)
French (fr)
Japanese (ja)
Inventor
卓之 平谷
恭平 和田
涼 小川
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Canon Inc
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Canon Inc
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Priority to EP20813501.2A priority Critical patent/EP3957662A4/en
Priority to CN202080037277.5A priority patent/CN113853395B/zh
Publication of WO2020241501A1 publication Critical patent/WO2020241501A1/ja
Priority to US17/528,659 priority patent/US12221505B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—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
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—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
    • 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
    • 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
    • C08F290/067—Polyurethanes; Polyureas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
    • B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources

Definitions

  • the present disclosure relates to a curable resin composition and a cured product thereof.
  • the cured resin layer is integrally laminated.
  • 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.
  • the photocurable resin composition is supplied onto the cured resin layer, and light is irradiated in the same manner to laminate and form a new cured resin layer bonded to the previously formed cured resin layer.
  • 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).
  • a photocurable resin composition capable of forming a three-dimensional model having high impact resistance comparable to that of general-purpose engineering plastics and high heat resistance that does not deform even at a relatively high temperature is available. It has been demanded. Further, in addition to the above, low water absorption that exhibits high dimensional stability even in a high humidity environment is required.
  • Patent Document 1 and Patent Document 2 disclose an optical three-dimensional modeling resin composition containing a urethane (meth) acrylate, an ethylenically unsaturated compound having a radically polymerizable group, rubber particles, and a radical polymerization initiator. ing.
  • An object of the present disclosure is to provide a curable resin composition capable of obtaining a cured product having low water absorption and excellent impact resistance and heat resistance.
  • the curable resin composition according to the present disclosure includes a polyfunctional urethane (meth) acrylate (A) having at least two (meth) acryloyl groups and at least two urethane groups in the molecule, and one in the molecule.
  • the content of the rubber particles (D) containing the radical polymerization initiator (E) and the radical polymerization initiator (D) is 8 parts by mass or more and 50 parts by mass with respect to a total of 100 parts by mass of the radically polymerizable compound not containing the (D). It is characterized in that it is not more than a part by mass.
  • the present embodiment an embodiment of the present invention (hereinafter, also referred to as “the present embodiment”) will be described.
  • the embodiments described below are merely one of the present embodiments, and the present invention is not limited to these embodiments.
  • the polyfunctional urethane (meth) acrylate (A) contained in the curable composition of the present embodiment is a urethane (meth) acrylate having at least two (meth) acryloyl groups and at least two urethane groups in the molecule. Is.
  • the polyfunctional urethane (meth) acrylate (A) includes, for example, a compound obtained by reacting a hydroxyl group-containing (meth) acrylate compound with a polyvalent isocyanate compound, or an isocyanate group-containing (meth) acrylate compound and a polyol compound. Those obtained by reacting with a compound can be used. In addition, a compound obtained by reacting a hydroxyl group-containing (meth) acrylate compound, a multivalent isocyanate compound, and a polyol compound can be used. Of these, from the viewpoint of achieving high impact resistance, a compound obtained by reacting a hydroxyl group-containing (meth) acrylate compound, a multivalent isocyanate compound, and a polyol compound is preferable.
  • hydroxyl group-containing (meth) acrylate-based compound examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
  • Hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylates, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, caprolactone-modified 2-hydroxyethyl (meth) acrylates.
  • polyvalent isocyanate-based compound examples include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylenedi isocyanate, and naphthalene diisocyanate.
  • aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylenedi isocyanate, and naphthalene diisocyanate.
  • polyol compound examples include polyether-based polyols, polyester-based polyols, polycarbonate-based polyols, polyolefin-based polyols, polybutadiene-based polyols, (meth) acrylic-based polyols, polysiloxane-based polyols, and the like. These polyol compounds may be used alone or in combination of two or more.
  • polyether polyol examples include alkylene structure-containing polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block co-weights of these polyalkylene glycols. Coalescence is mentioned.
  • the polyester-based polyol includes, for example, three types of components: a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid, a ring-opening polymer of a cyclic ester (lactone), a polyhydric alcohol, a polyvalent carboxylic acid, and a
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, and 2-methyl-1,3-tri.
  • Methylenediol 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, glycerin , Trimethylol propane, trimethylol ethane, cyclohexanediols (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol, sorbitol, etc.) and the like.
  • polyvalent carboxylic acid examples include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecandioic acid, 1,4.
  • aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecandioic acid, 1,4.
  • alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid and trimellitic acid.
  • cyclic ester examples include propiolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -caprolactone and the like.
  • polycarbonate-based polyol examples include a reaction product of a polyhydric alcohol and phosgene, a ring-opening polymer of a cyclic carbonate ester (alkylene carbonate, etc.), and the like.
  • polyhydric alcohol as the polycarbonate-based polyol examples include the polyhydric alcohol exemplified in the description of the polyester-based polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexa. Methylene carbonate and the like can be mentioned.
  • the polycarbonate-based polyol may be a compound having a carbonate bond in the molecule and having a hydroxyl group at the end, and may have an ester bond together with the carbonate bond.
