JP2006241193A - Ink composition, method for inkjet-recording and printed material by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition excellent in the dispersing property of a fine pigment and stability of the same, capable of forming a high picture quality image having a clear color tone and a high color-attaching power, curing by the irradiation of an active radiation and suitable for an inkjet recording, a method for inkjet-recording by using the ink composition and printed materials obtained from the same. <P>SOLUTION: This ink composition contains (a) a polymerizable compound, (b) a pigment and (c) a graft polymer having a polymerization unit consisting of at least a monomer expressed by general formula (1) [wherein, R<SP>1</SP>is H or methyl; R<SP>2</SP>is a 1-8C alkylene; X is -OR<SP>3</SP>or -OCOR<SP>4</SP>(wherein, R<SP>3</SP>, R<SP>4</SP>are each H, an alkyl or an aryl); and (n) is 2-200]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an ink composition suitably used for inkjet recording, an inkjet recording method, and a printed matter using the same. Specifically, an ink composition suitable for inkjet recording, an inkjet recording method capable of forming a high-quality image by being excellent in colorant dispersibility, excellent color developability, cured by irradiation with actinic radiation, and The present invention relates to a printed matter using the same.

  As an image recording method for forming an image on a recording medium such as paper based on an image data signal, there are an electrophotographic method, a sublimation type and a melt type thermal transfer method, an ink jet method and the like. Among these, the ink jet method can be implemented with an inexpensive apparatus, and the ink can be efficiently used because the ink is ejected only on the required image portion to directly form the image on the recording medium. Running cost is low. Furthermore, there is little noise and it is excellent as an image recording method.

According to the inkjet system, printing is possible not only on plain paper but also on non-water-absorbing recording media such as plastic sheets and metal plates. However, high speed and high image quality are important issues for printing. The time required for drying and curing the droplets after printing has a property of greatly affecting the sharpness of the image.
As one of the ink jet methods, there is a recording method using an ink for ink jet recording that can be cured by irradiation with actinic radiation. According to this method, a sharp image can be formed by irradiating with radiation immediately after printing and curing the ink droplets.
Such a curable ink composition is required to have high pigment dispersibility and stability over time in order to form a high-definition image having excellent color developability. In order to impart a clear color tone and high coloring power to the ink composition, it is essential to make the pigment finer. In particular, in the ink used for inkjet recording, since the ejected ink droplets greatly affect the sharpness of the image, the amount of ejected droplets is small, and the thickness of the ink cured film formed from the ink is small. It is essential to use finer particles. As described above, when the pigment particles are further miniaturized in order to obtain a high coloring power, it becomes difficult to disperse the fine particles, and aggregates are easily generated. Moreover, the problem that the viscosity of a composition rises by addition of a dispersing agent also arises. The occurrence of pigment aggregates and the increase in viscosity of the ink composition both have an adverse effect on ink ejection properties, and are not preferred for use in ink compositions.

Further, when the ink composition is used for ink jet recording, the ink composition is stored in a cartridge, heated during ejection, and cooled during non-ejection and storage, and thus undergoes repeated heating-cooling temperature changes. This temperature change also has an adverse effect on the pigment dispersibility, and there is a problem that the dispersibility of the pigment decreases with time, and viscosity and aggregation are likely to occur.
Accordingly, there is a need for an ink composition that has sufficient fluidity, stably disperses a finely divided pigment, and is excellent in the temporal stability of pigment dispersion. Various proposals have been made on dispersants for obtaining stable pigment dispersions.

In order to improve the affinity with the pigment, a basic group as a dispersant for an ink composition using a pigment derivative as a dispersant (see, for example, Patent Document 1) or a specific pigment such as phthalocyanine or quinacridone. There is known an ink composition using a polymer having the following (for example, see Patent Document 2). These are dispersants selected in connection with specific pigments, and have a problem of lacking versatility.
In addition, an ink composition that does not use an organic solvent and contains a dispersant such as poly (ethyleneimine) -poly (12-hydroxystearic acid) graft polymer, which is a special polymer compound, and a specific monomer that dissolves the dispersant. A thing (for example, refer patent document 3) is proposed.
Although this ink composition has certainly improved the dispersion stability of the pigment than the conventional one due to the function of the dispersant, the fineness of the pigment used is insufficient, and the further fine pigment particles There was still room for improvement in the dispersibility improvement effect. Furthermore, there is a problem that the dispersion stability is still insufficient when the temperature change is repeated for a long period of time.
JP 2003-119414 A JP 2003-321628 A JP 2004-131589 A

The object of the present invention, which was made in consideration of the above problems, is excellent in the dispersibility and stability of fine pigments, can form high-quality images with clear color tone and high coloring power, An object of the present invention is to provide an ink composition suitable for ink jet recording that can be cured by irradiation, and an ink jet recording method using the ink composition.
Another object of the present invention is to provide a printed matter obtained by using an ink composition that can be cured by irradiation with actinic radiation and has a clear color tone and high coloring power.

As a result of intensive studies, the present inventors have obtained excellent pigment dispersibility by using a graft polymer containing a specific polymerizable oligomer as a polymer unit as a pigment dispersant, and can be stored for a long time, or The inventors have found that an ink composition excellent in pigment dispersion stability in which a decrease in dispersion stability is effectively suppressed even after repeated temperature changes has been obtained, and the present invention has been completed.
That is, the present invention is as follows.
<1> An ink composition comprising a polymerizable compound, (b) a pigment, and (c) a graft polymer having a polymer unit composed of at least a monomer represented by the following general formula (1).

[In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkylene group having 1 to 8 carbon atoms. X ¹ represents —OR ³ or —OCOR ⁴ . Here, R ³ and R ⁴ represent a hydrogen atom, an alkyl group, or an aryl group. n represents 2 to 200. ]
<2> The ink composition according to <1>, wherein the graft polymer further includes a copolymer unit composed of a monomer having a nitrogen atom-containing group and an ethylenically unsaturated double bond.
<3> The ink composition according to <2>, wherein the monomer having a nitrogen atom-containing group and an ethylenically unsaturated double bond is represented by the following general formula (2).

[In the general formula (2), R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents an alkylene group having 1 to 12 carbon atoms. X ² represents any one selected from —N (R ⁷ ) (R ⁸ ), —R ⁹ N (R ¹⁰ ) (R ¹¹ ), or a basic nitrogen-containing heterocyclic group. R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and R ⁹ is an alkylene group having 1 to 12 carbon atoms. Represents. p and q are each independently 1 or 0. ]
<4> The <1> to <3>, wherein the graft polymer further has a copolymer unit composed of a polymerizable oligomer (macromonomer) having an ethylenically unsaturated double bond at the terminal. The ink composition according to one item.
<5> The ink composition according to any one of <1> to <4>, wherein the ink composition further comprises (d) a photopolymerization initiator.
<6> The ink composition according to <5>, wherein the (a) polymerizable compound is a radical polymerizable compound, and the (d) photopolymerization initiator is a photo radical generator.
<7> The ink composition according to <5>, wherein (a) the polymerizable compound is a cationic polymerizable compound, and (d) the photopolymerization initiator is a photoacid generator.
<8> The ink composition according to any one of <1> to <7>, which is an ink composition for inkjet recording.

<9> An ink jet comprising: a step of printing the ink composition according to <8> on a recording medium using an ink jet printer; and a step of irradiating the printed ink composition with actinic radiation to cure the ink composition. Recording method.
<10> A printed matter obtained by printing the ink composition according to <8> on a recording medium with an ink jet printer and then irradiating with active radiation to cure the ink composition.

