WO2014196536A1 - Composition de résine durcissable et article profilé tridimensionnel - Google Patents

Composition de résine durcissable et article profilé tridimensionnel Download PDF

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WO2014196536A1
WO2014196536A1 PCT/JP2014/064758 JP2014064758W WO2014196536A1 WO 2014196536 A1 WO2014196536 A1 WO 2014196536A1 JP 2014064758 W JP2014064758 W JP 2014064758W WO 2014196536 A1 WO2014196536 A1 WO 2014196536A1
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resin composition
curable resin
colorant
mass
compound
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Japanese (ja)
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千晴 本間
信夫 大金
栄治 中本
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CMET Inc
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CMET Inc
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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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a curable resin composition that is cured by irradiation with an active energy ray such as light, and a three-dimensionally shaped article that is manufactured using the curable resin composition.
  • a three-dimensional molded item having a high yellowness tends to be unfavorable by users. For this reason, recently, it has been required to provide a three-dimensional structure with high transparency and low yellowness.
  • the dye compound does not fade during radiation exposure, but does not mention fading of the curable resin composition during storage. If a three-dimensional molded article is manufactured using the curable resin composition in which fading has progressed, the yellowness of the resulting three-dimensional molded article increases.
  • An object of the present invention is to provide a three-dimensional structure having low yellowness and high transparency, and a curable resin having low storage fading for forming such a three-dimensional structure.
  • a curable resin composition that cures when irradiated with active energy rays.
  • the curable resin composition includes a polymerizable compound, a polymerization initiator that initiates a polymerization reaction of the polymerizable compound when irradiated with the active energy ray, and a purple or blue colorant having a p-toluidine structure. And containing.
  • a three-dimensionally shaped object cured by irradiating the curable resin composition with active energy rays contains a polymerizable compound, a polymerization initiator, and a purple or blue colorant having a p-toluidine structure.
  • the three-dimensional model has a total light transmittance of 60% or more in a test piece having a thickness of 10 mm, and a yellow index of 15 or less in accordance with JIS K-7373.
  • FIG. 1 The figure which shows the change of the light absorbency with respect to elapsed days about the unhardened curable resin composition of Examples 1-3 and the comparative example 1.
  • FIG. 2-5 The figure which shows the change of the light absorbency with respect to elapsed days about the uncured curable resin composition of Comparative Examples 2-5.
  • FIG. The figure which shows the yellowness and the transmittance
  • the curable resin composition is a modeling material that is cured by irradiation with active energy rays, and contains a polymerizable compound, a polymerization initiator, and a purple or blue colorant.
  • the polymerizable compound is composed of at least one of a cationic polymerizable compound and a radical polymerizable compound.
  • the polymerization initiator includes a cationic polymerization initiator.
  • the polymerizable compound includes a radical polymerizable compound
  • the polymerization initiator includes a radical polymerization initiator.
  • the polymerizable compound contains both a cationic polymerizable compound and a radical polymerizable compound, the shrinkage rate of the three-dimensional structure is lowered. Therefore, it is preferable because warpage and deformation of the three-dimensional structure are reduced and dimensional stability is excellent.
  • the active energy ray is an energy ray that can cure the curable resin composition, and is, for example, visible light, ultraviolet ray, electron beam, X-ray, radiation, high-frequency ray, or the like.
  • a dedicated modeling apparatus When manufacturing a three-dimensional molded article having a desired shape using the curable resin composition, a dedicated modeling apparatus is used.
  • the modeling apparatus is not particularly limited.
  • the modeling apparatus reads shape data from a three-dimensional CAD or a scanner, and converts the read shape data into cross-section data.
  • the modeling apparatus irradiates the curable resin composition with active energy rays based on the cross-sectional data to cure the curable resin composition, and obtains a cured layer corresponding to the cross-sectional shape.
  • a modeling apparatus manufactures a three-dimensional molded item by laminating
  • the cationically polymerizable compound may be an organic compound that causes at least one of a cationic polymerization reaction and a cationic crosslinking reaction to proceed when irradiated with active energy rays in the presence of a cationic polymerization initiator.
  • Representative examples include epoxy compounds, oxetane compounds, cyclic ether compounds other than oxetane, cyclic acetal compounds, cyclic lactone compounds, spiro orthoester compounds, vinyl ether compounds, and the like.
