JP2021084410A - Composition set for three-dimensional modeling, three-dimensional modeling article, manufacturing method of three-dimensional modeling article, two-dimensional or three-dimensional image forming device and two-dimensional or three-dimensional image forming method - Google Patents

Abstract

To provide a composition set for three-dimensional modeling in which a removal property of a support part, formation property of a smooth interface, scratch resistance, chemical resistance, heat resistance, and dimensionality are excellent.SOLUTION: There is provided a composition set for three-dimensional modeling, comprising: a composition for a support material for three-dimensional modeling; and a composition for a model material for three-dimensional modeling, in which the composition for the support material contains an acrylamide compound having an ester structure represented by formula (1), and the composition for the model material contains: a monofunctional polymerizable compound having a SP value of 9.5 or less and a glass transition temperature of 25°C or more in an amount of 5 mass% or more and 60 mass% or less based on the total amount of the composition for the model material; and a polyfunctional polymerizable compound in an amount of 40 mass% or more and 85 mass% or less based on the total amount of the composition for the model material, in which, in formula (1), R1 represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents formula (2) or formula (3).SELECTED DRAWING: Figure 2

Description

The present invention relates to a composition set for three-dimensional modeling, a three-dimensional model, a method for producing a three-dimensional model, a two-dimensional or three-dimensional image forming apparatus, and a two-dimensional or three-dimensional image forming method.

As a method of modeling a three-dimensional three-dimensional object, a material jet method using an inkjet recording device is known. In the material jet method, a curable composition is discharged to form a liquid film, the liquid film is cured to form a layer having a cross-sectional shape, and the layers are laminated to form a three-dimensional object. It is known that when a three-dimensional shape having an overhang portion is formed by a material jet method, the model portion of the overhang portion is supported by a support portion.

In the prior art, various compositions for model materials and compositions for support materials have been proposed in order to improve the removability of the support portion, the molding accuracy of the model portion, the smoothing of the surface, and the like.
In Patent Document 1, a model material containing a curable resin component having a predetermined SP value, a water-soluble monofunctional ethylenically unsaturated monomer, an alkylene oxide adduct containing an oxypropylene group, water, and a photopolymerization initiator. Support materials including are proposed.
Patent Document 2 proposes a curable composition containing an acrylamide compound.
Patent Document 3 proposes a set of a three-dimensional modeling composition having a first composition and a second composition, one of which has water disintegration property and the surface tension of the first composition is ST1. , It is proposed that | ST1-ST2 | ≦ 2 is satisfied when the surface tension of the second composition is ST2.

However, with respect to the prior art, further improvement in scratch resistance, chemical resistance, and heat resistance of the obtained three-dimensional model is required, and further improvement in removability of the support portion is also required. Further, after removing the support portion, the surface of the model portion in contact with the support portion is required to be smooth, but the conventional technique is still not at a satisfactory level, and further improvement is required. Further, in addition to these points, further improvement in dimensionality is required.

Therefore, an object of the present invention is to provide a composition set for three-dimensional modeling, which is excellent in support removal property, smooth interface formation, scratch resistance, chemical resistance, heat resistance, and dimensionality.

In order to solve the above problems, the composition set for three-dimensional modeling of the present invention is a composition for three-dimensional modeling having a composition for a support material for three-dimensional modeling and a composition for a model material for three-dimensional modeling. The composition for a support material contains an acrylamide compound having an ester structure represented by the following general formula (1) and a polymerization initiator, and the composition for a model material has an SP value of 9.5 or less and an SP value of 9.5 or less. The monofunctional polymerizable compound having a glass transition temperature of 25 ° C. or higher is contained in an amount of 5% by mass or more and 60% by mass or less based on the total amount of the composition for the model material, and the polyfunctional polymerizable compound is contained in the total amount of the composition for the model material. It is characterized by containing 40% by mass or more and 85% by mass or less, and containing a polymerization initiator.

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or the following general formula ( Represents 3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

However, in the general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

According to the present invention, it is possible to provide a composition set for three-dimensional modeling excellent in support removal property, smooth interface formation, scratch resistance, chemical resistance, heat resistance, and dimensionality.

It is the schematic which shows an example of the image forming apparatus in this invention. It is the schematic which shows an example of another image forming apparatus in this invention. It is a perspective view which shows an example of a three-dimensional model.

Hereinafter, the composition set for three-dimensional modeling, the three-dimensional model, the method for producing the three-dimensional model, the two-dimensional or three-dimensional image forming apparatus, and the two-dimensional or three-dimensional image forming method according to the present invention will be described with reference to the drawings. To do. The present invention is not limited to the embodiments shown below, and can be modified within the range conceivable by those skilled in the art, such as other embodiments, additions, modifications, and deletions. However, as long as the action and effect of the present invention are exhibited, it is included in the scope of the present invention.

