JP2020044778A - Molding material, molded article, three-dimensional molding apparatus, and method for producing three-dimensional molded article - Google Patents

Abstract

To provide a molding material which forms a soft part and is capable of suppressing the occurrence of separation at an interface between the soft part and a hard part.SOLUTION: The molding material for forming a molded article having a tensile elongation at break of 250% or more and 500% or less and a tensile strength at break of 0.01 MPa or more and 1 MPa or less contains a monomer and an oligomer. The total content of the monomer and the oligomer is 90 mass% or more and 97 mass% or less based on the total mass of the molding material. The ratio of (the content of the monomer)/(the content of the monomer and the content of the oligomer) is 0.75 or more and 0.95 or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a molding material, a molded object, a three-dimensional molding device, and a method of manufacturing a three-dimensional molded object.

  The three-dimensional printing apparatus is also called a 3D printer. As a three-dimensional modeling device, for example, a three-dimensional modeling material (hereinafter, also simply referred to as “molding material”) is arranged by using an inkjet method according to three-dimensional shape cross-sectional data, and is repeatedly cured by ultraviolet rays or the like. 2. Description of the Related Art An apparatus for manufacturing an original model is known.

  For example, Patent Literature 1 discloses “a method of manufacturing a three-dimensional structure by an inkjet-type lamination molding method, which is a radical polymerization type ultraviolet curable ink having an elongation within 12 hours after curing of 130% or more. A method for producing a three-dimensional structure, wherein the method is a model agent.

  Patent Document 2 discloses a monofunctional (meta) compound containing a compound represented by the general formula (1) or (2) as a three-dimensional modeling ink-jet ink composition having elongation and elasticity like rubber when cured. A) an ink-jet ink composition for three-dimensional modeling, comprising a photocurable reactive compound containing an acrylate and a polyfunctional monomer having a plurality of polymerizable groups having a carbon-carbon double bond in the molecule, The sum of the weight of the compound represented by the general formula (1) and the weight of the compound represented by the general formula (2) with respect to the total mass of the functional (meth) acrylate is 65% by mass or more; The mole fraction of the (meth) acrylate and the polyfunctional monomer satisfies the relationship of monofunctional (meth) acrylate / polyfunctional monomer = 99.9 / 0.1 to 92/8, and the inkjet ink for three-dimensional modeling Glass transition temperature of the cured product of the composition is less than 25 ° C., for three-dimensional modeling jet ink compositions are described.

  Patent Document 3 discloses, as a photocurable composition for 3D modeling having rubber-like elongation and elasticity, a monofunctional organic compound having a polymerizable group having rubber properties, and a side chain of a polyene, per mole of prepolymer. Disclosed is a photocurable composition for 3D modeling, comprising a prepolymer having 3 moles or more of an ethylene polymerizable group or an epoxy group, a monofunctional organic compound, and a photoinitiator for initiating polymerization of the prepolymer. Have been.

JP-A-2015-231684 WO 2015/56614 JP 2015-174919 A

In a method of manufacturing a three-dimensional structure by arranging a modeling material in a planar shape using an inkjet method, and then repeatedly curing the modeling material by ultraviolet light or the like, a molding material having a different composition is discharged from an inkjet head. Thus, a shaped article having regions having different hardnesses can be obtained.
However, in the case of a molded article having regions with different hardnesses, such as a soft part and a hard part, if repeated stress is applied to the molded article, the soft part has the influence of the stress, and peels off at the interface between the soft part and the hard part. May occur.

  The problem to be solved by the present invention is a shaped material that forms a soft part and has a tensile elongation at break of less than 250% or more than 500%, or a molded material that has a tensile strength at break of 1 MPa. An object of the present invention is to provide a molding material capable of suppressing occurrence of peeling at an interface between a hard part and a molding material which forms a superimposed molding.

Specific means for solving the above problems include the following aspects.
<1> A molding material that forms a molded article having a tensile elongation at break of 250% or more and 500% or less and a tensile strength at break of 0.01 MPa or more and 1 MPa or less.

<2> The modeling material according to <1>, comprising an oligomer having an elongation percentage of a homopolymer of 150% or more.
<3> The modeling material according to <2>, wherein the oligomer is a urethane (meth) acrylate oligomer.

<4> The molding material according to any one of <1> to <3>, including a monomer having a glass transition temperature of a homopolymer of 0 ° C or less.
<5> The modeling material according to <4>, wherein the monomer is a monomer having a glass transition temperature of a homopolymer of −71 ° C. or more and 0 ° C. or less.

<6> including monomers and oligomers,
The total content of the monomer and the oligomer is 90% by mass or more and 97% by mass or less based on the total mass of the molding material;
The modeling material according to <1>, wherein (content of the monomer) / (content of the monomer and content of the oligomer) is 0.75 or more and 0.95 or less.

<7> The molding material according to any one of <1> to <6>, including a granular material.
<8> The modeling material according to <7>, wherein the granular material is silicon dioxide.
<9> The molding material according to <7>, wherein the granular material includes carbon black.
<10> The molding material according to <7>, wherein the granular material includes at least one selected from the group consisting of titanium oxide and aluminum oxide.

<11> an oligomer having an elongation percentage of the homopolymer of 150% or more, a monomer having a glass transition temperature of the homopolymer of 0 ° C or less, and a polymerization initiator,
The total content of the monomer and the oligomer is 90% by mass or more and 97% by mass or less based on the total mass of the molding material;
A shaping material, wherein (content of the monomer) / (content of the monomer and content of the oligomer) is 0.75 or more and 0.95 or less.

<12> The modeling material according to <11>, wherein the oligomer is a urethane (meth) acrylate oligomer.
<13> The modeling material according to <11> or <12>, wherein the monomer is a monomer having a glass transition temperature of a homopolymer of −71 ° C. or more and 0 ° C. or less.

<14> The molding material according to any one of <11> to <13>, including a granular material.
<15> The modeling material according to <14>, wherein the granular material is silicon dioxide particles.
<16> The molding material according to <14>, wherein the granular material includes carbon black.
<17> The molding material according to <14>, wherein the granular material includes at least one selected from the group consisting of titanium oxide particles and aluminum oxide particles.

<18> a region A formed from a shaped article having a tensile elongation at break of 250% or more and 500% or less and a tensile strength at break of 0.01 MPa or more and 1 MPa or less;
A region B having a smaller tensile elongation at break than the region A;
A molded article having
<19> The shaped article according to <18>, wherein the difference in the tensile elongation at break between the region A and the region B is 240% or more.

