JP2021066806A - Pigment dispersion composition, curable composition, stored container, two-dimensional or three-dimensional image forming apparatus and method, cured product, decorated product, nail decoration material, and artificial nail - Google Patents

Abstract

To provide a pigment dispersion composition that is safe in skin sensitization and has excellent storage stability.SOLUTION: A pigment dispersion composition contains a pigment, an acrylamide compound represented by one of the general formulae (1) and (2), and a pigment dispersant. In the general formula (1), R1 is a hydrogen atom, or a C1-4 linear or branched alkyl group, R2 is a C1-4 linear or branched alkylene group, and R3 is a C1-4 linear or branched alkyl group. In the general formula (2), ring X is a C2-5 ring structure having a nitrogen atom, R4 is a single bond, or a C1-3 linear or branched alkylene group, and R5 is a C1-3 linear or branched alkyl group.SELECTED DRAWING: None

Description

The present invention relates to a pigment dispersion composition, a curable composition, a storage container, a two-dimensional or three-dimensional image forming apparatus and forming method, a cured product, a decorative body, a nail decorative material, and an artificial nail.

Since the curable composition is solvent-free, it does not generate volatile organic compounds (hereinafter, may be referred to as "VOC"), is environmentally advantageous, is quick-drying, and is a liquid non-absorbable recording medium. Has the advantage of being able to record.

The curable ink, which is a curable composition obtained from the pigment dispersion composition in the curable composition, is often required to be a pigment-based ink from the viewpoint of various durability, and the pigment is uniformly dispersed in the composition. I need to let you. It is known that a decrease in pigment dispersibility leads to a decrease in liquid permeability during filtration and a decrease in discharge property such as nozzle clogging.

Examples of means for uniformly dispersing the pigment in the pigment dispersion composition include resin coating of the pigment and addition of a dispersant. For example, as an ultraviolet curable inkjet ink having excellent ejection properties and storage stability, an inkjet ink in which the amount of released polymer dispersant not adsorbed on the pigment is 1.0% by mass or less of the total ink has been proposed (for example). , Patent Document 1).
Further, a method for producing an active energy ray-curable pigment dispersion in which a composition containing a pigment, a pigment dispersant, a polymerizable compound and a polymerization inhibitor is dispersed so that the difference between the maximum temperature and the minimum temperature is 8 ° C. or more is used. It has been proposed (see, for example, Patent Document 2).

An object of the present invention is to provide a pigment dispersion composition that is safe for skin sensitization and has excellent storage stability.

ただし、前記一般式（１）中、Ｒ^１は水素原子、又は炭素数１〜４の直鎖若しくは分岐のアルキル基を表し、Ｒ^２は炭素数１〜４の直鎖又は分岐のアルキレン基を表し、Ｒ^３は炭素数１〜４の直鎖又は分岐のアルキル基を表す。

ただし、前記一般式（２）中、環Ｘは窒素原子を含む炭素数２〜５の環構造を表し、Ｒ^４は単結合、又は炭素数１〜３の直鎖若しくは分岐のアルキレン基を表し、Ｒ^５は炭素数１〜３の直鎖又は分岐のアルキル基を表す。 The pigment dispersion composition of the present invention as a means for solving the above-mentioned problems contains a pigment, an acrylamide compound represented by any of the following general formulas (1) and (2), and a pigment dispersant. To do.

However, in the general formula (1), R ¹ represents a hydrogen atom or a linear or branched alkyl group ^{having 1 to 4 carbon atoms, and R 2} represents a linear or branched alkylene group having 1 to 4 carbon atoms. Representing, R ³ represents a linear or branched alkyl group having 1 to 4 carbon atoms.

However, in the general formula (2), the ring X represents a ring structure having 2 to 5 carbon atoms containing a nitrogen atom, and R ⁴ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms. , R ⁵ represent a linear or branched alkyl group having 1 to 3 carbon atoms.

According to the present invention, it is possible to provide a pigment dispersion composition that is safe in terms of skin sensitization and has excellent storage stability.

FIG. 1 is a schematic view showing an example of an image forming apparatus provided with an inkjet ejection means. FIG. 2 is a schematic view showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus). FIG. 3 is a schematic explanatory view illustrating an example of a method of performing three-dimensional modeling using a composition. FIG. 4A is a schematic view showing an example of a nail decorating device that decorates a human nail. FIG. 4B is an enlarged schematic view of the decoration means of FIG. 4A.

(Pigment dispersion composition)
The pigment dispersion composition of the present invention contains a pigment, an acrylamide compound represented by any of the above general formulas (1) and (2), and a pigment dispersant, and if necessary, a polymerization initiator and polymerization. Contains accelerators and other ingredients.

In the prior art, a polymerizable compound having an SI value of more than 3 was used, and there was a problem with skin sensitization. In addition, since the polar difference between the pigment dispersant (hereinafter, also referred to as “pigment-adsorbing component”) and the polymerizable compound used as the dispersion medium is large, the adsorption between the pigment and the dispersion medium becomes unstable, resulting in wettability. There was a problem that it was lowered and the storage / dispersion stability was lowered.

In the present invention, by containing the pigment, the acrylamide compounds represented by the above general formulas (1) and (2), and the pigment dispersant, the pigment dispersant is adsorbed on the pigment surface, and the space between the pigment and the dispersion medium. The balance of the affinity of the pigment is improved, the wettability of the pigment to the dispersion medium is improved, and a pigment dispersion composition having excellent storage stability can be obtained.

<Pigment>
The pigment is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include black pigment, cyan pigment, magenta pigment, yellow pigment and white pigment. These may be used alone or in combination of two or more.

Examples of the black pigment include carbon black, black iron oxide, and black titanium oxide.
Examples of the magenta pigment include C.I. I. Pigment Red 122, C.I. I. Pigment Red 202, C.I. I. Pigment Red 269, C.I. I. Pigment Violet 19, Bengala and the like. Further, as the magenta pigment, for example, any of the dyes of red 201, red 202, red 223, red 230 (1), red 104 (1), red 226, red 227, red 220, and red 228 is insolubilized. Examples include red pigments.
Examples of the cyan pigment include C.I. I. Pigment Blue 15: 3, C.I. I. Pigment blue 15: 4, pigment obtained by insolubilizing blue 1, navy blue, ultramarine, and the like.
Examples of the yellow pigment include C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 180, C.I. I. Examples thereof include pigments of Pigment Yellow 185 and iron oxide, and pigments obtained by insolubilizing any of the dyes consisting of yellow 4, yellow 5, and yellow 203.
Examples of the white pigment include sulfates of alkaline earth metals such as white titanium oxide and barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, fine powder silicic acid, silicas such as synthetic silicates, and silica. Examples thereof include calcium acid, alumina, alumina hydrate, zinc oxide, talc and clay.
Among these, carbon black, C.I. I. Pigment Red 122, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Yellow 155 and white titanium oxide are preferred. Also, from the viewpoint of safety, black iron oxide, black titanium oxide, red iron oxide, or red 201, red 202, red 223, red 230 (1), red 104 (1), red 226, red 227, red 220, red 228. Pigment insolubilized with any of the dyes, pigment with insolubilized blue 1, pigment with dark blue, ultramarine blue, iron oxide, yellow 4, yellow 5, yellow 203, white titanium oxide , Sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, fine powder silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Zinc, talc and clay are preferred.

As the pigment, it is preferable that the surface is surface-treated such as an acid treatment in order to obtain good dispersibility. The acidic treatment facilitates the adsorption of the basic dispersant polymer, and the steric repulsion effect can improve the dispersibility.

The surface treatment method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include known methods such as pigment derivative treatment, resin modification, oxidation treatment and plasma treatment.

As the pigment, a synthetic product or a commercially available product may be used. Examples of the commercially available product include the following.
Examples of commercially available black pigments include Special Black 250 (carbon black, manufactured by Orion (Degsa)), Special Black 350 (carbon black, manufactured by Orion (Degsa)), and Special Black 550 (carbon black, manufactured by Orion (Degsa)). ), MOGUL-E (carbon black, manufactured by Cabot), SUNBLACK X45 (carbon black, manufactured by Asahi Carbon), MA11 (carbon black, manufactured by Mitsubishi Chemical), MA14 (carbon black, manufactured by Mitsubishi Chemical) , MA220 (carbon black, manufactured by Mitsubishi Chemical Co., Ltd.), # 970 (carbon black, manufactured by Mitsubishi Chemical Co., Ltd.), C47-2222 D & C Black 2 (carbon black, manufactured by DIC Co., Ltd.), ABL-412HP (black iron oxide, manufactured by Titanium Industry Co., Ltd.) , BL-100HP (black iron oxide, manufactured by Titanium Industry Co., Ltd.), Tilac D (fine grain type), Tilac D (ultrafine grain type), TM-F (black titanium oxide, manufactured by Akaho Kasei Co., Ltd.) and the like.
Commercially available magenta pigments include, for example, EBtransp (CI Pigment Red 122, manufactured by Clariant Japan, surface treatment: derivative), trade name: RGT (CI Pigment Red 122, manufactured by DIC, surface treatment). : Derivative), E2Y (CI Pigment Red 122, manufactured by Clariant Japan, surface treatment: additive), trade name: SD108 (CI Pigment Red 122, manufactured by Sanyo Pigment, surface treatment: acidic), Product Name: RFS (CI Pigment Red 122 / CI Pigment Violet 19, DIC, Surface Treatment: Derivative), R-516HP (Bengala, Titanium Industry), R-800HP (Bengala, Titanium) (Manufactured by Kogyo Co., Ltd.), R-110P (Bengala, manufactured by Titanium Kogyo Co., Ltd.), D & C Red 6 Ba Lake (CI 15850), D & C Red 6 Ba Lake (CI 15850), D & C Red 6 Ba Lake (C) I. 15850), D & C Red 6 Sodium Salt (Red 201, CI 15850), D & C Red 7 Ca Lake (Red 202, CI 15850), D & C Red 7 Ca Lake (Red 202, CI) .15850), D & C Red 7 Ca Lake (Red 202, CI 15850), D & C Red 7 Ca Lake (Red 202, CI 15850), D & C Red 7 Ca Lake (Red 202, CI 15850). ), D & C Red 21 (Red 223, CI 45380), D & C Red 21 Al Lake (CI 45380), D & C Red 22 Al Lake (Red 230 (1), CI 45380), D & C Red 27 Al Lake (CI 45410), D & C Red 27 Al Lake (CI 45410), D & C Red 28 Al Lake (Red 104 (1), CI 45410), D & C Red 30 Al Lake (Red) 226, CI 73360), D & C Red 30 Talk Lake (Red 226, CI 73360), D & C Red 33 Al Lake (Red 227, CI 17200), D & C Red 34 Ca Lake (Red 220, CI 15880), D & C Red 36 (Red 228, CI 12085), D & C Red 40 Al Lake (CI 16035) ), Manganese Violet (C.I. I. 77742) and the like.
Examples of commercially available cyan pigments include LX-8091 (CI Pigment Blue 15: 4, manufactured by Toyo Color Co., Ltd.), B4G (CI Pigment Blue 15: 4, manufactured by Clariant Japan Co., Ltd.), and the like. D7110F (CI Pigment Blue 15: 4, manufactured by BASF), FD & C Blue 1 Al Lake (Blue 1, CI 42090), Iron Blue (CI 77510), Ultramarine Blue (CI). 77007), Ultramarine Pink (CI77707), Ultramarine Violet (CI77707) and the like.
Examples of commercially available yellow pigments include D1080J (CI Pigment Yellow 138, manufactured by BASF), 4G (CI Pigment Yellow 138, manufactured by Clariant Japan Co., Ltd.), and 4GC (CI Pigment Yellow). 155, Clarant Japan Co., Ltd.), P-HG (CI Pigment Yellow 180, Clariant Japan Co., Ltd.), BY2000GT (CI Pigment Yellow 180, DIC Co., Ltd.), First Yellow 531 (C.I. I. Pigment Yellow 74, manufactured by Dainichi Seika Kogyo Co., Ltd., FD & C Yellow 5 Al Lake (Yellow 4, CI 19140), FD & C Yellow 6 Al Lake (Yellow 5, CI 15985), D & C Yellow 10 Al Lake (Yellow 203, CI 47005) and the like can be mentioned.
Commercially available white pigments include, for example, TCR-52 (number average primary particle size: 230 nm, surface treatment: Al ₂ O ₃ , manufactured by Sakai Chemical Industry Co., Ltd.), S3618 (number average primary particle size: 230 nm, surface treatment: Al ₂ O ₃ , manufactured by Sakai Chemical Industry Co., Ltd., JR403 (number average primary particle size: 250 nm, manufactured by Teika Co., Ltd., surface treatment: Al ₂ O ₃ , SiO ₂ ), JR (number average primary particle size: 270 nm, Teika) Made by Co., Ltd., Surface treatment: None), Product name: JR301 (Number average primary particle size: 300 nm, Made by Teika Co., Ltd., Surface treatment: Al ₂ O ₃ ), Product name: R45M (Number average primary particle size: 290 nm, Manufactured by Sakai Chemical Co., Ltd., surface treatment: Al ₂ O ₃ , SiO ₂ ), trade name: Titanium Dioxide (titanium oxide, CI 77891, surface treatment: none) and the like.
These may be used alone or in combination of two or more.

<< Other color materials >>
The pigment dispersion composition of the present invention may contain other coloring materials in addition to the coloring materials described above, depending on the purpose and required properties of the pigment dispersion composition of the present invention. As the other coloring material, various other pigments and dyes that impart a glossy color such as black, white, magenta, yellow, green, orange, gold, and silver can be used.
Examples of the other pigments include inorganic pigments and organic pigments. These may be used alone or in combination of two or more.

