JP2008303309A - Actinic light-curable composition, curing method, actinic light-curable ink composition and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an actinic light-curable composition enhanced in shelf life of an actinic light-curable composition and actinic light-curable ink composition, and having excellent curability and substrate adhesiveness, a curing method thereof, an actinic light-curable ink composition and an image forming device. <P>SOLUTION: The actinic light-curable composition comprises a compound specified by a sulfonium salt and a specific cation polymerizable compound represented by the general formula (B). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an actinic ray curable composition (hereinafter also simply referred to as a composition), a curing method thereof, an actinic ray curable ink composition, and an image forming method.

  Conventional actinic ray curable compositions, in particular UV curable cationic polymerizable compositions, and cured products thereof are useful materials for various applications such as adhesives, inkjet inks, resists, display members such as color filters, etc. It has been known.

  An actinic ray curable composition that can be cured stably in various environments without releasing harmful benzene by using a triarylsulfonium salt having a specific structure as a photoacid generator has been disclosed. (For example, refer to Patent Document 1).

  However, since this actinic ray curable composition lacks sensitivity to actinic rays in the long wavelength region, it had a problem with the substrate adhesion of the cured product derived from the internal curability of the cured product, There is a problem that a gel-like product may be generated during storage of the composition, and further, improvement in the storage stability of the cured product has been desired.

  An actinic ray curable composition containing an anthracene derivative having a specific structure and a polyfunctional epoxide having a specific structure has been disclosed for improving the substrate adhesion of the active light curable composition. There is still a problem in storage stability, and further improvement has been desired for storage stability and substrate adhesion of the actinic ray curable composition.

  On the other hand, a photoacid generator having a structure in which a triarylsulfonium salt in which two aryl groups are linked to each other is multimerged and a radiation curable composition containing the photoacid generator have been disclosed (for example, see Patent Document 2). The technology aims to reduce toxicity / low molecular weight compounds generated during decomposition of the photoacid generator and to improve the solubility of the photoacid generator in the composition. The substrate adhesion was not sufficient.

Thus, excellent photoacid generators and cationically polymerizable compounds have been found so far, but by using these alone, excellent curability, excellent substrate adhesion, actinic ray curable composition And the storage stability of the actinic ray curable ink composition could not be made compatible.
JP 2006-104185 A International Publication Number WO2003 / 008404

  An object of the present invention is that the actinic ray curable composition and the actinic ray curable ink composition have good storage stability, and have an excellent curable property and excellent substrate adhesion, The curing method, the actinic ray curable ink composition, and the image forming method are provided.

  The above problem could be solved by the following configuration.

  1. An actinic ray curable composition comprising a compound represented by the following general formula (S) and a cationically polymerizable compound represented by the following general formula (B).

(In the formula, Rs _{1 to} Rs ₃ represent substituents, a, b and c each represent an integer of 0 to 4. X is a divalent linking group, which is a single bond or the following partial structural formula: Group (A-1),

(In the partial structural formula group (A-1), the * part is a bonding site. Rn ₁ represents a hydrogen atom or a substituent. K represents an integer of 1 to 6).

  L is a divalent linking group, and is a single bond or the following partial structural formula group (B-1)

(In the partial structural formula group (B-1), the * part is a bonding site. Rn ₁ represents a hydrogen atom or a substituent. K represents an integer of 1 to 6). A ⁻ represents a counter anion. )

(Wherein R ₂₀₁ and R ₂₀₂ each represent a substituent, m20 and n20 each represent 0, 1 or 2. r0 represents 1 to 3. L ₀ may contain an oxygen atom or a sulfur atom in the main chain. Represents an r0 + 1 valent linking group or a single bond having 1 to 15 carbon atoms.)
2. 2. The actinic ray curable composition according to 1 above, wherein in the general formula (S), X is any one of a single bond, a sulfur atom, and a carbonyl group.

  3. 3. The actinic ray curable composition as described in 1 or 2 above, wherein in the general formula (S), L is a single bond or a group selected from the following partial structural formula group (B-2).

(In the formula, * part is a binding site.)
4). In said general formula (S), c is an integer of 1-4, The actinic ray curable composition of any one of said 1-3 characterized by the above-mentioned.

  5. 5. The actinic ray curable composition according to any one of 1 to 4 above, which comprises a compound represented by the following general formula (1).

(In the formula, R ₁ to R ₇ and R ₁₀ each represent a hydrogen atom or a substituent, and R ₈ and R ₉ each represent a substituted or unsubstituted alkyl group.)
6). 6. The actinic ray curable composition as described in 5 above, wherein in the general formula (1), R ₁₀ is a tertiary alkyl group.

7). 7. The actinic ray curable composition as described in 5 or 6 above, wherein in the general formula (1), R ₁₀ is a t-butyl group or a t-pentyl group.

8). In the general formula (1), R ₁ and R ₇ are hydrogen atoms, and R ₈ and R ₉ are unsubstituted alkyl groups having 3 to 7 carbon atoms. Item 4. The actinic ray curable composition according to Item.

9. In Formula (1), actinic ray curable composition according to any one of the 5-8, wherein R ₈ and R ₉ is a straight chain alkyl group.

  10. 10. The actinic ray curable ink composition comprising the actinic ray curable composition according to any one of 1 to 9 above.

  11. 10. The curing method for an actinic ray curable composition, wherein the actinic ray curable composition according to any one of 1 to 9 is cured by irradiating with ultraviolet rays.

  12 11. An image forming method comprising forming an image by injecting or applying the actinic ray curable ink composition described in 10 above in an image-like manner and irradiating it with ultraviolet rays to cure.

  That is, the present inventors have found that a combination of a photoacid generator having a specific structure and a cationic polymerizable compound can achieve both excellent curability and storage stability of the composition.

  In addition, it has also been found that by combining a sensitizer having a structure unique to the present invention, the substrate adhesion can be improved without deteriorating the storage stability.

  The actinic ray curable composition, the curing method thereof, the actinic ray curable ink composition and the image forming method according to the present invention have good storage stability of the actinic ray curable composition and the actinic ray curable ink composition, Moreover, it has excellent curability and excellent substrate adhesion, and has an excellent effect.

  Hereinafter, the present invention will be described in more detail.

Description of the compound represented by the general formula (S) In the general formula (S), Rs _{1 to} Rs ₃ are substituents, and the substituents are not particularly limited, and may be alkyl groups (for example, methyl groups, ethyl groups). Group, propyl group, isopropyl group, butyl group, tert-butyl group, isobutyl group, sec-butyl group, pentyl group, tert-pentyl group, hexyl group, 2-methylpentyl group, isohexyl group, heptyl group, isoheptyl group, 1-propylbutyl group, octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, etc.), cycloalkyl group (for example, cyclopropyl group, cyclobutyl group, cyclopentyl) Group, cyclohexyl group, cycloheptyl group, etc.), alkenyl group (for example, vinyl group, 1 Propenyl, 2-propenyl, butenyl, 2-butenyl, allyl, etc.), cycloalkenyl (cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclooctadienyl, etc.), alkynyl ( For example, acetylenyl group, propynyl group, butynyl group, propargyl group, etc.), aryl group (for example, phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, pentacenyl group, etc.), heterocyclic group (for example, furyl group, Thienyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, pyrrolyl group, 2-quinolyl group, Aroma such as 1-isoquinyl group Group, for example, non-aromatic groups such as pyrrolidyl group, imidazolidyl group, morpholino group, oxazolidyl group, 2-tetrahydrofuranyl group, 2-tetrahydrothienyl group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group), halogen Atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, hydroxyl groups, carboxyl groups, alkoxy groups (for example, alkoxy groups formed by combining the aforementioned alkyl groups and oxygen atoms), aryloxy groups (as aryl groups) Is as defined above for the aryl group), silyloxy group, heterocyclic oxy group (the heterocyclic ring is as defined above for the heterocyclic group), acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group ( The alkoxy moiety is synonymous with the alkoxy group described above) An aryloxycarbonyloxy group (the aryl moiety is as defined above for the aryl group), an amino group, an alkyl and an arylamino group (the alkyl moiety and the aryl moiety are as defined above for the alkyl group and aryl group, respectively), Anilino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group (alkoxy moiety is synonymous with the aforementioned alkoxy group), aryloxycarbonylamino group (aryl moiety is synonymous with the aforementioned aryl group), sulfa Moylamino group, alkyl and arylsulfonylamino groups (the alkyl moiety and aryl moiety are as defined above for alkyl group and aryl group, respectively), mercapto group, alkylthio group (wherein the alkyl moiety is as defined above for alkyl group) , A reelthio group (wherein the aryl group is as defined above for the aryl group), a heterocyclic thio group (as the heterocycle is as defined above for the heterocyclic group), a sulfamoyl group, a sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group (the alkyl moiety and the aryl moiety are the same as those mentioned as the aforementioned alkyl group and aryl group, respectively), acyl group, aryloxycarbonyl group (the aryl moiety is exemplified as the aforementioned aryl group) As defined above), alkoxycarbonyl group (alkoxy moiety is as defined above for alkoxy group), carbamoyl group, aryl and heterocyclic azo group (aryl moiety and heterocyclic moiety are as defined above as aryl group and heterocyclic group), imide Group, silyl group, hydrazino group, ureido group, Ron acid, phosphato group, sulfato group and other known substituents. These groups may be further substituted with the same substituent. a, b and c are integers from 0 to 4, preferably 1 to 4, and more preferably 1 to 2. The plurality of Rs ₁ , Rs ₂ and Rs ₃ may be the same or different. Rs ₁ , Rs ₂ , and Rs3 may be linked by removing a hydrogen atom at an arbitrary position, and may be bonded by Rs ₁ , Rs ₂ , or Rs ₃ on the same benzene ring to form a ring. .