  • the cationically polymerizable compound may be composed of only one kind of compound or may be composed of a plurality of kinds of compounds. Moreover, it is preferable to contain an epoxy compound and an oxetane compound among each said compound.
  • an epoxy compound used as a cationically polymerizable compound an alicyclic epoxy compound, an aliphatic epoxy compound, an aromatic epoxy compound, etc. can be used, for example.
  • the alicyclic epoxy compound include polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring, a cyclohexene oxide structure-containing compound, or a cyclopentene oxide structure-containing compound.
  • the cyclohexene oxide structure-containing compound and the cyclopentene oxide structure-containing compound are obtained by epoxidizing a cyclohexene ring-containing compound and a cyclopentene ring-containing compound with an oxidizing agent, respectively.
  • Examples of the aliphatic epoxy compound used as the cationically polymerizable compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, glycidyl acrylate or glycidyl methacrylate. And a copolymer obtained by vinyl polymerization of at least one of glycidyl acrylate and glycidyl methacrylate and another vinyl monomer.
  • the aromatic epoxy compound examples include an aromatic compound having a phenolic hydroxyl group or a glycidyl ether of an alkylene oxide adduct thereof.
  • diglycidyl ethers of bisphenols such as bisphenol A, bisphenol E, bisphenol F, and bisphenol Z
  • glycidyl ethers obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenols and phenols or Glycidylated products of condensates of naphthols and aldehydes (phenolic resins, novolak resins, etc.), glycidylated products of the condensates of phenols or naphthols and xylylene glycol, and condensates of phenols and isopropenylacetophenone
  • a glycidyl compound which is a reaction product of phenols and dicyclopentadiene e.glycidyl compound which is a reaction product of phenols and dicycl
  • the cationic polymerizable compound one or more of such epoxy compounds can be used. Moreover, it is preferable that the polyepoxy compound which has a 2 or more epoxy group in 1 molecule contains 30 mass% or more with respect to the total mass of a cationically polymerizable compound.
  • oxetane compound one or more of various monooxetane compounds having one oxetane group in one molecule and various polyoxetane compounds having two or more oxetane groups in one molecule can be used.
  • a monooxetane monoalcohol compound having one oxetane group and one alcoholic hydroxyl group in one molecule is particularly preferably used.
  • a dioxetane compound having two oxetane groups is particularly preferably used.
  • the mass ratio of the monooxetane compound and the polyoxetane compound is preferably in the range of 5:95 to 95: 5.
  • the mass ratio is more preferably in the range of 10:90 to 90:10, and still more preferably in the range of 20:80 to 80:20.
  • the curable resin composition contains an oxetane compound in a proportion of 1% by mass to 35% by mass with respect to the total mass of the cationic polymerizable compound from the viewpoint of photocuring performance and improvement of molding property by reducing viscosity. It is preferable to contain in the ratio of 5 mass% or more and 20 mass% or less.
  • diglycidyl ether of alkylene diol having 4 to 10 carbon atoms can be used.
  • examples of the diglycidyl ether of alkylene diol having 4 to 10 carbon atoms include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, pentanediol diglycidyl ether, hexanediol diglycidyl ether, heptanediol diglycidyl.
  • Examples include ether, octanediol diglycidyl ether, nonanediol diglycidyl ether, and decanediol diglycidyl ether.
  • 1,6-hexanediol diglycidyl ether is preferable from the viewpoint of curing performance.
  • the radical polymerizable compound may be a compound that allows a reaction such as radical polymerization to proceed when irradiated with active energy rays in the presence of a radical polymerization initiator.
  • Representative examples include compounds having a (meth) acrylate group, unsaturated polyester compounds, allyl urethane compounds, polythiol compounds, and the like.
  • the radical polymerizable compound may be composed of only one type of compound or may be composed of a plurality of types of compounds. Among the above compounds, it is preferable to contain a compound having at least one (meth) acryloyloxy group in one molecule.
  • Such compounds include reaction products of epoxy compounds and (meth) acrylic acid, (meth) acrylic esters of alcohols, urethane (meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates. Etc. can be used.
  • the curable resin composition contains a polyalkylene glycol di (meth) acrylate such as polytetramethylene glycol di (meth) acrylate as at least a part of the radical polymerizable compound, and the proportion of the total amount of the radical polymerizable compound. It is preferable to set it as 1 to 40 mass% with respect to mass.
  • the ratio of the polyalkylene glycol di (meth) acrylate is in the above range, the toughness of the three-dimensional structure is increased.
