JP4581401B2 - Actinic ray curable inkjet ink composition, actinic ray curable inkjet ink set, image forming method and inkjet recording apparatus using the same - Google Patents

Description

  The present invention relates to an actinic ray curable inkjet ink composition, an actinic ray curable inkjet ink set that can stably record high-definition images, an image forming method using the same, and an inkjet recording apparatus.

  In recent years, the ink jet recording method can easily and inexpensively create an image, and thus has been applied to various printing fields such as photographs, various printing, marking, and special printing such as a color filter. In particular, inkjet recording devices that emit and control fine dots, inkjet inks with improved color reproduction range, durability, and emission suitability, and ink-jet ink absorbability, coloring material color development, surface gloss, etc. are dramatically improved. It is also possible to obtain image quality comparable to silver halide photography using special paper that has been selected. The image quality improvement of today's ink jet recording system is mainly achieved only when all of the ink jet recording apparatus, ink jet ink, and special paper are available.

  However, in an inkjet system that requires dedicated paper, the recording medium is limited, and the cost of the recording medium increases. Therefore, many attempts have been made to record on a transfer medium different from dedicated paper by an ink jet method. Specifically, a phase change ink jet method using a wax ink solid at room temperature, a solvent ink jet method using an ink mainly composed of a fast-drying organic solvent, or actinic rays such as ultraviolet rays (UV light) after recording. And actinic ray curable ink jet method for crosslinking.

  Among them, the actinic ray curable inkjet method has a relatively low odor compared to the solvent-based inkjet method. For example, ultraviolet curable inkjet inks are disclosed in JP-A-6-200204, JP-T 2000-504778, and the like. Has been.

  However, even if these actinic ray curable ink-jet inks are used, the dot diameter after landing greatly changes depending on the type of recording material and the working environment, and high-definition images can be obtained for various recording materials. It is impossible to form.

  In recent years, many ultraviolet curable inkjet inks using cationically polymerizable compounds have been proposed. These ultraviolet curable ink-jet inks do not receive an oxygen inhibition effect, but have a problem that they are easily affected by moisture (humidity) at a molecular level. In addition, generation of wrinkles due to curing shrinkage becomes a problem depending on the curing environment.

  Image formation by the ultraviolet curable ink jet method is characterized in that a high-quality image can be obtained at low cost, and that an image can be formed on a recording material that does not absorb ink. However, there is a problem peculiar to this ultraviolet curable ink jet system. For example, in the case of forming an image on a recording material that does not absorb ink, image deterioration due to mixing of landed dots with adjacent dots is remarkable. In particular, when high-definition image formation is required, dot mixing between landed colors becomes a serious problem. In response to the above problems, actinic ray curable inkjet inks using oxirane compounds, vinyl ether compounds, and oxetane compounds as photopolymerizable compounds have been disclosed (see, for example, Patent Documents 1 and 2). In addition, actinic ray curable inkjet inks using alicyclic epoxy compounds and oxetane compounds as photopolymerizable compounds have been disclosed (for example, see Patent Documents 3 and 4). However, in each of the proposed methods, the current situation is that dot bleeding is not sufficiently solved.

In the case of a general water-based ink jet method, this problem has been solved by improving the ink permeability to the recording material by using additives having various functions in dedicated paper and ink. However, there is still no solution for forming an image on a recording material having no ink absorbability. In the case of high-speed printing, the formed image is often wound, and in particular, development of an actinic ray curable inkjet ink composition having a rapid curing characteristic of the formed image is desired.
JP 2001-220526 A (Claims, Examples) JP 2002-188025 A (claims, examples) JP-A-2002-317139 (Claims, Examples) JP 2003-55449 A (claims, examples)

  The present invention has been made in view of the above problems, and an object thereof is an actinic ray curable inkjet ink composition that is excellent in curability, does not cause color mixing, and can stably record high-definition images. Object, actinic ray curable ink jet set, and image forming method and ink jet recording apparatus using the same.

  The above object of the present invention is achieved by the following configurations.

( 1 )
In the actinic ray curable inkjet ink composition containing at least a photopolymerizable compound and a coloring material, at least one of the photopolymerizable compounds is α-pinene oxide, and an epoxy group of the α-pinene oxide An actinic radiation curable inkjet ink composition comprising 0.1 to 10% by mass of a compound having a diol structure obtained by ring-opening with respect to the total mass of the actinic radiation curable inkjet ink composition.
(2)
In the actinic ray curable inkjet ink composition containing at least a photopolymerizable compound and a coloring material, at least one of the photopolymerizable compounds is 1,2: 8,9 diepoxy limonene, and the 1, The compound having a diol structure obtained by ring opening of the epoxy group of 2: 8,9 diepoxy limonene is contained in an amount of 0.1 to 10% by mass with respect to the total mass of the actinic ray curable inkjet ink composition. An actinic ray curable inkjet ink composition.
(3)
3. The actinic ray curable inkjet ink composition according to 1 or 2, further comprising a compound having an oxetane ring as the photopolymerizable compound.
(4)
The actinic ray curable inkjet ink composition according to any one of 1 to 3, wherein the colorant is a pigment.
(5)
The actinic ray curable inkjet ink composition according to any one of 1 to 4, wherein the colorant is an oil-soluble dye.
(6)
The actinic ray curable inkjet ink composition according to any one of 1 to 5, wherein the ink viscosity at 25 ° C. is 7 to 50 mPa · s.
(7)
An actinic ray comprising at least a yellow actinic ray curable inkjet ink composition, a magenta actinic ray curable inkjet ink composition, a cyan actinic ray curable inkjet ink composition, and a black actinic ray curable inkjet ink composition In the curable inkjet ink set, the actinic ray curable inkjet ink composition according to any one of 4 to 6, wherein all of the actinic ray curable inkjet ink composition is the actinic ray curable inkjet ink composition according to any one of 4 to 6. Ink set.
(8)
An actinic ray curable inkjet ink composition according to any one of 1 to 6 is jetted onto a recording material from an inkjet recording head, and printing is performed on the recording material, the actinic ray curing method An image forming method comprising irradiating actinic rays for 0.001 to 1 second after the ink jet ink composition is landed on the recording material.
(9)
An actinic ray curable inkjet ink composition according to any one of 1 to 6 is jetted onto a recording material from an inkjet recording head, and printing is performed on the recording material, the actinic ray curing method An image forming method, wherein the total thickness of the ink jet ink composition after landing on the recording material and curing by irradiation with actinic rays is 2 to 25 μm.
(10)
An image forming method in which the actinic ray curable inkjet ink composition according to any one of 1 to 6 is jetted onto a recording material from an inkjet recording head, and printing is performed on the recording material, the inkjet recording head An image forming method, wherein the amount of droplets of the actinic radiation curable inkjet ink composition discharged from each nozzle is 2 to 20 pl.
(11)
An image forming method in which the actinic ray curable inkjet ink composition according to any one of 1 to 6 is jetted onto a recording material from an inkjet recording head, and printing is performed on the recording material, the inkjet recording head Is a line head type ink jet recording head.
(12)
An image forming method for jetting an actinic ray curable ink jet ink set described in 7 on a recording material from an ink jet recording head and performing printing on the recording material, comprising the actinic ray curable ink jet ink set An image forming method comprising irradiating actinic rays for 0.001 to 1 second after the light-curable ink-jet ink composition has landed on the recording material.
(13)
An image forming method for jetting an actinic ray curable ink jet ink set described in 7 on a recording material from an ink jet recording head and performing printing on the recording material, comprising the actinic ray curable ink jet ink set An image forming method, wherein the light curable inkjet ink composition lands on the recording material and is cured by irradiation with actinic rays to have a total film thickness of 2 to 25 μm.
(14)
8. An image forming method in which an actinic ray curable ink jet ink set described in 7 is jetted onto a recording material from an ink jet recording head, and printing is performed on the recording material, wherein the activity ejected from each nozzle of the ink jet recording head An image forming method, wherein the amount of droplets of the actinic radiation curable inkjet ink composition constituting the light curable inkjet ink set is 2 to 20 pl.
(15)
An image forming method in which an actinic ray curable ink jet ink set according to 7 is used from an ink jet recording head to be ejected onto a recording material and printing is performed on the recording material. An image forming method comprising a recording head.
(16)
It is an inkjet recording apparatus used for the image forming method of any one of 8-11, Comprising: It discharges, after heating actinic-light curable inkjet ink composition and an inkjet recording head to 35 to 100 degreeC. An ink jet recording apparatus.
(17)
An inkjet recording apparatus used in the image forming method according to any one of 12 to 15, wherein the actinic ray curable inkjet ink set and the inkjet recording head are heated to 35 ° C to 100 ° C and then discharged. An inkjet recording apparatus.
In addition, the following actinic ray curable inkjet ink composition is also useful because it exhibits the same effect. That is, in the actinic ray curable inkjet ink composition containing at least a photopolymerizable compound and a color material, at least one of the photopolymerizable compounds has an alicyclic epoxy group represented by the following general formula (1). And 0.1 to 10% by mass of a compound having a diol structure represented by the following general formula (2) with respect to the total mass of the actinic ray curable inkjet ink composition. An actinic ray curable inkjet ink composition.