Rs _{1 to} Rs ₃ are preferably a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or an alkylamino group, and more preferably a halogen atom, an alkyl group, or an alkoxy group.

  X is a divalent linking group, and is a single bond or any group selected from the partial structural formula group (A-1).

Examples of the substituent represented by Rn ₁ include the same substituents as Rs ₁ to Rs _3, and an alkyl group, an aryl group, or an acyl group is preferable.

Rn ₁ may be bonded to any carbon atom of the general formula (S) to form a ring structure by removing any hydrogen atom and becoming a linking group.

  X is preferably a single bond, a sulfur atom or a carbonyl group, more preferably a carbonyl group.

  L is a divalent linking group and is a single bond or any group selected from the partial structural formula group (B-1).

Examples of the substituent represented by Rn ₁ include the same substituents as Rs ₁ to Rs _3, and an alkyl group, an aryl group, or an acyl group is preferable.

Rn ₁ may be bonded to any carbon atom of the general formula (S) to form a ring structure by removing any hydrogen atom and becoming a linking group.

  L is preferably a single bond or a partial structure represented by the partial structural formula group (B-2).

Z ⁻ represents a counter anion. Counter anions include complex ions such as BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF ₆ ⁻ , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ and CF _3. Examples thereof include sulfonate ions such as SO ₃ ^−, from the viewpoint of acid generation ability, borate ions and PF ₆ ⁻ are preferable, and PF ₆ ⁻ is more preferable.

  Specific examples of the compound represented by formula (S) are shown below, but the present invention is not limited thereto.

Method for synthesizing compound represented by general formula (S) The compound represented by general formula (S) may be produced by any method. For example, an existing cyclic sulfide compound is oxidized with various oxidizing agents to form cyclic sulfoxide. A compound that reacts with the oxygen atom of the sulfoxide to form a leaving group from the sulfur atom, and a nucleophilic reactant such as an alkylating agent or arylating agent in the presence of a suitable acid catalyst. By adding (a compound that is relatively nucleophilic with respect to the leaving group on S), a desired sulfonium structure can be formed.

  By subjecting this to salt exchange by a conventionally known method, the compound represented by the general formula (S) can be synthesized.

  It can also be synthesized by a method for synthesizing a corresponding compound described in International Publication No. WO2003 / 008404.

  Hereinafter, a method for synthesizing the compound represented by the general formula (S) will be described with specific examples, but the present invention is not limited thereto.

(Synthesis of Exemplary Compound: General Synthesis Method of Compound Represented by General Formula (S))
To 26 g of isopropylthioxanthone, 1000 ml of acetonitrile and 400 ml of water were added and dissolved, and then 205 g of ceric ammonium nitrate was further added and stirred for 4 hours.

  Water was added, the organic matter was extracted with ethyl acetate, washed with water, and dried over magnesium sulfate. After filtration and concentration, the residue was purified by silica gel chromatography to obtain 16 g of a sulfoxide form of isopropylthioxanthone.

  16 g of sulfoxide was slowly added with stirring to 20 ml of concentrated sulfuric acid in an ice-water bath, and after 1 hour, 10 g of diphenyl ether was added.

  After stirring overnight at room temperature, the reaction was stopped by pouring into water, extraction was performed with methylene chloride, and after concentration, purification was performed by silica gel chromatography.

This was dissolved in acetic acid and added dropwise to the stirring aqueous KPF ₆ solution, and the resulting solid was collected by filtration and dried to obtain 1 g of an intermediate. Next, a solution in which 2 g of isopropylthioxanthone sulfoxide and 2 g of aluminum chloride were dissolved in 150 g of tetrachloroethylene at room temperature was prepared, and 2 g of aluminum chloride was further added thereto, followed by stirring for 20 minutes. After adding 1 g of the above-mentioned intermediate and 1 g of aluminum chloride to this solution and stirring for 30 minutes, the organic phase was poured into water and the aqueous phase was washed with diethyl ether. An aqueous KPF ₆ solution was added to the solution, and the precipitated solid was collected by filtration to obtain 0.5 g of Exemplified Compound G.

  The addition amount of the compound represented by the general formula (S) of the present invention is not particularly limited, but is in the range of 0.01 parts by mass to 30 parts by mass when the total amount of the actinic ray curable composition is 100 parts by mass. It is preferable to add in the range of 0.1 to 20 parts by mass.

Cationic polymerizable compound represented by the general formula (B) In the general formula (B), R ₂₀₁ and R ₂₀₂ each represent a substituent, and m20 and n20 each represent 0, 1 or 2. r0 represents 1-3. L ₀ represents a C 1-15 r 0 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain.

In the general formula (B), R ₂₀₁ and R ₂₀₂ each represents a substituent. Examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl having 1 to 6 carbon atoms. Group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.), C1-C6 alkoxy group (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (eg, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), And alkoxycarbonyl groups (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) and the like. As the substituent, an alkyl group, an alkoxy group, and an alkoxycarbonyl group are preferable.

  m20 and n20 represent 0 to 2, and 0 or 1 is preferable.

L ₀ represents a C 1-15 r 0 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain.

  Examples of the divalent linking group having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain include the following groups, and these groups and —O— group, —S— group, —CO— group, Examples include groups formed by combining a plurality of —CS— groups.

Methylene group [—CH ₂ —]
An ethylidene group [> CHCH ₃ ],
Isopropylidene [> C (CH ₃ ) ₂ ]
1,2-ethylene group [—CH ₂ CH ₂ —],
1,2-propylene group [—CH (CH ₃ ) CH ₂ —],
1,3-propanediyl group [—CH ₂ CH ₂ CH ₂ —],
2,2-dimethyl-1,3-propanediyl group [—CH ₂ C (CH ₃ ) ₂ CH ₂ —],
2,2-dimethoxy-1,3-propanediyl group [—CH ₂ C (OCH ₃ ) ₂ CH ₂ —],
2,2-dimethoxymethyl-1,3-propanediyl group [—CH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ —],
1-methyl-1,3-propanediyl group [—CH (CH ₃ ) CH ₂ CH ₂ —],
1,4-butanediyl group [—CH ₂ CH ₂ CH ₂ CH ₂ —],
1,5-pentanediyl group [—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —],
An oxydiethylene group [—CH ₂ CH ₂ OCH ₂ CH ₂ —],
A thiodiethylene group [—CH ₂ CH ₂ SCH ₂ CH ₂ —],
3-oxothiodiethylene group [—CH ₂ CH ₂ SOCH ₂ CH ₂ —],
3,3-dioxothiodiethylene group [—CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ —],
1,4-dimethyl-3-oxa-1,5-pentanediyl group [—CH (CH ₃ ) CH ₂ O CH (CH ₃ ) CH ₂ —],
3-oxopentanediyl group [—CH ₂ CH ₂ COCH ₂ CH ₂ —],
1,5-dioxo-3-oxapentanediyl group [—COCH ₂ OCH ₂ CO—],
4-oxa-1,7-heptanediyl group [—CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —],
3,6-dioxa-1,8-diyl group _{[-CH 2 CH 2 OCH 2 CH} 2 OCH2CH2-],
1,4,7-trimethyl-3,6-dioxa-1,8-octanediyl group [—CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —],
5,5-dimethyl-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (CH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
5,5-dimethoxy-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
5,5-dimethoxymethyl-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —],
4,7-dioxo-3,8-dioxa-1,10-decandiyl group [—CH ₂ CH ₂ O—COCH ₂ CH ₂ CO—OCH ₂ CH ₂ —],
3,8-dioxo-4,7-dioxa-1,10-decandiyl group [—CH ₂ CH ₂ CO—OCH ₂ CH ₂ O—COCH ₂ CH ₂ —],
1,3-cyclopentanediyl group [-1,3-C ₅ H ₈ —],
1,2-cyclohexanediyl group [-1,2-C ₆ H _10- ],
1,3-cyclohexanediyl group [-1,3-C ₆ H _10- ],
1,4-cyclohexanediyl group [-1,4-C ₆ H _10- ],
2,5-tetrahydrofurandiyl group [2,5-C ₄ H ₆ O—]
p- phenylene _{[-p-C 6 H 4 -} ],
m- phenylene group _{[-m-C 6 H 4 -} ],
α, α′-o-xylylene group [—o—CH ₂ —C ₆ H ₄ —CH ₂ —],
α, α′-m-xylylene group [—m—CH ₂ —C ₆ H ₄ —CH ₂ —],
α, α′-p-xylylene group [—p—CH ₂ —C ₆ H ₄ —CH ₂ —],
Furan-2,5-diyl - bismethylene group _{[2,5-CH 2 -C 4 H} 2 O-CH 2 -]
Thiophene-2,5-diyl-bismethylene group [2,5-CH ₂ —C ₄ H ₂ S—CH ₂ —]
Isopropylidenebis -p- phenylene group _{[-p-C 6 H 4 -C} (CH 3) 2 -p-C 6 H 4 -]
Examples of the trivalent or higher linking group include groups formed by removing as many hydrogen atoms as necessary from the divalent linking groups listed above, and an —O— group, —S— group, —CO— group, Examples include groups formed by combining a plurality of —CS— groups.

