JP6840964B2 - 3D model, manufacturing method of 3D model and ink set - Google Patents

Description

The present invention relates to a three-dimensional model, a method for manufacturing a three-dimensional model, and an ink set.

The three-dimensional modeling device is also called a 3D printer. For example, according to the cross-sectional shape data of the three-dimensional shape, the colored ink composition is arranged by an inkjet method, and the colored ink composition is repeatedly cured by ultraviolet rays (UV), electron beam (EB), or the like to repeatedly perform a three-dimensional model (for example, industrial). Devices for manufacturing parts such as products, toys such as dolls, etc.) are known.

In a three-dimensional modeling apparatus, an apparatus is known in which a plurality of colored ink compositions such as cyan, magenta, yellow, and black are arranged and cured in order to use a color three-dimensional model.

Here, various proposals have been made regarding a three-dimensional modeling apparatus and a method for manufacturing a three-dimensional modeled object.

For example, Patent Document 1 describes "a coloring liquid containing at least a radical polymerizable compound, a radical polymerization initiator, and a colorant, and an undercoat liquid containing at least a cationically polymerizable compound and a cationic polymerization initiator. An ink set for inkjet recording, characterized in that it contains at least. "

Patent Document 2 states that "in an inkjet ink set composed of at least a color ink containing a colorant and a white ink, the surface tension of the white ink is lower than the surface tension of the color ink. Ink set for inkjet. ”Is disclosed.

Patent Document 3 states that "a resin precursor having radical polymerization property, a radical photopolymerization initiator for causing the resin precursor to undergo a radical polymerization reaction by light irradiation, a resin precursor having cationically polymerizable property, and the resin thereof. An inkjet ink comprising a cationic photopolymerization initiator for subjecting a precursor to a cationic polymerization reaction by irradiation with light and a colorant. "

Patent Document 4 provides "a light reflecting layer formed of an ink having light reflection property, a decorative layer, and a transparent layer formed of a transparent ink, and the decorative layer is the light reflection layer. A modeled object that is formed on the outside of the layer and is characterized in that the transparent layer is formed on the outside of the decorative layer. "

Patent Document 5 describes "a portion of a model formed by a laminating method, which has a decorative layer, and the ink filling density of the decorative layer does not satisfy a predetermined ink filling density with only the decorative ink. , A modeled object characterized in that the ink filling density of the decorative layer is compensated by the filling ink. "

Patent Document 6 states that "an image is formed by injecting an ink having a viscosity at 25 ° C. of 15 mPa · s or more and curable by light irradiation onto a substrate using an inkjet recording method and then irradiating with active light. In the image forming method, there is a means for controlling the viscosity of the ink to 12 mPa · s or less by heating the ink to 40 ° C. or higher before spraying, and after the ink is sprayed onto the substrate, An image forming method characterized by irradiating light when the viscosity of the ink is 15 mPa · s or less. ”Is disclosed.

Patent Document 7 states that "the following components: (a) an epoxy component containing one or more epoxy compounds; 0 to less than 30% by weight, preferably less than 28% by weight, more preferably 20% by weight of the epoxy component. % Is glycidyl type, (b) (i) free of hydroxyl groups; or (ii) contains hydroxyl groups but greater than or equal to one or more having a hydroxyl equivalent of 500 grams or less, preferably about 300 grams or less. A (meth) acrylate component comprising a functional (meth) acrylate; and preferably the (meth) acrylate component forms less than 20% by weight based on the total weight of the composition, (c) preferably in a polyester compound. A component containing two or more hydroxyl groups, preferably not an acrylated polyol, and preferably a polyether polyol compound, (d) a cationic photopolymerization initiator; and (e) an initiation of free radical photopolymerization. A photocurable composition comprising an agent. "

Japanese Unexamined Patent Publication No. 2008-248071 International Publication No. 2006/0879330 Japanese Unexamined Patent Publication No. 2006-0008998 Japanese Unexamined Patent Publication No. 2015-147327 Japanese Unexamined Patent Publication No. 2015-147328 Japanese Unexamined Patent Publication No. 2004-0344441 Japanese Patent Application Laid-Open No. 2007-516318

An object of the present invention is a cured product of a colored ink composition, which is colored in a three-dimensional model having a plurality of colored regions having different colors, as compared with the case where the colored regions having different colors are in direct contact with each other. The purpose of the present invention is to provide a three-dimensional model in which color mixing of regions is suppressed.

The above problem is solved by the following means.

The invention according to <1 > is
It is a cured product of a colored ink composition, and has a plurality of colored regions having different colors.
A three-dimensional modeled product having a transparent region which is a cured product of a transparent ink composition and having a transparent region interposed between a plurality of colored regions having different colors.

The invention according to <2 > is
The three-dimensional model according to < 1 > , wherein the colored region and the transparent region are bonded by a cationic polymer.

The invention according to <3 > is
The three-dimensional model according to < 1 > or < 2 > , wherein the tensile elastic modulus of the transparent region is smaller than the tensile elastic modulus of the colored region.

The invention according to <4 > is
A plurality of colored regions having different colors, which are cured products of a plurality of colored ink compositions having different colors, and a transparent region intervening between the plurality of colored regions having different colors, which are cured products of a transparent ink composition. , A method for producing a three-dimensional modeled product, which comprises a step of repeatedly ejecting and curing the colored ink composition and the transparent ink composition.

The invention according to <5 > is
The colored ink composition
Colorants, compounds with radically polymerizable groups, compounds with cationically polymerizable groups and photoradical polymerization initiators, or
It contains a colorant, a compound having a radically polymerizable group and a cationically polymerizable group, and a photoradical polymerization initiator.
The transparent ink composition
A compound having a radically polymerizable group, a compound having a cationically polymerizable group, a photoradical polymerization initiator, and a photocationic polymerization initiator, or
A compound having a radically polymerizable group and a cationically polymerizable group, a photoradical polymerization initiator, and a photocationic polymerization initiator.
The method for manufacturing a three-dimensional model according to <4 >.

The invention according to <6 > is
The method for producing a three-dimensional model according to < 5 > , wherein the difference between the contact angle of the cured product of the colored ink composition and the contact angle of the cured product of the transparent ink composition is 10 ° or more.

The invention according to <7 > is
Contains or contains a compound having a radically polymerizable group, a compound having a cationically polymerizable group, and a photoradical polymerization initiator.
A colored ink composition containing a compound having a radically polymerizable group and a cationically polymerizable group, and a photoradical polymerization initiator.
Compounds with radically polymerizable groups, compounds with cationically polymerizable groups, photoradical polymerization initiators and photocationic polymerization initiators, or
An ink set comprising a compound having a radically polymerizable group and a cationically polymerizable group, a photoradical polymerization initiator, and a transparent ink composition containing a photocationic polymerization initiator.

The invention according to <8 > is
The ink set according to < 7 > , wherein the difference between the contact angle of the cured product of the colored ink composition and the contact angle of the cured product of the transparent ink composition is 10 ° or more.

According to the invention according to < 1 > , in a three-dimensional model which is a cured product of a colored ink composition and has a plurality of colored regions having different colors, the case where the colored regions having different colors are in direct contact with each other is compared. As a result, a three-dimensional model in which color mixing in the colored region is suppressed is provided.

According to the invention according to < 2 > , a three-dimensional model having excellent bending strength as compared with the case where the colored region and the transparent region are bonded only by a radical polymer is provided.

According to the invention according to < 3 > , a three-dimensional model having excellent bending strength as compared with the case where the tensile elastic modulus of the transparent region is the same as or larger than that of the colored region is provided. ..

According to the invention according to < 4 > , there is provided a method for producing a three-dimensional modeled product in which color mixing of the colored region is suppressed as compared with the case where the colored region is in direct contact with a colored region having a different color.

According to the invention according to < 5 > , a method for producing a three-dimensional model having excellent bending strength is provided as compared with the case where the colored ink composition contains only a compound having an acryloyloxy group as a polymerizable compound. To.

According to the invention according to < 6 > , a colored region is compared with a case where the difference between the contact angle of the cured product of the colored ink composition and the contact angle of the cured product of the transparent ink composition is less than 10 °. A method for producing a three-dimensional model in which color mixing is suppressed is provided.