  • the weight average molecular weight of the polyfunctional urethane (meth) acrylate (A) of the curable resin composition of the present embodiment is preferably 1000 or more and 60,000 or less. More preferably, it is 2000 or more and 50,000 or less. When the weight average molecular weight is 1000 or more, the impact resistance of the cured product tends to increase remarkably as the crosslink density decreases, which is preferable. If the weight average molecular weight is larger than 60,000, the viscosity of the curable composition tends to increase and it tends to be difficult to handle, which is not preferable.
  • the weight average molecular weight (Mw) of the polyfunctional urethane (meth) acrylate (A) is the weight average molecular weight converted to the standard polystyrene molecular weight, and is high performance liquid chromatography (high performance GPC apparatus "HLC-8220 GPC” manufactured by Tosoh Corporation). It is measured by using two series of columns: Shodex GPCLF-804 (exclusion limit molecular weight: 2 ⁇ 10 6 , separation range: 300 to 2 ⁇ 10 6 ).
  • the radically polymerizable functional group equivalent of the polyfunctional urethane (meth) acrylate (A) is preferably 400 g / eq or more.
  • the radically polymerizable functional group equivalent is a value indicating the molecular weight per radically polymerizable functional group.
  • the impact resistance tends to decrease as the crosslink density increases, which is not preferable.
  • the content of the polyfunctional urethane (meth) acrylate (A) in the curable resin composition of the present embodiment is 100 parts by mass in total of the polyfunctional urethane (meth) acrylate (A) and other radically polymerizable compounds. On the other hand, it is preferably 5 parts by mass or more and 70 parts by mass or less. More preferably, it is 10 parts by mass or more and 60 parts by mass or less.
  • the content of the polyfunctional urethane (meth) acrylate (A) is within the above range, it is possible to achieve both high impact resistance and heat resistance. If the content of the polyfunctional urethane (meth) acrylate (A) is less than 5 parts by mass, the impact resistance tends to decrease.
  • the content of the polyfunctional urethane (meth) acrylate is more than 70 parts by mass, the heat resistance tends to decrease and the viscosity of the resin composition tends to be higher than the range suitable for the material of the stereolithography method.
  • the hydrophilic monofunctional radical-polymerizable compound (B) contained in the curable resin composition of the present embodiment is a compound having one radical-polymerizable functional group in the molecule and exhibiting water solubility.
  • the hydrophilic monofunctional radical polymerizable compound refers to a compound having a solubility in water of 2.5 [g / 100 g] or more.
  • the solubility in water represents the amount of the hydrophilic monofunctional radically polymerizable compound (B) that can be dissolved in 100 g of water at 25 ° C.
  • the hydrophilic monofunctional radically polymerizable compound (B) may be simply referred to as the compound (B).
  • Examples of 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.
  • hydrophilic monofunctional radically polymerizable compound (B) having a (meth) acryloyl group examples include a hydrophilic monofunctional acrylamide compound and a hydrophilic monofunctional (meth) acrylate compound.
  • hydrophilic monofunctional acrylamide compounds include (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N.
  • hydrophilic monofunctional acrylamide compounds include (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N.
  • hydrophilic monofunctional acrylamide compounds include (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N.
  • examples thereof include -dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide,
  • hydrophilic monofunctional (meth) acrylate-based compound examples include (meth) acrylic acid, methyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydrokipropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. , 4-Hydroxybutyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, methoxypolyethylene glycol methacrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N- Diethylaminoethyl (meth) acrylate, and the like.
  • examples of the hydrophilic monofunctional radically polymerizable compound having a vinyl group include vinyl acetate and a hydrophilic N-vinyl compound.
  • examples of the hydrophilic N-vinyl compound include N-vinylpyrrolidone, N-vinylcaprolactam, and N-vinylacetamide.
  • hydrophilic monofunctional radically polymerizable compound other than the above examples include styrene derivatives such as styrene sulfonic acid and salts thereof, and vinyl cyanide compounds such as (meth) acrylonitrile.
  • hydrophilic monofunctional radical polymerizable compounds may be used alone or in combination of two or more.
  • the preferable range of the content of the hydrophilic monofunctional radically polymerizable compound (B) in the curable resin composition of the present embodiment is the hydrophilic monofunctional radically polymerizable compound (B).
  • the solubility of the hydrophilic monofunctional radical polymerizable compound (B) in water is 20 [g / 100 g] or more, the content thereof is preferably 55 parts by mass with respect to 100 parts by mass in total with the radically polymerizable compound. It is less than or equal to, more preferably 50 parts by mass or less.
  • the content of the hydrophilic monofunctional radical polymerizable compound having a solubility in water of 20 [g / 100 g] or more is more than 55 parts by mass, the water absorption rate of the cured product of the curable resin composition becomes high. Therefore, when exposed to a high humidity environment, water is absorbed and the dimensional change tends to exceed the permissible range.
  • the solubility of the hydrophilic monofunctional radical polymerizable compound (B) in water is less than 20 [g / 100 g]
  • the content in the curable resin composition is 100 parts by mass in total with the radically polymerizable compound. On the other hand, it is preferably 65 parts by mass or less, and more preferably 60 parts by mass or less.