L ₀ may have a substituent.

  Examples of the substituent include, for example, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group). , Etc.), an alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group) Group, propionyl group, trifluoroacetyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, Etc.). Preferable examples of the substituent include an alkyl group, an alkoxy group, and an alkoxycarbonyl group.

L ₀ is preferably a divalent linking group having 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain, and more preferably a divalent linking group having 1 to 5 carbon atoms in which the main chain is composed of only carbon. preferable.

  Particularly preferred alicyclic epoxides are those represented by the following general formula (BI) or general formula (B-II) in terms of producing a cured film with high hardness and further improving the adhesion of the cured film to the substrate. It is a compound.

In the general formula (BI), R ₂₁₁ and R ₂₁₂ represent a substituent, and m21 and n21 represent 0, 1 or 2. p1 and q1 each represents 0 or 1. r1 represents 1-3. L ₁ represents a C 1-15 r 1 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain.

In the general formula (B-II), R ₂₂₁ and R ₂₂₂ represent substituents, and m22 and n22 represent 0, 1 or 2. p2 and q2 each represents 0 or 1. r2 represents 1-3. L ₂ represents a C 1-15 r 2 + 1 valent linking group or single bond which may contain an oxygen atom or a sulfur atom in the main chain.

  A particularly preferred alicyclic epoxide is a compound represented by the following general formula (B-III) or (B-IV) in that the curing sensitivity is high and the curing sensitivity is not easily affected by changes in the printing environment. .

In General Formula (B-III), R ₂₃₁ and R ₂₃₂ each represent a substituent, and m23 and n23 each represent 0 or 1. p3 and q3 each represents 0 or 1. r3 represents 1-3. L ₃ represents a C 1-15 r 3 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain.

In the general formula (B-IV), R ₂₄₁ and R ₂₄₂ represent substituents, and m24 and n24 represent 0 or h1. p4 and q4 each represents 0 or 1. r4 represents 1-3. L ₄ represents a C 1-15 r 4 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain.

  Furthermore, the alicyclic epoxy compound represented by general formula (B-III) or (B-IV) will be described.

In the above formula, R ₂₃₁ , R ₂₃₂ , R ₂₄₁ and R ₂₄₂ represent a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), C 1-6 Alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.), C 1-6 alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso- Propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, Etc.), alkoxycarbonyl groups (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) and the like. As the substituent, an alkyl group, an alkoxy group, and an alkoxycarbonyl group are preferable.

  m23, n23, m24 and n24 represent 0 to 2, and 0 or 1 is preferable.

L ₃ represents an r3 + 1-valent linking group having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain or a single bond, and L ₄ has 1 carbon atom which may contain an oxygen atom or a sulfur atom in the main chain. Represents an r4 + 1-valent linking group or a single bond of ˜15.

Examples of the divalent linking group having 1 to 15 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain, are the same as those described in the description of L ₀ .

L ₃ and L ₄ are preferably a divalent linking group having 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain, and a divalent linking group having 1 to 5 carbon atoms in which the main chain is composed solely of carbon. Groups are more preferred.

  Specific examples of the compound represented by formula (B) of the present invention are shown below, but the present invention is not limited to these.

  The amount of the compound represented by the general formula (B) is 10 with respect to 100 parts by mass of the actinic ray curable composition in consideration of curability due to the curing environment (temperature, humidity) and film physical properties after curing. It is preferable to contain ~ 40 mass.

  In the present invention, one type of the compound represented by the general formula (B) may be used alone, or two or more types may be used in appropriate combination.

  These alicyclic epoxy compounds may be produced by any method. For example, Maruzen KK Publishing, 4th Edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The Chemistry of Heterocyclic Compound-Volume No. 5, Small Ring Heterocycle part3 Oxiranes, John & Wiley and Sons, An Interc. 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Laid-Open No. 11-100308, Japanese Patent Laid-Open No. 4-36263, Japanese Patent Laid-Open No. 4-69360, and the like.

(Cationically polymerizable compound)
In the actinic ray curable composition and the actinic ray curable ink composition of the present invention (hereinafter also simply referred to as inkjet ink or ink), a cationically polymerizable compound is further added in addition to the compound represented by formula (B). It is preferable.

  The cationically polymerizable compound used in the actinic ray curable composition of the present invention is a type in which polymerization is caused by cationic polymerization, (1) a compound having an oxirane ring (also referred to as an epoxy compound), and (2) a styrene derivative. , (3) vinyl naphthalene derivatives, (4) vinyl ethers, (5) N-vinyl compounds, and (6) compounds having an oxetane ring. It is preferable to use at least one compound selected from a compound having an ionic group (also referred to as an epoxy compound) and a cationically polymerizable compound having an oxetane ring.

  The type having an oxirane ring of (1) is not particularly limited, and examples thereof include compounds having an oxirane ring in one molecule.

  Examples of such epoxy compounds include alicyclic epoxides (also referred to as alicyclic epoxies and alicyclic epoxy compounds), glycidyl esters of polybasic acids, glycidyl ethers of polyhydric alcohols, and polyoxyalkylene glycols. Glycidyl ethers, aromatic polyol glycidyl ethers, aromatic polyol glycidyl ether hydrogenated compounds, urethane polyepoxy compounds and epoxidized polybutadienes. These compounds can be used alone or in a mixture of two or more.

  An epoxy compound that can be suitably used in the present invention is an alicyclic epoxide compound.

Monofunctional epoxy compound In the actinic ray curable composition of the present invention, by using a monofunctional epoxide in combination, a further sensitivity enhancement effect or a cured film physical property improvement effect can be obtained.

  Although there will be no restriction | limiting in particular if it is a monofunctional alicyclic epoxide, In this invention, a monofunctional alicyclic epoxide is preferable and the monofunctional alicyclic epoxide represented by the following general formula (A) is more preferable.

In the general formula (A), R ₁₀₁ represents a substituent that does not contain a cationic polymerizable or radical polymerizable reactive functional group, and m10 represents 1, 2, 3, or 4.

Further, R ₁₀₁ in the general formula (A) represents a substituent that does not contain a cationic functional group or a radical polymerizable reactive functional group.

  Examples of the substituent include, for example, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group). , Etc.), a cycloalkyl group having 3 to 6 carbon atoms (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkoxy group having 1 to 20 carbon atoms (eg, methoxy group, ethoxy group) , N-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), C2-C20 acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.), carbon number An acyloxy group having 2 to 20 carbon atoms (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), Ruthio group (for example, acetylthio group, propionylthio group, trifluoroacetylthio group, etc.), C2-C20 alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), C2 -20 alkylthiocarbonyl groups (methylthiocarbonyl group, ethylthiocarbonyl group, tert-butylthiocarbonyl group, etc.) and the like.

  These groups may further have a substituent.

  Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n- Butoxy group, tert-butoxy group, etc.), C2-C20 acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.), C2-C20 acyloxy group (for example, acetoxy group, propionyloxy) Group, trifluoroacetoxy group, etc.), C2-C20 alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), C2-C20 alkylthiocarbonyl group (methylthiocarbonyl group) , Ethylthiocarbonyl group, tert-butylthiocarbonyl group, etc.) An aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, and the like are go up. As the substituent, a halogen atom, an alkoxy group, an acyloxy group, and an alkoxycarbonyl group are preferable.

  Among these, one kind of preferable alicyclic epoxide is a compound represented by the following general formula (AI).

In general formula (AI), R ₁₁₁ represents a substituent, and m11 represents 0, 1, 2, or 3.

R ₁₁₂ , R ₁₁₃ and R ₁₁₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.