[Wherein Y _{1 to} Y ₈ each represent a hydrogen atom, an unsubstituted or substituted alkyl group, a carbonyl group or an ether group, which may be different from each other. ]

[Wherein, Z _{1 to} Z ₈ each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, a carbonyl group or an ether group. ]

  According to the present invention, there is provided an actinic ray curable inkjet ink composition, an actinic ray curable inkjet ink set, which has excellent curability, does not cause color mixing, and can stably record high-definition images, and the It is possible to provide an image forming method and an ink jet recording apparatus using the above.

  Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

As a result of intensive investigations in view of the above problems, the present inventors have at least a photopolymerizable compound and an actinic ray curable inkjet ink composition containing a coloring material ,
1 ) An actinic ray curable inkjet ink composition comprising a compound having a diol structure obtained by ring-opening of an epoxy group of α-pinene oxide, wherein at least one photopolymerizable compound is α-pinene oxide. Actinic ray curable inkjet ink composition containing 0.1 to 10% by mass relative to the total mass of
2 ) At least one photopolymerizable compound is 1,2: 8,9 diepoxy limonene and has a diol structure obtained by ring opening of the epoxy group of the 1,2: 8,9 diepoxy limonene. An actinic ray curable inkjet ink composition containing 0.1 to 10% by mass of the compound having 0.1 to 10% by mass relative to the total mass of the actinic ray curable inkjet ink composition,
Thus, it is found that an actinic ray curable inkjet ink composition capable of high-speed curing with easy handling, no color mixing, and capable of stably recording high-definition images can be realized. It is up to the invention.

The compound having an epoxy group represented by the general formula (1) will be described.

In the general formula (1), Y _{1 to} Y ₈ may each be a hydrogen atom, an unsubstituted or substituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, t-butyl group, hexyl group, 2-ethylhexyl group, benzyl group, etc.), unsubstituted or substituted carbonyl group (eg, acetyl group, benzoyl group, etc.), or ether group (eg, alkyl ether group, aryl ether) Group).

  Specific examples of the compound having an epoxy group represented by the general formula (1) are shown below, but the present invention is not limited thereto.

  The addition amount of the compound having an epoxy group represented by the general formula (1) is preferably 10 to 80% by mass with respect to the total mass of the ink composition of the present invention. When the content is less than 10% by mass, the curability is remarkably lowered due to the curing environment (for example, temperature, humidity, etc.) and cannot be used. On the other hand, if the content exceeds 80% by mass, the physical properties of the film after curing become fragile and not suitable for practical use.

In the present invention, one kind of alicyclic epoxy compound represented by the above following general formula (1) may be used alone or may be used in combination of two or more kinds thereof. These epoxy compounds may be produced by any method. For example, Maruzen KK Publishing Co., Ltd., Fourth Edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. by Alfred Hasfner, The Chemistry of Heterocyclic compounds, Vol. 30, Y, Min. No. 5, 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Laid-Open No. 11-100308, Japanese Patent No. 2906275, Japanese Patent No. 2926262 and the like.

Next, a description will be given compounds containing diol structure represented above following general formula (2).

In the general formula (2), Z _{1 to} Z ₈ may be different from each other, a hydrogen atom, an unsubstituted or substituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, t-butyl group, hexyl group, 2-ethylhexyl group, benzyl group, etc.), unsubstituted or substituted carbonyl group (eg, acetyl group, benzoyl group, etc.), or ether group (eg, alkyl ether group, aryl ether) Group).

Amount represented by the diol compounds by the general formula (2) based on the total weight of i ink composition is one that is characterized by containing 0.1 to 10 mass%, preferably 0.5 ˜5 mass%. If it exceeds 10% by mass, the curing rate decreases. On the other hand, if it is less than 0.1% by mass, the desired effect due to the addition of the diol compound cannot be obtained.

Incidentally, the diol compound represented by the general formula in Lee ink composition (2) is a present inventors presume functions as a chain transfer agent during the curing reaction. Therefore, the active site that has stopped functioning at the polymerization terminal is regenerated by the addition, but if it is added more than necessary, the molecular weight of the polymer obtained will be small, and it will have the same characteristics as being substantially uncured. The necessary addition amount is naturally determined.

Diol compound represented by the general formula (2) is obtained by a conventional known synthetic methods, by hydrolysis before Symbol acid compound having an alicyclic epoxy group represented by the general formula (1) ( Those obtained by ring opening) are preferred. It is expected that a similar effect can be obtained if the diol is used, but if the diol is obtained from the alicyclic epoxy group represented by the general formula (1), the general formula may be used in the ink composition. The compatibility with the alicyclic epoxy compound represented by (1) becomes good and sufficient curability can be obtained, the adverse effects of addition due to phase separation and the like are suppressed, and the stability of the ink composition is improved.

Hereinafter, specific examples of the compound having a diol group represented by a general formula (2), the present invention is not limited thereto.