  • the curable resin composition contains, as the hydrophilic monofunctional radically polymerizable compound (B), both a compound having a solubility in water of 20 [g / 100 g] or more and a compound having a solubility of less than 20 [g / 100 g], the compound.
  • the upper limit of the content of (B) can be calculated by the following formula. That is, when the total of the hydrophilic monofunctional radically polymerizable compounds is 100 parts by mass and the content ratio of the hydrophilic monofunctional radically polymerizable compounds having a solubility in water of 20 [g / 100 g] or more is X parts by mass, (55). It can be calculated as ⁇ X + 65 ⁇ (100—X)) / 100 [parts by mass].
  • the content of the hydrophilic monofunctional radically polymerizable compound (B) in the curable resin composition of the present embodiment is determined by the solubility in water from the viewpoint of viscosity. Regardless, it is preferably 10 parts by mass or more. More preferably, it is 15% by mass or more. When the content of the hydrophilic monofunctional radical polymerizable compound (B) is 10 parts by mass or more, the increase in viscosity of the curable resin composition when the rubber particles (D) is added tends to be alleviated, which is preferable.
  • the preferable range of the content of the hydrophilic monofunctional radically polymerizable compound (B) in the curable resin composition is 10 parts by mass or more and 65 parts by mass or less with respect to 100 parts by mass in total with the radically polymerizable compound. It is more preferably 15 parts by mass or more and 55 parts by mass or less.
  • the hydrophobic monofunctional radically polymerizable compound (C) contained in the curable resin composition is a compound having one radically polymerizable functional group in the molecule and has a solubility in water of 2.5. Refers to those less than [g / 100g].
  • Examples of 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.
  • hydrophobic monofunctional radically polymerizable compound having the (meth) acryloyl group examples include a hydrophobic monofunctional acrylamide compound and a hydrophobic monofunctional (meth) acrylate compound.
  • hydrophobic monofunctional acrylamide compound examples include N-tert-butyl (meth) acrylamide, N-phenyl (meth) acrylamide, N- (meth) acryloylpiperidin, and the like.
  • hydrophobic monofunctional (meth) acrylate-based compound examples include methyl methacrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl.
  • hydrophobic monofunctional radical polymerizable compound having an ethylenically unsaturated group other than the above examples include styrene derivatives such as styrene, vinyltoluene, ⁇ -methylstyrene, and chlorostyrene, ethylmaleimide, propylmaleimide, and butylmaleimide.
  • Maleimides such as hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, vinyl esters such as vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnate, N-vinylphthalimide, N -N-vinyl compounds such as vinylcarbazole may be mentioned.
  • the content of the hydrophobic monofunctional radical polymerizable compound (C) in the curable resin composition is 100 in total with the radical polymerizable compound. It is preferably 5 parts by mass or more with respect to the mass part. More preferably, it is 10 parts by mass or more.
  • the content of the hydrophobic monofunctional radical polymerizable compound is less than 5 parts by mass, the water absorption rate becomes high, and water is absorbed in a high humidity environment, and the dimensional change tends to exceed the permissible range. That is, it is preferable that the water absorption rate is such that the dimensional change does not exceed the permissible range and does not cause a large change in mechanical properties.
  • the content thereof is less than 60 parts by mass with respect to a total of 100 parts by mass of the radical polymerizable compound of the present embodiment. Is preferable. More preferably, it is 55 parts by mass or less.
  • the content of the hydrophobic monofunctional radical polymerizable compound having an alicyclic hydrocarbon group is 60 parts by mass or more, the viscosity of the curable resin composition when the rubber particles (D) are added increases, and the curable resin composition is handled. Tends to be difficult. For example, when a curable resin composition is used as a modeling material for a stereolithography method, the modeling time may become long due to an increase in viscosity, or the modeling itself may become difficult.
  • hydrophobic monofunctional radical polymerizable compound having an alicyclic hydrocarbon group examples include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and cyclohexyl (meth) acrylate. , 4-t-Butylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, and the like.
  • the glass transition temperature (Tg) of the copolymer of the mixture of the hydrophobic monofunctional radically polymerizable compound (C) and the hydrophilic monofunctional radically polymerizable compound (B) is preferably 85 ° C. or higher. More preferably, it is 90 ° C. or higher.
  • the Tg of the copolymer can be determined by the FOX formula (formula (1)).
  • Wi is the mass ratio of each of the hydrophilic and hydrophobic monofunctional radically polymerizable compounds in the copolymer.
  • Tgi is the glass transition temperature (unit: absolute temperature) of the homopolymers of each of the hydrophilic and hydrophobic radically polymerizable compounds. Details of the FOX formula are described in Bulletin of the American Physical Society, Series 2, Volume 1, Issue 3, page 123 (1956). ing.
  • Tgi glass transition temperature
  • DSC differential scanning calorimetry
  • DMA dynamic viscoelasticity measurement
  • the hydrophilic monofunctional radical polymerizable compound (B) and the hydrophobic monofunctional radical polymerizable compound (C) are collectively referred to as a monofunctional radical polymerizable compound (B + C).
