JP2008024881A - Curable composition, ink composition, method for inkjet-recording, printed matter, and method for producing planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition having good curability and forming a cured film of good flexibility, an ink composition, a method for inkjet-recording using the ink composition, printed matter, and a method for producing a planographic printing plate using the ink composition excellent in curability. <P>SOLUTION: The curable composition (A) contains an ethylenically unsaturated compound represented by formula (1), wherein R<SB>1</SB>denotes a hydrogen atom, a halogen atom, or a 1-4C alkyl group, X<SB>1</SB>denotes a single bond, an ether bond, an ester bond, an amide bond, a carbonyl bond, an alkylene group that may be branched and has a carbon number of 20 or less, or a divalent linking group that is a combination thereof. R<SB>2</SB>denotes a polycyclic aromatic group that may have a halogen atom, a hydroxyl group, an amino group, a siloxane group, and a substituent having a carbon number of 30 or less, and m denotes an integer between 1 and 6. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a curable composition, an ink composition suitably used for inkjet recording, an inkjet recording method, a printed matter obtained using the ink composition, and a method for producing a lithographic printing plate.
Specifically, the ink suitable for ink-jet recording is capable of stable ink-jet recording for a long period of time, is cured with high sensitivity to irradiation with actinic radiation, and the cured product has sufficient flexibility even after the ink composition is cured. The present invention relates to a composition, an inkjet recording method, a printed matter using the composition, and a method for producing a lithographic printing plate obtained using the ink.

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, and an ink jet method. The electrophotographic system requires a process of forming an electrostatic latent image on a photosensitive drum by charging and exposure, and there is a problem that the system becomes complicated and consequently the manufacturing cost becomes high. In addition, although the thermal transfer system is inexpensive, there are problems such as high running costs and waste materials due to the use of ink ribbons.
On the other hand, the ink jet method is an inexpensive device and ejects ink only to a required image portion to form an image directly on a recording medium. Therefore, the ink can be used efficiently and the running cost is low. Furthermore, there is little noise and it is excellent as an image recording method.

  Ink compositions that can be cured by irradiation with radiation such as ultraviolet rays, particularly inks for ink jet recording (radiation curable ink jet recording inks), require ink compositions that cure with high sensitivity and form high-quality images. ing. By achieving high sensitivity, high curability is imparted by irradiation with actinic radiation, so that sufficient curing is achieved in addition to reducing power consumption and extending life by reducing the load on the actinic radiation generator. As a result, there are various advantages such as suppression of volatilization of uncured low molecular weight substances and reduction in the strength of the formed image. In addition, there is a demand for an ink composition in which the obtained image (printed material) does not easily crack or peel off, and the cured film has high flexibility. Due to the high flexibility of the cured film, there are advantages such that the printed material can be displayed and stored for a long period of time in various environments while maintaining high image quality, and the printed material can be easily handled. The improvement in image strength by increasing the sensitivity results in high printing durability in the image area when this ink composition is used for forming the image area of a lithographic printing plate.

An ink composition containing N-vinyl lactams has been disclosed as an ink composition that is cured with high sensitivity and has a high flexibility of a cured film (Patent Document 1). However, the ink composition described in Patent Document 1 is a high-viscosity ink composition containing a polymer and an oligomer as main components of the ink, and is difficult to be ejected by inkjet.
Further, an ink composition that can be cured by irradiation with radiation such as ultraviolet rays is disclosed (Patent Document 2). However, it does not sufficiently satisfy the curability and the flexibility of the cured film.

  Conventionally, when preparing a lithographic printing plate, a so-called PS plate having a structure in which an oleophilic photosensitive resin layer is provided on a hydrophilic support is used, and the photosensitive resin layer is exposed imagewise. Thus, an image is formed by improving or decreasing the solubility of the exposed portion in an alkaline developer, and the non-image portion is dissolved and removed. However, in recent years, digitization techniques for electronically processing, storing, and outputting image information using a computer have become widespread, and a new image output method corresponding to the technique has been demanded. In particular, a method capable of producing a printing plate without undergoing treatment with a developing solution has been studied, and a method of directly producing a lithographic printing plate using an ink composition for inkjet recording has been studied (for example, see Patent Document 3). This is preferably a printing plate having a desired image (preferably a hydrophobic image) by ejecting ink onto the surface of a hydrophilic support in an image-like manner by an inkjet method or the like and irradiating it with actinic radiation to cure it. Is what you get. In order to form an image portion of a lithographic printing plate, ink droplets ejected onto the support are quickly cured without causing bleeding, and the support is bent when the lithographic printing plate is mounted on a printing press. On the other hand, it is desired that the image portion follows well and does not cause damage such as cracks, and the present situation is that an ink composition suitable for such use is desired.

Japanese Patent No. 2880845 JP-T-2004-514014 JP 54-117203 A

The problem to be solved by the present invention is to provide a curable composition excellent in curability and cured film flexibility, an ink composition, an ink jet recording method using the ink composition, and a printed matter.
Another object of the present invention is to provide a method for producing a lithographic printing plate using an ink composition having excellent curability.

The problem to be solved by the present invention has been solved by the following <1>, <2>, <7>, <9> and <10>. It describes below with <3>-<6> and <8> which are preferable embodiments.
<1> (A) A curable composition containing an ethylenically unsaturated compound represented by the following formula (1),

（上記式（１）において、Ｒ₁は水素原子、ハロゲン原子、又は、炭素数１〜４のアルキル基を表し、Ｘ₁は、単結合、エーテル結合（−Ｏ−）、エステル結合（−Ｃ（Ｏ）Ｏ−または−ＯＣ（Ｏ）−）、アミド結合（―Ｃ（Ｏ）ＮＨ−、または、−ＮＨＣ（Ｏ）−）、カルボニル結合（−Ｃ（Ｏ）―）、分岐を有していても良い炭素数２０以下のアルキレン基、またはこれらを組み合わせた二価の連結基を表す。
Ｒ₂は多環芳香族基であって、ハロゲン原子、ヒドロキシル基、アミノ基、シロキサン基、炭素数３０以下の置換基を有していてもよく、ｍは１〜６の整数を表し、ｍが２以上である場合、ｍ個のエチレン性不飽和結合中に存在するｍ個のＲ₁及びＸ₁は、同じでも異なっていてもよく、それぞれ独立に上記の具体例より選択できる。）
＜２＞＜１＞に記載の硬化性組成物を含有するインク組成物、
＜３＞多環芳香族基がナフチル基である＜２＞に記載のインク組成物、
＜４＞（Ｂ）Ｎ−ビニルラクタム類を含有する＜２＞又は＜３＞に記載のインク組成物、
＜５＞（Ｂ）Ｎ−ビニルラクタム類がＮ−ビニルカプロラクタムである＜２＞〜＜４＞のいずれか１つに記載のインク組成物、
＜６＞インクジェット記録用である＜２＞〜＜５＞のいずれか１つに記載のインク組成物、
＜７＞（ａ¹）被記録媒体上に、＜２＞〜＜６＞のいずれか１つに記載のインク組成物を吐出する工程、及び、（ｂ¹）吐出されたインク組成物に活性放射線を照射して、該インク組成物を硬化する工程、を含むインクジェット記録方法、
＜８＞前記活性放射線が、発光ピーク波長が３５０〜４２０ｎｍの範囲にあり、且つ、被記録媒体表面での最高照度が１０〜２,０００ｍＷ/ｃｍ²となる紫外線を発生する発光ダイオードにより照射される紫外線である＜７＞に記載のインクジェット記録方法、
＜９＞＜７＞又は＜８＞に記載のインクジェット記録方法によって記録された印刷物、
＜１０＞（ａ²）親水性支持体上に、＜２＞〜＜６＞のいずれか１つに記載のインク組成物を吐出する工程、及び、（ｂ²）吐出されたインク組成物に活性放射線を照射して、該インク組成物を硬化させることにより、該インク組成物が硬化してなる疎水性画像を前記親水性支持体上に形成する工程、を含む平版印刷版の製造方法。

(In the above formula (1), R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and X ₁ represents a single bond, an ether bond (—O—), an ester bond (—C (O) O- or -OC (O)-), amide bond (-C (O) NH- or -NHC (O)-), carbonyl bond (-C (O)-), branched An alkylene group having 20 or less carbon atoms which may be present, or a divalent linking group in combination of these.
R ₂ is a polycyclic aromatic group, which may have a halogen atom, a hydroxyl group, an amino group, a siloxane group, or a substituent having 30 or less carbon atoms, m represents an integer of 1 to 6, m When m is 2 or more, m R ₁ and X ₁ present in m ethylenically unsaturated bonds may be the same or different, and can be independently selected from the above specific examples. )
<2> an ink composition containing the curable composition according to <1>,
<3> The ink composition according to <2>, wherein the polycyclic aromatic group is a naphthyl group,
<4> (B) The ink composition according to <2> or <3>, which contains N-vinyl lactams,
<5> (B) The ink composition according to any one of <2> to <4>, wherein the N-vinyllactam is N-vinylcaprolactam,
<6> The ink composition according to any one of <2> to <5>, which is for inkjet recording.
<7> (a ¹ ) A step of ejecting the ink composition according to any one of <2> to <6> on a recording medium; and (b ¹ ) active on the ejected ink composition. An ink jet recording method comprising a step of irradiating radiation to cure the ink composition;
<8> The actinic radiation is irradiated by a light emitting diode that generates ultraviolet rays having an emission peak wavelength in a range of 350 to 420 nm and a maximum illuminance on a recording medium surface of 10 to 2,000 mW / cm ^2. The inkjet recording method according to <7>, wherein the ultraviolet ray is
<9> Printed matter recorded by the inkjet recording method according to <7> or <8>,
<10> (a ² ) A step of discharging the ink composition according to any one of <2> to <6> on a hydrophilic support, and (b ² ) the discharged ink composition A method for producing a lithographic printing plate, comprising a step of irradiating actinic radiation to cure the ink composition to form a hydrophobic image formed by curing the ink composition on the hydrophilic support.

ADVANTAGE OF THE INVENTION According to this invention, the curable composition excellent in sclerosis | hardenability and a cured film softness | flexibility, the ink composition containing this curable composition, the inkjet recording method using this ink composition, and printed matter can be provided.
Moreover, according to this invention, the manufacturing method of the lithographic printing plate using this ink composition can be provided.

I. Curable composition (A) Ethylenically unsaturated compound The curable composition of this invention is characterized by containing (A) the ethylenically unsaturated compound represented by following formula (1).

上記式（１）において、Ｒ₁は水素原子、ハロゲン原子、又は、炭素数１〜４のアルキル基を表し、Ｘ₁は、単結合、エーテル結合（−Ｏ−）、エステル結合（−Ｃ（Ｏ）Ｏ−または−ＯＣ（Ｏ）−）、アミド結合（―Ｃ（Ｏ）ＮＨ−、または、−ＮＨＣ（Ｏ）−）、カルボニル結合（−Ｃ（Ｏ）―）、分岐を有していても良い炭素数２０以下のアルキレン基、またはこれらを組み合わせた二価の連結基を表す。
Ｒ₂は多環芳香族基であって、ハロゲン原子、ヒドロキシル基、アミノ基、シロキサン基、炭素数３０以下の置換基を有していてもよく、ｍは１〜６の整数を表し、ｍが２以上である場合、ｍ個のエチレン性不飽和結合中に存在するｍ個のＲ₁及びＸ₁は、同じでも異なっていてもよく、それぞれ独立に上記の具体例より選択できる。
以下、本発明について詳細に説明する。

In the above formula (1), R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and X ₁ represents a single bond, an ether bond (—O—), an ester bond (—C ( O) O- or -OC (O)-), amide bond (-C (O) NH- or -NHC (O)-), carbonyl bond (-C (O)-), branched It represents an alkylene group having 20 or less carbon atoms, or a divalent linking group in combination of these.
R ₂ is a polycyclic aromatic group, which may have a halogen atom, a hydroxyl group, an amino group, a siloxane group, or a substituent having 30 or less carbon atoms, m represents an integer of 1 to 6, m When m is 2 or more, m R ₁ and X ₁ present in m ethylenically unsaturated bonds may be the same or different, and can be independently selected from the above specific examples.
Hereinafter, the present invention will be described in detail.