According to the invention according to < 7 > , an ink used for producing a three-dimensional model having excellent bending strength as compared with the case where the colored ink composition contains only a compound having an acryloyloxy group as a polymerizable compound. A set is provided.

According to the invention according to < 8 > , the colored region is compared with the case where the difference between the contact angle of the cured product of the colored ink composition and the contact angle of the cured product of the transparent ink composition is less than 10 °. An ink set used for manufacturing a three-dimensional model in which color mixing is suppressed is provided.

It is a schematic diagram which shows an example of the 3D model which concerns on this Embodiment. It is a schematic diagram which shows an example of the 3D model | object which concerns on this Embodiment in the process of manufacturing. It is the schematic which shows the 3D model manufactured in Example. It is the schematic which shows the 3D model manufactured in the comparative example. It is the schematic which shows the 3D model manufactured in Example.

Hereinafter, embodiments that are an example of the present invention will be described.

<Three-dimensional model>
The three-dimensional model according to the present embodiment is a cured product of a colored ink composition, which is a plurality of colored regions having different colors and a plurality of transparent regions which are cured products of a transparent ink composition and have different colors. It has a transparent region interposed between the colored regions of the above.

In a three-dimensional model containing a plurality of colored regions, which is produced by forming a plurality of colored regions having different colors using a conventional colored ink composition of a plurality of colors, the colored regions having different colors are adjacent to each other. In some places, color mixing in the colored region (hereinafter, also simply referred to as “color mixing”) was observed.
On the other hand, in the three-dimensional model of the present embodiment, since the colored regions having different colors are in contact with each other through the transparent region, there is no place where the colored regions having different colors are in direct contact with each other, and color mixing is suppressed. To.

The fact that colored regions having different colors are in contact with each other through the transparent region means that a transparent region always exists between one colored region and another colored region having a different color.
Further, the surface of the three-dimensional model may be formed by the colored region, but from the viewpoint of impact resistance and protection of the colored area from dirt, the surface of the three-dimensional model is formed by the transparent region. Is preferable.

FIG. 1 is a schematic view showing an example of a three-dimensional model of the present embodiment. In the three-dimensional model 1, four colored regions 22, 24, 26, and 28 having different colors are in contact with each other through the transparent region 30 without being in direct contact with each other.
Further, the three-dimensional model 1 has a transparent region 30 on the surface of the three-dimensional model.

The thickness of the transparent region is preferably 0.1 μm or more, more preferably 0.5 μm or more, and further preferably 1 μm or more from the viewpoint of suppressing color mixing. The upper limit is not particularly limited, but from the viewpoint of color development, it is preferably 1 mm or less, and more preferably 0.5 mm or less.

Examples of the plurality of colored regions having different colors include colored regions such as cyan, magenta, yellow, black, white, light cyan, light magenta, green, and orange.
These colored regions are cured products of colored ink compositions such as cyan, magenta, yellow, black, white, light cyan, light magenta, green, and orange, respectively.
Details of the colored ink composition will be described later.
In the present embodiment, different colors means that the linear distance between two points representing two perceived colors in ^{La *} b ^{* space, that is, ΔE *} ab is given by the following equation.
ΔE ^* ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2
In the above ΔE ^* ab, the different colors are as follows.
ΔE ^* ab greater than or equal to 0 and less than 0.5: very slightly different.
ΔE ^* ab is 0.5 or more and less than 1.5: Slightly different.
ΔE ^* ab greater than or equal to 1.5 and less than 3.0: perceptibly different.
ΔE ^* ab is 3.0 or more and less than 6.0: significantly different.
ΔE ^* ab is 6.0 or more and less than 12.0: Very significantly different.
ΔE ^* ab is 12.0 or more: Another color system is used.
The color evaluation is measured by a color meter or the like such as a non-contact type TeleFlash system manufactured by X-Rite.

In the present embodiment, a region in which the transmittance of light having a wavelength of 380 nm or more and 780 nm or less when the optical path length is 1 cm is 80% or more is referred to as a transparent region, and a region having a wavelength of less than 80% is referred to as a colored region.
The transmittance is measured by measuring the optical path length and transmittance of the measurement sample using a spectrophotometer and correcting the optical path length based on the Beer-Lambert law.

It is considered that the transmittance of the transparent region and the transmittance of the transparent ink composition before curing are about the same. Therefore, if the transmittance of the transparent region is 80% or more, the transparent ink composition is better than the colored ink composition when irradiated with active radiation to cure the transparent ink composition and the colored ink composition. It is considered that the transparent ink composition cures before the colored ink composition because of its excellent transmittance of active radiation. As a result, it is presumed that the color mixing of the colored region is suppressed.
Further, if the transmittance is 80% or more, for example, when a three-dimensional model is manufactured by a method of ejecting ink while moving a modeling table that supports the three-dimensional model in the process of being manufactured, it is tertiary. The strain of the original model (hereinafter, also simply referred to as "strain") is suppressed.
The above strain causes the 3D model during manufacturing to be like a so-called "blurring" when the strength of the 3D model during manufacturing is weak and the movement of the 3D model cannot follow the movement of the modeling table. It is considered that this occurs as a result of the movement and the deviation of the discharge position with respect to the target position. However, if the transmittance is 80% or more, the transparent ink composition is cured before the colored ink composition, so that the strength of the three-dimensional model is increased, and the modeling table is moved during production. It is presumed that the occurrence of strain will be suppressed because the movement of the three-dimensional model will be easier to follow.
Further, the transmittance of the transparent region is more preferably 80% or more, and further preferably 81% or more, from the viewpoint of suppressing color mixing and suppressing the occurrence of strain. The upper limit of the transmittance is not particularly limited, and may be 100% or less.
Details of the transparent ink composition will be described later.

(Cationic polymer)
In the three-dimensional model of the present embodiment, from the viewpoint of the bending strength of the obtained three-dimensional model, it is preferable that the colored region and the transparent region are bonded by a cationic polymer.
The cationic polymer means a polymer formed by cationic polymerization.
The fact that the colored region and the transparent region are bonded by the cationic polymer means that one cationic polymer is present in both the colored region and the transparent region.
For example, a colored ink composition containing at least a compound having a cationically polymerizable group and a transparent ink composition containing at least a compound having a cationically polymerizable group and a cationic polymerization initiator are discharged so as to be in contact with each other and exposed to active radiation. When cured by, a compound having at least a cationically polymerizable group in the colored ink composition and a compound having at least a cationically polymerizable group in the transparent ink composition form a cationically polymerized product.
According to the above aspect, a three-dimensional model in which one cationic polymer is present in both the colored region and the transparent region can be obtained.
Cationic polymerization is more difficult to inhibit polymerization by oxygen than radical polymerization, has a long life of the polymerization initiation species, and has a long duration of polymerization, so that a more polymerized polymer can be obtained. Therefore, it is considered that the permeability of the polymer is high and the polymerization region is expanded.
Therefore, when the colored region and the transparent region are bonded by the cationic polymer, they are wider and deeper by the polymerized polymer than in the case where they are bonded only by the radical polymer. Since the ranges are combined, it is considered that the adhesion between the colored region and the transparent region is excellent.
As a result, it is presumed that the three-dimensional model can be obtained with excellent bending strength by suppressing the occurrence of peeling and cracking at the interface between the colored region and the transparent region.

The three-dimensional model in which the colored region and the transparent region are bonded by a cationic polymer is, for example, a colored ink composition containing a compound having a cationically polymerizable group and a compound having a cationically polymerizable group. , Obtained by forming with a transparent ink composition containing a photocationic polymerization initiator. The photocationic polymerization initiator may be contained in the colored ink composition, but is preferably contained in the transparent ink composition from the viewpoint of excellent light transmission and efficient polymerization.
It is confirmed by analysis of the colored region, the residue of the initiator contained in the transparent region, and the polymer that the colored region and the transparent region are bonded by the cationic polymer.
Specifically, attenuation of the amount of double-bonded functional organs by infrared analysis, structural change of polymerizable monomer to be cationically polymerized, absorption spectrum change from cationic polymerization reagent structure, weight of 350 ° C. or higher by thermal gravimetric analysis. It is possible to confirm by the amount of attenuation. Normally, a cationic polymerization monomer has many ring structures, and polymerization occurs when the ring structure is cleaved. Therefore, by measuring this absorption spectrum change, the colored region and the transparent region become cations. It is judged that they are bound by the polymer.