  • the content of the monofunctional radically polymerizable compound (B + C) is preferably 30 parts by mass or more and 90 parts by mass or less, and more preferably 50 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the radically polymerizable compound.
  • ⁇ Rubber particles (D)> By including the rubber particles (D) in the curable resin composition, the impact resistance of the cured product can be improved.
  • the type of rubber particles is not particularly limited.
  • Preferred compositions 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, and isoprene rubber. , Chloroprene rubber, natural rubber, silicon rubber, ethylene / propylene / diene monomer ternary copolymer rubber, acrylic rubber, acrylic / silicone composite rubber and the like.
  • the rubber particles are preferably composed of these compositions alone or in combination of two or more.
  • the glass transition temperature of the composition of the rubber particles is preferably 25 ° C. or lower. More preferably, it is 20 ° C. or lower. When the glass transition temperature is higher than 25 ° C., it tends to be difficult to obtain the effect of improving the impact resistance.
  • the glass transition temperature of the composition of the rubber particles can be determined by, for example, differential scanning calorimetry (DSC) or dynamic viscoelasticity measurement (DMA).
  • the rubber particles are more preferably rubber particles having a core-shell structure. Specifically, it is preferable that the rubber particles have the above-mentioned rubber particles as a core and further have a shell made of a polymer of a radically polymerizable compound that coats the outside thereof.
  • the dispersibility of rubber particles in the inside can be improved. As a result, a cured product in which the rubber particles are uniformly dispersed can be obtained, and the rubber particles can effectively function in the cured product to further improve the impact resistance.
  • the polymer of the radically polymerizable compound forming the shell is preferably graft-polymerized on the surface of the core via a chemical bond and has a form of covering a part or the whole of the core.
  • the rubber particles having a core-shell structure in which the shell is graft-polymerized on the core can be formed by graft-polymerizing a radical-polymerizable compound by a known method in the presence of the core particles. For example, by adding a radical polymerizable compound, which is a constituent of the shell, to polymerized latex particles dispersed in water, which can be prepared by emulsion polymerization, miniemulsion polymerization, suspension polymerization, seed polymerization, etc. Can be manufactured.
  • the form of the rubber particles having a core-shell structure includes a form in which a shell is provided on the core via an intermediate layer.
  • the above-mentioned composition can be used as the composition constituting the core of the rubber particles having the core-shell structure.
  • the core is particularly preferred.
  • a monofunctional radically polymerizable compound having one radically polymerizable functional group in the molecule can be preferably used.
  • the rubber particles having a shell containing a polymer of a monofunctional radically polymerizable compound are excellent in dispersibility when dispersed in a resin composition containing a radically polymerizable compound.
  • the monofunctional radically polymerizable compound used to form the shell can be appropriately selected in consideration of compatibility with the composition constituting the core and dispersibility in the resin composition.
  • one or a combination of two or more of the materials exemplified as the hydrophilic monofunctional radical polymerizable compound (B) and the hydrophobic monofunctional radical polymerizable compound (C) may be used.
  • the shell contains a polymer of a monofunctional radically polymerizable compound having a (meth) acryloyl group
  • the rubber particles are well dispersed in the curable resin composition and the increase in viscosity of the curable resin composition is suppressed. It is also preferable because it can be used.
  • rubber particles having a shell containing a polymer of a hydrophobic monofunctional radically polymerizable compound having a (meth) acryloyl group are particularly preferable.
  • the radically polymerizable compound for forming the shell a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound may be used in combination.
  • Forming a shell with a polyfunctional radically polymerizable compound tends to reduce the viscosity of the curable resin composition and facilitate handling.
  • the polyfunctional radically polymerizable compound used for shell formation is preferably 0 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the radically polymerizable compound used for shell formation.
  • the polyfunctional radically polymerizable compound used for shell formation can be appropriately selected in consideration of compatibility with the composition constituting the core and dispersibility in the resin composition.
  • One or a combination of two or more of the polyfunctional urethane (meth) acrylate (A) and the material later exemplified as the polyfunctional radically polymerizable compound may be used.
  • the mass ratio of the core to the shell in the rubber particles having the core-shell structure is preferably 1 part by mass or more and 200 parts by mass or less, and more preferably 2 parts by mass or more and 180 parts by mass with respect to 100 parts by mass of the core. It is as follows. When the mass ratio of the core and the shell is within the above range, it is possible to effectively improve the impact resistance by containing the rubber particles. When the amount of the shell is less than 1 part by mass, the dispersibility of the rubber particles in the curable resin composition is not sufficient, so that it tends to be difficult to obtain the effect of improving the impact resistance.
  • the dispersibility in the curable resin composition is excellent, but since the rubber particles are thickly covered with the shell, the effect of improving the impact resistance by the rubber component is reduced. It ends up. Therefore, it is necessary to add a large amount of rubber particles in order to obtain sufficient impact resistance, and the viscosity of the curable resin composition tends to increase, making handling difficult.
  • the average particle size of the rubber particles is preferably 20 nm or more and 10 ⁇ m or less, and more preferably 50 nm or more and 5 ⁇ m or less.