  • the ratio of the polyalkylene glycol di (meth) acrylate is 5% by mass or more and 20% by mass or less, the toughness of the three-dimensional model can be further increased.
  • the polyalkylene glycol di (meth) acrylate preferably has a number average molecular weight of 300 to 1500, more preferably 600 to 900. Specific examples include polytetramethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate.
  • polytetramethylene glycol di (meth) acrylate polypropylene glycol di (meth) acrylate
  • polyethylene glycol di (meth) acrylate polyethylene glycol di (meth) acrylate.
  • cationic polymerization initiator any polymerization initiator capable of initiating cationic polymerization of the cationic polymerizable compound when irradiated with active energy rays can be used.
  • an onium salt that releases a Lewis acid when irradiated with active energy rays is preferably used as the cationic polymerization initiator.
  • onium salts include aromatic sulfonium salts of Group VIIa elements, aromatic onium salts of Group VIa elements, aromatic onium salts of Group Va elements, and the like.
  • triarylsulfonium hexafluoroantimonate triphenylphenacylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexa Fluoroantimonate, bis- [4- (di4'-hydroxyethoxyphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexafluorophos Fate, diphenyliodonium tetrafluoroborate and the like.
  • One or more of the cationic polymerization initiators as described above can be used. Of these, aromatic sulfonium salts are more preferably used. Further, for the purpose of improving the reaction rate, a photosensitizer such as benzophenone, alkoxyanthracene, dialkoxyanthracene, thioxanthone and the like may be used together with the cationic polymerization initiator as necessary.
  • the curable resin composition preferably contains an aromatic thiol compound represented by the following structural formula (1) together with the aromatic sulfonium compound.
  • R 1 in the structural formula (1) include monovalent aromatic groups such as a phenyl group, a naphthyl group, an anthracenyl group, an indenyl group, and a tolyl group. These aromatic groups may not be substituted, but when they have a substituent, examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and a hydroxyl group.
  • aromatic thiol compound examples include benzene thiol, naphthalene thiol such as 1-naphthalene thiol and 2-naphthalene thiol, anthracene thiol, toluene thiol, and xylene thiol.
  • the content of the aromatic thiol compound is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.2% by mass or more and 2% by mass or less with respect to the total mass of the aromatic sulfonium compound.
  • the content of the aromatic thiol compound is less than the above range, the yellowness increases, and when it exceeds the above range, the photocurability tends to decrease.
  • the radical polymerization initiator may be any polymerization initiator that can initiate a radical polymerization reaction of a radical polymerizable compound when irradiated with active energy rays. Examples include benzyl or its dialkyl acetal compound, phenyl ketone compound, acetophenone compound, benzoin or its alkyl ether compound, benzophenone compound, thioxanthone compound, and the like.
  • examples of benzyl or a dialkyl acetal compound thereof include benzyl dimethyl ketal and benzyl- ⁇ -methoxyethyl acetal.
  • examples of the phenyl ketone compound include 1-hydroxy-cyclohexyl phenyl ketone.
  • acetophenone compounds include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 2-hydroxy-2-methyl- Examples thereof include propiophenone, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone.
  • 1-hydroxy-cyclohexyl phenyl ketone is preferable in that the yellowness of the shaped product is small.
  • benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, benzoin isobutyl ether, and the like.
  • benzophenone compounds examples include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, and the like.
  • thioxanthone compound examples include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and the like.
  • the curable resin composition comprises a cationic polymerizable compound and a radical polymerizable compound such that the mass ratio of the cationic polymerizable compound and the radical polymerizable compound is in the range of 30:70 to 90:10 (cationic polymerizable compound: radical polymerizable compound). It is preferable to contain a radically polymerizable compound. When the said mass ratio exists in this range, photocurability, modeling speed, and the dimensional stability of a molded article can be improved. Further, the mass ratio is preferably in the range of 50:50 to 90:10, and particularly preferably in the range of 60:40 to 90:10.
  • the curable resin composition further contains a radical polymerization initiator in a proportion of 0.1% by mass to 10% by mass and 1% by mass to 5% by mass with respect to the mass of the radical polymerizable compound. preferable.
  • the curable resin composition may contain a polyalkylene ether compound.
  • the polyalkylene ether compound include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polyethylene oxide-polypropylene oxide block copolymer.