  Further, in the ink composition of the present invention, α-pinene oxide which is an epoxy compound is used as a photopolymerizable compound, and a compound having a diol structure obtained by ring opening of an epoxy group of α-pinene oxide is used as an actinic ray. It is characterized by containing 0.1 to 10% by mass with respect to the total mass of the curable inkjet ink composition.

  In addition, in the ink composition of the present invention, 1,2: 8,9 diepoxy limonene, which is an epoxy compound, is used as the photopolymerizable compound, and further the ring opening of the epoxy group of 1,2: 8,9 diepoxy limonene. The compound having a diol structure obtained by the above is contained in an amount of 0.1 to 10% by mass with respect to the total mass of the actinic ray curable inkjet ink composition.

  Obtained by hydrolyzing (ring-opening) the compound having the alicyclic epoxy group represented by the general formula (1) and the alicyclic epoxy group represented by the general formula (1) with an acid or the like. Similar to the effect of the combination with the diol compound represented by the general formula (2), the compatibility between the epoxy compound and the ring-opening diol compound is good in the ink composition by combining any of the above. Thus, sufficient curability can be obtained, the adverse effects of addition due to phase separation and the like are suppressed, and the stability of the ink composition is improved.

  The ink composition of the present invention preferably contains a compound having an oxetane ring together with the above epoxy compounds.

  As the compound having an oxetane ring that can be used in the present invention, any known oxetane compound as introduced in JP-A Nos. 2001-220526 and 2001-310937 can be used.

  Further, the combined use of a monofunctional oxetane compound containing one oxetane ring and a polyfunctional oxetane compound containing two or more oxetane rings improves the film strength after curing and the adhesion to the recording material. preferable. However, if a compound having 5 or more oxetane rings is used, the viscosity of the ink composition becomes high, which makes it difficult to handle and increases the glass transition temperature of the ink composition. Sex is not enough. The compound having an oxetane ring used in the present invention is preferably a compound having 1 to 4 oxetane rings.

  Hereinafter, although the specific example of the compound which has an oxetane ring based on this invention is demonstrated, this invention is not limited to these.

  An example of a compound having one oxetane ring is a compound represented by the following general formula (I).

In general formula (I), R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group. , Furyl group or thienyl group. R ² is an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl- C2-C6 alkenyl group such as 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group, etc. A group having an aromatic ring, an alkylcarbonyl group having 2 to 6 carbon atoms such as an ethylcarbonyl group, a propylcarbonyl group, and a butylcarbonyl group, an alkylcarbonyl group having 2 to 6 carbon atoms such as an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group; Alkoxycarbonyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, pentylcarbamoyl Is N- alkylcarbamoyl group having a carbon number of 2-6 and the like. As the oxetane compound used in the present invention, it is particularly preferable to use a compound having one oxetane ring because the resulting composition has excellent tackiness, low viscosity and excellent workability.

  An example of a compound having two oxetane rings includes a compound represented by the following general formula (II).

In the general formula (II), R ¹ is the same group as that in the above general formula (I). R ³ is, for example, a linear or branched alkylene group such as an ethylene group, a propylene group or a butylene group, a linear or branched poly (alkyleneoxy) such as a poly (ethyleneoxy) group or a poly (propyleneoxy) group. ) Group, propenylene group, methylpropenylene group, butenylene group or other linear or branched unsaturated hydrocarbon group, alkylene group containing carbonyl group or carbonyl group, alkylene group containing carboxyl group, alkylene containing carbamoyl group Group.

Moreover, as R < ³ >, the polyvalent group selected from the group shown by the following general formula (III), (IV) and (V) can also be mentioned.

In the general formula (III), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. An alkoxy group having 1 to 4 carbon atoms, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.

In the general formula (IV), R ⁵ represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .

In general formula (V), R < ⁶ > is a C1-C4 alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, or an aryl group. n is an integer of 0-2000. R ⁷ is a methyl group, an ethyl group, a propyl group, a butyl group having 1 to 4 carbon atoms, or an aryl group. R ⁷ may further include a group selected from the groups represented by the following general formula (VI).

In the general formula (VI), R ⁸ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group. m is an integer of 0-100.

  Specific examples of the compound having two oxetane rings include the following compounds.

Illustrative compound 1 is a compound in which R ¹ is an ethyl group and R ³ is a carboxyl group in the general formula (II). Exemplary compound 2 is a compound in which, in the general formula (II), R ¹ is an ethyl group, R ³ is the general formula (V), R ⁶ and R ⁷ are methyl groups, and n is 1.

Among the compounds having two oxetane rings, preferred examples other than the above compounds include compounds represented by the following general formula (VII). In the general formula (VII), R ¹ has the same meaning as R ¹ in the general formula (I).

  Moreover, as an example of a compound having 3 to 4 oxetane rings, a compound represented by the following general formula (VIII) can be given.

In the general formula (VIII), R ¹ has the same meaning as R ¹ in the general formula (I). As R ⁹ , for example, a branched alkylene group having 1 to 12 carbon atoms such as groups represented by the following A to C, a branched poly (alkyleneoxy) group such as a group represented by the following D, or the following E And branched polysiloxy groups such as those shown. j is 3 or 4.

In the above A, R ¹⁰ is a lower alkyl group such as a methyl group, an ethyl group or a propyl group. Moreover, in said D, p is an integer of 1-10.

  Illustrative compound 3 is an example of a compound having 3 to 4 oxetane rings.

  Furthermore, examples of the compound having 1 to 4 oxetane rings other than those described above include compounds represented by the following general formula (IX).

In the general formula (IX), R ⁸ has the same meaning as R ⁸ in the general formula (VI). R ¹¹ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, or a trialkylsilyl group, and r is 1 to 4.

  Preferable specific examples of the oxetane compound used in the present invention include the following compounds.

  The method for producing each compound having an oxetane ring described above is not particularly limited, and may be a conventionally known method, for example, Pattisson (DB Pattison, J. Am. Chem. Soc., 3455, 79). (1957)) discloses a method for synthesizing an oxetane ring from a diol. In addition to these, compounds having 1 to 4 oxetane rings having a high molecular weight of about 1000 to 5000 are also included. Examples of these specific compounds include the following compounds.

  In the ink composition of the present invention, when the viscosity at 25 ° C. is 7 to 50 mPa · s, the ejection from the inkjet recording head is stable regardless of the curing environment (for example, temperature and humidity), and good curability. It is preferable to obtain

  The ink composition of the present invention preferably contains various known pigments as the color material. The pigments that can be preferably used in the present invention are listed below.