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, titanium oxide, and the like can be used.
Examples of the organic pigment include azo pigments such as insoluble azo pigments, condensed azo pigments, azolakes and chelate azo pigments, quinacridone pigments, perylene and perinone pigments, anthraquinone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments and quinophthalone pigments. Polycyclic pigments, dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), dyeing rake (basic dye type rake, acidic dye type rake), nitro pigment, nitroso pigment, aniline black, daylight Fluorescent pigments and the like can be mentioned. The dye is not particularly limited, but for example, acid dyes, direct dyes, reactive dyes, basic dyes and the like can be used, and one type may be used alone or two or more types may be used in combination. ..

The number average primary particle size of the pigment is preferably 30 nm or more and 180 nm or less, and more preferably 40 nm or more and 150 nm or less. When the number average primary particle size is 30 nm or more and 180 nm or less, the dispersibility can be improved. The number average primary particle size is such that 200 or more and 500 or less primary particles are sandwiched in a 10,000-fold field of view using a scanning electron microscope (device name: SU3500, manufactured by Hitachi High-Technologies Corporation). It can be obtained from the average value of the cumulative distribution by measuring the constant direction diameter at the distance between two parallel lines in a certain direction.

The content of the pigment is preferably 3% by mass or more and 30% by mass or less with respect to the total amount of the pigment composition. When the content is 3% by mass or more, the coloring property can be improved, and when the content is 30% by mass or less, an increase in viscosity can be suppressed and the ejection property can be improved.

ただし、前記一般式（１）中、Ｒ^１は水素原子、又は炭素数１〜４の直鎖若しくは分岐のアルキル基を表し、Ｒ^２は炭素数１〜４の直鎖又は分岐のアルキレン基を表し、Ｒ^３は炭素数１〜４の直鎖又は分岐のアルキル基を表す。

ただし、前記一般式（２）中、環Ｘは窒素原子を含む炭素数２〜５の環構造を表し、Ｒ^４は単結合、又は炭素数１〜３の直鎖若しくは分岐のアルキレン基を表し、Ｒ^５は炭素数１〜３の直鎖又は分岐のアルキル基を表す。
上記一般式（１）及び（２）の少なくともいずれかで表されるアクリルアミド化合物は、ＳＩ値が低いので、顔料分散組成物の皮膚感作性を抑制できる。 <Acrylamide compound>
The acrylamide compound has an acrylamide group and an ester structure, and is a polymerizable compound as a dispersion medium in the pigment dispersion composition.
The acrylamide group is polymerizable _{and refers to a group in which an acryloyl group (CH 2} = CH-CO-) is bonded to a nitrogen atom of an amine compound.
The acrylamide compound is a compound represented by at least one of the following general formulas (1) and (2).

However, in the general formula (1), R ¹ represents a hydrogen atom or a linear or branched alkyl group ^{having 1 to 4 carbon atoms, and R 2} represents a linear or branched alkylene group having 1 to 4 carbon atoms. Representing, R ³ represents a linear or branched alkyl group having 1 to 4 carbon atoms.

However, in the general formula (2), the ring X represents a ring structure having 2 to 5 carbon atoms containing a nitrogen atom, and R ⁴ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms. , R ⁵ represent a linear or branched alkyl group having 1 to 3 carbon atoms.
Since the acrylamide compound represented by at least one of the general formulas (1) and (2) has a low SI value, the skin sensitization property of the pigment dispersion composition can be suppressed.

In the general formula (1), R ¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
Examples of R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group and the like.
In the general formula (1), R ² represents a linear or branched alkylene group having 1 to 4 carbon atoms.
Examples of R ² include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, and a propane-1, 3-Diyl group, Butane-1,1-Diyl group, Butane-1,2-Diyl group, Butane-1,3-Diyl group, Butane-1,4-Diyl group, 2-Methylpropane-1,1- Examples thereof include a diyl group, a 2-methylpropane-1,2-diyl group, and a 2-methylpropane-1,3-diyl group.
In the general formula (1), R ³ represents a linear or branched alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 2 carbon atoms.
The R ^3, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, sec- butyl group, an isobutyl group, etc. tert- butyl group.
The total number of carbon atoms of R ¹ , R ² and R ³ is preferably 2 to 12, more preferably 2 to 6.

In the general formula (2), the ring X represents a ring structure containing a nitrogen atom and having 2 to 5 carbon atoms.
Examples of the ring X include aziridine, azetidine, pyrrolidine, piperidine and the like, and pyrrolidine and piperidine are preferable.
In the general formula (2), R ⁴ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms.
The R ^4, for example, a single bond, a methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane -1,3-Diyl group and the like can be mentioned.
In the general formula (2), R ⁵ represents a linear or branched alkyl group having 1 to 3 carbon atoms.
The R ^5, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group.
The total number of carbon atoms in the rings X, R ⁴ and R ⁵ is preferably 3 to 11, and more preferably 3 to 6.

Examples of the compound having an acrylamide group and an ester structure include N-acrylloylmorpholin, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N- (2-hydroxyethyl) acrylamide, and N-(. Hydroxymethyl) acrylamide, N- (butoxymethyl) acrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- (1,1-dimethyl-3-oxobutyl) acrylamide, 2-acrylamide-2-methylpropanesulfone Examples include acid. However, among these, it is difficult to find one that is safe in terms of skin sensitization, which is the effect of the present invention, and that is excellent in dispersibility.
The present invention has been found that the acrylamide compounds of the general formulas (1) and (2) satisfy the effects of the present invention by containing an ester structure having a neutral and appropriate polarity.

Examples of the compound represented by the general formula (1) or (2) include N-acryloyl-N-alkyl amino acid alkyl esters (including N-acryloyl proline alkyl esters) and N-acryloyl piperidine carboxylic acid alkyl esters. Be done. The alkyl group referred to in this paragraph means a linear or branched alkyl group having 1 to 4 carbon atoms, and among these, an alkyl group having 1 or 2 carbon atoms (that is, a methyl group or an ethyl group). ) Is preferable.

Specific examples of the above N-acryloyl-N-alkyl amino acid alkyl ester include, for example, N-acryloyl-N-methylglycine methyl ester, N-acryloyl-N-methylglycine ethyl ester, and N-acryloyl-N-methyl. Glycinpropyl ester, N-acryloyl-N-methylglycine butyl ester, N-acryloyl-N-ethylglycine methyl ester, N-acryloyl-N-ethylglycine ethyl ester, N-acryloyl-N-ethylglycine propyl ester, N- Acryloyl-N-propylglycine methyl ester, N-acryloyl-N-propylglycine ethyl ester, N-acryloyl-N-butylglycine methyl ester, N-acryloyl-N-methylalanine methyl ester, N-acryloyl-N-methylalanine Ethyl ester, N-acryloyl-N-methylalanine propyl ester, N-acryloyl-N-ethylalanine methyl ester, N-acryloyl-N-ethylalanine ethyl ester, N-acryloyl-N-propylalanine methyl ester, N-acryloyl -N-Methyl-β-alanine methyl ester, N-acryloyl-N-methyl-β-alanine ethyl ester, N-acryloyl-N-ethyl-β-alanine methyl ester, N-acryloyl-N-ethyl-β-alanine Examples thereof include ethyl ester, N-acryloyl-N-methylvalin methyl ester, N-acryloyl proline methyl ester, N-acryloyl proline ethyl ester and the like.

Specific examples of the above N-acryloyl piperidine carboxylic acid alkyl ester include, for example, N-acryloyl piperidine-2-carboxylic acid methyl, N-acryloyl piperidine-3-carboxylic acid methyl, and N-acryloyl piperidine-4-carboxylic acid. Methyl and the like can be mentioned.

A specific acrylamide compound represented by at least one of the above general formulas (1) and (2) other than the above N-acryloyl-N-alkyl amino acid alkyl ester and N-acryloyl piperidinecarboxylic acid alkyl ester. Examples thereof include methacryloyloxyethyl acrylamide and the like.

Further, as specific examples of the acrylamide compound represented by the general formula (1) or (2), groups a to h are shown, but the present invention is 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.

<< Example compound a1 group >>

<< Example compound a2 group >>

<< Example compound a3 group >>

<< Example compound a4 group >>

<< Example compound a5 group >>

<< Example compound a6 group >>

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.

<< Example compound b1 group >>

<< Example compound b2 group >>

<< Example compound b3 group >>

<< Example compound b4 group >>

<< Example compound b5 group >>

<< Example compound b6 group >>

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.

<< Example compound c1 group >>

<< Example compound c2 group >>

<< Example compound c3 group >>

<< Example compound c4 group >>

<< Example compound c5 group >>

<< Example compound c6 group >>

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.

<< Example compound d1 group >>

<< Example compound d2 group >>

<< Example compound d3 group >>

<< Example compound d4 group >>

<< Example compound d5 group >>

<< Example compound d6 group >>

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.

<< Example compound e1 group >>

<< Example compound e2 group >>

<< Example compound e3 group >>

<< Example compound e4 group >>

<< Example compound e5 group >>

<< Example compound e6 group >>

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.

<< Example compound f1 group >>

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.

<< Example compound g1 group >>

<< Example compound g2 group >>

<< Example compound g3 group >>

<< Example compound g4 group >>

<< Example compound g5 group >>

<< Example compound g6 group >>

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.

<< Example compound h1 group >>

Among the exemplified compounds a to h, the acrylamide compounds of the general formulas (1) and (2) (dispersion medium used for dispersing the pigment) include the exemplified compounds a1 in terms of dispersibility and low viscosity. -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 are preferable, and Example compound d1-1 and Exemplified compound d1- 2. Exemplified compound g1-1, exemplary compound g1-2, and exemplary compound g1-5 are more preferable from the viewpoint of curability. Since the particle size distribution becomes uniform due to the improvement of dispersibility, the inhibition of absorption of ultraviolet light can be suppressed by reducing excessively small particles and agglomerated particles, and the curability can be improved, and at the same time, the ejection property is improved. it can.

The method for synthesizing the acrylamide compounds of the general formulas (1) and (2) is not particularly limited, but is a method of reacting a compound having an activated acryloyl group such as acrylic acid chloride or acrylic anhydride with an amine compound. Can be mentioned. The amine compound that can be used when synthesizing the acrylamide compound may be either a primary amine or a secondary amine, but a tertiary amide that does not cause hydrogen bonds between amide groups and is advantageous for lowering the viscosity can be obtained. In that respect, it is preferably a secondary amine.

The molecular weight of the acrylamide compound is preferably 150 or more and 250 or less, and more preferably 150 or more and 200 or less. When the molecular weight is 150 or more, the odor due to the volatilization of the compound can be suppressed, and the stability of inkjet ejection can be improved, which is preferable. When the molecular weight is 250 or less, the curability of the composition is excellent, the strength of the cured product is improved, and the viscosity of the composition is not increased, which is preferable.

For application to the inkjet recording method, the acrylamide compound is preferably a colorless transparent to pale yellow transparent liquid having a low viscosity (100 mPa · s or less) at room temperature (25 ° C.). Further, for the safety of the user, those which do not show strong acidity or basicity and do not contain harmful formaldehyde as an impurity are preferable.

The content of the acrylamide compounds of the general formulas (1) and (2) is preferably 4.8% by mass or more and 94.8% by mass or less, preferably 9.8% by mass, based on the total amount of the pigment dispersion composition of the present invention. More preferably, it is 19.8% by mass or more and 84.8% by mass or less, and further preferably 19.8% by mass or more and 74.8% by mass or less. When the content of the acrylamide compound is 4.8% by mass or more, the wettability of the adhesive used in assembling the ink ejection head to the composition is improved, which is preferable. Further, when the content of the acrylamide compound is 94.8% by mass or less, the curability when the composition is irradiated with active energy rays is excellent, which is preferable.

<Pigment dispersant>
The pigment dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a dispersant polymer and a resin component for coating a pigment. Among these, the dispersant polymer is preferable.
The pigment dispersant has an effect of imparting wettability to the dispersion medium and an effect of imparting dispersion stability of the pigment in the medium. As the dispersant polymer, a block copolymer composed of a hydrophobic block and a hydrophilic block can be used, the hydrophilic block is oriented on the pigment surface, the hydrophobic block spreads to the dispersion medium side, and the dispersion is high due to its steric hindrance effect. Stability is obtained. On the other hand, the resin component that coats the pigment can be dispersed by covering the surface of the pigment with a resin to reduce the surface activity of the pigment and give it a dispersibility in a medium.

As the dispersant polymer, a copolymer containing a basic functional group-containing copolymer, an acrylic block copolymer, and an alkylol ammonium salt and containing an acid group is preferable. These may be used alone or in combination of two or more.
Examples of the basic group contained in the basic functional group-containing copolymer include an amino group, an imino group, an amide group, an imide group, and a nitrogen-containing heterocyclic group. Among these, an amino group is preferable from the viewpoint of dispersibility and viscosity reducing ability.
When the dispersant polymer is used, the steric repulsion effect associated with the adsorption of the dispersant can be improved, and high dispersion stability can be obtained. The dispersant polymer means a polymer having a weight average molecular weight of 1,000 or more.