Although the action of the present invention is not clear, in the present invention, as a pigment dispersant, a graft polymer containing a monomer having a plurality of alkylene oxide groups linked as polymerized units as represented by the general formula (1) is used. When used, when the trunk portion of the graft polymer is adsorbed to fine pigment particles, the polymer of the highly polar branch (graft portion) is stretched away from the pigment fine particles due to its polar repulsion. This is considered to improve the dispersibility of the fine particles. This dispersibility improving effect is particularly remarkable when a highly polar polymerizable monomer is used as a dispersion medium, since these graft portions have high affinity with the dispersion medium. In addition to the fine particle dispersibility due to this polarity, the graft parts of the graft polymer adsorbed on the surface of the adjacent fine particles cause steric repulsion to effectively suppress the aggregation of the fine particles. Is presumed to be possible.
Furthermore, in a preferred embodiment of the present invention, in addition to the monomer represented by the general formula (1), a polymerizable oligomer (macromonomer) having an ethylenically unsaturated double bond at the terminal is included as a copolymer unit. Thus, a graft polymer having two kinds of grafts with different polarities is obtained, and it has an advantage that excellent fine particle dispersion stability can be obtained regardless of the polarity of the polymerizable monomer used as a dispersion medium.

The ink composition of the present invention can be used for normal printing to form sharp images with excellent color developability and obtain high-quality printed materials, and is also suitable for the production of resists, color filters, and optical disks. It is also useful as an optical modeling material.
Further, by applying the ink jet recording method, a high-quality image can be directly formed on a non-absorbable recording medium based on digital data. Therefore, the ink composition of the present invention is a large-area printed material. It is also suitably used for production.

According to the present invention, an ink jet recording which is excellent in dispersibility and stability of fine pigments, can form a high quality image having a clear color tone and high coloring power, and can be cured by irradiation with actinic radiation. An ink composition suitable for use and an ink jet recording method using the ink composition can be provided.
In addition, the printed matter of the present invention can be cured by irradiation with actinic radiation, and has an effect that a high-quality image obtained by using an ink composition having a clear color tone and high coloring power is formed. .

The ink composition of the present invention contains (a) a polymerizable compound, (b) a pigment, and (c) a graft polymer having a polymerization unit composed of at least a monomer represented by the following general formula (1). It is characterized by containing.
The ink composition of the present invention is (a) a composition which is cured by applying some energy depending on the function of the polymerizable compound, but preferably contains (d) a polymerization initiator and is cured by irradiation with actinic radiation. It is. Here, the actinic radiation is not particularly limited as long as it can impart energy capable of generating a starting species in the ink composition by the irradiation, and is broadly α-ray, γ-ray, X-ray, ultraviolet ray, Including visible light, electron beam, etc. Among them, ultraviolet rays and electron beams are preferable from the viewpoint of curing sensitivity and device availability, and ultraviolet rays are particularly preferable. Therefore, as the ink composition of the present invention, Ink compositions that can be cured by irradiating ultraviolet rays as the radiation are preferred.

Hereinafter, each component used in the ink composition of the present invention will be described in order.
[(C) Graft polymer having a polymer unit composed of at least a monomer represented by the following general formula (1)]
First, (c) a graft polymer having a polymer unit composed of at least a monomer represented by the following general formula (1) (hereinafter referred to as (c) a specific polymer as appropriate) is a characteristic component in the present invention. To do.

[In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkylene group having 1 to 8 carbon atoms. X ¹ represents —OR ³ or —OCOR ⁴ . Here, R ³ and R ⁴ represent a hydrogen atom, an alkyl group, or an aryl group. n represents 2 to 200. ]

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 1 to 8 carbon atoms, among which an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is more preferable. X ¹ represents —OR ³ or —OCOR ⁴ . Here, R ³ represents a phenyl group substituted with a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or an alkyl group having 1 to 18 carbon atoms. R ⁴ represents an alkyl group having 1 to 18 carbon atoms. Moreover, n represents 2-200, 5-100 are preferable and 10-100 are especially preferable.
Examples of the polymerizable monomer having an ether group represented by the general formula (1) include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, and polytetra Examples include methylene glycol monomethacrylate, and these may be commercially available products or may be appropriately synthesized.

  The polymerizable monomer represented by the general formula (1) according to the present invention is also available as a commercial product as described above, and as a commercial product, methoxypolyethylene glycol methacrylate (trade name: NK ester M-40G, M -90G, M-230G (above, manufactured by Toa Synthetic Chemical Industry Co., Ltd.); trade names: Blemmer PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (above, Japan) (Oil and Fat Co., Ltd.)), polyethylene glycol monomethacrylate (Brandmer PE-90, PE-200, PE-350, manufactured by NOF Corporation), polypropylene glycol monomethacrylate (Brander PP-500, PP-800, PP-1000, manufactured by NOF Corporation), polyethylene glycol polymer Propylene glycol monomethacrylate (trade name: Blemmer 70PEP-370B, manufactured by Nippon Oil & Fats Co., Ltd.), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name: Blemmer 55PET-800, manufactured by Nippon Oil & Fats Co., Ltd.), polypropylene glycol polytetra And methylene glycol monomethacrylate (trade name: BLEMMER NHK-5050, manufactured by NOF Corporation).

  The specific polymer (c) of the present invention is preferably a graft copolymer having a copolymer unit composed of a monomer having a nitrogen atom-containing group and an ethylenically unsaturated double bond. As such a monomer, the nitrogen atom-containing group is preferably basic, and a monomer represented by the following general formula (2) is particularly preferable.

[In the general formula (2), R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents an alkylene group having 1 to 12 carbon atoms. X ² represents any one selected from —N (R ⁷ ) (R ⁸ ), —R ⁹ N (R ¹⁰ ) (R ¹¹ ), or a basic nitrogen-containing heterocyclic group. R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and R ⁹ is an alkylene group having 1 to 12 carbon atoms. Represents. p and q are each independently 1 or 0. ]

R ⁶ in the general formula (2) represents an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 2 to 3 carbon atoms. X ² is any one selected from —N (R ⁷ ) (R ⁸ ), —R ⁹ —N (R ¹⁰ ) (R ¹¹ ), or a basic nitrogen-containing heterocyclic group.
Here, R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is particularly preferable. As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is particularly preferable. R ⁹ represents an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 2 to 3 carbon atoms.
Examples of basic nitrogen-containing heterocyclic groups include pyridyl groups (particularly 1-pyridyl group and 2-pyridyl group), piperidino groups (1-piperidino group), pyrrolidyl groups (particularly 2-pyrrolidyl group), pyrrolidino groups and imidazolino groups. Or a morpholino group (4-morpholino group) is preferred, and a pyridyl group and an imidazolino group are particularly preferred.

  Furthermore, the monomer represented by the general formula (2) is particularly preferably a compound represented by any one of the following general formulas (2-2) to (2-4).

[However, R ²¹ has the same meaning as R ⁵ in the general formula (2), R ²² has the same meaning as R ^6, and X ²² has the same meaning as X ^2. ]

[However, R ³¹ is synonymous with R ⁵ in the general formula (2), and X ²³ is synonymous with X ² {preferably X ²³ is —N (R ³³ ) (R ³⁴ ) (where R ³³ and R ³⁴ have the same meanings as R ⁷ and R ⁸ , respectively, or —R ³⁵ —N (R ³⁶ ) (R ³⁷ ) (where R ³⁵ , R ³⁶ and R ³⁷ are R ⁷ , R ⁸ and R ⁹ ). }]

[However, R ⁴¹ has the same meaning as R ⁵ in formula (2), and X ²⁴ represents a pyrrolidino group, a pyrrolidyl group, a pyridyl group, a piperidino group or a morpholino group. ]

  Preferred examples of the compound represented by the general formula (2) include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and 1- (N, N-dimethylamino). ) -1,1-dimethylmethyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, piperidinoethyl (meth) acrylate, 1-pyrrolidinoethyl (meth) ) Acrylate, N, N-methyl-2-pyrrolidylaminoethyl (Meth) acrylate and N, N-methylphenylaminoethyl (meth) acrylate (above (meth) acrylates); dimethyl (meth) acrylamide, diethyl (meth) acrylamide, diisopropyl (meth) acrylamide, di-n-butyl (meth) ) Acrylamide, di-i-butyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and N, N-methylphenyl (meth) acrylamide (above) (Meth) acrylamides); 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) Acrylic net , 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (Meth) acrylamide (above aminoalkyl (meth) acrylamides); and vinylpyridine.

