JP2007246727A - Radiation-sensitive composition, ink composition, ink jet recording method, printed article, lithographic plate, and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition which is highly sensitively cured by the irradiation of active radiations and can suitably be used as an active composition excellent in heat stability, and to provide an ink jet recording method using the radiation-sensitive composition. <P>SOLUTION: This radiation-sensitive composition is characterized by containing at least one compound represented by formula (I) [X<SP>-</SP>is monovalent counter anion; Y<SB>1</SB>to Y<SB>4</SB>groups are each independently a monovalent substituent, or may be bound to each other to form a ring; R groups are each a substituent on the naphthalene ring, and two or more of the R groups may be bound to each other to form a ring; (n) is the number of the substituents R, and is an integer of 0 to 6]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a radiation-sensitive composition that changes its properties upon reaction with actinic radiation, and more particularly to image forming materials such as three-dimensional stereolithography, holography, lithographic printing plates, color proofs, photoresists, and color filters, The present invention relates to a curable composition that can be used for photo-curing resin material applications such as ink, paint, and adhesive.
The present invention also provides a radiation sensitive composition that can be suitably used as an ink composition, an ink jet recording method using the composition, a printed material, and a lithographic printing plate obtained using the radiation sensitive composition. The present invention also relates to a method for producing a lithographic printing plate. Specifically, an ink composition that can be cured with high sensitivity to radiation irradiation, can form a high-quality image, and has good thermal stability, an ink-jet recording method, and Further, the present invention relates to a printed material using the same, a lithographic printing plate obtained using the ink, and a method for producing the lithographic printing plate.

  As an image recording method for forming an image on a recording medium such as paper based on an image data signal, there are an electrophotographic method, a sublimation type and a melt type thermal transfer method, an ink jet method and the like. 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 method 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 system is an inexpensive apparatus and ejects ink only to a required image portion to form an image directly on a recording medium, so that ink can be used efficiently and 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, in particular ink jet recording inks (radiation curable ink jet recording inks), are required to provide sufficiently high sensitivity and high image quality. By achieving high sensitivity, high curability is imparted to radiation, reducing power consumption, extending life by reducing the load on the radiation generator, preventing the generation of low-molecular substances due to insufficient curing, etc. Profits are generated. In addition, when the sensitivity is increased, particularly when an ink composition, in particular, an ink jet recording ink is used as an image portion of a lithographic printing plate, the curing strength of the image portion is increased and high printing durability is obtained. .

  On the other hand, examples of the cationic polymerization initiator include compounds disclosed in the inventions described in Patent Documents 1 to 3, etc., but the polymerization efficiency of the cationic polymerizable compound is high, and the ink composition is sensitive to radiation irradiation. There is a need for an excellent one.

JP-A-6-184170 JP-A-9-202873 Japanese Patent Laid-Open No. 9-221652

An object of the present invention made in consideration of the above problems is to provide a radiation-sensitive composition that reacts with high sensitivity upon irradiation with actinic radiation, changes its properties, and has excellent thermal stability.
Another object of the present invention is to provide a photosensitive composition that can be suitably used as an ink composition that is cured with high sensitivity upon irradiation with actinic rays and has excellent thermal stability, and the photosensitive composition. An object of the present invention is to provide an ink jet recording method using an object.
Another object of the present invention is to provide a printed material, a lithographic printing plate, and a lithographic printing plate obtained by using a photosensitive composition that can be cured with high sensitivity by irradiation with actinic rays and has excellent thermal stability. It is in providing the manufacturing method of.

The above object was achieved by the following 1), 2), 4), 6), 7) and 8). It is shown below together with 3) and 5) which are preferred embodiments.
1) A photosensitive composition comprising a compound represented by formula (I),

式（Ｉ）中、Ｘ^-は１価の対アニオンを表し、Ｙ₁〜Ｙ₄は独立に１価の置換基を表し、互いに結合して環を形成してもよく、Ｒはナフタレン環上の置換基を表し、２以上のＲが互いに結合して環を形成してもよく、ｎは置換基Ｒの置換数であり、０〜６の整数を表す。
２）（ａ）式（Ｉ）で表される化合物、（ｂ）重合性化合物、及び、（ｃ）着色剤を含有するインク組成物、

In the formula (I), X ⁻ represents a monovalent counter anion, Y _{1 to} Y ₄ independently represent a monovalent substituent, and may be bonded to each other to form a ring, and R represents a naphthalene ring And two or more Rs may be bonded to each other to form a ring, and n is the number of substituents R and represents an integer of 0 to 6.
2) (a) an ink composition containing a compound represented by formula (I), (b) a polymerizable compound, and (c) a colorant,

式（Ｉ）中、Ｘ^-は１価の対アニオンを表し、Ｙ₁〜Ｙ₄は独立に１価の置換基を表し、互いに結合して環を形成してもよく、Ｒはナフタレン環上の置換基を表し、２以上のＲが互いに結合して環を形成してもよく、ｎは置換基Ｒの置換数であり、０〜６の整数を表す。
３）インクジェット記録用である２）に記載のインク組成物、

In the formula (I), X ⁻ represents a monovalent counter anion, Y _{1 to} Y ₄ independently represent a monovalent substituent, and may be bonded to each other to form a ring, and R represents a naphthalene ring And two or more Rs may be bonded to each other to form a ring, and n is the number of substituents R and represents an integer of 0 to 6.
3) The ink composition according to 2), which is for inkjet recording.

4) An inkjet recording method comprising: (a) a step of discharging an ink composition onto a recording medium; and (b) a step of irradiating the discharged ink composition with active radiation to cure the ink composition. An ink jet recording method, wherein the ink composition is the ink composition according to 2) or 3),
5) Ultraviolet rays irradiated by a light emitting diode that emits ultraviolet rays having the emission peak wavelength in the range of 350 to 420 nm and the maximum illuminance on the recording medium surface of 10 to 2,000 mW / cm ^2. 4) the inkjet recording method according to
6) Printed matter recorded by the inkjet recording method according to 4) or 5),
7) (a) a step of discharging the ink composition according to 2) or 3) onto a hydrophilic support, and (b) irradiating the discharged ink composition with actinic radiation to thereby form the ink composition. Forming a hydrophobic image on the hydrophilic support by curing the ink composition by curing the lithographic printing plate,
8) A lithographic printing plate produced by the method for producing a lithographic printing plate as described in 7).

According to the present invention, a radiation-sensitive composition that reacts with high sensitivity upon irradiation with actinic radiation, changes in structure and properties, and has excellent thermal stability, and cures with high sensitivity upon irradiation with actinic radiation to achieve heat stability. Excellent ink composition, and an ink jet recording method using the radiation sensitive composition can be provided.
Moreover, the printed matter obtained by using the radiation-sensitive composition that is cured with high sensitivity to the actinic radiation and has excellent thermal stability has high image quality and excellent image portion strength. Similarly, by using the radiation-sensitive composition of the present invention, it is possible to produce a lithographic printing plate with high printing durability and high image quality based on digital data.

  The radiation-sensitive composition of the present invention contains a compound represented by the formula (I).

式（Ｉ）中、Ｘ^-は１価の対アニオンを表し、Ｙ₁〜Ｙ₄は独立に１価の置換基を表し、互いに結合して環を形成してもよく、Ｒはナフタレン環上の置換基を表し、２以上のＲが互いに結合して環を形成してもよく、ｎは置換基Ｒの置換数であり、０〜６の整数を表す。
以下、本発明について詳細に説明する。

In the formula (I), X ⁻ represents a monovalent counter anion, Y _{1 to} Y ₄ independently represent a monovalent substituent, and may be bonded to each other to form a ring, and R represents a naphthalene ring And two or more Rs may be bonded to each other to form a ring, and n is the number of substituents R and represents an integer of 0 to 6.
Hereinafter, the present invention will be described in detail.

(1) Radiation-sensitive composition The radiation-sensitive composition of the present invention contains at least one compound represented by the formula (I) (hereinafter also referred to as “specific acid generating compound”). And the chemical structure and / or properties of the composition change in response to radiation.
In the present invention, the term “(actinic radiation)” is not particularly limited as long as it is an actinic radiation that can impart energy capable of generating reaction-initiating species in the radiation-sensitive composition by irradiation. And widely include α-rays, γ-rays, X-rays, ultraviolet rays, visible rays, electron beams, etc., among which ultraviolet rays and electron beams are preferred from the viewpoint of curing sensitivity and availability of the device, Ultraviolet light is preferred. Therefore, the radiation-sensitive composition of the present invention is preferably a radiation-sensitive composition that can be improved in solubility or curable by irradiation with ultraviolet rays as radiation.
When the composition is a photoresist, the solubility in a developing solution can be changed to an image by irradiating ultraviolet rays or the like in an image and then heating as necessary.
The radiation curable composition of the present invention preferably contains (b) a polymerizable compound in addition to (a) the specific acid generating compound, and further contains (c) a colorant. preferable.

The radiation-sensitive composition of the present invention can be suitably used as an ink composition and forms not only a high-quality and high-strength image for use in normal printing, but also a high-quality printed matter can be obtained. , Resist, color filter, optical disc production, semiconductor production process such as IC, liquid crystal, thermal head circuit board production, other photofabrication process, acid curable composition It is also useful as an optical modeling material, and is also useful as a photo-curing resin material such as paint and adhesive.
Further, by applying the ink jet recording method, it is possible to directly form a high-intensity image area with high sensitivity on a non-absorbable recording medium based on digital data. The sensitive composition is also preferably used for the production of a lithographic printing plate, particularly a lithographic printing plate having a large area of A2 or larger, and the obtained lithographic printing plate has excellent printing durability.

(A) Specific acid generating compound The radiation-sensitive composition of the present invention is characterized by containing at least one compound represented by formula (I). In the radiation-sensitive composition of the present invention, one type of specific acid generating compound may be used alone, or two or more types may be used in combination. The amount added is sufficient if it is sufficient to respond to radiation.

式（Ｉ）中、Ｘ^-は１価の対アニオンを表し、Ｙ₁〜Ｙ₄は独立に１価の置換基を表し、互いに結合して環を形成してもよく、Ｒはナフタレン環上の置換基を表し、２以上のＲが互いに結合して環を形成してもよく、ｎは置換基Ｒの置換数であり、０〜６の整数を表す。
式（Ｉ）で示される化合物は、二置換メチリウムナフタレンジイルジカチオン（以下、「特定カチオン」ともいう。）及びこれを電気的に中和するアニオン（以下、「対アニオン」ともいう。）とからなる。特定アニオンは、１価のアニオンの場合には２つであり、２価のアニオンの場合には１つである。また、置換基Ｒ中にアニオン基を有する分子内塩でも良い。

In the formula (I), X ⁻ represents a monovalent counter anion, Y _{1 to} Y ₄ independently represent a monovalent substituent, and may be bonded to each other to form a ring, and R represents a naphthalene ring And two or more Rs may be bonded to each other to form a ring, and n is the number of substituents R and represents an integer of 0 to 6.
The compound represented by the formula (I) includes a disubstituted methylium naphthalenediyl dication (hereinafter also referred to as “specific cation”) and an anion (hereinafter also referred to as “counter anion”) that electrically neutralizes the dication. Consists of. The specific anion is two in the case of a monovalent anion and one in the case of a divalent anion. Moreover, the inner salt which has an anion group in the substituent R may be sufficient.

First, the counter anion will be described.
The counter anion of the dimethylium salt in the compound represented by the formula (I) used in the present invention can be used without limitation as long as a dimethylium salt can be formed. As the counter anion, an anion having a small nucleophilicity is preferable. Counter anions include sulfonate anion, benzoylformate anion, PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , carboxylate anion, sulfinate anion, sulfate anion, borate anion, halogen anion, sulfonimide anion, Bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methyl anion, borate anion, ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , bis (alkylsulfonyl) imide anion, tris (alkyl) A sulfonyl) methyl anion is preferred.