  The curable composition of the present invention is preferably a composition that is cured by irradiation with actinic radiation in the presence of a polymerization initiator. The polymerization initiator is a compound that absorbs external energy and generates a polymerization initiating species. Examples of the active radiation applied to the curable composition as external energy include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays. The polymerization initiator and actinic radiation will be described in detail later.

The curable composition of this invention is characterized by including 1 or 2 or more of the ethylenically unsaturated compound shown to Formula (1).
The curable composition of the present invention can be used for various applications and is not limited. However, when used as an ink composition described in detail later, excellent curability and flexibility after curing can be obtained. Preferred embodiments are shown below.

Among the ethylenically unsaturated compounds represented by formula (1), m represents an integer of 1 to 6. When m is 2 or more, m R ₁ and X ₁ present in m ethylenically unsaturated bonds may be the same or different. m is preferably 1 to 3, and more preferably m is 1.

Among the ethylenically unsaturated compounds represented by the formula (1), R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and from the availability of materials, a hydrogen atom or a methyl group It is preferable that
In addition, the divalent linking group represented by X ₁ includes a single bond, an ether bond (—O—), an ester bond (—C (O) O— or —OC (O) —), and an amide bond (—C (O ) NH- or -NHC (O)-), carbonyl bond (-C (O)-), nitrogen atom (-N-), sulfur atom (-S-), optionally branched carbon Represents an alkylene group having a number of 20 or less, or a divalent linking group obtained by combining these, and the divalent linking group may have a branched structure, such as a hydroxyl group, an amino group, a thiol group, a halogen group, or a siloxane. It may have a substituent such as a group. In view of easy availability of the material, an ester bond or an amide bond in which the carbonyl carbon of X ₁ and the vinyl group are bonded is preferable.
Therefore, the ethylenically unsaturated group portion of the ethylenically unsaturated compound contained in the curable composition of the present invention (indicated by the parentheses in the formula (1)) is an acryloyloxy group, a methacryloyloxy group, an acrylamide group, A methacrylamide group is preferred.

In the formula (1), R ₂ represents a polycyclic aromatic group.
The polycyclic aromatics are classified into benzene type and non-benzene type depending on the structure of the ring component, and there are condensed polycyclic type and ring aggregate type from the molecular skeleton. Moreover, a polycyclic aromatic hydrocarbon and a polycyclic aromatic heterocycle are included.
In the present invention, the polycyclic aromatic group is preferably a condensed polycyclic group.

In the formula (1), preferred as the polycyclic aromatic group represented by R ₂ is a polycyclic aromatic group having 2 to 4 rings and is not limited. Group, naphthidiyl group, naphthytriyl group, anthryl group, anthridyl group, anthritriyl group, 1H-indenyl group, 1H-indenediyl group, 1H-indenetriyl group, 9H-fluorenylyl group, 9H-fluorenediyl group, 9H-fluorene Triyl group, 1H-phenalenyl group, 1H-phenalenediyl group, 1H-phenalenetriyl group, phenanthrenyl group, phenanthrenediyl group, phenanthrenetriyl group, triphenylenyl group, triphenylenediyl group, triphenylenetriyl group, pyrenyl group, Pyrenediyl group, pyrenetriyl group, naphthacenyl group, naphthacene Diyl group, naphthacentriyl group, tetraphenyl group, tetraphendiyl group, tetraphentriyl group, biphenylenyl group, biphenylenediyl group, biphenylenetriyl group, as-indacenyl group, as-indacenediyl group, as-indacentriyl group Group, s-indacenyl group, s-indacenediyl group, s-indacentriyl group, acenaphthylenyl group, acenaphthylenediyl group, acenaphthylenetriyl group, fluoranthenyl group, fluoranthenediyl group, fluoranthenetriyl group , Acephenanthrenyl group, acephenanthrylene diyl group, acephenanthrylene triyl group, aceanthrylenyl group, aceanthrylene diyl group, aceanthrylene triyl group, chrysenyl group, chrysenediyl group, chrysantylyl group, Pre Examples thereof include an iadenyl group, a preadendiyl group, and a preadentriyl group (including those having a monovalent group or a divalent group or more).
These polycyclic aromatic groups may be heterocyclic groups containing heteroatoms such as O, N, and S. Specifically, thiantreniyl group, thianthrene diyl group, thianthrene triyl group, isobenzofuraniyl group, isobenzofuranyl group, isobenzofurantriyl group, isochromenyl group, isochromendiyl group, isochromementriyl Group, 4H-chromeniyl group, 4H-chromendiyl group, 4H-chromenthryl group, xantheniyl group, xanthenediyl group, xanthenetriyl group, phenoxathiniyl group, phenoxathiindiyl group, phenoxathiintriyl group, Indolizinyl group, indolizine diyl group, indolizine triyl group, isoindole triyl group, isoindole diyl group, isoindole triyl group, indoliyl group, indole diyl group, indole triyl group, indazolyl group, indazole dii Group, indazole triyl group, plinyl group, purine diyl group, print triyl group, 4H-quinolidinyl group, 4H-quinolizine diyl group, 4H-quinolizine triyl group, isoquinolyl group, isoquinolidiyl group, isoquinolitriyl group, quinolyl group, Quinolidiyl group, quinolitriyl group, phthalazinyl group, phthalazinindiyl group, phthalazine triyl group, naphthyridinyl group, naphthyridinediyl group, naphthyridinetriyl group, quinoxalinini group, quinoxalinediyl group, quinoxalinetriyl group, quinazolinidyl group , Quinozolin triyl group, cinnolinyl group, cinnoline diyl group, cinnoline triyl group, pteridinyl group, pteridine diyl group, pteridine triyl group, carbazolyl group, carbazo Rudiyl group, carbazoletriyl group, β-carbolinyl group, β-carbolinediyl group, β-carbolinetriyl group, phenanthridinyl group, phenanthridinediyl group, phenanthridinetriyl group, acridinyl group, acridinediyl Group, acridinetriyl group, perimidinyl group, perimidinediyl group, perimidinetriyl group, phenanthrolinyl group, phenanthrolinediyl group, phenanthrolinetriyl group, phenazinyl group, phenazinediyl group, phenazinetriyl group, phenothiazinyl group Group, phenothiazinediyl group, phenothiazinetriyl group, phenoxazinyl group, phenoxazinediyl group, phenoxazinetriyl group and the like.
Moreover, these polycyclic aromatic groups may have one or more halogen atoms, hydroxyl groups, amino groups, thiol groups, siloxane groups, and substituents having 30 or less carbon atoms. In the present invention, the polycyclic aromatic group is more preferably a polycyclic aromatic group having 2 to 3 rings, and particularly preferably a naphthyl group.

  From the above, among the ethylenically unsaturated compounds represented by formula (1), [M-1] to [M-30] are preferably mentioned as specific examples of those contained in the curable composition. It is not limited.

II. Ink Composition The ink composition of the present invention contains (A) an ethylenically unsaturated compound represented by formula (1), (B) N-vinyl lactams, and (C) a polymerization initiator. Preferably, it contains one or more components selected from the group consisting of (D) a colorant, (E) a dispersant, and (F) a surfactant. Moreover, it is also preferable to add components ((H) and other components) such as (G) polymerizable compounds other than (A) and (B), sensitizing dyes and co-sensitizers, if necessary.

  In the present invention, when the ethylenically unsaturated compound represented by formula (1) (A) is used as a material for the ink composition, the ethylenically unsaturated compounds shown in the above M-1 to M-25 are preferably used. The ethylenically unsaturated compounds shown in M-5, M-8, M-12, M-17 and M-25 can be used more preferably.

  (A) The preferable content rate in the whole ink composition of the ethylenically unsaturated compound represented by Formula (1) is in the range of 5 wt% to 70 wt%, and more preferably 5 wt% to 50 wt%. . When the content is 5% by weight or more, good cured film flexibility can be imparted, and the ink can be kept at a low viscosity within the range of 70% by weight or less.

(B) N-vinyl lactam The ink composition of the present invention contains (B) an N-vinyl lactam represented by the following formula (2).

  In the formula (2), n represents an integer of 1 to 5, and n is 2 to 4 from the viewpoints of flexibility after the ink composition is cured, adhesion to a recording medium, and availability of raw materials. It is preferable that n is an integer of 2 or 4, and n is 4, that is, N-vinylcaprolactam is particularly preferable. N-vinylcaprolactam is preferable because it is excellent in safety, is generally available and can be obtained at a relatively low price, and provides particularly good ink curability and adhesion of a cured film to a recording medium.

  The N-vinyl lactams may have a substituent such as an alkyl group or an aryl group on the lactam ring, and may be linked with a saturated or unsaturated ring structure.

  The ink composition of the present invention contains N-vinyl lactams in an amount of 10% by weight or more based on the total ink. By containing N-vinyl lactams in an amount of 10% by weight or more of the whole ink, an ink composition having excellent curability, cured film flexibility, and cured film substrate adhesion can be provided. A more preferable content of the N-vinyl lactam in the ink composition is in the range of 10% by weight to 40% by weight. N-vinyl lactams are compounds having a relatively high melting point. A content of 40% by weight or less is preferable because it exhibits good solubility even at a low temperature of 0 ° C. or less, and the temperature range in which the ink composition can be handled becomes wide. More preferably, it is in the range of 12 wt% or more and 40 wt% or less, and particularly preferably in the range of 15 wt% or more and 35 wt% or less.

  The N-vinyl lactams may be contained in the ink composition alone or in a plurality of kinds.

(C) Polymerization initiator In the present invention, when the ink composition is cured using photoactive rays such as ultraviolet rays, a polymerization initiator is contained. As the polymerization initiator that can be used in the present invention, a known polymerization initiator can be used, and a radical polymerization initiator is preferably used. The polymerization initiator that can be used in the present invention may be used alone or in combination of two or more.

  The polymerization initiator that can be used in the ink composition of the present invention is a compound that absorbs external energy and generates a polymerization initiating species. External energy used for initiating polymerization is roughly divided into heat and actinic radiation, and a thermal polymerization initiator and a photopolymerization initiator are used, respectively. Examples of the active radiation include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays.

<Radical polymerization initiator>
Examples of radical polymerization initiators that can be used in the present invention include (a) aromatic ketones, (b) acylphosphine compounds, (c) aromatic onium salt compounds, (d) organic peroxides, (e) thios. Compound, (f) hexaarylbiimidazole compound, (g) ketoxime ester compound, (h) borate compound, (i) azinium compound, (j) metallocene compound, (k) active ester compound, (l) carbon halogen bond And (m) an alkylamine compound. These radical polymerization initiators may use the above compounds (a) to (m) alone or in combination. The radical polymerization initiator in the present invention is preferably used alone or in combination of two or more.

  Preferable examples of (a) aromatic ketones, (b) acylphosphine compounds, and (e) thio compounds include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. FOUASSIER, J.A. F. RABEK (1993), pp. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in 77-117. 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 JP-B-47-22326. Α-substituted benzoin compounds, benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, Benzoin ethers described in JP-A-60-26403, JP-A-62-81345, JP-B-1-34242, US Pat. No. 4,318,791, and α-aminobenzophenones described in European Patent 0284561A1, P-di (dimethyla) described in JP-A-2-211452 Nobenzoyl) benzene, thio-substituted aromatic ketone described in JP-A-61-194062, acylphosphine sulfide described in JP-B-2-9597, acylphosphine described in JP-B-2-9596, JP-B-63- Examples thereof include thioxanthones described in Japanese Patent No. 61950, and coumarins described in Japanese Patent Publication No. 59-42864.