The specific polymer (c) according to the present invention is particularly preferably a graft copolymer containing a copolymer unit composed of a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal.
Such a polymer having an ethylenically unsaturated double bond at the terminal is also called a macromonomer because it is a compound having a predetermined molecular weight. In a preferred embodiment of the present invention, since a graft polymer is prepared by using such a macromonomer together, the polarity is different from the graft caused by the monomer represented by the general formula (1), and a desired chain length is obtained. There is also an advantage that a graft polymer having (molecular weight) can be easily obtained.

The polymerizable oligomer optionally used in the present invention comprises a polymer chain part and a part of a polymerizable functional group having an ethylenically unsaturated double bond at its terminal. It is preferable from the viewpoint of obtaining a desired graft polymer that such a group having an ethylenically unsaturated double bond is present only at one end of the polymer chain.
Moreover, it is preferable that this macromonomer has the number average molecular weight (Mn) of polystyrene conversion in the range of 1000-10000, and the range of 2000-9000 is especially preferable.
The polymer chain portion is a homopolymer or copolymer selected from (meth) acrylate, styrene and derivatives thereof, and is particularly preferably a polymer of alkyl (meth) acrylate.

The group having an ethylenically unsaturated double bond is preferably a (meth) acryloyl group or a vinyl group, and particularly preferably a (meth) acryloyl group.
The polymerizable oligomer is preferably an oligomer represented by the following general formula (3).

[However, R ¹¹ and R ¹³ each independently represents a hydrogen atom or a methyl group, R ¹² represents an alkylene group having 1 to 12 carbon atoms (preferably an alkylene group having 2 to 8 carbon atoms, (For example, a hydroxyl group) and may be further linked via an ester bond, an ether bond, an amide bond, etc. Y is a phenyl group or a phenyl having an alkyl group having 1 to 4 carbon atoms. A group or —COOR ¹⁴ (wherein R ¹⁴ represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or an arylalkyl group having 7 to 10 carbon atoms), and q is 20 to 200. Y is preferably a phenyl group or —COOR ¹⁵ (wherein R ¹⁵ is an alkyl group having 1 to 4 carbon atoms).

  Preferable examples of the polymerizable oligomer (macromonomer) include a (meth) acryloyl group at one molecular end of polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and poly-i-butyl (meth) acrylate. Can be mentioned. As such polymerizable oligomers available on the market, one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toagosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer ( Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-terminal methacryloylated poly-n-butyl acrylate oligomer (Mn = 6000, trade name: AB-6, Toa Gosei Chemical Co., Ltd.) ) Made).

The graft polymer used in the present invention may contain other monomer as a copolymer unit in addition to the monomer represented by the general formula (1) and the polymerizable oligomer which is a preferred copolymerization component. Good.
The other monomer that can be used as the copolymerization component here is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an aromatic vinyl compound (eg, styrene, α-methylstyrene, vinyltoluene) , (Meth) acrylic acid alkyl esters (eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and i-butyl (meth) acrylate)), (meth) acrylic acid alkyl aryl esters (eg, Benzyl (meth) acrylate), glycidyl (meth) acrylate, vinyl carboxylates (eg, vinyl acetate and vinyl propionate), vinyl cyanide (eg, (meth) acrylonitrile and α-chloroacrylonitrile), and aliphatic conjugates Dienes (eg, 1,3-butadiene and isop Ren), (meth) acrylic acid, and the like. Among these, unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid alkyl aryl ester, and carboxylic acid vinyl ester are preferable.
As content of this other monomer in the said graft polymer, 5-70 mass% is preferable, for example. When the content is less than 5% by mass, the physical properties of the coating film may not be controlled. When the content exceeds 70% by mass, the ability as a pigment dispersant may not be sufficiently exhibited.

  The specific polymer (c) of the present invention includes a copolymer comprising the monomer represented by the general formula (1), the alkyl (meth) acrylate macromonomer, and the monomer having a nitrogen-containing group, or these It is a copolymer comprising a polymerizable oligomer and a monomer, and a monomer having an ethylenically unsaturated double bond copolymerizable therewith. The copolymer preferably has a repeating unit derived from the monomer represented by the general formula (1) in a range of 10 to 90% by mass, particularly 20 to 80% by mass, based on all repeating units. Moreover, it is preferable to have a repeating unit derived from a monomer having a nitrogen-containing group, which is used in combination, in a range of 10 to 80% by weight, particularly 20 to 60% by weight, based on the total repeating units, It is preferable to have the repeating unit derived from the polymerizable oligomer of 10 to 80% by mass, particularly 20 to 60% by mass of the total repeating units.

  Furthermore, when using the other monomer copolymerizable with these, it is preferable to have the repeating unit derived from this monomer in the range of 5-70 mass% of all the repeating units. The weight average molecular weight (Mw) of the copolymer is preferably in the range of 1,000 to 200,000, and particularly preferably in the range of 2000 to 100,000. This weight average molecular weight is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).

(C) Although the example of the said graft copolymer used suitably for a specific polymer is shown below, this invention is not restrict | limited to these.
(1) N-vinylimidazole / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(2) N-vinylcarbazole / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(3) N-vinyltriazole / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(4) N-vinylimidazole / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polystyrene copolymer,
(5) N-vinylcarbazole / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polystyrene copolymer,
(6) N-vinylimidazole / polyethylene glycol mono (meth) acrylate / methyl (meth) acrylate / terminal methacryloylated polystyrene copolymer,
(7) N-vinylimidazole / polyethylene glycol mono (meth) acrylate / benzyl (meth) acrylate / terminal methacryloylated polystyrene copolymer,
(8) Vinylpyridine / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(9) N, N-dimethyl-2-piperidylethyl acrylate / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(10) 4-morpholinoethyl acrylate / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,

(11) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(12) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polystyrene copolymer,
(13) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / methyl (meth) acrylate-terminated methacryloylated polystyrene copolymer,
(14) A copolymer of a copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated methyl (meth) acrylate and 2-hydroxyethyl methacrylate,
(15) A copolymer of a copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate,
(16) a copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate;
(17) 3- (N, N-dimethylamino) propylacrylamide / polypropylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(18) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol polypropylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(19) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(20) 3- (N, N-dimethylamino) propylacrylamide / polypropylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(21) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate copolymer (22) Styrene / polyethylene glycol mono (meth) acrylate copolymer (23) t-octylacrylamide / polyethylene Glycol mono (meth) acrylate copolymer

  Such a graft polymer is obtained by radical polymerization of a monomer represented by the general formula (1), a methyl (meth) acrylate macromer used in combination as desired, a monomer having a nitrogen atom-containing group, and other monomers in a solvent. Can be obtained. At that time, a radical polymerization initiator is generally used, but in addition to the initiator, a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) may be added and synthesized.

In the ink composition of the present invention, only one type of (c) specific polymer may be added, or two or more types may be used in combination. The content of the specific polymer (c) in the ink composition is preferably 1 to 100% by mass and more preferably 5 to 50% by mass with respect to the added amount of the pigment.
In the ink composition of the present invention, a known pigment dispersant can be used in combination with (c) the specific polymer as long as the effect is not impaired. As this addition amount, it is preferable that it is 50 mass% or less of (c) specific polymer.

[(A) Polymerizable compound]
The curable ink composition of the present invention contains (a) a polymerizable compound. The polymerizable compound (a) used in the present invention is not particularly limited as long as it is a compound that causes a polymerization reaction and cures by applying some energy, and can be used regardless of the type of monomer, oligomer, or polymer. In particular, (d) various known polymerizable monomers known as photocationically polymerizable monomers and photoradically polymerizable monomers that cause a polymerization reaction by an initiation species generated from a photopolymerization initiator that is optionally added are preferable. .
One or more polymerizable compounds can be used in combination for the purpose of adjusting the reaction rate, ink physical properties, cured film physical properties, and the like. The polymerizable compound may be a monofunctional compound or a polyfunctional compound.

  Examples of the cationic polymerizable monomer used as the polymerizable compound (a) in the present invention include, for example, JP-A Nos. 6-9714, 2001-31892, 2001-40068, 2001-55507, 2001-310938, Examples thereof include epoxy compounds, vinyl ether compounds, oxetane compounds and the like described in each publication such as 2001-310937 and 2001-220526.