The monovalent organic groups Y _{1 to} Y ₄ are alkyl groups (including cycloalkyl groups, bicycloalkyl groups, and tricycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, and aryl groups. , Heterocyclic group (also referred to as “heterocyclic group”), cyano group, carboxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group or aryl Examples include a sulfinyl group, an alkylsulfonyl group or an arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and a carbamoyl group, and an aryl group is preferable. Preferred examples of the aryl group include aryl groups having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group. The aryl group may have a substituent and may have a substituent described later.

  The naphthalenediyl group may be substituted with one or more substituents R, for example, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydrocarbon ring group, a heterocyclic group, or an alkoxy group. These groups may further have a substituent described later.

  The substituent is preferably a monovalent nonmetallic atomic group excluding hydrogen, and a substituent that does not affect the radiation absorption of the specific cation or the reactivity of the excited specific cation. Such permissible substituent groups can be exemplified below.

  Permissible substituent groups include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkyl groups, aryl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups. Group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N- Arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-ary Rucarbamoyloxy group, alkylsulfoxy group, arylsulfur group Alkoxy group, an acylthio group, can be exemplified.

In the case where the radiation-sensitive composition of the present invention contains a polymerizable compound, since the specific acid-generating compound is contained, the polymerization rate is improved and the sensitivity can be increased.
In particular, since it has high acceptor properties and easily accepts electrons, when used in combination with a donor compound such as a sensitizing dye, the photolysis efficiency is further improved, the amount of acid generation is increased, and as a result, the polymerization rate is improved, Sensitivity can be increased. On the other hand, although the detailed reason is unknown, the solid of the onium part is bulky and stable compared to conventional onium compounds.

  The method for synthesizing the specific acid generating compound (A) is not particularly limited, but various acid generating compounds can be synthesized by a known synthesis method or a known anion exchange method. Examples of the known synthesis method include the method described in Org. Lett., 2004, vol. 6, p. 4563-4565, J. Am. Chem. Soc., 2005, vol. 127, p. 9696-9697. It can be illustrated by the literature described in the said literature.

  The specific acid generating compound is preferably a compound obtained by combining the specific cation and the specific anion described above as specific examples, and more preferably the following compounds I-1 to I-12. In the following specific examples, Me represents a methyl group, and Et represents an ethyl group.

In addition, compounds in which the dications of the compounds described in I-1 to I-12 above are shared and the anion is changed from ClO ₄ ⁻ to the following anions are also effective in the present invention.

The radiation-sensitive composition of the present invention includes a chemically sensitized positive resist. Chemically sensitized positive resists are publicly known, and are described, for example, in Section 3.3 in Chapter 3, “Positive Resist”, edited by Organic Electronics Materials Research Group, “Short Wavelength Photoresist Material”, published in 1988. In this resist, a resin (acid-decomposable polymer) that decomposes by the action of an acid and increases its solubility in an alkaline developer by the acid generated by the photolysis of an onium salt having absorption in the ultraviolet region. ) Based on the principle of changing to an alkali-soluble state like an image. Due to heat amplification, the number of chemical reactions (quantum efficiency) per photon absorbed in the resist can be 1 or more, and in some cases about 10 ⁵ .
The specific acid generating compound of the present invention can be combined with an acid-decomposable polymer to form a positive resist. Acid-decomposable polymers are exemplified in Table 3.6 (pages 60-63) of the above publication. ). The resin that decomposes by the action of an acid and increases the solubility in an alkaline developer will be described in detail later.

(B) Cationic polymerizable compound The radiation-sensitive composition of the present invention may contain a polymerizable compound. As the polymerizable compound, a cationic polymerizable compound described below can be preferably used, but a radical polymerizable compound described later can be used in combination.
A cationically polymerizable compound can also be preferably used for the polymerizable compound (b) used in the ink composition of the present invention, but a radically polymerizable compound can be used in combination.
The cationic polymerizable compound used in the present invention is not particularly limited as long as it is a compound that initiates a polymerization reaction by a cationic polymerization initiating species generated by photolysis of a specific acid generating compound and cures, and is known as a photo cationic polymerizable monomer. Various known 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 cationic polymerization-based photocurable resin is known, and recently, a photocationic polymerization-based photocurable resin sensitized to a visible light wavelength region of 400 nm or more, For example, they are disclosed in JP-A-6-43633 and JP-A-8-324137.

  Examples of the epoxy compound include aliphatic epoxides, alicyclic epoxides, aromatic epoxides, etc., and the aromatic epoxides include polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof and epichlorohydrin. Di- or polyglycidyl ether produced by the reaction, for example, di- or polyglycidyl ether of bisphenol A or its alkylene oxide adduct, di- or polyglycidyl ether of hydrogenated bisphenol A or its alkylene oxide adduct, and novolak Type epoxy resin and the like. Here, examples of the alkylene oxide include ethylene oxide, propylene oxide, and epoxy resin.

As the alicyclic epoxide, cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Or a cyclopentene oxide containing compound is mentioned preferably.
Examples of the aliphatic epoxide include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, or 1 Of diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or alkylene oxide adduct thereof, polyethylene glycol or alkylene oxide adduct thereof Dialkylidyl ether, polypropylene glycol, or polyalkylene glycol jig represented by diglycidyl ether of alkylene oxide adducts thereof Glycidyl ether and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

The monofunctional and polyfunctional epoxy compounds that can be used in the present invention are exemplified in detail.
Examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide. 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, etc. It is done.

  Examples of polyfunctional epoxy compounds include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S Glycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexane Silmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6 '-Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate) , Epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether Glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,13-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-di Examples thereof include epoxy octane, 1,2,5,6-diepoxycyclooctane and the like.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.

  Examples of the vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, Di- or trivinyl ether compounds such as methylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n-propyl Pills vinyl ether, isopropyl vinyl ether, isopropenyl ether -O- propylene carbonate, dodecyl vinyl ether, and a monovinyl ether compounds such as diethylene glycol monovinyl ether.

Below, monofunctional vinyl ether and polyfunctional vinyl ether are illustrated in detail.
Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methyl Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether , Tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxy Examples include ethyl vinyl ether, phenyl ethyl vinyl ether, phenoxy polyethylene glycol vinyl ether, and the like.

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

The oxetane compound that can be used in the present invention refers to a compound having at least one oxetane ring, and is known as described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217. These oxetane compounds can be arbitrarily selected and used.
The compound having an oxetane ring that can be used in the radiation-sensitive composition of the present invention is preferably a compound having 1 to 4 oxetane rings in its structure. By using such a compound, it becomes easy to maintain the viscosity of the radiation-sensitive composition within a favorable range of handling properties, and when used as an ink composition, High adhesion can be obtained.

  Examples of the compound having 1 to 2 oxetane rings in the molecule include compounds represented by the following formulas (1) to (3).

R ^a1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group, or a thienyl group. When two R ^a1 are present in the molecule, they may be the same or different.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferred examples of the fluoroalkyl group include those in which any hydrogen of these alkyl groups is substituted with a fluorine atom.
R ^a2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a group having an aromatic ring, an alkylcarbonyl group having 2 to 6 carbon atoms, or 2 to 6 carbon atoms. Represents an alkoxycarbonyl group, and an N-alkylcarbamoyl group having 2 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkenyl group include a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, and 2-methyl-2. -Propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like. Examples of the group having an aromatic ring include phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group and the like. Can be mentioned. As the alkylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, etc., as an alkoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, etc., as an N-alkylcarbamoyl group, Examples thereof include an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, and a pentylcarbamoyl group. R ^a2 may have a substituent, and examples of the substituent include an alkyl group of 1 to 6 and a fluorine atom.

R ^a3 represents a linear or branched alkylene group, a linear or branched poly (alkyleneoxy) group, a linear or branched unsaturated hydrocarbon group, a carbonyl group or an alkylene group containing a carbonyl group, a carboxyl group Represents an alkylene group containing, an alkylene group containing a carbamoyl group, or a group shown below. Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the poly (alkyleneoxy) group include a poly (ethyleneoxy) group and a poly (propyleneoxy) group. Examples of the unsaturated hydrocarbon group include a propenylene group, a methylpropenylene group, and a butenylene group.

When R ^a3 is the above polyvalent group, R ^a4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, Represents a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.
R ^a5 represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .
R ^a6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group, and n is an integer of 0 to 2,000. R ^a7 represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a monovalent group having the following structure. In the following formula, R ^a8 is an alkyl group having 1 to 4 carbon atoms or an aryl group, and m is an integer of 0 to 100.

  Examples of the compound represented by the formula (1) include 3-ethyl-3-hydroxymethyloxetane (OXT-101: manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane. (OXT-212: manufactured by Toagosei Co., Ltd.) and 3-ethyl-3-phenoxymethyloxetane (OXT-211: manufactured by Toagosei Co., Ltd.). Examples of the compound represented by the formula (2) include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (OXT-121: manufactured by Toagosei Co., Ltd.). Examples of the compound represented by the formula (3) include bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221: manufactured by Toagosei Co., Ltd.).

  As a compound which has 3-4 oxetane rings, the compound shown by following formula (4) is mentioned, for example.

In the formula (4), R ^a1 has the same ^{meaning as} in the formula (1). In addition, as R ^a9 which is a polyvalent linking group, for example, a branched polyalkylene group having 1 to 12 carbon atoms such as groups represented by the following A to C, a branched poly ( An alkyleneoxy) group or a branched polysiloxy group such as a group represented by E below. j is 3 or 4.

In the above A, R ^a10 represents a methyl group, an ethyl group or a propyl group. Moreover, in said D, p is an integer of 1-10.

  Another embodiment of the oxetane compound that can be suitably used in the present invention includes a compound represented by the following formula (5) having an oxetane ring in the side chain.

In the formula (5), R ^a1 and R ^a8 have the same ^{meaning as} in the above formula. R ^a11 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group or a trialkylsilyl group, and r is 1 to 4.

The compound having such an oxetane ring is described in detail in JP-A No. 2003-341217, paragraph numbers 0021 to 0084, and the compound described herein can be suitably used in the present invention. Further, oxetane compounds described in JP-A-2004-91556 can also be used in the present invention. This is described in detail in paragraphs 0022 to 0058.
Among the oxetane compounds used in the present invention, it is preferable to use a compound having one oxetane ring from the viewpoint of viscosity and adhesiveness of the radiation-sensitive composition.

<Epoxy resin>
Examples of the epoxy resin used in the present invention include a reaction product of bisphenol A and epichlorohydrin having a molecular weight of about 900 or more, a reaction product of bromobisphenol A and epichlorohydrin, a phenol novolak or o-cresol novolak and epichlorohydrin, and the like. The reaction product has an oxycyclohexane skeleton as described in JP-A-60-161973, JP-A-63-221121, JP-A-64-9216, and JP-A-2-140219. Examples thereof include polyfunctional epoxy resins, but are not limited to these compounds.

The cationically polymerizable compound that can be used in the present invention may be used alone or in combination of two or more, but from the viewpoint of effectively suppressing shrinkage during curing, an oxetane compound and It is preferable to use a vinyl ether compound in combination with at least one compound selected from epoxy compounds.
The content of the cationically polymerizable compound (B) in the radiation-sensitive composition is preferably 10 to 95% by weight, more preferably 30 to 90% by weight, still more preferably 50 to 85%, based on the total solid content of the composition. It is in the range of wt%.