<C. I. Pigment Yellow>
1, 2, 3, 12, 13, 14, 16, 17, 73, 74, 75, 81, 83, 87, 93, 95, 97, 98, 109, 114, 120, 128, 129, 138, 151, 154
<C. I. Pigment Red>
5, 7, 12, 22, 38, 48: 1, 48: 2, 48: 4, 49: 1, 53: 1, 57: 1, 63: 1, 101, 112, 122, 123, 144, 146, 168, 184, 185, 202
<C. I. Pigment Violet>
19, 23
<C. I. Pigment Blue>
1, 2, 3, 15: 1, 15: 2, 15: 3, 15: 4, 18, 22, 27, 29, 60
<C. I. Pigment Green>
7, 36
<C. I. Pigment White>
6, 18, 21
<C. I. Pigment Black>
7
Further, as carbon black pigments, No. manufactured by Mitsubishi Kasei Co., Ltd. 2300, no. 900, MCF-88, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B, Columbia-made Rave 700, Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Cabot Regal 400R, Regal 330R, Regal 660R, Moul L, Monarch 700, M 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, ColorBlack FW1, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW18, Color Black FW18, Color Black FW18, Color Black FW18, Color Black FW18, Color Black FW18, Color Black FW18 Black S170, Printex 35, Printex U, Printex V, Printex 140U, Printex 140V, Special Black 6, Special Black 6, Special Black 4A, Special Beck 4 G-15, Maxsorb G-08, etc. can be used.

  In the present invention, white ink can be used in order to improve the color concealment property with a transparent recording material such as a plastic film. In particular, in soft packaging printing and label printing, it is preferable to use white ink, but since the discharge amount increases, the use amount is naturally from the viewpoint of the above-described discharge stability and the occurrence of curling and wrinkling of the recording material. There is a limit.

  For the dispersion of the pigment, for example, a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, or the like can be used. Further, a dispersing agent can be added when dispersing the pigment. As the dispersant, a polymer dispersant is preferably used, and examples of the polymer dispersant include Avecia's Solsperse series and Ajinomoto Fine-Techno's PB series. Moreover, it is also possible to use a synergist according to various pigments as a dispersion aid. These dispersants and dispersion aids are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. The dispersion medium is used using a solvent or a polymerizable compound. However, the radiation curable ink used in the present invention is preferably solvent-free because it reacts and cures immediately after ink landing. If the solvent remains in the cured image, the solvent resistance deteriorates and the VOC of the remaining solvent arises. Therefore, it is preferable in view of dispersibility that the dispersion medium is not a solvent but a polymerizable compound, and among them, a monomer having the lowest viscosity is selected.

  The pigment is preferably dispersed so that the average particle diameter of the pigment particles is 0.08 to 0.5 μm, and the maximum particle diameter is 0.3 to 10 μm, preferably 0.3 to 3 μm. The selection of the dispersion medium, the dispersion conditions, and the filtration conditions are appropriately set. 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. The pigment concentration is preferably 1% by mass to 10% by mass of the entire composition.

  In the ink composition of the present invention, various known dyes are preferably used as the color material.

  The dyes that can be preferably used in the present invention are listed below.

  Various dyes such as azo dyes, azomethine dyes, quinone dyes, phthalocyanine dyes, and methine dyes can be used.

<C. I. Solvent Yellow>
1, 2, 3, 4, 14, 16, 19, 29, 56, 79, 82, 83, 88
<C. I. Solvent Red>
1, 18, 24, 27, 43, 51, 72, 73, 84, 132, 218
<C. I. Solvent Violet>
3
<C. I. Solvent Blue>
1, 2, 11, 35, 40, 44, 67, 70
<C. I. Solvent Green>
3
<C. I. Solvent Black>
3, 7, 22, 27, 29, 34, 43, 70
<C. I. Disperse Yellow>
5, 42, 54, 64, 79, 82, 93, 99, 100, 119, 122, 124, 126, 160, 184: 1, 186, 198, 199, 204, 224, 237
<C. I. Disperse Orange>
13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119, 163
<C. I. Disperse Red>
54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 143, 145, 152, 153, 154, 159, 164, 167: 1, 177, 181, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356, 362
<C. I. Disperse Violet>
33
<C. I. Disperse Blue>
56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 224, 225, 257, 266, 267, 287, 354, 358, 365, 368
<C. I. Disperse Green>
6: 1, 9
In addition to the above oil-soluble dyes, Orient Chemical Industry Co., Ltd., Valifast Yellow 4120, Varifast Yellow 3150, Varifast Yellow 3108, Varifast Yellow 2310N, Variast Fast 3043, Varifast Fast 3110, Valifast R3 Blue 2610, Vari Blue Blue 2606, Vari Blue Blue 1603, Oil Yellow GG-S, Oil Yellow 3G, Oil Yellow 129, Oil Yellow 107, Oil Yellow R 105, Oil Scarlet 308R Oil 0.18 , Oil Red 5B, Oil Pink 312, Oil Blue BOS, Oil Blue 613, Oil Blue 2N, Oil Black BY, Oil Black BS, Oil Black 860, Oil Black 5970, Oil Black 5906, Oil Black 5906 Kayset Yellow SF-G, Kayset Yellow K-CL, Kayset Yellow GN, Kayset Yellow AG, Kayase Yellow et 2G, Kayset Red SF-4G, Kayset Red K-BL, Kayset Red K-BL, Kayset Red Kay K-FL, FS Yell manufactured by Arimoto Chemical Industry Co., Ltd. w 1015, FS Magenta 1404, FS Cyan 1522, FS Blue 1504 and the like can also be used.

  In the ink composition of the present invention, the concentration of the oil-soluble dye is preferably 1% by mass to 15% by mass of the whole ink composition.

  Various additives other than those described above can be used in the actinic ray curable ink of the present invention. For example, surfactants, leveling additives, matting agents, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, and waxes can be added. In addition, for the purpose of improving storage stability, any known basic compound can be used, but representative examples include basic organic compounds such as basic alkali metal compounds, basic alkaline earth metal compounds, and amines. Compounds and the like. It is also possible to combine a radically polymerizable monomer and an initiator into a radical / cation hybrid type curable ink.

Basic compounds can also be added. By containing the basic compound, not only the ejection stability becomes good, but also the generation of wrinkles due to curing shrinkage is suppressed even under low humidity.
As the basic compound, any known compounds can be used, and typical examples include basic alkali metal compounds, basic alkaline earth metal compounds, and basic organic compounds such as amines.

  Examples of the basic alkali metal compound include alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (lithium carbonate, sodium carbonate, potassium carbonate, etc.), alkali metals. Alcoholate (sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, etc.).

  Examples of the basic alkaline earth metal compound include alkaline earth metal hydroxides (magnesium hydroxide, calcium hydroxide, etc.), alkali metal carbonates (magnesium carbonate, calcium carbonate, etc.), and alkali metals. Alcoholate (magnesium methoxide, etc.).

  Examples of the basic organic compound include amines and nitrogen-containing heterocyclic compounds such as quinoline and quinolidine. Among these, amines are preferable from the viewpoint of compatibility with the photopolymerization monomer, for example, octylamine, naphthylamine, Xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, trioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine and triethanolamine, etc. Is mentioned.

  The concentration when the basic compound is present is preferably in the range of 10 to 1000 ppm by mass, particularly 20 to 500 ppm by mass relative to the total amount of the photopolymerizable monomer. In addition, a basic compound may be used individually or may be used in combination of multiple.

  Furthermore, water can be added to suppress curing in an ink state such as in an ink tank, piping, or head. The amount of water added is preferably 0.1% by weight or more and less than 8% by weight of the entire composition.