(Tensile modulus)
In the three-dimensional model of the present embodiment, it is preferable that the tensile elastic modulus of the transparent region is smaller than the tensile elastic modulus of the colored region. When a uniform pressure (or tension) is applied to an object, its volume shrinks (or expands).
According to the above aspect, it is considered that the impact resistance of the three-dimensional modeled object is excellent.
This is because the hard (high tensile elastic modulus) colored region is wrapped with the soft (small tensile elastic modulus) transparent region, so that an impact such as dropping and a load such as twisting are absorbed by the transparent region. It is presumed to be.
The tensile elastic modulus of the transparent region is preferably 5 Mpa or more and 40 MPa or less, more preferably 10 Mpa or more and 40 Mpa or less, and further preferably 20 Mpa or more and 40 Mpa or less from the viewpoint of impact resistance.
The tensile elastic modulus of the colored region is preferably 10 MPa or more and 80 MPa or less, more preferably 20 MPa or more and 70 MPa or less, and further preferably 20 MPa or more and 50 MPa or less from the viewpoint of impact resistance.
The difference in tensile elastic modulus between the transparent region and the colored region is preferably 5 MPa or more and 70 MPa or less, more preferably 10 MPa or more and 50 MPa or less, and further preferably 10 MPa or more and 30 MPa or less.
The tensile elastic modulus is measured by a tensile tester according to ASTM D-638.

(Size of colored area)
The size of one colored region surrounded by the transparent region ^{is preferably 1000 mm 3} or less, ^{more preferably 125 mm 3} or less, and ^{further preferably 1 mm 3} or less. The lower limit is not particularly limited, but it is preferably ^{1 × 10-6} mm ^{3 or more in terms of the manufacturing suitability of the inkjet.}
When the size of each colored region is 1 mm ³ or less, the amount of the transparent region contained in the three-dimensional modeled object is large, and the impact resistance and bending strength of the obtained three-dimensional modeled object are excellent.
When one colored region ^{exceeds 10 mm 3} , even if the colored regions of the same color do not differ in color, they are divided into a plurality of colored regions of the same color, and the colored regions of the same color are separated from each other through the transparent region. Contact is also useful.
Further, the coloring density of the three-dimensional model may be controlled by arranging the transparent region between the colored regions.

(Ink layer)
The three-dimensional model according to the present embodiment ejects at least one of a colored ink composition and a transparent ink composition (hereinafter, collectively referred to as “ink composition”), and is cured and colored by exposure to active radiation. It is formed by repeating ejection and exposure (curing) of at least one of the ink compositions, that is, forming at least one of a region and a transparent region (hereinafter, collectively referred to as “region”).
A layer of a cured ink composition formed by one ejection and exposure (curing) is referred to as an ink layer (hereinafter, also simply referred to as "layer").
By curing the ejected ink composition to form an ink layer and further ejecting and curing the ink composition on the ink layer, a large number of ink layers are laminated to obtain a three-dimensional model. That is, the three-dimensional model according to the present embodiment is a laminated body of a large number of ink layers. The three-dimensional model according to the present embodiment preferably has one or more ink layers, and more preferably two or more ink layers. It is more preferable to have 3 or more.
The thickness of the ink layer is preferably 0.1 μm or more and 10 μm or less, more preferably 0.5 μm or more and 5 μm or less, and further preferably 1.0 μm or more and 3 μm or less.
The number and thickness of the ink layers can be measured by cutting out a three-dimensional model, observing the layers with a transmissive or reflective electron microscope, and measuring with a measuring instrument.

(Transparent ink composition)
The transparent ink composition contains a compound having a radically polymerizable group, a compound having a cationically polymerizable group, a photoradical polymerization initiator, a photocationic polymerization initiator, or a radically polymerizable group, and a cationically polymerizable group. It is preferable to contain the compound, the photoradical polymerization initiator, and the photocationic polymerization initiator.
According to the above aspect, the transparent ink composition that easily transmits light is cured before the colored ink composition by radical polymerization to form a transparent region, so that color mixing is suppressed and distortion is suppressed. Will be done. Further, when the shaku-shaku ink composition contains at least a compound having a cationically polymerizable group, the colored region and the transparent region are bonded by the cationic polymer, so that a three-dimensional model having excellent bending strength can be obtained. can get.

In the present embodiment, a region in which the light transmittance of a wavelength of 380 nm or more and 780 nm or less when the optical path length is 1 cm is 80% or more is referred to as a transparent ink composition, and a region of less than 80% is referred to as a colored ink composition.
The transmittance is measured by measuring the optical path length and transmittance of the measurement sample using a spectrophotometer and correcting the optical path length based on the Beer-Lambert law.
Further, the transmittance of the transparent ink composition is more preferably 80% or more, and further preferably 81% or more, from the viewpoint of suppressing color mixing and suppressing the occurrence of strain. The upper limit of the transmittance is not particularly limited, and may be 100% or less.

-First aspect-
A first aspect of the transparent ink composition in the present embodiment is a transparent ink composition containing a compound having a radically polymerizable group, a compound having a cationically polymerizable group, a photoradical polymerization initiator, and a photocationic polymerization initiator. It is a thing.

[Compounds with radically polymerizable groups]
As the compound having a radically polymerizable group, various monomers, oligomers, and prepolymers that polymerize by a radical polymerization reaction to form a polymer can be used.

As the radically polymerizable group, a (meth) acryloxy group or a (meth) acrylamide group is preferable, and a (meth) acryloxy group is more preferable.

Specifically, examples of the compound having a radically polymerizable group preferably include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate and the like. Among these, urethane (meth) acrylate is preferable as the compound having a radically polymerizable group.
In addition, in this specification, (meth) acrylate means both acrylate and methacrylate, and (meth) acrylic means both acrylic and methacrylic. Further, the (meth) acryloyl means both an acryloyl group and a methacryloyl group.

-Urethane (meth) acrylate-
Urethane (meth) acrylate (hereinafter, also simply referred to as "urethane (meth) acrylate") is a compound having a urethane structure and two or more (meth) acryloyl groups in one molecule. The urethane (meth) acrylate may be a monomer or an oligomer, but may be an oligomer.

The functional number (the number of (meth) acryloyl groups) of the urethane (meth) acrylate is preferably 2 or more and 20 or less (preferably 2 or more and 15 or less).

Examples of the urethane (meth) acrylate include a reaction product using a polyisocyanate compound, a polyol compound, and a hydroxyl group-containing (meth) acrylate. Specifically, the urethane (meth) acrylate is, for example, a prepolymer obtained by reacting a polyisocyanate compound and a polyol compound, and is a reaction between a prepolymer having an isocyanate group at the terminal and a hydroxyl group-containing (meth) acrylate. The product is mentioned. Examples of the urethane (meth) acrylate include a reaction product of a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate.

-Polyisocyanate compound Examples of the polyisocyanate compound include chain saturated hydrocarbon isocyanate, cyclic saturated hydrocarbon isocyanate, aromatic polyisocyanate and the like. Among these, as the polyisocyanate compound, a chain saturated hydrocarbon isocyanate having no light absorption band in the near-ultraviolet region and a cyclic saturated hydrocarbon isocyanate having no light absorption band in the near-ultraviolet region are preferable.
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, norbornan 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, Examples thereof include 3-phenyldiisocyanate and 1,5-naphthalenediisocyanate.

-Polyol compound Examples of the polyol compound include diols and polyhydric alcohols.
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, 1, 10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,2-dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, etc. ) Etc. can be mentioned.
Examples of the polyhydric alcohol include alkylene polyhydric alcohols containing 3 or more hydroxyl groups (eg, glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butantriol). , Erythritol, sorbitol, pentaerythritol, dipentaerythritol, mannitol, etc.).

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

Examples of the polyether polyol include a multimer of a polyhydric alcohol, an adduct of a polyhydric alcohol and an alkylene oxide, a ring-opening polymer of an alkylene oxide, and the like.
Here, examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, and 1, 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-Nonandiol, 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, and tetrahydrofuran.