Y ₁₁ and Y ₁₂ each independently represent O or S, p11 represents 0, 1 or 2, q11 represents 0 or 1, r11 represents 0 or 1, and s11 represents 0 or 1.

  Furthermore, the alicyclic epoxy compound represented by general formula (AI) is demonstrated.

In the general formula (AI), R ₁₁₁ represents a substituent.

  Examples of the substituent include, for example, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group). Etc.), C1-20 alkoxy groups (eg, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butoxy, etc.), acyl Group (for example, each group such as acetyl group, propionyl group, trifluoroacetyl group), acyloxy group having 1 to 20 carbon atoms (for example, each group such as acetoxy group, propionyloxy group, trifluoroacetoxy group), carbon number 1 ~ 20 alkoxycarbonyl groups (each group such as methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group), carbon number -20 alkylthiocarbonyl groups (methylthiocarbonyl group, ethylthiocarbonyl group, tert-butylthiocarbonyl group, etc.), aryloxycarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, cyano groups, nitro groups, etc. It is done. As the substituent, an alkyl group, an alkoxy group, and an alkoxycarbonyl group are preferable.

R ₁₁₂ , R ₁₁₃ and R ₁₁₄ represent a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group include the same groups as those in the examples of the alkyl group for R ₁₁₁ described above.

  Examples of the substituent of the alkyl group having a substituent include, for example, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkoxy group having 1 to 20 carbon atoms (for example, a methoxy group, an ethoxy group, n- Propoxy group, iso-propoxy group, each group such as n-butoxy group, tert-butoxy group), acyl group (for example, each group such as acetyl group, propionyl group, trifluoroacetyl group), 1 to 20 carbon atoms Acyloxy group (for example, each group such as acetoxy group, propionyloxy group, trifluoroacetoxy group), C1-C20 alkoxycarbonyl group (each group such as methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group) An alkylthiocarbonyl group having 2 to 20 carbon atoms (methylthiocarbonyl group, ethylthiocarbonyl group) tert-butylthiocarbonyl group, etc.), aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, cyano group, nitro group and the like. Preferred examples of the substituent include an alkoxy group and an alkoxycarbonyl group. is there.

Y ₁₁ and Y ₁₂ represent O or S, and O is preferable.

m ₁₁ represents 0 to 3, and preferably 1 or 2. p ₁₁ represents 0, 1 or 2, and q ₁₁ , r ₁₁ and s ₁₁ represent 0 or 1.

  The compound represented by the following general formula (A-II) is also a kind of preferable alicyclic epoxide.

In the general formula (A-II), R ₁₂₁ represents a substituent, and m12 represents 0, 1 or 2.

R ₁₂₂ , R ₁₂₃ and R ₁₂₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.

Y ₂₁ and Y ₂₂ each independently represents O or S, p12 represents 0, 1 or 2, q12 represents 0 or 1, r12 represents 0 or 1, and s12 represents 0 or 1.

  Furthermore, the alicyclic epoxy compound represented by the general formula (A-II) will be described.

In the above formula, R ₁₂₁ represents a substituent, and examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 20 carbon atoms (for example, a methyl group). , Ethyl group, propyl group, isopropyl group, butyl group, etc.), alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert) -Butoxy group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group having 1 to 20 carbon atoms (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.) An alkoxycarbonyl group having 1 to 20 carbon atoms (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) , An alkylthiocarbonyl group having 2 to 20 carbon atoms (methylthiocarbonyl group, ethylthiocarbonyl group, tert-butylthiocarbonyl group, etc.), aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, cyano group, nitro group, etc. Is mentioned. As the substituent, an alkyl group, an alkoxy group, and an alkoxycarbonyl group are preferable.

Y ₂₁ and Y ₂₂ represent —O— or —S—, and —O— is particularly preferable.

m ₁₂ represents 0 to 2, and 0 or 1 is preferable. p ₁₂ represents 0, 1 or 2, and q ₁₂ , r ₁₂ and s ₁₂ represent 0 or 1.

R ₁₂₂ , R ₁₂₃ and R _{124 each} represents a hydrogen atom or a substituted or unsubstituted alkyl group.

Examples of the alkyl group include the same groups as those in the examples of the alkyl group for R ₁₁₁ described above.

  Examples of the substituent of the alkyl group having a substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, ethoxy group, n- Propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group having 1 to 20 carbon atoms (for example, Acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), C1-C20 alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), C2-C20 alkylthio Carbonyl group (methylthiocarbonyl group, ethylthiocarbonyl group, tert-butylthio) Carbonyl group, etc.), an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, etc., and preferred as substituents, an alkoxy group, an alkoxycarbonyl group.

  The compounds represented by the following general formula (A-III), general formula (A-IV) or general formula (AV) are also a kind of preferred alicyclic epoxides.

In the general formula (A-III), R ₁₃₁ represents a substituent, and m13 represents 0, 1 or 2.

R ₁₃₂ , R ₁₃₃ and R ₁₃₄ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. p13 represents 0, 1 or 2, and q13 represents 0 or 1.

In the general formula (A-IV), R ₁₄₁ represents a substituent, and m14 represents 0, 1 or 2. R ₁₄₂ , R ₁₄₃ and R ₁₄₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. p14 represents 0, 1 or 2.

In the general formula (A-V), R ₁₅₁ represents a substituent, and m15 represents 0, 1 or 2. R154 represents a hydrogen atom or a substituted or unsubstituted alkyl group. s15 represents 0 or 1.

  Furthermore, the alicyclic epoxy compound represented by general formula (A-III), general formula (A-IV), and general formula (AV) will be described.

In the above formula, R ₁₃₁ , R ₁₄₁ , and R ₁₅₁ each represent a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), alkyl having 1 to 20 carbon atoms. Group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.), C1-C20 alkoxy group (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group having 1 to 20 carbon atoms (for example, acetoxy group, propionyloxy group, trimethyl group) Fluoroacetoxy group, etc.), C1-C20 alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxyca) Bonyl group, etc.), C2-C20 alkylthiocarbonyl group (methylthiocarbonyl group, ethylthiocarbonyl group, tert-butylthiocarbonyl group, etc.), aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, cyano group , A nitro group, and the like. As the substituent, an alkyl group, an alkoxy group, and an alkoxycarbonyl group are preferable.

m ₁₃ , m ₁₄ and m ₁₅ represent 0 to 2, and 0 or 1 is preferable. p ₁₃ and p ₁₄ represent 0, 1 or 2, and q ₁₃ and s ₁₅ represent 0 or 1.

R ₁₃₂ , R ₁₃₃ , R ₁₃₄ , R ₁₄₂ , R ₁₄₃ , R ₁₄₄ , and R ₁₅₄ represent a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group include the same groups as those in the examples of the alkyl group for R ₁₁₁ described above.

  Examples of the substituent of the alkyl group having a substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, ethoxy group, n- Propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group having 1 to 20 carbon atoms (for example, Acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), C1-C20 alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), C2-C20 alkylthio Carbonyl group (methylthiocarbonyl group, ethylthiocarbonyl group, tert-butylthio) Carbonyl group, etc.), an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, etc., and preferred as substituents, an alkoxy group, an alkoxycarbonyl group.

  A compound represented by the following general formula (A-VI) is also a kind of preferable alicyclic epoxide.

In the general formula (A-VI), R ₁₆₁₁ and R ₁₆₁₂ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ₁₆₂ , R ₁₆₃ and R ₁₆₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. q16 represents 0 or 1.

  Furthermore, the alicyclic epoxy compound represented by general formula (A-VI) is demonstrated.

In the general formula (A-VI), R ₁₆₁₁ and R ₁₆₁₂ are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, etc.), and the alkyl group is preferably a methyl group, an ethyl group, or a propyl group.

R ₁₆₂ , R ₁₆₃ and R ₁₆₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.

Examples of the alkyl group include the same groups as those in the examples of the alkyl group for R ₁₁₁ described above. Examples of the substituent of the alkyl group having a substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, ethoxy group, n- Propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group having 1 to 20 carbon atoms (for example, Acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), C1-C20 alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), C2-C20 alkylthio Carbonyl group (methylthiocarbonyl group, ethylthiocarbonyl group, tert-butylthio) Carbonyl group, etc.), an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, etc., and preferred as substituents, an alkoxy group, an alkoxycarbonyl group. q16 represents 0 or 1.

  Specific examples of the monofunctional epoxy compound of the present invention are shown below, but the present invention is not limited thereto.

  As addition amount of the monofunctional epoxy compound of this invention, it is preferable to contain 10-20 mass parts with respect to 100 mass parts of actinic-light curable compositions.

  In the present invention, one type of monofunctional alicyclic epoxide may be used alone, or two or more types may be used in appropriate combination.