The amine value of the dispersant polymer is preferably 10 mgKOH / g or more and 100 mgKOH / g or less, and more preferably 20 mgKOH / g or more and 85 mgKOH / g or less. When the amine value is 10 mgKOH / g or more and 100 mgKOH / g or less, it is considered that the promotion of the polymerization reaction with the polymerizable compound which is a component of the composition can be suppressed even during long-term storage or heating. Therefore, it is presumed that the viscosity change is small even during long-term storage or heating, and that it has high storage stability.
As for the amine value, 1 g of the dispersant polymer was dissolved in 100 mL of methylisobutylketone, and an automatic titrator (device name: GT-200, Mitsubishi Chemical Analytical Co., Ltd.) was used with a 0.01 mol / L methylisobutylketone chlorate solution. Potentiometric titration can be performed using Tick), the potential difference can be measured, and the amine value can be calculated based on the obtained potential difference.

The dispersant polymer may be a synthetic one or a commercially available product.
Commercially available products of the basic functional group-containing copolymer include, for example, trade name: Solsperse 20000 (amine value: 35.9 mgKOH / g), trade name: Solsperse 24000 (amine value: 41.6 mgKOH / g), and commercial products. Name: Solsperse 32000 (amine value: 31.2 mgKOH / g), Product name: Solsperse 33000 (amine value: 43.0 mgKOH / g), Product name: Solsperse 35000 (amine value: 32.0 mgKOH / g), Product name: Solsperse 39000 (amine value: 25.7 mgKOH / g), trade name: Solsperse 71000 (amine value: 75.0 mgKOH / g), trade name: Solsperse 73000 (amine value: 80.0 mgKOH / g), trade name: Solsperse 74000 (Amine value: 81.0 mgKOH / g), Product name: Solsperse 88000 (Amine value: 33.0 mgKOH / g), Product name: Solsperse J180 (Amine value: 27.6 mgKOH / g), Product name: Solsperse J200 (Amine) Value: 18.6 mgKOH / g) and other sol sparse series manufactured by Nippon Louvre Resol Co., Ltd., trade name: DisperBYK-162 (amine value: 13 mgKOH / g), trade name: DisperBYK-163 (amine value: 10 mgKOH / g) , Product name: DisperBYK-168 (amine value: 11 mgKOH / g), product name: BYKJET-9151 (amine value: 17.2 mgKOH / g), product name: BYKJET-9152 (amine value: 27.3 mgKOH / g), etc. BYKJET series manufactured by Big Chemie Japan Co., Ltd., Product name: Ajispar PB821 (amine value: 11.2 mgKOH / g), Product name: Ajispar PB822 (amine value: 18.2 mgKOH / g), Product name: Ajisper PB824 (amine) Price: 17.0 mgKOH / g), trade name: Ajisper PB881 (amine value: 17.4 mgKOH / g) and the like, such as Ajinomoto Fine Techno Co., Ltd.'s Ajispar series.
Examples of commercially available products of the acrylic block copolymer include trade name: DisperBYK-2050 (amine value: 30.7 mgKOH / g), trade name: DisperBYK-2055 (amine value: 45.1 mgKOH / g), and trade name. : DisperBYK-2150 (amine value: 56.7 mgKOH / g), trade name: DisperBYK-2155 (amine value: 52.5 mgKOH / g) and the like, DisperBYK series manufactured by Big Chemie Japan Co., Ltd. and the like can be mentioned.
Commercially available products of the copolymer containing the alkyrammonium salt and containing an acid group include, for example, trade name: DisperBYK-140 (amine value: 76 mgKOH / g), trade name: DisperBYK-180 (amine value:: 94 mgKOH / g) and the like.

The content of the pigment dispersant is preferably 10% by mass or more and 70% by mass or less, and more preferably 15% by mass or more and 40% by mass or less with respect to the pigment. When the content is 10% by mass or more, the dispersibility can be improved by the steric repulsion effect of the dispersant polymer adsorbed on the pigment, and when it is 70% by mass or less, the amount of the liberated dispersant polymer not adsorbed on the pigment. It is possible to reduce the viscosity of the ink. Further, since the amount of the dispersant polymer that is not adsorbed is small, the increase in the tincture property of the ink is suppressed, and the liquid permeability and the ejection property are improved. In addition, the amount of the dispersant polymer that is not adsorbed also affects the physical properties of the film, and a small amount of the dispersant polymer that is not adsorbed reduces the curing inhibitory component of the film, resulting in curability and a base material. It is also expected to improve the adhesion with.

<Other ingredients>
The other components are not particularly limited, but for example, conventionally known polymerizable compounds, organic solvents, polymerization inhibitors, slip agents (surfactants), penetration promoters, wetting agents (moisturizers), fixing agents, etc. Examples thereof include antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, and thickeners.

<< Polymerizable compound >>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polyfunctional polymerizable compounds described below having a skin sensitization SI value of 3 or less, general formulas (1) and (2). Examples thereof include polymerizable compounds other than acrylamide.

<< Polymerization inhibitor >>
Examples of the polymerization inhibitor include p-methoxyphenol, 4-methoxy-1-naphthol, methylhydroquinone, hydroquinone, t-butylhydroquinone, di-t-butylhydroquinone, methquinone, 2,2'-dihydroxy-3, 3'-di (α-methylcyclohexyl) -5,5'-dimethyldiphenylmethane, p-benzoquinone, di-t-butyldiphenylamine, 9,10-di-n-butoxycyantrasen, 4,4'-[1, Examples thereof include 10-dioxo-1,10-decandylbis (oxy)] bis [2,2,6,6-tetramethyl] -1-piperidinyloxy.
The content of the polymerization inhibitor is preferably 0.005% by mass or more and 3% by mass or less with respect to the total amount of the polymerization initiator. When the content is 0.005% by mass or more, the storage stability can be improved and the increase in viscosity can be suppressed in a high temperature environment, and when the content is 3% by mass or less, the curability can be improved.

<< Surfactant >>
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include higher fatty acid-based surfactants, silicone-based surfactants, and fluorine-based surfactants.
The content of the surfactant is preferably 0.1% by mass or more and 3% by mass or less, more preferably 0.2% by mass or more and 1% by mass or less, based on the total amount of the curable composition. When the content is 0.1% by mass or more, the wettability can be improved, and when the content is 3% by mass or less, the curability can be improved. When the content is within a more preferable range, the wettability and the leveling property can be improved.

<< Organic Solvent >>
The pigment dispersion composition and the curable composition of the present invention 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.

<Preparation of pigment dispersion composition>
The pigment dispersion composition of the present invention can be prepared by using the above-mentioned various components, and the preparation means and conditions thereof are not particularly limited. For example, a polymerizable monomer, a pigment, a dispersant and the like can be prepared by using a ball mill, a kitty mill, or the like. By putting it in a disperser such as a disc mill, a pin mill, or a dyno mill, and dispersing it to prepare a pigment dispersion, the pigment dispersion is further mixed with a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, and the like. Can be adjusted.

<< Dispersion method >>
As a method for dispersing the pigment dispersion composition of the present invention, a disperser using a medium such as a ball mill, a sand mill or a bead mill may be used, or a medialess disperser may be used. As a dispersion method, it is effective to carry out the main dispersion in a state of a high pigment concentration of about twice the target pigment concentration of the dispersion, and dilute with a dispersion medium to the target pigment concentration before extracting the dispersion. In the high pigment concentration state, it is expected that the ratio of the pigment to the dispersant polymer increases, the number of contacts between the dispersant polymer and the pigment increases, and the adsorption of the dispersant polymer to the pigment is promoted.

As the dispersion medium in the dispersion device using the media, it is preferable to use zirconia beads from the viewpoint of dispersibility and dispersion efficiency. Moreover, you may use these dispersion methods in combination of 2 or more types. For example, in the case of ball mill dispersion, a dispersion liquid having a uniform particle size distribution is obtained by performing two-step dispersion such as dispersion using zirconia beads having a diameter of 5 mm and then dispersing using zirconia beads having a diameter of 1 mm. Obtainable.

Since the medialess disperser does not apply excessive energy to the pigment, the pigment particles are not crushed, the adsorption of the dispersant polymer on the pigment surface is promoted, and the dispersion stability can be improved. In addition to preventing overdispersion, media-derived contamination does not occur, so that the generation of fine powder and coarse powder in the system can be suppressed. Since these can improve the uniformity of the particle size distribution, high ink ejection properties can be obtained.
Examples of the medialess dispersion device include a dispersion device that utilizes a high-speed shearing force such as a collision dispersion type and an ultrasonic dispersion type, a dispersion device that utilizes high-speed stirring, and the like.
Examples of the disperser using the high-speed shearing force include a device name: NanoVita Series Lab Machine C-ES008 (manufactured by Yoshida Kikai Kogyo Co., Ltd.).
The temperature of the dispersion liquid at the time of dispersion is preferably 5 ° C. or higher and 60 ° C. or lower. When the temperature is 5 ° C. or higher and 60 ° C. or lower, the curing reaction of the monomer can be suppressed. It is also possible to add a small amount of a polymerization inhibitor in advance in order to suppress the curing reaction.

<Use of pigment dispersion composition>
Applications of the pigment dispersion composition of the present invention include, for example, a paint for applying to nails, a curable composition described later, and the like.

(Curing composition and curable ink)
The curable composition of the present invention preferably contains the above-mentioned pigment dispersion composition, more preferably contains a polyfunctional polymerizable compound having an SI value of 3 or less in a skin sensitization test, and further needs to be contained. Contains other ingredients accordingly.
The curable ink of the present invention (hereinafter, may be referred to as “ink”) comprises the curable composition of the present invention. The curable composition and ink of the present invention can be used for both handwriting and inkjet, but are preferably for inkjet.
The curable composition may be either a thermosetting composition or an active energy ray-curable composition, but is preferably an active energy ray-curable composition in terms of curability.

<<< Polyfunctional polymerizable compound with a skin sensitization SI value of 3 or less >>>
The polyfunctional polymerizable compound having a skin sensitizing SI value of 3 or less is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate. , Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate. ) Acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylpropanthry (meth) acrylate, captolactone-modified dipentaerythritol hexa (meth) acrylate and the like. However, it is not limited to these. The (meth) acrylic acid ester means an acrylic acid ester or a methacrylic acid ester, and has the same meaning for (meth) acrylate and the like. These may be used alone or in combination of two or more.

Examples of the polyfunctional polymerizable compound having a skin sensitizing SI value of 3 or less include a urethane (meth) acrylate derivative obtained by reacting a (meth) acrylic acid ester having a hydroxy group with a compound having an isocyanate group, and (meth) acrylic. An epoxy (meth) acrylate derivative obtained by reacting an acid with a compound having an epoxy group can also be exemplified.
In addition to the (meth) acrylic acid derivative, vinyl ethers such as diethylene glycol divinyl ether, triethylene glycol divinyl ether, and cyclohexanedimethanol divinyl ether; allyl compounds such as diallyl phthalate and triallyl trimellitate can also be used. it can.

The polyfunctional polymerizable compound having a skin sensitizing SI value of 3 or less is preferably contained in the composition in an amount of 1.0% by mass or more and 60.0% by mass or less, preferably 5.0% by mass or more and 40.0% by mass or less. It is more preferably contained below, and more preferably 10.0% by mass or more and 30.0% by mass or less. Further, as the polyfunctional polymerizable compound having a skin sensitization SI value of 3 or less, only one kind may be used, or two or more kinds may be used in combination.
By using a polyfunctional polymerizable compound having a skin sensitization SI value of 3 or less, the curability and viscosity of the composition and the hardness and adhesion of the cured product can be easily adjusted according to the purpose of use. it can.

<<< Polymerizable compounds other than acrylamide of general formulas (1) and (2) >>>
The polymerizable compound is not particularly limited as long as it can carry out a polymerization reaction with active energy rays (ultraviolet rays, electron beams, etc.), and can be appropriately selected depending on the intended purpose. From the viewpoint of adjusting the physical properties and the like, one type may be used alone, or two or more types may be used in combination.
Examples of the polymerizable compound include radically polymerizable polymerizable compounds and polymerizable oligomers.
Examples of the radically polymerizable polymerizable compound include (meth) acrylate compounds, (meth) acrylamide compounds, and aromatic vinyl compounds. These may be used alone or in combination of two or more. In the present specification, (meth) acrylate means at least one of acrylate and methacrylate, and (meth) acrylic means at least one of acrylic and methacrylic.

-(Meta) acrylate compound-
Examples of the (meth) acrylate compound include monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional (meth) acrylate, tetrafunctional (meth) acrylate, and pentafunctional (meth) acrylate. , Hexfunctional (meth) acrylate and the like. These may be used alone or in combination of two or more.

Examples of the monofunctional (meth) acrylate include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, and isodecyl (meth) acrylate. ) Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate , Butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (meth) acrylate, benzyl (meth) acrylate, butoshikimethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate , Alkoxymethyl (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetra Fluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) Acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidi Loxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilyl Chrylate (meth) acrylate, trimethylsilylpropyl (Meta) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide mono Alkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxytyl succinic acid, 2-methacryloyloxy Hexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropylphthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (Meta) acrylate, ethylene oxide-modified phenol (meth) acrylate, ethylene oxide-modified cresol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, propylene oxide-modified nonylphenol (meth) acrylate, ethylene oxide-modified -2-ethylhexyl (meth) ) Acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, benzyl acrylate and the like can be mentioned. These may be used alone or in combination of two or more. Among these, phenoxyethyl (meth) acrylate, benzyl acrylate, -2- (2-vinyloxyethoxy) ethyl acrylate, 2-hydroxyethyl (meth) acrylate from the viewpoint of low viscosity, low odor, and high curability. , 3-Hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate are preferable, and phenoxyethyl (meth) is preferable from the viewpoint of compatibility with a photopolymerization initiator and other monomers. Acrylate, benzyl acrylate, and -2- (2-vinyloxyethoxy) ethyl acrylate are particularly preferred.