As a result of diligent studies, the inventors have found the following findings and arrived at the present invention.
By containing an acrylamide compound having an ester structure represented by the following general formula (1) and a polymerization initiator as the composition for the support material, the removability of the support portion formed by the composition for the support material is removable. And excellent in interface formation.
The composition for the model material contains a monofunctional polymerizable compound having an SP value of 9.5 or less and a glass transition temperature of 25 ° C. or more in an amount of 5% by mass or more and 60% by mass or less based on the total amount of the composition for the model material. By containing the polymerizable compound in an amount of 40% by mass or more and 85% by mass or less based on the total amount of the composition for the model material and containing the polymerization initiator, the model portion formed by the composition for the model material has scratch resistance and scratch resistance. Has excellent chemical resistance and heat resistance.

Then, by producing a three-dimensional model by using the composition for the support material and the composition for the model material in combination in the present invention, the support portion and the model portion can form an interface without bleeding from each other, and the interface can be formed. An excellent three-dimensional model can be obtained. Further, the removability of the support portion is improved due to the fact that the support portion and the model portion can form an interface without bleeding from each other. When the SP value of the support material and the SP value of the model material are significantly different, better interface formation can be obtained and the removability of the support portion is further improved. Further, according to the three-dimensional modeling composition set of the present invention, the curing shrinkage of the model portion can be suppressed and the dimensionality can be improved.
Good interface formation means that the surface of the model portion in contact with the support portion is smooth after the support portion is removed.

Hereinafter, in the present invention, unless otherwise specified, the "support portion" represents a cured product formed by the composition for a support material, and the "support material" represents a composition for a support material. Unless otherwise specified, the "model portion" represents a cured product formed by the composition for the model material, and the "model material" represents the composition for the model material.

(Composition set for 3D modeling)
The composition set for three-dimensional modeling of the present embodiment includes a composition for a support material for three-dimensional modeling and a composition for a model material for three-dimensional modeling. Hereinafter, a description will be given with specific examples.

<Composition for support material>
The composition for a support material contains an acrylamide compound having an ester structure represented by the following general formula (1) and a polymerization initiator, and may contain other components if necessary.

<< Acrylamide compound >>
The acrylamide compound having an ester structure in this embodiment is represented by the following general formula (1).

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or the following general formula ( Represents 3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

However, in the general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

_{R 1} in the general formula (1) represents an alkyl group having 1 to 6 carbon atoms, which may be a straight chain or a branched chain.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a neopentyl group. A hexyl group and the like can be mentioned.
X in the general formula (1) represents an alkylene group having 1 to 6 carbon atoms, which may be a straight chain or a branched chain.
Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group and a butylene group.
Y in the general formula (1) represents the general formula (2) or the general formula (3).

_{R 2} in the general formula (2) represents an alkyl group having 1 to 10 carbon atoms, which may be a straight chain or a branched chain.
Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a neopentyl group. Examples thereof include a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
* In the general formula (2) represents a binding site with X.

_{R 2} in the general formula (3) represents an alkyl group having 1 to 10 carbon atoms, which may be a straight chain or a branched chain.
Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a neopentyl group. Examples thereof include a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
* In the general formula (3) represents a binding site with X.

The acrylamide compound represented by the general formula (1) has an ester structure at the terminal of tertiary acrylamide which is monofunctional and does not have a ring structure. In general, since a low molecular weight tertiary acrylamide compound has volatility, it strongly feels an odor peculiar to a monomer, which causes discomfort in handling a cured composition containing these compounds.

It is possible to suppress the volatility of the acrylamide compound and reduce the odor by introducing a highly polar functional group into such a low molecular weight tertiary acrylamide compound or increasing the molecular weight. However, in that case, there is a problem that the viscosity is increased, and the restrictions on the use of the curable composition, particularly the ink for inkjet, are increased.

Therefore, the tertiary acrylamide compound represented by the general formula (1) has an ester structure at the terminal portion. Therefore, the odor can be suppressed due to the decrease in volatility due to the ester structure. It is also considered that the curability is improved by the interaction between molecules due to the presence of the ester structure. Further, since the tertiary acrylamide compound having an ester structure does not form a strong hydrogen bond, it is considered that the increase in viscosity is small and the low viscosity can be maintained. As a result, the acrylamide compound represented by the general formula (1) can be suitably used as a curable composition, and among them, an ink jet ink.

In general, since acrylamide compounds have high acute oral toxicity, there are concerns about the safety of curable compositions containing these compounds, and care must be taken in handling.
On the other hand, the acrylamide compound having an ester structure in the present invention tends to have low acute oral toxicity. Among them, when Y in the general formula (1) is the case of the general formula (3), the acute oral toxicity tends to be very low. Therefore, the curable composition containing the acrylamide compound in the present invention is expected to have low acute oral toxicity and can enhance safety.