Examples of the epoxy compound include aromatic epoxides and alicyclic epoxides.
Examples of monofunctional epoxy compounds that can be used in the present invention include, for example, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3 -Vinylcyclohexene oxide etc. are mentioned.

Examples of polyfunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol. S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclo) Xylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6 '-Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate) , Epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether Glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8- Examples include diepoxyoctane and 1,2,5,6-diepoxycyclooctane.
Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.

  Examples of monofunctional vinyl ethers that can be used in the present invention include, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, Cyclohexylmethyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether Methoxypolyethylene Coal vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, Examples include chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxypolyethylene glycol vinyl ether, and the like.

Examples of polyfunctional vinyl ethers include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F. Divinyl ethers such as alkylene oxide divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol Hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide addition Examples thereof include polyfunctional vinyl ethers such as pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.
As the vinyl ether compound, a di- or trivinyl ether compound is preferable from the viewpoints of curability, adhesion to a recording medium, surface hardness of the formed image, and the like, and a divinyl ether compound is particularly preferable.

The oxetane compound in the present invention refers to a compound having an oxetane ring, and a known oxetane compound can be arbitrarily selected and used as described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217. .
The compound having an oxetane ring that can be used in the ink composition of the present invention is preferably a compound having 1 to 4 oxetane rings in the structure. By using such a compound, it becomes easy to maintain the viscosity of the ink composition in a good handling property range, and it is possible to obtain high adhesion of the cured ink to the recording medium. .

Examples of the monofunctional oxetane used in the present invention include, for example, 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methyl Benzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3- Ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl- 3-Oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl) 3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ) Ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2- Tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanyl) Til) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, Examples include pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, and the like.

  Examples of the polyfunctional oxetane include, for example, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) Bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1 , 3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl -3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3- Ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3 -Oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl- -Oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3 -Ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3 -Ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl) 3-oxetanylmethyl) ether, polyfunctional oxetane such as EO-modified bisphenol F (3- ethyl-3-oxetanylmethyl) ether.

The compound having such an oxetane ring is described in detail in the above-mentioned JP-A No. 2003-341217, paragraph numbers [0021] to [0084], and the compounds described herein can be suitably used in the present invention.
Among the oxetane compounds used in the present invention, it is preferable to use a compound having 1 to 2 oxetane rings from the viewpoint of the viscosity and tackiness of the ink composition.

  In the ink composition of the present invention, these polymerizable compounds may be used alone or in combination of two or more. From the viewpoint of effectively suppressing shrinkage during ink curing. It is preferable to use at least one oxetane compound in combination with at least one compound selected from an epoxy compound and a vinyl ether compound.

In the present invention, it is also preferable to use various known radically polymerizable monomers that cause a polymerization reaction by an initiating species generated from a photoradical initiator as the polymerizable compound (a).
Examples of the radical polymerizable monomer include (meth) acrylates, (meth) acrylamides, aromatic vinyls and the like. In the present specification, when referring to both or one of “acrylate” and “methacrylate”, when referring to both “(meth) acrylate” and “acryl” and / or “methacryl”, “(meth) acryl” And may be described respectively.

Examples of the (meth) acrylate used in the present invention include the following.
As monofunctional (meth) acrylate, hexyl group (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, Stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2- Ethihexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (meth) ) Acrylate, benzyl (meth) acrylate, butoxymethyl (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-tetrafluoroethyl (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, glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,

2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate , Dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) 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 monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacrylate Leuoxytyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meta ) Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified acrylate Tetrazole (meth) acrylate, EO-modified nonylphenol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, EO-modified 2-ethylhexyl (meth) acrylate.

  Specific 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, butylethylpropanediol (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate Bisphenol F polyethoxydi (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butylpropanediol di ( Examples include meth) acrylate, 1,9-nonanedi (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and tricyclodecane di (meth) acrylate.

Specific examples of trifunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, propionate dipentaerythritol tri (meth) acrylate, tri ((meta ) Acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate Rate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated glycerin triacrylate.
Specific examples of tetrafunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, ethoxylated penta Examples include erythritol tetra (meth) acrylate.
Specific examples of the pentafunctional (meth) acrylate include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.
Specific examples of hexafunctional (meth) acrylate include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, captolactone modified dipentaerythritol hexa (meth) acrylate Etc.

  Examples of (meth) acrylamides used in the present invention include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, Nn-butyl ( (Meth) acrylamide, Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, (meth) acryloylmorpholine.

  Specific examples of aromatic vinyls used in the present invention include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo. Styrene, vinyl benzoic acid methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3- Hexyl styrene, 4-hexyl styrene, 3-octyl styrene, 4-octyl styrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allyl styrene, isopropenyl styrene, butenyls Ren, octenyl styrene, 4-t-butoxycarbonyl styrene, 4-methoxystyrene, and a 4-t-butoxystyrene.

  Furthermore, as the radical polymerizable monomer in the present invention, vinyl esters [vinyl acetate, vinyl propionate, vinyl versatate, etc.], allyl esters [eg, allyl acetate], halogen-containing monomers [vinylidene chloride, vinyl chloride, etc.], Vinyl ether [methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy vinyl ether, 2-ethylhexyl vinyl ether, methoxyethyl vinyl ether, cyclohexyl vinyl ether, chloroethyl vinyl ether, etc.], vinyl cyanide [(meth) acrylonitrile, etc.], olefins [ethylene, propylene, etc. ] Etc. are mentioned.

Among these, as the radically polymerizable monomer in the present invention, (meth) acrylates and (meth) acrylamides are preferable from the viewpoint of curing speed, and tetrafunctional or higher (meth) acrylate is particularly preferable from the viewpoint of curing speed. Further, from the viewpoint of the viscosity of the ink composition, it is preferable to use the above polyfunctional (meth) acrylate together with monofunctional or bifunctional (meth) acrylate and (meth) acrylamide.
The content of the polymerizable compound (a) in the ink composition is suitably 50 to 95% by mass, preferably 60 to 92% by mass, more preferably 70 to 90% by mass, based on the total solid content of the composition. It is.

[(B) Pigment]
The ink composition of the present invention contains a pigment as an essential component. The ink composition of the present invention is such that a pigment having a fine particle diameter is uniformly and stably dispersed in the ink composition by the function of the specific polymer (c) that is preferably used as a pigment dispersant. As a result, a sharp image with excellent color developability can be formed.
There is no restriction | limiting in particular in the pigment which can be used here, According to a use, a well-known various pigment can be selected suitably and can be used. In addition, since a pigment is included as a colorant, an image obtained by the ink composition of the present invention is excellent in weather resistance.

The pigment preferably used in the present invention will be described.
The pigment is not particularly limited, and all commercially available organic pigments and inorganic pigments, and those obtained by dyeing resin particles with a dye can be used. Furthermore, commercially available surface-treated pigments can also be used as long as the effects of the present invention are not impaired.
Examples of these pigments include, for example, “Pigment Dictionary” (2000), edited by Seijiro Ito. Herbst, K.M. Hunger “Industrial Organic Pigments”, JP 2002-12607 A, JP 2002-188025 A, JP 2003-26978 A, and JP 2003-342503 A3.

  Specific examples of organic pigments and inorganic pigments that can be used in the present invention include C.I. I. Pigment Yellow 1 (Fast Yellow G etc.), C.I. I. A monoazo pigment such as C.I. Pigment Yellow 74; I. Pigment Yellow 12 (disaji yellow AAA, etc.), C.I. I. Disazo pigments such as C.I. Pigment Yellow 17; I. Non-benzidine type azo pigments such as CI Pigment Yellow 180; I. Azo lake pigments such as C.I. Pigment Yellow 100 (eg Tartrazine Yellow Lake); I. Condensed azo pigments such as CI Pigment Yellow 95 (Condensed Azo Yellow GR, etc.); I. Acidic dye lake pigments such as C.I. Pigment Yellow 115 (such as quinoline yellow lake); I. Basic dye lake pigments such as CI Pigment Yellow 18 (Thioflavin Lake, etc.), anthraquinone pigments such as Flavantron Yellow (Y-24), isoindolinone pigments such as Isoindolinone Yellow 3RLT (Y-110), and quinophthalone yellow Quinophthalone pigments such as (Y-138), isoindoline pigments such as isoindoline yellow (Y-139), C.I. I. Nitroso pigments such as C.I. Pigment Yellow 153 (nickel nitroso yellow, etc.); I. And metal complex salt azomethine pigments such as CI Pigment Yellow 117 (copper azomethine yellow, etc.).