  These monofunctional alicyclic epoxides may be produced by any method. For example, see Maruzen KK Publishing, 4th Edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The Chemistry of Heterocyclic Compound, Vol. 6, Vol. 42, Vol. 42, Vol. 42, Vol. , Adhesion, Vol. 30, No. 7, 42, 1986, JP-A-11-1000037, JP-A-4-36263, JP-A-4-69360 and the like.

(2) Styrene derivatives For example, styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, etc. (3) Vinyl naphthalene derivatives For example, 1-vinyl naphthalene, α-methyl-1-vinyl naphthalene, β-methyl-1-vinyl naphthalene, 4-methyl-1-vinyl naphthalene, 4-methoxy-1-vinyl naphthalene, etc. (4) Vinyl ether For example, isobutyl ether, ethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether, p-methoxyphenyl vinyl ether, α-methylphenyl vinyl ether, β-methylisobutyl vinyl ether, β-chloroisobutyl vinyl ether, etc. (5) N-vinyl Compounds For example, N-vinylcarbazole, N-vinylpyrrolidone, N-vinylindole, N-vinylpyrrole, N-vinylphenothiazine, N-vinylacetanilide, N-vinylethylacetamide, N-vinylsuccinimide, N-vinylphthalimide, N-vinylcaprolactam, N-vinylimidazole, etc. (6) Compounds having an oxetane ring As compounds having an oxetane ring, any known compounds such as those disclosed in JP-A-2001-220526 and 2001-310937 Oxetane compounds can be used. Further, the combined use of a monofunctional oxetane compound containing one oxetane ring and a polyfunctional oxetane compound containing two or more oxetane rings improves the film strength after curing and the adhesion to the recording material. preferable. However, if a compound having 5 or more oxetane rings is used, the viscosity of the actinic radiation curable ink composition becomes high, making it difficult to handle, and increasing the glass transition temperature of the actinic radiation curable ink composition. For this reason, the obtained cured product has insufficient adhesiveness.

  The compound having an oxetane ring used in the present invention is preferably a compound having 1 to 4 oxetane rings.

  In the actinic ray curable composition of the invention, it is preferable to use an oxetane compound in which the 2-position of the oxetane ring is not substituted together with the compound represented by the general formula (S).

  Hereinafter, the oxetane compound in which the 2-position is not substituted will be described.

  As an example of the oxetane compound in which the 2-position is not substituted, a compound represented by the following general formula (101) can be given.

In General Formula (101), R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group. , Furyl group or thienyl group.

R ² is an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl- C2-C6 alkenyl group such as 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group, etc. A group having an aromatic ring, an alkylcarbonyl group having 2 to 6 carbon atoms such as an ethylcarbonyl group, a propylcarbonyl group, and a butylcarbonyl group, an alkylcarbonyl group having 2 to 6 carbon atoms such as an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group; Alkoxycarbonyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, pentylcarbamoyl Is N- alkylcarbamoyl group having a carbon number of 2-6 and the like.

  As the oxetane compound used in the present invention, it is particularly preferable to use a compound having two oxetane rings because the resulting composition has excellent tackiness, low viscosity and excellent workability.

  An example of a compound having two oxetane rings includes a compound represented by the following general formula (102).

In General Formula (102), R ¹ is the same group as that in General Formula (101).

R ³ is, for example, a linear or branched alkylene group such as an ethylene group, a propylene group or a butylene group, a linear or branched poly (alkyleneoxy) such as a poly (ethyleneoxy) group or a poly (propyleneoxy) group. ) Group, propenylene group, methylpropenylene group, butenylene group or other linear or branched unsaturated hydrocarbon group, alkylene group containing carbonyl group or carbonyl group, alkylene group containing carboxyl group, alkylene containing carbamoyl group Group.

Moreover, as R < ³ >, the polyvalent group selected from the group shown by the following general formula (103), (104) and (105) can also be mentioned.

In General Formula (103), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. An alkoxy group having 1 to 4 carbon atoms, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.

In the general formula (104), R ⁵ represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .

In General Formula (105), R ⁶ represents an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group. n is an integer of 0-2000. R ⁷ is a methyl group, an ethyl group, a propyl group, a butyl group having 1 to 4 carbon atoms, or an aryl group. R ⁷ may further include a group selected from the group represented by the following general formula (106).

In General Formula (106), R ⁸ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group. m is an integer of 0-100.

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

Exemplary compound 11 is a compound in which R ¹ is an ethyl group and R ³ is a carboxyl group in the general formula (102).

The exemplified compound 12 is a compound in which R ¹ is an ethyl group, R ³ is the general formula (105), R ⁶ and R ⁷ are methyl groups, and n is 1 in the general formula (102).

In the compound having two oxetane rings, a preferred example other than the above compound is a compound represented by the following general formula (107). In formula (107), R ¹ has the same meaning as R ¹ in the general formula (101).

  Moreover, as an example of a compound having 3 to 4 oxetane rings, a compound represented by the following general formula (108) can be given.

In formula (108), R ¹ has the same meaning as R ¹ in the general formula (101).

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

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

  Illustrative compound 13 is an example of a compound having 3 to 4 oxetane rings.

  Furthermore, examples of the compound having 1 to 4 oxetane rings other than those described above include compounds represented by the following general formula (109).

In formula (109), R ⁸ has the same meaning as R ⁸ in the general formula (106). R ¹¹ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, or a trialkylsilyl group, and r is 1 to 4.

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

  The production method of each compound having an oxetane ring described above is not particularly limited, and may be a conventionally known method. For example, Pattison (DB Pattison, J. Am. Chem. Soc., 3455, 79 ( 1957)) discloses a method for synthesizing an oxetane ring from a diol.

  In addition to these, compounds having 1 to 4 oxetane rings having a high molecular weight of about 1000 to 5000 are also included. Examples of these specific compounds include the following compounds.

  It is preferable to use a sensitizer together with the actinic ray curable composition of the present invention, and it is more preferable that the sensitizer is a 9,10-dietherified anthracene compound, which is represented by the general formula (1). Most preferably, it is a compound.

Compound represented by the general formula (1) In the general formula (1), R ₁ to R ₇ and R ₁₀ are hydrogen atoms or substituents shown below, and the substituents represented by R ₁ to R ₇ are particularly There is no limitation, and alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, iso-butyl group, sec-butyl group, pentyl group, tert-pentyl group, hexyl group, Heptyl, octyl, nonyl, 2-ethylhexyl, decyl, dodecyl, etc.), cycloalkyl (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.), alkenyl (eg, Vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, allyl group, etc.), cycloalkenyl group (cyclopente Group, cyclopentadienyl group, cyclohexenyl group, cyclooctadienyl group, etc.), alkynyl group (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, propargyl group, etc.), aromatic Aromatic hydrocarbon group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, Pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, pyrrolyl group, 2-quinolyl group, 1-isoquinyl group, etc.), non-aromatic heterocyclic group (for example, pyrrolidyl group, imidazolidyl group) , Morpholino group, oxazolidyl group, 2-tetrahydrofuranyl group, 2- Tiger tetrahydrothienyl group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group), a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group, and the like. These groups may be further substituted, and examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, and a hydroxyl group. , Carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, anilino group, acylamino group, aminocarbonylamino group , Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, Alkyl and arylsulfonyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, silyl groups, hydrazino groups, ureido groups, boronic acid groups, Examples thereof include a phosphato group, a sulfato group, and other known substituents.

R _{1 to} R ₇ are preferably a hydrogen atom or an aliphatic group (an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, etc.), and more preferably a hydrogen atom, an alkyl group, or a cyclo group. It is an alkyl group. Preferred alkyl groups include, for example, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group. , N-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, etc. Alkyl group, isobutyl group, isopropyl group, isopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2-ethylbutyl group, 3 , 3-dimethylbutyl group, 3-methylhexyl group, 5-methylhexyl group, 2-ethylhexyl group, 2,4,4-trimethylpentyl group, -Propylpentyl group, sec-butyl group, sec-pentyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, sec-hexyl group, 1,3-dimethylbutyl group, 1,2-dimethylbutyl group, Examples include a branched alkyl group such as a sec-heptyl group, a sec-octyl group, a tert-butyl group, a tert pentyl group, a 1,1-diethylpropyl group, and a 1,1-dimethylpentyl group. Preferred cycloalkyl groups Includes a cycloheptyl group, a cyclohexyl group, a cyclopentyl group, a 1-methyl-1-cycloheptyl group, a 1-methyl-1-cyclohexyl group, and the like.

R ₁₀ is preferably a tertiary alkyl group, and examples thereof include a t-butyl group, a t-pentyl group, a t-hexyl group, a t-heptyl group, a 1-methylcyclohexyl group, and the like. A pentyl group is more preferable.