The acrylamide compound represented by the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose, but the compound represented by the following general formula (4) is preferable.

However, in the general formula (4), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 3 carbon atoms, and R ₂ represents an alkyl group having 1 to 4 carbon atoms. ..

The alkyl group having 1 to 6 carbon atoms represented by R _1, may be straight chain structure, it may be a branched structure, for example, a methyl group, an ethyl group, a propyl group, an isopropyl radical, n -Butyl group, s-butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group and the like can be mentioned. Among these, _{an alkyl group having R 1} having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.

The alkylene group having 1 to 3 carbon atoms represented by X may have a linear structure or a branched structure, for example, a methylene group, an ethylene group, a propylene group, a methylmethylene group, or a dimethyl group. Examples include a methylene group. Among these, a methylene group, a methylmethylene group and a dimethylmethylene group are preferable, and a methylene group and a methylmethylene group are more preferable.

The alkyl group having 1 to 4 carbon atoms represented by R ₂ may have a linear structure or a branched structure, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or n. -Butyl group, s-butyl group, isobutyl group, t-butyl group and the like can be mentioned. Among these, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, an isobutyl group are preferred, R ₂ is more preferably an alkyl group having 1 to 3 carbon atoms.

Next, as specific examples of the acrylamide compound represented by the general formula (1), groups a to h are shown, but the examples are not limited thereto.

Examples of the exemplified compound a group include the compounds of the a1 to a6 groups shown below. These may be used alone or in combination of two or more.

Examples of the exemplified compound b group include the compounds of the b1 to b6 groups shown below. These may be used alone or in combination of two or more.

Examples of the exemplified compound c group include the compounds of the c1 to c6 groups shown below. These may be used alone or in combination of two or more.

Examples of the exemplified compound d group include the compounds of the d1 to d6 groups shown below. These may be used alone or in combination of two or more.

Examples of the exemplified compound e group include the compounds of the e1 to e6 groups shown below. These may be used alone or in combination of two or more.

Examples of the exemplified compound f group include the following compounds of the f1 group. These may be used alone or in combination of two or more.

Examples of the example compound g group include the following compounds in the g1 to g6 groups. These may be used alone or in combination of two or more.

Examples of the exemplified compound h group include the following compounds of the h1 group. These may be used alone or in combination of two or more.

Among the exemplified compounds a to h, Exemplified Compound a1-1, Exemplified Compound a1-4, Exemplified Compound a6-1, Exemplified Compound d1-1, Exemplified Compound d1-2, Exemplified Compound d1-4, Exemplified Compound d1 -5, Exemplified Compound d3-2, Exemplified Compound d4-1, Exemplified Compound d4-5, Exemplified Compound d6-1, Exemplified Compound d6-4, Exemplified Compound g1-1, Exemplified Compound g1-2, and Exemplified Compound g1- 5, is preferred, and exemplary compound d1-1, exemplary compound d1-2, exemplary compound g1-1, exemplary compound g1-2, and exemplary compound g1-5 are more preferred.

The acrylamide compound represented by the general formula (1) can be used by mixing two or more different compounds with each other, and the different compounds in this case also include structural isomers. The mixing ratio is not particularly limited.

The content of the acrylamide compound represented by the general formula (1) is preferably 20% by mass or more and 98% by mass or less, more preferably 30% by mass or more and 90% by mass or less, based on the total amount of the curable composition. It is particularly preferably 30% by mass or more and 80% by mass or less.

The acrylamide compound represented by the general formula (1) ^{can be structurally analyzed by using 1 1} H-NMR spectrum and IR spectrum.

<< Polymerization Initiator >>
As the polymerization initiator, any substance that generates radicals by irradiation with light, particularly ultraviolet rays having a wavelength of 220 nm to 400 nm, can be used without any limitation. Examples of such a photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, p, p-bisdiethylaminobenzophenone, and the like. Michler Ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-propyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzyl methyl ketal, thioxanthone, 2-chlorothioxanthone, 2-hydroxy- 2-Methyl-1-phenyl-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 1-hydroxycyclohexylphenylketone, azobisisobuty Examples thereof include lonitrile, benzoyl peroxide, and di-tert-butyl peroxide.

These may be used alone or in combination of two or more. Of these, it is preferable to select a polymerization initiator that matches the ultraviolet wavelength of the ultraviolet irradiation device used for modeling.

The content of the polymerization initiator is preferably 0.5% by mass or more and 10% by mass or less with respect to the total amount of the composition for the support material.