  C. As a thing which exhibits red or magenta color, C.I. I. Monoazo pigments such as CI Pigment Red 3 (Toluidine Red, etc.); I. Disazo pigments such as C.I. Pigment Red 38 (Pyrazolone Red B, etc.); I. Pigment Red 53: 1 (Lake Red C, etc.) and C.I. I. Azo lake pigments such as C.I. Pigment Red 57: 1 (Brilliant Carmine 6B); I. Condensed azo pigments such as C.I. Pigment Red 144 (condensed azo red BR, etc.); I. Acidic dye lake pigments such as C.I. Pigment Red 174 (Phloxine B Lake, etc.); I. Basic dye lake pigments such as C.I. Pigment Red 81 (Rhodamine 6G ′ Lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Red 177 (eg, dianthraquinonyl red); I. Thioindigo pigments such as C.I. Pigment Red 88 (Thioindigo Bordeaux, etc.); I. Perinone pigments such as C.I. Pigment Red 194 (perinone red, etc.); I. Perylene pigments such as C.I. Pigment Red 149 (perylene scarlet, etc.); I. Pigment violet 19 (unsubstituted quinacridone), C.I. I. Quinacridone pigments such as CI Pigment Red 122 (quinacridone magenta, etc.); I. Isoindolinone pigments such as CI Pigment Red 180 (isoindolinone red 2BLT, etc.); I. And alizarin lake pigments such as CI Pigment Red 83 (Mada Lake, etc.).

  As a pigment exhibiting blue or cyan, C.I. I. Disazo pigments such as C.I. Pigment Blue 25 (Dianisidine Blue, etc.); I. Phthalocyanine pigments such as C.I. Pigment Blue 15 (phthalocyanine blue, etc.); I. Acidic dye lake pigments such as C.I. Pigment Blue 24 (Peacock Blue Lake, etc.); I. Basic dye lake pigments such as C.I. Pigment Blue 1 (Viclotia Pure Blue BO Lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Blue 60 (Indantron Blue, etc.); I. And alkali blue pigments such as CI Pigment Blue 18 (Alkali Blue V-5: 1).

As a pigment exhibiting green, C.I. I. Pigment green 7 (phthalocyanine green), C.I. I. Phthalocyanine pigments such as C.I. Pigment Green 36 (phthalocyanine green); I. And azo metal complex pigments such as CI Pigment Green 8 (Nitroso Green).
As a pigment exhibiting an orange color, C.I. I. An isoindoline pigment such as C.I. Pigment Orange 66 (isoindoline orange); I. And anthraquinone pigments such as CI Pigment Orange 51 (dichloropyrantron orange).

Examples of the black pigment include carbon black, titanium black, and aniline black.
Specific examples of the white pigment include basic lead carbonate (2PbCO ₃ Pb (OH) ₂ , so-called silver white), zinc oxide (ZnO, so-called zinc white), titanium oxide (TiO ₂ , so-called titanium white), Strontium titanate (SrTiO ₃ , so-called titanium strontium white) or the like can be used.

  Here, titanium oxide has a smaller specific gravity than other white pigments, a large refractive index, and is chemically and physically stable, so that it has a large hiding power and coloring power as a pigment. Excellent durability against other environments. Therefore, it is preferable to use titanium oxide as the white pigment. Of course, other white pigments (may be other than the listed white pigments) may be used as necessary.

For dispersion of the pigment, for example, a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint shaker, a kneader, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, or a wet jet mill is used. Can do.
When the pigment is dispersed, the specific pigment dispersant (c) is added.
Moreover, when adding a pigment, it is also possible to use a synergist according to various pigments as a dispersion aid if necessary. The dispersion aid is preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the pigment.

  As a dispersion medium for various components such as pigments in the ink composition, a solvent may be added, or the solvent (a) polymerizable compound which is a low molecular weight component may be used as a dispersion medium. The ink composition of the present invention is a radiation curable ink, and is preferably solvent-free in order to cure the ink after it is applied to a recording medium. This is because if the solvent remains in the cured ink image, the solvent resistance is deteriorated or a VOC (Volatile Organic Compound) problem of the remaining solvent occurs. From such a viewpoint, it is preferable to use a polymerizable compound (a) as the dispersion medium, and in particular, to select a polymerizable monomer having a low viscosity from the viewpoint of improving dispersibility and handling properties of the ink composition.

The average particle size of the pigment used here is preferably about 0.01 to 0.4 [mu] m, more preferably 0.02 to 0.2 [mu] m, because the finer the particle, the better the color developability. The selection of (b) pigment, (c) pigment dispersant, dispersion medium, dispersion conditions, and filtration conditions are set so that the maximum particle size is 0.3 to 10 μm, preferably 0.3 to 3 μm. By controlling the particle size, clogging of the head nozzle can be suppressed, and ink storage stability, ink transparency, and curing sensitivity can be maintained. In the present invention, since the specific polymer (c) excellent in dispersibility and stability is used as a dispersant, a uniform and stable dispersion can be obtained even when a fine particle pigment is used.
The particle size of the pigment in the ink composition can be measured by a known measurement method. Specifically, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, a laser diffraction / scattering method, and a dynamic light scattering method.
The pigment is preferably added in an amount of 1 to 20% by mass in terms of solid content in the ink composition, and more preferably 2 to 10% by mass.

In the ink composition of the present invention, various additives can be used in combination with the essential components according to the purpose. These optional components will be described.
[(D) Photopolymerization initiator]
The ink composition of the present invention preferably contains a photopolymerization initiator for radical polymerization or cationic polymerization.
The photopolymerization initiator in the present invention undergoes a chemical change through the action of light or the interaction with the electronically excited state of the sensitizing dye to generate at least one of radicals, acids, and bases. A compound.
The photopolymerization initiator is an actinic ray to be irradiated, for example, 400 to 200 nm ultraviolet ray, far ultraviolet ray, g ray, h ray, i ray, KrF excimer laser beam, ArF excimer laser beam, electron beam, X ray, molecular beam. Or what has a sensitivity to an ion beam etc. can be selected suitably, and can be used.

  Specific photopolymerization initiators known to those skilled in the art can be used without limitation, and specifically, for example, Bruce M. et al. Monroe et al., Chemical Review, 93, 435 (1993). R. S. By Davidson, Journal of Photochemistry and biologic A: Chemistry, 73.81 (1993). J. P. Faussier “Photoinitiated Polymerization—Theory and Applications”: Rapra Review vol. 9, Report, Rapra Technology (1998). M. Tsunooka et al. , Prog. Polym. Sci. , 21, 1 (1996). Many are described. There are many chemical amplification type photoresists and compounds used for photocationic polymerization described in (Organic Electronics Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), pages 187-192). Has been. Further, F.I. D. Saeva, Topics in Current Chemistry, 156, 59 (1990). G. G. Maslak, Topics in Current Chemistry, 168, 1 (1993). H., et al. B. Shuster et al, JACS, 112, 6329 (1990). , I. D. F. Eaton et al, JACS, 102, 3298 (1980). A group of compounds that undergo oxidative or reductive bond cleavage through interaction with the electronically excited state of a sensitizing dye as described in the above.

  Preferred photopolymerization initiators include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) hexaarylbiimidazole compounds, (e) ketoxime ester compounds, f) borate compounds, (g) azinium compounds, (h) metallocene compounds, (i) active ester compounds, (j) compounds having a carbon halogen bond, and the like.