R ₈ and R ₉ are alkyl groups which may be substituted, and examples of the alkyl group include 2-octyldodecyl group and 2-decyltetradecyl group in addition to the alkyl groups exemplified as R _{1 to} R ₇ described above. Examples of substituents that can be substituted for these include halogen atoms, alkyl groups, cycloalkyl groups, halogenated alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, carboxyls Group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, anilino group, acylamino group, aminocarbonylamino group, alkoxy Carbonylamino group, aryloxycarboni Amino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group , Aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, silyl group, hydrazino group, ureido group, boronic acid group, phosphato group, sulfato group, and other known substituents It is done. R ₈ and R ₉ are preferably unsubstituted.

R ₈ and R ₉ may be the same or different, but are preferably the same.

R ₈ and R ₉ are preferably a group that is not branched on the carbon atom located at the α-position of the oxygen atom in the general formula (1), and more preferably a straight chain.

  The group not branched on the carbon atom located at the α-position of the oxygen atom in the general formula (1) will be described in detail. For example, groups represented by the following (A), (C), (D) Is a group not branched on the carbon atom located at the α-position of the oxygen atom in the general formula (1), and (B) is a carbon atom located at the α-position of the oxygen atom in the general formula (1) This is a branched group.

R ₈ and R ₉ each preferably have 1 to 20 carbon atoms, more preferably 1 to 9, and most preferably 3 to 7.

  In the actinic ray curable composition of the present invention, the compounds represented by the general formula (1) are specifically listed as compounds represented by the general formula (1) described in Japanese Patent Application No. 2006-169815. The compounds listed as compounds represented by the general formula (1) described in SBW-016 (b9643) can be used, but the present invention is not limited thereto.

  Although there is no restriction | limiting in particular in the addition amount of the compound represented by General formula (1) of this invention, It exists in the range of 0.01 mass part to 30 mass parts with respect to 100 mass parts of actinic-light curable compositions. Is preferable, and it is more preferable to be within the range of 0.1 to 10 parts by mass.

Pigment / Other Additives In addition to the components described above, various additives can be used in the actinic ray curable composition of the present invention.

  It is used when the actinic ray curable composition of the present invention is used as an actinic ray curable actinic ray curable ink composition or an inkjet ink (hereinafter also simply referred to as ink) using the actinic ray curable ink composition. As the coloring material that can be used, various coloring materials that can be dissolved or dispersed in the main component of the polymerizable compound can be used, but pigments are preferable from the viewpoint of weather resistance.

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

C. I. Pigment Yellow-1, 3, 12, 13, 14, 17, 81, 83, 87, 95, 109, 42,
C. I. Pigment Orange-16, 36, 38,
C. I. Pigment Red-5, 22, 38, 48: 1, 48: 2, 48: 4, 49: 1, 53: 1, 57: 1, 63: 1, 144, 146, 185, 101,
C. I. Pigment Violet-19, 23,
C. I. Pigment Blue-15: 1, 15: 3, 15: 4, 18, 60, 27, 29,
C. I. Pigment Green-7, 36,
C. I. Pigment White-6, 18, 21,
C. I. Pigment Black-7,
For the dispersion of the pigment, for example, a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, or the like can be used.

  It is also possible to add a dispersant when dispersing the pigment.

  As the dispersant, a polymer dispersant is preferably used, and examples of the polymer dispersant include Solsperse series manufactured by Avecia.

  Moreover, it is also possible to use a synergist according to various pigments as a dispersion aid.

  These dispersants and dispersion aids are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the pigment.

  The dispersion medium is used using a solvent or a polymerizable compound. However, the actinic ray curable ink composition of the present invention is preferably solvent-free because it reacts and cures immediately after ink landing.

  If the solvent remains in the cured image, the solvent resistance deteriorates and the VOC of the remaining solvent arises. Therefore, it is preferable in view of dispersibility that the dispersion medium is not a solvent but a polymerizable compound, and among them, a monomer having the lowest viscosity is selected.

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

  By controlling the particle size, clogging of the head nozzle can be suppressed, and the storage stability, ink transparency, and curing sensitivity of the actinic ray curable ink composition can be maintained.

  In the inkjet ink of the present invention, the colorant concentration is preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the actinic ray curable ink composition.

  In the present invention, a thermal base generator can also be used for the purpose of improving ejection stability and storage stability.

  Examples of the thermal base generator include compounds that release amines by decomposition by reactions such as organic acid and base salts that are decomposed by decarboxylation by heating, intramolecular nucleophilic substitution reaction, Rossen rearrangement, Beckmann rearrangement, etc. Those which cause some kind of reaction by heating and release a base are preferably used.

  Specifically, the salt of trichloroacetic acid described in British Patent No. 998,949, the salt of alpha-sulfonylacetic acid described in US Pat. No. 4,060,420, and the propionic acids described in JP-A-59-157737 Salts, 2-carboxycarboxamide derivatives, salts with a base component described in JP-A-59-168440 and a thermally decomposable acid using an alkali metal or an alkaline earth metal in addition to an organic base, JP-A-59-180537 Hydroxam carbamates utilizing the Lossen rearrangement described in No. 5, and aldoxime carbamates described in JP-A No. 59-195237 that generate nitriles by heating.

  In addition, British Patent No. 998,945, US Pat. No. 3,220,846, British Patent No. 279,480, Japanese Patent Laid-Open Nos. 50-22625, 61-32844, 61-51139, 61 The thermal base generators described in Nos. -52638, 61-51140, 61-53634 to 61-53640, 61-55644, 61-55645 and the like are useful.

  More specifically, guanidine trichloroacetate, methylguanidine trichloroacetate, potassium trichloroacetate, guanidine phenylsulfonylacetate, guanidine p-chlorophenylsulfonylacetate, guanidine p-methanesulfonylphenylsulfonylacetate, potassium phenylpropiolate, phenylpropiool Examples include acid guanidine, cesium phenylpropiolate, guanidine p-chlorophenylpropiolate, guanidine p-phenylene-bis-phenylpropiolate, tetramethylammonium phenylsulfonylacetate, and tetramethylammonium phenylpropiolate. The thermal base generator can be used in a wide range.

  The actinic ray curable ink composition of the present invention is an acid that newly generates an acid by an acid generated by actinic ray irradiation that has already been known, such as those disclosed in JP-A-8-248561 and 9-34106. It is also possible to contain a proliferating agent.

  The actinic ray curable ink composition of the present invention is produced by well dispersing the pigment together with an actinic ray curable composition and a pigment dispersant using an ordinary dispersing machine such as a sand mill. It is preferable to prepare a concentrated solution having a high pigment concentration in advance and dilute with an active energy ray-curable compound. Sufficient dispersion is possible even with dispersion by a normal disperser, so it does not take excessive dispersion energy and does not require a great amount of dispersion time. Ink excellent in the quality is prepared. The ink is preferably filtered through a filter having a pore diameter of 3 μm or less, more preferably 1 μm or less.

  The actinic ray curable composition of the present invention may be used after adjusting the viscosity or the like so as to impart desired physical properties depending on the application. When the actinic ray curable composition of the present invention is used as an actinic ray curable ink or an inkjet ink using an actinic ray curable ink, it is preferable to adjust the viscosity at 25 ° C. to a high level of 7 to 40 mPa · s. An ink having a viscosity of 7 to 40 mPa · s at 25 ° C. exhibits stable ejection characteristics even from a normal head having a frequency of 4 to 10 kHz to a high frequency head of 10 to 50 kHz.

  When the viscosity of the ink of the present invention is in the above range, there is no decrease in the followability of the discharge, and the discharge stability is excellent.

  In addition, the ink-jet ink of the present invention preferably has an electrical conductivity of 10 μS / cm or less and no electrical corrosion inside the head in the piezo head.

  Further, in the continuous type, it is necessary to adjust the electric conductivity by the electrolyte. In this case, it is necessary to adjust the electric conductivity to 0.5 mS / cm or more.

  In the present invention, the surface tension of the ink at 25 ° C. is preferably in the range of 25 to 40 mN / m.

  If the surface tension of the ink at 25 ° C. is in the above range, stable emission can be obtained and a desired dot diameter can be obtained.

  In order to adjust the surface tension, a surfactant may be contained as necessary.

  Examples of the surfactant preferably used in the ink according to the present invention include anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, and fatty acid salts, polyoxyethylene alkyl ethers, and polyoxyethylene alkyl. Nonionic surfactants such as allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, and surfactants having a polymerizable group Compound etc. are mentioned.

  Of these, particularly preferred are surface active compounds having a polymerizable group such as an unsaturated bond, oxirane, or oxetane ring, such as silicone-modified acrylate, fluorine-modified acrylate, silicone-modified epoxy, fluorine-modified epoxy, silicone-modified oxetane, and fluorine-modified oxetane. .

  In addition to the above-described constituent elements, various additives can be used in the actinic ray curable composition of the present invention.

  For example, leveling additives, matting agents, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, and waxes can be added. In order to improve the adhesion with the recording medium, it is also effective to add a trace amount of organic solvent.