  In the radiation sensitive composition of the present invention, a radical polymerizable compound can be used in combination with the cationic polymerizable compound as the polymerizable compound. The radical polymerizable compound will be described in the section (N) Other polymerizable compound.

<Radical polymerization initiator>
In the compound represented by the formula (I) of the present invention, (O) other polymerization initiator (radical polymerization initiator) described later can be used in combination. As the radical polymerization initiator that can be used in the present invention, a known radical polymerization initiator can be used in combination. The said polymerization initiator may be used independently and may use 2 or more types together.

(2) Resist composition When using the radiation sensitive composition of this invention as a resist composition, this composition may contain the component shown to following (C)-(J).

(C) A resin that decomposes by the action of an acid and increases the solubility in an alkaline developer (hereinafter also referred to as “component (C)”).
The radiation sensitive composition of this invention may contain (C) resin which decomposes | disassembles with an acid and the solubility in an alkali developing solution increases.
The component (C) is a resin having a group that can be decomposed by an acid (hereinafter also referred to as “acid-decomposable group”) in the main chain or side chain of the resin, or both of the main chain and the side chain. Among these, a resin having a group capable of decomposing with an acid in the side chain is more preferable.

A group preferable as a group that can be decomposed by an acid is a group in which a hydrogen atom of a —COOH group or —OH group is substituted with a group capable of leaving with an acid.
In the present invention, the acid-decomposable group is preferably an acetal group or a tertiary ester group.

  The base resin in the case where these acid-decomposable groups are bonded as side chains is an alkali-soluble resin having —OH or —COOH groups in the side chains. For example, the alkali-soluble resin mentioned later can be mentioned.

  The alkali dissolution rate of these alkali-soluble resins is preferably 170 kg / sec or more as measured with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 330 Å / second or more (Å is angstrom).

  From this point of view, particularly preferred alkali-soluble resins are o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene). Hydroxystyrene structural units such as a part of poly (hydroxystyrene), O-alkylated or O-acylated product, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, hydrogenated novolak resin, etc. An alkali-soluble resin containing a repeating unit having a carboxyl group such as (meth) acrylic acid or norbornenecarboxylic acid. Note that (meth) acrylic acid represents acrylic acid, methacrylic acid, or a mixture thereof, and (meth) acrylate represents acrylate, methacrylate, or a mixture thereof.

  Examples of the preferred repeating unit having an acid-decomposable group in the present invention include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, (meth) acrylic acid tertiary alkyl ester, and the like. 2-Adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate are more preferred.

  The component (C) that can be used in the present invention is an acid soluble in an alkali-soluble resin as disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. It can be obtained by reacting a precursor of a group capable of decomposing with an acid, or copolymerizing an alkali-soluble resin monomer having a group capable of decomposing with an acid with various monomers.

  When the radiation-sensitive composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, or high-energy light (EUV, etc.) having a wavelength of 50 nm or less, the component (C) resin contains hydroxystyrene repeating units. It is preferable to have. More preferably, hydroxystyrene / hydroxystyrene copolymer protected with an acid-decomposable group and hydroxystyrene / (meth) acrylic acid tertiary alkyl ester are preferred.

  In the radiation-sensitive composition of the present invention, the amount of the component (C) resin that can be used in the present invention in the entire radiation-sensitive composition is preferably 40 to 99.99% by weight in the total solid content. Preferably it is 50-99 weight%, More preferably, it is 80-96 weight%.

(D) A dissolution inhibiting compound having a molecular weight of 3,000 or less (hereinafter also referred to as “component (D)” or “dissolution inhibiting compound”), which is decomposed by the action of an acid to increase the solubility in an alkaline developer.
The radiation-sensitive composition of the present invention preferably contains a component (D) particularly when used as a resist composition.
(D) As a dissolution inhibiting compound having a molecular weight of 3,000 or less that decomposes by the action of an acid to increase the solubility in an alkaline developer, the permeability at 220 nm or less is not lowered, so Proceeding of SPIE, 2724, 355 An alicyclic or aliphatic compound containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in (1996) is preferred. Examples of the acid-decomposable group and alicyclic structure are the same as those described above for the alicyclic hydrocarbon-based acid-decomposable resin.

  When the radiation-sensitive composition of the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, it preferably contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. The phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.

  The molecular weight of the dissolution inhibiting compound in the present invention is 3,000 or less, preferably 300 to 3,000, and more preferably 500 to 2,500.

  The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, based on the solid content of the radiation-sensitive composition.

(E) Resin soluble in alkali developer (hereinafter also referred to as “component (E)” or “alkali-soluble resin”)
The radiation-sensitive composition of the present invention preferably contains the component (E) particularly when used as a resist composition.
The alkali dissolution rate of the alkali-soluble resin is preferably 20 kg / sec or more as measured with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 200 Å / second or more (Å is angstrom).

  Examples of alkali-soluble resins that can be used in the present invention include novolak resins, hydrogenated novolak resins, acetone-pyrogallol resins, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, and hydrogenated polyhydroxystyrene. , Halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, partially O-alkylated product of hydroxyl group of polyhydroxystyrene (for example, 5-30 mol% O-methylated product, O- (1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O- (t-butoxycarbonyl) methylated product Etc.) or O-acylated product (for example, 5 to 5) 0 mol% o-acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl Examples thereof include, but are not limited to, group-containing methacrylic resins and derivatives thereof, and polyvinyl alcohol derivatives.

  Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrenes, partially O-alkylated polyhydroxystyrenes, Alternatively, O-acylated product, styrene-hydroxystyrene copolymer, and α-methylstyrene-hydroxystyrene copolymer.

  The novolak resin is obtained by subjecting a predetermined monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

  Moreover, the weight average molecular weight of alkali-soluble resin is 2,000 or more, Preferably it is 5,000-200,000, More preferably, it is 5,000-100,000.

  Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

  These (E) alkali-soluble resins in the present invention may be used in combination of two or more.

  The usage-amount of alkali-soluble resin is 40 to 97 weight% with respect to solid content of the whole composition of a radiation sensitive composition, Preferably it is 60 to 90 weight%.

(F) An acid crosslinking agent that crosslinks with the alkali-soluble resin by the action of an acid (hereinafter also referred to as “(F) component” or “crosslinking agent”).
A crosslinking agent may be used in the radiation-sensitive composition of the present invention.

Any crosslinking agent can be used as long as it is a compound that crosslinks a resin soluble in an alkaline developer by the action of an acid, but the following (1) to (3) are preferred.
(1) Hydroxymethyl, alkoxymethyl, and acyloxymethyl forms of phenol derivatives.
(2) A compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group.
(3) A compound having an epoxy group.

  The alkoxymethyl group preferably has 6 or less carbon atoms, and the acyloxymethyl group preferably has 6 or less carbon atoms.

(G) Basic compound The radiation-sensitive composition of the present invention preferably contains (G) a basic compound in order to reduce a change in performance over time from exposure to heating.
Preferable structures include structures represented by the following formulas (A) to (E).

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl having 1 to 20 carbons, a cycloalkyl group having 3 to 20 carbons or an aryl group having 6 to 20 carbons, R ²⁵⁰ and R ²⁵¹ may combine with each other to form a ring. These may have a substituent. Examples of the alkyl group and cycloalkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, and 1 to 1 carbon atoms. A 20 hydroxyalkyl group or a C 3-20 hydroxycycloalkyl group is preferred.
These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.
In the formula, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.

  Preferable compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine, and may have a substituent. More preferred compounds include compounds having an imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, hydroxyl groups and / or Or the aniline derivative which has an ether bond etc. can be mentioned.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. As compounds having a diazabicyclo structure, 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0]. ] Undec-7-ene. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium. Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of aniline compounds include 2,6-diisopropylaniline and N, N-dimethylaniline. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  These basic compounds are used alone or in combination of two or more. The usage-amount of a basic compound is 0.001 to 10 weight% normally based on solid content of a radiation sensitive composition, Preferably it is 0.01 to 5 weight%. In order to obtain a sufficient addition effect, 0.001% by weight or more is preferable, and 10% by weight or less is preferable in terms of sensitivity and developability of the non-exposed area.

(H) Fluorine and / or silicon-based surfactant The radiation-sensitive composition of the present invention is further used, particularly when used as a resist composition, as a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon It is preferable to contain any one of a surfactant or a surfactant containing both a fluorine atom and a silicon atom, or two or more thereof.

  When the radiation-sensitive composition of the present invention contains fluorine and / or a silicon-based surfactant, adhesion and development defects can be obtained with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. It is possible to provide a resist pattern with less.

  Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, JP 2002-277862 A, US Patent Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098 , Nos. 5,576,143, 5,294,511, and 5,824,451, and the following commercially available surfactants are listed below. It is also possible to use Mom.

  Examples of commercially available surfactants that can be used include F-top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (manufactured by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176, F189, and R08. (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine type surfactant or silicon type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

  As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. It may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy) (Ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) copolymer, acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group Mention coalescence Kill.

  The amount of fluorine and / or silicon surfactant used is preferably 0.0001 to 2% by weight, more preferably 0.001 to 1% by weight, based on the total amount of the radiation sensitive composition (excluding the solvent). It is.

(I) Organic solvent The radiation-sensitive composition of the present invention may be used by dissolving each component in a predetermined organic solvent, particularly when used as a resist composition.

  Examples of the organic solvent that can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl. Ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N -Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc.

  In the present invention, the organic solvent may be used alone or in combination, but it is preferable to use a mixed solvent containing two or more solvents having different functional groups. As the mixed solvent having different functional groups, a mixed solvent in which a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group are mixed, or a mixed solvent in which a solvent having an ester structure and a solvent having a ketone structure are mixed. Is preferably used. Thereby, the generation of particles during storage of the resist solution can be reduced.

  Examples of the solvent having a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Propylene glycol monomethyl ether and ethyl lactate are more preferable.

  Examples of the solvent having no hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide. Of these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are more preferable, and propylene glycol monomethyl ether acetate, ethyl ethoxypropio Nate, 2-heptanone and cyclohexanone are particularly preferred.

  The mixing ratio (weight) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is usually 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. is there. A mixed solvent containing 50% by weight or more of a solvent having no hydroxyl group is preferable in terms of coating uniformity.

In a mixed solvent in which a solvent having an ester structure and a solvent having a ketone structure are mixed, examples of the solvent having a ketone structure include cyclohexanone and 2-heptanone, and cyclohexanone is preferable. Examples of the solvent having an ester structure include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, γ-butyrolactone, and butyl acetate, with propylene glycol monomethyl ether acetate being preferred.
The mixing ratio (weight) of the solvent having an ester structure and the solvent having a ketone structure is usually 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. is there. A mixed solvent containing 50% by weight or more of a solvent having an ester structure is particularly preferable from the viewpoint of coating uniformity.

(J) Other additives In the radiation-sensitive composition of the present invention, particularly when used as a resist composition, if necessary, a dye, a plasticizer, a surfactant other than the above component (H), a photosensitization. An agent, a compound that promotes solubility in a developer, and the like can be contained.

  The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable.

  The preferable addition amount of these dissolution promoting compounds is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the resin of component (C) or the resin of component (E). It is preferably 50% by weight or less from the viewpoint of suppressing development residue and preventing pattern deformation during development.

  Such a phenol compound having a molecular weight of 1,000 or less is obtained by, for example, the method described in JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. It can be easily synthesized by those skilled in the art with reference.

  Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

  In the present invention, a surfactant other than the (H) fluorine-based and / or silicon-based surfactant may be added. Specifically, nonionic interfaces such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan aliphatic esters, polyoxyethylene sorbitan aliphatic esters, etc. Mention may be made of activators.

  These surfactants may be added alone or in some combination.