  • Another example is a polyether having an oxytetramethylene unit having an alkyl substituent represented by (—CH 2 CH 2 CH (R 2 ) CH 2 O—) bonded thereto. “R 2 ” is a lower alkyl group.
  • Other examples include polyethers in which oxytetramethylene units are randomly bonded.
  • the content of the polyalkylene ether compound is 0.5% by mass to 30% by mass with respect to the total mass of the curable resin composition. It is preferable that it is 1 mass% or more and 20 mass% or less, and it is especially preferable that it is 1 mass% or more and 15 mass% or less.
  • the curable resin composition may contain one or more kinds of alkylene diols having 4 to 10 carbon atoms.
  • alkylene diol having 4 to 10 carbon atoms include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol. Of these, 1,6-hexanediol is preferred from the viewpoint of photocuring performance.
  • the curable resin composition when the curable resin composition contains an alkylene diol, the curable resin composition preferably contains the alkylene diol in a proportion of 0.3% by mass to 10% by mass with respect to the total mass. More preferably, it is contained in a proportion of 5% by mass or more and 5% by mass or less.
  • the proportion of the alkylene diol is in the above range, the toughness of the three-dimensional structure is improved. Moreover, since the viscosity of the curable resin composition is lowered, the moldability is improved.
  • the colorant is a purple or blue colorant.
  • “purple or blue” is a color including reddish purple, purple, blue, green blue, and blue green, and at least when the colorant is added to the curable resin composition, the curable resin composition is It exhibits a purple to blue color.
  • the colorant and the curable resin composition to which the colorant is added absorb light having a wavelength included in the wavelength region of 500 to 750 nm.
  • the inventor conducted a storage stability (fading) screening test by adding various colorants to the curable resin composition, and as a result, the colorant having a p-toluidine structure represented by the following structural formula (2) Has been found to have excellent storage stability.
  • Conventional colorants such as crystal violet have a great fading. Therefore, in order to continuously reduce the yellowness of the three-dimensional structure, measures such as adding a colorant when the uncured curable resin composition fades are necessary. That is, the measure of adding a colorant corresponding to the fading of each of the resin composition in the resin tank in the modeling apparatus and the resin composition to be replenished after modeling requires complicated and inefficient work.
  • the color fading of the colorant having a p-toluidine structure is small.
  • anthraquinone colorant or the like as a colorant having a p-toluidine structure because the color and transparency of the three-dimensional structure are excellent and its fading property is low.
  • An anthraquinone colorant having a p-toluidine structure has an anthraquinone ring represented by the following structural formula (3).
  • anthraquinone colorant having a p-toluidine structure examples include quinizarin blue represented by the following structural formula (4A), sudan blue represented by the structural formula (4B), and acid represented by the structural formula (4C).
  • Examples thereof include violet 34, quinizarin green SS represented by the structural formula (4D), toluidine blue (CAS number 3209-30-1) represented by the structural formula (4E), and the like.
  • the content of the colorant can be appropriately changed depending on the type of the colorant, the polymerizable compound, the polymerization initiator, and the composition thereof, and is 0.01 ppm or more and 10 ppm or less with respect to the total mass of the curable resin composition. Is preferred.
  • the content of the colorant exceeds 10 ppm, the color of the colorant itself is noticeable in many colorants, and the light transmittance of the three-dimensional structure decreases to an unfavorable appearance.
  • the content of the colorant is less than 0.01 ppm, the yellow color of the three-dimensional structure is noticeable according to the yellowness.
  • the content of the colorant is more preferably from 0.1 ppm to 7 ppm, and further preferably from 0.2 ppm to 2 ppm.
  • the yellowness can be further reduced, and the transmittance of a sample having a thickness of 10 mm obtained by curing the curable resin composition can be 60% or more.
  • the light transmittance of the whole three-dimensional object varies, but when the total light transmittance of a sample with a thickness of 10 mm is 60% or more, it has high transparency and has an internal shape. Can be obtained.
  • the manufacturing method of the three-dimensional model will be described together with the action of the colorant.
  • a known method and a modeling apparatus such as a 3D printer can be used for manufacturing the three-dimensional model.
  • the curable resin composition in a liquid state is selectively irradiated with ultraviolet rays that are active energy rays to produce a cured layer based on the cross-sectional shape.
  • an uncured curable resin composition is supplied to the cured layer, and ultraviolet rays are selectively irradiated based on the cross-sectional data to newly form a cured layer continuous with the cured layer.