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

Examples of the polycarbonate polyol include a reaction product of glycol and alkylene carbonate, a reaction product of glycol and diaryl carbonate, and a reaction product of glycol and 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-ethyldiphenyl carbonate, 4-propyldiphenyl carbonate, 4,4'-dimethyldiphenyl carbonate, 2-tolyl-4-tolyl carbonate, 4,4'. Examples thereof include -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 so on.

-Hydrogen group-containing (meth) acrylate Examples of the hydrogen group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy. -3-Phenoxypropyl (meth) acrylate, glycerindi (meth) acrylate, trimethylpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like can be mentioned. Examples of the hydrogen group-containing (meth) acrylate include an adduct of a glycidyl group-containing compound (for example, alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, etc.) and (meth) acrylic acid.

-Urethane (meth) acrylate weight average molecular weight-
The weight average molecular weight of the urethane (meth) acrylate is preferably 500 or more and 5000 or less, and more preferably 1000 or more and 3000 or less.
The weight average molecular weight of urethane (meth) acrylate is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

-Compounds with other radically polymerizable groups-
Examples of the compound having a radically polymerizable group include compounds having other radically polymerizable groups in addition to the above.
Examples of other compounds having a radically polymerizable group include (meth) acrylates (monofunctional (meth) acrylates, polyfunctional (meth) acrylates) and the like, which are exemplified below.

Examples of the monofunctional (meth) acrylate include a linear, branched, or cyclic alkyl (meth) acrylate, a (meth) acrylate having a hydroxyl group, a (meth) acrylate having a heterocycle, and a (meth) acrylamide compound. And so on.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl. Examples thereof include (meth) acrylate, cyclohexyl (meth) acrylate, 4-t-cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate.
Examples of the (meth) acrylate having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and methoxypolyethylene glycol mono (meth) acrylate. Examples thereof include polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, and polyethylene glycol-polypropylene glycol block polymer mono (meth) acrylate.
Examples of the (meth) acrylate having a heterocycle include tetrahydrofurfuryl (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, and 4- (meth) acryloyloxy. Examples thereof include methyl-2-cyclohexyl-1,3-dioxolane and adamantyl (meth) acrylate.
Examples of the (meth) acrylamide compound include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N. Included are'-dimethyl (meth) acrylamide, N, N'-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide and the like.

Among the polyfunctional (meth) acrylates, the bifunctional (meth) acrylate includes, for example, 1,10-decanediol diacrylate, 2-methyl-1,8-octanediol diacrylate, and 2-butyl-2-. Ethyl-1,3-propanediol diacrylate, 1,9-nonanediol diacrylate, 1,8-octanediol diacrylate, 1,7-heptanediol diacrylate, polytetramethylene glycol diacrylate, 3-methyl-1 , 5-Pentanediol Diacrylate, 1,6-Hexanediol Diacrylate, Neopentyl glycol Diacrylate, Neopentyl glycol diacrylate hydroxypivalate, Tripropylene glycol diacrylate, 1,4-Butanediol diacrylate, Dipropylene glycol Diacrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, EO (ethylene oxide) modified bisphenol A diacrylate, PO (propylene oxide) modified bisphenol A diacrylate, EO modified hydrogenated bisphenol A diacrylate, EO (ethylene oxide) ) Modified bisphenol F diacrylate and the like.

Among the polyfunctional (meth) acrylates, examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and pentaerythritol triacrylate. Glycerin triacrylate ethoxylated, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate ethoxylated, EO (ethylene oxide) modified diglycerin tetraacrylate, dimethylolpropane tetraacrylate-modified acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. Can be mentioned.

The compound having a radically polymerizable group may be used alone or in combination of two or more.

[Compound having a cationically polymerizable group]
As the compound having a cationically polymerizable group, various monomers, oligomers, and prepolymers that are polymerized by a cationic polymerization reaction to form a polymer can be used.

Examples of the cationically polymerizable group include an epoxy group, an oxetane group, and a vinyl group. Examples of the compound having a cationically polymerizable group are preferably an epoxy compound, an oxetane compound, and a vinyl ether compound from the viewpoint of curability. Alternatively, the oxetane compound is more preferable.

-Epoxy compounds and oxetane compounds-
The epoxy compound used in the present embodiment is not particularly limited, and known epoxy compounds are used, and aromatic epoxides, alicyclic epoxides, aliphatic epoxides and the like are preferable.
Examples of the aromatic epoxide include diglycidyl ether or polyglycidyl ether of bisphenol A (including an alkylene oxide adduct), diglycidyl ether or polyglycidyl ether of hydrogenated bisphenol A (including an alkylene oxide adduct), and Novolac type epoxy resin and the like can be mentioned. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

Examples of the alicyclic epoxide include cyclohexene oxide and cyclopentene oxide-containing compounds.
The cyclohexene oxide or cyclopentene oxide-containing compound is prepared by epoxidizing a compound having a cycloalkane ring such as at least one cyclohexene or cyclopentene ring with an appropriate oxidizing agent (hydrogen peroxide, peracid, etc.). Obtained by
Examples of the aliphatic epoxide include diglycidyl ether or polyglycidyl ether of an aliphatic polyhydric alcohol (including an alkylene oxide adduct). Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

The aromatic epoxy monomer is not particularly limited, and examples thereof include an epoxy monomer having a bisphenol skeleton, an epoxy monomer having a dicyclopentadiene skeleton, an epoxy monomer having a naphthalene skeleton, an epoxy monomer having an adamanten skeleton, and a fluorene skeleton. Examples thereof include an epoxy monomer having a biphenyl skeleton, an epoxy monomer having a bi (glycidyloxyphenyl) methane skeleton, an epoxy monomer having a xanthene skeleton, and an epoxy monomer having an anthracene skeleton and a pyrene skeleton. These epoxy monomers may be used alone or in combination of two or more.

The oxetane monomer used in the present embodiment is not particularly limited, but for example, a monofunctional or bifunctional oxetane monomer is used.
More specifically, for example, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toa Synthetic Co., Ltd., trade name OXT101, etc.), di (1-ethyl-3-oxetanyl) methyl ether (manufactured by Toa Synthetic Co., Ltd.) , Trade name OXT221, etc.), 3-Ethyl-3- (2-ethylhexyloxymethyl) oxetane (manufactured by Toa Synthetic Co., Ltd., trade name OXT212, etc.) and the like are preferably mentioned.

Examples of the aromatic oxetane monomer include 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene (manufactured by Toa Synthetic Co., Ltd., trade name OXT121, etc.) and 3-ethyl-3- (phenoxy). Methyl) oxetane (manufactured by Toa Synthetic Co., Ltd., trade name OXT211 etc.), and the like can be mentioned.

Examples of the vinyl ether compound include alkylene glycol divinyl ether, alkylene glycol monovinyl ether, polyalkylene glycol divinyl ether, alkylenediol divinyl ether, cycloalkylene dimethanol divinyl ether, hydroxyalkyl monovinyl ether, and trimethylolpropantrivinyl ether.
As the alkylene group, an alkylene group having 2 or more and 20 or less carbon atoms is preferable, and an alkylene group having 2 or more and 10 or less carbon atoms is more preferable.

The compound having a cationically polymerizable group may be used alone or in combination of two or more.
The content of the compound having a cationically polymerizable group in the transparent ink composition shall be 2% by mass or more and 98% by mass or less with respect to the total mass of the transparent ink composition from the viewpoint of the bending strength of the transparent region and the colored region. It is more preferable that it is 5% by mass or more and 95% by mass or less, and further preferably 30% by mass or more and 70% by mass or less.

[Photoradical polymerization initiator]
The photoradical polymerization initiator is not particularly limited, and is, for example, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-alkyl. Examples thereof include dione compounds, disulfide compounds, fluoroamine compounds and aromatic sulfoniums.
Among the above compounds, phosphine oxides are preferable from the viewpoint of curability.
Examples of acetophenones include 2,2-ethoxyacetophenone, p-methylacetophenone, 1-hydroxydimethylphenylketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-. Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone and the like can be mentioned.
Examples of 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 benzophenones include benzophenone, 2,4-chlorobenzophenone, 4,4-dichlorobenzophenone, p-chlorobenzophenone and the like.
Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF, IRGACURE TPO) and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (BASF, IRGACURE). 819) and the like.