Examples of the bifunctional (meth) acrylate include 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 2,4-. Dimethyl-1,5-pentanediol di (meth) acrylate, butyl ethyl propanediol (meth) acrylate, ethoxylated cyclohexane methanol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, hydroxy Neopentyl glycol di (meth) acrylate of pivalate, bisphenol F polyethoxydi (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butylpropanediol di (meth) acrylate, 1,9- Examples thereof include nonandi (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and tricyclodecanedi (meth) acrylate. These may be used alone or in combination of two or more.

Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, alkylene oxide-modified tri (meth) acrylate of trimethylolpropane, and pentaerythritol tri (meth). Acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide-modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((() Meta) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, etc. Can be mentioned. These may be used alone or in combination of two or more.

Examples of the tetrafunctional (meth) acrylate include sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate propionate. These may be used alone or in combination of two or more.

Examples of the pentafunctional (meth) acrylate include sorbitol penta (meth) acrylate. These may be used alone or in combination of two or more.

Examples of the hexafunctional (meth) acrylate include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, and captolactone-modified dipentaerythritol hexa (meth). Examples include acrylate. These may be used alone or in combination of two or more.

-(Meta) acrylamide compound-
Examples of the (meth) acrylamide compound include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-n-butyl (meth) acrylamide. N-t-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl Examples thereof include (meth) acrylamide, (meth) acryloylmorpholin, and hydroxyethyl (meth) acrylamide. These may be used alone or in combination of two or more. Of these, (meth) acryloyl morpholine is preferred.

-Aromatic vinyl compounds-
Examples of the aromatic vinyl compound include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrene, and vinyl benzoic acid. Methyl ester, 3-methyl styrene, 4-methyl styrene, 3-ethyl styrene, 4-ethyl styrene, 3-propyl styrene, 4-propyl styrene, 3-butyl styrene, 4-butyl styrene, 3-hexyl styrene, 4- Hexyl styrene, 3-octyl styrene, 4-octyl styrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allyl styrene, isopropenyl styrene, butenyl styrene, octenyl styrene, 4-t- Butoxycarbonylstyrene, 4-methoxystyrene, 4-t-butoxystyrene and the like can be mentioned. These may be used alone or in combination of two or more.

-Polymerizable oligomer-
The polymerizable oligomer preferably has one or more ethylenically unsaturated double bonds. The oligomer means a polymer in which the number of repetitions of the monomer structural unit is 2 or more and 20 or less.
The weight average molecular weight of the polymerizable oligomer is not particularly limited and may be appropriately selected depending on the intended purpose. In terms of polystyrene, it is preferably 1,000 or more and 30,000 or less, and 5,000 or more and 20,000 or less. Is more preferable. The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

Examples of the polymerizable oligomer include urethane acrylic oligomers (for example, aromatic urethane acrylic oligomers, aliphatic urethane acrylic oligomers, etc.), epoxy acrylate oligomers, polyester acrylate oligomers, and other special oligomers. These may be used alone or in combination of two or more. Among these, oligomers having 2 or more and 5 or less unsaturated carbon-carbon bonds are preferable, and oligomers having 2 unsaturated carbon-carbon bonds are more preferable. When the number of unsaturated carbon-carbon bonds is 2 or more and 5 or less, good curability can be obtained.

As the polymerizable oligomer, a commercially available product can be used, and as the commercially available product, for example, UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV- manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 3200B, UV-3300B, UV-3700B, UV-6640B, UV-8630B, UV-7000B, UV-7610B, UV-1700B, UV-7630B, UV-6300B, UV-6640B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7630B, UV-7640B, UV-7650B, UT-5449, UT-5454; Sartmer's CN902, CN902J75, CN929, CN940, CN944, CN944B85, CN959, CN961E75, CN961H81, CN962, CN963, CN963A80, CN963B80, CN963E75, CN963E80, CN963J85, CN964, CN965, CN965A80, CN966, CN966A80, CN966B85, CN966H90, CN966J75, CN9668, CN9669, CN970, CN970 CN973A80, CN973H85, CN973J75, CN975, CN977, CN977C70, CN978, CN980, CN981, CN981A75, CN981B88, CN982, CN982A75, CN982B88, CN982E75, CN983, CN984, CN985, CN9985B88 CN997, CN999, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009, CN9010, CN9011 CN9290, CN9782, CN9783, CN9788, CN9893; EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, KRM8200, EBECRYL manufactured by Daicel Cytec Co., Ltd. 5129, EBECRYL8210, EBECRYL8301, EBECRYL8804, EBECRYL8807, EBECRYL9260, KRM7735, KRM8296, KRM8452, EBECRYL4858, EBECRYL8402, EBECRYL9270, EBECRYL9270, etc. These may be used alone or in combination of two or more.
Further, instead of a commercially available product, a synthetic product obtained by synthesis can be used, and a synthetic product and a commercially available product can be used in combination.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the same components as the pigment dispersion composition, a polymerization initiator, and a hydrogen donor.

<< Polymerization Initiator >>
The polymerization initiator may be any one capable of generating active species such as radicals and cations by the energy of active energy rays and initiating the polymerization of a polymerizable compound (monomer or oligomer). As such a polymerization initiator, known radical polymerization initiators and cationic polymerization initiators can be used alone or in combination of two or more, and among them, it is preferable to use a radical polymerization initiator. The content of the polymerization initiator is preferably 5% by mass or more and 20% by mass or less with respect to the total amount of the curing type composition in order to obtain a sufficient curing rate.

Examples of the radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), and hexaarylbiimidazole compounds. , Ketooxime ester compound, borate compound, azinium compound, metallocene compound, active ester compound, compound having carbon halogen bond, alkylamine compound and the like. These may be used alone or in combination of two or more.
Further, in addition to the polymerization initiator, a polymerization accelerator can also be used in combination.

The polymerization accelerator is not particularly limited, and for example, ethyl p-dimethylaminobenzoate, -2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, -2-dimethylaminoethyl benzoate, and the like. Examples thereof include amine compounds such as butoxyethyl p-dimethylaminobenzoate. These may be used alone or in combination of two or more.

<< Hydrogen donor >>
In the curable composition of the present invention, the compound having a benzophenone skeleton or the like initiates polymerization by the polymerization initiation mechanism shown below. That is, a compound having a benzophenone skeleton or the like is excited by light irradiation. Then, the excited molecule abstracts hydrogen from a nearby compound, and a radical is generated on the hydrogen-extracted compound, which becomes a radical polymerization initiation point. As a result, the compound having a benzophenone skeleton or the like exhibits a function as a photoradical polymerization initiator. That is, if there is a compound capable of extracting hydrogen together with a compound having a benzophenone skeleton or the like, the polymerization is initiated by the above-mentioned polymerization initiation mechanism. Therefore, for example, if hydrogen is extracted from the radically polymerizable compound used in the present invention, the polymerization may start from there.

On the other hand, in the curable composition of the present invention, a hydrogen donating compound in which hydrogen is easily extracted can coexist. In that case, hydrogen transfer from the hydrogen-donating compound can be performed more smoothly to the compound molecule having a benzophenone skeleton excited by light irradiation, and the polymerization can proceed more efficiently. That is, by adding it to a polymerization initiator having no absorption at 365 to 405 nm, it is possible to greatly improve the polymerization reactivity while maintaining low yellowing.

The hydrogen donating compound used in the present invention may be any compound that can smoothly donate hydrogen to a compound molecule having a benzophenone skeleton excited by light irradiation.

Such compounds include, for example, diethylamine, diphenylamine, triethylamine, tributylamine, diethanolamine, triethanolamine, N, N-diethylethanolamine, N, N-diethylmethylamine, dipropylamine, N, N-dimethylaniline. , P-Diethylaminobenzoate ethyl, p-dimethylaminobenzoate ethyl and other amino group compounds, methanol, ethanol, propanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, butanediol, phenol and other hydroxyl group compounds. , Tetrahydrofuran, tetrahydropyran, dioxane, trioxane, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and other compounds with ether bonds, butanthiol, propanethiol, hexanedithiol, decandithiol, n-dodecyl mercaptoene. , Dodecyl (4-methylthio) phenyl ether, benzenethiol, 4-dimethylmercaptobenzene, 2-mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, 3-mercapto-1,2-propanediol , Mercapto compounds such as mercaptophenol, or disulfides obtained by oxidizing them, butyl thioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, butanediol bis (3-mercaptoisobutyrate), 1, 4-butanediol bisthioglycolate, 1,4-butanediol bisthiopropionate, octyl β-mercaptopropionate, methoxybutyl β-mercaptopropionate, trishydroxyethyltristhiopropionate, trimethylpropanthris ( 3-Mercaptoisobutyrate), Trimethylolpropanthris (3-Mercaptobutyrate), Trimethylolpropanthris (3-Mercaptopropionate), Trimethylolpropanetris (β-thiopropionate), Trimethylolpropanetris Thioglycolate, trimetylolpropanetristhiopropionate, pentaerythritoltetrakis (3-mercaptopropionate), pentaerythritoltetrakis thioglycolate, pentaerythritoltetrakis Thiopropionate, thioglycolic acid, thiosalicylic acid, thioapple acid, mercaptoacetic acid, 2-mercaptoethanesulfonic acid, 2-mercaptonicotinic acid, 2-mercaptopropionic acid, 3-mercaptopropanesulfonic acid, 3-mercaptopropionic acid, 3-Mercaptobutyric acid, 4-Mercaptobutane sulfonic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 2-mercapto-3-3 Pyrizinol, 2-mercaptoimidazole, 2-mercaptoethylamine, 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 6-trimercapto-s-triazine, N- (2-mercaptopropionyl) glycine, N- (3-mercaptopropionyl) ) Alanine, diisopropylthioxanthone, diethylthioxanthone, thiophosphites, tris (2-hydroxyethyl) trimercaptopropionate, and other compounds having a mercapto group such as isocyanurate are preferably used.

Compounds having an amino group are particularly preferably used because of their low hydrogen transfer energy, among which methyl 2- (N, N-dimethylamino) benzoate and ethyl 4- (N, N-dimethylamino) benzoate are used. , 4- (N, N-diethylamino) ethyl benzoate, 1,3-di ({α-4- (dimethylamino) benzoylpoly [oxy (1-methylethylene)]} oxy) -2,2-bis ( {Α-4- (dimethylamino) benzoylpoly [oxy (1-methylethylene)]} oxymethyl) propane and {α-4- (dimethylamino) benzoylpoly (oxyethylene) -poly [oxy (1-methylethylene)] )]-A mixture of poly (oxyethylene)} 4- (dimethylamino) benzoate (manufactured by Rambson, "Speedcure 7040") and the like are more preferably used.

When the hydrogen donating compound in the present invention is used, the amount used is usually preferably 0.01% by mass or more and 50% by mass or less, preferably 0.1% by mass, based on the radically polymerizable compound in the photopolymerizable composition of the present invention. % Or more and 20% by mass or less are more preferable.

The static surface tension of the curable ink at 25 ° C. is preferably 20 mN / m or more and 40 mN / m or less, and more preferably 28 mN / m or more and 35 mN / m or less.
The static surface tension was measured at 25 ° C. using a static surface tension meter (CBVP-Z type manufactured by Kyowa Interface Science Co., Ltd.). The static surface tension assumes the specifications of a commercially available inkjet ejection head such as GEN5 manufactured by Ricoh Printing Systems Co., Ltd.

In the present invention, the 50% cumulative volume particle size of the pigment in the curable composition is 100 nm or more and 160 nm or less, and the distribution width of the particle size distribution obtained from the following formula (2) is 60 nm or less. preferable.
Distribution width of particle size distribution = (84% cumulative volume particle size-16% cumulative volume particle size) / 2 ... (2)

When the 50% cumulative volume particle size is 100 nm or more and 160 nm or less, the effect of improving the dispersibility and improving the liquid permeability and the discharge property is obtained.
Further, when the distribution width of the particle size distribution obtained from the above formula (2) is 60 nm or less, the dispersed particle size becomes sharp and the liquid permeability and the discharge property are improved.
A more preferable 50% cumulative volume particle size is 100 nm or more and 140 nm or less.
A more preferable distribution width of the particle size distribution obtained from the above formula (2) is 50 nm or less.

The 50% cumulative volume particle size (D50) and the distribution width of the particle size distribution can be obtained as follows.
The 50% cumulative volume particle size (D50) was obtained by diluting the obtained curable composition about 2000 times with a polymerizable compound used as a dispersion medium, and using a particle size distribution meter (trade name: UPA150, Nikkiso). Measured using (manufactured by Co., Ltd.).
As the distribution width of the particle size distribution, 84% cumulative volume particle size (D84) and 16% cumulative volume particle size (D16) were measured in the same manner as the 50% cumulative volume particle size (D50), and the above. It can be obtained by the formula (2).