<< Other ingredients >>
-Color material-
The composition for the support material may contain a coloring material. As the coloring material, various pigments and dyes that impart black, white, magenta, cyan, yellow, green, orange, glossy colors such as gold and silver, etc., depending on the purpose and required characteristics of the composition in the present invention. Can be used. The content of the coloring material may be appropriately determined in consideration of the desired color density, dispersibility in the composition, etc., and is not particularly limited, but is 0. It is preferably 1 to 20% by mass. The composition for a support material in the present invention may be colorless and transparent without containing a coloring material, and in that case, for example, it can be used as an overcoat layer for protecting an image.
As the pigment, an inorganic pigment or an organic pigment can be used, and one type may be used alone or two or more types may be used in combination.
As the inorganic pigment, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide can be used.
Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azolakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments and quinophthalones. Polycyclic pigments such as pigments, dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), dyeing lake (basic dye type lake, acidic dye type lake), nitro pigment, nitroso pigment, aniline black, Daylight fluorescent pigments can be mentioned.
In addition, a dispersant may be further contained in order to improve the dispersibility of the pigment. The dispersant is not particularly limited, and examples thereof include dispersants commonly used for preparing pigment dispersions such as polymer dispersants.
As the dye, for example, an acid dye, a direct dye, a reactive dye, and a basic dye can be used, and one type may be used alone or two or more types may be used in combination.

-Organic solvent-
The composition for the support material may contain an organic solvent, but it is preferable not to contain it if possible. If the composition does not contain an organic solvent, particularly a volatile organic solvent (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled is further enhanced, and it is possible to prevent environmental pollution. .. The "organic solvent" means, for example, a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from the reactive monomer. is there. Further, "not containing" the organic solvent means that it is substantially not contained, and it is preferably less than 0.1% by mass.

− Other −
Further, the other components are not particularly limited, but for example, conventionally known surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration promoters, wetting agents (moisturizers), fixing agents. , Viscosity stabilizers, fungicides, preservatives, antioxidants, UV absorbers, chelating agents, pH regulators, thickeners and the like.

The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include higher fatty acid surfactants, silicone surfactants and fluorine surfactants. Examples of commercially available products include TEGO WET270, BYK3150, BYK3151 and KF353.

The polymerization inhibitor can enhance the storage stability (storage stability) of the curable composition and prevent head clogging due to thermal polymerization when the curable composition is heated to reduce its viscosity and discharged. be able to.
The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, and a cuperon complex of aluminum. These may be used alone or in combination of two or more.
The content of the polymerization inhibitor is preferably 200 ppm or more and 20,000 ppm or less.

Further, the composition for the support material preferably does not contain a polyfunctional monomer. When the polyfunctional monomer is contained, the polyfunctional monomer is preferably less than 0.1% by mass based on the total amount of the composition for the support material. In this case, the removability of the support portion is more excellent.

<Composition for model material>
The composition for a model material in the present embodiment contains a monofunctional polymerizable compound having an SP value of 9.5 or less and a glass transition temperature of 25 ° C. or more in an amount of 5% by mass or more and 60% by mass or less based on the total amount of the composition for the model material. It contains a polyfunctional polymerizable compound in an amount of 40% by mass or more and 85% by mass or less based on the total amount of the composition for the model material, and contains a polymerization initiator. Further, other components may be contained if necessary.

<< Monofunctional polymerizable compound >>
The monofunctional polymerizable compound contained in the composition for the model material has an SP value of 9.5 or less and a glass transition temperature of 25 ° C. or more. Further, it is contained in an amount of 5% by mass or more and 60% by mass or less with respect to the total amount of the composition for the model material.

SP means a solubility parameter, which is a measure of the solubility of substances, and it is known that the smaller the difference in SP value between substances, the greater the mutual solubility.

The SP value is calculated from the following formula.
SP = [(ΔH-RT) / V] ^1/2
In the formula, V represents the molar volume (cc / mol), ΔH represents the latent heat of vaporization (cal / mol), and R represents the gas constant 1.987 cal / mol ° K.

The SP value of the monofunctional polymerizable compound contained in the composition for the model material is 9.5 or less. If the SP value exceeds 9.5, the interface with the support portion in the model portion is not smooth and becomes rough. The SP value is more preferably 9.0 or less. The lower limit is preferably 8.5 or more.

The monofunctional polymerizable compound having an SP value of 9.5 or less is not limited, but for example, a linear or branched alkyl (meth) acrylate [compound having 4 to 30 carbon atoms (hereinafter abbreviated as C), for example, Methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate and t-butyl (meth) acrylate]; Meta) acrylates [compounds of C6-20, such as cyclohexyl (meth) acrylates, 4-t-cyclohexyl (meth) acrylates, isobornyl (meth) acrylates and dicyclopentanyl (meth) acrylates] and the like.

Further, the weighted average value of the SP values obtained from the monofunctional polymerizable compound and the polyfunctional polymerizable compound (below) contained in the composition for the model material is preferably 9.5 or less, more preferably 9.0. It is as follows. When it is 9.5 or less, the smoothness of the interface between the model portion and the support portion can be improved.