(3) Pattern Forming Method The radiation-sensitive composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the mixed solvent, and applying the solution on a predetermined support as follows. it can.

For example, a radiation-sensitive composition is applied onto a substrate (eg, silicon / silicon dioxide coating) used in the manufacture of precision integrated circuit elements by a suitable application method such as a spinner or coater, dried, and then radiation-sensitive. A film is formed.
The radiation sensitive film is irradiated with actinic radiation through a predetermined mask, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.
Exposure (immersion exposure) may be performed by filling a liquid having a higher refractive index than air between the radiation-sensitive film and the lens during irradiation with actinic radiation. Thereby, resolution can be improved.

Examples of the active radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, etc., but preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, specifically Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, electron beam, etc. ArF excimer laser, F ₂ excimer laser, EUV (13 nm), electron A beam is preferred.

In the development step, an alkaline developer is used as follows. As an alkaline developer of the resist composition, inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by weight.
The pH of the alkali developer is usually from 10.0 to 15.0.

(4) Ink composition The radiation-sensitive composition of the present invention can be suitably used as an ink composition.
An ink composition containing the radiation-sensitive composition of the present invention (hereinafter also simply referred to as “ink”) is curable by radiation, and comprises (A) at least one compound represented by formula (I): And (B) a cationically polymerizable compound, and if necessary, (K) a colorant, (L) a sensitizing dye, (M) a co-sensitizer, (N) another polymerizable compound, O) Other polymerization initiators and (P) other components may be included.

(K) Colorant 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 rich in color reproducibility are preferable, and known colorants such as soluble dyes are used. Any agent can be selected and used. The colorant that can be suitably used in the ink composition of the present invention or the ink composition for inkjet recording preferably does not function as a polymerization inhibitor in a polymerization reaction that is a curing reaction. This is because the sensitivity of the curing reaction by actinic radiation is not reduced.

(K-1) Pigment The pigment that can be used in the present invention is not particularly limited. For example, organic or inorganic pigments having the following numbers described in the color index can be used.

  That is, as red or magenta pigment, Pigment Red 3, 5, 19, 22, 31, 38, 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, blue or cyan pigments include Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16 17-1, 22, 27, 28, 29, 36, 60, as green pigment, Pigment Green 7, 26, 36, 50, as yellow pigment, Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193, Pigment Black 7, 28, 26, etc. can be used as the black pigment.

The white pigment is not particularly limited as long as it makes the ink composition white. Usually, white pigments used in this field can be used. Examples of such white pigments include inorganic white pigments, organic white pigments, and white pigments. It is preferable to use the hollow polymer fine particles.
Examples of inorganic white pigments include alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, silicas such as finely divided silicic acid and synthetic silicates, calcium silicate, alumina, alumina Examples thereof include hydrates, titanium oxide, zinc oxide, talc, and clay. In the present invention, titanium oxide is particularly preferable from the viewpoint of concealability, colorability, and dispersed particle size.

  Examples of the organic white pigment include organic compound salts disclosed in JP-A No. 11-129613 and alkylene bismelamine derivatives disclosed in JP-A Nos. 11-14365 and 2001-234093.

  Specific examples of commercially available white pigments include Shigenox OWP, Shigenox OWPL, Shigenox FWP, Shigenox FWG, Shigenox UL, and Shigenox U (all trade names manufactured by Hackol Chemical Co., Ltd.).

Examples of the white hollow polymer fine particles include fine particles showing thermoplasticity substantially made of an organic polymer as disclosed in US Pat. No. 4,089,800. White pigments may be used alone or in combination.
A fluorescent whitening agent may be used in combination with the white ink. As the fluorescent brightening agent, various fluorescent brightening agents known in the art can be used, and examples thereof include benzoxazole-based, coumarin-based, and pyrazoline-based compounds. It is an oxazolyl stilbene-based fluorescent whitening agent. Examples thereof include fluorescent whitening agents described in JP-A Nos. 59-42993, 59-52689, 62-280069, 61-242871, and JP-A-4-219266.

(K-2) Oil-soluble dye The oil-soluble dye that can be used in the present invention is described below.
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 mass 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.

  In the present invention, the oil-soluble dye may be used alone or in combination of several kinds. In addition, other water-soluble dyes, disperse dyes, pigments, and other colorants may be contained as necessary as long as the effects of the present invention are not impaired.

  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, and acridines. And dyes and acridinone dyes.

  Of the oil-soluble dyes that can be used in the present invention, any magenta dye can be used. For example, aryl or hetaryl 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 and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; condensed polycyclic dyes such as dioxazine dyes, etc. Can be mentioned.

  Among the oil-soluble dyes that can be used in 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 part of the chromophore is dissociated. In this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Alternatively, it may be an organic cation such as pyridinium or a quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.

  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. Among these, particularly preferred are the Black 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 Bile 2OSe 2B eO (Manufactured by Co., Ltd.), Aizen Spillon 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, a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent. Preferred examples thereof 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;

  Particularly preferred oil-soluble dyes include azo or azomethine dyes represented by the following formula (1) or (2). The dye represented by the following formula (2) is known as a dye formed from a coupler and a developing agent by oxidation in a photographic material.

In the above formulas (1) and (2), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, hydroxy group , Nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl Group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl Group, phosphoryl group, acyl group, carboxyl group or sulfo group Represents a group.

In the formulas (1) and (2), in particular, R ² is a hydrogen atom, a halogen atom, an aliphatic group, an alkoxy group, an aryloxy group, an amide group, a ureido group, or a sulfamoylamino group among the above substituents. It is preferably an alkoxycarbonylamino group or a sulfonamide group.

In the present invention, the aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group and a substituted aralkyl group. The aliphatic group may have a branch or may form a ring. The number of carbon atoms in the aliphatic group is preferably 1-20, and more preferably 1-18. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of the substituent of the alkyl moiety of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, and the substituted aralkyl group include the substituents exemplified in the description of R ^{1 to} R ⁴ . The example of the substituent of the aryl part of a substituted aralkyl group is the same as the example of the substituent of the following substituted aryl group.

In the present invention, the aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, particularly preferably phenyl. The aryl part of the substituted aryl group is the same as the above aryl group. Examples of the substituent of the substituted aryl group include the substituents exemplified in the description of R ^{1 to} R ⁴ .

In the formulas (1) and (2), A represents —NR ⁵ R ⁶ or a hydroxy group, and R ⁵ and R ⁶ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. . A is preferably —NR ⁵ R ⁶ . R ⁵ and R ⁶ may be bonded to each other to form a ring. R ⁵ and R ⁶ are each preferably a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, each having a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or 1 carbon atom. Most preferred is a substituted alkyl group of ˜18.

In the formulas (1) and (2), B ¹ represents = C (R ³ )-or = N-, and B ² represents -C (R ⁴ ) = or -N =. The case where B ¹ and B ² are not simultaneously -N = is preferred, and the case where B ¹ is = C (R ³ )-and B ² is -C (R ⁴ ) = is more preferred. Any of R ¹ and R ⁵ , R ³ and R ^6, and R ¹ and R ² may be bonded to each other to form an aromatic ring or a heterocyclic ring.

In the formula (1), Y represents an unsaturated heterocyclic group. Y is preferably a 5-membered or 6-membered unsaturated heterocyclic ring. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. N, O, and S can be mentioned as an example of the hetero atom of a heterocyclic ring.
Examples of the unsaturated heterocyclic ring include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, thiophene ring, benzothiazole ring, benzoxazole ring, benzoisothiazole ring, pyrimidine ring, pyridine ring, and quinoline. A ring or the like is preferable. In addition, the unsaturated heterocyclic group may have the substituents exemplified in R ^{1 to} R ⁴ .

In the formula (2), X represents a color photographic coupler residue. The following are preferred as the residues of the color photographic coupler.
Yellow coupler: U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, 4,248,961, and JP-B-58-10939 British Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,649, European Patent 249,473A, Couplers represented by formulas (I) and (II) of No. 502,424A, couplers represented by formulas (1) and (2) of No. 513,496A (particularly Y-28 on page 18), No. 568,037A, the coupler represented by the formula (I) of claim 1, US Pat. No. 5,066,576, column 1, line 45 to 55, the coupler represented by the general formula (I), General of paragraph 0008 of 274425 A coupler represented by (I), a coupler described in claim 1 on page 40 of European Patent 498,381A1 (particularly D-35 on page 18), and represented by formula (Y) on page 4 of 447,969A1. Couplers (especially Y-1 (page 17), Y-54 (page 41)), represented by the formulas (II) to (IV) in columns 7 to 58 of column 7 of US Pat. No. 4,476,219. Couplers (particularly II-17, 19 (column 17), II-24 (column 19)).

  Magenta couplers: US Pat. Nos. 4,310,619, 4,351,897, European Patent 73,636, US Pat. Nos. 3,061,432, 3,725,067, Research Disclosure No. 24220 (June 1984), ibid. 24230 (June 1984), JP-A-60-33552, JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, U.S. Pat. No. 500,630, No. 4,540,654, No. 4,556,630, International Publication No. WO88 / 04795, JP-A-3-39737 (L-57 (page 11, lower right), L-68 (12 (Lower right of page), L-77 (lower right of page 13)), [A-4] -63 (page 134), [A-4] -73, -75 (page 139) of European Patent 456,257, 486, 965, M-4, -6 (page 26), M-7 (page 27), 571, 959A, M-45 (page 19), and JP-A-5-204106, M-1 (Page 6), paragraph 0237 M- 2, US Pat. No. 3,061,432 and No. 3,725,067.

  Cyan coupler: U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, European Patent 73,636, Japanese Patent Laid-Open No. 4-204843 CX-1,3,4,5,11,12,14,15 (pages 14 to 16); JP-A-4-43345, C-7,10 (page 35), 34,35 (page 37), ( I-1), (I-17) (pages 42-43); a coupler represented by general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385.

  Other couplers described in JP-A-62-215272 (page 91), JP-A-2-33144 (pages 3, 30), EP 355,660A (pages 4, 5, 45, 47) Is also useful.

  Of the oil-soluble dyes represented by the formula (1), a dye represented by the following formula (3) is particularly preferably used as the magenta dye.

In the formula (3), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ¹ is σp value is preferably 0.30 to 1.0 electron-withdrawing group. Preferred examples of the substituent include the electron-withdrawing substituents described later, and among them, an acyl group having 2 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, a nitro group, and a cyano group. , An alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, and a halogenated alkyl group having 1 to 12 carbon atoms are preferable. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an arylsulfonyl group having 6 to 18 carbon atoms, and most preferred is a cyano group.

In the formula (3), Z ² represents a hydrogen atom, an aliphatic group or an aromatic group.
In said Formula (3), R < ¹ > -R < ⁶ > is synonymous with each of the said Formula (1).

In the formula (3), Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Among these, Q is preferably a group composed of a nonmetallic atom group necessary for forming a 5- to 8-membered ring. Among these, an aromatic group or a heterocyclic group is particularly preferable. The 5- to 8-membered ring may be substituted, may be a saturated ring, or may have an unsaturated bond. Preferred nonmetallic atoms include nitrogen atoms, oxygen atoms, sulfur atoms or carbon atoms. Specific examples of such a ring structure include, for example, a benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring. , A benzimidazole ring, an oxazole ring, a benzoxazole ring, an oxane ring, a sulfolane ring, a thiane ring, and the like. When these rings further have a substituent, the substituent is the substituent of the formula (1). group exemplified in R ¹ to R ⁴ can be mentioned.

  In addition, about the preferable structure of the compound represented by the said Formula (3), it describes in Unexamined-Japanese-Patent No. 2001-335714.

  Of the dyes represented by the formula (2), a dye represented by the following formula (4) is particularly preferably used as the magenta dye.