  (C) As aromatic onium salt compounds, elements of Groups 15, 16 and 17 of the periodic table, specifically N, P, As, Sb, Bi, O, S, Se, Te, or I fragrances Group 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. The diazonium salts described in the specifications of U.S. Pat. Nos. 2,974,279, 279210, and 422570, U.S. Pat. Nos. 3,902,144, 4,933,377, 4,760013, 4,734,344, and 2,833,827 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, JP-A-63) -138345, JP-A-63 142345, JP-A-63-142346, and JP-B-46-42363, specifically 1-methoxy-4-phenylpyridinium tetrafluoroborate, etc. The compounds described in JP-A 52-147277, 52-14278, and 52-14279 are preferably used. Generates radicals and acids as active species.

  (D) The 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 ′, Perester ester compounds such as 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone and di-t-butyldiperoxyisophthalate Thing is preferable.

  (F) Examples of hexaarylbiimidazole compounds include lophine dimers described in JP-B Nos. 45-37377 and 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 ' Tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 Examples include ', 5,5'-tetraphenylbiimidazole.

  (G) Examples of the ketoxime ester compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxyiminopentane-3. -One, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminotan-2-one, 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.

  (H) Examples of the borate compound include compounds described in US Pat. Nos. 3,567,453, 4,343,891, European Patents 109,772, and 109,773. Can be mentioned.

  (I) Examples of azinium salt compounds include JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, JP-A-63-143537, and JP-B-46-42363. The compound group which has NO bond of each gazette description can be mentioned.

  (J) Examples of metallocene compounds include titanocenes described in JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, and JP-A-2-4705. Examples thereof include 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.

  (K) Examples of the active ester compound include the specifications of European Patent Nos. 0290750, 046083, 156153, 271851, and 0388343, U.S. Pat. Nos. 3,901,710, and 4,181,531. Nitrobenzol ester compounds described in JP-A-60-198538 and JP-A-53-133022, 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 compound, Japanese Examined Patent Publication No. 62-6223, Japanese Examined Publication No. 63 No. 14340, and compounds, and the like described in the JP-A No. 59-174831.

  (L) Preferred examples of the compound having a carbon halogen bond include, for example, 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.

In the ink composition of the present invention, the total amount of polymerization initiator used is preferably 0. 0 relative to the total amount of (A) curable compound, (B) N-vinyl lactam and (G) polymerizable compound. It is in the range of 01 to 35% by weight, more preferably 0.5 to 20% by weight, and still more preferably 1.0 to 15% by weight. The ink composition can be cured at 0.01% by weight or more, and a cured film having a uniform degree of curing can be obtained at 35% by weight or less.
Moreover, when using the sensitizing dye mentioned later for the ink composition of this invention, the total usage-amount of a polymerization initiator is the weight ratio of a polymerization initiator: sensitizing dye with respect to a sensitizing dye, Preferably it is 200: It is 1-1: 200, More preferably, it is the range of 50: 1 to 1:50, More preferably, it is the range of 20: 1 to 1: 5.

(D) Colorant When the ink composition of the present invention is used for forming an image portion of a lithographic printing plate, it is not particularly necessary to form a colored image, but to improve the visibility of the formed image portion, or When it is going to form a colored image using an ink composition, a coloring agent can be contained.

  The colorant that can be used in the present invention is not particularly limited, but pigments and oil-soluble dyes that are excellent in weather resistance and excellent in color reproducibility are preferable, and are arbitrarily selected from known colorants such as soluble dyes. Can be used. The colorant that can be suitably used in the ink composition of the present invention or the ink composition for inkjet recording functions as a polymerization inhibitor in a polymerization reaction that is a curing reaction from the viewpoint of not reducing the sensitivity of the curing reaction by actinic radiation. It is preferred to select compounds that do not.

<Pigment>
Although it does not necessarily limit as a pigment which can be used for this invention, For example, the organic or inorganic pigment of the following number described in a color index can be used.
Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 42, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53. : 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 , 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36,
Pigment Blue 1,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,17-1,22,27,28,29,36,60 as a blue or cyan pigment ,
As a green pigment, Pigment Green 7, 26, 36, 50,
Examples of yellow pigments include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 120, and 137. , 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193,
As the black pigment, Pigment Black 7, 28, 26,
As a white pigment, Pigment White 6, 18, 21
Etc. can be used according to the purpose.

<Oil-soluble dye>
Below, the oil-soluble dye which can be used by this invention is demonstrated.
The oil-soluble dye that can be used in the present invention means a dye that is substantially insoluble in water. Specifically, the solubility in water at 25 ° C. (the weight of the dye that can be dissolved in 100 g of water) is 1 g or less, preferably 0.5 g or less, more preferably 0.1 g or less. Accordingly, the oil-soluble dye means a so-called water-insoluble pigment or oil-soluble dye, and among these, an oil-soluble dye is preferable.

  Among the oil-soluble dyes that can be used in the present invention, any yellow dye can be used. For example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; for example, azomethine dyes having open-chain active methylene compounds as coupling components; Examples include methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dye species such as quinophthalone dyes, nitro / nitroso dyes, acridine And dyes and acridinone dyes.

  Of the oil-soluble dyes usable in the present invention, any magenta dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines as coupling components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles as coupling components; for example arylidene dyes, styryl dyes, merocyanine dyes, oxonol dyes Methine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone; condensed polycyclic dyes such as dioxazine dyes, etc. Can be mentioned.

  Among the oil-soluble dyes applicable to the present invention, any cyan dye can be used. For example, indoaniline dyes, indophenol dyes or azomethine dyes having pyrrolotriazoles as coupling components; polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes Phthalocyanine dyes; anthraquinone dyes; for example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components; indigo / thioindigo dyes;

  Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of chromophore (chromogenic atomic group) is dissociated. In this case, the counter cation may be an alkali metal or ammonium. Such inorganic cations may be used, and organic cations such as pyridinium and quaternary ammonium salts may be used, and furthermore, polymer cations having such a partial structure may be used.

Although not limited to the following, preferred specific examples include C.I. I. Solvent Black 3, 7, 27, 29 and 34; C.I. I. Solvent Yellow 14, 16, 19, 29, 30, 56, 82, 93 and 162; C.I. I. Solvent Red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73, 109, 122, 132 and 218; I. Solvent Violet 3; C.I. I. Solvent Blue 2,11,25,35,38,67 and 70; I. Solvent Green 3 and 7; I. Solvent orange 2; and the like.
Particularly preferred among these are: Nubian Black PC-0850, Oil Black HBB, Oil Yellow 129, Oil Yellow 105, Oil Pink 312, Oil Red 5B, Oil Scallet 308, Vali Fast Blue chemistry 2606e B2 (Manufactured by Co., Ltd.), Aizen Spiron Blue GNH (manufactured by Hodogaya Chemical Co., Ltd.), Neopen Yellow 075, Neopen Magenta SE1378, Neopen Blue 808, Neopen Blue FF4012, and Neo42 Cy FF4012.
In the present invention, the oil-soluble dye may be used alone or in combination of several kinds.

Moreover, when using an oil-soluble dye as a colorant, other water-soluble dyes, disperse dyes, pigments, and other colorants can be used in combination as long as the effects of the present invention are not impaired.
In the present invention, a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent. The disperse dye generally includes a water-soluble dye, but in the present invention, the disperse dye is preferably used as long as it is soluble in a water-immiscible organic solvent. Preferable specific examples of the disperse dye include C.I. I. Disperse Yellow 5,42,54,64,79,82,83,93,99,100,119,122,124,126,160,184: 1,186,198,199,201,204,224 and 237 C. I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; I. Disperse Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135, 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 and 362; I. Disperse Violet 33; C.I. 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 and 368; I. Disperse Green 6: 1 and 9;

  It is preferable that the colorant that can be used in the present invention is appropriately dispersed in the ink after being added to the ink composition of the present invention or the ink composition for inkjet recording. For dispersing the colorant, for example, a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, or a paint shaker can be used.

In the preparation of the ink composition of the present invention, the colorant may be blended by direct addition with each component. It can also be blended. Moreover, the radically polymerizable compound etc. which are used for this invention can be used preferably as a medium.
In the present invention, in order to avoid deterioration of solvent resistance when the solvent remains in the cured image and the problem of VOC (Volatile Organic Compound) of the remaining solvent, the colorant is a radical polymerizable compound. It is preferable to add and mix in advance in such a medium. In consideration of only dispersibility, it is preferable to select a monomer having the lowest viscosity as the polymerizable compound used for the addition of the colorant.

  These colorants may be used by appropriately selecting one type or two or more types according to the purpose of use of the ink composition.

When using a colorant such as a pigment that remains solid in the ink composition of the present invention, the average particle diameter of the colorant particles is preferably 0.005 to 0.5 μm, more preferably 0. It is preferable to set the colorant, the dispersant, the medium, the dispersion conditions, and the filtration conditions so as to be 0.01 to 0.45 μm, more preferably 0.015 to 0.4 μm. This particle size control is preferable because clogging of the head nozzle can be suppressed and ink storage stability, ink transparency, and curing sensitivity can be maintained.
The content of the colorant in the ink composition of the present invention is appropriately selected depending on the color and the purpose of use. Is preferred.

(E) Dispersant It is preferable to add a dispersant when dispersing the colorant. The type of the dispersant is not particularly limited, but a polymer dispersant is preferably used. Dispersor BYK-101, DisperBYK-102, DisperBYK-103, DisperBYK-106, DisperBYK-111, DisperBYK-161, DisperBYK-162, DisperBYK-164D, DisperBYK-164D, , DisperBYK-168, DisperBYK-170, DisperBYK-171, DisperBYK-174, DisperBYK-182 (manufactured by BYK Chemie), EFKA4010, EFKA4046, EFKA5080, EFKA5504, EFKA5504, EFKA5504, 62, polymer dispersing agents such as EFKA7500, EFKA7570, EFKA7575, EFKA7580 (manufactured by Fuka Additive), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse) 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, 32000, 36000, 39000, 41000, 71000, etc. (Abyssia); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ( Manufactured by Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.), “Disparon KS-860, 873SN, 874 (polymer dispersant), # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester type) ”.
In addition, pigment derivatives such as a phthalocyanine derivative (trade name: EFKA-745 (manufactured by Efka)), Solsperse 5000, 12000, Solsperse 22000 (manufactured by Avicia) can also be used.
The content of the dispersant in the ink composition of the present invention is appropriately selected depending on the purpose of use, but generally it is preferably 0.01 to 5% by weight with respect to the total weight of the ink composition.

(F) Surfactant It is preferable to add a surfactant to the ink composition of the present invention in order to impart stable discharge properties for a long time.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826.
The content of the surfactant in the ink composition of the present invention is appropriately selected depending on the purpose of use, but generally it is preferably 0.0001 to 1% by weight with respect to the total weight of the ink composition. .

  Components other than (A) to (F) can be added to the ink composition of the present invention as necessary. Examples include polymerizable compounds, sensitizing dyes, co-sensitizers, ultraviolet absorbers, antioxidants, antifading agents, conductive salts, solvents, polymer compounds, basic compounds, and the like.

(G) Polymerizable compound The ink composition of the present invention may contain other polymerizable compounds in addition to the components (A) and (B).

<Radically polymerizable compound>
Use of a radically polymerizable compound in combination is preferable because an ink composition having further excellent curability can be provided (hereinafter, “radical polymerizable compound” means a radically polymerizable compound excluding components (A) and (B). Needless to say.
Examples of the radical polymerizable compound are described in JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-9-80675, and the like. A photocurable material using a photopolymerizable composition is known.

  The radical polymerizable compound is a compound having an ethylenically unsaturated bond capable of radical polymerization, and may be any compound as long as it has at least one ethylenically unsaturated bond capable of radical polymerization in the molecule. , Oligomers, polymers and the like having a chemical form. The radical polymerizable compound may contain one kind at an arbitrary ratio in order to improve the desired properties, and may contain two or more kinds.

  Examples of the polymerizable compound having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and salts thereof, Saturated anhydrides, acrylonitrile, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated urethane (meth) acrylic monomers or prepolymers, epoxy monomers or prepolymers, urethane monomers or prepolymers A (meth) acrylic acid ester such as a polymer is preferably used.