  (A) As a preferable example of aromatic ketones, “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. FOUASSIER J.M. F. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in RABEK (1993), p77-117. More preferable examples of (a) aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, and α-substituted benzoin compounds described in JP-B-47-22326. Benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, JP-B-60-26403, Benzoin ethers described in JP-A-62-81345, JP-B-1-34242, US Pat. No. 4,318,791, α-aminobenzophenones described in European Patent 0284561A1, JP-A-2-21152 P-Di (dimethylaminobenzoyl) benzene JP-A-61-194062 discloses a thio-substituted aromatic ketone, JP-B-2-9597 discloses an acylphosphine sulfide, JP-B-2-9596 discloses an acylphosphine, JP-B-63-61950 describes Examples thereof include thioxanthones and coumarins described in JP-B-59-42864.

  (B) As aromatic onium salts, elements of Group V, VI and VII of the Periodic Table, specifically N, P, As, Sb, Bi, O, S, Se, Te, or I Aromatic onium salts are included. For example, iodonium salts described in European Patent No. 104143, US Pat. No. 4,837,124, Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-96514, European Patent Nos. 370693, 233567, and 297443 are disclosed. , 294442, 279210, and 422570, sulfonium salts described in U.S. Pat. Nos. 3,902,144, 4,933,377, 4760013, 4,734,444, and 2,833,827, Diazonium salts (such as benzenediazonium which may have a substituent), diazonium salt resins (formaldehyde resin of diazodiphenylamine, etc.), N-alkoxypyridinium salts, etc. (for example, US Pat. No. 4,743,528, Kaisho 63-1383 No. 5, JP-A-63-142345, JP-A-63-142346, and JP-B-46-42363, specifically 1-methoxy-4-phenylpyridinium tetra And the compounds described in JP-B Nos. 52-147277, 52-14278, and 52-14279 are preferably used. Generates radicals and acids as active species.

  (C) “Organic peroxide” includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include 3,3′4,4′-tetra- ( t-butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'- Peroxide esters such as tetra- (p-isopropylcumylperoxycarbonyl) benzophenone and di-t-butyldiperoxyisophthalate are preferred.

  (D) Examples of hexaarylbiimidazoles include lophine dimers described in JP-B-45-37377 and JP-B-44-86516, such as 2,2'-bis (o-chlorophenyl) -4,4 ', 5. , 5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2, 2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4', 5,5 ' -Tet Phenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole and the like.

  (E) As ketoxime esters, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxy Examples include imino-1-phenylpropan-1-one.

Examples of the (f) borate salt which is another example of the photopolymerization initiator in the present invention include U.S. Pat. Nos. 3,567,453 and 4,343,891, European Patents 109,772 and 109,773. The compounds described in No. are listed.
Examples of (g) azinium salt compounds which are other examples of photopolymerization initiators include JP-A Nos. 63-138345, 63-142345, 63-142346, and 63-63. No. 143537 and Japanese Patent Publication No. Sho 46-42363 can be mentioned.

Examples of (h) metallocene compounds which are other examples of photopolymerization initiators include JP 59-152396, JP 61-151197, JP 63-41484, and JP 2-249. And titanocene compounds described in JP-A-2-4705 and iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.
Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopenta And dienyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium.

  (I) Examples of active ester compounds include European Patent Nos. 0290750, 046083, 156153, 271851 and 0388343, U.S. Pat. Nos. 3,901,710 and 4,181,531. JP-A-60-198538 and JP-A-53-133022, nitrobenzester compounds, European Patents 0199672, 84515, 199672, 0441115, and 0101122. No. 4,618,564, U.S. Pat. No. 4,371,605 and U.S. Pat. No. 4,431,774, JP-A 64-18143, JP-A-2-245756, and JP-A-4-365048. Iminosulfonate compounds, Japanese Examined Patent Publication Nos. 62-6223, Sho 63 No. 14340, and compounds and the like described in the JP-A-59-174831.

  (J) Preferred examples of the compound having a carbon halogen bond include those described in Wakabayashi et al., Bull. Chem. Soc. Examples include compounds described in Japan, 42, 2924 (1969), compounds described in British Patent 1388492, compounds described in JP-A-53-133428, compounds described in German Patent 3333724, and the like. .

  F.F. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, and the like. A compound as described in German Patent No. 2641100, a compound described in German Patent No. 3333450, a compound group described in German Patent No. 3021590, or a compound group described in German Patent No. 3021599, etc. Can be mentioned.

  Preferable specific examples of the compounds represented by the above (a) to (j) include those shown below.

(D) A photoinitiator can be used individually by 1 type or in combination of 2 or more types.
The content of the (d) photopolymerization initiator in the ink composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably in terms of the total solid content of the ink composition. Is 1-7 mass%.

[Sensitizing dye]
In the present invention, a sensitizing dye may be added for the purpose of improving the sensitivity of the photopolymerization initiator. Examples of preferred sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
Polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, squalium) ), Coumarins (eg 7-diethylamino-4-methylcoumarin).

  More preferable examples of the sensitizing dye include compounds represented by the following general formulas (IX) to (XIII).

(In Formula (IX), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents a basic nucleus of the dye in combination with the adjacent A ¹ and the adjacent carbon atom. Represents a nonmetallic atomic group to be formed, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. W represents an oxygen atom or a sulfur atom.)
(In the formula (X), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ³ —, where L ³ represents —O— or —S—. W has the same meaning as that shown in formula (IX).)
(In the formula (XI), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.)

(In Formula (XII), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, wherein R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, substituted Or an unsubstituted aryl group, L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A ³ , A ^4, and adjacent carbon atoms; ⁶⁰ and R ⁶¹ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, or can be bonded to each other to form an aliphatic or aromatic ring.
(In the formula (XIII), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or —NR ⁶⁷ —. R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represents a hydrogen atom or a monovalent non-metallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ may be bonded to each other to form an aliphatic or aromatic ring. it can.)

  Preferred specific examples of the compounds represented by the general formulas (IX) to (XIII) include the exemplified compounds (A-1) to (A-20) shown below.

[Co-sensitizer]
Further, the ink composition of the present invention may contain a known compound having a function of further improving sensitivity or suppressing inhibition of polymerization by oxygen as a co-sensitizer.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

Other examples include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, and JP-A-56-75643. Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, and the like. .
Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Donors, sulfur compounds described in JP-A-6-308727 (eg, trithiane), phosphorus compounds described in JP-A-6-250387 (diethylphosphite, etc.), Si-- described in Japanese Patent Application No. 6-191605 H, Ge-H compound, etc. are mentioned.

In the ink composition of the present invention, in addition to the essential components (a) to (c) and the preferred optional component (d) and the sensitizing dye and co-sensitizer used together with the component (d), Various additives can be used in combination depending on the purpose. For example, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance of the obtained image and preventing discoloration. In addition, an antioxidant can be added to improve the stability of the ink composition.
The ink composition of the present invention further includes various organic and metal complex anti-fading agents, and conductive materials such as potassium thiocyanate, lithium nitrate, ammonium thiocyanate, and dimethylamine hydrochloride for the purpose of controlling ejection properties. In order to improve the adhesion to the volatile salts and the recording medium, a trace amount of organic solvent can be added.

Various polymer compounds can be added to the ink composition in order to adjust film properties. Examples of polymer compounds include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, vinyl resins, acrylic resins. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination.
In addition, nonionic surfactants, cationic surfactants, organic fluoro compounds, and the like can be added to adjust liquid properties. In addition, for example, leveling additives, matting agents, In order to improve the adhesion to the recording medium such as waxes for adjusting film physical properties, polyolefin, PET, etc., a tackifier that does not inhibit the polymerization can be contained.

  The ink composition of the present invention preferably has an ink viscosity of 5 to 30 mPa · s, more preferably 7 to 20 mPa · s at the temperature at the time of ejection in consideration of ejection properties, and is in the above range. It is preferable to adjust the composition ratio appropriately. The ink viscosity at 25 to 30 ° C. is 10 to 200 mPa · s, preferably 15 to 100 mPa · s. By setting the viscosity at room temperature high, even when a porous recording medium is used, ink penetration into the recording medium can be prevented, uncured monomer can be reduced, and odor can be reduced. Dot bleeding at the time of landing can be suppressed, and as a result, the image quality is improved. If the ink viscosity at 25 to 30 ° C. is less than 10 mPa · s, the effect of preventing bleeding is small, and conversely if it is greater than 200 mPa · s, there is a problem in the delivery of the ink liquid.

