WO2014196536A1

WO2014196536A1 - Curing resin composition and three-dimensional formed article

Info

Publication number: WO2014196536A1
Application number: PCT/JP2014/064758
Authority: WO
Inventors: 千晴本間; 信夫大金; 栄治中本
Original assignee: シーメット株式会社
Priority date: 2013-06-04
Filing date: 2014-06-03
Publication date: 2014-12-11
Also published as: JP2014234478A; JP6161961B2

Abstract

This curing resin composition is cured through irradiation with rays of activation energy. The curing resin composition contains a polymerizable compound, a polymerization initiator, and a coloring agent. The polymerization initiator, through irradiation with rays of activation energy, initiates a polymerization reaction of the polymerizable compound. The coloring agent is a purple or blue coloring agent having a p-toluidine structure.

Description

Curable resin composition and three-dimensional model

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.

Conventionally, a method for producing a three-dimensional model from the curable resin composition has been proposed by irradiating the curable resin composition with an active energy ray such as ultraviolet rays to cure the curable resin composition. .

Many of the three-dimensional shaped objects have a pale yellow color in a state where no colorant is contained. 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.

There has been proposed a method of changing the hue of a three-dimensional structure by adding a colorant such as a diarylmethane dye to the curable resin composition (see Patent Document 1).

JP-T-2007-501318

The document describes that 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.

In one embodiment of the present invention, a curable resin composition that cures when irradiated with active energy rays is provided. 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.

In another aspect, a three-dimensionally shaped object cured by irradiating the curable resin composition with active energy rays is provided. The curable resin composition 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.

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. 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. The figure which shows the yellowness and the transmittance | permeability with respect to a coloring agent density | concentration about the hardened | cured material using the curable resin composition of Example 5. FIG. The figure which shows the yellowness and the transmittance | permeability with respect to a coloring agent density | concentration about the hardened | cured material using the curable resin composition of Example 6. FIG.

Hereinafter, one embodiment of a three-dimensional model manufactured using a curable resin composition and the composition concerned is described.
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. When the polymerizable compound includes a cationic polymerizable compound, the polymerization initiator includes a cationic polymerization initiator. When the polymerizable compound includes a radical polymerizable compound, the polymerization initiator includes a radical polymerization initiator. When 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.

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. For example, 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 | stacking this hardening layer.

(Cationically polymerizable compound)
Next, the cationic polymerizable compound will be described. 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.

As 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.
Examples of 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.

Examples of the aromatic epoxy compound include an aromatic compound having a phenolic hydroxyl group or a glycidyl ether of an alkylene oxide adduct thereof. Specifically, for example, 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 And a glycidyl compound which is a reaction product of phenols and dicyclopentadiene.

As 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.

As the 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.

As the monooxetane compound, a monooxetane monoalcohol compound having one oxetane group and one alcoholic hydroxyl group in one molecule is particularly preferably used.
As the polyoxetane compound, a dioxetane compound having two oxetane groups is particularly preferably used.

In particular, the mass ratio of the monooxetane compound and the polyoxetane compound is preferably in the range of 5:95 to 95: 5. When the mass ratio is within this range, the moisture absorption rate of the curable resin composition in a high humidity state is reduced. Therefore, the curing sensitivity of the curable resin composition can be maintained, and the toughness of the model can be increased. 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.

In addition, 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.

As the cationically polymerizable compound, 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. Among these, 1,6-hexanediol diglycidyl ether is preferable from the viewpoint of curing performance.

(Radically polymerizable compound)
Next, the radical polymerizable compound will be described. The radically 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. Specific examples of 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. When the ratio of the polyalkylene glycol di (meth) acrylate is in the above range, the toughness of the three-dimensional structure is increased. When 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. However, when there is too much content of polyalkylene glycol di (meth) acrylate, the heat distortion temperature of a three-dimensional molded item will become low, and heat resistance will fall.

(Cationic polymerization initiator)
As the 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. Among them, as the cationic polymerization initiator, an onium salt that releases a Lewis acid when irradiated with active energy rays is preferably used. Examples of such 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. Specifically, for example, 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. By three-dimensionally modeling using a curable resin composition containing an aromatic thiol compound, a three-dimensional composition having a low yellowness and being colorless and transparent or having a color tone and appearance close to it can be obtained.

Specific examples of 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. Specific examples of the aromatic thiol compound 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. When 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.

(Radical polymerization initiator)
Next, the radical polymerization initiator will be described. 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.