  Specifically, (poly) ethylene glycol mono (meth) acrylate, (poly) ethylene glycol (meth) acrylate methyl ester, (poly) ethylene glycol phenyl ether mono (meth) acrylate, phenoxyethyl (meth) acrylate, (poly ) Ethylene glycol (meth) acrylate ethyl ester, (poly) propylene glycol mono (meth) acrylate, (poly) propylene glycol (meth) acrylate methyl ester, (poly) propylene glycol (meth) acrylate ethyl ester, neopentyl glycol di ( (Meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (me) ) Acrylate, PO adduct di (meth) acrylate of bisphenol A, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, EO adduct di (meth) acrylate of bisphenol A, EO-modified pentaerythritol triacrylate, PO modified pentaerythritol triacrylate, EO modified pentaerythritol tetraacrylate, PO modified pentaerythritol tetraacrylate, EO modified dipentaerythritol tetraacrylate, PO modified dipentaerythritol tetraacrylate, EO modified trimethylolpropane triacrylate, PO modified trimethylolpropane Triacrylate, EO modified tetramethylol methane tetraacrylate, PO modified tet Methylol methane tetraacrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, isooctyl acrylate, n-lauryl acrylate, n-tridecyl acrylate, n-cetyl acrylate, n-stearyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, N-methylolacrylamide, diacetone Kurylamide, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, n-decyl methacrylate, isooctyl methacrylate, n-lauryl methacrylate, n-tridecyl methacrylate, n- Cetyl methacrylate, n-stearyl methacrylate, dimethylaminomethyl methacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, other, allyl glycidyl ether, diallyl phthalate, Derivatives of allyl compounds such as triallyl trimellitate, 1,6-hexanediol diacrylate, , 9-nonanediol diacrylate, 1,10-decanediol diacrylate, 2-ethylhexyl-diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, hydroxypivalic acid neopentyl glycol diacrylate, 2-acryloyloxyethyl phthalic acid, tetramethylolmethane triacrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, dimethylol tricyclodecane diacrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethyl succinic acid , Modified glycerin triacrylate, bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, 2-acryloyloxyethyl hex Hydrophthalic acid, dipentaerythritol hexaacrylate, pentaerythritol triacrylate tolylene diisocyanate urethane prepolymer, lactone-modified flexible acrylate, butoxyethyl acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydi Examples include propylene glycol acrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, and more specifically, Junzo Yamashita, “Crosslinking Handbook” (1981, Taiseisha); "UV / EB Curing Handbook (Raw Materials)" (1985, Polymer Publications); Rad Tech Research Group “Application and Market of UV / EB Curing Technology”, page 79 (1989, CMC); Eiichiro Takiyama “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun), etc. And known radically polymerizable or crosslinkable monomers, oligomers and polymers can be used.

  Furthermore, it is also preferable to use a vinyl ether compound as the radical polymerizable compound. Suitable vinyl ether compounds include, for example, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol. Di- or trivinyl ether compounds such as divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octade Vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, n- propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether -O- propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

  Of these vinyl ether compounds, divinyl ether compounds and trivinyl ether compounds are preferable from the viewpoints of curability, adhesion, and surface hardness, and divinyl ether compounds are particularly preferable. A vinyl ether compound may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.

  In the present invention, the monomers listed as the polymerizable compound described above have high reactivity, low viscosity, and excellent adhesion to a recording medium.

  In the present invention, oligomers and polymers can be used together. Here, an oligomer means a compound having a molecular weight (weight average molecular weight for those having a molecular weight distribution) of 2,000 or more, and a polymer has a molecular weight (weight average molecular weight for those having a molecular weight distribution) of 10. Means more than 1,000 compounds. The oligomer or polymer may or may not have a radical polymerizable group. When the radically polymerizable group in one molecule of the oligomer or polymer is 4 or less (in terms of a compound having a molecular weight distribution, the average of the total number of molecules contained is 4 or less), an ink composition having excellent flexibility can be obtained. preferable. It can also be preferably used in the sense that the viscosity of the ink is adjusted to an optimum viscosity for jetting.

<Cationically polymerizable compound>
The ink composition of the present invention can be used in combination with a cationically polymerizable compound as necessary. When a cationic polymerizable compound is used in combination, a cationic polymerization initiator is also preferably used as a polymerization initiator.
The cationically polymerizable compound that can be used in the present invention is not particularly limited as long as it is a compound that initiates a polymerization reaction with an acid generated from a photoacid generator and cures. Cationic polymerizable monomers can be used. Examples of the cationic polymerizable monomer include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and 2001-2001. Examples thereof include epoxy compounds, vinyl ether compounds, oxetane compounds and the like described in each publication such as No. 220526.

  In addition, as the cationic polymerizable compound, for example, a polymerizable compound applied to a cationic polymerization type photocurable resin is known, and recently, a photo cationic polymerization type sensitized in a visible light wavelength region of 400 nm or more. Examples of the polymerizable compound applied to the photocurable resin are disclosed in JP-A-6-43633 and JP-A-8-324137. These can also be applied to the ink composition of the present invention.

<Cationic polymerization initiator>
In the ink composition of the present invention, when a cationic polymerizable compound is used in combination, a cationic polymerization initiator is preferably used in combination.

First, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ salt of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, phosphonium, etc. be able to. Secondly, sulfonated products that generate sulfonic acid can be mentioned. Thirdly, a halide that generates hydrogen halide can also be used. Fourthly, an iron allene complex can be mentioned.

(H) Other components Other components than the above components can be added to the ink composition of the present invention, if necessary.
Examples of other components include sensitizing dyes, co-sensitizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, solvents, polymer compounds, and basic compounds.

<Sensitizing dye>
A sensitizing dye may be added to the ink composition of the present invention to absorb specific actinic radiation and promote decomposition of the polymerization initiator, particularly when used for ink jet recording. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with the polymerization initiator, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the polymerization initiator undergoes a chemical change and decomposes to generate radicals, acids or bases.
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 (for example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquinone), squalium (for example, squalium) ), Coumarins (eg 7-diethylamino-4-methylcoumarin).

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

In the formula (IX), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² forms a basic nucleus of the dye together with the adjacent A ¹ and the adjacent carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic nucleus of the dye. Good. W represents an oxygen atom or a sulfur atom.

In formula (X), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with 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 together with adjacent A ₂ and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents 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—, —NR ⁶² — or —NR ⁶³ —, wherein R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ , A ^4, and adjacent carbon atoms, and R ⁶⁰ , R ⁶¹ each independently represents a hydrogen atom or a monovalent non-metallic atomic group, or may 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 represent a hydrogen atom or a monovalent non-metallic atomic group; R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ each represent an aliphatic or aromatic ring. Can be combined to form.

Preferable specific examples of the compounds represented by formulas (IX) to (XIII) include (E-1) to (E-20) shown below.
In some of the following exemplary compounds, the hydrocarbon chain is described by a simplified structural formula in which the symbols of carbon (C) and hydrogen (H) are omitted.

  The content of the sensitizing dye in the ink composition of the present invention is appropriately selected depending on the purpose of use, but generally it is preferably 0.05 to 4% by weight based on the weight of the whole ink composition. .

<Co-sensitizer>
The ink composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye to actinic radiation or suppressing the polymerization inhibition of the polymerizable compound by oxygen.
Examples of such co-sensitizers include amines such as MR Sander et al., "Journal of Polymer Society", Vol. 10, p. Publication, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research Disclosure 33825 Specific examples thereof include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

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.
The content of the co-sensitizer in the ink composition of the present invention is appropriately selected depending on the purpose of use, but is generally 0.05 to 4% by weight with respect to the weight of the entire ink composition. preferable.

<Ultraviolet absorber>
In the present invention, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance of the obtained image and preventing discoloration.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194843, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492 and 56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in US Pat. No. 24239, stilbene-based and benzoxazole-based compounds that absorb ultraviolet rays and emit fluorescence, so-called fluorescent brighteners.
The addition amount is appropriately selected according to the purpose, but generally it is preferably 0.5 to 15% by weight in terms of solid content.

<Antioxidant>
An antioxidant can be added to improve the stability of the ink composition. Examples of the antioxidant include European published patents, 223739, 309401, 309402, 310551, 310552, 359416, and 3435443. JP, 54-85535, 62-262417, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, Examples thereof include those described in Kaihei 3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by weight in terms of solid content.

<Anti-fading agent>
In the ink composition of the present invention, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of the metal complex anti-fading agent include nickel complexes and zinc complexes. No. 17643, VII, I to J, No. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544 at page 527, ibid. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of representative compounds described in JP-A-62-215272, pages 127 to 137 can be used. .
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by weight in terms of solid content.

<Conductive salts>
Conductive salts such as potassium thiocyanate, lithium nitrate, ammonium thiocyanate, and dimethylamine hydrochloride can be added to the ink composition of the present invention for the purpose of controlling ejection properties.

<Solvent>
In order to improve the adhesion to the recording medium, it is also effective to add a very small amount of an organic solvent to the ink composition of the present invention.
As the solvent that can be used in the ink composition of the present invention, when a resin is used for the internal structure of the polymerizable particles, the solubility parameter value (SP value) of the resin and the solubility parameter value of the solvent to be used are The difference is preferably 2 or more, and more preferably 3 or more.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether Examples include ether solvents.
In this case, it is effective to add the solvent within a range that does not cause the problem of solvent resistance and VOC, and the amount is preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight with respect to the whole ink composition. % Range.

<Polymer compound>
Various polymer compounds can be added to the ink composition of the present invention in order to adjust film physical properties. High molecular 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. Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, as a copolymer composition of the polymer compound, a copolymer containing “carboxyl group-containing monomer”, “alkyl methacrylate ester”, or “alkyl acrylate ester” as a structural unit is also preferably used.

<Basic compound>
The basic compound is preferably added from the viewpoint of improving the storage stability of the ink composition. As the basic compound that can be used in the present invention, known basic compounds can be used. For example, basic inorganic compounds such as inorganic salts, and basic organic compounds such as amines can be preferably used. .

In addition to this, if necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, polymerization to inhibit the adhesion to recording media such as polyolefin and PET, and the like, The tackifier which does not do can be contained.
As a tackifier, specifically, a high molecular weight adhesive polymer (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms) described in JP-A-2001-49200, 5-6p. An ester with an alcohol having, an ester of (meth) acrylic acid and an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer comprising an ester of (meth) acrylic acid and an aromatic alcohol having 6 to 14 carbon atoms) And a low molecular weight tackifier resin having a polymerizable unsaturated bond.

[Ink composition properties]
In the present invention, an ink composition having a viscosity of 40 mPa · s or less at 25 ° C. is used in consideration of dischargeability. Preferably, it is 5 mPa · s to 40 mPa · s, and more preferably 7 mPa · s to 30 mPa · s. Moreover, it is preferable that the viscosity in discharge temperature (for example, 25-80 degreeC, Preferably 25-50 degreeC) is 3-15 mPa * s, More preferably, it is 3-13 mPa * s. It is preferable that the composition ratio of the ink composition of the present invention is appropriately adjusted so that the viscosity is in the above range. By setting the viscosity at room temperature high, even when a porous recording medium is used, ink penetration into the recording medium can be avoided, and uncured monomers and odors can be reduced. Furthermore, it is preferable that ink bleeding at the time of ink droplet landing can be suppressed, and as a result, the image quality is improved.

  The surface tension of the ink composition of the present invention at 25 ° C. is preferably 20 to 35 mN / m. More preferably, it is 23-33 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 35 mN / m or less.

III. Inkjet recording method and inkjet recording apparatus The ink composition of the present invention is used for inkjet recording.
In the inkjet recording method of the present invention, the ink composition of the present invention is ejected onto a recording medium (support, recording material, etc.) for inkjet recording, and actinic radiation is applied to the ink composition ejected onto the recording medium. It is a method of forming an image by irradiating and curing the ink.