  In this case, it is effective to add in the range where the solvent resistance and VOC problems do not occur, and the amount used is in the range of 0.1 to 5%, preferably 0.1 to 3%. It is also possible to combine a radically polymerizable monomer and an initiator into a radical / cation hybrid type curable ink.

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

  In the image forming method of the present invention, it is preferable that the ink is heated together with the ink jet nozzles during ink ejection so that the ink liquid has a low viscosity. As heating temperature, it is 35-100 degreeC, 35-80 degreeC, Preferably it is 35-60 degreeC.

  In the present invention, the total ink film thickness after the ink has landed and cured by irradiation with actinic rays is preferably 2 to 20 μm.

  In the actinic ray curable ink jet recording in the screen printing field, the total ink film thickness currently exceeds 20 μm, but in the flexible packaging printing field where the recording material is often a thin plastic material, the recording material described above is used. Not only because of curling and wrinkling problems, but also because it has the problem of changing the texture and texture of the entire printed matter.

  Moreover, in this invention, it is preferable that the amount of droplets discharged from each nozzle is 2 to 15 pl.

  In the present invention, in order to form a high-definition image, it is preferable that the irradiation timing is as early as possible. However, in the present invention, light irradiation is started at a timing at which the viscosity or moisture content of the ink is in a preferable state. Is preferred.

  Specifically, as the irradiation condition of the generated light, actinic light irradiation is preferably started within 0.001 to 1.0 seconds after ink landing, and more preferably 0.001 to 0.4 seconds. Further, it is preferable to terminate the light irradiation after 0.1 to 3 seconds, preferably within 0.2 to 1 second, until the ink fluidity is lost.

  By setting it as the above condition, enlargement of the dot diameter and bleeding between the dots can be prevented.

  In the present invention, the basic method of actinic ray irradiation is disclosed in JP-A-60-132767. According to this, the light source is provided on both sides of the recording head unit, and the recording head and the light source are scanned by the shuttle method. Irradiation is performed after a certain period of time after ink landing.

  Further, the curing is completed by another light source that is not driven. In US Pat. No. 6,145,979, as an irradiation method, a method using an optical fiber or a method of applying a collimated light source to a mirror surface provided on the side surface of a recording head unit and irradiating the recording unit with UV light is disclosed. ing. Any of these irradiation methods can be used in the image forming method of the present invention.

  In addition, irradiation with actinic rays is divided into two stages. First, actinic rays are irradiated by the above-described method within 0.001 to 1.0 seconds after ink landing, and further, actinic rays are irradiated after all printing is completed. The method is also a preferred embodiment. By dividing the irradiation of actinic rays into two stages, it is possible to further suppress the shrinkage of the recording material that occurs during ink curing.

  Examples of light sources used in actinic ray irradiation include mercury arc lamps, xenon arc lamps, fluorescent lamps, carbon arc lamps, tungsten-halogen copying lamps, high pressure mercury lamps, metal halide lamps, electrodeless UV lamps, low pressure mercury lamps, and UV lasers. , Xenon flash lamps, insect traps, black lights, germicidal lamps, cold cathode tubes, LEDs, and the like, but are not limited to these, and among these, fluorescent tubes are preferred because of their low energy and low cost.

A light source having a light emission wavelength peak at 250 to 370 nm, preferably 270 to 320 nm is preferable in terms of sensitivity. The illuminance is 1 to 3000 mW / cm ² , preferably 1 to 200 mW / cm ² . In addition, in the case of curing with an electron beam, the curing is usually performed with an electron beam having an energy of 300 eV or less, but it is also possible to cure instantaneously with an irradiation amount of 1 to 5 Mrad.

  The ink jet ink of the present invention is used to print an image on a recording medium (also referred to as a base material). As the recording medium, all of a wide range of conventional synthetic resins used in various applications are used. Specific examples include polyester, polyvinyl chloride, polyethylene, polyurethane, polypropylene, acrylic resin, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutadiene terephthalate, and the like. The thickness and shape of the synthetic resin substrate are not limited at all.

  As a base material that can be used in the present invention, a non-absorbent support can be used in addition to normal uncoated paper, coated paper, etc. Among them, a non-absorbent support is used as the base material. It is preferable.

  In the present invention, various non-absorbing plastics and films thereof can be used as the non-absorbing support. Examples of the various plastic films include PET film, OPS film, OPP film, ONy film, and PVC film. , PE fill and TAC film.

  As other plastic substrates, polycarbonate, acrylic resin, ABS, polyacetal, PVA, rubbers and the like can be used. It can also be applied to metals and glasses.

  Among these recording materials, the structure of the present invention is effective particularly when an image is formed on a PET film, an OPS film, an OPP film, an ONy film, or a PVC film that can be shrunk by heat. These substrates are not only susceptible to curling and deformation of the film due to curing shrinkage of the ink composition and heat generation during the curing reaction, but also the ink film is difficult to follow the shrinkage of the substrate.

  The surface energies of these various plastic films differ greatly, and it has been a problem in the past that the dot diameter after ink landing varies depending on the recording material.

  The constitution of the present invention includes an OPP film having a low surface energy, an OPS film, and a PET having a relatively large surface energy, but the substrate preferably has a wetting index of 40 to 60 mN / m.

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

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

Example 1
A compound represented by general formula (S), a comparative compound, a cationic polymerizable compound, and a sensitizer were mixed as shown in Table 1 to prepare actinic ray curable compositions 1 to 49. The compounds used in the examples are shown below.

<Polymerizable compound 1>
Celoxide 2021P: manufactured by Daicel Chemical Industries, Ltd. Celoxide 3000: manufactured by Daicel Chemical Industries, Ltd. <polymerizable compound 2>
OXT-101: manufactured by Toagosei Co., Ltd. OXT-212: manufactured by Toagosei Co., Ltd. OXT-221: manufactured by Toagosei Co., Ltd. Using the obtained actinic ray curable compositions 1 to 49, a curing test was conducted as follows and evaluated. The results are shown in Tables 3 and 4.

(Curing of actinic ray curable composition)
The actinic ray curable compositions shown in Tables 1 and 2 were applied to a PET film to a thickness of 3 μm, and the substrate was heated to 40 ° C., and a 120 W / cm metal halide lamp (MAL400NL manufactured by Nippon Battery Co., Ltd.) was used. Irradiation was performed within 1 second using a 3 kW power source as a light source.

  This experiment was performed under no filter conditions or with filter conditions.

  Conditions with filter: A Pyrex (registered trademark) glass plate having a thickness of 1.5 mm was attached to the light source as a filter, and light with a wavelength of 300 nm or less was substantially cut.

  The light source distances were 10 cm, 5 cm, and 3 cm, respectively.

(Evaluation of curability)
After 5 minutes from irradiation with actinic light, the surface of the cured product was strongly rubbed with Kimwipe and visually observed.

◎: Cured sufficiently at 10 cm (Kimwipe does not have a cured product component) ○: Not cured sufficiently at 10 cm, but cured sufficiently at 5 cm △: Not cured sufficiently at 5 cm, but sufficient at 3 cm Curing ×: Thing that does not cure sufficiently even at 3 cm ◎, ○, Δ are at a level where there is no practical problem.

(Evaluation of storage stability)
<Generation of gel-like material>
The actinic ray curable compositions of Tables 1 and 2 were sealed in a sealed glass container, stored at 50 ° C. for 1 week, and the inside of the container was visually observed.

◎: No occurrence of gel-like product ○: No occurrence of gel-like product △: Appearance of fine gel-like product ×: Significant generation of gel-like product What is ◎, ○ is a level that is not a problem in practice.

[Evaluation of cured product]
The physical properties and storage stability were evaluated using a cured product that was cured by irradiation with actinic rays under the same conditions as in the above-described curing test except that the light source distance was set to 2 cm.

(Evaluation of substrate adhesion)
Cello tape (registered trademark) was applied in the range of 2 cm × 1 cm square of the cured product and strongly pressed, peeled off perpendicularly to the surface of the cured product, and the state of the subsequent cured product was visually observed.

A: The cured product is not peeled off from the substrate at all. ○: A part is peeled off. X: Most part is peeled off.

(Evaluation of storage stability)
After the cured product was stored at 70 ° C. for 4 days, the cured product was smelled and evaluated in the following manner.

<Odor>
◎: No odor ○: Slight odor ×: Obvious odor ◎ and ○ are practically no problem level.

  As is apparent from Tables 3 and 4, the actinic ray curable composition of the present invention has extremely good curability, storage stability of the composition, adhesion of the cured product to the substrate, and storage stability of the cured product. I understand.

Example 2
<Ink composition>
5 parts by mass of a dispersant (PB822 Ajinomoto Fine Techno Co., Ltd.) and each actinic ray curable composition described in Table 3 were put into a stainless beaker and stirred for 1 hour while heating on a 65 ° C. hot plate. Mix and dissolve.