<20> a first discharge unit that stores the modeling material according to any one of <1> to <17> as a first modeling material, and discharges the first modeling material;
A second shaping material forming a second shaping material having a smaller tensile elongation at break than the first shaping material formed from the first shaping material is accommodated, and the second shaping material is made adjacent to the first shaping material. A second discharge unit that discharges
A light irradiation unit that irradiates light that cures the discharged first modeling material and the second modeling material;
A three-dimensional modeling device comprising:

<21> a first discharging step of using the modeling material according to any one of <1> to <17> as a first modeling material and discharging the first modeling material to form a first layer;
A first light irradiation step of irradiating light for curing the first layer;
A second modeling material forming a second modeling product having a smaller tensile elongation at break than the first modeling product formed from the first modeling material is discharged adjacent to the first modeling material to form a second layer. A second ejection step of forming
A second light irradiation step of irradiating light for curing the second layer;
A method for producing a three-dimensional structure having:

  According to <1>, <7> to <10>, a shaped material that forms a shaped article having a tensile elongation at break of less than 250% or more than 500%, or a shaped article having a tensile strength at break of more than 1 MPa A shaped material capable of suppressing occurrence of peeling at an interface with a hard part as compared with a formed material to be formed is provided.

According to <2> or <3>, compared to the case where an oligomer having an elongation percentage of a homopolymer of less than 150% is used, a shaped material capable of suppressing occurrence of peeling at an interface between a hard part and a molding material is provided. Provided.
According to <4> or <5>, there is provided a molding material capable of suppressing the occurrence of peeling at the interface with the hard part, as compared with a case where only a monomer having a glass transition temperature exceeding 0 ° C. is used. .
<6> When the total content of the monomer and the oligomer is less than 90% by mass or more than 97% by mass, or (the content of the monomer) / (the content of the monomer and the content of the oligomer) is less than 0.75 or 0 A shaped material that can suppress the occurrence of peeling at the interface with the hard part as compared with the case where it exceeds .95 is provided.

  According to <11> to <17>, compared with the case where an oligomer having an elongation percentage of a homopolymer of less than 150% is used or the case where only a monomer having a glass transition temperature exceeding 0 ° C. is used, a hard part is used. And a shaped material capable of suppressing occurrence of peeling at an interface between the shaped material and the material.

  According to <18> or <19>, as compared with the case where there is a region A where the tensile elongation at break is less than 250% or more than 500% or a region A where the tensile strength at break is more than 1 MPa, A shaped object capable of suppressing occurrence of separation at an interface between them is provided.

  According to <20> or <21>, as the first shaping material, a shaping material forming a shaped object having a tensile elongation at break of less than 250% or more than 500%, or a shaping having a tensile strength at break of more than 1 MPa. A three-dimensional modeling apparatus for manufacturing a three-dimensional object that can suppress occurrence of separation at an interface between a hard part and a method for manufacturing a three-dimensional object is provided as compared with a case of using a molding material that forms an object. .

It is a schematic structure figure showing an example of a three-dimensional fabrication device concerning this embodiment. It is a flowchart showing an example of a manufacturing method of a three-dimensional structure concerning this embodiment. It is a flowchart showing an example of a manufacturing method of a three-dimensional structure concerning this embodiment. It is a flowchart showing an example of a manufacturing method of a three-dimensional structure concerning this embodiment.

Hereinafter, an embodiment which is an example of the present invention will be described.
Note that members having substantially the same function are denoted by the same reference numerals throughout the drawings, and redundant description may be omitted as appropriate.
In the present specification, “(meth) acryl” is a term used in a concept including both acryl and methacryl, and “(meth) acrylate” is used as a concept including both acrylate and methacrylate. Is a word that is
In the present specification, “oligomer” is a polymer containing a structural unit derived from a monomer and has a polymerizable group in the molecule, and has a weight average molecular weight of 500 or more and 10,000 or less. Points to

(Shaping material)
The molding material according to the first embodiment is a molding material that forms a molded article having a tensile elongation at break of 250% or more and 500% or less and a tensile strength at break of 0.01 MPa or more and 1 MPa or less.
In order to form a molded article having the above-described tensile elongation at break and tensile strength at break, the molding material is composed of oligomers and monomers which are polymerizable compounds, as well as particulate matter, a photopolymerization initiator, a polymerization inhibitor, and an oxygen scavenger. , A surfactant, and other additives.

The modeling material according to the second embodiment includes an oligomer having an elongation percentage of a homopolymer of 150% or more, a monomer having a glass transition temperature of the homopolymer of 0 ° C. or less, and a polymerization initiator. The total content is 90% by mass or more and 97% by mass or less based on the total mass of the molding material, and (monomer content) / (monomer content and oligomer content) is 0.75 or more and 0.95 or less. It is a shaping material.
By using such a shaped material, a shaped product having a tensile elongation at break of 250% or more and 500% or less and a tensile strength at break of 0.01 MPa or more and 1 MPa or less can be obtained.

The soft part, which is a shaped article having a tensile elongation at break of 250% or more and 500% or less and a tensile strength at break of 0.01 MPa or more and 1 MPa or less, is likely to have peeling at an interface between adjacent hard parts. Can be suppressed.
The reason is presumed as follows.
That is, since the soft portion as described above has a sufficiently high tensile elongation at break, the compressive stress generated by the deformation of the hard portion, the tensile stress, etc. can be deformed and released by itself, and peeling at the interface is prevented. It is presumed to be.

[Tensile breaking elongation and tensile breaking strength]
The tensile elongation at break and the tensile strength at break of the molded article formed from the molded material according to the first and second embodiments are measured as follows.
First, a test piece is prepared as follows using the shaped materials according to the first and second embodiments.
That is, the molding material is poured into a container surrounded by a frame material made of a silicone resin, and is irradiated with UV light from a high-pressure mercury lamp with an output of 1500 W for 3 minutes to produce a rectangular parallelepiped test piece having a length of 50 mm × a width of 10 mm × a thickness of 5 mm.
Subsequently, the test piece was set in a test apparatus, and an applied load (tensile breaking strength) and a breaking elongation (tensile breaking elongation) at which the sample piece was tensile-ruptured were measured under the following conditions.
・ Testing equipment: Aiko Engineering Co., Ltd., precision load measuring instrument MODEL-1605N
・ Pulling speed: 10mm / min

Hereinafter, the components included in the modeling material according to the first and second embodiments will be described.
Note that items common to the first embodiment and the second embodiment will be described as this embodiment.

[Oligomer]
The modeling material according to the present embodiment preferably contains an oligomer.
In particular, in order to keep the tensile elongation at break and the tensile strength at break of the formed shaped material within the above ranges, the shaped material is an oligomer having a homopolymer elongation of 150% or more (hereinafter, “specific oligomer”). ).
That is, by including the specific oligomer, it is possible to obtain a shaped material capable of forming a shaped article having both the tensile elongation at break and the tensile strength at break in the above-mentioned ranges. For the same reason, among the specific oligomers, an oligomer having a homopolymer elongation of 200% or more is particularly preferable.

Here, the elongation percentage of the homopolymer of the oligomer is determined as follows.
That is, after applying a mixture obtained by mixing oligomer: photopolymerization initiator (Irgacure 184) = 100: 4 (mass ratio) on a PET film so as to have a film thickness of 100 μm using an applicator, high-pressure mercury of 80 W / cm ² . One lamp was set at a height of 18 cm, and moved under the belt twice at a belt speed of 2.5 m / min to cure the resin, thereby producing a 15 mm-wide strip-shaped test piece (at this time, the integrated light amount: 800 ml / minute). It was cm ^2.).
Using this test piece, the elongation is measured at 23 ° C. and 50% RH atmosphere at a distance between chucks of 25 mm and a tensile speed of 10 mm / min according to JIS K 5600.
In the case where a commercial product is used as the oligomer, the value of the elongation percentage described in a catalog or the like in which the commercial product is described may be adopted.