  Any known photoacid generator can be used in the ink composition of the present invention.

  As the photoacid generator, for example, a chemically amplified photoresist or a compound used for photocationic polymerization is used (edited by Organic Electronics Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), 187. To page 192). Examples of compounds suitable for the present invention are listed below.

First, B (C ₆ F ₅ ) ⁴⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ salts of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, phosphonium, etc. be able to.

  Specific examples of onium compounds that can be used in the present invention are shown below.

  Secondly, sulfonated substances that generate sulfonic acid can be mentioned, and specific compounds thereof are exemplified below.

  Thirdly, halides that generate hydrogen halide can also be used, and specific compounds thereof are exemplified below.

  Fourthly, an iron allene complex can be mentioned.

  As a recording material that can be used in the present invention, in addition to ordinary uncoated paper, coated paper, etc., various non-absorbable plastics and films used for so-called soft packaging can be used. For example, polyethylene terephthalate (PET) film, stretched polystyrene (OPS) film, stretched polypropylene (OPP) film, stretched nylon (ONy) film, polyvinyl chloride (PVC) film, polyethylene (PE) film, triacetyl cellulose (TAC) ) A film can be mentioned. As other plastics, polycarbonate, acrylic resin, ABS, polyacetal, PVA, rubbers and the like can be used. Moreover, it is applicable also to metals and glass. Among these recording materials, the structure of the present invention is effective particularly when an image is formed on a PET film, an OPS film, an OPP film, an ONy film, or a PVC film that can be shrunk by heat. These substrates are not only susceptible to curling and deformation of the film due to ink curing shrinkage and heat generation during the curing reaction, but also the ink film is difficult to follow the substrate shrinkage.

  The surface energy of these various plastic films varies greatly depending on the characteristics of the material, and it has been a problem that the dot diameter after ink landing changes depending on the recording material. With the configuration of the present invention, a good high-definition image can be formed on a wide range of recording materials having a surface energy of 35 to 60 mN / m, including OPP films having a low surface energy, OPS films, and PET having a relatively large surface energy. .

  In the present invention, it is more advantageous to use a long (web) recording material in terms of the cost of the recording material such as packaging cost and production cost, the production efficiency of the print, and the ability to cope with printing of various sizes. is there.

  The actinic ray curable inkjet ink set of the present invention includes at least a yellow actinic ray curable inkjet ink composition, a magenta actinic ray curable inkjet ink composition, a cyan actinic ray curable inkjet ink composition, and a black actinic ray. In the actinic radiation curable inkjet ink set composed of the curable inkjet ink composition, all of the actinic radiation curable inkjet ink composition is the actinic radiation curable inkjet ink composition of the present invention, When an inkjet image is formed using the actinic ray curable inkjet ink set of the invention, an image in which color mixing is solved can be formed.

  Furthermore, in order to form a photographic image by inkjet, so-called dark and light inks having different color material contents can be prepared and used. It is also preferable for color reproduction to use special color inks such as red, green, blue, and white as necessary.

  Next, the image forming method of the present invention will be described.

  In the image forming method of the present invention, a method is preferred in which the ink is ejected and drawn on a recording material by an ink jet recording method, and then the ink is cured by irradiation with an actinic ray such as ultraviolet rays.

(Total ink film thickness after ink landing)
In the present invention, the total ink film thickness after the ink has landed on the recording material and cured by irradiation with actinic rays is preferably 2 to 25 μm. In the actinic ray curable ink jet recording in the screen printing field, the total ink film thickness currently exceeds 25 μm, but in the flexible packaging printing field where the recording material is often a thin plastic material, the recording material described above is used. In addition to the problem of curling and wrinkles, there is a problem in that the entire printed material is changed in its strain and texture.

  Here, “total ink film thickness” means the maximum value of the film thickness of the ink drawn on the recording material, and even for a single color, other two colors are superimposed (secondary color), three colors are superimposed, four colors are used. Even when recording is performed by the overlapping (white ink base) inkjet recording method, the meaning of the total ink film thickness is the same.

(Ink ejection conditions)
As the ink ejection conditions, it is preferable from the viewpoint of ejection stability that the recording head and ink are heated to 35 to 100 ° C. and ejected. Actinic radiation curable ink has a large viscosity fluctuation range due to temperature fluctuations, and the viscosity fluctuations directly affect the droplet size and droplet ejection speed, causing image quality degradation. It is necessary to keep. The control range of the ink temperature is set temperature ± 5 ° C., preferably set temperature ± 2 ° C., more preferably set temperature ± 1 ° C.

  Moreover, in this invention, it is preferable that the amount of droplets discharged from each nozzle is 2 to 20 pl. Originally, in order to form a high-definition image, it is necessary for the amount of droplets to be within this range, but when discharging with this amount of droplets, the above-described discharge stability becomes particularly severe. According to the present invention, even when the ink is ejected with a small droplet amount such as 2 to 20 pl, the ejection stability is improved and a high-definition image can be stably formed.

(Light irradiation conditions after ink landing)
In the image forming method of the present invention, the actinic ray is preferably irradiated for 0.001 second to 1.0 second after the ink landing, more preferably 0.001 second to 0. .5 seconds. In order to form a high-definition image, it is particularly important that the irradiation timing is as early as possible.

  As a method for irradiating actinic rays, the basic method is disclosed in JP-A-60-132767. According to this, the light source is provided on both sides of the head unit, and the head and the light source are scanned by the 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 US Pat. No. 6,145,979, as an irradiation method, a method using an optical fiber or a method of applying a collimated light source to a mirror surface provided on the side of the head unit and irradiating the recording unit with UV light is disclosed. Yes. Any of these irradiation methods can be used in the image forming method of the present invention.

  In addition, irradiation with actinic rays is divided into two stages. First, actinic rays are irradiated by the above-described method within 0.001 to 2.0 seconds after ink landing, and further, actinic rays are irradiated after all printing is completed. The method is also a preferred embodiment. By dividing the irradiation of actinic rays into two stages, it is possible to further suppress the shrinkage of the recording material that occurs during ink curing.

  Conventionally, in the UV ink jet system, a light source with high illuminance in which the total power consumption of the light source exceeds 1 kW · hr is usually used in order to suppress dot spreading and bleeding after ink landing. However, when these light sources are used, particularly in printing on a shrink label or the like, the shrinkage of the recording material is so large that it cannot be used practically.

  In the present invention, it is preferable to use an actinic ray having a maximum illuminance in a wavelength region of 254 nm, and a high-definition image can be formed even when a light source having a total power consumption of 1 kW · hr or more is used, and the recording material is contracted. Is also within a practically acceptable level.

  In the present invention, it is preferable that the total power consumption of the light source for irradiating actinic rays is less than 1 kW · hr. Examples of the light source having a total power consumption of less than 1 kW · hr include, but are not limited to, a fluorescent tube, a cold cathode tube, a hot cathode tube, and an LED.

  Next, an ink jet recording apparatus (hereinafter simply referred to as a recording apparatus) of the present invention will be described.