<Viscosity>
The viscosity of the curable composition of the present invention may be appropriately adjusted according to the application and the application means, and is not particularly limited. For example, when a discharge means for discharging the composition from a nozzle is applied, the viscosity is not particularly limited. The viscosity in the range of 20 ° C. to 65 ° C., preferably the viscosity at 25 ° C. is preferably 3 to 40 mPa · s, more preferably 5 to 15 mPa · s, and particularly preferably 6 to 12 mPa · s. Further, it is particularly preferable that the viscosity range is satisfied without containing the organic solvent. For the above viscosity, a cone rotor (1 ° 34'x R24) was used with a cone plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., the rotation speed was 50 rpm, and the temperature of constant temperature circulating water was 20 ° C. It can be appropriately set and measured in the range of ~ 65 ° C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

The rate of change in viscosity of the cured composition is preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less. When the viscosity change rate is 15% or less, the storage stability is excellent and the dispersibility can be improved. The viscosity change rate can be obtained from the following formula (3). Further, the viscosity at the viscosity change rate was determined by using a cone plate type rotational viscometer (device name: VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd.) at a constant temperature circulating water temperature of 25 ° C. and a rotation speed of 50 rpm. And the shear rate can be measured under the condition of 191.4 sec-1.
Viscosity change rate (%)
= ((Viscosity after storage at 70 ° C. for 14 days-Initial viscosity) / Initial viscosity) × 100… (3)

<Use>
The application of the curable composition of the present invention is not particularly limited as long as it is a field in which the pigment dispersion composition and the curable material are generally used, and can be appropriately selected depending on the intended purpose. For example, a molding resin. , Paints, adhesives, insulating materials, mold release agents, coating materials, sealing materials, various resists, various optical materials and the like.
Further, the curable composition of the present invention is used as an ink to not only form two-dimensional characters and images, and design coatings on various substrates, but also form a three-dimensional three-dimensional image (three-dimensional model). It can also be used as a material for three-dimensional modeling. This three-dimensional modeling material may be used, for example, as a binder between powder particles used in a powder lamination method in which three-dimensional modeling is performed by repeatedly curing and laminating a powder layer, and is also shown in FIGS. 2 and 3. It may be used as a three-dimensional constituent material (model material) or a support member (support material) used in such a layered manufacturing method (stereolithography). In addition, FIG. 3 is a method of discharging the curable composition of the present invention into a predetermined region, irradiating the cured composition with active energy rays, and sequentially laminating the cured compositions to perform three-dimensional modeling (details will be described later). Is to irradiate the storage pool (accommodation portion) 1 of the curable composition 5 of the present invention with active energy rays 4 to form a hardened layer 6 having a predetermined shape on a movable stage 3, and sequentially stack these to form a three-dimensional shape. Is a way to do.
As a three-dimensional modeling device for modeling a three-dimensional model using the curable composition of the present invention, a known one can be used, and the present invention is not particularly limited, but for example, a means for accommodating the composition and a means for supplying the composition. , Those equipped with a discharge means, an active energy ray irradiation means, and the like.
The present invention also includes a cured product obtained by curing a curable composition and a molded product obtained by processing a structure in which the cured product is formed on a substrate. The molded product is, for example, a cured product or structure formed in the form of a sheet or a film, which has been subjected to molding processing such as heat stretching or punching. For example, automobiles, OA equipment, and electricity. -Suitably used for applications that require molding after decorating the surface, such as electronic devices, meters for cameras, panels for operation units, and the like.
The base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paper, thread, fiber, fabric, leather, metal, plastic, glass, wood, ceramics, or a composite material thereof and the like. From the viewpoint of processability, a plastic base material is preferable.
Further, the composition of the present invention not only forms a design coating film on two-dimensional characters, images, and various substrates, but also, for example, a cured product obtained by curing the composition or the cured product can be used. It also includes nails and artificial nails made by processing a structure formed on a nail-shaped plastic base material. Since the composition of the present invention is excellent in removability and nail adhesion, it is particularly suitable as a base coat for artificial nail compositions.

(Accommodation container)
The storage container of the present invention (hereinafter, also referred to as “composition storage container”) means a container in which a curable composition is stored, and is suitable for use in the following applications. For example, when the curable composition of the present invention is used for ink, the container containing the ink can be used as an ink cartridge or an ink bottle, whereby in operations such as ink transfer and ink replacement. , It is not necessary to touch the ink directly, and it is possible to prevent the fingers and clothes from getting dirty. In addition, it is possible to prevent foreign substances such as dust from being mixed into the ink. The shape, size, material, etc. of the container itself may be suitable for the intended use and usage, and is not particularly limited, but the material is a light-shielding material that does not transmit light, or the container blocks light. It is desirable that it is covered with a sex sheet or the like.

(Image forming method and image forming device)
The image forming apparatus of the present invention is a two-dimensional or three-dimensional image forming apparatus.
The image forming apparatus of the present invention has an accommodating portion for accommodating the curable composition of the present invention, an imparting means for imparting the curable composition, and a curing means for curing the curable composition, and is further required. It has other means depending on the situation.
The image forming method of the present invention is a two-dimensional or three-dimensional image forming method.
The image forming method of the present invention includes an imparting step of imparting the curable composition of the present invention, a curing step of curing the curable composition, and further includes other steps as necessary.

The image forming method of the present invention can be suitably carried out by the image forming apparatus of the present invention, the applying step can be performed by the applying means, the curing step can be performed by the curing means, and other steps. Can be done by other means.

<Accommodation>
The accommodating portion is not particularly limited as long as it can accommodate the curable composition of the present invention, and can be appropriately selected depending on the intended purpose, and the above-mentioned accommodating container is preferable.

<Granting means and granting process>
The imparting step is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a discharge step. The discharge means 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.

<Curing means and curing process>
The curing step is not particularly limited as long as the curable composition of the present invention can be cured, and can be appropriately selected depending on the intended purpose. Examples thereof include a heating step and an active energy ray irradiation step. A curing step using active energy rays is preferable.
Examples of the means for curing the curable composition of the present invention include heat curing or curing with active energy rays, and among these, curing with active energy rays is preferable.
The active energy rays used for curing the active energy ray-curable composition of the present invention include polymerizable components in the composition such as electron beams, α rays, β rays, γ rays, and X rays in addition to ultraviolet rays. It is not particularly limited as long as it can impart the energy required for advancing the polymerization reaction of. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Further, in the case of ultraviolet irradiation, mercury-free is strongly desired from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light emitting device is very useful industrially and environmentally. Further, the ultraviolet light emitting diode (UV-LED) and the ultraviolet laser diode (UV-LD) are compact, have a long life, have high efficiency, and are low in cost, and are preferable as an ultraviolet light source.
Among these, it is preferable to use a UV-LED as a light source capable of irradiating ultraviolet rays having a peak at a wavelength of 365 nm or more and 405 nm or less.

<Other means and other processes>
The other steps are not particularly limited and can be appropriately selected according to the purpose.
The other means are not particularly limited and may be appropriately selected depending on the purpose.

Here, the image forming apparatus of the present invention will be described with reference to the drawings.
FIG. 1 is an example of an image forming apparatus provided with an inkjet ejection means. The ink is ejected to the recording medium 22 supplied from the supply roll 21 by the color printing units 23a, 23b, 23c, and 23d including the ink cartridges of the yellow, magenta, cyan, and black color curable inks and the ejection head. 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, 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.
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.
The recorded matter recorded by the ink 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 an uneven surface to be printed, metal, ceramic, and the like. It also includes those printed on the surface to be printed made of various materials. 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.

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 the first curable composition from the discharge head unit 30 for a modeled object to the discharge head unit 31 for a support. , 32 to discharge the second curable composition having a composition different from that of the first curable composition, and the adjacent ultraviolet irradiation means 33 and 34 are laminated while curing each of these compositions. More specifically, for example, the second curable composition is discharged from the support discharge head units 31 and 32 onto the modeled object support substrate 37, irradiated with active energy rays and solidified to form a reservoir. After forming the first support layer to have, the first curable composition is discharged from the discharge head unit 30 for a modeled object into the reservoir, and is irradiated with active energy rays to be solidified to solidify the first modeled object. By repeating the step of forming the layer 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.

(Cured product)
The cured product of the present invention is a two-dimensional or three-dimensional image. The two-dimensional or three-dimensional image is obtained by applying either the curable composition of the present invention or the curable ink of the present invention onto a substrate and curing the image.
The two-dimensional or three-dimensional image is not only printed on a smooth surface such as ordinary paper or resin film, but also recorded on a recording surface having irregularities, or from various materials such as metal and ceramics. Including those recorded on the recording surface.
Examples of the two-dimensional image include characters, symbols, figures, combinations thereof, and solid images.
Examples of the three-dimensional image include a three-dimensional model.
The average thickness of the three-dimensional model is not particularly limited and can be appropriately selected depending on the intended purpose, and is preferably 10 μm or more.
The two-dimensional or three-dimensional image is preferably cured by using light emitting diode light having an irradiation amount of active energy rays of 500 mJ / cm ^{2 or less.}

Further, the stretchability of the cured product in the present invention is expressed as the stretchability at 180 ° C. as a ratio of (length after tensile test-length before tensile test) / (length before tensile test). It is preferably 50% or more, and more preferably 100% or more.

(Decorative body)
The decorative body is formed by surface decoration made of a cured product on a base material.
As the cured product, the same product as the cured product of the present invention can be used.

The base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paper, thread, fiber, fabric, leather, metal, plastic, glass, wood, ceramics, or a composite material thereof and the like. From the viewpoint of workability, plastic is preferable.

(Nail decoration material, artificial nail)
The curable composition of the present invention is preferably used for artificial nails as an artificial nail composition.
The artificial nail composition contains the curable composition of the present invention, and further contains other components as needed.
The artificial nail composition includes pigments, colorants such as dyes, metal powders, inorganic fillers such as calcium carbonate, talc, silica, alumina, and aluminum hydroxide, and flame retardants, as long as the characteristics of the present invention are not impaired. An appropriate amount of additives such as an organic filler, an antioxidant, a polymerization inhibitor, a defoaming agent, a coupling agent, a leveling agent, and a leology control agent may be blended.
Nail decorating materials include manicures, pedicures, sculptures, gel nails and the like used to decorate or reinforce nails.
Artificial nails also include those that form artificial resin nails on the nails (self-made nails).

The artificial nail composition is a composition that is applied on human or animal nails or on other artificial nails and then cured by exposure to form artificial nails. Further, the artificial nail formed by the artificial nail composition of the present invention can also be removed by a removing method using an organic solvent or the like.
The artificial nail in the present invention refers to a layer formed on a human or animal nail or on another artificial nail for the purpose of beautification and / or protection. Further, for example, examples of the above-mentioned other artificial nails include a resin base material (nail nail) having an arbitrary shape for the purpose of beautifying and / or protecting the nail.
In addition, "human and animal claws and other artificial claws" are also simply referred to as "claw".

The shape of the artificial nail is not particularly limited and may be formed into a desired shape. For example, it may be formed so as to cover the surface of the nail, it may be formed only on a part of the nail, or it may be formed into a shape larger than the nail for extension of the nail by using nail foam or the like. You may.
Further, the thickness of the artificial nail composition of the present invention can be controlled by coating. The thickness of the entire artificial nail is not particularly limited as long as it can be taken by the artificial nail, but it is preferably in the range of 10 μm or more and 2,000 μm or less from the viewpoint of durability and removability. ..

As an example, the artificial nail is composed of a primer layer (a layer between the nail and the base layer to improve the adhesion when the base layer alone does not have sufficient adhesion to the nail) and a base layer in order from the nail. (Layer between nail and color layer to improve adhesion and prevent color transfer to nail), color layer (layer containing color material), top layer (to improve durability, luster and aesthetics) Generally, the artificial nail composition of the present invention has a layer structure containing any one or more of the outermost layer), etc., but the artificial nail composition of the present invention comprises a base layer, a color layer, and / or a top layer. Any of them can be suitably used.
Above all, from the viewpoint of durability and removability, it is preferable that the layer obtained by curing the artificial nail composition of the present invention is in contact with the nail.
In addition, the upper layer (the surface opposite to the nail when the artificial nail layer is used as a reference) or the lower layer (the surface between the artificial nail layer and the nail) of the artificial nail layer formed by the artificial nail composition is separately colored. It may have a primer layer, a base layer, a color layer, and / or a top layer for the purpose of providing gloss and / or adhesion.

The artificial nail composition of the present invention is a photocurable artificial nail composition (also referred to as "artificial nail composition for gel nails") as a nail decoration material, and is an artificial nail composition that can be cured by active energy rays. Is.

The artificial nail composition of the present invention is a photocurable artificial nail composition (also referred to as "artificial nail composition for gel nails") as a nail decoration material, and is an artificial nail composition that can be cured by active energy rays. Is.

Here, FIG. 4A is a schematic view showing an example of a nail decorating device for decorating a human nail, and FIG. 4B is an enlarged schematic view of the decorating means of FIG. 4A.
In FIG. 4A, 101 is a decorating means, 102 is a fixing means, 104 is a cover, and 105 is a hand of a person to be decorated. Further, in FIG. 4B, 110 is an enlarged view of an ultraviolet lamp, 111 is an inkjet head, and 112 is an enlarged view of a decorating means 101 provided with a camera.
According to the nail decorating device 100 shown in FIGS. 4A and 4B, the hand of the person to be decorated is fixed by the fixing means 102, positioned by the camera 112, and the nail to be decorated is subjected to the present invention from the inkjet head. The artificial nail composition of No. 1 is discharged, and the nail is decorated by irradiating the nail with ultraviolet rays by the ultraviolet lamp 110. The decorating means 101 can be moved in the direction of the arrow in FIG. 4A.

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 pigment dispersion composition and curable composition>
The abbreviations, compound names, manufacturer names and product names of the raw materials used for preparing the pigment dispersion composition and the curable composition are shown in Tables 1-1 to 1-3. The monomer, which is an acrylamide compound, was synthesized by the methods shown in Synthesis Examples 1 to 5. The synthesized compound was identified by nuclear magnetic resonance spectroscopy (device used: "JNM-ECX500" manufactured by JEOL Ltd.), and the purity was measured by gas chromatography (device used: "GCMS-QP2010" manufactured by Shimadzu Corporation). Plus ”). These chemical analyzes were performed by a standard method.