  • the active energy ray include the energy rays described above, and ultraviolet rays having a wavelength of 300 to 400 nm are particularly preferable.
  • This curable resin composition is used as a modeling material in the three-dimensional modeling field.
  • a shape confirmation model for verifying the appearance design in the preliminary stage
  • a test model for confirming the functionality of parts
  • a master model for producing molds and molds
  • a direct mold for prototype molds etc.
  • the three-dimensional model contains a blue or purple colorant, and the colorant has only low fading. Therefore, the content of the colorant is small, the yellowness of the three-dimensional structure is low, and the transparency is high.
  • the concentration of purple or blue varies depending on the colorant
  • the total light transmittance of a test piece having a thickness of 10 mm is 60% or more while satisfying the above-mentioned range, and the yellow index according to JIS K-7373 is 15 or less. If the content rate of a coloring agent is adjusted so that it may become, while improving the transparency of a three-dimensional molded item, yellowness can be reduced. For this reason, the beauty
  • the three-dimensional model has high transparency, for example, the internal shape of the three-dimensional model can be easily confirmed.
  • the advantages listed below can be obtained. (1) Since the curable resin composition containing a polymerizable compound and a polymerization initiator contains a purple or blue colorant, the yellow degree exhibited by the polymerizable compound and the polymerization initiator can be reduced. Since the colorant has a p-toluidine structure, it has only a low color fading when contained in the curable resin composition. Therefore, even when the content of the colorant in the curable resin composition is reduced to keep the yellowness of the curable resin composition low, the curable resin composition can be used for a long period of time. Therefore, a three-dimensional molded item having high transparency can be continuously obtained from the curable resin composition.
  • the concentration of the colorant is in the range of 0.01 ppm or more and 10 ppm or less with respect to the total mass of the curable resin composition, the yellow color of the three-dimensional structure using the curable resin composition is increased. The degree can be reduced.
  • the colorant contains at least one of anthraquinone colorants. For this reason, while reducing the yellowness of a three-dimensional molded item, the state in which the yellowness fell can be maintained.
  • the spectral transmittance obtained in this way is numerically calculated by the method defined in JIS-K7373 using the software (UV Solutions) attached to the spectrophotometer, so that the conditions for the auxiliary illuminant C and the field of view of 2 degrees are obtained. Calculated as yellowness.
  • Example 1 6.5 parts by mass of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“Cel-2021P” manufactured by Daicel Corporation), hydrogenated bisphenol A diglycidyl ether (manufactured by Shin Nippon Rika Co., Ltd.
  • Example 2 The polymerizable compound, cationic polymerization initiator and radical polymerization initiator are the same as in Example 1.
  • a colorant 1 ppm of Sudan Blue (manufactured by Tokyo Chemical Industry) was added instead of quinizarin blue.
  • An 80 ° C. accelerated test was conducted in the same manner as in Example 1, and the absorbance at 638 nm was measured over time. As shown in FIG. 1, the absorbance immediately after preparation was 0.045, and the absorbance after 70 days was 0.038.
  • Example 3 The polymerizable compound, cationic polymerization initiator and radical polymerization initiator are the same as in Example 1.
  • a coloring agent 2.4 ppm of Acid Violet 34 (manufactured by Tokyo Chemical Industry) was added instead of quinizarin blue.
  • An 80 ° C. accelerated test was conducted in the same manner as in Example 1, and the absorbance at 566 nm was measured over time. As shown in FIG. 1, the absorbance immediately after preparation was 0.041, and the absorbance after 14 days was 0.038.
  • Example 4 The polymerizable compound, cationic polymerization initiator and radical polymerization initiator are the same as in Example 1.
  • a colorant 1 ppm of quinizarin green SS (manufactured by Tokyo Chemical Industry) was added instead of quinizarin blue.
  • An 80 ° C. accelerated test was conducted in the same manner as in Example 1, and the absorbance at 638 nm was measured over time. The absorbance immediately after preparation was 0.045, and the absorbance after 28 days was 0.044.
  • Example 1 The polymerizable compound, cationic polymerization initiator and radical polymerization initiator are the same as in Example 1. Instead of quinizarin blue, 0.85 ppm of Disperse Blue 14 (manufactured by Tokyo Chemical Industry) was added as a colorant. An 80 ° C. accelerated test was conducted in the same manner as in Example 1, and the absorbance at 643 nm was measured over time. As shown in FIG. 1, the absorbance immediately after preparation was 0.047, and the absorbance after 60 days was 0.010. As shown in the following structural formula (5), Disperse Blue 14 is a colorant having an anthraquinone structure, not a colorant having a p-toluidine structure. The content of Disperse Blue 14 was set to 0.85 ppm so that the absorbance at a wavelength of 643 nm immediately after the preparation of the curable resin composition was the same as that in Example 1.