The glass transition temperature Tg of the monofunctional polymerizable compound contained in the composition for the model material is 25 ° C. or higher. If the Tg is less than 25 ° C., good scratch resistance cannot be obtained for the model portion, and the obtained three-dimensional model is easily scratched. In addition, good heat resistance cannot be obtained for the model portion, and the shape is deformed when the temperature rises. The glass transition temperature Tg of the monofunctional polymerizable compound is more preferably 80 ° C. or higher.

The monofunctional polymerizable compound having a glass transition temperature Tg of 25 ° C. or higher is not limited, and examples thereof include isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate], acryloyl morpholine, and N-vinylcaprolactam. Can be mentioned.

Further, the weighted average value of the glass transition temperature determined by the monofunctional polymerizable compound and the polyfunctional polymerizable compound (below) contained in the composition for the model material is preferably 80 ° C. or higher, more preferably 100 ° C. or higher. Is. When the temperature is 80 ° C. or higher, the scratch resistance of the three-dimensional model is more excellent.

The content of the monofunctional polymerizable compound contained in the composition for the model material is 5% by mass or more and 60% by mass or less with respect to the total amount of the composition for the model material. If it is less than 5% by mass, the shrinkage of the three-dimensional model becomes large, and if it exceeds 60% by mass, the scratch resistance and heat resistance of the three-dimensional model are inferior.

<< Polyfunctional Polymerized Compound >>
The polyfunctional polymerizable compound contained in the composition for the model material is contained in an amount of 40% by mass or more and 85% by mass or less based on the total amount of the composition for the model material. If it is less than 40% by mass, the scratch resistance and heat resistance of the three-dimensional model are inferior, and if it exceeds 85% by mass, the shrinkage of the three-dimensional model becomes large.

Examples of the polyfunctional polymerized compound include those having two or more (preferably 2-3) ethylenically unsaturated groups in the molecule. Further, from the viewpoint of reducing the SP value, a hydrophobic polyfunctional ethylenically unsaturated monomer having no urethane group is preferable.

In particular, the polyfunctional polymerizable compound contained in the composition for the model material preferably contains a bifunctional monomer. When the bifunctional monomer is contained, it is preferably contained in an amount of 50% by mass or more and 80% by mass or less with respect to the total amount of the composition for the model material.
By containing the bifunctional monomer, the shrinkage of the three-dimensional model can be reduced, and the scratch resistance and heat resistance can be further improved. Further, when the content is in the above range, the shrinkage of the three-dimensional model can be reduced, and the scratch resistance and heat resistance can be further improved.

Examples of the polyfunctional polymerized compound include linear or branched alkylene glycol di (meth) acrylate [C10-25 compounds, for example, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate. , 1,9-Nonandiol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate ], An alicyclic-containing di (meth) acrylate [compounds of C10 to 30, for example, dimethylol tricyclodecandi (meth) acrylate] and the like.

From the viewpoint of improving the molding accuracy to withstand the molding temperature (50 to 90 ° C.) during curing of the model portion and from the viewpoint of heat resistance during use of the optical model itself, it is more preferable that the homopolymer has a high glass transition point ( (50 ° C or higher), that is, neopentyl glycol di (meth) acrylate among branched alkylene glycol di (meth) acrylates, 3-methyl-1,5-pentanediol di (meth) acrylate, and alicyclic-containing di (meth) acrylate. Dimethylol tricyclodecandi (meth) acrylate of meta) acrylate, among these, highly reactive acrylate, that is, neopentyl glycol diacrylate, 3-methyl-1,5- Pentandiol diacrylate and dimethylol-tricyclodecanediacrylate.
The polyfunctional polymerized compound may be used alone or in combination of two or more if necessary.

<< Polymerization Initiator >>
As the polymerization initiator contained in the composition for the model material, the same composition as the composition for the support material can be used, and the content can be the same.

<< Other ingredients >>
The composition for a model material may contain other components if necessary, and examples thereof include a coloring material and an organic solvent, and further include a surfactant, a polymerization inhibitor, a leveling agent, a defoaming agent, and a fluorescent agent. Whitening agents, penetration promoters, wetting agents (moisturizing agents), fixing agents, viscosity stabilizers, fungicides, preservatives, antioxidants, UV absorbers, chelating agents, pH adjusters, thickeners, etc. Can be mentioned.
These can be the same as the composition for the support material, and the content can be the same.