<Amine value of dispersant polymer>
As the amine value of the dispersant polymer, 1 g of the dispersant polymer was dissolved in 100 mL of methyl isobutyl ketone, and potentiometric titration was performed with a 0.01 mol / L methyl isobutyl ketone solution of chlorate to measure the potential difference. The amine value was calculated based on the obtained potential difference. The potentiometric titration was measured using an automatic titration device (device name: GT-200, manufactured by Mitsubishi Chemical Analytical Co., Ltd.).

(Synthesis Example 1)
<Synthesis of N-acryloyl-N-methylglycine methyl ester (A1-1)>
Stir N-methylglycine methyl ester hydrochloride (manufactured by Sigma-Aldrich Japan LLC, reagent) 0.30 mol, potassium carbonate (manufactured by Kanto Chemical Co., Inc., reagent) 0.45 mol, and 400 mL of water at 0 ° C to 10 ° C. The mixture was mixed, and 0.33 mol of acrylic acid chloride (manufactured by Wako Pure Chemical Industries, Ltd., reagent) was slowly added dropwise while maintaining the temperature. After completion of the dropping, the mixture was extracted 3 times with 400 mL of ethyl acetate (manufactured by Kanto Chemical Co., Inc., reagent), and the ethyl acetate layers were combined and washed once with 400 mL of water. Ethyl acetate was distilled off under reduced pressure at 40 ° C. to obtain 0.20 mol of the desired N-acryloyl-N-methylglycine methyl ester (A1-1) as a nearly colorless and transparent liquid. The purity was 98.3% by mass.
The molecular weight of N-acryloyl-N-methylglycine methyl ester (A1-1) is 157.2, which is a known compound (CAS Registry Number 72065-23-7).

(Synthesis Example 2)
<Synthesis of N-acryloyl-N-methylglycine ethyl ester (A1-2)>
In Synthesis Example 1, the target N- was obtained in the same manner as in Synthesis Example 1 except that N-methylglycine methyl ester hydrochloride was changed to N-methylglycine ethyl ester hydrochloride (manufactured by Tokyo Kasei Kogyo Co., Ltd., reagent). 0.22 mol of acryloyl-N-methylglycine ethyl ester (A1-2) was obtained as a nearly colorless and transparent liquid. The purity was 98.5% by mass.
The molecular weight of N-acryloyl-N-methylglycine ethyl ester (A1-2) is 171.2, which is a known compound (CAS Registry Number 170116-05-9).

(Synthesis Example 3)
<Synthesis of N-acryloyl-N-methylalanine methyl ester (A1-3)>
In Synthesis Example 1, the target N- was the same as in Synthesis Example 1 except that N-methylglycine methyl ester hydrochloride was changed to N-methylalanine methyl ester hydrochloride (manufactured by Tokyo Kasei Kogyo Co., Ltd., reagent). 0.22 mol of acryloyl-N-methylalanine methyl ester (A1-3) was obtained as a nearly colorless and transparent liquid. The purity was 98.5% by mass.
The molecular weight of N-acryloyl-N-methylalanine methyl ester (A1-3) was 171.2.

(Synthesis Example 4)
<Synthesis of N-acryloylpiperidin-4-carboxylate ethyl (A1-4)>
In Synthesis Example 1, the target N-acryloyl was obtained in the same manner as in Synthesis Example 1, except that N-methylglycine methyl ester hydrochloride was changed to ethyl piperidine-4-carboxylate (manufactured by Tokyo Kasei Kogyo Co., Ltd., reagent). 0.27 mol of ethyl piperidin-4-carboxylate (A1-4) was obtained as a nearly colorless and transparent liquid. The purity was 99.2% by mass.
The molecular weight of ethyl N-acryloylpiperidin-4-carboxylate (A1-4) is 211.3, which is a known compound (CAS Registry Number 845907-79-1).

(Synthesis Example 5)
57.1 g (250 mmol) of 1,3-glycerol dimethacrylate manufactured by Tokyo Chemical Industry Co., Ltd. was added to 1000 mL of dehydrated dichloromethane, the inside of the flask was replaced with argon gas, and then 36.0 g (360 mmol) of triethylamine was added. Next, after cooling to about −10 ° C., 24.0 g (300 mmol) of chloride acetate was slowly added dropwise so that the temperature inside the system became −10 ° C. to −5 ° C., and the mixture was stirred at room temperature for 2 hours. Further, after removing the precipitate by filtration, the filtrate was washed with water, a saturated aqueous solution of sodium hydrogen carbonate, and a saturated aqueous solution of sodium chloride. Next, it was dried over sodium sulfate and then concentrated under reduced pressure to obtain a yellow oil. Further, 2,000 g of Wakogel C300 (manufactured by Wako Pure Chemical Industries, Ltd.) is filled, and the yellow oily substance is purified by column chromatography using hexane and ethyl acetate as the eluate, and the compound represented by the above chemical formula is purified. 18.0 g (yield of about 28%) of the colorless oily substance of (A2-6) was obtained. The purity was 99.1% by mass.

(Example 1-1)
<Preparation of pigment dispersion of Bk-1>
Dispersant polymer (trade name: Azisper PB821, manufactured by Ajinomoto Fine-Techno Co., Ltd., amine value: 10.0 mgKOH / g) 6.0 parts by mass was placed in 79.0 parts by mass of compound A1-1 79.0 parts and at 25 ° C. for 4 hours. A dispersion medium was prepared by stirring and dissolving.
In a 50 mL mayonnaise bottle (trade name: UM sample bottle, manufactured by AS ONE Co., Ltd.), 80 parts by mass of zirconia balls having a diameter of 2 mm, carbon black (trade name: Special Black 250, manufactured by Orion Co., Ltd.), 3.75 parts by mass, said dispersion. 21.25 parts by mass of the medium was added and dispersed in a ball mill under the following conditions for 2 days to prepare [Example Bk-1] (pigment concentration: 15% by mass).

-Ball mill conditions-
Media: YTZ ball diameter 2 mm
(Zirconia ball, manufactured by Nikkato Corporation)
Mill: MIX-ROTAR VMR-5 (manufactured by AS ONE Corporation)
Rotation speed: Mayonnaise bottle rotation speed 75 rpm

(Examples 1-2 to 1-55, Comparative Examples 1-1 to 1-10)
In the preparation of the pigment dispersion composition of Example 1-1, except that the types of pigments, dispersant polymers, and acrylamide compounds and their contents were changed to those shown in Tables 4-1 to 4-6 below. , Examples 1-1 to 1-55 (Bk-1 to Bk-10, Ma-1 to Ma-15, Cy-1 to Cy-10, Ye-1 to Ye) in the same manner as in Example 1-1. -10, and Wh-1 to Wh-10), and Comparative Examples 1-1 to 1-10 (Bk-11 to Bk-12, Ma-16 to Ma-17, Cy-11 to Cy-12, Ye- 11-Ye-12 and Wh-11-Wh-12) pigment dispersion compositions were prepared.

The skin sensitization (SI value) and storage stability of the obtained pigment dispersion compositions of Examples 1-1 to 1-55 and Comparative Examples 1-1 to 1-10 were evaluated as follows. .. The results are shown in Tables 4-1 to 4-6.

<SI value evaluation method>
The SI value was measured as follows according to a skin sensitization test by the LLNA method (Local Lymph Node Assay). The evaluation results are shown in Tables 4-1 to 4-6.

[Test material]
<< Positive control substance >>
As the positive control substance, α-hexyl cinnamaldehyde (HCA, manufactured by Wako Pure Chemical Industries, Ltd.) was used.

<< Medium >>
As the medium, a mixed solution of acetone (manufactured by Wako Pure Chemical Industries, Ltd.) and olive oil (manufactured by Fujimi Pharmaceutical Industries, Ltd.) at a volume ratio (acetone: olive oil) = 4: 1 was used.

<< Animals used >>
Female mice were acclimated for 8 days, including 6 days of quarantine, for each of the test substance, positive control, and vehicle control. No abnormalities were found in any of the animals during the quarantine and acclimation period.
Using the body weight measured 2 days before the start of sensitization, the animals were divided into 2 groups (4 animals / group) so that the average body weight of the individual was within ± 20% of the total body weight by the random sampling method by body weight group. .. The age of the animals at the onset of sensitization was 8-9 weeks. Animals that were excluded from the grouping were excluded from the study.
Animals used were identified by applying oil-based ink to the tail throughout the test period, while cages were labeled and identified.

<< Breeding environment >>
The animals used had a temperature of 21 ° C to 25 ° C, a relative humidity of 40% to 70%, a ventilation rate of 10 to 15 times / hour, and a light-dark cycle of 12 hours (lighting at 7 o'clock) throughout the entire breeding period including the quarantine and acclimation period. It was bred in the breeding room of the barrier system set to 19:00).
A polycarbonate cage was used as the breeding cage. The animals used were bred in 4 animals / cage.
As the feed, a solid feed MF for laboratory animals (manufactured by Oriental Yeast Co., Ltd.) was used, and the animals used were allowed to freely ingest. As drinking water, tap water to which sodium hypochlorite (Purax, manufactured by Oyalux) was added so that the chlorine concentration was approximately 5 ppm was freely ingested by the animals used by a water bottle. The floor was made of sunflake (fir wood, electric plane shavings, manufactured by Charles River Japan). As the feed and breeding equipment, those sterilized by autoclave (121 ° C., 30 minutes) were used.
The cage and bedding were replaced at the time of grouping and on the day of ingestion of the auricular lymph nodes (at the time of removal from the breeding room), and the water bottle and rack were replaced at the time of grouping.

[Test method]
<< Group composition >>
Table 2 shows the group composition used in the SI value measurement test.

[Preparation]
<< Test substance >>
Table 3 shows the weighing conditions of the test substance. The test substance was weighed in a volumetric flask, and the volume was adjusted to 1 mL while adding a medium. The preparation liquid was placed in a light-shielded airtight container (made of glass).

<< Positive control substance >>
Approximately 0.25 g of HCA was accurately weighed and a 25.0 w / v% solution was prepared as 1 mL with the addition of medium. The preparation was placed in a light-tight airtight container (made of glass).

<< BrdU >>
200 mg of 5-bromo-2'-deoxyuridine (BrdU, manufactured by Nacalai Tesque, Inc.) was accurately weighed in a volumetric flask, physiological saline (manufactured by Otsuka Pharmaceutical Factory, Ltd.) was added, and ultrasonic irradiation was performed to dissolve it. .. Then, the volume was adjusted to 20 mL to prepare a 10 mg / mL solution (BrdU preparation solution). The prepared solution was sterilized by filtration using a sterilized filtration filter and placed in a sterilized container.

<< Preparation time and storage period >>
The positive control substance preparation solution was prepared the day before the start of sensitization and stored in a cool place except when in use. The vehicle and test substance preparation solution were prepared on each sensitization day. BrdU solution was prepared 2 days before administration and stored in a cool place until the day of administration.

[Sensitization and administration of BrdU]
<< Sensitization >>
25 μL of each test substance and positive control substance preparation solution and medium were applied to both auricles of animals. A micropipettor was used for application. This operation was performed once a day for 3 consecutive days.

<< Administration of BrdU >>
Approximately 48 hours after the final sensitization, 0.5 mL of BrdU preparation was intraperitoneally administered per animal.

[Observation and inspection]
<< General condition >>
All animals used in the test were observed at least once a day from the start date of sensitization to the date of collection of auricular lymph nodes (the date of removal from the breeding room). In the calculation method of the observation date, the sensitization start date was set to Day 1.

<< Weight measurement >>
Body weight was measured on the day of sensitization start and the day of collection of auricular lymph nodes (the day of removal from the breeding room). In addition, the average value and standard error of body weight for each group were calculated.

<< Collection and mass measurement of auricular lymph nodes >>
Animals were euthanized approximately 24 hours after BrdU administration and auricular lymph nodes were collected. Peripheral tissue was removed and bilateral auricular lymph nodes were mass weighed together. In addition, the average value and standard error of the auricular lymph node weight for each group were calculated. After the mass measurement, each individual was cryopreserved in a biomedical freezer set at −20 ° C.

<< Measurement of BrdU uptake >>
After returning the auricular lymph nodes to room temperature, they were ground and suspended while adding physiological saline. After filtering this suspension, 3 wells were dispensed into 96-well microplates for each individual, and the amount of BrdU uptake was measured by the ELISA method. Reagents were obtained from a multi-plate reader (FLUOstar OPTIMA, manufactured by BMG LABTECH) using a commercially available kit (Cell Proliferation ELISA, BrdU colorimetric, Cat. No. 1647229, manufactured by Roche Diagnostics). Regarding the absorbance of the individual (OD370 nm-OD492 nm, BrdU uptake), the average value of 3 wells was taken as the BrdU measurement value of each individual.

[Evaluation of results]
<< Calculation of Stimulation Index (SI) >>
As shown by the following formula, the SI value of each individual was calculated by dividing the BrdU measured value of each individual by the average value of the BrdU measured values of the medium control group. The SI value of each test group was the average value of SI of each individual. The SI value was rounded off to the first decimal place and displayed up to the first decimal place.