  • the average particle size is less than 20 nm, the increase in viscosity in the curable resin composition due to the addition and the interaction between the rubber particles caused by the increase in the specific surface area of the rubber particles decrease the heat resistance of the cured product. And tends to cause a decrease in impact resistance.
  • the average particle size is larger than 10 ⁇ m, the rubber particles (rubber component) are difficult to disperse in the curable resin composition, and the effect of improving the impact resistance by adding the rubber particles tends to decrease.
  • the average particle size of the rubber particles in the present invention is an arithmetic (number) average particle size and can be measured by using a dynamic light scattering method.
  • the rubber particles can be dispersed in a suitable organic solvent and measured using a particle size distribution meter.
  • the gel fraction of the rubber particles is preferably 5% or more. When the gel fraction is less than 5%, both impact resistance and heat resistance tend to decrease, which is not preferable.
  • the gel fraction can be determined by the following procedure.
  • the dried rubber particles W1 [g] are immersed in a sufficient amount of toluene and left at room temperature for 7 days. Then, the solid content is taken out by centrifugation or the like and dried at 100 ° C. for 2 hours, and the amount of the solid content obtained after drying is measured. Assuming that the mass of the solid content obtained after drying is W2 [g], it can be calculated by the following formula.
  • Gel fraction (%) W2 / W1 x 100
  • the content of rubber particles in the curable resin composition shall be 8 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass in total of the radically polymerizable compound. Preferably, it is 10 parts by mass or more and 40 parts by mass or less. If the content of the rubber particles is less than 8 parts by mass, the effect of improving the impact resistance due to the addition of the rubber particles cannot be obtained. Further, when the content of the rubber particles is more than 50 parts by mass, the heat resistance of the obtained cured product is remarkably lowered. In addition, the viscosity of the curable resin composition increases remarkably, making it difficult to handle.
  • Radar polymerization initiator (E) As the radical polymerization initiator (E), a photoradical polymerization initiator or a thermal radical polymerization initiator can be used.
  • the photoradical polymerization initiator is mainly classified into an intramolecular cleavage type and a hydrogen abstraction type.
  • an 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 (meth).
  • Polymerization of the ethylenically unsaturated compound containing an acryloyl radical 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 to generate radicals, which act as a polymerization initiator and radicals. Polymerization of the 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 benzylmethyl ketal-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 as a benzylmethyl ketal-based photoradical polymerization initiator (Irgacure (registered trademark) 651, manufactured by BASF).
  • Benzylmethyl ketal-based photoradical polymerization initiator Irgacure (registered trademark) 651, manufactured by BASF.
  • ⁇ -hydroxyalkylphenone-based photoradical polymerization initiators 2-hydroxy-2-methyl-1-phenylpropan-1-one (DaroCure 1173, manufactured by BASF), 1-hydroxycyclohexylphenylketone (Irgacure), etc.
  • agent examples include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907, manufactured by BASF) or 2-benzylmethyl-2-dimethylamino-1- (4-). Morphorinophenyl) -1-butanone (Irgacure 369, manufactured by BASF) and the like, but are not limited thereto.
  • Acylphosphine oxide-based photoradical polymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucillin TPO, manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819).
  • 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.
  • Examples of the hydrogen abstraction type radical polymerization initiator 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.
  • anthraquinone derivatives such as 2-ethyl-9,10-anthraquinone and 2-t-butyl-9,10-anthraquinone
  • thioxanthone derivatives such as isopropylthioxanthone and 2,4-diethylthioxanthone.
  • 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 with respect to 100 parts by mass of the radically polymerizable compound contained in the curable resin composition. More preferably, it is 0.1 part by mass or more and 10 parts by mass or less. If the amount of the photoradical polymerization initiator is small, the polymerization tends to be insufficient. If an excessive amount of the polymerization initiator is added, the molecular weight does not increase, and the heat resistance or impact resistance may decrease.
  • the radically polymerizable compound is a combination of a polyfunctional urethane (meth) acrylate (A), a monofunctional radically polymerizable compound (B + C), and other polyfunctional radically polymerizable compounds.
  • 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 0.1 part by mass, with respect to 100 parts by mass of the radically polymerizable compound contained in the curable resin composition. It is 10 parts by mass or less. If an excessive amount of the polymerization initiator is added, the molecular weight does not increase, and the heat resistance or impact resistance may decrease.
  • the curable resin composition may contain other components as long as the object and effect of the present invention are not impaired.
  • Examples of other components include polyfunctional radically polymerizable compounds and additives other than polyfunctional urethane (meth) acrylate (A).
  • a polyfunctional radically polymerizable compound having a radically polymerizable functional group equivalent of less than 300 g / eq When a polyfunctional radically polymerizable compound having a radically polymerizable functional group equivalent of less than 300 g / eq is contained, the content thereof is 20 parts by mass with respect to a total of 100 parts by mass of the radically polymerizable compounds contained in the curable resin composition. The following is preferable. More preferably, it is 18 parts by mass or less.
  • the radically polymerizable functional group equivalent is a value indicating the molecular weight per radically polymerizable functional group.