Specifically, examples of benzyl or a dialkyl acetal compound thereof include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal. Examples of the phenyl ketone compound include 1-hydroxy-cyclohexyl phenyl ketone. Examples of 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. In particular, 1-hydroxy-cyclohexyl phenyl ketone is preferable in that the yellowness of the shaped product is small.

Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, benzoin isobutyl ether, and the like.

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, and the like.

Examples of the thioxanthone compound 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.

(Additive)
Moreover, the curable resin composition may contain a polyalkylene ether compound. When the polyalkylene ether compound is contained, the toughness of the shaped article is improved. Preferable examples of 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.

When the curable resin composition contains a polyalkylene ether compound, 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.

Moreover, the curable resin composition may contain one or more kinds of alkylene diols having 4 to 10 carbon atoms. Examples of the 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.

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. When 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.

(Coloring agent)
Next, the colorant added to the curable resin composition will be described. The colorant is a purple or blue colorant. Note that “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. In other words, 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. Therefore, it is unnecessary to add a colorant additionally, and the initial content of the colorant in the curable resin composition can be reduced, and the small content can be continuously maintained. In particular, it is preferable to use an 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).

Specific examples of the anthraquinone colorant having a p-toluidine structure 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. When 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. When 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. Further, 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. When the content of the colorant is within these ranges, 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. Depending on the thickness and shape of the three-dimensional object to be formed, 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.

Next, 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. For example, based on the cross-sectional data described above, 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. Next, 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. By repeating this laminating operation, a three-dimensional model can be finally obtained. Examples of 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. For example, there are 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. Can be mentioned.

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. Although 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 | look about the color of a three-dimensional molded item can be improved. In addition, since the three-dimensional model has high transparency, for example, the internal shape of the three-dimensional model can be easily confirmed.

According to the embodiment, 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.

(2) Since 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.

(3) 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.

Next, the embodiment will be described more specifically with reference to examples and comparative examples. The present invention is not limited to these examples.
(A) Absorbance of curable resin composition:
Using an ultraviolet-visible spectrophotometer ("U-3900H" manufactured by Hitachi High-Technologies Corporation), put an uncured curable resin composition in a quartz cell, and determine the absorbance of the curable resin composition at a specified double beam wavelength. It was measured.

(B) Yellowness of the three-dimensional structure:
Optical three-dimensional modeled object obtained in Example 5 and Example 6 below (length × width × thickness = 45 mm × 20 mm × 10 mm cuboid) [ultraviolet light (high pressure mercury lamp) (wavelength 365 nm; intensity 3 mW / cm ² ) Is then cured for 20 minutes and then attached to an ultraviolet-visible spectrophotometer ("U-3900H" manufactured by Hitachi High-Technologies Corporation) equipped with an integrating sphere with a diameter of 60 mm, and the spectral transmittance at a thickness of 10 mm is measured. did. 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.

(C) Total light transmittance of the three-dimensional structure:
(B) For the same optical three-dimensional structure as in the yellowness measurement, the double-beam standard illuminant D65 spectral transmittance was measured using an ultraviolet-visible spectrophotometer ("U-3900H" manufactured by Hitachi High-Technologies Corporation). Asked.

(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. “ HBE-100 "), 30 parts by weight, aromatic triglycidyl ether compound [2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3 -Epoxypropoxy) phenyl] ethyl] phenyl] propane] ("VG3101L" manufactured by Printec Co., Ltd.) 30 parts by mass, 7.5 parts by mass of 3-ethyl-3-hydroxymethyloxetane ("OXT101" manufactured by Toagosei Co., Ltd.) Bis (3-ethyl-3-oxetanylmethyl) ether (“OXT221” manufactured by Toagosei Co., Ltd.) 1 5 parts by mass, 1,6-hexanediol diglycidyl ether (“EX-212” manufactured by Nagase ChemteX Corporation) 3 parts by mass, dipentaerythritol polyacrylate (“A-9550W” manufactured by Shin-Nakamura Chemical Co., Ltd.) 10 Part by mass, 8 parts by mass of lauryl acrylate (“NK Ester-LA” manufactured by Shin-Nakamura Chemical Co., Ltd.), polytetramethylene ether glycol (“PTG-850SN” manufactured by Hodogaya Chemical Co., Ltd., number average molecular weight 801 to 890) 1 0.5 part by mass, 0.8 part by mass of 1,6-hexanediol, “CPI-200K” manufactured by San Apro Co., Ltd. [cationic polymerization initiator solution containing a compound corresponding to an aromatic sulfonium compound at a concentration of 50% by mass] 3.5 parts by mass, 1-hydroxy-cyclohexyl phenyl ketone ("Iraki" manufactured by BASF A -184 "to prepare a radical polymerization initiator) 2.5 parts by mass of the curable resin composition of 2-naphthalene thiol 0.025 parts by mixed well. Further, 1 ppm of quinizarin blue (manufactured by Tokyo Chemical Industry Co., Ltd.) as a colorant was contained with respect to the total mass of the curable resin composition. The absorbance of the curable resin composition immediately after this preparation was 0.044 (wavelength 583 nm).