Further, as the radical polymerization initiator, various compounds described in "Application and Market of UV / EB Curing Technology (CMC Publishing, supervised by Yoneho Tabata / edited by Radtech Study Group)" are also used.

From the viewpoint of curability, the content of the photoradical polymerization initiator is preferably 0.1 part by mass or more and 15 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less, based on the total mass of the transparent ink composition. ..

A photosensitizer may be used in addition to the photoradical polymerization initiator. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone, thioxanthone, and the like.

[Photocationic polymerization initiator]
As a photocationic polymerization initiator for subjecting a compound having a cationically polymerizable group to a cationic polymerization reaction by light irradiation, various conventionally known photocationic polymerization initiators are used. Specific examples of the photocationic polymerization initiator include diazonium salts, iodonium salts (diaryliodonium salts and the like), sulfonium salts (triarylsulfonium salts and the like), iron arene complexes, organic polyhalogen compounds and the like. Among these, as diazonium salt, iodonium salt and sulfonium salt, Japanese Patent Publication No. 54-14277, Japanese Patent Publication No. 54-14278, Japanese Patent Application Laid-Open No. 51-56885, US Pat. No. 3,708,296, No. 3 Examples thereof include the compounds described in No. 853,002 and the like.

Particularly suitable compounds, diazonium, ammonium, iodonium, sulfonium, _B aromatic onium compounds such as phosphonium ^{_{(C 6 F 5) 4 -}} , PF 6 -, AsF 6 -, SbF 6 -, CF 3 SO 3 - Examples thereof include salts, and among them, those having a borate compound as a counter anion are preferable because of their high acid generation ability. Further, a sulfonate that generates sulfonic acid, a halide that photogenerates hydrogen halide, an iron allen complex, and the like are also suitable. Further, as the photocationic polymerization initiator, the photoacid generator compound described on pages 55 to 78 of "Molecular Design of Super LSL Resist" (Kyoritsu Shuppan, 1990) by Yuzuru Tsuda is used.

Commercially available compounds are also used as the photocationic polymerization initiator. As commercially available compounds, IRGACURE250, 270 and 290 manufactured by BASF are preferable.

The photocationic polymerization initiator may be used alone or in combination of two or more. From the viewpoint of curability, the content of the photocationic polymerization initiator in the transparent ink composition is preferably 0.1% by mass or more and 20% by mass or less, and 1% by mass or more and 15% by mass with respect to the total mass of the transparent ink composition. % Or less is more preferable.

[Colorant]
The transparent ink composition preferably does not contain a colorant described later.
When the transparent ink composition contains a colorant, the content of the colorant is preferably 1% or less, preferably 0.5% or less, based on the total mass of the transparent ink composition from the viewpoint of transparency. More preferably, it is more preferably 0.1% or less.

[Polymerization inhibitor]
Examples of the polymerization inhibitor include phenolic polymerization inhibitors (eg, p-methoxyphenol, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene, 2,2'-methylenebis (for example). 4-Methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), etc.), hindered amines, hydroquinone Well-known polymerization inhibitors such as monomethyl ether (MEHQ) and hydroquinone can be mentioned.

The content of the polymerization inhibitor is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.1% by mass or more and 10% by mass or less, based on the total mass of the compound having a radically polymerizable group.
The polymerization inhibitor may be used alone or in combination of two or more.

[Surfactant]
Examples of the surfactant include silicone-based surfactants, acrylic-based surfactants, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, and fluorine-based surfactants. Well-known surfactants can be mentioned.

The content of the surfactant is preferably 0.05% by mass or more and 15% by mass or less, and more preferably 0.1% by mass or more and 10.0% by mass or less, based on the total mass of the transparent ink composition.
The surfactant may be used alone or in combination of two or more.

[Other additives]
Other than the above, other additives include, for example, solvents, sensitizers, fixing agents, fungicides, preservatives, antioxidants, UV absorbers, chelating agents, thickeners, dispersants, polymerization accelerators. , Penetration promoters, wetting agents (moisturizers) and other well-known additives.

[Characteristics of transparent ink composition]
The surface tension of the transparent ink composition is, for example, in the range of 18 mN / m or more and 70 mN / m or less.
Here, the surface tension is a value measured in an environment of 23 ° C. and 55% RH using a Wilhelmy type surface tension meter (manufactured by Kyowa Interface Science Co., Ltd.).

The viscosity of the transparent ink composition is, for example, in the range of 3 mPa · s or more and 100 mPa · s or less.
Here, the viscosity is a value measured using Leomat 115 (manufactured by Contravens) as a measuring device under the conditions of ^{a measurement temperature of 23 ° C. and a shear rate of 1400s -1.}

The contact angle of the cured product of the transparent ink composition is preferably 50 ° or more and 104 ° or less, more preferably 50 or more and 90 ° or less, and further preferably 60 ° or more and 90 ° or less.
The difference between the contact angle of the cured product of the colored ink composition and the contact angle of the cured product of the transparent ink composition is preferably 5 ° or more, more preferably 10 ° or more, and 15 ° or more. Is more preferable. The upper limit of the difference in contact angles is not particularly limited, but may be 50 ° or less.
For the above contact angle, please describe the method for producing the cured product and the method for measuring the contact angle. The measurement was carried out at 25 ° C. at room temperature using an aqueous solvent and using a fully automatic contact angle meter DMo-1101 manufactured by Kyowa Interface Science Co., Ltd.
The measurement sample was formed into a flat plate sample having a thickness of about 10 μm and 1 cm × 1 cm square after UV curing.
As for the UV condition, a UV-LED light source of 365 nm (surface irradiation type manufactured by CCS Co., Ltd.) was used, and irradiation was performed for 2 seconds with an irradiance of ^{150 mW / cm 2.}

-Second aspect-
A second aspect of the transparent ink composition in the present embodiment is a transparent ink composition containing a radically polymerizable group, a compound having a cationically polymerizable group, a photoradical polymerization initiator, and a photocationic polymerization initiator. It is a thing.
By containing a compound having a radically polymerizable group and a cationically polymerizable group, a three-dimensional model having superior bending strength can be obtained.

The photoradical polymerization initiator and the photocationic polymerization initiator in the second aspect of the transparent ink composition are the photoradical polymerization initiator and the photocationic polymerization initiator in the first aspect of the transparent ink composition. It is synonymous and the preferred embodiment is the same.
In the second aspect, the transparent ink composition preferably contains the compound having a radically polymerizable group and the compound having a cationically polymerizable group described in the first aspect of the transparent ink composition.
Further, the characteristics of the colorant, the polymerization inhibitor, the surfactant, other additives, and the transparent ink composition in the second aspect of the transparent ink composition are also the characteristics of the transparent ink composition in the first aspect of the transparent ink composition. It is synonymous with the properties of colorants, polymerization inhibitors, surfactants, other additives, and transparent ink compositions, and the preferred embodiments are also the same.

[Compounds having radically polymerizable groups and cationically polymerizable groups]
The (meth) acryloyl group is preferable as the radically polymerizable group in the compound having a radically polymerizable group and the cationically polymerizable group, and the vinyl ether group is preferable as the cationically polymerizable group.

Examples of the compound having a radically polymerizable group and a cationically polymerizable group include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, ethyloxetane methyl vinyl ether, cyclohexanedimethanol vinyl glycidyl ether and the like. ..

Commercially available compounds may be used as the compounds having a radically polymerizable group and a cationically polymerizable group. For example, VEEA and VEEM (both manufactured by Nippon Catalyst Co., Ltd.), EOXTVE and CHDMVG (both by Maruzen Petrochemical Co., Ltd.) may be used. (Made by Co., Ltd.).

The radically polymerizable group and the compound having a cationically polymerizable group may be used alone or in combination of two or more.
The content of the radical-polymerizable group and the compound having a cationically polymerizable group in the transparent ink composition is 5% by mass or more and 95% by mass or less with respect to the total mass of the transparent ink composition from the viewpoint of curability. It is more preferable, it is more preferably 10% by mass or more and 90% by mass or less, and further preferably 30% by mass or more and 70% by mass or less.