  • Example 2 The polymerizable compound, cationic polymerization initiator and radical polymerization initiator are the same as in Example 1.
  • a colorant 0.21 ppm of crystal violet (manufactured by Tokyo Chemical Industry) was added instead of quinizarin blue.
  • the absorbance at 590 nm was 0.041
  • the absorbance after 28 days at room temperature was 0.022
  • fading was observed.
  • 0.5 ppm of crystal violet was added, an 80 ° C. accelerated test was conducted in the same manner as in Example 1, and the absorbance at 590 nm was measured over time. As shown in FIG. 2, the absorbance immediately after preparation was 0.071, and the absorbance after 4 days was 0.006.
  • Example 3 The polymerizable compound, cationic polymerization initiator and radical polymerization initiator are the same as in Example 1. Instead of quinizarin blue, 0.5 ppm of ethyl violet (manufactured by Tokyo Kasei) was added as a colorant. An 80 ° C. accelerated test was conducted in the same manner as in Example 1, and the absorbance at 596 nm was measured over time. As shown in FIG. 2, the absorbance immediately after preparation was 0.113, and the absorbance after 33 days was 0.010.
  • Example 4 The polymerizable compound, cationic polymerization initiator and radical polymerization initiator are the same as in Example 1. Instead of quinizarin blue, 0.5 ppm of basic blue 7 (manufactured by Tokyo Kasei) was added as a colorant. An 80 ° C. accelerated test was conducted in the same manner as in Example 1, and the absorbance at 615 nm was measured over time. As shown in FIG. 2, the absorbance immediately after preparation was 0.081, and the absorbance after 81 days was 0.014.
  • Example 5 The polymerizable compound, cationic polymerization initiator and radical polymerization initiator are the same as in Example 1. Instead of quinizarin blue, 10 ppm of quinacridone (manufactured by Tokyo Chemical Industry) was added as a colorant. An 80 ° C. accelerated test was conducted in the same manner as in Example 1, and the absorbance at 580 nm was measured over time. As shown in FIG. 2, the absorbance immediately after preparation was 0.059, and the absorbance after 5 days was 0.038.
  • Example 5 As a polymerizable compound, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, Cel-2021P) 5.0 parts by mass, hydrogenated bisphenol A diglycidyl ether (Nippon Riken) Co., Ltd., HBE-100) 58 parts by mass, 3-ethyl-3-hydroxymethyloxetane (Toagosei Co., Ltd., OXT101) 4.5 parts by mass, bis (3-ethyl-3-oxetanylmethyl) ether (Toago Synthetic Co., Ltd., OXT221) 12.5 parts by mass, dipentaerythritol polyacrylate (Shin Nakamura Chemical Co., Ltd., A-9550W) 10 parts by mass, polytetramethylene ether glycol (Hodogaya Chemical Co., Ltd., PTG-) 850SN,
  • cationic polymerization initiator As a cationic polymerization initiator, 4.0 parts by mass of “CPI-200K” manufactured by Sun Apro Co., Ltd. and 2.0 parts by mass of 1-hydroxy-cyclohexyl phenyl ketone (manufactured by BASF, Irgacure-184) as a radical polymerization initiator. was used.
  • cationic polymerization initiator radical polymerization initiator quinizarin blue (manufactured by Tokyo Chemical Industry Co., Ltd.) as a colorant is 1 ppm, 1.5 ppm, 3 ppm, 5 ppm, respectively, based on the total mass of the curable resin composition.
  • Each curable resin composition added with 6 ppm and 7 ppm was prepared.
  • a three-dimensional modeled object was prepared using an ultrahigh-speed optical modeling system (manufactured by Nabtesco, SOLIFORM 250).
  • light from a semiconductor laser (Spectra Physics, rated output 400 mW, wavelength 355 nm) was irradiated to the curable resin composition under the condition of a liquid surface irradiation energy of 100 mJ / cm 2 , 20 mm long, 45 mm wide.
  • a test piece having a thickness of 10 mm was formed.