  In the above formula (4), G is a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, alkoxy group, aryloxy group, alkylthio group, arylthio group, ester group, amino group, carbamoyl group, sulfonyl group Represents a group, a sulfamoyl group, a ureido group, a urethane group, an acyl group, an amide group or a sulfonamide group.

In said formula (4), R < ¹ >, R < ² >, A, B < ¹ > and B < ² > are synonymous with each of said formula (2), and those preferable ranges are also the same.

  In the formula (4), L is an aliphatic group, aromatic group, heterocyclic group, cyano group, alkoxy group, aryloxy group, alkylthio group, arylthio group, ester group, amino group, carbamoyl group, sulfonyl group, sulfamoyl. Represents a group of atoms that form a 5- or 6-membered nitrogen-containing heterocycle optionally substituted with at least one of a group, a ureido group, a urethane group, an acyl group, an amide group, and a sulfonamide group, Furthermore, a condensed ring may be formed with another ring.

In the compound represented by the formula (4), A is preferably —NR ⁵ R ⁶ , L preferably forms a 5-membered nitrogen-containing heterocyclic ring, and examples of the 5-membered nitrogen-containing heterocyclic ring include imidazole. Rings, triazole rings and terazole rings are included.

Examples of magenta dye compounds (M-0 to 6, a-21 to 25) among the dyes represented by the formula (1) and the formula (2) are shown below. It is for explaining in detail, and the present invention is not limited by these.
In the present invention, M-0, M-4, M-6, and a-21 can be used, and M-4, M-6, and a-21 can be particularly preferably used.

  Other examples of the colorant compound that can be used in the present invention are described in, for example, JP-A Nos. 2001-240763, 2001-181549, and JP-A-2001-335714. It is not limited to these.

  The compound represented by the formula (3) can be synthesized, for example, with reference to the methods described in JP-A No. 2001-335714 and JP-A No. 55-161856. The compound represented by the formula (4) can be referred to, for example, the methods described in JP-A-4-1267772 and JP-B-7-94180 and JP-A-2001-240763. Can be synthesized.

  Of the dyes represented by the formula (2), a pyrrolotriazole azomethine dye represented by the following formula (5) can be particularly preferably used as the cyan dye.

In the formula (5), A, R ¹ , R ² , B ¹ and B ² have the same meanings as those in the formula (2), and preferred ranges thereof are also the same.

In the formula (5), Z ³ and Z ⁴ are each independently synonymous with G in the formula (4). Z ³ and Z ⁴ may be bonded to each other to form a ring structure. It is more preferable that Z ³ is an electron-attracting group having a Hammett substituent constant σp value of 0.30 or more because the absorption is sharp. Z ³ is more preferably an electron-withdrawing group having a Hammett substituent constant σp value of 0.45 or more, and most preferably an electron-withdrawing group having a Hammett substituent constant σp value of 0.60 or more. And those having a sum of Hammett substituent constants σp values of Z ³ and Z ⁴ of 0.70 or more exhibit an excellent hue as cyan, and are more preferable.

In the formula (5), M is an atomic group forming a 1,2,4-triazole ring condensed with the 5-membered ring in the formula (5), and two atoms in the condensed part with the 5-membered ring One of B ³ and B ⁴ is a nitrogen atom and the other is a carbon atom.

  The compound represented by the formula (5) is preferably used as a cyan dye, but can also be used as a magenta dye by changing a substituent.

  Here, Hammett's substituent constant σp value used in this specification will be described. Hammett's rule is an empirical rule proposed by L. P. Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. Substituent constants determined by Hammett's rule include σp value and σm value, and these values can be found in many general books. For example, JA Dean edition, “Lange's Handbook of Chemistry” 12th edition, 1979 (Mc Graw-Hill), “Chemical domain” extra edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, but this is limited to only a substituent having a known value that can be found in the above-mentioned book. Needless to say, it also includes substituents that would be included in the range when measured based on Hammett's rule even if the value is unknown. The formulas (1) to (5) include those that are not benzene derivatives, but the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value is used in this sense.

  Examples of the electron withdrawing group having a Hammett substituent constant σp value of 0.60 or more include a cyano group, a nitro group, and an alkylsulfonyl group (for example, a methanesulfonyl group and an arylsulfonyl group (for example, a benzenesulfonyl group)). As the electron withdrawing group having a Hammett σp value of 0.45 or more, in addition to the above, an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m- Chlorophenoxycarbonyl), alkylsulfinyl groups (eg n-propylsulfinyl), arylsulfinyl groups (eg phenylsulfinyl), sulfamoyl groups (eg N-ethylsulfamoyl, N, N-dimethylsulfamoyl), halogenated Alkyl groups (eg, trif (Loromethyl).

  Examples of the electron withdrawing group having a Hammett substituent constant σp value of 0.30 or more include, in addition to the above, an acyloxy group (for example, acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), Halogenated alkoxy groups (for example, trifluoromethyloxy), halogenated aryloxy groups (for example, pentafluorophenyloxy), sulfonyloxy groups (for example, methylsulfonyloxy), halogenated alkylthio groups (for example, difluoromethylthio), An aryl group (eg, 2,4-dinitrophenyl, pentachlorophenyl) substituted with two or more electron-withdrawing groups having a σp value of 0.15 or more, and a heterocyclic ring (eg, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl) Can do. In addition to the above, specific examples of the electron withdrawing group having a σp value of 0.20 or more include a halogen atom.

  Moreover, in this invention, the oil-soluble dye represented by a following formula (AI) can be used preferably.

In formula (AI): X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , —CONR ₁ R ₂ , It represents a group selected from -CO ₂ R ₁ and a sulfo group. Here, Z is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. Represents a substituted heterocyclic group. R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted It represents a substituted aryl group or a substituted or unsubstituted heterocyclic group. However, R ₁ and R ₂ are not both hydrogen atoms. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. Y ₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. _{a 1 ~a 4, b 1 ~b} 4 represents the number of _{X 1 ~X 4, Y 1 ~Y} 4, each independently, an integer of 0-4. However, the sum of a _{1 to} a ₄ is 2 or more.

  Of the oil-soluble dyes represented by the formula (AI), an oil-soluble dye represented by the following formula (A-II) can be particularly preferably used.

Formula (A-II) _{in: X 11 ~X 14, Y 11} ~Y 18 , and M are the same as _{X 1 ~X 4, Y 1 ~Y} 4, M in Formula (A-I) synonymous . a ₁₁ ~a ₁₄ each independently represent a integer of 1 or 2.

  Illustrative compound (AII-17) is shown as a specific example of formula (A-II), but this is for the purpose of illustrating the present invention in detail, and the present invention is not limited thereby. .

  In the present invention, it is preferable to use an oil-soluble dye having an oxidation potential nobler than 1.0 V (SCE). The oxidation potential is more preferable as it is noble, the oxidation potential is more noble than 1.1 V (SCE), more preferably 1.2 V (SCE).

  A person skilled in the art can easily measure the value of the oxidation potential (Eox). Regarding this method, for example, “New Instrumental Methods in Electrochemistry” by P. Delahay (1954, published by Interscience Publishers), “Electrochemical Methods” by AJ Bard et al. (1980, published by John Wiley & Sons), Akira Fujishima et al. It is described in the book "Electrochemical measurement method" (1984, published by Gihodo Publishing Co., Ltd.).

Specifically, the oxidation potential is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁶ mol / in a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate. Approximate the oxidization wave in a straight line by dissolving 1 liter and sweeping to the oxidation side (noble side) using carbon (GC) as the working electrode and rotating platinum electrode as the counter electrode by cyclic voltammetry and DC polarography equipment Then, the intermediate potential of the line segment formed by the intersection of this straight line and the residual current / potential line and the intersection of the straight line and the saturation current line (or the intersection of the straight line parallel to the vertical axis passing through the peak potential value) Values are measured as values for SCE (saturated calomel electrode). Although this value may be deviated by several tens of mil volts due to the influence of the liquid potential difference or the liquid resistance of the sample solution, the reproducibility of the potential can be ensured by inserting a standard sample (for example, hydroquinone). The supporting electrolyte and solvent to be used can be selected appropriately depending on the oxidation potential and solubility of the test sample. The supporting electrolytes and solvents that can be used are described in Akira Fujishima et al., “Electrochemical measurement method” (1984, published by Gihodo Publishing Co., Ltd.), pages 101 to 118.
In the concentration range of the measurement solvent and the phthalocyanine compound sample, the oxidation potential in a non-associated state is measured.

The value of Eox represents the ease of transfer of electrons from the sample to the electrode, and the greater the value (the higher the oxidation potential), the less transfer of electrons from the sample to the electrode, in other words, less oxidation.
When a dye having a low oxidation potential is used, polymerization inhibition by the dye is large and curability is lowered. When a dye having a noble oxidation potential is used, there is almost no polymerization inhibition.

The colorant that can be used in the present invention is preferably added to the ink composition of the present invention or the ink composition for inkjet recording and then appropriately dispersed in the ink. 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.
It is also possible to add a dispersant when dispersing the colorant. The type of the dispersant is not particularly limited, but a polymer dispersant is preferably used, and examples of the polymer dispersant include Solsperse series manufactured by Zeneca. Moreover, it is also possible to use a synergist according to various pigments as a dispersion aid. In the present invention, these dispersant and dispersion aid are preferably added in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the colorant.
The colorant may be added directly to the ink composition of the present invention, but may be added in advance to a dispersion medium such as a solvent or a polymerizable compound used in the present invention in order to improve dispersibility. In the present invention, in order to avoid the problem of 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 added to the polymerizable compound. It is preferable to add. Further, as a polymerizable compound to be used, it is preferable in view of dispersion suitability to select a monomer having the lowest viscosity.

  In the present invention, the average particle diameter of the colorant particles is preferably 0.005 to 0.5 μm, more preferably 0.01 to 0.45 μm, and still more preferably 0.015 to 0.3 μm. The maximum particle size of the colorant is preferably 0.3 to 10 μm, more preferably 0.3 to 3 μm. It is preferable to set the colorant, the dispersant, the dispersion medium, the dispersion conditions, and the filtration conditions so that the maximum particle diameter is obtained. 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.

(L) Sensitizing dye

The ink composition of the present invention preferably contains a sensitizing dye for the purpose of improving the acid generation efficiency of the photoacid generator and increasing the photosensitive wavelength. As the sensitizer, a photoacid generator is preferably sensitized by an electron transfer mechanism or an energy transfer mechanism.
Examples of the sensitizing dye used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in the wavelength region of 300 nm to 450 nm.
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.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, Carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives and the like, and further, European Patent No. 568, No. 993, U.S. Pat. No. 4,508,811, No. 5,227,227, JP-A-2001-125255, JP-A-11-271969, etc. All It is.

  Among them, the sulfonium salt in the present invention may be combined with polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), thioxanthones, distyrylbenzenes, and styrylbenzenes. It is preferable from the viewpoint of starting efficiency, and most preferably combined with distyrylbenzenes, styrylbenzene, and diphenylbutadienes.

The content of the (d) sensitizing dye in the ink composition of the present invention is preferably 0.01 to 20% by mass with respect to the total mass of the ink composition from the viewpoint of the colorability of the ink. 1-15 mass% is more preferable, More preferably, it is the range of 0.5-10 mass%.
(D) A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
In addition, the content ratio of (d) the sensitizing dye and the (a) specific onium salt in the ink composition is, in terms of weight ratio, from the viewpoint of improving the decomposition rate of the specific onium salt and transmitting light. a / d = 100 to 0.05 is preferable, a / d = 50 to 0.1 is more preferable, and a / d = 10 to 0.5 is still more preferable.