Furthermore, 20 ml of the curable resin composition to which this colorant was added was placed in a glass vial and subjected to an acceleration test using a heat oven at 80 ° C. (“MOV-112F” manufactured by SANYO). The absorbance at 583 nm was obtained over time. It was measured. As shown in FIG. 1, the absorbance after 70 days was 0.043.

(Example 2)
The polymerizable compound, cationic polymerization initiator and radical polymerization initiator are the same as in Example 1. As 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. As 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. As 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.

All of the colorants added in Examples 1 to 4 described above have a p-toluidine functional group in the anthraquinone skeleton. Immediately after the preparation, the decrease in absorbance in the 80 ° C. accelerated test from 14 to 70 days is 0.007 or less, and the fading is extremely low. From Arrhenius's law, it is presumed that it is more difficult to fade at room temperature, suggesting that it has storage stability as a colorant.

(Comparative 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.

(Comparative Example 2)
The polymerizable compound, cationic polymerization initiator and radical polymerization initiator are the same as in Example 1. As a colorant, 0.21 ppm of crystal violet (manufactured by Tokyo Chemical Industry) was added instead of quinizarin blue. Immediately after the preparation, the absorbance at 590 nm was 0.041, the absorbance after 28 days at room temperature was 0.022, and fading was observed. Further, 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.

(Comparative 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.

(Comparative 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.

(Comparative 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, number molecular weight 801-890) 4.0 parts by weight It had. 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. In addition to these polymerizable compounds, 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.

Furthermore, using each curable resin composition, a three-dimensional modeled object was prepared using an ultrahigh-speed optical modeling system (manufactured by Nabtesco, SOLIFORM 250). At this time, 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) (Shin-Nakamura Chemical Co., Ltd.) 10 parts by mass, manufactured by A-PTMG-65) It was. 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. In addition to these polymerizable compounds, cationic polymerization initiators and radical polymerization initiators, 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.

3, a curve L1 represents the result for the test piece of Example 5. In FIG. 4, 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 (%), and 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.

3 and 4, it can be seen that as the content of quinizarin blue increases, the yellow index decreases and the yellowness decreases as indicated by the curves L1 and L3. Moreover, as shown in FIG. 3, 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. Have. In this composition, when the content of quinizarin blue is increased to 7 ppm, the yellow index reaches around “0”. On the other hand, as shown in FIG. 4, 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. Have In this composition, when the content of quinizarin blue increases to about 1.5 ppm, the yellow index reaches around “0”.

Also, as shown by curves L2 and L4 in FIGS. 3 and 4, the total light transmittance decreases as the content of quinizarin blue increases. As shown in FIG. 3, when the content of quinizarin blue is 7 ppm or less, the transmittance is 60% or more. As described above, in Example 6, when the content of quinizarin blue increases to about 1.5 ppm, the yellow index reaches around “0”. As shown in FIG. 4, in Example 6, even if the content of quinizarin blue is 1.5 ppm, the transmittance exceeds 80%.

Claims

A curable resin composition that cures when irradiated with active energy rays,
A polymerizable compound;
A polymerization initiator that initiates a polymerization reaction of the polymerizable compound by being irradiated with the active energy ray;
A curable resin composition comprising a purple or blue colorant having a p-toluidine structure.
The curable resin composition according to claim 1, wherein the content of the colorant is in the range of 0.01 ppm to 10 ppm with respect to the total mass of the uncured curable resin composition.
The curable resin composition according to claim 1 or 2, wherein the colorant contains an anthraquinone colorant.
The curable resin composition according to claim 3, wherein the anthraquinone colorant contains at least one of quinizarin blue, sudan blue, acid violet 34, quinizarin green SS, and toluidine blue.
A three-dimensional structure cured by irradiating an active energy ray to a curable resin composition containing a polymerizable compound, a polymerization initiator, and a purple or blue colorant having a p-toluidine structure, A three-dimensional structure having 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.