  The recording apparatus of the present invention will be described below with reference to the drawings as appropriate. Note that the recording apparatus of the drawings is merely one aspect of the recording apparatus of the present invention, and the recording apparatus of the present invention is not limited to this drawing.

  FIG. 1 is a front view showing the configuration of the main part of the recording apparatus of the present invention. The recording apparatus 1 includes a head carriage 2, a recording head 3, an irradiation unit 4, a platen unit 5, and the like. In the recording apparatus 1, the platen unit 5 is installed under the recording material P. The platen unit 5 has a function of absorbing ultraviolet rays, and absorbs excess ultraviolet rays that have passed through the recording material P. As a result, a high-definition image can be reproduced very stably.

  The recording material P is guided by the guide member 6 and moves from the near side to the far side in FIG. 1 by the operation of the conveying means (not shown). A head scanning unit (not shown) scans the recording head 3 held by the head carriage 2 by reciprocating the head carriage 2 in the Y direction in FIG.

  The head carriage 2 is installed on the upper side of the recording material P, and stores a plurality of recording heads 3 to be described later according to the number of colors used for image printing on the recording material P, with the discharge ports arranged on the lower side. The head carriage 2 is installed with respect to the main body of the recording apparatus 1 in such a manner that it can reciprocate in the Y direction in FIG. 1, and reciprocates in the Y direction in FIG. 1 by driving the head scanning means.

  In FIG. 1, the head carriage 2 is white (W), yellow (Y), magenta (M), cyan (C), black (K), light yellow (Ly), light magenta (Lm), and light cyan (Lc). Although the drawing is carried out assuming that the recording heads 3 of light black (Lk) and white (W) are accommodated, the number of colors of the recording heads 3 accommodated in the head carriage 2 is determined as appropriate. Is.

  The recording head 3 has a discharge port by operating a discharge means (not shown) provided with a plurality of actinic ray curable inks (for example, UV curable ink) supplied by an ink supply means (not shown). To the recording material P. The UV ink ejected by the recording head 3 is composed of a coloring material, a polymerizable monomer, an initiator, and the like, and the monomer crosslinks when the initiator acts as a catalyst when irradiated with ultraviolet rays. It has the property of being cured by a polymerization reaction.

  During the scanning in which the recording head 3 moves from one end of the recording material P to the other end of the recording material P in the Y direction in FIG. 1 by driving the head scanning means, a certain area (landing possible area) in the recording material P On the other hand, UV ink is ejected as ink droplets, and ink droplets are landed on the landable area.

  The above scanning is performed as many times as necessary, and after UV ink is ejected toward one landable area, the recording material P is appropriately moved from the front to the back in FIG. 1, the recording head 3 discharges UV ink to the next landable area adjacent in the depth direction in FIG.

  By repeating the above operation and ejecting the UV ink from the recording head 3 in conjunction with the head scanning means and the conveying means, an image composed of an aggregate of UV ink droplets is formed on the recording material P.

  The irradiation unit 4 includes an ultraviolet lamp that emits ultraviolet light in a specific wavelength region with stable exposure energy and a filter that transmits ultraviolet light of a specific wavelength. Here, as the ultraviolet lamp, a mercury lamp, a metal halide lamp, an excimer laser, an ultraviolet laser, a cold cathode tube, a hot cathode tube, a black light, an LED (light emitting diode) and the like can be applied. A cathode tube, a hot cathode tube, a mercury lamp or black light is preferred. In particular, a low-pressure mercury lamp, a hot cathode tube, a cold cathode tube, and a germicidal lamp that emit ultraviolet light having a wavelength of 254 nm are preferable because they can prevent bleeding and control the dot diameter efficiently. By using black light as the radiation source of the irradiation means 4, the irradiation means 4 for curing the UV ink can be produced at low cost.

  The irradiating means 4 has substantially the same shape as the maximum one that can be set by the recording apparatus (UV inkjet printer) 1 among the landable areas in which the recording head 3 ejects UV ink by one scan driven by the head scanning means. , Having a shape larger than the landable area.

  The irradiation means 4 is fixed on both sides of the head carriage 2 so as to be substantially parallel to the recording material P.

  As described above, as a means for adjusting the illuminance of the ink discharge portion, not only the entire recording head 3 is shielded, but in addition, the ink discharge of the recording head 3 is determined from the distance h1 between the irradiation means 4 and the recording material P. It is effective to increase the distance h2 between the portion 31 and the recording material P (h1 <h2), or to increase the distance d between the recording head 3 and the irradiation means 4 (d is increased). Further, it is more preferable to provide a bellows structure 7 between the recording head 3 and the irradiation means 4.

  Here, the wavelength of the ultraviolet rays irradiated by the irradiation means 4 can be changed as appropriate by replacing the ultraviolet lamp or filter provided in the irradiation means 4.

  The ink of the present invention has excellent ejection stability and is particularly effective when an image is formed using a line head type recording apparatus.

  FIG. 2 is a top view illustrating another example of the configuration of the main part of the ink jet recording apparatus.

  The ink jet recording apparatus shown in FIG. 2 is called a line head system, and a plurality of ink jet recording heads 3 of each color are fixedly arranged on the head carriage 2 so as to cover the entire width of the recording material P. ing.

  On the other hand, on the downstream side of the head carriage 2, there is provided irradiation means 4 arranged so as to cover the entire width of the recording material P and cover the entire area of the ink printing surface. As the ultraviolet lamp used in the illuminating means 4, the same one as described in FIG. 1 can be used.

  In this line head system, the head carriage 2 and the irradiating means 4 are fixed, and only the recording material P is conveyed, and ink ejection and curing are performed to form an image.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these.

Example 1
<< Preparation of pigment dispersion >>
[Preparation of Pigment Dispersion D-1]
The following compounds were put in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a hot plate at 65 ° C.

PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd., polymer dispersant) 6 parts OXT221 (manufactured by Toa Gosei Co., Ltd., oxetane compound) 74 parts Next, after cooling the above solution to room temperature, the following pigment was added thereto, and the diameter of 1 mm 200 g of zirconia beads were sealed in a glass bottle and sealed with a paint shaker for 4 hours, and then the zirconia beads were removed to prepare pigment dispersion D-1.

C. I. Pigment Blue 15: 4 20 parts [Preparation of Pigment Dispersion D-2]
The following compounds were put in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a hot plate at 65 ° C.

PB822 (manufactured by Ajinomoto Fine-Techno Co., Ltd., polymer dispersant) 6 parts OXT211 (manufactured by Toa Gosei Co., Ltd., oxetane compound) 74 parts Next, after cooling the above solution to room temperature, the following pigment was added thereto, 200 g of zirconia beads were put in a glass bottle and sealed, and after a dispersion treatment for 4 hours with a paint shaker, the zirconia beads were removed to prepare pigment dispersion D-2.

C. I. Pigment Black 7 20 parts <Preparation of ink composition>
Each of the pigment dispersions prepared above or the oil-soluble dye listed in Table 1 was mixed with the additives listed in Table 1 in order, and this was filtered through a 1.0 μm membrane filter to obtain ink compositions 1 to 12. Was prepared. In addition, the numerical value described in Table 1 represents mass%.