More specifically, the inkjet recording method of the present invention comprises (a ¹ ) a step of ejecting the ink composition of the present invention onto a recording medium, and (b ¹ ) actinic radiation on the ejected ink composition. And a step of curing the ink composition.
By including the steps (a ¹ ) and (b ¹ ), the ink jet recording method of the present invention forms an image with the ink composition cured on the recording medium.

In the step (a ¹ ) in the ink jet recording method of the present invention, an ink jet recording apparatus described in detail below can be used.

[Inkjet recording device]
There is no restriction | limiting in particular as an inkjet recording device used for the inkjet recording method of this invention, The well-known inkjet recording device which can achieve the target resolution can be selected arbitrarily and can be used. That is, any known inkjet recording apparatus including a commercially available product can eject ink onto a recording medium in the step (a ¹ ) of the inkjet recording method of the present invention.
Examples of the ink jet recording apparatus that can be used in the present invention include an apparatus including an ink supply system, a temperature sensor, and an actinic radiation source.
The ink supply system includes, for example, an original tank containing the ink composition of the present invention, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The piezo-type inkjet head has a multi-size dot of 1 to 100 pl, preferably 8 to 30 pl, for example, 320 × 320 to 4000 × 4000 dpi, preferably 400 × 400 to 1600 × 1600 dpi, and more preferably 720 × 720 dpi. It can drive so that it can discharge with the resolution of. In the present invention, dpi represents the number of dots per 2.54 cm.

  As described above, since it is desirable that the radiation-curable ink, like the ink composition of the present invention, has a constant temperature for the ink to be ejected, heat insulation and heating are performed from the ink supply tank to the inkjet head portion. It can be carried out. 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 flow rate and the environmental temperature. The temperature sensor can be provided in the vicinity of the ink supply tank and the nozzle of the inkjet head. 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 heat energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

Using the ink jet recording apparatus, the ink composition of the present invention is ejected by heating the ink composition to preferably 25 to 80 ° C., and preferably 25 to 50 ° C., so that the viscosity of the ink composition is 3 It is preferable to carry out after lowering to ˜15 mPa · s, preferably 3 to 13 mPa · s. In particular, it is preferable to use an ink composition having an ink viscosity at 25 ° C. of 50 mPa · s or less as the ink composition of the present invention since it can be discharged satisfactorily. By using this method, high ejection stability can be realized.
A radiation curable ink composition such as the ink composition of the present invention generally has a higher viscosity than a water-based ink usually used in ink jet recording inks, and therefore has a large viscosity fluctuation due to temperature fluctuations during ejection. The ink viscosity fluctuation has a great influence on the change of the droplet size and the change of the droplet discharge speed, and causes the image quality deterioration. Therefore, it is necessary to keep the temperature of the ink at the time of ejection as constant as possible. Therefore, in the present invention, it is appropriate that the control range of the ink temperature is ± 5 ° C. of the set temperature, preferably ± 2 ° C. of the set temperature, more preferably ± 1 ° C. of the set temperature.

Next, (b ¹ ) a step of curing the ink composition by irradiating the discharged ink composition with actinic radiation will be described.
The ink composition ejected on the recording medium is cured by irradiation with actinic radiation. This is because the polymerization initiator contained in the ink composition of the present invention is decomposed by irradiation with actinic radiation to generate radicals, acids, bases, and other starting species, and the function of the starting species is polymerization of a radical polymerizable compound. This is because the reaction occurs and is promoted. At this time, if a sensitizing dye is present together with the polymerization initiator in the ink composition, the sensitizing dye in the system absorbs actinic radiation to be in an excited state, and promotes decomposition of the polymerization initiator by contacting with the polymerization initiator. And a more sensitive curing reaction can be achieved.

  Here, α rays, γ rays, electron beams, X rays, ultraviolet rays, visible light, infrared rays, or the like can be used as the active radiation used. Although the peak wavelength of actinic radiation is based also on the absorption characteristic of a sensitizing dye, it is preferable that it is 200-600 nm, for example, it is more preferable that it is 300-450 nm, and it is further more preferable that it is 350-420 nm.

In addition, the polymerization initiation system of the ink composition of the present invention has sufficient sensitivity even with a low output actinic radiation. Accordingly, it is appropriate that the exposure surface illuminance is 10 to 4,000 mW / cm ² , preferably 20 to 2,500 mW / cm ² .

Mercury lamps and gas / solid lasers are mainly used as actinic radiation sources, and mercury lamps and metal halide lamps are widely known as light sources used for curing UV photocurable ink jet recording inks. Yes. However, from the viewpoint of environmental protection, mercury-free is strongly desired, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally. Furthermore, LED (UV-LED) and LD (UV-LD) are small, have a long lifetime, high efficiency, and low cost, and are expected as light sources for photo-curable ink jets.
Further, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. If even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit actinic radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. The actinic radiation source particularly preferred in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength at 350 to 420 nm.
Incidentally, it is preferable that maximum illumination intensity of the LED on a recording medium is 10 to 2,000 mW / cm ^2, more preferably 20 to 1,000 mW / cm ^2, particularly preferably 50 to 800 mW / cm ² .

The ink composition of the present invention is suitably irradiated with such actinic radiation for, for example, 0.01 to 120 seconds, preferably 0.1 to 90 seconds.
Actinic radiation irradiation conditions and a basic irradiation method are disclosed in JP-A-60-132767. Specifically, the light source is provided on both sides of the head unit including the ink ejection device, and the head unit and the light source are scanned by a so-called shuttle method. Irradiation with actinic radiation takes a certain time (for example, 0.01 to 0.5 seconds, preferably 0.01 to 0.3 seconds, more preferably 0.01 to 0.15 seconds) after ink landing. Will be done. In this way, by controlling the time from ink landing to irradiation to an extremely short time, it is possible to prevent the ink that has landed on the recording medium from spreading before curing. Further, since the ink can be exposed to a porous recording medium before the ink penetrates to a deep part where the light source does not reach, residual unreacted monomer can be suppressed, and as a result, odor can be reduced. Therefore, it is preferable.
Further, curing may be completed by another light source that is not driven. WO99 / 54415 pamphlet discloses a method using an optical fiber and a method of applying a collimated light source to a mirror surface provided on the side surface of the head unit and irradiating the recording unit with UV light as an irradiation method. The curing method can also be applied to the ink jet recording method of the present invention.

By adopting the ink jet recording method as described above, 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. By superimposing the inks in the order of low lightness, the irradiation line can easily reach the lower ink, and good curing sensitivity, reduction of residual monomers, reduction of odor, and improvement of adhesion can be expected. In addition, irradiation can be performed by discharging all colors and collectively exposing, but exposure for each color is preferable from the viewpoint of promoting curing.
In this manner, the ink composition of the present invention can form an image on the surface of a recording medium by being cured with high sensitivity by irradiation with actinic radiation.

IV. Lithographic printing plate and production method thereof A lithographic printing plate can be produced by applying and curing the ink composition of the present invention on a hydrophilic support using the inkjet recording method of the present invention.
Hereinafter, a method for producing a lithographic printing plate (a method for producing a lithographic printing plate of the present invention) to which the inkjet recording method of the present invention is applied, and a lithographic printing plate obtained by the method (lithographic printing plate of the present invention) will be described.

The lithographic printing plate of the present invention has a hydrophilic support and a hydrophobic image formed on the hydrophilic support. This method for producing a lithographic printing plate includes the following steps.
(A ²⁾ on a hydrophilic support, a step of discharging the ink composition of the present invention and,
(B ² ) Actinic radiation is applied to the ejected ink composition to cure the ink composition, whereby a hydrophobic image formed by curing the ink composition is formed on the hydrophilic support. It is a process.
That is, a lithographic printing plate can be produced in the same manner as in the ink jet recording method of the present invention except that a support having a hydrophilic surface suitable for a lithographic printing plate support is used as the recording medium. .

Conventionally, a lithographic printing plate is obtained by exposing a so-called PS plate having a structure in which a lipophilic photosensitive resin layer is provided on a hydrophilic support as described above, and solubilizing or curing the exposed portion. It was manufactured by forming an image and dissolving and removing non-image areas.
On the other hand, the lithographic printing plate of the present invention is applied directly to the surface of the hydrophilic support according to the digitized image information by applying the lithographic printing plate production method of the present invention (inkjet recording method of the present invention). A hydrophobic image portion can be formed by injecting an object and curing it. This makes it possible to produce a lithographic printing plate more easily than in the past.

[Hydrophilic support used for lithographic printing plates]
The lithographic printing plate of the present invention has a hydrophilic support and a hydrophobic image formed on the surface of the support by the ink composition of the present invention.

The lithographic printing plate support (recording medium) onto which the ink composition of the present invention is discharged is not particularly limited, and any dimensionally stable plate-like support can be used. However, in consideration of the image quality of the obtained printed matter, the surface is preferably a hydrophilic support.
The material used as the support can be used as the support as it is when it has hydrophilicity, and when it does not have hydrophilicity, the surface thereof may be subjected to water immersion treatment.
Materials used for the support include, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate) Cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper or plastic film laminated or vapor-deposited with the above metals, etc. Is mentioned. A preferable support includes a polyester film and an aluminum plate. Among these, an aluminum plate that has good dimensional stability and is relatively inexpensive is preferable.

  The aluminum plate is a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or a plastic laminated on a thin film of aluminum or aluminum alloy. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is preferably 10% by weight or less. In the present invention, a pure aluminum plate is preferable. However, since completely pure aluminum is difficult to manufacture in terms of refining technology, it may contain a slightly different element. The composition of the aluminum plate is not specified, and a known material can be used as appropriate.

The thickness of the support is preferably 0.1 to 0.6 mm, and more preferably 0.15 to 0.4 mm.
Prior to using the aluminum plate, it is preferable to perform surface treatment such as roughening treatment or anodizing treatment. By the surface treatment, it becomes easy to improve hydrophilicity and secure adhesion between the hydrophobic image and the support. Prior to roughening the aluminum plate, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like for removing rolling oil on the surface is performed as desired.

The surface roughening treatment of the aluminum plate is performed by various methods. For example, mechanical surface roughening treatment, electrochemical surface roughening treatment (surface roughening treatment for dissolving the surface electrochemically), chemical treatment, etc. Surface roughening treatment (roughening treatment that chemically selectively dissolves the surface).
As a method for the mechanical surface roughening treatment, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Also, a transfer method in which the uneven shape is transferred with a roll provided with unevenness in the aluminum rolling step may be used.
Examples of the electrochemical surface roughening treatment include a method in which an alternating current or a direct current is used in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Another example is a method using a mixed acid as described in JP-A-54-63902.
The surface-roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide, sodium hydroxide or the like, if necessary, further neutralized, and if desired, wear resistant. In order to increase the anodic oxidation treatment.

As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.
The conditions for anodizing treatment vary depending on the electrolyte used and cannot be specified in general. In general, however, the electrolyte concentration is 1 to 80% by weight solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / day. dm ² , voltage 1 to 100 V, and electrolysis time 10 seconds to 5 minutes are preferable. The amount of the anodized film formed is preferably from 1.0 to 5.0 g / m ^2, and more preferably 1.5 to 4.0 g / m ^2. Within this range, good printing durability and good scratch resistance of the non-image area of the lithographic printing plate can be obtained, which is preferable.

  As the support used in the present invention, a substrate that has been surface-treated as described above and has an anodized film may be used as it is. However, the adhesion to the hydrophobic image, the hydrophilicity, the stain resistance, etc. are further improved. In order to improve, if necessary, the micropore enlargement treatment or sealing treatment of the anodized film described in JP-A-2001-253181 and JP-A-2001-322365, and a hydrophilic compound are contained. A surface hydrophilization treatment immersed in an aqueous solution can be selected as appropriate. Of course, the enlargement process and the sealing process are not limited to those described above, and any conventionally known method can be performed.

(Sealing treatment)
Sealing treatment includes vapor sealing, single treatment with zirconic fluoride, treatment with an aqueous solution containing an inorganic fluorine compound such as treatment with sodium fluoride, vapor sealing with addition of lithium chloride, sealing with hot water. Hole processing is also possible.
Among these, a sealing treatment with an aqueous solution containing an inorganic fluorine compound, a sealing treatment with water vapor, and a sealing treatment with hot water are preferable. Each will be described below.