(Colored ink composition)
The colored ink composition according to the present embodiment contains a colorant, a compound having a radically polymerizable group, a compound having a cationically polymerizable group and a photoradical polymerization initiator, or a radically polymerizable group and a cationically polymerizable group. Contains a compound having a photoradical polymerization initiator and a photoradical polymerization initiator.
According to the above aspect, the colored region is rapidly formed by radical polymerization having a high curing rate, so that the production speed of the three-dimensional model is excellent, and the transparent ink composition has at least a cationically polymerizable group and light. When the cationic polymerization initiator is contained, the colored region and the transparent region are further bonded by the cationic polymer, so that a three-dimensional molded product having excellent bending strength can be obtained.

-First aspect-
The first aspect of the colored ink composition in the present embodiment is a colored ink composition containing a colorant, a compound having a radically polymerizable group, a compound having a cationically polymerizable group, and a photoradical polymerization initiator. ..

[Colorant]
As the colorant, various conventionally known colorants such as pigments and dyes can be used, and pigments are particularly preferable from the viewpoint of improving the weather resistance of the three-dimensional modeled object.

The pigment is not particularly limited, and all commercially available organic pigments and inorganic pigments, pigments are dispersed in a resin or the like as a dispersion medium, or a resin is grafted on the pigment surface. Etc. are used. Further, those obtained by dyeing resin particles with a dye are also used.

Specific examples of the organic pigment and the inorganic pigment used in the present embodiment include the compounds described in paragraphs 0036 to 0039 of Japanese Patent No. 5372295, and these are also applied to the present embodiment.

For the dispersion of pigments, for example, a disperser such as a ball mill, sand mill, attritor, roll mill, jet mill, homogenizer, paint shaker, kneader, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, etc. is used. Can be done.

When dispersing the pigment, a dispersant may be added. Dispersants include hydroxyl group-containing carboxylic acid esters, long-chain polyaminoamide and high molecular weight acid ester salts, high molecular weight polycarboxylic acid salts, high molecular weight unsaturated acid esters, high molecular weight copolymers, modified polyacrylates, and aliphatics. Examples thereof include polyvalent carboxylic acid, naphthalene sulfonic acid formarin condensate, polyoxyethylene alkyl phosphate ester, pigment derivative and the like. It is also preferable to use a commercially available polymer dispersant such as the Solspace series manufactured by Lubrizol.
Further, as the dispersion aid, a sinargist corresponding to various pigments is also used.
It is preferable to add 1 part by mass or more and 50 parts by mass or less of these dispersants and dispersion aids to 100 parts by mass of the pigment.

In the colored ink composition, a solvent may be added as a dispersion medium for various components such as pigments, but it is preferably solvent-free. This is because if the solvent remains in the colored region, the solvent resistance deteriorates or the solvent remains (VOC, Volatile Organic Compound). From the above viewpoint, a compound having a radically polymerizable group is used as the dispersion medium, and it is particularly preferable to select a low-viscosity cationically polymerizable monomer from the viewpoint of improving dispersion suitability and handling of the ink composition.

The volume average particle size of the pigment particles is preferably 0.01 μm or more and 2 μm or less, and more preferably 0.02 μm or more and 0.1 μm or less. The maximum particle size is preferably 3 μm or less, and more preferably 1 μm or less. Pigments, dispersants, selection of dispersion medium, dispersion conditions, and filtration conditions are set so as to fall within the above range. By this particle size control, clogging of the head nozzle is suppressed, and the storage stability and curing sensitivity of the colored ink composition are maintained.
The volume average particle size is measured by the Microtrac UPA particle size analyzer UPA-UT151 (manufactured by Microtrac). The measurement is performed by placing 1000-fold diluted ink in a measurement cell. As the input value at the time of measurement, the viscosity of the ink diluent is used as the viscosity, and the refractive index of the pigment particles is used as the refractive index of the particles.

The content of the colorant is preferably 0.01% by mass or more and 50% by mass or less, and more preferably 0.1% by mass or more and 20% by mass or less, based on the total mass of the colored ink composition. When an oil-soluble dye is used as the colorant, it is particularly preferably 0.01% by mass or more and 10% by mass or less with respect to the total mass (including the solvent) of the colored ink composition.

[Compounds with radically polymerizable groups]
The compound type of the compound having a radically polymerizable group in the colored ink composition is synonymous with the compound type of the compound having a radically polymerizable group in the first aspect of the above-mentioned transparent ink composition, and the preferred embodiment is also the same. ..
The compound having a radically polymerizable group may be used alone or in combination of two or more.
The content of the compound having a radically polymerizable group in the colored ink composition is preferably 5% by mass or more and 95% by mass or less, preferably 10% by mass, based on the total mass of the colored ink composition from the viewpoint of curability. It is more preferably 90% by mass or more, and further preferably 15% by mass or more and 85% by mass or less.

[Compound having a cationically polymerizable group]
The compound type of the compound having a cationically polymerizable group in the colored ink composition is synonymous with the compound type of the compound having a cationically polymerizable group in the first aspect of the above-mentioned transparent ink composition, and the preferred embodiment is also the same. ..
The compound having a cationically polymerizable group may be used alone or in combination of two or more.
The content of the compound having a cationically polymerizable group in the colored ink composition is preferably 5% by mass or more and 95% by mass or less, preferably 10% by mass, based on the total mass of the colored ink composition from the viewpoint of curability. It is more preferably 90% by mass or more, and further preferably 15% by mass or more and 85% by mass or less.

[Photoradical polymerization initiator]
The compound type of the photoradical polymerization initiator in the colored ink composition is synonymous with the compound type of the photoradical polymerization initiator in the first aspect of the transparent ink composition described above, and the preferred embodiment is also the same.
The photoradical polymerization initiator may be used alone or in combination of two or more.
From the viewpoint of curability, the content of the photoradical polymerization initiator in the colored ink composition is preferably 0.5% by mass or more and 20% by mass or less, preferably 1.0% by mass, based on the total mass of the colored ink composition. It is more preferably% or more and 15% by mass or less, and further preferably 1.0% by mass or more and 10% or less.

[Photocationic polymerization initiator]
The colored ink composition may contain a photocationic polymerization initiator.
The compound type of the photocationic polymerization initiator in the colored ink composition is synonymous with the compound type of the photocationic polymerization initiator in the first aspect of the transparent ink composition described above, and the preferred embodiment is also the same.
The photocationic polymerization initiator may be used alone or in combination of two or more.
When the colored ink composition contains a photocationic polymerization initiator, the content of the photocationic polymerization initiator is 0.1% by mass or more and 15% by mass with respect to the total mass of the colored ink composition from the viewpoint of curability. % Or less, more preferably 0.1% by mass or more and 10% by mass or less, and further preferably 0.1% by mass or more and 10% by mass or less.
Further, from the viewpoint of the bending strength of the three-dimensional model, the content of the photocationic polymerization initiator in the colored ink composition is preferably smaller than the content of the photocationic polymerization initiator in the transparent ink composition.

The polymerization inhibitor, surfactant, and other additives in the first aspect of the colored ink composition are also the polymerization inhibitor, surfactant, and other additives in the first aspect of the transparent ink composition. , And other additives, and preferred embodiments are also the same.

[Characteristics of colored ink composition]
The surface tension of the colored ink composition is, for example, in the range of 18 mN / m or more and 70 mN / m or less.
Here, the surface tension is a value measured in an environment of 23 ° C. and 55% RH using a Wilhelmy type surface tension meter (manufactured by Kyowa Interface Science Co., Ltd.).

The viscosity of the colored ink composition is, for example, in the range of 3 mPa · s or more and 100 mPa · s or less.
Here, the viscosity is a value measured using Leomat 115 (manufactured by Contravens) as a measuring device under the conditions of ^{a measurement temperature of 23 ° C. and a shear rate of 1400s -1.}

The contact angle of the cured product of the colored ink composition is preferably 50 ° or more and 104 ° or less, more preferably 50 ° or more and 90 ° or less, and further preferably 60 ° or more and 90 ° or less.