<Evaluation of skin sensitization>
The SI value (Stimulation Index) of the composition prepared by the above method was determined by the LLNA method defined in the OECD test guideline 429 and the like, and the results are shown in Tables 4-1 to 4-6. In the following evaluation criteria, B or higher is practical.
[Evaluation criteria]
A: SI value is less than 1.6 B: SI value is 1.6 or more and 3 or less C: SI value is more than 3 and less than 6 D: SI value is 6 or more

<Storage stability>
For the pigment dispersion compositions of Examples 1-1 to 1-55 and Comparative Examples 1-1 to 1-10, a cone plate type rotational viscometer (device name: VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd.) was used. The initial viscosity immediately after production was measured under the conditions that the temperature of the constant temperature circulating water was 25 ° C., the rotation speed was 50 rpm, and the shear rate was 191.4 sec-1. Then, the pigment dispersion composition was allowed to stand at 70 ° C. for 14 days. Then, the viscosity after storage was measured under the same conditions as the measurement of the initial viscosity. The viscosity change rate was calculated from the following formula (3). The lower the viscosity change rate, the better the storage stability and the better the dispersibility.
Viscosity change rate (%)
= ((Viscosity after storage at 70 ° C. for 14 days-Initial viscosity) / Initial viscosity) × 100… (3)
"Storage stability" was evaluated based on the following evaluation criteria using the measured values of the viscosity change rate.
-Evaluation criteria-
A: Viscosity change rate is 5% or less B: Viscosity change rate is more than 5% and 15% or less C: Viscosity change rate is more than 15% and 30% or less D: Viscosity change rate is more than 30%

In Tables 4-1 to 4-6 above, the trade names and manufacturing company names of pigments and pigment dispersants are as follows.
-Pigment-
-Special Black250: Carbon Black, manufactured by Orion-Special Black350: Carbon Black, manufactured by Orion-D & C Black No. 2: Carbon black, manufactured by Daito Kasei Kogyo Co., Ltd. ・ RGT: C.I. I. Pigment Red 122, manufactured by DIC Corporation, R-110P: Bengala, manufactured by Titan Kogyo Co., Ltd., R-516HP: Bengala, manufactured by Titan Kogyo Co., Ltd., R-800HP: Bengala, manufactured by Titan Kogyo Co., Ltd. Red 202, C.I. I. 15850, manufactured by Daito Kasei Kogyo Co., Ltd. D & C Red 22 Al Lake: Red 230 (1), C.I. I. 45380, manufactured by Daito Kasei Kogyo Co., Ltd. D & C Red 28 Al Lake: Red 104 (1), C.I. I. 45410, manufactured by Daito Kasei Kogyo Co., Ltd. D & C Red 30: Red 226, C.I. I. 73360, manufactured by Daito Kasei Kogyo Co., Ltd. LX-8091: C.I. I. Pigment Blue 15: 4, manufactured by Toyo Color Co., Ltd., D7110F: C.I. I. Pigment Blue 15: 4, manufactured by BASF, D7079: C.I. I. Pigment Blue 15: 3, BASF FD & C Blue 1 Al Lake: Blue 1, C.I. I. 42090, manufactured by Daito Kasei Kogyo Co., Ltd., 4GC: C.I. I. Pigment Yellow 155, manufactured by Clariant Japan Co., Ltd. First Yellow 531: C.I. I. Pigment Yellow 74, manufactured by Dainichiseika Kogyo Co., Ltd. D1080J: C.I. I. Pigment Yellow 138, manufactured by BASF, 4G: C.I. I. Pigment Yellow 155, manufactured by Clariant Japan Co., Ltd. FD & C Yellow 5 Al Lake: Yellow 4, C.I. I. 19140, Daito Kasei Kogyo Co., Ltd. ・ TCR-52: Titanium oxide, Sakai Chemical Industry Co., Ltd. ・ S3618: Titanium oxide, Sakai Chemical Industry Co., Ltd. ・ JR403: Titanium oxide, Tayca Corporation ・ R45M: Titanium oxide, Titanium Dioxide manufactured by Sakai Chemical Industry Co., Ltd .: Titanium oxide, C.I. I. 77891, manufactured by Daito Kasei Kogyo Co., Ltd.-Pigment dispersant-
-BYKJET-9151: Manufactured by Big Chemie, amine value: 17.2 mgKOH / g
-BYKJET-9152: Manufactured by Big Chemie, amine value: 27.3 mgKOH / g
-Polymerizable compound-
・ ACMO (Acroyl morpholine, trade name: ACMO, manufactured by KJ Chemicals Co., Ltd.)
・ PEA (Phenoxyethyl acrylate, trade name: Viscoat # 192, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

(Example 2-1)
Example 1-1 (Bk-1) pigment dispersion 20.0 parts by mass, acrylamide compound A1-1 74.8 parts by mass, polymerization initiator C-1 (trade name: DETX-s, Nippon Kayaku Co., Ltd.) (Manufactured) 5.0 parts by mass, polymerization inhibitor (trade name: Metoquinone, manufactured by Nippon Kayaku Co., Ltd.) 0.1 parts by mass, and surfactant (trade name: BYK-UV3510, manufactured by Big Chemie Japan Co., Ltd.) 0 .1 part by mass was mixed and filtered through a membrane filter to remove coarse particles to obtain a curable composition (curable ink) of Example 2-1.

(Examples 2-2-2-40 and Comparative Examples 2-1-2-10)
In Example 2-1 in the same manner as in Example 2-1 except that the composition and content are changed to those shown in Tables 5-1 to 5-5, Examples 2-2-2-40 and A curable composition of Comparative Examples 2-1 to 2-10 was obtained. The numerical value in the table represents the content (mass%).

Next, the viscosity change rate and skin sensitization of the curable compositions of Examples 2-1 to 2-40 and Comparative Examples 2-1 to 2-10 were evaluated by the same method as described above. In addition, the liquid permeability, discharge stability curability (integrated irradiation light amount required for curing), and adhesion were evaluated as follows. The results are shown in Tables 6-1 to 6-5.

<Liquid permeability>
For the curable compositions of Examples 2-1 to 2-40 and Comparative Examples 2-1 to 2-10, 100 mL of each composition was filtered through a 10.0 μm hydrophobic PTFE membrane filter under a pressurized condition of 50 kPa. Then, the initial liquid permeability was evaluated based on the following evaluation criteria.
-Evaluation criteria-
A: 100 mL is fully passed B: 50 mL or more and less than 75 mmL is passed C: 25 mL or more and less than 50 mmL is passed D: Only less than 25 mL is passed

<Discharge stability>
As an inkjet recording device, a piezo type inkjet head capable of controlling the temperature of ink from the ink supply system to the head portion was used. This inkjet recording device is filled with the curable compositions of Examples 2-1 to 2-40 and Comparative Examples 2-1 to 2-10, the temperature is adjusted to a viscosity of 10 mPa · s, and the ejection speed is 3 kHz. The initial discharge evaluation was performed in. Discharge was continuously performed for 60 minutes, and after 60 minutes, evaluation was performed according to the following evaluation criteria. Using a cone plate type viscometer capable of temperature control, the temperature condition at which the ink viscosity was 10.0 ± 0.5 mPa · s was set. It was investigated and used as the heating condition at the time of printing.
-Evaluation criteria-
A: Normal discharge from 95% or more nozzles B: Normal discharge from 90% or more and less than 95% nozzle C: Normal discharge from 70% or more and less than 90% nozzle D: Nozzle less than 70% discharges normally

<Curable (integrated irradiation light required for curing)>
The curable compositions of Examples 2-1 to 2-40 and Comparative Examples 2-1 to 2-10 were used as a recording medium (trade name: Cosmoshine A4300 coated PET film, manufactured by Toyobo Co., Ltd., average thickness: 100 μm, color. A solid image of 10 cm × 10 cm was obtained using an evaluation printer obtained by modifying the printer (device name: SG7100, manufactured by Ricoh Co., Ltd.) for (transparent). ^{The obtained solid image was subjected to an illuminance of 1 W / cm 2} and an irradiation amount of 500 mJ / cm using a UV-LED device for an inkjet printer (device name: UV-LED module (single pass water cooling, manufactured by Ushio Electric Co., Ltd.)). ^{The curing treatment was carried out so as to be 2,} and an image (cured product) of 10 cm × 10 cm having an average thickness of 10 μm was obtained.
The irradiation amount was measured using an ultraviolet intensity meter (device name: UM-10) and a light receiving unit (device name: UM-400) (all manufactured by Konica Minolta Co., Ltd.). Further, as a method for measuring the average thickness, the thickness was measured using an electronic micrometer (manufactured by Anritsu Co., Ltd.), and the average thickness was determined from the average value of 10 points. Further, the evaluation printer is changed to an MH2620 head (manufactured by Ricoh Co., Ltd.) that can heat and eject the head portion and can handle high-viscosity ink by using the transport and drive unit of the device name: SG7100.
The obtained image (cured product) was rubbed 10 times with a load of ^{50 g / cm 2} by a white cotton cloth attached to a clock meter (device name: No. 416, manufactured by Yasuda Seiki Seisakusho Co., Ltd.). Then, using a reflection spectroscopic densitometer (device name: X-Rite939, manufactured by X-Rite), the concentration of the white cotton cloth before and after the reciprocating friction is measured, and the concentration after the reciprocating friction is measured before the reciprocating friction. The value obtained by subtracting the concentration was calculated, and the "curability" was evaluated based on the following evaluation criteria.
-Evaluation criteria-
A: 0.001 or less B: 0.001 or more 0.005 or less C: 0.005 or more 0.009 or less D: 0.009 or more

<Adhesion (evaluation of internal curability)>
Using the curable compositions of Examples 2-1 to 2-40 and Comparative Examples 2-1 to 2-10, an image of 10 cm × 10 cm having an average thickness of 10 μm (cured) in the same manner as in the curability evaluation. I got a thing). The solid part of the obtained image (cured product) is cut with a cutter knife at 1 mm intervals into a base mesh of 100 squares according to JIS K5400, and cellophane adhesive tape (trade name: Scotch mending tape (18 mm)) manufactured by 3M Co., Ltd. ), And the masses that did not peel off while looking at the loupe (trade name: PEAK No. 1961 (× 10), manufactured by Tokai Sangyo Co., Ltd.) were counted, and the "adhesiveness" was evaluated based on the following evaluation criteria. ..
-Evaluation criteria-
A: 100 squares that did not peel off 100 squares B: 100 squares that did not peel off 80 squares or more and 99 squares or less C: 100 squares that did not peel off 40 squares or more and 79 squares or less D: 100 The number of squares that did not peel off was 39 or less.

As can be seen from the results in Tables 6-1 to 6-5, it can be seen that the curable composition (curable ink) of the present invention can achieve both liquid permeability, ejection property and storage stability, as well as curability and adhesion. ..
When the amount of dispersant adsorbed is within the range of the present invention, it is considered that the pigment particles do not aggregate and the dispersibility is good. In addition, it is considered that the liquid permeability and the vomiting property are improved due to the absence of the excess liberated dispersant. At the same time, it is considered that the curability and adhesion are improved by the absence of the excess dispersant.

ただし、前記一般式（１）中、Ｒ^１は水素原子、又は炭素数１〜４の直鎖若しくは分岐のアルキル基を表し、Ｒ^２は炭素数１〜４の直鎖又は分岐のアルキレン基を表し、Ｒ^３は炭素数１〜４の直鎖又は分岐のアルキル基を表す。