-Sealing treatment with aqueous solution containing inorganic fluorine compound-
As the inorganic fluorine compound used for the sealing treatment with an aqueous solution containing an inorganic fluorine compound, a metal fluoride is preferably exemplified.
Specifically, for example, sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, sodium fluoride zirconate, potassium fluoride zirconate, sodium fluoride titanate, potassium fluoride titanate, zircon fluoride Ammonium acid, ammonium fluoride titanate, potassium fluoride titanate, fluorinated zirconate, fluorinated titanate, hexafluorosilicic acid, nickel fluoride, iron fluoride, phosphor fluoride, ammonium fluoride phosphate It is done. Among these, sodium fluorinated zirconate, sodium fluorinated titanate, fluorinated zirconic acid, and fluorinated titanic acid are preferable.

The concentration of the inorganic fluorine compound in the aqueous solution is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more in terms of sufficiently sealing the micropores of the anodized film. Further, in terms of stain resistance, the content is preferably 1% by weight or less, and more preferably 0.5% by weight or less.
It is preferable that the aqueous solution containing an inorganic fluorine compound further contains a phosphate compound. When the phosphate compound is contained, the hydrophilicity of the surface of the anodized film is improved, so that on-machine developability and stain resistance can be improved, which is preferable.

Suitable examples of the phosphate compound include phosphates of metals such as alkali metals and alkaline earth metals.
Specifically, for example, zinc phosphate, aluminum phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, dihydrogen phosphate Potassium, dipotassium hydrogen phosphate, calcium phosphate, sodium ammonium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, ferrous phosphate, ferric phosphate, sodium dihydrogen phosphate, sodium phosphate, hydrogen phosphate Disodium, lead phosphate, diammonium phosphate, calcium dihydrogen phosphate, lithium phosphate, phosphotungstic acid, ammonium phosphotungstate, sodium phosphotungstate, ammonium phosphomolybdate, sodium phosphomolybdate, sodium phosphite , Tripolyphosphate Potassium, and sodium pyrophosphate. Among these, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate are preferable.
The combination of the inorganic fluorine compound and the phosphate compound is not particularly limited, but the aqueous solution contains at least sodium zirconate fluoride as the inorganic fluorine compound and contains at least sodium dihydrogen phosphate as the phosphate compound. It is preferable.
The concentration of the phosphate compound in the aqueous solution is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, in terms of improvement in on-press developability and stain resistance. In terms of solubility, it is preferably 20% by weight or less, and more preferably 5% by weight or less.

The ratio of each compound in the aqueous solution is not particularly limited, but the weight ratio of the inorganic fluorine compound and the phosphate compound is preferably 1/200 to 10/1, and preferably 1/30 to 2/1. Is more preferable.
The temperature of the aqueous solution is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, 100 ° C. or lower, more preferably 80 ° C. or lower.
The aqueous solution preferably has a pH of 1 or more, more preferably has a pH of 2 or more, preferably has a pH of 11 or less, and more preferably has a pH of 5 or less.
A method for sealing with an aqueous solution containing an inorganic fluorine compound is not particularly limited, and examples thereof include an immersion method and a spray method. These may be used alone or in combination, or may be used in combination of two or more.
Of these, the dipping method is preferred. When processing using the dipping method, the processing time is preferably 1 second or longer, more preferably 3 seconds or longer, 100 seconds or shorter, and 20 seconds or shorter. More preferred.

-Sealing treatment with water vapor-
Examples of the sealing treatment with water vapor include a method of bringing pressurized or normal pressure water vapor into contact with the anodized film continuously or discontinuously.
The temperature of the water vapor is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 105 ° C. or lower.
The pressure of the water vapor is preferably in the range (1.008 × 10 ^{5 to} 1.043 × 10 ⁵ Pa) from (atmospheric pressure−50 mmAq) to (atmospheric pressure + 300 mmAq).
The time for which the water vapor is contacted is preferably 1 second or longer, more preferably 3 seconds or longer, 100 seconds or shorter, and more preferably 20 seconds or shorter.

-Sealing treatment with hot water-
Examples of the sealing treatment with hot water include a method of immersing an aluminum plate on which an anodized film is formed in hot water.
The hot water may contain an inorganic salt (for example, phosphate) or an organic salt.
The temperature of the hot water is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 100 ° C. or lower.
Further, the time of immersion in hot water is preferably 1 second or longer, more preferably 3 seconds or longer, 100 seconds or shorter, more preferably 20 seconds or shorter.

  As the hydrophilization treatment for the support in the present invention, U.S. Pat. Nos. 2,714,066, 3,181,461, 3,280,734, and 3,902,734 are each used. There are alkali metal silicate methods as described in the specification. In this method, the support is immersed in an aqueous solution such as sodium silicate or electrolytically treated. In addition, the treatment with potassium zirconate fluoride described in JP-B 36-22063, U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689, And a method of treating with polyvinylphosphonic acid as described in each specification of No.272.

  In the present invention, the support preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to a hydrophobic image, good printing durability and good stain resistance are obtained, which is preferable.

(A ² ) Step of discharging the ink composition of the present invention onto the hydrophilic support First, the ink composition of the present invention is discharged onto the hydrophilic support. In this step, a conventionally known ink jet recording apparatus can be used as described in the ink jet recording method. In addition, when ink is ejected using this ink jet recording apparatus, the preferable ranges of the temperature and viscosity of the ink and the control methods thereof are also the same.

(B ²⁾ the ink composition ejected to actinic radiation by irradiating, by curing the ink composition, the surface of the step hydrophilic supports the ink composition forms a hydrophobic image formed by curing The ink composition discharged above is cured by irradiation with actinic radiation. The details of the curing mechanism are the same as those described in the ink jet recording method. Further, the actinic radiation source used for curing the ink composition or the preferable irradiation condition thereof is also the same as described in the ink jet recording method.

  Through the above steps, a hydrophobic image formed by curing the ink composition of the present invention is formed on the surface of the hydrophilic support, and a lithographic printing plate is obtained.

In this way, by applying the inkjet recording method of the present invention to produce a lithographic printing plate, the dot diameter of the landed ink is constant even for various lithographic printing plate supports having different surface wettability. As a result, a hydrophobic image can be accurately formed.
Further, as described above, the ink composition of the present invention can be cured with high sensitivity by actinic radiation, and can form a hydrophobic region (hydrophobic image) excellent in adhesion to the support and film quality.
For these reasons, the planographic printing plate of the present invention has high image quality and excellent printing durability.
In addition, it cannot be overemphasized that the ink composition of this invention is useful not only as an image part of such a lithographic printing plate but as a generally used ink composition.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the following description, “parts” means “parts by weight” unless otherwise specified.

The materials used in the present invention are as shown in the following (A) to (H).
(A) Curable composition / Exemplary compound M-5 (1-naphthyl acrylate)
・ Exemplary compound M-8 (Naphthalene-2,6-diacrylate)
-Exemplary compound M-12 (1-naphthyl methacrylate)
Exemplified compound M-17 (1-naphthylethyl acrylate)
Exemplified compound M-25 (1-naphthylethylacrylamide)
(B) N-vinyl lactams / N-vinyl caprolactam (manufactured by Aldrich)
(C) Polymerization initiator / Lucirin TPO (photoinitiator, manufactured by BASF)
・ Benzophenone (Photoinitiator, Wako Pure Chemical Industries, Ltd.)
・ Irgacure 184 (Photoinitiator, manufactured by Ciba Specialty Chemicals)
(D) Colorant / Irgalite Blue GLVO (Cyan Pigment, Ciba Specialty Chemicals)
・ CINQUASIA MAGENTA RT-335 D (Magenta pigment, manufactured by Ciba Specialty Chemicals)
・ NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant)
・ SPECIAL BLACK 250 (Black pigment, manufactured by Ciba Specialty Chemicals)
・ KRONOS2300 (white pigment, manufactured by KRONOS)
(E) Dispersant: Solsperse 32000 (Abyssia)
(F) Surfactant • Byk 307 (surfactant, manufactured by BYK Chemie)
(G) Polymerizable compound / NK ester AMP-10G (phenoxyethyl acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ Tetrahydrofurfuryl acrylate (ALDRICH)
Actilane 421 (propoxylated neopentyl glycol diacrylate, manufactured by Akcros)
(H) Other components: Firstcure ST-1 (polymerization inhibitor, manufactured by Chem First)
-Firstcure ITX (sensitizer, manufactured by Chem First)

(Adjustment of cyan mill base A)
(D) Irgalite Blue GLVO 300 parts (G) Actylene 421 (Akcros acrylate monomer) 500 parts (E) Solsperse 32000 200 parts were stirred and mixed to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Adjustment of magenta mill base B)
(D) CINQUASIA MAGENTA RT-335 D 300 parts (G) Actilane 421 (Akcros acrylate monomer 300 parts (E) Solsperse 32000 400 parts) was stirred and mixed to obtain a pigment ink. In a mill M50 (manufactured by Eiger), dispersion was performed for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Adjustment of yellow mill base C)
(D) 300 parts of NOVOPERM YELLOW H2G (G) 300 parts of Actirane 421 (Akcros acrylate monomer) (E) 400 parts of Solsperse 32000 were stirred and mixed to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Adjustment of Black Mill Base D)
(D) 300 parts of SPECIAL BLACK 250 (G) Actylene 421 (Akcros acrylate monomer) 300 parts (E) Solsperse 32000 400 parts were stirred and mixed to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 7 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Adjustment of white mill base E)
(D) 500 parts of KRONOS2300 (G) 400 parts of NK ester AMP-10G (E) 100 parts of Solsperse 32000 were stirred and mixed to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Inkjet image recording method)
Next, recording on a recording medium was performed using an inkjet recording experimental apparatus having a piezoelectric inkjet nozzle. The ink supply system was composed of an original tank, supply piping, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head, and heat insulation and heating were performed from the ink supply tank to the inkjet head portion. Temperature sensors were provided near the ink supply tank and the nozzles of the ink jet head, respectively, and temperature control was performed so that the nozzle portions were always 45 ° C. ± 2 ° C. The piezo-type inkjet head was driven so that 8 to 30 pl multi-size dots could be ejected at a resolution of 720 × 720 dpi. After landing, UV light was condensed to an exposure surface illuminance of 1,630 mW / cm ² , and the exposure system, main scanning speed, and ejection frequency were adjusted so that irradiation started 0.1 seconds after ink landed on the recording medium. . Further, the integrated light amount irradiated to the image was set to 1,500 mJ / cm ² . As an ultraviolet lamp, a HAN250NL high-cure mercury lamp (manufactured by GS Yuasa Corporation) was used. In the present invention, dpi represents the number of dots per 2.54 cm. As a recording medium, an ester film E5000 (film thickness 125 μm, manufactured by Toyobo Co., Ltd.) was used.

(Curability evaluation method)
In accordance with the inkjet recording method, a solid image having an average film thickness of 12 μm was drawn, and the degree of stickiness of the image was evaluated by palpation on the image surface after ultraviolet irradiation. The curability was evaluated according to the following criteria.
3: No stickiness in the image.
2: The image is slightly sticky.
1: Uncured ink is not hardened to transfer to the hand.

(Flexibility evaluation method: Bending test)
In this example, a bending test was performed as a method for evaluating the flexibility of the cured film.

  According to the inkjet image recording method, an ester film E5000 (film thickness 125 μm, manufactured by Toyobo Co., Ltd.) was used as a recording medium, and three solid images having an average film thickness of 12 μm, 24 μm, and 36 μm were drawn. In the bending test, the recording material on which the image was formed was bent once at 25 ° C. and evaluated by the presence or absence of cracks in the image area. In general, when the average film thickness is increased, distortion applied to the image portion when the image portion is bent increases, and cracks are likely to occur. That is, by testing whether the image portion is cracked with a thicker film thickness, a measure of flexibility can be obtained.