  • the crosslink density of the cured product becomes high and at the same time, the crosslink density becomes non-uniform. Tend. Therefore, when an impact is applied from the outside, a part where stress is concentrated is generated, the effect of improving the impact resistance expected by adding rubber particles cannot be obtained, and the Charpy impact strength may be the same as that of the conventional technique. is there.
  • the content thereof is 50 parts by mass with respect to 100 parts by mass of the total of the radically polymerizable compounds contained in the curable resin composition. It is preferably less than.
  • the content of the polyfunctional radically polymerizable compound having a radically polymerizable functional group equivalent of 300 g / eq or more is more than 50 parts by mass, the heat resistance is lowered and the crosslink density of the cured product is increased, and by adding rubber particles, It tends to be difficult to obtain the expected effect of improving impact resistance.
  • Examples of the radically polymerizable functional group of the polyfunctional radically polymerizable compound other than the polyfunctional urethane (meth) acrylate (A) include an ethylenically unsaturated group.
  • Examples of the ethylenically unsaturated group include a (meth) acryloyl group and a vinyl group.
  • Examples of the polyfunctional radical polymerizable compound include a polyfunctional (meth) acrylate compound, a vinyl ether group-containing (meth) acrylate compound, a polyfunctional (meth) acryloyl group-containing isocyanurate compound, and a polyfunctional (meth) acrylamide compound. Examples thereof include compounds, polyfunctional maleimide compounds, polyfunctional vinyl ether compounds, and polyfunctional aromatic vinyl compounds.
  • 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.
  • 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 ( Examples thereof include meta) acrylate and 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate.
  • Examples of the polyfunctional (meth) acryloyl group-containing isocyanurate compound include tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, and ⁇ -caprolactone-modified tris- (2-acryloyloxyethyl) isocyanate. Nurate and the like.
  • polyfunctional (meth) acrylamide compound examples include N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, N, N'-(1,2-dihydroxyethylene) bisacrylamide, N, N'. -Methylenebismethacrylamide, N, N', N''-triacryloyldiethylenetriamine and the like can be mentioned.
  • 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 Aalkylene oxide divinyl ether, and bisphenol Falkylene.
  • Examples thereof include oxide 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.
  • Additives include property modifiers, photosensitizers, polymerization initiation aids, leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, etc. to impart desired physical properties to the cured product.
  • properties modifiers include property modifiers, photosensitizers, polymerization initiation aids, leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, etc. to impart desired physical properties to the cured product.
  • examples thereof include silane coupling agents, inorganic fillers, pigments, dyes, antioxidants, flame retardants, thickeners, defoamers and the like.
  • the amount of the additive added is 0.05 parts by mass with respect to 100 parts by mass in total of the polyfunctional urethane (meth) acrylate (A), the monofunctional radically polymerizable compound (B + C) and other polyfunctional radically polymerizable compounds. It is preferably 25 parts by mass or less. More preferably, it is 0.1 part by mass or more and 20 parts by mass or less. Within this range, desired physical properties can be imparted to the cured product or the curable resin composition without lowering the impact resistance of the obtained cured product or increasing the water absorption rate.
  • 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
  • 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.
  • photoensitizers 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.
  • examples include amine compounds and xanthone compounds.
  • the curable resin composition includes a polyfunctional urethane (meth) acrylate (A), a monofunctional radically polymerizable compound (B + C), rubber particles (D), a radical polymerization initiator (E), and if necessary, other components.
  • Ingredients are placed in a stirring container in appropriate amounts and stirred.
  • the stirring temperature is usually 20 ° C. or higher and 120 ° C. or lower, preferably 40 ° 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, by selectively irradiating the curable resin composition of the present embodiment with active energy rays to supply the energy required for curing, a modeled product having a desired shape can be produced.
  • the viscosity at 25 ° C. is preferably 50 mPa ⁇ s or more and 5,000 mPa ⁇ s or less, more preferably 75 mPa ⁇ s or more 4, It is 500 mPa ⁇ s or less.
  • a cured product (modeled product) obtained by curing the curable resin composition according to the present invention can be produced by using a known stereolithography method and apparatus.
  • a preferable stereolithography method there is a step of repeating curing of a curable resin composition to a predetermined thickness based on slice data generated from three-dimensional shape data of a manufacturing object (modeling model).
  • the method There are roughly two types, the free liquid level method and the regulated liquid level method.
  • FIG. 1 shows a configuration example of the stereolithography apparatus 100 using the free liquid level method.
  • the stereolithography apparatus 100 has a tank 11 filled with a liquid photocurable resin composition 10. Inside the tank 11, a modeling stage 12 is provided so as to be driveable in the vertical direction by a drive shaft 13.
  • the irradiation position of the light energy ray 15 for curing the photocurable resin composition 10 emitted from the light source 14 is changed by the galvanometer mirror 16 controlled by the control unit 18 according to the slice data, and the surface of the tank 11 is scanned. Will be done.
  • the scanning range is indicated by a thick broken line.
  • the thickness d of the photocurable resin composition 10 cured by the light energy rays 15 is a value determined based on the setting at the time of generating the slice data, and the accuracy of the obtained modeled object (three-dimensional shape data of the article to be modeled). Affects reproducibility).