The details of each additive described in abbreviations in Table 1 are as follows.
Initiator (oil-soluble dye)
* 1: C.I. I. Solvent Blue 70
* 2: Oil Black 860 (Orient Chemical Co., Ltd.)
[Oxetane compound]
OXT-221: Di [1-ethyl (3-oxetanyl)] methyl ether (manufactured by Toagosei Co., Ltd.)
OXT-212: Toagosei Co., Ltd. [Epoxy compound]
EP-1: Exemplary compound EP-1
DEP: 1,2: 8,9 diepoxyquimonene PO: α-pinene oxide [diol compound]
DI-1: Exemplary compound DI-1
DI-2: Exemplary compound DI-2
DI-3: Exemplary compound DI-3
DI-14: Exemplary compound DI-14
DI-17: Exemplary compound DI-17
EG: Ethylene glycol PEG: Phenyl ethylene glycol [Photoinitiator]
SP-152: Triphenylsulfonium salt (“Adekaoptomer SP-152” manufactured by Asahi Denka Co., Ltd.)
[Surfactant]
F475: Megafax F475 Perfluoroalkyl group-containing acrylic oligomer (Dainippon Ink & Chemicals, Inc.)
<< Evaluation of curability >>
Each prepared ink composition was coated on a polyethylene terephthalate film (thickness 150 μm) with a wire bar so that the wet film thickness was about 5 μm, and then an illuminance of 80 mW / cm ² (the illuminance was UVPF-A1 (Iwasaki). The value at 254 nm) using a low pressure mercury lamp for 30 seconds.

  Next, the coated surface after irradiation with the low-pressure mercury lamp was touched with a finger, and the curability was evaluated according to the following criteria.

◎: almost no stickiness on the surface of the formed image ○: slightly sticky on the surface of the formed image △: There is a sticky feeling on the surface of the formed image, but the image does not peel off even when rubbed. X: The formed image flows without being cured. Table 1 shows the evaluation results obtained as described above.

  As apparent from the results shown in Table 1, the ink composition of the present invention comprising a specified amount of a compound having an alicyclic epoxy group defined in the present invention and a compound having a diol structure defined in the present invention, It can be seen that the curing rate is higher than that of the comparative example and the curability is excellent.

Example 2
<< Preparation of pigment dispersion >>
[Preparation of Pigment Dispersion D-3]
The following compounds were put in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a hot plate at 65 ° C.

Solspers 32000 (manufactured by Avicia Co., Ltd., polymer dispersant) 6 parts OXT221 (manufactured by Toa Gosei Co., Ltd., oxetane compound) 74 parts Next, after cooling the above solution to room temperature, the following pigment was added thereto, and the diameter was 1 mm. 200 g of zirconia beads were put in a glass bottle and sealed, and after a dispersion treatment for 4 hours with a paint shaker, the zirconia beads were removed to prepare pigment dispersion D-3.

C. I. Pigment Red 57: 1 20 parts [Preparation of Pigment Dispersion D-4]
The following compounds were put in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a hot plate at 65 ° C.

PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd., polymer dispersant) 6 parts OXT101 (manufactured by Toa Gosei Co., Ltd., oxetane compound) 74 parts Next, after cooling the above solution to room temperature, the following pigment was added thereto, 200 g of zirconia beads were sealed in a glass bottle and sealed with a paint shaker for 4 hours, and then the zirconia beads were removed to prepare pigment dispersion D-4.

C. I. Pigment Yellow 13 20 parts [Preparation of Pigment Dispersion D-5]
The following compounds were put in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a hot plate at 65 ° C.

PB822 (manufactured by Ajinomoto Fine-Techno Co., Ltd., polymer dispersant) 6 parts OXT211 (manufactured by Toa Gosei Co., Ltd., oxetane compound) 74 parts Next, after cooling the above solution to room temperature, the following pigment was added thereto, 200 g of zirconia beads were put in a glass bottle and sealed, and after a dispersion treatment for 4 hours in a paint shaker, the zirconia beads were removed to prepare pigment dispersion D-5.

C. I. 20 parts of Pigment Yellow 138 [Preparation of Pigment Dispersion D-6]
The following compounds were put in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a hot plate at 65 ° C.

PB822 (manufactured by Ajinomoto Fine-Techno Co., Ltd., polymer dispersant) 6 parts OXT211 (manufactured by Toa Gosei Co., Ltd., oxetane compound) 74 parts Next, after cooling the above solution to room temperature, the following pigment was added thereto, 200 g of zirconia beads were put in a glass bottle and sealed, and after a dispersion treatment with a paint shaker for 4 hours, the zirconia beads were removed to prepare pigment dispersion D-6.

C. I. Pigment Violet 19 20 parts [Preparation of Pigment Dispersion D-7]
The following compounds were put in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a hot plate at 65 ° C.

PB822 (manufactured by Ajinomoto Fine-Techno Co., Ltd., polymer dispersant) 6 parts OXT211 (manufactured by Toa Gosei Co., Ltd., oxetane compound) 74 parts Next, after cooling the above solution to room temperature, the following pigment was added thereto, 200 g of zirconia beads were put in a glass bottle and sealed, and after a dispersion treatment with a paint shaker for 4 hours, the zirconia beads were removed to prepare pigment dispersion D-6.

C. I. Pigment Blue 15: 4 20 parts [Preparation of Pigment Dispersion D-8]
The following compounds were put in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a hot plate at 65 ° C.

PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd., polymer dispersant) 6 parts OXT221 (manufactured by Toa Gosei Co., Ltd., oxetane compound) 74 parts Next, after cooling the above solution to room temperature, the following pigment was added thereto, and the diameter of 1 mm 200 g of zirconia beads were put in a glass bottle and sealed, and after a dispersion treatment with a paint shaker for 4 hours, the zirconia beads were removed to prepare pigment dispersion D-6.

C. I. Pigment Black 7 20 parts << Preparation of ink composition and ink set >>
Using each pigment dispersion prepared in the above and each pigment dispersion prepared in Example 1, the additives listed in Tables 2 to 7 were sequentially mixed, and this was filtered through a 1.0 μm membrane filter. Ink sets 1 to 6 were prepared by preparing each ink composition and combining them. In addition, the numerical value of Tables 2-7 represents the mass%.

<< Inkjet image formation >>
[Image Forming Method A]
Each of the ink sets 1 to 3 prepared above is loaded into an ink jet recording apparatus having the structure shown in FIG. 1 having a piezo ink jet nozzle, and each of the lengths of 600 mm in width and 500 m in length shown in Table 8 is provided. Images 1 to 9 were obtained by continuously performing the following image recording on the recording material. The ink supply system was composed of an ink tank, a supply pipe, a front chamber ink tank just before the head, a pipe with a filter, and a piezo head. The ink was insulated from the front chamber tank to the head portion and heated at 50 ° C. The piezo head was driven so that 2 to 20 pl multi-size dots could be ejected at a resolution of 720 × 720 dpi, and each ink was ejected continuously. After landing, it is cured instantaneously (less than 0.5 seconds after landing) by the lamp units on both sides of the carriage. After recording, the total ink film thickness was measured and found to be in the range of 2.3 to 13 μm. In the present invention, dpi represents the number of dots per 2.54 cm. Inkjet images were formed in an environment of 25 ° C. and 30% RH according to the above method.