(M) 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 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, page 3173 (1972), Japanese Examined Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51-82102. Publication, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research Disclosure 33825 Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like can be mentioned.

  Other examples of co-sensitizers include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142773, and JP-A-56. And the like. Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. Etc.

  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.

(N) Other polymerizable compound As described above, the radiation-sensitive composition of the present invention can contain a polymerizable compound, and the ink composition contains (b) a polymerizable compound. As these polymerizable compounds, the above-mentioned cationic polymerizable compounds can be preferably used, but radically polymerizable compounds can be used in combination.
<Radically polymerizable compound>
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. Only one kind of radically polymerizable compound may be used, or two or more kinds thereof may be used in combination at an arbitrary ratio in order to improve desired properties. In addition, a polyfunctional compound having two or more functional groups is preferable to a monofunctional compound. More preferably, two or more polyfunctional compounds are used in combination for controlling performance such as reactivity and physical properties.

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, Examples thereof include radically polymerizable compounds such as anhydrides having a saturated group, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes.
Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol Diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaery Acrylic acid derivatives such as lithol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate , Lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol Methacryl derivatives such as tan trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate More specifically, Yamashita Shinzo, “Cross-linking agent handbook” (1981, Taiseisha); Kato Kiyomi, “UV / EB curing handbook (raw material)” (1985, Polymer) Radtech Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) ) And the like, or radically polymerizable or crosslinkable monomers known in the industry, Oligomers and polymers can be used.
The radically polymerizable compound that can be used in the present invention is a compound having one or more carbon-carbon double bonds (ethylenically unsaturated bonds) that can be radically polymerized. Any compound having one bond may be used, including compounds having chemical forms such as monomers, oligomers and polymers. Only one kind of radically polymerizable compound may be used, or two or more kinds thereof may be used in combination at an arbitrary ratio in order to improve desired properties.

(O) Other Polymerization Initiator As described above, in the ink composition of the present invention, (O) another polymerization initiator can be used in combination with the specific acid-generating compound represented by the formula (I). Examples of other polymerization initiators that can be used in the present invention include known radical polymerization initiators. The said polymerization initiator may be used independently and may use 2 or more types together.
The radical polymerization initiator that can be used in the ink composition of the present invention is a compound that absorbs external energy to generate 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>
The radical polymerization initiator that can be used in the present invention includes (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiphenyls. An imidazole compound, (f) a ketoxime ester compound, (g) a borate compound, (h) an azinium compound, (i) a metallocene compound, (j) an active ester compound, (k) a compound having a carbon halogen bond, and (l) Preferred examples include alkylamine compounds. These radical polymerization initiators may be used alone or in combination with the above compounds (a) to (l). The radical polymerization initiator in the present invention is preferably used alone or in combination of two or more.

(P) Other components Other components can be added to the ink composition of the present invention as necessary. Examples of other components include basic compounds, polymerization inhibitors, solvents, and cationic polymerizable monomers.
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. .
The polymerization inhibitor is preferably added from the viewpoint of improving the storage stability. Further, when the ink composition of the present invention is used as an ink composition for ink jet recording, it is preferably discharged at a temperature in the range of 40 to 80 ° C. with a reduced viscosity, and also for preventing head clogging due to thermal polymerization. It is preferable to add a polymerization inhibitor. The polymerization inhibitor is preferably added in an amount of 200 to 20,000 ppm based on the total amount of the ink composition of the present invention. Examples of the polymerization inhibitor include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, and cuperon Al.

In view of the fact that the ink composition of the present invention and the ink composition for ink jet recording are radiation curable ink compositions, it is preferable that no solvent is contained so that the ink composition can react quickly and be cured immediately after landing of the ink composition. However, a predetermined solvent can be included as long as the curing rate of the ink composition is not affected. In the present invention, an organic solvent or water can be used as the solvent. In particular, the organic solvent can be added in order to improve the adhesion to the recording medium (support such as paper). The addition of an organic solvent is effective because the problem of volatile organic compounds (VOC) can be avoided. The amount of the organic solvent is, for example, in the range of 0.1 to 5% by weight, preferably 0.1 to 3% by weight, based on the total weight of the ink composition of the present invention.
As a means for preventing a decrease in sensitivity due to the light-shielding effect of the colorant that can be used in the ink composition, in addition to a combination of a cationic polymerizable compound and a cationic polymerization initiator, and a combination of a radical polymerizable compound and a radical polymerization initiator Also, a radical-cation hybrid type curable ink using these polymerizable compounds and a polymerization initiator in combination may be used.

  In addition to this, a known compound can be added to the ink composition of the present invention as necessary. For example, surfactants, leveling additives, matting agents, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, waxes and the like are appropriately selected and added. be able to. In order to improve the adhesion to a recording medium such as polyolefin or PET, it is also preferable to contain a tackifier that does not inhibit the polymerization. Specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, pages 5 to 6 (for example, (meth) acrylic acid and an alcohol having an alkyl group having 1 to 20 carbon atoms). Ester, (meth) acrylic acid and a C3-14 alicyclic alcohol ester, (meth) acrylic acid and a C6-14 aromatic alcohol ester copolymer), and polymerizability Examples thereof include a low molecular weight tackifying resin having an unsaturated bond.

(5) Properties of Ink Composition As described above, the ink composition of the present invention contains (A) a specific acid generating compound, (B) a cationic polymerizable compound, and optionally (K) a colorant. To do. These components are preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and (B) a cation, based on the total weight of the ink composition. The polymerizable compound is preferably 10 to 95% by weight, more preferably 30 to 93% by weight, still more preferably 50 to 90% by weight. When a colorant is used, (K) the colorant is preferably 1 to 10%. It is appropriate that the amount is contained in an amount of 2% by weight, more preferably 2 to 8% by weight so that the total weight% of each component is 100% by weight.

  When the obtained ink composition is used for inkjet recording, the viscosity of the ink composition is determined at a discharge temperature (for example, 40 to 80 ° C., preferably 25 to 30 ° C.) in consideration of discharge properties. , Preferably 7 to 30 mPa · s, more preferably 7 to 20 mPa · s. For example, the viscosity of the ink composition of the present invention at room temperature (25 to 30 ° C.) is preferably 35 to 500 mPa · s, more preferably 35 to 200 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. Further, it is preferable because 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 is, for example, preferably 20 to 30 mN / m, more preferably 23 to 28 mN / m. When recording on various recording media such as polyolefin, PET, coated paper, and non-coated paper, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and the wettability is preferably 30 mN / m or less.

(6) Inkjet recording method and apparatus The ink composition of the present invention is preferably used for inkjet recording.
An ink jet recording method that can be suitably employed in the present invention will be described below.

(6-1) Inkjet recording method The present invention ejects the ink composition onto a recording medium (support, recording material, etc.) and irradiates the ink composition ejected onto the recording medium with actinic radiation. Thus, a method for forming an image by curing ink is provided. That is, the present invention
(A) a step of discharging an ink composition onto a recording medium; and
(B) an inkjet recording method comprising a step of irradiating the discharged ink composition with actinic radiation to cure the ink composition,
The present invention relates to an ink jet recording method in which the ink composition is the ink composition of the present invention.
The cured ink composition forms an image on the recording medium.
The peak wavelength of the active radiation is preferably 200 to 600 nm, more preferably 300 to 450 nm, and more preferably 350 to 420 nm. The output of active radiation is preferably 2,000 mJ / cm ² or less, more preferably from 10 to 2,000 mJ / cm ^2, more preferably be 20 to 1,000 mJ / cm ² Particularly preferably, it is 50 to 800 mJ / cm ² .

Further, the inkjet recording method of the present invention will be described by taking as an example a method for producing a lithographic printing plate, which includes forming an image by discharging an ink composition onto the lithographic printing plate.
The lithographic printing plate of the present invention has a hydrophilic support and a hydrophobic image formed on the hydrophilic support. The method for producing the lithographic printing plate comprises the following steps:
(A) a step of discharging the ink composition of the present invention onto a hydrophilic support; and
(B) A step of irradiating the discharged ink composition with actinic radiation to cure the ink composition, thereby forming a hydrophobic image formed by curing the ink composition on the hydrophilic support. including.

(6-1-1) Hydrophilic support used for lithographic printing plate Here, the lithographic printing plate has a support and an image formed on the support.
Conventionally, so-called PS plates having a configuration in which a lipophilic photosensitive resin layer is provided on a hydrophilic support have been widely used as lithographic printing plates. As a method for producing the PS plate, a desired printing plate is usually obtained by performing mask exposure (surface exposure) through a lith film and then dissolving and removing the non-exposed portion. However, in recent years, digitization technology that electronically processes, stores, and outputs image information using a computer has become widespread, and a new image output method corresponding to the technology has been demanded. In particular, computer-to-plate (CTP) technology has been developed that scans highly-preferred light such as laser light according to digitized image information without using a lithographic film, and directly produces a printing plate. Yes.
Examples of a method for obtaining a lithographic printing plate that enables such scanning exposure include a method of directly producing a lithographic printing plate using an ink composition or an ink composition for ink jet recording. This is because ink is ejected onto a support, preferably a hydrophilic support, by an ink jet method or the like, and exposed to actinic radiation, whereby the ink composition or the ink for ink jet recording is exposed to a desired portion. A printing plate having an image (preferably a hydrophobic image) is obtained. An ink composition or ink jet recording ink suitable for such a system is the ink composition or ink jet recording ink of the present invention.
The support (recording medium) onto which the ink composition or ink for ink jet recording of the present invention is discharged is not particularly limited as long as it is a dimensionally stable plate-like support. The support is preferably a hydrophilic support. 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 on which the above-mentioned metal is laminated or deposited. 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, but completely pure aluminum is difficult to manufacture in terms of refining technology, and therefore 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 from 0.1 to 0.6 mm, more preferably from 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 is easy to improve hydrophilicity and secure adhesion between the image recording layer 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 planographic 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, but it has adhesion to the upper layer, hydrophilicity, resistance to contamination, heat insulation, etc. In order to further 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 to be performed can be selected as appropriate. Of course, these enlargement processing and sealing processing 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 an aqueous solution containing an 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. Of 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 the 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. Of 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. Is preferred.
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, from the viewpoint of improving on-press developability and stain resistance. Further, 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, preferably 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.
The 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 the treatment is performed using the dipping method, the treatment time is preferably 1 second or longer, more preferably 3 seconds or longer, and preferably 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 water vapor pressure 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).
Further, 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, more preferably 20 seconds or shorter.

<Sealing treatment with hot water>
Examples of the sealing treatment with water vapor include a method in which an aluminum plate on which an anodized film is formed is immersed 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, more preferably 100 seconds or shorter, and even more preferably 20 seconds or shorter.
Examples of the hydrophilization treatment used in the present invention include US Pat. Nos. 2,714,066, 3,181,461, 3,280,734, and 3,902,734. There is an alkali metal silicate method as described in the book. 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 the image recording layer, good printing durability and good stain resistance are obtained, which is preferable.

(6-1-2) Step of discharging the ink composition onto the hydrophilic support When the ink composition of the present invention or the ink composition for inkjet recording is discharged onto the surface of the hydrophilic support, the ink composition The ink composition or ink composition for inkjet recording is preferably heated to 40 to 80 ° C., more preferably 25 to 30 ° C., and the viscosity of the ink composition is preferably 7 to 30 mPa · s, more preferably 7 to 20 mPa · s. It is preferable that the ink is discharged after being lowered. In particular, the use of an ink composition having an ink viscosity of 35 to 500 mP · s at 25 ° C. is preferable because a great effect can be obtained. 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 that is usually used in an ink composition or an ink for inkjet recording. Viscosity fluctuation of the ink has a great influence on the change of the droplet size and the change of the droplet discharge speed, and consequently 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 temperature control range is set to ± 5 ° C. of the set temperature, preferably ± 2 ° C. of the set temperature, more preferably set temperature ± 1 ° C.