The evaluation criteria are as follows.
4: In all samples having an average film thickness of 12 μm, 24 μm, and 36 μm, no cracks occur in the bent portion of the image portion.
3: Cracks do not occur in samples having an average film thickness of 12 μm and 24 μm, but cracks occur in a bent portion of the image portion in a sample having an average film thickness of 36 μm.
2: Cracks do not occur in samples having an average film thickness of 12 μm, but cracks occur in the bent portions of the image portion in samples having an average film thickness of 24 μm and 36 μm.
1: In all samples having an average film thickness of 12 μm, 24 μm, and 36 μm, cracks occur in the bent portion of the image portion.

(Viscosity measurement method)
The viscosity in this example was measured using a B-type viscometer: Brookfield LVDV-I (manufactured by Brookfield) at 25 ° C. and a rotor rotation speed of 20 rpm.

(Example 1)
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 20 mPa · s.
(Cyan ink composition)
(D) (E) Cyan Mill Base A 6.0 parts (A) M-5 (1-naphthyl acrylate) 35.4 parts (B) N-vinylcaprolactam 25.0 parts (G) NK ester AMP -10G 20.0 parts-(H) Firstcure ST-1 0.05 parts-(C) Lucirin TPO (BASF photoinitiator) 8.5 parts-(C) Benzophenone (photoinitiator) 3.0 parts -(C) Irgacure 184 (CSC photoinitiator) 2.0 parts-(F) Byk 307 (BYK Chemie antifoam) 0.05 parts

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

(Example 2)
The following components were stirred with a high-speed water-cooled stirrer to obtain a magenta UV inkjet ink. The viscosity was 22 mPa · s.
(Magenta ink composition)
(D) (E) Magenta mill base B 12.0 parts (A) M-5 (1-naphthyl acrylate) 35.4 parts (B) N-vinylcaprolactam 25.0 parts (G) NK ester AMP -10G 14.0 parts-(H) Firstcure ST-1 0.05 parts-(C) Lucirin TPO (BASF photoinitiator) 8.5 parts-(C) Benzophenone (photoinitiator) 3.0 parts -(C) Irgacure 184 (CSC photoinitiator) 2.0 parts-(F) Byk 307 (BYK Chemie antifoam) 0.05 parts

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

(Example 3)
The following components were stirred with a high-speed water-cooled stirrer to obtain a yellow UV inkjet ink. The viscosity was 22 mPa · s.
(Yellow color ink composition)
(D) (E) Yellow mill base B 12.0 parts (A) M-5 (1-naphthyl acrylate) 35.4 parts (B) N-vinylcaprolactam 25.0 parts (G) NK ester AMP -10G 14.0 parts-(H) Firstcure ST-1 0.05 parts-(C) Lucirin TPO (BASF photoinitiator) 8.5 parts-(C) Benzophenone (photoinitiator) 3.0 parts -(C) Irgacure 184 (CSC photoinitiator) 2.0 parts-(F) Byk 307 (BYK Chemie antifoam) 0.05 parts

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

Example 4
The following components were stirred with a high-speed water-cooled stirrer to obtain a black UV inkjet ink. The viscosity was 20 mPa · s.
(Black ink composition)
(D) (E) Black mill base A 6.0 parts (A) M-5 (1-naphthyl acrylate) 35.4 parts (B) N-vinylcaprolactam 25.0 parts (G) NK ester AMP -10G 20.0 parts-(H) Firstcure ST-1 0.05 part-(C) Lucirin TPO (BASF photoinitiator) 8.5 parts-(C) Benzophenone (photoinitiator) 3.0 parts -(C) Irgacure 184 (CSC photoinitiator) 2.0 parts-(F) Byk 307 (BYK Chemie antifoam) 0.05 parts

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

(Example 5)
The following components were stirred with a high-speed water-cooled stirrer to obtain a white UV inkjet ink. The viscosity was 24 mPa · s.
(White ink composition)
(D) (E) White mill base E 31.0 parts (A) M-5 (1-naphthyl acrylate) 26.4 parts (B) N-vinylcaprolactam 18.0 parts (G) NK ester AMP -10G 10.0 parts-(H) Firstcure ST-1 0.05 parts-(C) Lucirin TPO (BASF photoinitiator) 8.5 parts-(C) Benzophenone (photoinitiator) 3.0 parts -(C) Irgacure 184 (CSC photoinitiator) 2.0 parts-(F) Byk 307 (BYK Chemie antifoaming agent) 0.05 parts-Firstcure ITX 1.0 part

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

(Example 6)
The following components were stirred with a high-speed water-cooled stirrer to obtain a clear UV inkjet ink. The viscosity was 17 mPa · s.
(Clear color ink composition)
-(A) M-5 (1-naphthyl acrylate) 40.4 parts-(B) N-vinylcaprolactam 25.0 parts-(G) NK ester AMP-10G 21.0 parts-(H) Firstcure ST-1 0.05 parts (C) Lucirin TPO (BASF photoinitiator) 8.5 parts (C) benzophenone (photoinitiator) 3.0 parts (C) Irgacure 184 (CSC photoinitiator) 2.0 parts. (F) Byk 307 (defoamer manufactured by BYK Chemie) 0.05 part

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

(Example 7)
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 24 mPa · s.
(D) (E) Cyan Mill Base A 6.0 parts (A) M-5 (1-naphthyl acrylate) 50.4 parts (G) NK ester AMP-10G 30.0 parts (H) Firstcure ST -1 0.05 parts · (C) Lucirin TPO (BASF photoinitiator) 8.5 parts · (C) Benzophenone (photoinitiator) 3.0 parts · (C) Irgacure 184 (CSC photoinitiator) Agent) 2.0 parts (F) Byk 307 (antifoaming agent manufactured by BYK Chemie) 0.05 parts

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

(Example 8)
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 19 mPa · s.
(Cyan ink composition)
(D) (E) Cyan Mill Base A 6.0 parts (A) M-12 (1-naphthyl methacrylate) 15.4 parts (B) N-vinylcaprolactam 25.0 parts (G) NK ester AMP -10G 40.0 parts-(H) Firstcure ST-1 0.05 parts-(C) Lucirin TPO (BASF photoinitiator) 8.5 parts-(C) Benzophenone (photoinitiator) 3.0 parts -(C) Irgacure 184 (CSC photoinitiator) 2.0 parts-(F) Byk 307 (BYK Chemie antifoam) 0.05 parts

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

Example 9
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 20 mPa · s.
(Cyan ink composition)
(D) (E) Cyan Mill Base A 6.0 parts (A) M-17 (1-naphthylethyl acrylate) 20.4 parts (B) N-vinylcaprolactam 25.0 parts (G) NK ester AMP-10G 35.0 parts-(H) Firstcure ST-1 0.05 parts-(C) Lucirin TPO (BASF photoinitiator) 8.5 parts-(C) Benzophenone (photoinitiator) 3.0 Parts (C) Irgacure 184 (CSC photoinitiator) 2.0 parts (F) Byk 307 (BYK Chemie defoamer) 0.05 parts

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

(Example 10)
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 22 mPa · s.
(Cyan ink composition)
-(D) (E) Cyan Mill Base A 6.0 parts-(A) M-25 (1-naphthylethylacrylamide) 12.4 parts-(B) N-vinyl caprolactam 25.0 parts-(G) NK ester AMP-10G 43.0 parts-(H) Firstcure ST-1 0.05 part-(C) Lucirin TPO (BASF photoinitiator) 8.5 parts-(C) Benzophenone (photoinitiator) 3.0 Parts (C) Irgacure 184 (CSC photoinitiator) 2.0 parts (F) Byk 307 (BYK Chemie defoamer) 0.05 parts

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

(Example 11)
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 18 mPa · s.
(Cyan ink composition)
-(D) (E) Cyan mill base A 6.0 parts-(A) M-5 (1-naphthyl acrylate) 35.4 parts-(B) N-vinylcaprolactam 25.0 parts-(G) Tetrahydrofurfuryl Acrylate 20.0 parts · (H) Firstcure ST-1 0.05 parts · (C) Lucirin TPO (BASF photoinitiator) 8.5 parts · (C) Benzophenone (photoinitiator) 3.0 parts (C) Irgacure 184 (CSC photoinitiator) 2.0 parts (F) Byk 307 (BYK Chemie antifoam) 0.05 parts

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

Example 12
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 18 mPa · s.
(Cyan ink composition)
(D) (E) Cyan Mill Base A 6.0 parts (A) M-8 (Naphthalene 2,6-diacrylate) 10.4 parts (B) N-vinylcaprolactam 25.0 parts (G) Tetrahydrofurfuryl acrylate 45.0 parts · (H) Firstcure ST-1 0.05 parts · (C) Lucirin TPO (BASF photoinitiator) 8.5 parts · (C) Benzophenone (photoinitiator) 0 part (C) Irgacure 184 (CSC photoinitiator) 2.0 part (F) Byk 307 (BYK Chemie antifoam) 0.05 part

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

(Example 13)
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 20 mPa · s.
(Cyan ink composition)
(D) (E) Cyan Mill Base A 6.0 parts (A) M-5 (1-naphthyl acrylate) 34.4 parts (B) N-vinylcaprolactam 25.0 parts (G) NK ester AMP -10G 20.0 parts-(H) Firstcure ST-1 0.05 parts-(C) Lucirin TPO (BASF photoinitiator) 8.5 parts-(C) Benzophenone (photoinitiator) 3.0 parts -(C) Irgacure 184 (CSC photoinitiator) 2.0 parts-(F) Byk 307 (BYK Chemie antifoaming agent) 0.05 parts-Firstcure ITX 1.0 part

(Evaluation of ink)
The UV light after landing is condensed to an exposure surface illuminance of 350 mW / cm ² , and the integrated light quantity irradiated to the image is 1,500 mJ / cm ^{2. The} lamp is a UV-LED lamp: NCCU033 (Nichia Corporation) Inkjet image recording was carried out by the same method as that for inkjet recording except using the above-mentioned. The evaluation results of curability and flexibility are shown in Table 1.

(Example 14)
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 20 mPa · s.
(Cyan ink composition)
(D) (E) Cyan Mill Base A 6.0 parts (A) M-5 (1-naphthyl acrylate) 34.4 parts (B) N-vinylcaprolactam 25.0 parts (G) NK ester AMP -10G 20.0 parts-(H) Firstcure ST-1 0.05 parts-(C) Lucirin TPO (BASF photoinitiator) 8.5 parts-(C) Benzophenone (photoinitiator) 3.0 parts -(C) Irgacure 184 (CSC photoinitiator) 2.0 parts-(F) Byk 307 (BYK Chemie antifoaming agent) 0.05 parts-Firstcure ITX 1.0 part

(Evaluation of ink)
The UV light after landing is condensed to an exposure surface illuminance of 450 mW / cm ² , and the integrated light amount irradiated to the image is set to 8,000 mJ / cm ^2. High-pressure mercury lamp: Inkjet image recording was performed by the same method as the above inkjet recording except that SHP270W (manufactured by Phoenix Electric) was used. There was no missing dot in the obtained image, and a bright image with a thickness of 12 μm could be drawn. The evaluation results of curability and flexibility are shown in Table 1.