-Second aspect-
The second aspect of the colored ink composition in the present embodiment is a compound containing a radically polymerizable group, a compound having a cationically polymerizable group, and a photoradical polymerization initiator.
By containing a compound having a radically polymerizable group and a cationically polymerizable group, a three-dimensional model having superior bending strength can be obtained.

The photoradical polymerization initiator in the second aspect of the colored ink composition is synonymous with the photoradical polymerization initiator in the first aspect of the transparent ink composition, and the preferred embodiments are also the same.
In the second aspect, the colored ink composition preferably contains the compound having a radically polymerizable group and the compound having a cationically polymerizable group described in the first aspect of the colored ink composition.
In the second aspect, the colored ink composition may contain a photocationic polymerization initiator. The photocationic polymerization initiator is synonymous with the photocationic polymerization initiator described in the first aspect of the colored ink composition, and the preferred embodiment is also the same.
Further, the characteristics of the colorant, the polymerization inhibitor, the surfactant, other additives, and the colored ink composition in the second aspect of the colored ink composition are also the characteristics of the colored ink composition in the first aspect of the colored ink composition. It is synonymous with the properties of colorants, polymerization inhibitors, surfactants, other additives, and colored ink compositions, and the preferred embodiments are also the same.

[Compounds having radically polymerizable groups and cationically polymerizable groups]
The compound species of the compound having a radically polymerizable group and the cationically polymerizable group in the colored ink composition is the compound having the radically polymerizable group and the cationically polymerizable group in the second aspect of the above-mentioned transparent ink composition. It is synonymous with species and has the same preferred embodiments.
As the compound of the compound having a radically polymerizable group and a cationically polymerizable group, one kind may be used alone, or two or more kinds may be used in combination.
The content of the radically polymerizable group and the compound having a cationically polymerizable group in the colored ink composition is 50% by mass or more and 99% by mass or less with respect to the total mass of the colored ink composition from the viewpoint of curability. It is more preferable, it is more preferably 60% by mass or more and 98% by mass or less, and further preferably 70% by mass or more and 95% by mass or less.

<Manufacturing method of 3D model>
The method for producing a three-dimensional model of the present embodiment is a cured product of a plurality of colored ink compositions having different colors, a plurality of colored regions having different colors, and a cured product of the transparent ink composition, which has the above-mentioned colors. The step of repeatedly forming the colored ink composition and the transparent ink composition by repeatedly ejecting and curing the transparent region interposed between the plurality of different colored regions is included.
In the method for producing a three-dimensional model of the present embodiment, first, at least one of a colored ink composition and a transparent ink composition is ejected onto a modeling table and cured by exposure to form an ink layer.
In the present embodiment, the ink layer formed by curing the colored ink composition is referred to as a colored ink layer, and the ink layer formed by curing the transparent ink composition is referred to as a transparent ink layer.
The colored region is a region formed by one or more colored ink layers, and the transparent region is a region formed by one or more transparent ink layers.
The ink composition ejected to the modeling table finally becomes the surface (first layer) of the three-dimensional modeled object. Since the surface of the three-dimensional modeled object is preferably formed by a transparent region, it is preferable to eject only the transparent ink composition onto the modeling table.
In the above ejection, when a plurality of colored ink compositions having different colors are ejected, the transparent ink compositions are ejected so as to intervene between the colored ink compositions having different colors so that the colored ink compositions having different colors do not come into contact with each other. To do.
After exposure, at least one of the colored ink composition and the transparent ink composition is ejected onto the formed colored ink layer or transparent ink layer, and the mixture is cured by exposure to cure at least one of the second colored ink layer and the transparent ink layer. Form one.
Similarly, the third and subsequent ink layers are formed by repeating ejection and exposure.
In the ejection of the colored ink composition of the second and subsequent layers, the colored ink composition is not ejected on the colored ink layers of different colors, but is ejected on the colored ink layer of the same color or on the transparent ink layer. Will be done.
According to the above aspect, a colored region which is a cured product of the colored ink composition and a transparent region which is a cured product of the transparent ink composition and is interposed between a plurality of colored regions having different colors are formed.
The number of repeated discharges and exposures is not particularly limited, but is preferably once or more.
According to the method for producing a three-dimensional model of the present embodiment, the colored region and another colored region having a different color come into contact with each other through the transparent region, so that color mixing is suppressed.

The colored ink composition and the transparent ink composition used in the method for producing the three-dimensional model of the present embodiment are synonymous with the colored ink composition and the transparent ink composition described in the three-dimensional model of the present embodiment. , The preferred embodiment is the same.

The method for manufacturing the three-dimensional model of the present embodiment will be described with reference to FIG.
FIG. 2 is a schematic view showing an example of a three-dimensional model in the process of being manufactured.
The three-dimensional model in the process of being manufactured in FIG. 2 is a three-dimensional model when ejection and exposure are repeated eight times. On the modeling table 10, a transparent ink layer 20 and colored inks having different colors are used. Layers 12, 14, 16 and 18 are manufactured up to the eighth layer.
At least one of the colored ink composition and the transparent ink composition corresponding to one layer is ejected by one ejection, and is cured by the subsequent exposure to form one layer of ink.

In FIG. 2, in order to manufacture a three-dimensional model whose surface is a transparent region, the transparent ink layer 20 is formed by ejecting and exposing only the transparent ink composition onto the modeling table 10 as the first layer. Is formed.
For convenience in the description, FIG. 2 describes the embodiment as having one transparent ink layer 20 between the colored ink layer 18 and the modeling table, but in the actual production of a three-dimensional model, the colored ink layer is described. It is preferable that a transparent region of 0.5 mm is formed between the and the modeling table by forming a layer having a thickness of 100 μm 50 times, for example.
In the formation of the second layer in FIG. 2, by ejecting the colored ink composition and the transparent ink composition, the colored ink composition is combined with another colored ink composition having a different color in one layer. Contact through the clear ink composition. As a result, as shown in the second layer in FIG. 2, colored ink layers 12 and 18 having different colors are in contact with each other via the transparent ink layer 20 in one layer.
Further, in the formation of the 6th to 7th layers, the colored ink composition comes into contact with the colored ink layers having different colors via the transparent ink layer in the height direction of the three-dimensional modeled product in the middle of production. Specifically, a transparent ink composition is ejected as the sixth layer on the fifth colored ink layer 18 and exposed to form the transparent ink layer 20, and seven layers are formed on the sixth transparent ink layer 20. The colored ink composition is ejected as eyes to form the colored ink layer 16.
As a result, as shown in the 5th to 7th layers, the colored ink layers 18 and 16 having different colors come into contact with each other via the transparent ink layer 20 in the height direction of the three-dimensional model in the process of manufacturing. ..
For convenience in the description, FIG. 2 describes an embodiment in which one transparent ink layer 20 is provided as the sixth layer, but in actual production of a three-dimensional model, colored ink having a color different from that of the colored ink layer is described. It is preferable that a transparent region having a thickness of 0.5 mm is formed between the layers by forming a layer having a thickness of 100 μm 50 times, for example.

As the ejection method, a known ejection method is used without particular limitation. For example, a piezo method using the vibration pressure of the piezo element, a charge control method using electrostatic attraction to eject ink, and an electric signal can be used. Examples thereof include an acoustic inkjet method in which an ink is irradiated instead of an acoustic beam and the ink is ejected by using radiation pressure, and a thermal inkjet method in which the ink is heated to form bubbles and the generated pressure is used.

The amount of ink droplets to be ejected is not particularly limited, but is preferably 1 pL or more and 200 pL or less, and 5 pL or more and 100 pL or less, from the viewpoint of the fineness of the obtained three-dimensional model and the production speed of the three-dimensional model. Is preferable. (Reference pL: 10 pL of picolitre has a resolution of 1200 dpi, 30 pL is about 900 dpi)

The active radiation to be irradiated in the exposure is not particularly limited, and examples thereof include ultraviolet rays and electron beams. Among them, ultraviolet rays are preferable from the viewpoint of versatility.
The peak wavelength of ultraviolet light (ultraviolet light) is preferably 200 nm or more and 420 nm or less, more preferably 240 nm or more and 400 nm or less, and further preferably 300 nm or more and 400 nm or less.
Exposure surface illuminance when the actinic radiation is irradiated, for example, 10 mW / cm ² or more 8000 MW / cm ² or less are preferred, 100 mW / cm ² or more 1000 mW / cm ² or less being more preferred.
Examples of the irradiation means include an ultraviolet irradiation lamp (halogen lamp, high-pressure mercury lamp, etc.), a laser, a light emitting diode (LED), an electron beam irradiation device, and the like.