The specific oligomer preferably has one or more radically polymerizable groups in the molecule. The radical polymerizable group is not particularly limited, but an ethylenically unsaturated group is preferable, and a (meth) acryloyl group is particularly preferable.
That is, the specific oligomer is particularly preferably a (meth) acrylate oligomer having at least one (meth) acryloyl group in the molecule.

Specific oligomers include, for example, urethane (meth) acrylate oligomer, polybutadiene (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, and polyether (meth) acrylate oligomer.
Among them, urethane (meth) acrylate oligomer is preferable as the specific oligomer from the viewpoints of compatibility with other components and improvement in tensile breaking strength.

-Urethane (meth) acrylate oligomer-
The urethane (meth) acrylate oligomer has a urethane bond in the molecule and has one or more (meth) acryloyl groups in the molecule.
More specifically, the urethane (meth) acrylate oligomer has a structural unit including a urethane bond “—NHC (＝ O) O—” or “—OC (＝ O) NH—”, and It is a monomer having one or more (meth) acryloyl groups in the molecule.
The number of (meth) acryloyl groups in the urethane (meth) acrylate oligomer is preferably from 1 to 20, more preferably from 2 to 10, and even more preferably from 2 to 4.

  As the urethane (meth) acrylate oligomer, a polyether urethane acrylate oligomer or a polyester urethane acrylate oligomer is used because the hardness can be easily adjusted and the mechanical strength, heat resistance, abrasion resistance, and chemical resistance are excellent. Preferably, there is.

Examples of the urethane (meth) acrylate oligomer include a reaction product using a polyisocyanate compound, a polyol compound, and a (meth) acrylate having a hydroxy group.
Specifically, the urethane (meth) acrylate oligomer includes, for example, a prepolymer obtained by reacting a polyisocyanate compound and a polyol compound, and a prepolymer having an isocyanate group at a terminal and a (meth) acrylate having a hydroxy group. And a reaction product of
Hereinafter, components for obtaining a urethane (meth) acrylate oligomer will be described.

-Polyisocyanate compound Examples of the polyisocyanate compound include chain saturated hydrocarbon isocyanates, cyclic saturated hydrocarbon isocyanates, and aromatic polyisocyanates.

Examples of the chain saturated hydrocarbon isocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.
Examples of the cyclic saturated hydrocarbon isocyanate include isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated toluene diisocyanate.
Examples of the aromatic polyisocyanate include 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate, 6-isopropyl-1, 3-phenyl diisocyanate, 1,5-naphthalenediisocyanate and the like can be mentioned.

-Polyol compound Examples of the polyol compound include polyhydric alcohols such as diols.
Examples of the diol include alkylene glycols (eg, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4- Butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecandio Le, 1,2-dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, etc.) and the like.

  Examples of polyhydric alcohols other than diols include, for example, alkylene polyhydric alcohols containing three or more hydroxyl groups (for example, glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4 -Butanetriol, erythritol, sorbitol, pentaerythritol, dipentaerythritol, mannitol, etc.).

  Examples of the polyol compound include a polyether polyol, a polyester polyol, and a polycarbonate polyol.

Examples of the polyether polyol include a polymer of a polyhydric alcohol, an adduct of a polyhydric alcohol and an alkylene oxide, and a ring-opened polymer of an alkylene oxide.
Here, as the polyhydric alcohol, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, 2-hexanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,8-octanediol , 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol and the like.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and the like.

Examples of the polyester polyol include a reaction product of a polyhydric alcohol and a dibasic acid, and a ring-opened polymer of a cyclic ester compound.
Here, the polyhydric alcohol includes, for example, the polyhydric alcohol exemplified in the description of the polyether polyol.
Examples of the dibasic acid include carboxylic acids (eg, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, etc.), and anhydrides of carboxylic acids.
Examples of the cyclic ester compound include ε-caprolactone, β-methyl-δ-valerolactone, and the like.

Examples of the polycarbonate polyol include a reaction product of a glycol with an alkylene carbonate, a reaction product of a glycol with a diaryl carbonate, and a reaction product of a glycol with a dialkyl carbonate.
Here, examples of the alkylene carbonate include ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, and the like.
Examples of the diaryl carbonate include diphenyl carbonate, 4-methyldiphenyl carbonate, 4-ethyldiphenylcarbonate, 4-propyldiphenylcarbonate, 4,4′-dimethyldiphenylcarbonate, 2-tolyl-4-tolylcarbonate, and 4,4 ′. -Diethyldiphenyl carbonate, 4,4'-dipropyldiphenyl carbonate, phenyltoluyl carbonate, bischlorophenyl carbonate, phenylchlorophenyl carbonate, phenylnaphthyl carbonate, dinaphthyl carbonate, and the like.
Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, di-n-amyl carbonate, and diisoamyl carbonate. And the like.

-(Meth) acrylate having a hydroxy group Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, -Hydroxy-3-phenoxypropyl (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like.
Examples of the (meth) acrylate having a hydroxy group include an adduct of a glycidyl group-containing compound (eg, alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate) and (meth) acrylic acid.

-Weight average molecular weight of urethane (meth) acrylate oligomer-
The weight average molecular weight of the urethane (meth) acrylate oligomer is preferably from 500 to 5,000, more preferably from 1,000 to 3,000.
The weight average molecular weight of the urethane (meth) acrylate oligomer is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

The oligomer may be used alone or in combination of two or more.
The content of the oligomer in the molding material is preferably 5% by mass or more and 30% by mass or less with respect to the total mass of the molding material, from the viewpoint of obtaining a molded product in which the tensile elongation at break and the tensile strength at break are in the above ranges. It is more preferably from 25% by mass to 25% by mass, and more preferably from 10% by mass to 20% by mass.
Further, the modeling material may contain an oligomer that does not correspond to the specific oligomer, in addition to the specific oligomer. In that case, the content of the specific oligomer in all the oligomers contained in the molding material is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 100% by mass.
Here, the oligomer that does not correspond to the specific oligomer refers to an oligomer having an elongation percentage of a homopolymer of less than 150%.

[monomer]
The modeling material according to the present embodiment preferably contains a monomer.
In particular, in order to set the tensile elongation at break and tensile strength at break of the formed molding material in the above-mentioned ranges, the molding material is a monomer having a glass transition temperature of a homopolymer of 0 ° C. or lower (hereinafter, “specific monomer”). ").
That is, by including the specific monomer, it is possible to obtain a shaped material capable of forming a shaped article having both the tensile elongation at break and the tensile strength at break within the above-mentioned ranges. For the same reason, among the specific monomers, a monomer having a glass transition temperature of a homopolymer of −71 ° C. or more and 0 ° C. or less is particularly preferable.