<Difference in SP value>
The weighted average value of the SP value obtained by the polymerizable compound contained in the composition for the support material and the weighted average value of the SP value obtained by the monofunctional polymerizable compound and the polyfunctional polymerizable compound contained in the composition for the model material. The difference from the above is preferably 0.9 or more and less than 3.0. When the SP value of the support material and the SP value of the model material are significantly different, better interface formation can be obtained and the removability of the support portion is further improved.
The "difference" represents an absolute value, and may be obtained by subtracting a small value from a large value. Further, the SP value of the support material can be obtained in the same manner as the model material.

(Three-dimensional model)
The three-dimensional model of the present invention is obtained by curing the composition set for three-dimensional model of the present invention.
The three-dimensional model obtained by the composition set for three-dimensional modeling of the present invention includes not only those printed on a smooth surface such as ordinary paper or resin film, but also those printed on a surface to be printed having irregularities. It also includes those printed on the surface to be printed, which is made of various materials such as metal and ceramic. Further, by superimposing two-dimensional images, it is possible to form a partially three-dimensional image (an image composed of two-dimensional and three-dimensional) or a three-dimensional object.

The three-dimensional model of the present invention is excellent in scratch resistance, chemical resistance, and heat resistance by using the composition for the support material and the composition for the model material in the present invention. In addition, it is possible to obtain a three-dimensional model having good removability of the support portion and a smooth interface with the support portion in the model portion. Further, a three-dimensional model having excellent dimensionality can be obtained.

(Manufacturing method of three-dimensional model)
Using the three-dimensional modeling composition set of the present invention, a cured product forming step of applying the support material composition and the model material composition on a base material and irradiating the active energy rays to form a cured product. It has a support material removing step of immersing the cured product in water and removing the support material from the cured product by ultrasonic vibration.

The ultrasonic vibration is performed by putting a cured product in which a support material and a model material are integrated into an ultrasonic device and using an arbitrary cleaning liquid. For example, it is preferable to use an MCU-38 manufactured by AS ONE Corporation as an apparatus, use ion-exchanged water as the cleaning liquid, and set the ultrasonic vibration time to 5 hours.

(Two-dimensional or three-dimensional image forming device and two-dimensional or three-dimensional image forming method)
The two-dimensional or three-dimensional image forming apparatus of the present invention includes an accommodating portion accommodating the three-dimensional modeling composition set of the present invention, and an irradiation means for irradiating active energy rays.

The two-dimensional or three-dimensional image forming method of the present invention includes an irradiation step of irradiating the three-dimensional modeling composition set of the present invention with active energy rays.

In order to cure the curable composition with active energy rays, an irradiation step of irradiating the active energy rays is provided, and the image forming apparatus of the present invention comprises an irradiation means for irradiating the active energy rays and the present invention. A storage unit for accommodating the three-dimensional modeling composition set of the above is provided, and the container may be stored in the storage unit. Further, it may have a discharge process and a discharge means for discharging the composition for the support material and the composition for the model material. The method of discharging is not particularly limited, and examples thereof include a continuous injection type and an on-demand type. Examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.

FIG. 1 is an example of an image forming apparatus provided with an inkjet ejection means. Ink is ejected to the recording medium 22 supplied from the supply roll 21 by each color printing unit 23a, 23b, 23c, 23d provided with an ink cartridge for each color active energy ray-curable ink of yellow, magenta, cyan, and black and an ejection head. Will be done. Then, the light sources 24a, 24b, 24c, and 24d for curing the ink are irradiated with active energy rays to cure the ink, and a color image is formed. After that, the recording medium 22 is conveyed to the processing unit 25 and the printed matter take-up roll 26. Each printing unit 23a, 23b, 23c, 23d may be provided with a heating mechanism so that the ink is liquefied at the ink ejection portion. Further, if necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. Further, as an inkjet recording method, a serial method in which the head is moved to eject ink onto the recording medium or a recording medium is continuously moved with respect to a recording medium that moves intermittently according to the width of the ejection head. Any of the line methods of ejecting ink onto the recording medium from the head held at a fixed position can be applied.

The recording medium 22 is not particularly limited, and examples thereof include paper, film, ceramics, glass, metal, and composite materials thereof, and may be in the form of a sheet. Further, the configuration may be such that only single-sided printing is possible, or double-sided printing is also possible. Not limited to those used as general recording media, cardboard, building materials such as wallpaper and flooring, concrete, cloth for clothing such as T-shirts, textiles, leather and the like can be appropriately used.

Further, the activation energy rays from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing a plurality of colors, the activation energy rays may be irradiated from the light source 24d. As a result, energy saving and cost reduction can be achieved.

FIG. 2 is a schematic view showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus) according to the present invention. The image forming apparatus 39 of FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged to transfer a composition for a model material from a discharge head unit 30 for a modeled object, and discharge head units 31 and 32 for a support. A composition for a support material having a composition different from that of the composition for a model material is discharged from the above, and these compositions are laminated while being cured by adjacent ultraviolet irradiation means 33 and 34.