  • the slice pitch was 0.1 mm, and the average modeling time per layer was 2 minutes.
  • Example 6 As a polymerizable compound, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, Cel-2021P) 5.0 parts by mass, hydrogenated bisphenol A diglycidyl ether (Nippon Riken) Co., Ltd., HBE-100) 55 parts by mass, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd., OXT101), 10 parts by mass, tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 15 parts by mass of A-DCP), 2.0 parts by mass of dipentaerythritol polyacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-9550W), polytetramethylene glycol diacrylate (number average molecular weight 650)
  • a cationic polymerization initiator As a cationic polymerization initiator, 4.0 parts by mass of “CPI-200K” manufactured by Sun Apro Co., Ltd. and 2.0 parts by mass of 1-hydroxy-cyclohexyl phenyl ketone (manufactured by BASF, Irgacure-184) as a radical polymerization initiator. was used.
  • curable resins containing 1 ppm and 1.5 ppm of quinizarin blue (manufactured by Tokyo Chemical Industry) as a colorant with respect to the total mass of the curable resin composition.
  • a composition was prepared. Using these curable resin compositions, test pieces having a length of 20 mm, a width of 45 mm, and a thickness of 10 mm were formed in the same manner as in Example 5.
  • a curve L1 represents the result for the test piece of Example 5.
  • curve L3 shows the results for the test piece of Example 6.
  • the vertical axis on the left side of each graph indicates the yellow index (YI)
  • the vertical axis on the right side indicates the total light transmittance (%)
  • the horizontal axis indicates the content (ppm) of quinizarin blue.
  • the yellow index having a content rate of “0” is based on a test piece obtained by curing a curable resin composition containing no colorant.
  • the yellow index of the curable resin composition in Example 5 is about 13 in the state which does not contain a coloring agent, and the curable resin composition in Example 5 has a relatively high yellowness.
  • the yellow index of the curable resin composition in Example 6 is about 6 in the state containing no colorant, and the curable resin composition in Example 6 has a relatively low yellowness.
  • the yellow index reaches around “0”.
  • the total light transmittance decreases as the content of quinizarin blue increases.
  • the transmittance is 60% or more.
  • the yellow index reaches around “0”.
  • the transmittance exceeds 80%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur une composition de résine durcissable qui est durcie par exposition à des rayons d'énergie d'activation. La composition de résine durcissable contient un composé polymérisable, un initiateur de polymérisation et un agent colorant. L'initiateur de polymérisation, par exposition à des rayons d'énergie d'activation, amorce la réaction de polymérisation du composé polymérisable. L'agent colorant est un agent colorant mauve ou bleu ayant une structure de p-toluidine.
PCT/JP2014/064758 2013-06-04 2014-06-03 Composition de résine durcissable et article profilé tridimensionnel Ceased WO2014196536A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016188308A (ja) * 2015-03-30 2016-11-04 シーメット株式会社 光学的立体造形用樹脂組成物

Families Citing this family (1)

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JP2019099666A (ja) * 2017-12-01 2019-06-24 サンアプロ株式会社 光学的立体造形用樹脂組成物

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6199157A (ja) * 1984-10-22 1986-05-17 Canon Inc 静電荷像現像用部材
JPS6254276A (ja) * 1985-05-28 1987-03-09 Canon Inc 正荷電性トナー及び画像形成方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62229127A (ja) * 1985-12-09 1987-10-07 Nippon Paint Co Ltd 感光性樹脂版材
JP4010637B2 (ja) * 1998-03-17 2007-11-21 株式会社リコー 孔版印刷方法
EP1965919A2 (fr) * 2005-11-11 2008-09-10 Molecular Vision Limited Dispositif microfluidique
JP5507256B2 (ja) * 2006-12-13 2014-05-28 スリーエム イノベイティブ プロパティズ カンパニー 酸性成分及び光退色性染料を有する歯科用組成物の使用方法
JP2014038180A (ja) * 2012-08-15 2014-02-27 Konica Minolta Inc 光学フィルム、光学フィルムの製造方法、偏光板及び液晶表示装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6199157A (ja) * 1984-10-22 1986-05-17 Canon Inc 静電荷像現像用部材
JPS6254276A (ja) * 1985-05-28 1987-03-09 Canon Inc 正荷電性トナー及び画像形成方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016188308A (ja) * 2015-03-30 2016-11-04 シーメット株式会社 光学的立体造形用樹脂組成物

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