Here, the glass transition temperature of the monomer is determined by differential scanning calorimetry (DSC) of a homopolymer (that is, a homopolymer).
First, a homopolymer (homopolymer) can be prepared as follows.
Using azodiisobutyronitrile (AIBN) as a thermal polymerization initiator and toluene as a solvent, monomers / AIBN / toluene = 1 / 0.01 / 10 (mass ratio) were mixed and polymerized at 65 ° C. for 8 hours under a nitrogen atmosphere. Perform the reaction. After completion of the reaction, the mixture is cooled, purified by reprecipitation using a poor solvent such as ethanol, and dried under reduced pressure at 60 ° C. for 8 hours to obtain a homopolymer.
The obtained homopolymer is subjected to differential scanning calorimetry (DSC), and the glass transition temperature is determined from the obtained DSC curve. More specifically, it is determined from the obtained DSC curve as “extrapolated glass transition onset temperature” described in JIS K-2120: 1987 “Method for measuring glass transition temperature” of “Method for measuring transition temperature of plastic”.
When a commercial product is used as the monomer, a glass transition temperature (Tg) value described in a catalog or the like in which the commercial product is described may be used.

The monomer (including the specific monomer) used in the molding material preferably has one or more radically polymerizable groups in the molecule. The radical polymerizable group is the same as the specific oligomer described above, and the preferred examples are also the same.
Further, the number of (meth) acryloyl groups contained in the monomer is preferably from 1 to 4, more preferably from 1 to 2, and even more preferably 1.
That is, the monomer is particularly preferably a monofunctional (meth) acrylate having at least one (meth) acryloyl group in the molecule.

-Monofunctional (meth) acrylate-
The monofunctional (meth) acrylate is not limited in its structure, but from the viewpoint of availability and procurement cost, for example, an alkyl (meth) acrylate having a linear, branched, or cyclic alkyl group is exemplified. Can be The alkyl group of the alkyl (meth) acrylate may be unsubstituted or may have a substituent.
The substituent that can be introduced into the alkyl group of the alkyl (meth) acrylate is not particularly limited, but a substituent containing an oxygen atom is preferable. Specifically, an ethyleneoxy group, a propyleneoxy group, a phenoxy group, Group, carbamoyloxy group, ester group (—C (＝ O) OR), a heterocyclic group containing an oxygen atom (for example, a group obtained by removing one hydrogen atom from a dioxane ring, a hydrogen atom from a dioxolane ring) And a group obtained by removing one of them.
These substituents may further have a substituent, and examples of the substituent include an alkyl group, an ethyleneoxy group, and a propyleneoxy group.

  Examples of the alkyl (meth) acrylate having an unsubstituted alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. ) Acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-t-cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate and the like. .

  Examples of the alkyl (meth) acrylate having a substituted alkyl group include phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, m-phenoxybenzyl (meth) acrylate, and 2- (N-butylcarbamoyloxy) (meth) acrylate. 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-ethylhexylEO (ethylene oxide) -modified (meth) acrylate, 2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, Examples thereof include cyclic trimethylolpropane formal acrylate, and acrylic acid multimer esters of ethoxyethoxyethanol.

  Among them, dicyclopentanyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and (meth) are used as monomers from the viewpoint of facilitating the tensile elongation at break and tensile strength at break of the formed molding material within the above ranges. 2- (N-butylcarbamoyloxy) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, cyclic triacrylate Acrylic acid multimeric esters of methylolpropane formal acrylate and ethoxyethoxyethanol are preferred.

The monomers may be used alone or in combination of two or more.
From the viewpoint of obtaining a molded article having a tensile elongation at break and a tensile strength at break within the above-mentioned ranges, the content of the monomer in the molding material is preferably 60% by mass or more and 95% by mass or less based on the total mass of the molding material. Preferably, it is 70% by mass or more and 95% by mass or less, more preferably 70% by mass or more and 90% by mass or less.
In addition, the modeling material may include a monomer that does not correspond to the specific monomer, in addition to the specific monomer. In that case, the content of the specific monomer in all the monomers contained in the molding material is preferably 20% by mass or more, and particularly preferably 30% by mass or more.
Here, the monomer which does not correspond to the specific monomer means a monomer having a glass transition temperature exceeding 0 ° C., and is preferably selected from the above-mentioned monofunctional (meth) acrylate.

[Relationship between oligomer and monomer]
The modeling material according to the present disclosure includes an oligomer and a monomer, and the total content of the monomer and the oligomer is 90% by mass or more and 97% by mass or less based on the total mass of the molding material (preferably, 92% by mass or more and 97% by mass or less). ), And the ratio of (monomer content) / (monomer content and oligomer content) is preferably 0.75 or more and 0.95 or less (preferably 0.78 or more and 0.92 or less).
By satisfying these ratios, it is easy to obtain a shaped article having a tensile elongation at break and a tensile strength at break within the above ranges.

[Granular material]
The shaped material of the present disclosure preferably contains a granular material from the viewpoint of obtaining a shaped product having a tensile elongation at break and a tensile strength at break within the above-described ranges.
The granular material is not particularly limited as long as it can reinforce the strength of the molding material, and may be any of an inorganic granular material and an organic granular material.
For example, as the granular material, silicon dioxide particles capable of reinforcing the strength while imparting transparency to the molded article; black particulate matter such as carbon black capable of reinforcing the strength while imparting color to the molded article; White particles such as titanium oxide particles and aluminum oxide particles;
In addition, as the granular material capable of reinforcing the strength while imparting a color to the molded object, for example, a yellow pigment, a magenta pigment, a cyan pigment, and the like can be mentioned.

The volume average particle diameter of the granular material is preferably from 0.01 μm to 50 μm, more preferably from 0.02 μm to 10 μm, from the viewpoint of reinforcing the strength of the molding material and imparting a tint.
Here, the volume average particle diameter of the granular material is obtained by observing 100 primary particles at a magnification of 40,000 times using a SEM (Scanning Electron Microscope) apparatus, and measuring the longest diameter and the shortest diameter of each particle by image analysis of the primary particles. The sphere equivalent diameter is measured from the intermediate value. The 50% diameter (D50v) in the cumulative frequency of the obtained sphere equivalent diameters is determined, and this is measured as the volume average particle diameter of the granular material.

The granular materials may be used alone or in combination of two or more.
When the molding material of the present disclosure includes a granular material, the content of the granular material is preferably from 0.01% by mass to 10% by mass, and more preferably from 0.1% by mass to 3% by mass, based on the total mass of the molding material. The following is more preferred.

[Photopolymerization initiator]
The photopolymerization initiator is not limited as long as it contributes to the above-described curing reaction of the oligomer and the monomer, and a photoradical polymerization initiator is preferable.
The photo-radical polymerization initiator is not particularly limited and includes, for example, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-alkyl Examples include dione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, and the like.
Among the above, phosphine oxides are preferred from the viewpoint of curability of the molding material.