(Comparative Example 1)
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 15 mPa · s.
(Cyan ink composition)
(D) (E) cyan mill base A 6.0 parts (A) N-vinylcaprolactam 25.0 parts (G) NK ester AMP-10G 55.4 parts (H) Firstcure ST-1 0.05 Part (C) Lucirin TPO (BASF photoinitiator) 8.5 part (C) Benzophenone (photoinitiator) 3.0 part (C) Irgacure 184 (CSC photoinitiator) 2.0 Parts (F) Byk 307 (defoamer manufactured by BYK Chemie) 0.05 parts

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

(Comparative Example 2)
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 15 mPa · s.
(Cyan ink composition)
-(D) (E) Cyan Mill Base A 6.0 parts-(G) NK Ester AMP-10G 80.4 parts-(H) Firstcure ST-1 0.05 parts-(C) Lucirin TPO (made by BASF) Initiator) 8.5 parts (C) Benzophenone (photoinitiator) 3.0 parts (C) Irgacure 184 (CSC photoinitiator) 2.0 parts (F) Byk 307 (BYK Chemie) Defoamer) 0.05 parts

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

(Comparative Example 3)
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 16 mPa · s.
(Cyan ink composition)
(D) (E) Cyan mill base A 6.0 parts (G) NK ester AMP-10G 30.4 parts (G) Actylene 421 50.0 parts (H) Firstcure ST-1 0.05 parts C) Lucirin TPO (BASF Photoinitiator) 8.5 parts, (C) Benzophenone (Photoinitiator) 3.0 parts, (C) Irgacure 184 (CSC Photoinitiator) 2.0 parts, ( F) Byk 307 (antifoaming agent manufactured by BYK Chemie) 0.05 parts

(Evaluation of ink)
Inkjet image recording was performed using the obtained ink composition. The evaluation results of curability and flexibility are shown in Table 1.

Hereinafter, Table 1 shows the evaluation results of Examples 1 to 14 and Comparative Examples 1 to 3.
Abbreviations are as follows. PEA is phenoxyethyl acrylate (NK ester AMP-10G, manufactured by Shin-Nakamura Chemical Co., Ltd.), THFA is tetrahydrofurfuryl acrylate (manufactured by ALDRICH), and NPGPODA is propoxylated neopentyl glycol diacrylate (Actilane 421, manufactured by Akcros). Show.

(Example 15)
(Production of support)
Si: 0.06 wt%, Fe: 0.30 wt%, Cu: 0.025 wt%, Mn: 0.001 wt%, Mg: 0.001 wt%, Zn: 0.001 wt%, Ti: It contains 0.03% by weight, and the balance is prepared using Al and an inevitable impurity aluminum alloy. After the molten metal treatment and filtration, an ingot having a thickness of 500 mm and a width of 1200 mm is obtained by a DC casting method. Produced. After the surface was shaved with a chamfering machine with an average thickness of 10 mm, it was kept soaked at 550 ° C. for about 5 hours, and when the temperature dropped to 400 ° C., rolling with a thickness of 2.7 mm using a hot rolling mill A board was used. Furthermore, after performing heat processing using a continuous annealing machine at 500 degreeC, it finished by cold rolling to 0.24 mm in thickness, and obtained the aluminum plate of JIS1050 material. The obtained aluminum had an average crystal grain size with a minor axis of 50 μm and a major axis of 300 μm. After making this aluminum plate into width 1030mm, it used for the surface treatment shown below and produced the aluminum support body.

(surface treatment)
In the surface treatment, the following various treatments (i) to (x) were continuously performed. In addition, after each process and water washing, the liquid draining was performed with the nip roller.

(I) Mechanical surface roughening treatment While supplying a suspension of a polishing agent (pumice) having a specific gravity of 1.12 and water as a polishing slurry liquid to the surface of the aluminum plate, a mechanical roughening is performed by a rotating nylon brush. Surface treatment was performed. The average particle size of the abrasive was 30 μm, and the maximum particle size was 100 μm. The material of the nylon brush was 6 · 10 nylon, the hair length was 45 mm, and the hair diameter was 0.3 mm. The nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers (φ200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.

(Ii) Alkaline etching treatment The aluminum plate obtained above was subjected to an etching treatment by spraying using an aqueous solution having a caustic soda concentration of 2.6 wt%, an aluminum ion concentration of 6.5 wt%, and a temperature of 70 ° C. / M ² dissolved. Then, water washing by spraying was performed.

(Iii) Desmut treatment Desmut treatment was performed by spraying with a 1% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by weight of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut treatment was a waste liquid from a process of performing an electrochemical surface roughening treatment using alternating current in a nitric acid aqueous solution.

(Iv) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 10.5 g / L aqueous solution of nitric acid (containing 5 g / L of aluminum ions and 0.007% by weight of ammonium ions) at a liquid temperature of 50 ° C. AC power supply waveform is 0.8 msec until the current value reaches the peak from zero, duty ratio is 1: 1, and trapezoidal rectangular wave alternating current is used to perform electrochemical surface roughening treatment with the carbon electrode as the counter electrode. went. Ferrite was used for the auxiliary anode.

The current density was 30 A / dm ² at the peak current value, and the amount of electricity was 220 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Then, water washing by spraying was performed.

(V) Alkaline etching treatment An aluminum plate was subjected to an etching treatment by spraying at 32 ° C. using an aqueous solution having a caustic soda concentration of 26% by weight and an aluminum ion concentration of 6.5% by weight, and the aluminum plate was dissolved at 0.50 g / m ² . Removes the smut component mainly composed of aluminum hydroxide that was generated when electrochemical roughening treatment was performed using the alternating current of the previous stage, and also melted the edge part of the generated pit to smooth the edge part. did. Then, water washing by spraying was performed.

(Vi) Desmut treatment Desmut treatment was performed by spraying with a 15% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (containing 4.5% by weight of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used in the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in the nitric acid aqueous solution.

(Vii) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a hydrochloric acid 5.0 g / L aqueous solution (containing 5 g / L of aluminum ions) at a temperature of 35 ° C. The AC power supply waveform has a time until the current value reaches a peak from zero, 0.8 msec, a duty ratio of 1: 1, and a trapezoidal trapezoidal wave alternating current is used to perform an electrochemical surface roughening treatment using a carbon electrode as a counter electrode. went. Ferrite was used for the auxiliary anode.

The current density was 25 A / dm ² at the peak current value, and the amount of electricity was 50 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. Then, water washing by spraying was performed.

(Viii) Alkaline etching treatment The aluminum plate was sprayed at 32 ° C. using an aqueous solution having a caustic soda concentration of 26% by weight and an aluminum ion concentration of 6.5% by weight to dissolve the aluminum plate by 0.12 g / m ² . Removes the smut component mainly composed of aluminum hydroxide that was generated when electrochemical roughening treatment was performed using the alternating current of the previous stage, and also melted the edge part of the generated pit to smooth the edge part. did. Then, water washing by spraying was performed.

(Ix) Desmut treatment The desmut treatment was performed by spraying with an aqueous solution of sulfuric acid having a concentration of 25% by weight (containing 0.5% by weight of aluminum ions) at a temperature of 60 ° C., and then washed with water by spraying.

(X) Anodizing treatment Anodizing treatment was performed using an anodizing apparatus (first and second electrolysis section length 6 m, first and second feeding section length 3 m, first and second feeding section length 2.4 m each). It was. Sulfuric acid was used as the electrolytic solution supplied to the first and second electrolysis units. All electrolytes had a sulfuric acid concentration of 50 g / L (containing 0.5% by weight of aluminum ions) and a temperature of 20 ° C. Then, water washing by spraying was performed. The final oxide film amount was 2.7 g / m ² .

(Hydrophilic layer by silicate)
The support thus treated was immersed in a No. 3 sodium silicate aqueous solution at 70 ° C. for 13 seconds, and then washed with water and dried. Using a surface roughness meter of surfcom type 575A manufactured by Tokyo Seimitsu Co., Ltd., the surface roughness Ra was measured as an average of 5 repetitions with a cutoff of 0.8 mm and a measurement length of 3 mm. there were.

(Ink receiving layer)
The ink receiving layer coating solution having the composition described in Table 2 was applied with a wire bar and dried at 80 ° C. for 15 seconds to form a coating film, thereby obtaining a support on which the ink receiving layer was formed. The coating amount of the ink receiving layer was 20 mg / m ² .

(Inkjet recording)
The same ink composition as in Example 1 was subjected to ink jet recording on the support on which the ink receiving layer was formed as follows.
When drawing, a shear mode piezo head (CA3 manufactured by Toshiba Tec Corporation: minimum droplet volume 6 pL, number of nozzles 318, nozzle density 150 nozzles / 25.4 mm) was used as a head, and one of the heads was placed on a movable carriage. The head-scanning drawing device installed in is used. Ink introduced into an ink tank having a capacity of 2 L having a pressure reducing function, degassed to −40 kPa, and degassed dissolved gas in the ink, was passed through a static pressure type pressure control tank (capacity 50 mL) with an inner diameter of 2 mm. The head was introduced into the Teflon (registered trademark) flexible tube. By controlling the height of the hydrostatic pressure tank with respect to the head, the internal pressure of the head is adjusted to -6.6 kPa, and the meniscus shape at the nozzle portion of the head is controlled. The head was circulated with a water circulation temperature controller (SCINICS CH-201) so that the ink temperature in the head was 45 ° C. The head drive voltage was 24 V, and ejection was performed in an 8-value multi-drop mode or a binary mode. The dot formation frequencies are 4.8 kHz and 12 kHz, respectively. In the 8-value multi-drop mode, the drawing pitch is 600 dpi (head scan speed 203 mm / s) × recording medium conveyance direction 600 dpi in the binary mode, and the head scanning direction 1200 dpi (head scan speed 254 mm / s) × recording medium conveyance direction in the binary mode. That is, bidirectional interlaced printing of the head was performed while sequentially moving the recording medium. Further, as the head cleaning means, there was a wiping means made of a non-woven cloth that wiped without contact with the nozzle plate of the head, and cleaning was carried out as appropriate.

(exposure)
After ink jetting, 1 second to 60 seconds later, exposure was performed with a high-pressure mercury lamp 3 kW to prepare a lithographic printing plate.

(Image evaluation)
It was 35 micrometers when the diameter of the obtained image dot was measured using the optical microscope.

(Print test)
The obtained lithographic printing plate is manufactured by Dainippon Ink & Chemicals, Inc. using IF102 (Fuji Photo Film Co., Ltd.) dampening solution with a Lislon printing machine manufactured by Komori Corporation without gumming. DIC-GEOS (N) black ink was used for printing. It was confirmed that 10,000 or more high-quality prints free from white spots in the image area and stains in the non-image area were obtained, and the printing durability was at a level causing no problem in practice.

Claims (10)

(A) A curable composition comprising an ethylenically unsaturated compound represented by the following formula (1).

In the above formula (1),
R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms,
X ₁ is a single bond, an ether bond (—O—), an ester bond (—C (O) O— or —OC (O) —), an amide bond (—C (O) NH—, or —NHC ( O)-), a carbonyl bond (—C (O) —), an optionally substituted alkylene group having 20 or less carbon atoms, or a divalent linking group obtained by combining these.
R ₂ is a polycyclic aromatic group, which may have a halogen atom, a hydroxyl group, an amino group, a siloxane group, or a substituent having 30 or less carbon atoms,
m represents an integer of 1 to 6, and when m is 2 or more, m R ₁ and X ₁ present in m ethylenically unsaturated bonds may be the same or different and are independent of each other. It can be selected from the above specific examples.   An ink composition comprising the curable composition according to claim 1.   The ink composition according to claim 2, wherein the polycyclic aromatic group is a naphthyl group.   The ink composition according to claim 2 or 3, comprising (B) N-vinyl lactams.   (B) The ink composition according to any one of claims 2 to 4, wherein the N-vinyllactam is N-vinylcaprolactam.   The ink composition according to any one of claims 2 to 5, which is for inkjet recording. (A ¹⁾ onto a recording medium, a step of discharging the ink composition according to any one of claims 2-6 and,
(B ¹ ) An inkjet recording method comprising a step of irradiating the discharged ink composition with actinic radiation to cure the ink composition. The actinic radiation is ultraviolet light emitted by a light emitting diode that generates ultraviolet light having an emission peak wavelength in the range of 350 to 420 nm and a maximum illuminance on the recording medium surface of 10 to 2,000 mW / cm ^2. The inkjet recording method according to claim 7.   Printed matter recorded by the ink jet recording method according to claim 7 or 8. (A ²⁾ on a hydrophilic support, a step of discharging the ink composition according to any one of claims 2-6 and,
(B ² ) Actinic radiation is applied to the ejected ink composition to cure the ink composition, whereby a hydrophobic image formed by curing the ink composition is formed on the hydrophilic support. A process for producing a lithographic printing plate comprising a step.