More specifically, for example, on the modeled object support substrate 37, the composition for the support material is discharged from the support discharge head units 31 and 32, irradiated with active energy rays and solidified to have a reservoir portion. After forming one support layer, the composition for a model material is discharged from the discharge head unit 30 for a model material into the reservoir, and is irradiated with active energy rays to be solidified to form the first model material layer. By repeating the process a plurality of times while lowering the stage 38 that is movable in the vertical direction according to the number of times of stacking, the support layer and the modeled object layer are laminated to produce the three-dimensional modeled object 35.
After that, the support laminated portion 36 is removed as needed. In FIG. 2, only one discharge head unit 30 for a modeled object is provided, but two or more may be provided.

Note that "for modeled objects" has the same meaning as for model materials, and "for supports" has the same meaning as for support materials.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Preparation of composition for support material and composition for model material)
A composition for a support material and a composition for a model material were prepared according to the formulations shown in Tables 1 and 2 below. In Table 2, the weighted average represents the weighted average of the monofunctional monomer and the bifunctional monomer.

The following is shown in the table.
9D-11: Exemplified compound d1-1, manufactured by Ricoh 9D-05: Exemplified compound a1-4, manufactured by Ricoh 9D-03: Exemplified compound a1-1, manufactured by Ricoh B1060: N- (butoxymethyl) acrylamide, Tokyo Manufactured by Kasei Kogyo Co., Ltd. CTFA: Trimethylol propanformal acrylate Non-polymerizable compound: Ion-exchanged water Omnirad TPO: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide MEHQ: 4-methoxyphenol IBXA: Isobornyl acrylate LA: Lauryl Acrylate ACMO: Acryloylmorpholin PEA: Phenoxyethyl acrylate TPGDA: Tripropylene glycol diacrylate

(Example 1)
<Manufacturing and evaluation of three-dimensional objects>
The apparatus shown in FIG. 2 was filled with [support material 1] as a composition for a support material and [model material 1] as a composition for a model material. Next, the composition is discharged from the head unit onto the modeled object support substrate, ^{irradiated with ultraviolet rays at 300 mJ / cm 2} to solidify, and the process of forming the modeled object layer is repeated, and the support portion and the model portion are integrally formed. [Three-dimensional model 1] having the structure shown in FIG. 3 was obtained. In the [three-dimensional model 1], the support portion is formed by the [support material 1], and the model portion is formed by the [model material 1]. As for the shape of the [three-dimensional model 1], the model portion has the shape of the portion of reference numeral 10 shown in FIG. 3, and the support portion has the shape of the portion of reference numeral 20 shown in FIG.
The following evaluation was performed on the obtained [three-dimensional model 1]. The results are shown in Table 3.

-Evaluation of support removal property-
Regarding the removability of the support part, for the obtained [three-dimensional model 1], a large ultrasonic cleaner MCU-38 manufactured by AS ONE Corporation was used as an apparatus, and ion-exchanged water was used as a cleaning medium for more than 5 hours. The support part was removed by ultrasonic vibration and evaluated according to the following criteria.
[Evaluation criteria]
〇: The support part can be manually peeled off and removed.
X: The support part cannot be removed manually, and the support part remains on the surface of the model part.

The evaluation described below was carried out using the model part after the above-mentioned support part removability test was carried out.

-Evaluation of interface formation-
The model portion of the obtained [three-dimensional model 1] was immersed in 100 ml of ion-exchanged water in a beaker. It was taken out after 24 hours, and the state of the cured product surface of the model part that the support part was in contact with was evaluated according to the following criteria.
[Evaluation criteria]
⊚: A particularly high gloss and smooth surface is obtained visually.
〇: A smooth surface is obtained visually.
X: Surface roughness is visually confirmed.

-Evaluation of scratch resistance-
The model part of the obtained [3D model 1] is a clock meter (manufactured by Daiei Kagaku Seiki Seisakusho, model number: C-1) and a white cotton cloth for wear (manufactured by the Japanese Standards Association, model number: Kanakin No. 3). ) Was used, and the surface of the model portion after being scraped 10 times with a load of 9N was evaluated according to the following criteria.
[Evaluation criteria]
〇: There is no scratch on the surface of the model part visually.
X: There is a scratch on the surface of the model part visually.

-Evaluation of heat resistance-
With the model portion of the obtained [three-dimensional model 1] as the initial state, L * a * b * was measured using XRite. Then, the model part was stored in an environment of 70 ° C. and 40% RH for 24 hours, and L * a * b * was measured in the same manner. The difference between the above initial value and the value after storage was evaluated according to the following criteria.
[Evaluation criteria]
⊚: ΔE ≦ 1.5.
〇: ΔE ≦ 3.0.
X: ΔE> 3.0.