Examples of the acetophenones include 2,2-ethoxyacetophenone, p-methylacetophenone, 1-hydroxydimethylphenylketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone and the like.
Examples of the benzoins include benzoin benzene sulfonic acid ester, benzoin toluene sulfonic acid ester, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like.
Examples of the benzophenones include benzophenone, 2,4-chlorobenzophenone, 4,4-dichlorobenzophenone, p-chlorobenzophenone and the like.
Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (commercially available products: IGM Resins, Omnirad TPO), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ( Commercially available products include IGM Resins, Omnirad 819).

The photopolymerization initiator may be used alone or in combination of two or more.
The content of the photopolymerization initiator in the molding material is preferably from 1% by mass to 10% by mass, more preferably from 1% by mass to 8% by mass, and more preferably from 2% by mass to 6% by mass, based on the total mass of the molding material. The following are more preferred.

[Oxygen scavenger]
Examples of the oxygen scavenger include an amine-based oxygen scavenger and an organic phosphorus-based oxygen scavenger.
The amine-based oxygen scavenger is an oxygen scavenger having an amino group, such as ethyl 4- (dimethylamino) benzoate.
The organic phosphorus-based oxygen scavenger is an oxygen scavenger having a phosphorus atom, such as triphenylphosphine (TPP) and triethylphosphite (TEP).
Among them, from the viewpoint of safety, amine oxygen scavengers are preferable, and ethyl 4- (dimethylamino) benzoate is particularly preferable.

The oxygen scavenger may be used alone or in combination of two or more.
The content of the oxygen scavenger in the molding material is preferably from 0.1% by mass to 0.5% by mass, more preferably from 0.1% by mass to 0.4% by mass, based on the total mass of the molding material.

[Polymerization inhibitor]
Examples of the polymerization inhibitor include, for example, phenol-based polymerization inhibitors (for example, p-methoxyphenol, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene, 2,2′-methylenebis ( 4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), etc., hindered amine, hydroquinone Well-known polymerization inhibitors such as monomethyl ether (MEHQ) and hydroquinone are exemplified.

The polymerization inhibitors may be used alone or in combination of two or more.
The content of the polymerization inhibitor in the molding material is preferably 0.1% by mass or more and 1% by mass or less, more preferably 0.2% by mass or more and 0.6% by mass or less based on the total mass of the molding material.

[Surfactant]
Examples of the surfactant include silicone surfactants, acrylic surfactants, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, and fluorine surfactants. Well-known surfactants may be mentioned.
In particular, among surfactants, a surfactant having a radical polymerizable group is preferable, and a silicone-based surfactant having a radical polymerizable group (for example, TEGO (registered trademark) RAD 2010, TEGO (registered trademark) manufactured by Evonik) RAD 2011) is particularly preferred.

One type of surfactant may be used alone, or two or more types may be used in combination.
The content of the surfactant in the molding material is preferably from 0.1% by mass to 0.5% by mass, more preferably from 0.1% by mass to 0.4% by mass, based on the total mass of the molding material. .

[Other additives]
Other additives include, for example, colorants, solvents, sensitizers, fixing agents, fungicides, preservatives, antioxidants, ultraviolet absorbers, chelating agents, thickeners, dispersants, polymerization accelerators, Well-known additives such as a penetration enhancer and a wetting agent (humectant) can be used.

[Characteristics of molding materials]
Surface tension The surface tension of the shaped material is preferably, for example, in the range of 20 mN / m to 35 mN / m, and more preferably in the range of 24 mN / m to 30 mN / m.
Here, the surface tension is a value measured using a Wilhelmy surface tensiometer (manufactured by Kyowa Interface Science Co., Ltd.) in an environment of 23 ° C. and 55% RH.

Viscosity The viscosity of the shaped material at 55 ° C. is preferably from 10 mPa · s to 100 mPa · s, more preferably from 10 mPa · s to 60 mPa · s.
Here, the viscosity is measured at a measuring temperature of 55 ° C. and a shear rate of 200 (1 / s) using TVE-25L manufactured by Toki Sangyo as a measuring device.

(Model)
The modeled object according to the present embodiment has a tensile breaking elongation of 250% or more and 500% or less, and a tensile strength at break of 0.01 MPa or more and 1 MPa or less. And a region B having a small tensile elongation at break.
The region A corresponds to a soft portion formed from a molded product obtained from the molded material according to the first and second embodiments described above, and the region B has a smaller tensile elongation at break than the region A. It corresponds to a hard part formed from.
In the modeled object according to the present embodiment, even when a repeated stress is applied, peeling does not easily occur at the interface between the region A as the soft portion and the region B as the hard portion.
In particular, in a molded article in which the difference in tensile elongation at break between the soft region A and the hard region B is 240% or more, even if a repeated stress is applied, the soft region A and the hard region are not affected. The effect that peeling hardly occurs at the interface with a certain region B is remarkably exhibited.

The tensile elongation at break in the region A is preferably 250% or more and 450% or less.
Further, the tensile breaking strength in the region A is preferably from 0.1 MPa to 1 MPa.

The shaping material for forming the region B is not particularly limited as long as a shaped material having a smaller tensile elongation at break than the region A can be formed, and includes, for example, an oligomer, a monomer, a photopolymerization initiator, a surfactant, and the like. A conventionally known molding material that is cured by polymerization or crosslinking is used.
Specific examples of the modeling material for forming the region B include, for example, a model material (a photocurable compound containing urethane (meth) acrylate) described in JP-A-2006-132773, and JP-A-2017-052177. Modeling materials described in paragraphs [0077] to [0109] of the Japanese Patent Application Laid-Open Publication No. Hei 10-135233, a molding material described in Japanese Patent Application No. 2018-135233 (monomer A having one radical polymerizable group in a molecule, radical polymerizable group and cation A monomer B having a polymerizable group in the molecule, a monomer C having no urethane group and having two or more radical polymerizable groups in the molecule, a monomer C having a urethane group and a radical polymerizable group A molding material containing two or more monomers D, a photopolymerization initiator E, and an oxygen scavenger F) is preferable.

[Three-dimensional printing apparatus and method for manufacturing three-dimensional printing object]
The three-dimensional modeling apparatus according to the present embodiment accommodates the modeling materials according to the above-described first and second embodiments as a first modeling material, and discharges the first modeling material, and a first molding unit. A second molding material forming a second modeling material having a smaller tensile elongation at break than the first modeling material formed from the material, and discharging the second modeling material so as to be adjacent to the first modeling material; A three-dimensional modeling apparatus, comprising: a discharge unit; and a light irradiation unit configured to irradiate light that cures the discharged first and second modeling materials.

    In the three-dimensional modeling apparatus according to the present embodiment, the first modeling material according to the first and second embodiments is used as a first modeling material, and the first modeling material is discharged to form a first layer. An ejection step, a first light irradiation step of irradiating light for curing the first layer, and a second step of forming a second shaped article having a smaller tensile elongation at break than the first shaped article formed from the first shaped material. A second discharging step of discharging the modeling material so as to be adjacent to the first modeling material to form a second layer, and a second light irradiation step of irradiating light for curing the first layer and the second layer; Is carried out.