(6-1-3) Irradiating the discharged ink composition with active radiation to cure the ink composition, whereby a hydrophobic image formed by curing the ink composition is formed on the hydrophilic support. Step of forming the ink composition ejected on the surface of the hydrophilic support is cured by irradiation with actinic radiation. This is because the sensitizing dye in the polymerization initiation system contained in the ink composition of the present invention absorbs actinic radiation to be in an excited state, and the polymerization initiator is decomposed by contact with the polymerization initiator in the polymerization initiation system. This is because the polymerizable compound is cured by radical polymerization.
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. The peak wavelength of the actinic radiation is, for example, from 200 to 600 nm, preferably from 300 to 450 nm, more preferably from 350 to 450 nm, although it depends on the absorption characteristics of the sensitizing dye. In the present invention, the polymerization initiation system has sufficient sensitivity even with a low-power active radiation. Therefore, the output of active radiation is, for example, 2,000 mJ / cm ² or less, preferably 10 to 2,000 mJ / cm ² , more preferably 20 to 1,000 mJ / cm ² , and still more preferably 50 to 800 mJ. An irradiation energy of / cm ² is appropriate. The active radiation, the illumination intensity on the exposed surface is, for example, 10 to 2,000 mW / cm ^2, preferably, it is suitable to be irradiated at 20 to 1,000 mW / cm ^2.

The ink composition of the present invention is appropriately irradiated with such actinic radiation, for example, for 0.01 to 120 seconds, and preferably for 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. .
Further, the curing may be completed by another light source that is not driven. In WO99 / 54415, as an irradiation method, a method using an optical fiber or a method in which a collimated light source is applied to a mirror surface provided on the side surface of the head unit to irradiate the recording unit with UV light is disclosed.

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 a color with low 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.
Thus, the ink composition of the present invention is cured by irradiation with actinic radiation to form a hydrophobic image on the surface of the hydrophilic support.

(6-2) Inkjet recording apparatus There is no restriction | limiting in particular as an inkjet recording apparatus used for this invention, A commercially available inkjet recording apparatus can be used. That is, in the present invention, recording can be performed on a recording medium using a commercially available inkjet recording apparatus.
Examples of the ink jet recording apparatus that can be used in the present invention include 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 4,000 × 4,000 dpi, preferably 400 × 400 to 1,600 × 1,600 dpi. More preferably, it can be driven so as to discharge at a resolution of 720 × 720 dpi. 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 has a constant temperature for the ejected ink, heat insulation and heating can be performed from the ink supply tank to the inkjet head portion. The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors at each piping site and perform heating control according to the ink flow rate and the environmental temperature. The temperature sensor can be provided near 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 thermal energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

As the active radiation source, a mercury lamp, a gas / solid laser or the like is mainly used, and a mercury lamp and a metal halide lamp are widely known as the ultraviolet light curable ink jet. 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 life, have high efficiency, and are low in cost, and are expected as light sources for photocurable 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. When 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.
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 .

  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.

Example as photosensitive composition An epoxy group-containing polycarboxylic acid resin was synthesized as follows. 361.0 g (2 equivalents) of a phenol novolac type epoxy resin (Nippon Kayaku Co., Ltd., EPPN-503, epoxy equivalent 180.5), dimethylolpropionic acid 134.1 g (1 mol) carbitol acetate 86.7 g And 37.1 g of solvent naphtha were charged, and the mixture was heated and stirred at 90 ° C. to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 1.86 g (0.007 mol) of triphenylphosphine, heated to 100 ° C., reacted for about 20 hours, and when the acid value became 0.7 mgKOH / g or less, Next, the mixture was cooled to 50 ° C., charged with 1.07 g (0.007 mol) of cumene hydroperoxide, 169.4 g of carbitol acetate and 72.6 g of solvent naphtha and reacted for about 3 hours to obtain triphenylphosphine as a reaction catalyst. Oxidized to deactivate the catalytic activity. Next, 184.2 g (1.21 mol) of tetrahydrophthalic anhydride was charged and reacted at 95 ° C. for 10 hours to obtain an epoxy group-containing polycarboxylic acid resin (solid content concentration 65%). The acid value of the product (solid content) was about 100 mgKOH / g.

  Using the epoxy group-containing polycarboxylic acid resin thus obtained, a resin composition shown in the following Table 1 was prepared.

  The chemical structure of Compound A, a specific acid generator used as an initiator, is as follows:

The resin composition was spin-coated on a glass substrate at 1,000 rpm for 30 seconds, pre-baked in an oven at 80 ° C. for 30 minutes, and then step tablet (Kodak Co., Ltd.) using a high-pressure mercury lamp at an exposure amount of 2,000 mJ / cm ^2. Product No. 2) was baked. Next, it was post-baked in an oven at 90 ° C. for 10 minutes, then developed with a 1% sodium carbonate aqueous solution, and then the number of stepped steps in which a cured film that was dissolved and not removed by development, that is, a residual film remained, was confirmed. As a result, in Comparative Example 1, the remaining film remained only up to 5 steps (exposure amount 316 mJ / cm ² ), whereas in Example 1 using Compound A, 8 steps (exposure amount 112 mJ / cm ² ). The remaining film remained until the clear sensitizing effect of Compound A was confirmed.

Evaluation of stability over time Except for using the above sample sealed with aluminum kraft paper and allowed to stand at 60 ° C. for 4 days, changes due to storage of sensitivity were examined in the same manner as in sensitivity evaluation. Next, the ratio between the sensitivity at 60 ° C. for 4 days and the sensitivity at 60 ° C. for 4 days is taken (sensitivity at 60 ° C. for 4 days / sensitivity for 4 days). Was measured. The smaller the absolute value of this number, the less the influence of forced aging, that is, the higher the storage safety.

Resist Examples 1 and 2 and Comparative Example 1
<Resist preparation>
The components shown in Table 2 below were dissolved in a solvent to prepare a solution having a solid concentration of 12% by mass, and this was filtered through a 0.1 μm polytetrafluoroethylene filter or a polyethylene filter to prepare a positive resist solution. The prepared positive resist solution was evaluated by the following method, and the results are also shown in Table 2.

  The chemical structure of the acid generating compound A used is as shown below.

Resin 1 in Table 2 has the following structure. Abbreviations are summarized below.

[Basic compounds]
DIA: 2,6-diisopropylaniline

[Surfactant]
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)

〔solvent〕
A1: Propylene glycol methyl ether acetate B1: Propylene glycol methyl ether

<Resist evaluation>
An anti-reflective coating DUV-42 manufactured by Brewer Science Co., Ltd. is uniformly applied to a thickness of 600 angstroms on a silicon substrate subjected to hexamethyldisilazane treatment by a spin coater, and dried on a hot plate at 100 ° C. for 90 seconds. And drying at 190 ° C. for 240 seconds. Thereafter, each positive resist solution was applied by a spin coater and dried at 120 ° C. for 90 seconds to form a 0.30 μm resist film.
The resist film was exposed with an ArF excimer laser stepper (NA = 0.6 manufactured by ISI) through a mask, and immediately after the exposure, it was heated on a hot plate at 120 ° C. for 90 seconds. Further, the resist film was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried to obtain a line pattern.

Pattern collapse evaluation method:
When an exposure amount that reproduces a 130 nm line and space 1: 1 mask pattern is an optimum exposure amount, and a dense pattern of line and space 1: 1 and an isolated pattern of line and space 1:10 are exposed at the optimum exposure amount Therefore, the line width that resolves the pattern without falling down in a fine mask size is defined as the limit pattern falling line width. A smaller value indicates that a finer pattern is resolved without falling, and pattern falling is less likely to occur.

  From the evaluation results shown in Table 2, it can be seen that, in ArF exposure, the photosensitive composition of the present invention has a narrow limit pattern collapse line width.

  Examples of the ink composition and comparative examples will be shown below to describe the present invention more specifically. However, the present invention is not limited to these examples.

<< Preparation of pigment dispersion >>
According to the method described below, yellow, magenta, cyan, black, and white pigment dispersions 1 were prepared. The dispersion conditions are adjusted appropriately using a known dispersion device so that the average particle diameter of each pigment particle is in the range of 0.2 to 0.3 μm, and then the filter is heated under heating. Prepared by filtration.
(Yellow pigment dispersion 1)
C. I. Pigment Yellow 13 20 parts by weight Polymer dispersing agent (Solsperse series manufactured by Zeneca) 20 parts by weight OXT-221 (manufactured by Toagosei Co., Ltd.) 60 parts by weight (magenta pigment dispersion 1)
C. I. Pigment Red 57: 1 20 parts by weight Polymer dispersing agent (Solsperse series manufactured by Zeneca) 20 parts by weight OXT-221 (manufactured by Toagosei Co., Ltd.) 60 parts by weight (cyan pigment dispersion 1)
C. I. Pigment Blue 15: 3 20 parts by weight Polymer dispersing agent (Solsperse series manufactured by Zeneca) 20 parts by weight OXT-221 (manufactured by Toagosei Co., Ltd.) 60 parts by weight (Black pigment dispersion 1)
C. I. Pigment Black 7 20 parts by weight Polymer dispersant (Solsperse series manufactured by Zeneca) 20 parts by weight OXT-221 (manufactured by Toagosei Co., Ltd.) 60 parts by weight

(White pigment dispersion 1)
Titanium oxide (average particle size 0.15 μm, refractive index 2.52) 25 parts by weight Neutral polymer dispersant PB822 (manufactured by Ajinomoto Fine Techno Co.) 14 parts by weight OXT-221 (manufactured by Toagosei Co., Ltd.) 60 parts by weight

<Preparation of ink>
Example 1
(Yellow ink 1)
Yellow pigment dispersion 1 5 parts by weight Specific compound A 6 parts by weight Sensitizing dye: 9,10-dibutoxyanthracene 3 parts by weight Polymerizable compound Monomer: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy Rate (Celoxide 2021A: manufactured by Daicel UCB)
40 parts by weight Monomer: 3,7-bis (3-oxetanyl) -5-oxanonane (OXT-221: manufactured by Toagosei Co., Ltd.) 45 parts by weight Surfactant: BYK307 (manufactured by BYK Chemie) 1 part by mass The chemical structure of the specific (acid generating) compound A used is shown below.

(Magenta ink 1)
Magenta pigment dispersion 1 5 parts by weight Specific compound A 6 parts by weight Sensitizing dye: 9,10-dibutoxyanthracene 3 parts by weight Polymerizable compound Monomer: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy Rate (Celoxide 2021A: manufactured by Daicel UCB)
40 parts by weight Monomer: 3,7-bis (3-oxetanyl) -5-oxanonane (OXT-221: manufactured by Toagosei Co., Ltd.) 45 parts by weight Surfactant: BYK307 (manufactured by BYK Chemie) 1 part by weight

(Cyan ink 1)
Cyan pigment dispersion 1 5 parts by weight Specific compound A 6 parts by weight Sensitizing dye: 9,10-dibutoxyanthracene 3 parts by weight Polymerizable compound Monomer: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy Rate (Celoxide 2021A: manufactured by Daicel UCB)
40 parts by weight Monomer: 3,7-bis (3-oxetanyl) -5-oxanonane (OXT-221: manufactured by Toagosei Co., Ltd.) 45 parts by weight Surfactant: BYK307 (manufactured by BYK Chemie) 1 part by weight

(Black ink 1)
Black pigment dispersion 1 5 parts by weight Specific compound A 6 parts by weight Sensitizing dye: 9,10-dibutoxyanthracene 3 parts by weight Polymerizable compound Monomer: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy Rate (Celoxide 2021A: manufactured by Daicel UCB)
40 parts by weight Monomer: 3,7-bis (3-oxetanyl) -5-oxanonane (OXT-221: manufactured by Toagosei Co., Ltd.) 45 parts by weight Surfactant: BYK307 (manufactured by BYK Chemie) 1 part by weight

(White ink 1)
White pigment dispersion 1 5 parts by weight Specific compound A 6 parts by weight Sensitizing dye: 9,10-dibutoxyanthracene 3 parts by weight Polymerizable compound Monomer: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy Rate (Celoxide 2021A: manufactured by Daicel UCB)
40 parts by weight Monomer: 3,7-bis (3-oxetanyl) -5-oxanonane (OXT-221: manufactured by Toagosei Co., Ltd.) 45 parts by weight Surfactant: BYK307 (by BYK Chemie) 1 part by weight

  Each color ink 1 prepared as described above was filtered with a filter having an absolute filtration accuracy of 2 μm to obtain each color ink 1.