  • the thickness d is achieved by the control unit 18 controlling the drive amount of the drive shaft 13.
  • the control unit 18 controls the drive shaft 13 based on the setting, and the photocurable resin composition having a thickness d is supplied onto the stage 12.
  • the liquid curable resin composition on the stage 12 is selectively irradiated with light energy rays based on the slice data so that a cured layer having a desired pattern can be obtained, and the cured layer is formed.
  • the uncured curable resin composition having a thickness d is supplied to the surface of the cured layer.
  • the light energy rays 15 are irradiated based on the slice data, and a cured product integrated with the previously formed cured layer is formed.
  • the three-dimensional model obtained in this way is taken out from the tank 11, the unreacted curable resin composition remaining on the surface thereof is removed, and then washed if necessary.
  • an alcohol-based organic solvent typified by alcohols such as isopropyl alcohol and ethyl alcohol can be used.
  • a ketone-based organic solvent typified by acetone, ethyl acetate, methyl ethyl ketone or the like, or an aliphatic organic solvent typified by terpenes may be used.
  • post-cure by light irradiation or heat irradiation may be performed, if necessary. Post-cure can cure the unreacted curable resin composition that may remain on the surface and inside of the three-dimensional model, suppress the stickiness of the surface of the three-dimensional model, and the three-dimensional model. The initial strength can be improved.
  • Examples of the light energy beam used for manufacturing a three-dimensional model include ultraviolet rays, electron beams, X-rays, and radiation. Among them, ultraviolet rays having a wavelength of 300 nm or more and 450 nm or less are preferably used from an economical point of view.
  • an ultraviolet 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 can be used.
  • the laser light source is preferably adopted because it has excellent light-collecting property, can increase the energy level, shorten the modeling time, and can obtain high modeling accuracy.
  • a pointillism method or a stippling method is used using light energy rays squeezed into dots or lines.
  • the resin can be cured by the line drawing method.
  • the resin may be cured by irradiating the active energy rays in a planar manner 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 stereolithography device using the regulated liquid level method has a configuration in which the stage 12 of the stereolithography device 100 of FIG. 1 is provided so as to pull up the modeled object above the liquid level, and the light irradiation means is provided below the tank 11. Become.
  • Typical modeling examples of the regulated liquid level method are as follows. First, the support surface of the support stage provided so as to be able to move up and down and the bottom surface of the tank containing the curable resin composition are installed so as to be at a predetermined distance between the support surface of the support stage and the bottom surface of the tank. A curable resin composition is supplied.
  • the curable resin composition between the stage support surface and the bottom surface of the tank is selectively illuminated by a laser light source or a projector according to the slice data. Is irradiated. By irradiation with light, the curable resin composition between the stage support surface and the bottom surface of the tank is cured, and a solid cured resin layer is formed. After that, the support stage is raised and the cured resin layer is peeled off from the bottom surface of the tank.
  • A-1 Bifunctional urethane acrylate; "KAYARAD UX-6101” (manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight (measured value): 6.7 x 10 3 )
  • A-2 Bifunctional urethane acrylate; "KAYARAD UX-8101” (manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight (measured value): 3.3 x 10 3 )
  • A-3 Bifunctional urethane acrylate; "CN9001NS” (manufactured by Arkema, weight average molecular weight (measured value): 5.4 x 10 3 )
  • B-1 Acryloyl morpholine
  • ACMO manufactured by KJ Chemicals
  • B-2 N, N-diethylacrylamide
  • DEAA manufactured by KJ Chemicals
  • B-3 N-vinylcaprolactam
  • B-4 2-hydroxyethyl methacrylate
  • B-5 diacetone acrylamide
  • DAAM manufactured by KJ Chemicals
  • ⁇ Manufacturing of acetone dispersion of rubber particles D-1> In a 1 L glass container, 185 parts by mass of polybutadiene latex (Nipol LX111A2: manufactured by Nippon Zeon Co., Ltd.) (equivalent to 100 parts by mass of polybutadiene rubber particles) and 315 parts by mass of deionized water were charged, and the mixture was stirred at 60 ° C. while performing nitrogen substitution. Further, 0.005 parts by mass of ethylenediaminetetraacetic acid disodium (EDTA), 0.001 parts by mass of ferrous sulfate heptahydrate, and 0.2 parts by mass of sodium formaldehyde sulfoxylate were added.
  • EDTA ethylenediaminetetraacetic acid disodium
  • the radically polymerizable compound forming the shell (17.5 parts by mass of methyl methacrylate (MMA), 17.5 parts by mass of isobornyl methacrylate (IBMA)), and 0.1 parts by mass of cumene hydroperoxide.
  • MMA methyl methacrylate
  • IBMA isobornyl methacrylate
  • cumene hydroperoxide 0.1 parts by mass of cumene hydroperoxide.
  • the radically polymerizable compound was graft-polymerized on the surface of the polybutadiene rubber particles.
  • the reaction is terminated by further stirring for 2 hours, and an aqueous dispersion of core-shell type rubber particles D-1 having a polybutadiene rubber as a core and a copolymer of MMA and IBMA as a shell is prepared. Obtained.