ただし、前記一般式（２）中、環Ｘは窒素原子を含む炭素数２〜５の環構造を表し、Ｒ^４は単結合、又は炭素数１〜３の直鎖若しくは分岐のアルキレン基を表し、Ｒ^５は炭素数１〜３の直鎖又は分岐のアルキル基を表す。
＜２＞ 前記顔料分散剤が、塩基性官能基含有共重合体、アクリルブロック共重合体、及びアルキロールアンモニウム塩を含有し酸基を有する共重合体のいずれかである分散剤ポリマーであり、
前記分散剤ポリマーのアミン価が、１０ｍｇＫＯＨ／ｇ以上１００ｍｇＫＯＨ／ｇ以下である前記＜１＞に記載の顔料分散組成物である。
＜３＞ 前記顔料が、カーボンブラック、黒酸化鉄、及び黒色酸化チタンのいずれかであることを特徴とする前記＜１＞から＜２＞のいずれかに記載の顔料分散組成物である。
＜４＞ 前記顔料が、Ｃ．Ｉ．ピグメントレッド１２２、Ｃ．Ｉ．ピグメントレッド２０２、Ｃ．Ｉ．ピグメントレッド２６９、Ｃ．Ｉ．ピグメントバイオレット１９、及びベンガラのいずれかの顔料、並びに赤２０１、赤２０２、赤２２３、赤２３０（１）、赤１０４（１）、赤２２６、赤２２７、赤２２０、及び赤２２８のいずれかの染料を不溶化処理した顔料のいずれかである前記＜１＞から＜２＞のいずれかに記載の顔料分散組成物である。
＜５＞ 前記顔料が、Ｃ．Ｉ．ピグメントブルー１５：３、Ｃ．Ｉ．ピグメントブルー１５：４、青色１を不溶化処理した顔料、紺青、及び群青のいずれかである前記＜１＞から＜２＞のいずれかに記載の顔料分散組成物である。
＜６＞ 前記顔料が、Ｃ．Ｉ．ピグメントイエロー７４、Ｃ．Ｉ．ピグメントイエロー１３８、Ｃ．Ｉ．ピグメントイエロー１５５、Ｃ．Ｉ．ピグメントイエロー１８０、Ｃ．Ｉ．ピグメントイエロー１８５、及び黄酸化鉄のいずれかの顔料、並びに黄色４、黄色５、及び黄色２０３の染料を不溶化処理した顔料のいずれかである前記＜１＞から＜２＞のいずれかに記載の顔料分散組成物である。
＜７＞ 前記顔料が、白色酸化チタン、硫酸バリウム等のアルカリ土類金属の硫酸塩、炭酸カルシウム等のアルカリ土類金属の炭酸塩、微粉ケイ酸、合成ケイ酸塩等のシリカ類、ケイ酸カルシウム、アルミナ、アルミナ水和物、酸化亜鉛、及びタルク、クレイのいずれかである前記＜１＞から＜２＞のいずれかに記載の顔料分散組成物である。
＜８＞ 前記顔料分散剤の含有量が、前記顔料に対して、１０質量％以上７０質量％以下である前記＜１＞から＜７＞のいずれかに記載の顔料分散組成物である。
＜９＞ 有機溶剤を含まない前記＜１＞から＜８＞のいずれかに記載の顔料分散組成物である。
＜１０＞ 前記＜１＞から＜９＞のいずれかに記載の顔料分散組成物を含有することを特徴とする硬化型組成物である。
＜１１＞ 皮膚感作性試験のＳＩ（Ｓｔｉｍｕｌａｔｉｏｎ Ｉｎｄｅｘ）値が３以下である多官能重合性化合物を更に含有する前記＜１０＞に記載の硬化型組成物である。
＜１２＞ 有機溶剤を含まない前記＜１０＞から＜１１＞のいずれかに記載の硬化型組成物である。
＜１３＞ 手描き用である前記＜１０＞から＜１２＞のいずれかに記載の硬化型組成物である。
＜１４＞ 前記＜１０＞から＜１３＞のいずれかに記載の硬化型組成物を含有することを特徴とする硬化型インクである。
＜１５＞ インクジェット用であることを特徴とする前記＜１４＞に記載の硬化型インクである。
＜１６＞ 前記＜１０＞から＜１３＞のいずれかに記載の硬化型組成物が容器中に収容されてなることを特徴とする組成物収容容器である。
＜１７＞ 前記＜１０＞から＜１３＞のいずれかに記載の硬化型組成物を容器中に収容する収容部と、
前記＜１０＞から＜１３＞のいずれかに記載の硬化型組成物の少なくともいずれかを付与する付与手段と、
前記＜１０＞から＜１３＞のいずれかに記載の硬化型組成物を硬化させる硬化手段と、
を有することを特徴とする２次元又は３次元の像形成装置である。
＜１８＞ 前記硬化手段が、波長３６５ｎｍ以上４０５ｎｍ以下にピークを有する紫外線を照射するＵＶ−ＬＥＤである前記＜１７＞に記載の像形成装置である。
＜１９＞ 前記＜１０＞から＜１３＞のいずれかに記載の硬化型組成物を付与する付与工程と、前記硬化型組成物を硬化させる硬化工程と、を含むことを特徴とする２次元又は３次元の像形成方法である。
＜２０＞ 前記硬化工程において、波長３６５ｎｍ以上４０５ｎｍ以下にピークを有する紫外線をＵＶ−ＬＥＤで照射する前記＜１９＞に記載の像形成方法である。
＜２１＞ 前記＜１０＞から＜１３＞のいずれかに記載の硬化型組成物を含有することを特徴とする硬化物である。
＜２２＞ 基材上に前記＜２１＞に記載の硬化物からなる表面加飾が施されてなることを特徴とする加飾体である。
＜２３＞ 人工爪用である前記＜１０＞から＜１３＞のいずれかに記載の硬化型組成物である。
＜２４＞ 前記＜１０＞から＜１３＞のいずれかに記載の硬化型組成物を含むことを特徴とする爪加飾材である。
＜２５＞ 前記＜２３＞に記載の硬化型組成物を硬化してなることを特徴とする人工爪である。 Examples of aspects of the present invention are as follows.
<1> Pigments and
An acrylamide compound represented by any of the following general formulas (1) and (2) and
Pigment dispersant and
It is a pigment dispersion composition characterized by containing.

However, in the general formula (1), R ¹ represents a hydrogen atom or a linear or branched alkyl group ^{having 1 to 4 carbon atoms, and R 2} represents a linear or branched alkylene group having 1 to 4 carbon atoms. Representing, R ³ represents a linear or branched alkyl group having 1 to 4 carbon atoms.

However, in the general formula (2), the ring X represents a ring structure having 2 to 5 carbon atoms containing a nitrogen atom, and R ⁴ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms. , R ⁵ represent a linear or branched alkyl group having 1 to 3 carbon atoms.
<2> The pigment dispersant is a dispersant polymer that is any one of a basic functional group-containing copolymer, an acrylic block copolymer, and a copolymer containing an alkylolammonium salt and having an acid group.
The pigment dispersion composition according to <1>, wherein the amine value of the dispersant polymer is 10 mgKOH / g or more and 100 mgKOH / g or less.
<3> The pigment dispersion composition according to any one of <1> to <2>, wherein the pigment is any one of carbon black, black iron oxide, and black titanium oxide.
<4> The pigment is C.I. I. Pigment Red 122, C.I. I. Pigment Red 202, C.I. I. Pigment Red 269, C.I. I. Pigment Violet 19, any pigment of Bengala, and any of Red 201, Red 202, Red 223, Red 230 (1), Red 104 (1), Red 226, Red 227, Red 220, and Red 228. The pigment dispersion composition according to any one of <1> to <2>, which is one of the pigments obtained by insolubilizing a dye.
<5> The pigment is C.I. I. Pigment Blue 15: 3, C.I. I. The pigment dispersion composition according to any one of <1> to <2>, which is any of Pigment Blue 15: 4, a pigment obtained by insolubilizing Blue 1, dark blue, and ultramarine.
<6> The pigment is C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 180, C.I. I. The above-mentioned <1> to <2>, which is one of the pigments of Pigment Yellow 185 and yellow iron oxide, and any of the pigments obtained by insolubilizing the dyes of Yellow 4, Yellow 5, and Yellow 203. It is a pigment dispersion composition.
<7> The pigments are white titanium oxide, sulfate of alkaline earth metal such as barium sulfate, carbonate of alkaline earth metal such as calcium carbonate, fine powder silicic acid, silica such as synthetic silicate, silicic acid. The pigment dispersion composition according to any one of <1> to <2>, which is any of calcium, alumina, alumina hydrate, zinc oxide, and talc and clay.
<8> The pigment dispersion composition according to any one of <1> to <7>, wherein the content of the pigment dispersant is 10% by mass or more and 70% by mass or less with respect to the pigment.
<9> The pigment dispersion composition according to any one of <1> to <8>, which does not contain an organic solvent.
<10> A curable composition comprising the pigment dispersion composition according to any one of <1> to <9>.
<11> The curable composition according to <10>, which further contains a polyfunctional polymerizable compound having an SI (Stimulation Index) value of 3 or less in a skin sensitization test.
<12> The curable composition according to any one of <10> to <11>, which does not contain an organic solvent.
<13> The curable composition according to any one of <10> to <12>, which is for hand-drawing.
<14> A curable ink containing the curable composition according to any one of <10> to <13>.
<15> The curable ink according to <14>, which is for inkjet use.
<16> The composition container is characterized in that the curable composition according to any one of <10> to <13> is contained in the container.
<17> An accommodating portion for accommodating the curable composition according to any one of <10> to <13> in a container, and an accommodating portion.
An imparting means for imparting at least one of the curable compositions according to any one of <10> to <13>.
A curing means for curing the curable composition according to any one of <10> to <13>,
It is a two-dimensional or three-dimensional image forming apparatus characterized by having.
<18> The image forming apparatus according to <17>, wherein the curing means is a UV-LED that irradiates ultraviolet rays having a peak at a wavelength of 365 nm or more and 405 nm or less.
<19> A two-dimensional or two-dimensional structure comprising a applying step of imparting the curable composition according to any one of <10> to <13> and a curing step of curing the curable composition. This is a three-dimensional image forming method.
<20> The image forming method according to <19>, wherein the UV-LED irradiates ultraviolet rays having a peak at a wavelength of 365 nm or more and 405 nm or less in the curing step.
<21> A cured product containing the curable composition according to any one of <10> to <13>.
<22> A decorative body characterized in that a surface decoration made of the cured product according to <21> is applied on a base material.
<23> The curable composition according to any one of <10> to <13> for artificial nails.
<24> A nail decorating material comprising the curable composition according to any one of <10> to <13>.
<25> An artificial nail characterized in that the curable composition according to <23> is cured.

The pigment dispersion composition according to any one of <1> to <9>, the curable composition according to any one of <10> to <13>, or any of the above <14> to <15>. The curable ink, the storage container according to <16>, the image forming apparatus according to any one of <17> to <18>, and the image forming apparatus according to any one of <19> to <20>. The method, the cured product according to <21>, the decorative body according to <22>, the cured composition according to <23>, the nail decorative material according to <24>, and the above < The artificial nail according to 25> can solve the conventional problems and achieve the object of the present invention.

1 Storage pool (accommodation)
3 Movable stage 4 Active energy ray 5 Curing type composition 6 Curing layer 21 Supply roll 22 Recording medium 23a, 23b, 23c, 23d Printing unit 24a, 24b, 24c, 24d Light source 25 Processing unit 26 Printed matter winding roll 30 Modeled object Discharge head unit 31, 32 Discharge head unit for support 33, 34 Ultraviolet irradiation means 35 Three-dimensional model 36 Support laminate 37 Model support substrate 38 Stage 39 Image forming device

Japanese Unexamined Patent Publication No. 2005-263898 Japanese Unexamined Patent Publication No. 2015-48376

Claims (20)

With pigments
An acrylamide compound represented by at least one of the following general formulas (1) and (2),
Pigment dispersant and
A pigment dispersion composition comprising.

However, in the general formula (1), R ¹ represents a hydrogen atom or a linear or branched alkyl group ^{having 1 to 4 carbon atoms, and R 2} represents a linear or branched alkylene group having 1 to 4 carbon atoms. Representing, R ³ represents a linear or branched alkyl group having 1 to 4 carbon atoms.

However, in the general formula (2), the ring X represents a ring structure having 2 to 5 carbon atoms containing a nitrogen atom, and R ⁴ represents a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms. , R ⁵ represent a linear or branched alkyl group having 1 to 3 carbon atoms. The pigment dispersant is a dispersant polymer that is any one of a basic functional group-containing copolymer, an acrylic block copolymer, and a copolymer containing an alkylolammonium salt and having an acid group.
The pigment dispersion composition according to claim 1, wherein the amine value of the dispersant polymer is 10 mgKOH / g or more and 100 mgKOH / g or less. The pigment dispersion composition according to any one of claims 1 to 2, wherein the pigment is any one of carbon black, black iron oxide, and black titanium oxide. The pigment is C.I. I. Pigment Red 122, C.I. I. Pigment Red 202, C.I. I. Pigment Red 269, C.I. I. Pigment Violet 19, any pigment of Bengala, and any of Red 201, Red 202, Red 223, Red 230 (1), Red 104 (1), Red 226, Red 227, Red 220, and Red 228. The pigment dispersion composition according to any one of claims 1 to 2, which is one of the pigments obtained by insolubilizing the dye. The pigment is C.I. I. Pigment Blue 15: 3, C.I. I. The pigment dispersion composition according to any one of claims 1 and 2, which is any of Pigment Blue 15: 4, a pigment obtained by insolubilizing Blue 1, dark blue, and ultramarine. The pigment is C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 180, C.I. I. The pigment dispersion composition according to any one of claims 1 and 2, which is one of pigments of Pigment Yellow 185 and iron oxide, and pigments obtained by insolubilizing the dyes of Yellow 4, Yellow 5, and Yellow 203. Stuff. The pigments are white titanium oxide, sulfate of alkaline earth metal such as barium sulfate, carbonate of alkaline earth metal such as calcium carbonate, fine powder silicic acid, silica such as synthetic silicate, calcium silicate, alumina. , Alumina hydrate, zinc oxide, talc, and clay. The pigment dispersion composition according to any one of claims 1 and 2. The pigment dispersion composition according to any one of claims 1 to 7, wherein the content of the pigment dispersant is 10% by mass or more and 70% by mass or less with respect to the pigment. A curable composition comprising the pigment dispersion composition according to any one of claims 1 to 8. The curable composition according to claim 9, further comprising a polyfunctional polymerizable compound having a SI (Stimulation Index) value of 3 or less in a skin sensitization test. The curable composition according to any one of claims 9 to 10, which is for inkjet or for handwriting. A container for containing the curable composition according to any one of claims 9 to 11, wherein the curable composition is contained in the container. An accommodating portion for accommodating the curable composition according to any one of claims 9 to 11.
The imparting means for imparting the curable composition and
A curing means for curing the curable composition and
A two-dimensional or three-dimensional image forming apparatus characterized by having. The image forming apparatus according to claim 13, wherein the curing means is a UV-LED that irradiates ultraviolet rays having a peak at a wavelength of 365 nm or more and 405 nm or less. A two-dimensional or three-dimensional image forming method comprising a applying step of imparting the curable composition according to any one of claims 9 to 11 and a curing step of curing the composition. A cured product containing the cured product of the curable composition according to any one of claims 9 to 11. A decorative body characterized in that a surface decoration made of the cured product according to claim 16 is applied on a base material. The curable composition according to any one of claims 9 to 11, which is for artificial nails. A nail decoration material comprising the curable composition according to claim 18. An artificial nail characterized in that the curable composition according to claim 18 is cured.

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