<Inkjet image recording>
Next, recording on a recording medium was performed using a commercially available inkjet recording 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 70 ° 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 100 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 exposure time was variable, and exposure energy was irradiated. In the present invention, dpi represents the number of dots per 2.54 cm.

Each of the inks prepared above was emitted in the order of black → cyan → magenta → yellow → white at an environmental temperature of 25 ° C., and each color was irradiated with ultraviolet rays by a metal halide lamp Vzero085 manufactured by Integration Technology. The exposure was performed at a total exposure energy of 500 mJ / cm ² uniformly for each color as energy for complete curing so that tackiness disappeared by palpation. As recording media, each color image was recorded on a grained aluminum support, a transparent biaxially stretched polypropylene film having a printability, a soft vinyl chloride sheet, cast coated paper, and commercially available recycled paper. However, in both cases, a high-resolution image without dot bleeding was obtained. Furthermore, even on high-quality paper, the ink was sufficiently cured without causing the ink to turn around, and there was almost no odor due to unreacted monomers. Further, the ink recorded on the film had sufficient flexibility, and the ink was not cracked even when it was bent, and there was no problem in the adhesion test by peeling the cello tape (registered trademark).

(Examples 2 to 10 and Comparative Examples 1 to 3)
<Preparation of ink>
Magenta inks 2 to 11 were prepared according to the method described below.

(Example 2: Magenta ink 2)
Magenta ink 2 was prepared in the same manner as magenta ink 1 except that the sensitizing dye of magenta ink 1, 9,10-dibutoxyanthracene was omitted.
(Example 3: Magenta ink 3)
Magenta ink 3 was prepared in the same manner as magenta ink 1 except that Darocur ITX manufactured by Ciba Specialty Chemicals was used instead of the sensitizing dye: 9,10-dibutoxyanthracene of magenta ink 1.

(Example 4: Magenta ink 4)
Magenta ink 4 was prepared in the same manner as magenta ink 1 except that IRGACURE 907 manufactured by Ciba Specialty Chemicals was used instead of the sensitizing dye: 9,10-dibutoxyanthracene of magenta ink 1.

(Example 5: Magenta ink 5)
Magenta ink 5 was prepared in the same manner as magenta ink 1 except that compound Z2 was used instead of the sensitizing dye: 9,10-dibutoxyanthracene of magenta ink 1.

(Example 6: Magenta ink 6)
Magenta ink 6 was prepared in the same manner as magenta ink 1 except that (Celoxide 3000: manufactured by Daicel UCB) was used instead of the monomer of magenta ink 1 (Celoxide 2021A: manufactured by Daicel UCB).

(Example 7: Magenta ink 7)
Magenta ink 7 was prepared in the same manner as magenta ink 1 except that phenothiazine (manufactured by Aldrich) was used instead of the sensitizing dye: 9,10-dibutoxyanthracene of magenta ink 1.

(Example 8: Magenta ink 8)
Magenta ink 8 was prepared in the same manner as magenta ink 1 except that 3 parts by weight of octylamine was added as a basic compound to magenta ink 1.

(Example 9: Magenta ink 9)
Magenta ink 9 was prepared in the same manner as magenta ink 1 except that 9,10-dibutoxyanthracene of magenta ink 1 was changed to the following compound Z1.

(Example 10: Magenta ink 10)
Magenta pigment dispersion 1 5 parts by weight Specific compound A 6 parts by weight Sensitizing dye: 9,10-dibutoxyanthracene 3 parts by weight Polymerizable compound Monomer: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy Rate (Celoxide 2021A: manufactured by Daicel UCB)
30 parts by weight Monomer: 3,7-bis (3-oxetanyl) -5-oxanonane (OXT-221: manufactured by Toagosei Co., Ltd.) 45 parts by weight Surfactant: BYK307 (by BYK Chemie) 1 part by weight radical polymerization Monomer: 1,6-hexanediol diacrylate 10 parts by weight

(Comparative Example 1: Magenta ink 11)
Magenta ink 11 was prepared with the following composition.
Magenta pigment dispersion 1 5 parts by weight Diphenyliodonium perchlorate salt (manufactured by Tokyo Chemical Industry) 6 parts by weight Sensitizing dye: 9,10-dibutoxyanthracene 3 parts by weight Polymerizable compound Monomer: 3,4-epoxycyclohexylmethyl-3 ', 4'-Epoxycyclohexanecarboxylate (Celoxide 2021A: manufactured by Daicel UCB)
40 parts by weight Monomer: 3,7-bis (3-oxetanyl) -5-oxanonane (OXT-221: manufactured by Toagosei Co., Ltd.) 45 parts by weight Surfactant: BYK307 (by BYK Chemie) 1 part by weight

(Comparative Example 2: Magenta ink 12)
Magenta ink 12 was prepared with the following composition.
Magenta pigment dispersion 1 5 parts by weight Irgacure 250 (manufactured by Ciba Specialty Chemicals) 6 parts by weight Sensitizing dye: 9,10-dibutoxyanthracene 3 parts by weight Polymerizable compound Monomer: 3,4-epoxycyclohexylmethyl-3 ', 4'-Epoxycyclohexanecarboxylate (Celoxide 2021A: manufactured by Daicel UCB)
40 parts by weight Monomer: 3,7-bis (3-oxetanyl) -5-oxanonane (OXT-221: manufactured by Toagosei Co., Ltd.) 45 parts by weight Surfactant: BYK307 (by BYK Chemie) 1 part by weight

(Comparative Example 3: Magenta ink 13)
Magenta ink 13 was prepared in the same manner as magenta ink 11 except that 9,10-dibutoxyanthracene of magenta ink 11 was changed to DarocurITX (manufactured by Ciba Specialty Chemicals).

  Crude magenta inks 2 to 13 prepared as described above were filtered through a filter having an absolute filtration accuracy of 2 μm to obtain magenta inks 2 to 13, respectively.

(Example 11: Magenta ink 14)
C. I. Prepared in the same manner as Magenta Ink 1 except that the following compound M-1 (oxidation potential + 1.37 V) was used as an oil-soluble dye instead of Pigment Red 57: 1, and filtered through a filter having an absolute filtration accuracy of 2 μm. And magenta ink 14.

(Example 12: Magenta ink 15)
C. I. Prepared in the same manner as Magenta Ink 1 except that the following compound M-2 (oxidation potential +0.94 V) was used as an oil-soluble dye instead of Pigment Red 57: 1, and filtered with a filter having an absolute filtration accuracy of 2 μm. And magenta ink 15.

<Inkjet image recording>
Using the magenta inks 2 to 15 prepared as described above, magenta images were produced in the same manner as in the method described in Example 1.

(Example 13: Magenta ink 9)
Using the magenta ink 1, a magenta image was produced in the same manner as described in Example 1 except that an ultraviolet light emitting diode (UV-LED) was used instead of the metal halide lamp Vzero085 manufactured by Integration Technology. .
In this example, NCCU033 manufactured by Nichia Chemical was used as the UV-LED. The LED outputs ultraviolet light having a wavelength of 365 nm from one chip. When a current of about 500 mA is applied, light of about 100 mW is emitted from the chip. A plurality of these are arranged at intervals of 7 mm, and a power of 0.3 W / cm ² is obtained on the surface of the recording medium (hereinafter also referred to as a medium). The exposure time after the droplet ejection and the exposure time can be changed according to the transport speed of the medium and the distance between the head and the LED in the transport direction. In this embodiment, the exposure is performed about 0.5 seconds after landing.
The exposure energy on the medium could be adjusted between 0.01 and 15 J / cm ² depending on the setting of the distance to the medium and the conveyance speed.

(Comparative Example 4)
A magenta image was produced using the magenta ink 12 in the same manner as in Example 13.

<Evaluation of inkjet image>
Next, each of the formed images was evaluated for curing sensitivity, thermal stability, and printing durability by the methods described below.

1. Measurement of Curing Sensitivity Superimposing high quality paper on the print sample immediately after exposure, evaluating the transferability of the color material to high quality paper when passed through the pressure roller (50 kg / cm2), and the amount of exposure energy (mJ / cm at which transfer is lost) ² ) was defined as curing sensitivity. The smaller the value, the higher the sensitivity.

2. Evaluation of thermal stability After the prepared ink was stored at 75% RH and 60 ° C. for 3 days, the ink viscosity at the injection temperature was measured, and the increase in the ink viscosity was expressed as the viscosity ratio after storage / before storage. . When the viscosity does not change and is close to 1.0, the storage stability is good, and when it exceeds 1.5, clogging may occur at the time of injection, which is not preferable.

3. Evaluation of printing durability The image printed on the grained aluminum support prepared above was used as a printing plate, and after printing with a Heidel KOR-D machine, the number of completed sheets was compared as a printing durability index (Example) 1 was set to 100). A larger numerical value is preferable because it has a higher printing durability.

Claims (8)

(A) A radiation-sensitive composition comprising a compound represented by formula (I).

In the formula (I), X ⁻ represents a monovalent counter anion, Y _{1 to} Y ₄ independently represent a monovalent substituent, and may be bonded to each other to form a ring, and R represents a naphthalene ring The above substituents are represented, and two or more Rs may be bonded to each other to form a ring, and n is the number of substituents R, and represents an integer of 0 to 6. (A) a compound represented by formula (I),
An ink composition containing (b) a polymerizable compound, and (c) a colorant.

In the formula (I), X ⁻ represents a monovalent counter anion, Y _{1 to} Y ₄ independently represent a monovalent substituent, and may be bonded to each other to form a ring, and R represents a naphthalene ring The above substituents are represented, and two or more Rs may be bonded to each other to form a ring, and n is the number of substituents R, and represents an integer of 0 to 6.   The ink composition according to claim 2, which is for inkjet recording. (A) a step of discharging an ink composition onto a recording medium; and
(B) a step of irradiating the discharged ink composition with actinic radiation to cure the ink composition;
An inkjet recording method comprising:
An ink jet recording method, wherein the ink composition is the ink composition according to claim 2. The active 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 surface of the recording medium of 10 to 2,000 mW / cm ^2. The ink jet recording method according to claim 4.   Printed matter recorded by the ink jet recording method according to claim 4 or 5. (A) a step of discharging the ink composition according to claim 2 or 3 onto a hydrophilic support; and
(B) A step of irradiating the discharged ink composition with actinic radiation to cure the ink composition, thereby forming a hydrophobic image formed by curing the ink composition on the hydrophilic support. ,
A method for producing a lithographic printing plate comprising   A lithographic printing plate produced by the method for producing a lithographic printing plate according to claim 7.