  • the aqueous dispersion of core-shell type rubber particles obtained in the above procedure was put into 450 parts by mass of acetone and mixed uniformly. Substitution with acetone was carried out using a centrifuge to obtain an acetone dispersion of core-shell type rubber particles D-1.
  • the average particle size of the core-shell type rubber particles D-1 measured by the dynamic light scattering method was 0.25 ⁇ m.
  • ⁇ Manufacturing of acetone dispersion of rubber particles D-2> A core-shell type rubber particle by mixing 20 parts by mass of rubber particles D-2 (Kaneace M-511 (manufactured by Kaneka Co., Ltd.)) and 80 parts by mass of acetone and dispersing them using an ultrasonic homogenizer until they become primary particles. An acetone dispersion of D-2 was obtained. The average particle size of the core-shell type rubber particles D-2 measured by the dynamic light scattering method was 0.23 ⁇ m.
  • E-1 Photoradical generator; "Irgacure819” (manufactured by BASF) [Other components (polyfunctional radical polymerizable compound) (F)]
  • F-1 Polycarbonate diol diacrylate "UM-90 (1/3) DM" (molecular weight: about 900, radically polymerizable functional group equivalent: about 450 g / eq, manufactured by Ube Kosan Co., Ltd.)
  • F-2 Ethoxylated isocyanuric acid triacrylate "A-9300” (molecular weight: 423, radically polymerizable functional group equivalent: 141 g / eq, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
  • 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 twice for 180 seconds with an ultraviolet irradiator (manufactured by HOYA CANDEO OPTRONICS, trade name "LIGHT SOURCE EXECURE 3000"). .. The obtained cured product was placed in a heating oven at 70 ° C. and heat-treated 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.
  • Tg Glass transition temperature (Tg) of polymer of monofunctional radically polymerizable compound
  • the Tg of the polymer of the monofunctional radically polymerizable compound is calculated by using the above-mentioned FOX formula for the polymer of the generally known monofunctional radically polymerizable compound, and the viscoelasticity measuring device (Physica MCR302, Anton) otherwise. Measured by Pearl Co., Ltd.).
  • Table 1 shows the case where the Tg of the polymer of the monofunctional radically polymerizable compound is 85 ° C. or higher as ⁇ , and the case where the temperature is lower than 85 ° C. is x.
  • Viscosity of curable resin composition The viscosity of the curable resin composition was measured by a rotary rheometer method. Specifically, it was measured as follows using a viscoelasticity measuring device (Physica MCR302, manufactured by Anton Pearl Co., Ltd.). A measuring device equipped with a cone plate type measuring jig (CP25-2, manufactured by Anton Pearl Co., Ltd .; 25 mm diameter, 2 °) is filled with about 0.5 mL of a sample and adjusted to 25 ° C. It was measured at a data interval of 6 seconds under a constant shear rate condition of 50s -1 , and the value at 120 seconds was taken as the viscosity. The viscosity was evaluated according to the following criteria. A (very good): viscosity less than 2.0 Pa ⁇ s B (good): viscosity 2.0 Pa ⁇ s or more and less than 5.0 Pa ⁇ s C (bad): viscosity 5.0 Pa ⁇ s or more
  • the curable resin compositions prepared in Examples 1 to 13 had a viscosity in a range suitable as a modeling material used in the stereolithography method.
  • the obtained cured product was excellent in impact resistance and heat resistance, had a low water absorption rate, and was also excellent in water resistance.
  • the cured product according to Comparative Example 1 obtained from the curable resin composition not containing the hydrophobic monofunctional radical polymerizable (C) had a high water absorption rate and was at a level that caused a problem in practical use.
  • the cured product according to Comparative Example 3 obtained from the curable resin composition having a low content of the rubber particles (D) of 5 parts by mass did not sufficiently improve the impact resistance.
  • the cured product according to Comparative Example 4 obtained from a curable resin composition in which the glass transition temperature of the polymer of the monofunctional radical polymerizable compound was as low as less than 85 ° C. was not sufficient in heat resistance.
  • the cured product according to Comparative Example 5 obtained from a curable resin composition having a polyfunctional radical polymerizable compound having a radically polymerizable functional group equivalent of less than 300 g / eq and a large content of 25 parts by mass is resistant to the cured product. The improvement in impact resistance was not sufficient.
  • the cured product according to Comparative Example 6 obtained from a curable resin composition having a radically polymerizable functional group equivalent of 300 g / eq or more and a content of a polyfunctional radically polymerizable compound as high as 50 parts by mass is The heat resistance was not sufficient.
  • a curable resin composition having a viscosity suitable for a stereolithography method, and curing having good impact resistance, low water absorption rate, and heat resistance by curing the composition. It was confirmed that the product could be obtained.

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US12221505B2 (en) 2019-05-24 2025-02-11 Canon Kabushiki Kaisha Curable resin composition and cured object thereof
US12441876B2 (en) 2019-05-24 2025-10-14 Canon Kabushiki Kaisha Curable resin composition and cured product thereof, and method for producing three-dimensional shaped product

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