-Evaluation of chemical resistance-
The model part of the obtained [three-dimensional model 1] was immersed in a 10% sodium hydroxide aqueous solution at 25 ° C. for 24 hours, and the state of the model part before and after the immersion was evaluated according to the following criteria.
[Evaluation criteria]
⊚: There is no visual change.
〇: A slight change in surface quality is visually observed.
X: Significant changes in surface properties are observed visually.

-Evaluation of dimensionality-
Regarding the length of the model part of the obtained [three-dimensional model 1] in the long axis direction, the length of the actually measured model part with respect to the length in the model part design drawing input as a print file was evaluated according to the following criteria.
[Evaluation criteria]
⊚: The ratio of the difference between the design drawing and the measured value is within 1%.
〇: The ratio of the difference between the design drawing and the measured value is within 5%.
X: The ratio of the difference between the design drawing and the measured value exceeds 5%.

(Examples 2 to 8 and Comparative Examples 1 to 7)
In Example 1, a three-dimensional model was produced and evaluated in the same manner as in Example 1 except that [Support Material 1] and [Model Material 1] were changed as shown in Table 3, respectively.

The results obtained are shown in Table 3.

(Comparative Example 8)
In Example 1, when a three-dimensional model was manufactured using [support material 1] as a model material and [model material 1] as a support material, the model portion collapsed in the support portion removing step.

10 Model part 20 Support part 21 Supply roll 22 Recording medium 23 Each color printing unit 24 Light source 25 Processing unit 26 Printed matter take-up roll 30 Discharge head unit for shaped objects 31, 32 Discharge head unit for support 33, 34 Ultraviolet irradiation means 35 Three-dimensional model 36 Support laminated part 37 Model support substrate 38 Stage

Japanese Patent No. 5890990 JP-A-2018-80321 JP-A-2018-167445

Claims (11)

A three-dimensional modeling composition set having a support material composition for three-dimensional modeling and a model material composition for three-dimensional modeling.
The composition for a support material contains an acrylamide compound having an ester structure represented by the following general formula (1) and a polymerization initiator.
The composition for a model material contains a monofunctional polymerizable compound having an SP value of 9.5 or less and a glass transition temperature of 25 ° C. or more in an amount of 5% by mass or more and 60% by mass or less based on the total amount of the composition for the model material. A three-dimensional modeling composition set containing a functionally polymerizable compound in an amount of 40% by mass or more and 85% by mass or less based on the total amount of the composition for the model material, and containing a polymerization initiator.

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or the following general formula ( Represents 3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

However, in the general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X. The solid according to claim 1, wherein the weighted average value of the SP values obtained from the monofunctional polymerizable compound and the polyfunctional polymerizable compound contained in the composition for a model material is 9.5 or less. Modeling composition set. The composition set for three-dimensional modeling according to claim 1 or 2, wherein the acrylamide compound represented by the general formula (1) is a compound represented by the following general formula (4).

However, in the general formula (4), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 3 carbon atoms, and R ₂ represents an alkyl group having 1 to 4 carbon atoms. .. The composition set for three-dimensional modeling according to any one of claims 1 to 3, wherein the polyfunctional polymerizable compound contained in the composition for a model material contains a bifunctional monomer. Any of claims 1 to 4, wherein the weighted average value of the glass transition temperature obtained by the monofunctional polymerizable compound and the polyfunctional polymerizable compound contained in the composition for a model material is 80 ° C. or higher. The composition set for three-dimensional modeling described in Crab. Any of claims 1 to 5, wherein the support material composition does not contain a polyfunctional monomer, or contains a polyfunctional monomer in an amount of less than 0.1% by mass based on the total amount of the support material composition. The composition set for three-dimensional modeling described in Crab. The weighted average value of the SP values obtained from the polymerizable compound contained in the support material composition, and the SP values obtained from the monofunctional polymerizable compound and the polyfunctional polymerizable compound contained in the model material composition. The composition set for three-dimensional modeling according to any one of claims 1 to 6, wherein the difference from the weighted average value of is 0.9 or more and less than 3.0. A three-dimensional model obtained by curing the three-dimensional modeling composition set according to any one of claims 1 to 7. Using the three-dimensional modeling composition set according to any one of claims 1 to 7, the support material composition and the model material composition are applied onto a base material, and the cured product is irradiated with active energy rays. And the cured product forming process to form
A method for producing a three-dimensional model, which comprises a support material removing step of immersing the cured product in water and removing the support material from the cured product by ultrasonic vibration. A two-dimensional or three-dimensional structure including a housing unit containing the three-dimensional modeling composition set according to any one of claims 1 to 7, and an irradiation means for irradiating active energy rays. Image forming device. A two-dimensional or three-dimensional image forming method comprising an irradiation step of irradiating the three-dimensional modeling composition set according to any one of claims 1 to 7 with active energy rays.

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