Here, the discharging method in the first discharging step and the second discharging step is not particularly limited, but is preferably discharging by an ink jet method, and more preferably discharging using an ink jet head.
The inkjet head is not particularly limited, and a known inkjet head is used. For example, a piezo-type inkjet head can be used.
Further, the number of inkjet heads and the number of nozzles in the inkjet head are not particularly limited, and may be set as appropriate.
The discharge temperatures of the first and second molding materials are not particularly limited, and are adjusted according to the discharge temperatures of the first and second molding materials to be used.
There is no particular limitation on the discharge amount of the first molding material and the second molding material as well, and it is only necessary to discharge an amount having a target thickness. Further, if necessary, the ejection may be performed plural times.

Further, the “light” in the light irradiation step may be light having a wavelength at which the first molding material and the second molding material are cured, and unless otherwise specified, not only visible light, but also ultraviolet light, infrared light, and the like. Shall be included.
Further, the first molding material and the second molding material may be cured at once or may be separately cured.

  In the three-dimensional modeling apparatus including the first discharging unit, the second discharging unit, and the light irradiating unit, for example, the forming material according to the first and second embodiments described above is discharged and cured by light irradiation. The first modeling material (that is, the region A (soft portion) described above) is formed, and the second modeling material that forms the second modeling product having a smaller tensile elongation at break than the first modeling product is discharged and irradiated with light. To form a second shaped object (that is, the above-described region B (hard portion)).

Hereinafter, as an example of the three-dimensional printing apparatus according to the present embodiment, a three-dimensional printing apparatus including a first discharge unit, a second discharge unit, and a light irradiation unit will be described with reference to the drawings.
FIG. 1 is a schematic configuration diagram illustrating an example of a three-dimensional printing apparatus including a first ejection unit, a second ejection unit, and a light irradiation unit, among the three-dimensional printing apparatus according to the present embodiment.

The three-dimensional printing apparatus 101 according to the present embodiment is an ink-jet type three-dimensional printing apparatus. As shown in FIG. 1, the three-dimensional printing apparatus 101 includes, for example, a printing unit 10 and a printing table 20. In addition, the three-dimensional modeling apparatus 101 is configured such that the three-dimensional modeling apparatus 101 is detachably attached to the first modeling material cartridge 30 that stores the modeling materials according to the above-described first and second embodiments, and that the three-dimensional modeling apparatus 101 is more tensilely broken than the first modeling object. A second modeling material cartridge 32 for accommodating a second modeling material forming a second modeling product having a small elongation. In FIG. 1, MD _A indicates a first modeled object (ie, region A (soft portion)), and MD _B indicates a second modeled object (ie, region B (hard portion)).

The modeling unit 10 is, for example, a first modeling material discharge head 12 (an example of a first discharging unit) that discharges a droplet of a modeling material according to the above-described first and second embodiments, and a first modeling object. A second modeling material discharge head 14 (an example of a second discharging unit) that discharges a droplet of a second modeling material forming a second modeling product having a small tensile elongation at break, and a light irradiation device 16 that irradiates light. Have.
In addition, a support material ejection head for forming a support portion (support portion) that supports at least a part of the region A formed of the first modeling material and the region B formed of the second modeling material may be provided. Good. Further, although not shown, the modeling unit 10 includes, for example, extra first and second molding materials among the first and second molding materials (including the support material when using the support material) discharged onto the molding table 20. A rotating roller for removing and shaping the modeling material (including the supporting material when using the supporting material) may be provided.

  The shaping unit 10 is configured to move in a main scanning direction and a sub-scanning direction intersecting (for example, orthogonally) with the shaping area of the shaping table 20 by a driving device (not shown), for example, a so-called carriage method. Has become.

  Each of the first molding material discharge head 12 and the second molding material discharge head 14 employs a piezoelectric (piezoelectric) discharge head that discharges droplets of each material by pressure. Each discharge head is not limited to this, and may be a discharge head of a type that discharges each material by pressure from a pump.

The first modeling material discharge head 12 is connected to, for example, the first modeling material cartridge 30 through a supply pipe (not shown). Then, the molding material is supplied to the first molding material ejection head 12 by the first molding material cartridge 30.
The second modeling material discharge head 14 is connected to, for example, the second modeling material cartridge 32 through a supply pipe (not shown). Then, the molding material is supplied to the second molding material discharge head 14 by the second molding material cartridge 32.

Each of the first molding material discharge head 12 and the second molding material discharge head 14 has a short shape in which an effective discharge region (a region where nozzles for discharging the molding material and the support material are arranged) is smaller than the molding region of the molding table 20. Discharge head.
In addition, each of the first molding material discharge head 12 and the second molding material discharge head 14 has, for example, an effective discharge region (an arrangement region of a nozzle for discharging a molding material and a support material) in a molding region on the molding table 20. A long head having a width (length in a direction intersecting (for example, perpendicular to) the moving direction (main scanning direction) of the modeling unit 10) may be used. In this case, the molding unit 10 is configured to move only in the main scanning direction.

The light irradiation device 16 may be any device that irradiates light having a wavelength at which the first and second molding materials are cured, and for example, an ultraviolet irradiation device that irradiates ultraviolet light is used.
Examples of the ultraviolet irradiation device include a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a deep ultraviolet lamp, a lamp that excites a mercury lamp from the outside using a microwave without electrodes, an ultraviolet laser, a xenon lamp, and a UV-LED (ultraviolet light emitting diode). A device having a light source such as) is applied.
Among these, the ultraviolet irradiation device is preferably an ultraviolet laser or a UV-LED (ultraviolet light emitting diode) from the viewpoint of suppressing a rise in temperature during the production of the three-dimensional structure.

  The modeling table 20 has a surface having a modeling region where the first and second modeling materials are discharged to form a modeling object. Then, the modeling table 20 is moved up and down by a driving device (not shown).

  Next, an operation (a method of manufacturing a three-dimensional structure) of the three-dimensional structure forming apparatus 101 according to the present embodiment will be described.

  First, for example, using a computer (not shown), three-dimensional CAD (Computer Aided Design) data of a three-dimensional modeled object formed by the first and second modeling materials is used as data for three-dimensional modeling, for example, as first and third data. Two-dimensional shape data (slice data) for forming the second modeled object is generated. At this time, if necessary, two-dimensional shape data (slice data) for forming the support portion with the support material may be generated. In the two-dimensional shape data for forming the support portion, the width of the object at the upper position is larger than the width of the object at the lower position, and when there is a so-called overhanging portion, the overhang portion is moved downward. A support portion is formed so as to further support.

Next, the first modeling material is discharged from the first modeling material discharge head 12 while moving the modeling unit 10 based on the two-dimensional shape data for forming the modeling object, and the first modeling material is discharged onto the modeling table 20. 1 Form a layer of the shaped material. The layer of the first modeling material is irradiated with light by the light irradiation device 16 to cure the first modeling material and form a layer that becomes a part of the first modeling object.
In this way, a first layer LAY1 composed of a layer that becomes a part of the first model object is formed (see FIG. 2). Here, in FIG. 2, MD _A1 indicates a layer that becomes a part of the first modeled object in the first layer LAY1.