[Image Forming Method B]
In the above formation method A, the line head recording type ink jet recording apparatus shown in FIG. 2 was used as the ink jet recording apparatus, and each of the ink sets 4 to 6 was loaded to form an image. ~ 18 were obtained.

  The details of the abbreviations of the recording materials shown in Table 8 are as follows.

OPP: oriented polypropylene
PET: Polyethylene terephthalate
Shrink OPS: Oriented polystyrene for shrink use on the market
Moreover, the detail of each irradiation light source of Table 8 is as follows.

Irradiation light source A: High pressure mercury lamp VZero085 (manufactured by INTEGRATION TECHNOLOGY)
Irradiation light source B: Low-pressure mercury lamp (Iwasaki Electric special order product)
Moreover, the illumination intensity of each irradiation light source of Table 8 measured and displayed the integrated illumination intensity of 254 nm using UVPF-A1 by Iwasaki Electric Co., Ltd. and displayed.

<Evaluation of inkjet recording image>
Each image recorded by the above image forming method was subjected to the following evaluations.

[Evaluation of color mixing]
At 720 dpi, printing was performed so that 1 dot of each color of Y, M, C, and K was adjacent to each other, each adjacent color dot was enlarged with a loupe, the degree of bleeding was visually observed, and color mixing was evaluated according to the following criteria.

◎: Adjacent dot shape maintains a perfect circle and no blurring ○: Adjacent dot shape maintains a perfect circle and almost no blur △: Adjacent dot is slightly blurred and the dot shape is slightly displaced X: Adjacent dots are blurred and mixed. Table 9 shows the evaluation results obtained as described above.

  As is clear from the results shown in Table 9, all of the ink compositions of the present invention containing a specified amount of a compound having an alicyclic epoxy group defined in the present invention and a compound having a diol structure defined in the present invention. It can be seen that the constructed ink set of the present invention has a reduced color blur when each color image is formed, and the color mixing of each color dot is extremely small as compared with the comparative example.

It is a front view which shows an example of a structure of the principal part of the inkjet recording device of this invention. It is a top view which shows another example of a structure of the principal part of the inkjet recording device of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Inkjet recording device 2 Head carriage 3 Inkjet recording head 31 Ink ejection port 4 Irradiation means 5 Platen part 6 Guide member 7 Bellows structure P Recording material

Claims (17)

In the actinic ray curable inkjet ink composition containing at least a photopolymerizable compound and a coloring material, at least one of the photopolymerizable compounds is α-pinene oxide, and an epoxy group of the α-pinene oxide An actinic radiation curable inkjet ink composition comprising 0.1 to 10% by mass of a compound having a diol structure obtained by ring-opening with respect to the total mass of the actinic radiation curable inkjet ink composition. In the actinic ray curable inkjet ink composition containing at least a photopolymerizable compound and a coloring material, at least one of the photopolymerizable compounds is 1,2: 8,9 diepoxy limonene, and the 1, The compound having a diol structure obtained by ring opening of the epoxy group of 2: 8,9 diepoxy limonene is contained in an amount of 0.1 to 10% by mass with respect to the total mass of the actinic ray curable inkjet ink composition. An actinic ray curable inkjet ink composition. The actinic ray curable inkjet ink composition according to claim 1, further comprising a compound having an oxetane ring as the photopolymerizable compound. The actinic ray curable inkjet ink composition according to claim 1, wherein the colorant is a pigment. The actinic ray curable inkjet ink composition according to claim 1, wherein the colorant is an oil-soluble dye. The actinic ray curable inkjet ink composition according to claim 1, wherein the ink viscosity at 25 ° C. is 7 to 50 mPa · s. An actinic ray composed of at least a yellow actinic ray curable inkjet ink composition, a magenta actinic ray curable inkjet ink composition, a cyan actinic ray curable inkjet ink composition, and a black actinic ray curable inkjet ink composition The actinic ray curable ink set according to any one of claims 4 to 6, wherein all of the actinic ray curable inkjet ink composition is the actinic ray curable inkjet ink composition according to any one of claims 4 to 6. Type inkjet ink set. An image forming method in which the actinic ray curable ink jet ink composition according to any one of claims 1 to 6 is jetted onto a recording material from an ink jet recording head, and printing is performed on the recording material. An image forming method comprising irradiating actinic rays for 0.001 to 1 second after the light-curable ink-jet ink composition has landed on the recording material. An image forming method in which the actinic ray curable ink jet ink composition according to any one of claims 1 to 6 is jetted onto a recording material from an ink jet recording head, and printing is performed on the recording material. An image forming method, wherein the light curable inkjet ink composition lands on the recording material and is cured by irradiation with actinic rays to have a total film thickness of 2 to 25 μm. An image forming method for printing an actinic ray curable inkjet ink composition according to any one of claims 1 to 6 on a recording material from an inkjet recording head, wherein the inkjet recording head performs printing on the recording material. An image forming method, wherein the amount of droplets of the actinic ray curable inkjet ink composition discharged from each nozzle of a recording head is 2 to 20 pl. An image forming method for printing an actinic ray curable inkjet ink composition according to any one of claims 1 to 6 on a recording material from an inkjet recording head, wherein the inkjet recording head performs printing on the recording material. An image forming method, wherein the recording head is a line head type ink jet recording head. An actinic ray curable ink jet ink set according to claim 7 is jetted onto a recording material from an ink jet recording head, and printing is performed on the recording material. An actinic ray is irradiated for 0.001 to 1 second after the actinic ray curable inkjet ink composition that has landed on the recording material. An actinic ray curable ink jet ink set according to claim 7 is jetted onto a recording material from an ink jet recording head, and printing is performed on the recording material. An image forming method, wherein the actinic ray curable inkjet ink composition to be landed on the recording material is cured with irradiation with actinic rays to have a total film thickness of 2 to 25 μm. An actinic ray curable ink jet ink set according to claim 7 is jetted onto a recording material from an ink jet recording head, and printing is performed on the recording material. The image forming method discharges from each nozzle of the ink jet recording head. An image forming method, wherein the amount of droplets of the actinic radiation curable inkjet ink composition constituting the actinic radiation curable inkjet ink set is 2 to 20 pl. An image forming method in which an actinic ray curable ink jet ink set according to claim 7 is used to eject from an ink jet recording head onto a recording material and printing is performed on the recording material. An image forming method characterized by being an ink jet recording head. It is an inkjet recording device used for the image forming method of any one of Claims 8-11, Comprising: It discharges, after heating an actinic-light curable inkjet ink composition and an inkjet recording head to 35 to 100 degreeC. An ink jet recording apparatus. It is an inkjet recording device used for the image forming method of any one of Claims 12-15, Comprising: It discharges, after heating an actinic-light curable inkjet ink set and an inkjet recording head to 35 to 100 degreeC. An ink jet recording apparatus.

Images