Further, in order to form a support region for supporting the three-dimensional modeled object, the support region forming ink may be further ejected at the time of ejection.
For example, when the width of the modeled object at the upper position is larger than the width of the modeled object at the lower position and there is a so-called overhanging portion, a support region for supporting this overhanging portion from below is formed.
The support area is removed from the feature, for example after repeated ejection and exposure.
As the support region forming ink, known inks used for forming the support region are used without limitation, and examples thereof include the support materials described in JP-A-2016-132773 and JP-A-2016-043610.

<Ink set>
The ink set of the present embodiment contains a compound having a radically polymerizable group, a compound having a cationically polymerizable group, and a photoradical polymerization initiator, or a compound having a radically polymerizable group and a cationically polymerizable group. In addition, a colored ink composition containing a photoradical polymerization initiator, a compound having a radically polymerizable group, a compound having a cationically polymerizable group, a photoradical polymerization initiator and a photocationic polymerization initiator, or a radically polymerizable group. And a transparent ink composition containing a compound having a cationically polymerizable group, a photoradical polymerization initiator, and a photocationic polymerization initiator.

The colored ink composition contained in the ink set of the present embodiment has the same meaning as the colored ink composition described in the three-dimensional model of the present embodiment, and the preferred embodiment is also the same.
The transparent ink composition contained in the ink set of the present embodiment has the same meaning as the transparent ink composition described in the three-dimensional model of the present embodiment, and the preferred embodiment is also the same.

The ink set of the present embodiment may include a plurality of colored ink compositions. For example, an ink set containing five colored ink compositions of cyan, magenta, yellow, black, and white can be mentioned.

Hereinafter, the present embodiment will be described in more detail with reference to Examples and Comparative Examples, but the present embodiment is not limited to the following Examples. Unless otherwise specified, "parts" and "%" are based on mass.

<Ink preparation>
Each component shown in Tables 1 and 2 below is mixed, and the colored ink compositions C-1 to C-3, M-1 to M-3, Y-1 to Y-3, and W-1 to W- 3 and the transparent ink compositions T-1 to T-3 were prepared. In Table 1, the description of "-" indicates that the compound is not contained.

The abbreviations described in Table 1 are as follows.
-U-15HA: Urethane acrylate oligomer, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.-UA-4200: Urethane acrylate oligomer, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.-U-200PA: Urethane acrylate oligomer, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. Made by UV-3300B: Ether type oligomer, manufactured by Nippon Synthetic Chemical Co., Ltd. ・ IBXA: Isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. ・ TEGORad2011: Silicone surfactant, manufactured by Ebonic, ethyl carbitol acrylate : 2- (2-ethoxyethoxy) ethyl, Viscort # 190, manufactured by Osaka Organic Chemical Industry Co., Ltd. ・ VEEA: 2- (2-vinyloxyethoxy) ethyl acrylate, manufactured by Nippon Catalyst Co., Ltd., OXT-212: 2 -Ethylhexyl oxetane, manufactured by Toa Synthetic Co., Ltd. OXT-221: 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, manufactured by Toa Synthetic Co., Ltd. PR122: Pigment Red 122 , Sanyo Dye Co., Ltd. ・ PB15: 3: Pigment Blue 15: 3, Sanyo Dye Co., Ltd. ・ PY-150: Pigment Yellow 150, Sanyo Dye Co., Ltd. ・ Titanium oxide: Titanium oxide, Titanium GENORAD16 manufactured by Kogyo Co., Ltd .: Acrylate ester, RAHN manufactured by BAPO: Irgacure 819, BASF manufactured by Irgacure 290: Triarylsulfonium tetrakis- (pentafluorophenyl) borate, manufactured by BASF

Using the ink compositions shown in Table 2, the three-dimensional shaped objects shown in FIGS. 3 and 4, respectively, were prepared.
The three-dimensional model was produced using PolyJet3D (a modified machine manufactured by Altech Co., Ltd.).
3 and 4 are front views of the three-dimensional model, and each ink composition is ejected from above in the paper surface in FIG. 3 or 4 to manufacture the three-dimensional model.
The manufacturing conditions for the three-dimensional model were a discharge rate of 50 pL, an ink heating temperature of 50 ° C., a UV-LED (365 nm wavelength), and an illuminance of 500 mW / cm ² .

In FIGS. 3 and 4, 22 is a colored region (cyan), 24 is a colored region (yellow), 26 is a colored region (magenta), 28 is a colored region (white), and 30 is a transparent region. Represents.
The three-dimensional objects shown in FIGS. 3 and 4 have the same shape and the same size, and the size of each part is shown in FIG.

<Bending strength evaluation>
The bending strength of the three-dimensional model was measured using a precision universal testing machine (manufactured by Shimadzu Corporation, Autograph AG-Xplus series).
Specifically, the bending strength was measured according to the bending test standard ASTM D790, and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2.
A: Bending strength is 30 mN / m or more B: Bending strength is 15 mN / m or more and less than 30 mN / m C: Bending strength is 10 mN / m or more and less than 15 mN / m D: Bending strength is less than 10 mN / m Is

<Color mixing evaluation>
The interface between the colored region and the transparent region or the interface between the colored region and another colored region was observed using an optical microscope, and sensory evaluation was performed according to the following evaluation criteria.
A: There is almost no bleeding.
B: Slight bleeding is confirmed, but the interface boundary is almost straight.
C: There is exudation and color mixing, and the interface boundary can be discriminated.
D: Colors are mixed and the interface boundary is unknown.

1,2,3 Three-dimensional model 10 Modeling table 12, 14, 16, 18 Colored ink layer 20 Transparent ink layer 22 Colored area (cyan)
24 Colored area (yellow)
26 Colored area (magenta)
28 Colored area (white)
30 transparent area

Claims (5)

It is a cured product of a colored ink composition, and has a plurality of colored regions having different colors.
It is a transparent region which is a cured product of the transparent ink composition, and has a transparent region interposed between a plurality of colored regions having different colors.
And the colored region and the transparent region, the 3D object that are coupled by cationic polymers. It is a cured product of a colored ink composition, and has a plurality of colored regions having different colors.
It is a transparent region which is a cured product of the transparent ink composition, and has a transparent region interposed between a plurality of colored regions having different colors.
Tensile modulus of the transparent region, the tensile 3D object not smaller than the elastic modulus of the colored region. A plurality of colored regions having different colors, which are cured products of a plurality of colored ink compositions having different colors, and a transparent region intervening between the plurality of colored regions having different colors, which are cured products of a transparent ink composition. The method for producing a three-dimensional model according to claim 1 or 2, further comprising a step of repeatedly ejecting and curing the colored ink composition and the transparent ink composition. A plurality of colored regions having different colors, which are cured products of a plurality of colored ink compositions having different colors, and a transparent region intervening between the plurality of colored regions having different colors, which are cured products of a transparent ink composition. , A method for producing a three-dimensional modeled product, which comprises a step of repeatedly ejecting and curing the colored ink composition and the transparent ink composition.
The colored ink composition
Colorant, a compound having a radical polymerizable group, containing a compound having a cationically polymerizable group and photoradical polymerization initiator, or,
It contains a colorant, a compound having a radically polymerizable group and a cationically polymerizable group, and a photoradical polymerization initiator.
The transparent ink composition
Compound having a radical polymerizable group, a compound having a cationically polymerizable group, a radical photopolymerization initiator, containing及beauty photo cationic polymerization initiator, or,
Compound having a radical polymerizable group and a cationically polymerizable group, a radical photopolymerization initiator, as well contains a cationic photopolymerization initiator,
A method for manufacturing a three-dimensional model. The contact angle of the cured product of the color ink composition, the difference between the contact angle of the cured product of the transparent ink composition is 10 ° or more, a manufacturing method of a three-dimensional molded article according to claim 4.