  The surface tension of the ink composition of the present invention is preferably 20 to 30 mN / m, more preferably 23 to 28 mN / m. When recording on various recording media such as polyolefin, PET, coated paper, and non-coated paper, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and the wettability is preferably 30 mN / m or less.

The ink composition of the present invention thus adjusted is suitably used as an ink for inkjet recording. The ink composition is printed on a recording medium by an inkjet printer, and then the printed ink composition is irradiated with radiation to be cured and recorded.
In the printed matter obtained with this ink, the image portion is cured by irradiation with radiation such as ultraviolet rays, and the strength of the image portion is excellent. Therefore, in addition to image formation with ink, for example, an ink receiving layer (image image of a lithographic printing plate) Part), and can be used for various purposes.

[Inkjet recording method and inkjet recording apparatus]
Next, an ink jet recording method and an ink jet recording apparatus that can be suitably employed in the present invention will be described below.

  In the ink jet recording method, it is preferable that the ink composition is heated to 40 to 80 ° C. to lower the viscosity of the ink composition to 7 to 30 mPa · s and then ejected. Stability can be achieved. In general, radiation curable ink compositions generally have a higher viscosity than aqueous inks, so that the viscosity fluctuation range due to temperature fluctuations during printing is large. This viscosity variation of the ink composition directly affects the droplet size and droplet ejection speed as it is, which causes image quality deterioration. Therefore, it is necessary to keep the ink composition temperature as constant as possible during printing. is there. The control range of the ink composition temperature is preferably set temperature ± 5 ° C., more preferably set temperature ± 2 ° C., and further preferably set temperature ± 1 ° C.

  One feature of the ink jet recording apparatus is that it includes a means for stabilizing the temperature of the ink composition, and the portion to be kept at a constant temperature is a piping system from an ink tank (an intermediate tank if there is an intermediate tank) to the nozzle ejection surface. All of the members are targeted.

  The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors in each piping portion and perform heating control according to the ink composition flow rate and the environmental temperature. Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air. In order to shorten the printer start-up time required for heating or to reduce the loss of thermal energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

By adding the photopolymerization initiator (d) to the ink composition of the present invention, an actinic radiation curable ink composition is obtained.
The irradiation conditions of actinic radiation in such an ink will be described. A basic irradiation method is disclosed in JP-A-60-132767. Specifically, a light source is provided on both sides of the head unit, and the head and the light source are scanned by a shuttle method. Irradiation is performed after a certain period of time after ink landing. Further, the curing is completed by another light source that is not driven. In WO99 / 54415, as an irradiation method, a method using an optical fiber or a method in which a collimated light source is applied to a mirror surface provided on the side surface of the head unit to irradiate the recording unit with UV light is disclosed. In the present invention, these irradiation methods can be used.

  In the present invention, the ink composition is heated to a constant temperature, and the time from landing to irradiation is desirably 0.01 to 0.5 seconds, preferably 0.01 to 0.3 seconds, and more preferably Preferably, radiation is applied after 0.01 to 0.15 seconds. Thus, by controlling the time from landing to irradiation to an extremely short time, it is possible to prevent the landing ink from bleeding before being cured. Also, since the ink composition can be exposed to a porous recording medium before it penetrates deeper than the light source reaches, unreacted monomer remains, and as a result, odor can be reduced. Can do. By using the inkjet recording method described above and the ink composition of the present invention in combination, a great synergistic effect is brought about. In particular, when an ink composition having an ink viscosity of 10 to 200 mPa · s at 25 ° C. is used, a great effect can be obtained. By adopting such a recording method, the dot diameter of the landed ink can be kept constant even on various recording media having different surface wettability, and the image quality is improved. In addition, in order to obtain a color image, it is preferable to superimpose in order from the color with the lowest brightness. When inks with low lightness are stacked, it is difficult for the irradiation line to reach the lower ink, and the curing sensitivity is hindered, the residual monomer is increased, odor is generated, and the adhesion is liable to occur. Irradiation can be performed by injecting all colors and exposing them together, but exposure for each color is preferable from the viewpoint of curing acceleration.

There is no restriction | limiting in particular as an inkjet recording device used for this invention, A commercially available inkjet recording device can be used. That is, in the present invention, recording can be performed on a recording medium using a commercially available inkjet recording apparatus.
According to the preferable ejection conditions, the ink composition of the present invention repeats heating and cooling. However, depending on the function of the specific polymer (c) that is suitably used as a pigment dispersant, such temperature conditions are satisfied. Even when stored below, the pigment dispersibility is suppressed from being lowered, and excellent color developability can be obtained over a long period of time. In addition, there is an advantage that a drop in discharge property due to aggregation of the pigment is also suppressed.

[Recording medium]
The recording medium to which the ink composition of the present invention can be applied is not particularly limited, and various non-absorbing resin materials used for ordinary non-coated paper, coated paper, and so on, so-called soft packaging, or the like. A resin film formed into a film can be used, and examples of the various plastic films include PET film, OPS film, OPP film, ONy film, PVC film, PE film, and TAC film. In addition, examples of the plastic that can be used as a recording medium material include polycarbonate, acrylic resin, ABS, polyacetal, PVA, and rubbers. Metals and glasses can also be used as the recording medium.

  The printed matter of the present invention can be obtained by printing the ink composition of the present invention on a recording medium using an ink jet printer, and then preferably irradiating the cured ink composition with actinic radiation and curing. The printed matter of the present invention has a high-quality image with excellent color developability and sharpness because the ink used for image formation contains fine pigment particles uniformly and stably dispersed, and the weather resistance of the image Therefore, it can be applied to a wide range of fields.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the embodiments in these examples.
[Example 1]
[(C) Synthesis of specific polymer]
(Synthesis Example 1)
15 parts by mass of 1-methoxy-2-propylacetate was introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), and heated while flowing nitrogen into the flask at 78 ° C. The temperature rises to Separately, the following monomer solution and initiator solution were added dropwise simultaneously over 2 hours. After the addition, 0.08 part by mass of V-65 was further added, and the mixture was heated and stirred at 78 ° C. for 3 hours. The obtained reaction solution was poured into 1000 parts of hexane while stirring, and the resulting precipitate was heated and dried to obtain graft polymer 1.

(Monomer solution)
・ Dimethylaminoethyl acrylate 4.1 mass parts ・ Methoxypolyethylene glycol methacrylate (NK ester M-230G, manufactured by Toagosei Co., Ltd.) 25.9 mass parts ・ 1-methoxy-2-propyl acetate 45 mass parts (initiator solution) )
・ 2,2-Azobis (2,4-dimethylvaleronitrile)
(Wako Pure Chemical Industries, Ltd. V-65) 0.04 parts by mass-1-methoxy-2-propyl acetate 9.6 parts by mass

(Synthesis Example 2)
A graft polymer 2 was obtained in the same manner as in Synthesis Example 1 except that the (monomer solution) in Synthesis Example 1 was changed to the following composition.
(Monomer solution)
3- (N, N-dimethylaminopropylacrylamide) 4.5 parts by mass Polymethyl methacrylate having a methacryloyl group at the terminal (number average molecular weight 6000, AA-6 manufactured by Toagosei Co., Ltd.) 19.5 parts by mass Methoxypolyethylene glycol methacrylate (NK ester M-230G manufactured by Shin-Nakamura Chemical Co., Ltd.) 6.0 parts by mass 1-methoxy-2-propyl acetate 45 parts by mass

(Synthesis Example 3)
A graft polymer 3 was obtained in the same manner as in Synthesis Example 1 except that 4.1 parts by mass of dimethylaminoethyl acrylate in Synthesis Example 1 was changed to 4.1 parts by mass of N-vinylimidazole.
(Synthesis Example 4)
A graft polymer 4 was obtained in the same manner as in Synthesis Example 1 except that 4.1 parts by mass of dimethylaminoethyl acrylate in Synthesis Example 1 was changed to 4.1 parts by mass of t-octylacrylamide.