  At the time of forming the first layer LAY1, the second molding material discharge head 14 moves the molding material 10 based on the two-dimensional data for forming the second molding material from the second molding material discharge head 14 as necessary. And a layer of the second modeling material may be formed on the modeling table 20 adjacent to the layer of the first modeling material. Then, the layer of the second modeling material is irradiated with light by the light irradiation device 16 to cure the second modeling material and form a layer that becomes a part of the second modeling object.

  Further, at the time of forming the first layer LAY1, the support material is discharged from the support material discharge head (not shown) while moving the modeling unit 10 based on the two-dimensional data for forming the support portion, if necessary. The layer of the support material may be formed on the molding table 20 by discharging and adjacent to the layer of the first molding material. Then, the light irradiation device 16 irradiates the layer of the support material with light to cure the support material and form a layer that becomes a part of the support portion.

  Next, the modeling table 20 is lowered. The descending of the modeling table 20 is set to the thickness of the second layer (the second layer that is a part of the molded article) to be formed next.

Next, similarly to the first layer LAY1, a second layer LAY2 composed of a layer (see FIG. 3) that is a part of the first model object is formed (see FIG. 3). Here, in FIG. 3, MD _A2 indicates a layer that becomes a part of the first modeled object in the second layer LAY2.
When forming the second layer LAY2, one or both of a layer that is a part of the second modeled object and a layer that is a part of the support part may be formed as necessary.

Then, the operation of forming the first layer LAY1 and the second layer LAY2 is repeatedly performed to form up to the n-th layer LAYn. As a result, a modeled object in which the first modeled object and the second modeled object are adjacent to each other is formed (see FIG. 4). Here, in FIG. 4, MD _An indicates a layer that is a part of the first modeling object in the n-th layer LAYn, and MD _{B4 to} MD _B6 indicate the second modeling objects in the fourth layer LAY4 to the sixth layer LAY6. The layer which becomes a part of is shown.

After that, the target three-dimensional object can be obtained by removing the support part from the object including the first and second objects as necessary.
Here, the removal of the support portion may be performed, for example, by a method of removing by hand (breakaway method), a method of removing by spraying a gas, or a method of immersing a three-dimensional structure having a support portion in hot water to remove the support portion. Is dissolved and removed (immersion method), a method of injecting hot water into a three-dimensional model having a support portion to remove the support portion by water pressure while dissolving the support portion (injection method), and the like are adopted. From the viewpoint of a simple removal method, removal by an immersion method is more preferable. In the immersion method, ultrasonic irradiation is also preferably used together.
The obtained three-dimensional structure may be subjected to post-processing such as polishing.

  Hereinafter, the present embodiment will be described in detail with reference to examples, but the present embodiment is not limited to these examples. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

<Preparation of first molding materials 1 to 16>
First components 1 to 16 were prepared by mixing the components shown in Tables 1 to 3 below.
Details of each component described in Tables 1 to 3 below are as follows.

(Oligomer)
UA-1138P: urethane (meth) acrylate oligomer ("UA-1138P" Shin-Nakamura Chemical Co., Ltd., elongation percentage of homopolymer: 200%)
-UA-3573AB: urethane (meth) acrylate oligomer ("UA-3573AB" Shin-Nakamura Chemical Co., Ltd., elongation percentage of homopolymer: 1000%)
UA-3773AB: Urethane (meth) acrylate oligomer of Shin-Nakamura Chemical Co., Ltd. ("UA-3773AB" Shin-Nakamura Chemical Co., Ltd., growth rate of homopolymer: 1000%)

(monomer)
DCPA: dicyclopentanyl acrylate (Tokyo Chemical Industry Co., Ltd., glass transition temperature: 120 ° C.)
-P2H-A: phenoxydiethylene glycol acrylate ("Light acrylate P2H-A" Kyoeisha Chemical Co., Ltd., glass transition temperature Tg: -21 ° C)
-BACE-A: 2- (N-butylcarbamoyloxy) acrylate (Aldrich, glass transition temperature Tg: -15 ° C)
* Medol 10: 2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate ("Medol 10", Osaka Organic Chemical Industry, glass transition temperature Tg: -10 ° C)
V- # 200: cyclic trimethylolpropane formal acrylate ("Biscoat # 200", Osaka Organic Chemical Industry, glass transition temperature Tg: 27 ° C)
V- # 190: 2- (2-ethoxyethoxy) ethyl acrylate ("Biscoat # 190" Osaka Organic Chemical Industry Co., Ltd., glass transition temperature Tg: -67 ° C)
V- # 190D: Acrylic acid polymer ester of ethoxyethoxyethanol ("Biscoat # 190D" Osaka Organic Chemical Industry Co., Ltd., glass transition temperature Tg: -47 ° C)

(Other components)
-Genorad 21: polymerization inhibitor ("Genorad 21" Rahn AG (Switzerland))
-BAPO: Photopolymerization initiator ("Omnirad 819" IGM Resins)
EDB: oxygen scavenger ("Omnirad EDB (ethyl 4- (dimethylamino) benzoate)" IGM Resins)
-TEGO Rad 2011: surfactant ("TEGO (registered trademark) Rad 2011" Evonik)
-Silicon dioxide: granular material ("ADAMANANO YA050C" Admatics, volume average particle size: 0.050 μm)
・ Carbon black: granular material (“RCF # 25”, Mitsubishi Chemical Corporation, volume average particle size: 0.047 μm)
-Titanium oxide: granular material ("Super Titania G-1" Showa Denko KK, volume average particle size 0.25 µm)

[Viscosity of molding material]
The viscosity at 55 ° C. of each obtained shaped material was measured by the method described above.
The results are shown in Tables 1 to 3.

[Measurement of molded object obtained from first molding material]
A dumbbell-shaped test piece was prepared using each of the obtained first shaped materials as described above, and the tensile strength at break and the tensile elongation at break were measured using this.
The results are shown in Tables 1 to 3.

<Preparation of second molding material 1>
The following components were mixed to prepare a second molding 1.
-Urethane acrylate (NK Oligo UA-4400, Shin-Nakamura Chemical): 15.0 parts by mass-EO-modified bisphenol A diacrylate (Aronix M-211B, Toagosei): 26.0 parts by mass-Dicyclopentanyl acrylate (Tokyo Kasei): 24.4 parts by mass, 2- (2-vinyloxyethoxy) ethyl acrylate (VEEA, Nippon Shokubai): 29.7 parts by mass, photopolymerization initiator (Omnirad 819, IGM Resins): 4.0 Parts by mass, polymerization inhibitor (Genorad21, Rahn AG): 0.3 parts by mass, oxygen scavenger (Ominrad EDB, IGM Resins): 0.2 parts by mass, surfactant (TEGO Rad2011, Evonik Japan): 0.4 Mass The viscosity at 55 ° C. of the second molding material 1 was 12.3 mPa · s. .

[Measurement of molded object obtained from second molding material]
A dumbbell-shaped test piece was prepared as described above using each of the obtained second shaped materials, and the tensile elongation at break was measured using this.
The results are shown in Tables 4 and 5.