  Next, after adding 3 parts by mass of the following various pigments to this solution, it was sealed in a plastic bottle together with 200 g of zirconia beads having a diameter of 1 mm, and subjected to dispersion treatment for 2 hours using a paint shaker.

  Next, the zirconia beads are removed, and various additives such as photoacid generators, photopolymerization initiators, basic compounds, and surfactants are added in combinations shown in Table 3 to prevent printer clogging. An ink composition was prepared by filtration through a 0.8 μm membrane filter.

  The above operation was performed for each color of K, C, Y, M, and W to prepare ink composition sets 101 to 141.

  The following pigments were used.

K: C.I. I. Pigment Black-7
C: C.I. I. Pigment Blue-15: 3
M: C.I. I. Pigment Red-57: 1
Y: C.I. I. Pigment Yellow-13
W: Titanium oxide (anatase type: particle size 0.2 μm)

  The compounds used are shown below.

(Basic compound)
Basic compound A: N-ethyldiethanolamine (surfactant)
F1405: Megafax F1405 Perfluoroalkyl group-containing ethylene oxide adduct (manufactured by Dainippon Ink & Chemicals, Inc.)
(Compatibilizer)
145P: Halitac 145P (rosin-modified maleic resin (manufactured by Harima Chemical Co.))
<< Inkjet image forming method >>
Image forming method A (no filter)
Each of the ink composition sets 101 to 138 prepared above is loaded into an ink jet recording apparatus having a piezo ink jet nozzle, and the recording material is 600 mm wide and 20 m long (manufactured by YUPO Corporation, synthetic paper YUPO FGS). The following image recording was performed continuously.

  The ink supply system was composed of an ink tank, a supply pipe, a front chamber ink tank immediately before the head, a pipe with a filter, and a piezo head.

  In addition, the head portion is heated according to the viscosity of each curable composition ink, and multi-size dots having a droplet amount of 2 to 15 pl are set to 720 × 720 dpi (where dpi is the number of dots per inch, that is, 2.54 cm). The cured composition ink described above was continuously ejected by being driven so as to be ejected at a resolution of (represented).

  The recording material was heated to 50 ° C. by a surface heater.

  After landing, it was cured instantaneously (less than 0.5 seconds after landing) with an irradiation light source (metal halide lamp) on both sides of the carriage (MAL400NL power = 3 kW · hr 120 W / cm, manufactured by Nippon Batteries Co., Ltd.).

  When the total ink film thickness was measured after image recording, it was in the range of 2.3 to 13 μm.

  The inkjet image was formed by printing in an environment of 30 ° C./80% RH and 25 ° C./20% RH according to the above method.

  In addition, the illumination intensity of each irradiation light source measured the integrated illumination intensity of 254 nm using UVPF-A1 by Iwasaki Electric Co., Ltd.

Image forming method B (with filter)
An image was formed in the same manner as in the image forming method A, except that one Pyrex (registered trademark) glass having a thickness of 1 mm was used as a filter (wavelength of 300 nm or less was substantially cut) during exposure.

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

(Character quality)
A 6-point MS Mincho type character was printed at the target density, and the character roughness was magnified with a loupe, and the character quality was evaluated according to the following criteria.

◎: No rusting ○: Slight rustling is visible △: Gashesiness is visible, but it can be recognized as characters and can be used at the last minute ×: Levels that are harsh and characters are faint and cannot be used.

(Mixed colors (bleeds, wrinkles))
Print at 720 dpi so that each dot of each color Y, M, C, K, W is adjacent to each other, enlarge each adjacent color dot with a loupe, visually observe the state of bleeding and wrinkles, and mix colors according to the following criteria Was evaluated.

◎: Adjacent dot shape keeps perfect circle and no blur ○: Adjacent dot shape keeps almost perfect circle and almost no blur △: Adjacent dots are slightly blurred and dot shape is slightly displaced , The level that can be used at the end ×: The level where the adjacent dots are blurred and mixed, and there is a wrinkle in the overlapping part, so it cannot be used.

(Evaluation of ink storage stability 1)
The prepared ink composition was placed in a sealed container for each color and stored in a dark place at 20 ° C. for 2 months, and then image formation and tests similar to those described above were performed to determine storage stability.

○: No significant change in test results even after 2 months storage △: A large change was observed in one or more items in any test ×: Ink viscosity increased and image formation failed ○ is storage stability with no practical problem.

(Evaluation of ink storage stability 2)
Among the prepared ink compositions, yellow ink was placed in a glass sample tube, sealed, and stored at 30 ° C. for 1 week, and then generation of a gel-like material in the sample tube was confirmed.

○: No gel generation was confirmed Δ: Slight gel generation was confirmed ×: Clear gel generation was confirmed ○ is a level having no practical problem.

(Evaluation of substrate adhesion of ink cured film)
Use the best cured ink film in the same sample, apply cello tape (registered trademark) to the 2cm x 1cm square area of the ink cured film and press it firmly, and quickly peel off perpendicularly to the ink cured film surface. Thereafter, the state of the cured ink film was visually observed. This test was repeated 5 times.

◎: The ink cured film was not peeled off from the substrate at all 5 degrees. ○: The peeling was partially observed only once. △: The peeling was partially observed twice or more, or only once. Mostly peeled off ×: Mostly peeled off more than 2 degrees ◎, ○ is a level that does not cause any practical problems.

(Evaluation of ink cured film storage stability)
The most cured ink film in the same sample was used, and the cured ink film was stored at 50 ° C. for 5 days. The smell of the cured product was sniffed and evaluated in the following manner.

<Odor>
○: No odor △: Slight odor ×: Obvious odor ○ is a level that does not cause any practical problems.

  From the results of Tables 7 to 10, it can be seen that the sample of the present invention has high image quality and high substrate adhesion, and is excellent in ink storage stability and storage stability of the cured ink film.

Claims (12)

An actinic ray curable composition comprising a compound represented by the following general formula (S) and a cationically polymerizable compound represented by the following general formula (B).

(In the formula, Rs _{1 to} Rs ₃ represent substituents, a, b and c each represent an integer of 0 to 4. X is a divalent linking group, which is a single bond or the following partial structural formula: Group (A-1),

(In the partial structural formula group (A-1), the * part is a bonding site. Rn ₁ represents a hydrogen atom or a substituent. K represents an integer of 1 to 6).
L is a divalent linking group, and is a single bond or the following partial structural formula group (B-1)

(In the partial structural formula group (B-1), the * part is a bonding site. Rn ₁ represents a hydrogen atom or a substituent. K represents an integer of 1 to 6). A ⁻ represents a counter anion. )

(Wherein R ₂₀₁ and R ₂₀₂ each represent a substituent, m20 and n20 each represent 0, 1 or 2. r0 represents 1 to 3. L ₀ may contain an oxygen atom or a sulfur atom in the main chain. Represents an r0 + 1 valent linking group or a single bond having 1 to 15 carbon atoms.) In the said general formula (S), X is any one of a single bond, a sulfur atom, and a carbonyl group, The actinic-light curable composition of Claim 1 characterized by the above-mentioned. The actinic ray curable composition according to claim 1 or 2, wherein in the general formula (S), L is a single bond or a group selected from the following partial structural formula group (B-2).

(In the formula, * part is a binding site.) In the said general formula (S), c is an integer of 1-4, The actinic-light curable composition of any one of Claims 1-3 characterized by the above-mentioned. The actinic ray curable composition according to any one of claims 1 to 4, comprising a compound represented by the following general formula (1).

(In the formula, R ₁ to R ₇ and R ₁₀ each represent a hydrogen atom or a substituent, and R ₈ and R ₉ each represent a substituted or unsubstituted alkyl group.) In Formula (1), actinic ray curable composition according to claim 5, wherein R ₁₀ is a tertiary alkyl group. In the general formula (1), actinic ray curable composition according to claim 5 or 6, characterized in that R ₁₀ is a t- butyl group or a t- pentyl group. In the general formula _{(1), R 1, R} 7 is a hydrogen atom, any one of claims 5-7 which R ₈ and R _9, characterized in that an unsubstituted alkyl group having from 3 to 7 carbon atoms 2. The actinic ray curable composition according to item 1. In Formula (1), actinic ray curable composition according to any one of claims 5-8, wherein R ₈ and R ₉ is a straight chain alkyl group. An actinic ray curable ink composition comprising the actinic ray curable composition according to any one of claims 1 to 9. A curing method for an actinic ray curable composition, comprising curing the actinic ray curable composition according to any one of claims 1 to 9 by irradiating with ultraviolet rays. An image forming method, wherein the actinic ray curable ink composition according to claim 10 is ejected or coated in an image-like manner, and an image is formed by irradiating the composition with ultraviolet rays and curing the composition.