[Example 1]
(C) A specific polymer shown below is dissolved in (a) a polymerizable compound, (b) is put together with a pigment into a motor mill M50 (manufactured by Eiger), and zirconia beads having a diameter of 0.65 mm are used. / S was performed for 6 hours to obtain an active energy ray-curable ink stock solution. Next, (d) a photopolymerization initiator was added to the ink stock solution and mixed gently, and then pressure filtered with a membrane filter to obtain an active energy ray-curable inkjet ink of Example 1.

(B) Pigment [phthalocyanine pigment PB15: 3] 5.0 parts (c) Specific polymer [graft polymer 1 obtained in Synthesis Example 1] 2.5 parts (a) Polymerizable compound [hexanediol Diacrylate]
(HDDA: Daicel UCB Co., Ltd.) 60.0 parts (a) Polymerizable compound [captolactone-modified dipentaerythritol hexaacrylate, DPCA-60: Nippon Kayaku Co., Ltd.) 27.5 parts (d ) Photopolymerization initiator [acylphosphine oxide compound]
(Lucirin TPO-L: manufactured by BASF) 5.0 parts

[Examples 2 to 4]
The same procedure as in Example 1 was conducted except that (c) the graft polymer 1 as the specific polymer used in Example 1 was changed to the graft polymers 2 to 4 obtained in Synthesis Examples 2 to 4, respectively. 2 to 4 active energy ray-curable inkjet inks were obtained.

[Comparative Example 1]
The same procedure as in Example 1 was performed except that “SORPERSE 24000GR” (manufactured by Avecia), which is a commercially available pigment dispersant, was used in place of the graft polymer 1 which is the specific polymer (c) used in Example 1. The active energy ray-curable inkjet ink of Comparative Example 1 was obtained.
[Comparative Example 2]
A comparative example was carried out in the same manner as in Example 1 except that (c) graft polymer 1 as a specific polymer used in Example 1 was replaced with Avecia's “SORPERSE 32000” as a commercially available pigment dispersant. 2 active energy ray-curable inkjet ink was obtained.

[Examples 5-8, Comparative Examples 3-4]
Inkjet inks of Examples 5 to 8 and Comparative Examples 3 to 4 were the same except that (B) Pigment PB15: 3 used in Examples 1 to 4 and Comparative Examples 1 and 2 was changed to PY-120. A composition was obtained.

[Examples 9 to 12, Comparative Examples 5 to 6]
Inks of Examples 9 to 12 and Comparative Examples 5 to 6 were the same except that (a) the polymerizable compound and (d) the photopolymerization initiator were changed to the following in Examples 1 to 4 and Comparative Examples 1 and 2. Ink was obtained.

(A) Polymerizable compound: Oxetane compound
(OXT-221: manufactured by Toa Gosei Co., Ltd.) 70.0 parts (a) Polymerizable compound: Epoxy compound
(Celoxide 3000: manufactured by Daicel Chemical Industries, Ltd.) 17.5 parts (d) Photopolymerization initiator: triphenylsulfonium salt
(Adekaoptomer SP-150, manufactured by Asahi Denka) 5.0 parts

[Examples 13 to 16, Comparative Examples 7 to 8]
Inkjet inks of Examples 13 to 16 and Comparative Examples 7 to 8 were obtained in the same manner as in Examples 7 to 9 and Comparative Examples 5 to 6 except that the pigment PB15: 3 was changed to the quinacridone pigment PR122.

[Evaluation of ink composition]
The obtained inkjet ink was evaluated according to the following method. The results are shown in Table 1.
(1. Viscosity)
The viscosity of each inkjet ink at 25 ° C. was measured using an E-type viscometer.
A: Less than 30 mPas B: 30 mPas or more, less than 100 mPas C: 100 mPas or more (a level causing a discharge problem)
(2. Stability)
After each ink-jet ink was stored at 25 ° C. for 1 month and stored at 70 ° C. for 24 hours, the dispersion state was evaluated by visual observation and change in viscosity.
◎: Precipitation does not occur and viscosity does not increase ○: Precipitation does not occur and viscosity increases slightly, but there is no problem with ejection performance △: Precipitation does not occur, but ejection performance decreases due to increase in viscosity However, it is a practically problematic level ×: the occurrence of precipitates is observed

(3. Average particle diameter)
For each inkjet ink, the light scattering diffraction type particle size distribution measuring device (LA910, (Ltd.) Horiba) a volume-based average particle diameter D ₅₀ was used to measured and evaluated.
A: D ₅₀ is less than 100 nm B: D ₅₀ is 100 nm or more, less than 200 nm C: D ₅₀ is 200 nm or more

(4. Curability)
The obtained ink composition was printed on art paper with an ink jet printer (printing density 300 dpi, droplet ejection frequency 4 kHz, nozzle number 64), and then an energy of 100 mJ / cm ^{2 with} a Deep UV lamp (US-7, SP-7). The sample was exposed under the following conditions to obtain a print sample.
The cured film was touched with a finger, and the presence or absence of stickiness was evaluated according to the following criteria.
A: No stickiness B: Slight stickiness C: Extremely sticky (5. Heat cycle property)
The obtained ink composition was subjected to a temperature increase / decrease cycle of 25 ° C. to 60 ° C. 10 times, then printed with the ink jet printer, observed for the absence of nozzles, and evaluated according to the following criteria.
○: High quality image formed with no missing nozzles Δ: Some satellites were observed and image defects were observed x: Nozzle missing occurred and image defects were significant

From Table 1, the ink composition of the present invention can be cured with high sensitivity to radiation irradiation, can form a high-quality image without stickiness, and is subjected to long-term storage and repeated temperature changes. In the case of storage at 1, the viscosity did not increase due to a decrease in the dispersibility of the pigment, and both the dispersibility and the dispersion stability of the pigment were good.
On the other hand, in the comparative example using a commercially available polymer dispersant, the initial pigment dispersibility is good, but in particular, storage under a high temperature condition and heat cycle property due to repeated heating are inferior, which causes a practical problem. It was a level.

Claims (10)

An ink composition comprising (a) a polymerizable compound, (b) a pigment, and (c) a graft polymer having a polymer unit composed of at least a monomer represented by the following general formula (1).

[In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkylene group having 1 to 8 carbon atoms. X ¹ represents —OR ³ or —OCOR ⁴ . Here, R ³ and R ⁴ represent a hydrogen atom, an alkyl group, or an aryl group. n represents 2 to 200. ]   The ink composition according to claim 1, wherein the graft polymer further includes a copolymer unit composed of a monomer having a nitrogen atom-containing group and an ethylenically unsaturated double bond. The ink composition according to claim 2, wherein the monomer having a nitrogen atom-containing group and an ethylenically unsaturated double bond is represented by the following general formula (2).

[In the general formula (2), R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents an alkylene group having 1 to 12 carbon atoms. X ² represents any one selected from —N (R ⁷ ) (R ⁸ ), —R ⁹ N (R ¹⁰ ) (R ¹¹ ), or a basic nitrogen-containing heterocyclic group. R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and R ⁹ is an alkylene group having 1 to 12 carbon atoms. Represents. p and q are each independently 1 or 0. ]   4. The graft polymer according to any one of claims 1 to 3, wherein the graft polymer further has a copolymer unit composed of a polymerizable oligomer (macromonomer) having an ethylenically unsaturated double bond at a terminal. The ink composition as described.   The ink composition according to any one of claims 1 to 4, wherein the ink composition further comprises (d) a photopolymerization initiator.   The ink composition according to claim 5, wherein the (a) polymerizable compound is a radical polymerizable compound, and the (d) photopolymerization initiator is a photo radical generator.   The ink composition according to claim 5, wherein the (a) polymerizable compound is a cationic polymerizable compound, and the (d) photopolymerization initiator is a photoacid generator.   The ink composition according to any one of claims 1 to 7, wherein the ink composition is an ink composition for inkjet recording.   An ink jet recording method comprising: a step of printing the ink composition according to claim 8 on a recording medium using an ink jet printer; and a step of irradiating the printed ink composition with an active radiation to cure the ink composition.   A printed matter obtained by printing the ink composition according to claim 8 on a recording medium using an ink jet printer, and then irradiating with active radiation to cure the ink composition.