<Examples and comparative examples>
[Preparation of molded object]
A three-dimensional model was obtained using each of the obtained modeling materials.
Specifically, the three-dimensional printing apparatus uses a Polaris head (model number: PQ512 / 85) manufactured by Fuji Film Dimatics as an inkjet head, and a Subzero-055 (100 w / cm strength) manufactured by INTEGRATION TECHNOLOGY LTD as an ultraviolet irradiation light source. ) Was selected, and these were installed in a shaping device including a drive unit and a control unit, and this was used as a shaping device for testing.
Note that the modeling apparatus is a method in which the ink jet head and the light source reciprocate together, and each time a single scan is performed, a layer of the first modeling article and the layer of the second modeling article each having a thickness of 20 μm and ultraviolet rays are formed. A device for performing a curing treatment by irradiation to form a three-dimensional modeled object. Further, in the modeling apparatus, the first and second modeling materials are supplied from a storage tank via a Tygon 2375 chemical resistant tube manufactured by Saint-Gobain by a liquid feed pump under light-shielding conditions, and then a profile star A050 filter (filtered by Nippon Pall Co., Ltd.) is used. (Accuracy: 5 μm), and the liquid is sent to the inkjet head after removing foreign matter.
By using the three-dimensional modeling apparatus, the first modeling material and the second modeling material described in Tables 4 and 5 are used in combination, and when viewed from the top, the length is 90 mm, the width is 30 mm, and the length is around each of the four corners. 6 mm from the side, a plate-like object having a fixing hole of 4 mm in diameter centered on the position of 12.5 mm from the short side, and having a thickness of 1 mm on the layer of the second model having a thickness of 1 mm when viewed in cross section. A three-dimensional structure having a thickness of 5 mm was formed by laminating a layer of a first structure having a thickness of 3 mm and a layer of a second structure having a thickness of 1 mm.

Using the obtained three-dimensional structure as a measurement sample, the first structure (that is, the region A (soft part)) formed by the first structure and the second structure by the following method were used. The peeling of the interface between the second model (that is, the region B (hard portion)) was evaluated.
That is, using a measurement sample, the apparatus was stopped at a bending angle of ± 12 deg and a repetition rate of 25 Hz for 40 minutes every 1000 times using a plane bending fatigue tester (PBF-30x, Tokyo Koki Co., Ltd.). A plane bending test was performed by visually observing whether or not air had entered due to peeling.
The evaluation criteria were as follows.
-Evaluation criteria-
-No peeling occurs even after 5000 times or more; A (◎)
-Peeling occurs after 4000 times or more and less than 5000 times; B (O)
-Peeling occurs after 3000 times or more and less than 4000 times; C (△)
・ Exfoliation occurs after less than 3000 times; D (×)
The larger the number of times of the plane bending test when the peeling was confirmed, the more the peeling at the interface was suppressed.
The results are shown in Tables 4 and 5.

  As is clear from Tables 4 and 5, as in the examples, a molded article having a tensile elongation at break of 250% or more and 500% or less and a tensile strength at break of 0.01 MPa or more and 1 MPa or less is obtained. It was found that when the material was used, peeling was suppressed at the interface with the hard part as compared with the comparative example.

10 Modeling Unit 12 First Modeling Material Discharge Head 14 Second Modeling Material Discharge Head 16 Light Irradiation Device 20 Modeling Table 30 First Modeling Material Cartridge 32 Second Modeling Material Cartridge 101 Three-Dimensional Modeling Device

Claims (21)

  A shaped material that forms a shaped article having a tensile elongation at break of 250% or more and 500% or less and a tensile strength at break of 0.01 MPa or more and 1 MPa or less.   The shaped material according to claim 1, comprising an oligomer having an elongation percentage of the homopolymer of 150% or more.   The molding material according to claim 2, wherein the oligomer is a urethane (meth) acrylate oligomer.   The molding material according to any one of claims 1 to 3, wherein the homopolymer contains a monomer having a glass transition temperature of 0 ° C or lower.   The molding material according to claim 4, wherein the monomer is a monomer having a glass transition temperature of a homopolymer of −71 ° C. or more and 0 ° C. or less. Including monomers and oligomers,
The total content of the monomer and the oligomer is 90% by mass or more and 97% by mass or less based on the total mass of the molding material;
The molding material according to claim 1, wherein (content of the monomer) / (content of the monomer and content of the oligomer) are 0.75 or more and 0.95 or less.   The shaped material according to any one of claims 1 to 6, which comprises a granular material.   The shaped material according to claim 7, wherein the granular material is silicon dioxide.   The shaped material according to claim 7, wherein the granules include carbon black.   The shaped material according to claim 7, wherein the particulate matter includes at least one selected from the group consisting of titanium oxide and aluminum oxide. An oligomer having an elongation percentage of the homopolymer of 150% or more, a monomer having a glass transition temperature of 0 ° C. or less of the homopolymer, and a polymerization initiator,
The total content of the monomer and the oligomer is 90% by mass or more and 97% by mass or less based on the total mass of the molding material;
A shaping material, wherein (content of the monomer) / (content of the monomer and content of the oligomer) is 0.75 or more and 0.95 or less.   The molding material according to claim 11, wherein the oligomer is a urethane (meth) acrylate oligomer.   The shaped material according to claim 11, wherein the monomer is a monomer having a glass transition temperature of a homopolymer of −71 ° C. or more and 0 ° C. or less.   The shaped material according to any one of claims 11 to 13, comprising a granular material.   The shaped material according to claim 14, wherein the particulate matter is silicon dioxide particles.   The shaped material according to claim 14, wherein the granules include carbon black.   The shaped material according to claim 14, wherein the particulate matter includes at least one selected from the group consisting of titanium oxide particles and aluminum oxide particles. A region A formed from a shaped article having a tensile elongation at break of 250% or more and 500% or less and a tensile strength at break of 0.01 MPa or more and 1 MPa or less;
A region B having a smaller tensile elongation at break than the region A;
A molded article having   The shaped article according to claim 18, wherein the difference in the tensile elongation at break between the region A and the region B is 240% or more. A first discharging unit that stores the modeling material according to any one of claims 1 to 17 as a first modeling material, and discharges the first modeling material,
A second shaping material forming a second shaping material having a smaller tensile elongation at break than the first shaping material formed from the first shaping material is housed, and the second shaping material is adjacent to the first shaping material. A second discharge unit that discharges
A light irradiation unit that irradiates light that cures the discharged first modeling material and the second modeling material;
A three-dimensional modeling device comprising: A first discharging step of using the modeling material according to any one of claims 1 to 17 as a first modeling material, discharging the first modeling material, and forming a first layer;
A first light irradiation step of irradiating light for curing the first layer;
A second shaped material forming a second shaped object having a smaller tensile elongation at break than the first shaped material formed from the first shaped material is discharged so as to be adjacent to the first shaped material, and a second shaped material is discharged. A second discharging step of forming a layer,
A second light irradiation step of irradiating light for curing the second layer;
A method for producing a three-dimensional structure having: