JP2004339487A - Polymerizable composition for active energy ray-curable ink and printed matter obtained by curing the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polymerizable composition for an active energy ray-curable ink which has such curability and chemical resistance that polymerizable compositions for active energy ray-curable ink has, is hard to inhibit the curing reaction in the presence of air(oxygen), has an adhesive property to a base material made of a plastic such as a PET (polyethylene terephthalate film) film, and is excellent in the balance of physical properties. <P>SOLUTION: The polymerizable composition for an active energy ray-curable ink comprises a new polymerizable compound having a specific structure (formula (1)). The printed matter is obtained by curing the composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polymerizable composition for an active energy ray-curable ink, and a printed material obtained by curing the composition.

  More specifically, the present invention improves the curability and chemical resistance of the polymerizable composition for an active energy ray-curable ink, so that a radical curing reaction when air (oxygen) is interposed is hardly inhibited, and The present invention relates to a polymerizable composition for an active energy ray-curable ink having good adhesion to various printing substrate surfaces (particularly, various plastics), and a printed material obtained by curing the composition.

  Although the use of the polymerizable composition for an active energy ray-curable ink according to the present invention is not particularly limited, the composition has good adhesion to various plastics, particularly to polyethylene terephthalate (hereinafter referred to as “PET”) films. It has the property of being excellent in wettability with pigments, flow properties as ink compositions, and curability.

  2. Description of the Related Art Conventionally, as a printing ink, an ink using an organic solvent has been frequently used from the viewpoints of solubility of a polymer, wetness with a substrate without a drying speed, and the like. However, in recent years, it has been pointed out that printing inks using an organic solvent have problems in toxicity to workers, fire danger, environmental pollution, drying speed, and waste of solvent. For this reason, there is a tendency that a printing ink containing no organic solvent as an essential component is required. This tendency is becoming stronger with the recent rise in environmental awareness. Among the printing inks that do not contain such an organic solvent as an essential component, one of the most prominent ones is a solventless printing ink that utilizes curing by irradiation with active energy rays.

  However, when the solvent-free photocurable printing ink described above is used, it is inevitable that the volume shrinkage occurs and the adhesion to the substrate surface is easily reduced. Furthermore, the adhesion of these active energy ray-curable ink compositions to plastic substrates tends to be insufficient.

  JP-A-3-215543 (Patent Document 1) discloses a composition containing a styrene-acrylic polymer and a monomer to improve these disadvantages. However, although the above composition improves the adhesion to a plastic substrate to some extent, the degree of the improvement is not sufficient, and sufficient physical properties cannot be obtained in terms of curability and coating film properties. Had.

  In addition, in curing the polymerizable composition for an active energy ray-curable ink, the presence of air (oxygen) inhibits a radical curing reaction, so that it is necessary to perform active energy ray irradiation in an inert gas atmosphere. For this reason, there is also a limitation in terms of a device for the irradiation.

  To overcome these problems, there is an epoxy-based photo-cationic curable resin. However, the curable resin has low photoreactivity, and thus requires large UV energy during curing. Therefore, there are drawbacks that a high UV energy irradiation device is required and irradiation time is long. As a method for improving the low reactivity of such a photocationically curable resin, a method using an alicyclic epoxy compound as a base resin or a diluent (for example, JP-A-5-186755 (Patent Document 2)) And a method using a cationic photocurable resin using a compound having a propenyl ether terminal group (JP-A-9-137108 (Patent Document 3)).

  However, in the method using an alicyclic epoxy compound as a base resin or a diluent, the reaction speed is slower than that of a conventional photo-radical curable resin, and the types of alicyclic epoxy compounds that can be industrially obtained are limited. Therefore, it was difficult to obtain one satisfying practical performance.

  In addition, the method using a photocationically curable resin using a compound having a propenyl ether terminal group has a drawback that physical properties of a cured product differ due to moisture.

  Therefore, while having the curability and chemical resistance of the polymerizable composition for an active energy ray-curable ink, the curing reaction in the presence of air (oxygen) is relatively unlikely to be inhibited. There has been a demand for a polymerizable composition for an active energy ray-curable ink which has good adhesion to a substrate and has good physical balance.

JP-A-3-215543 JP-A-5-186755 JP-A-9-137108

  An object of the present invention is to provide a polymerizable composition for an active energy ray-curable ink which has solved the above-mentioned disadvantages of the prior art, and a printed material obtained by printing and curing the composition on a substrate. is there.

  Another object of the present invention is to provide an active energy ray-curable ink and a printed material obtained by printing and curing the ink on a substrate.

  Further, another object of the present invention is to have the curability and chemical resistance of the polymerizable composition for an active energy ray-curable ink, and at the same time, hardly inhibit the curing reaction in the presence of air (oxygen), A polymerizable composition for an active energy ray-curable ink having good physical property balance, even with a plastic substrate such as a PET film, and a printed material obtained by printing and curing the composition on a substrate Is to provide.

  As a result of intensive studies, the present inventors have found that by using a polymerizable composition obtained by using a novel polymerizable compound having a specific structure as an essential component, the characteristics of the polymerizable composition for an active energy ray-curable ink can be improved. Radical curing reaction is hardly hindered when air (oxygen) is interposed without substantial loss, and it is difficult to inhibit the radical curing reaction on various printing substrate surfaces (especially with conventional polymerizable compositions for active energy ray-curable inks). It has been found that an ink composition having adhesiveness to a plastic substrate such as PET, which has not been obtained, can be obtained, and the present invention has been completed.

  That is, the present invention (I) relates to a polymerizable composition for an active energy ray-curable ink containing the polymerizable compound represented by the general formula (1) as an essential component.

  General formula (1)

(Wherein, R ¹ independently represents at least one or more organic residues selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and R ² represents an alcohol compound or a phenol compound. Or n represents an organic residue derived from a carboxylic acid compound, n represents an integer of 0 to 20. R ² further contains a group represented by the general formula (2) and / or the general formula (3). be able to.)

General formula (2)

(Wherein, R ¹ independently represents at least one or more organic residues selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n is an integer of 0-20. Represents.)

General formula (3)

(In the formula, R ³ represents either H or CH _3. )

  Further, the present invention (II) relates to a polymerizable composition for an active energy ray-curable ink, which comprises a polymerizable compound represented by the general formula (1) and a monomer having a radical polymerizable unsaturated group as essential components.

  The "monomer having a radically polymerizable unsaturated group" described in the present specification is a compound having one or more radically polymerizable unsaturated groups in a molecule, and the viscosity of the composition is reduced by adding the compound. And a compound capable of increasing the curing rate. However, in the present specification, the category of the polymerizable compound represented by the general formula (1) is applied preferentially to the “monomer having a radical polymerizable unsaturated group” (that is, the general formula ( In the case of a compound included in the category of the polymerizable compound represented by 1), even if the compound has a viscosity that can be used for adjusting the viscosity, it is regarded as a “monomer having a radical polymerizable unsaturated group”. Defined as not included).

  In the present invention (III), the polymerizable composition for an active energy ray-curable ink according to any one of the present invention (I) and the present invention (II) further contains a radical polymerizable initiator. And a polymerizable composition for an active energy ray-curable ink.

  Furthermore, the present invention (IV) relates to a printed matter obtained by printing and curing a polymerizable composition for an active energy ray-curable ink according to any one of the present invention (I) to the present invention (III).

  Further, the present invention includes, for example, the following items.

[1] A polymerizable composition for an active energy ray-curable ink, comprising a polymerizable compound represented by the general formula (1).

General formula (1)

(Wherein, R ¹ independently represents at least one or more organic residues selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and R ² represents an alcohol compound or a phenol compound. Or an organic residue derived from a carboxylic acid compound, and n represents an integer of 0 to 20. The organic residue further includes a group represented by the general formula (2) and / or the general formula (3). May be substituted.)

General formula (2)

(Wherein, R ¹ independently represents at least one or more organic residues selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n is an integer of 0-20. Represents.)

General formula (3)

(In the formula, R ³ represents either H or CH _3. )

[2] A polymerizable composition for an active energy ray-curable ink, comprising a polymerizable compound represented by the general formula (1) and a monomer having a radical polymerizable unsaturated group.

[3] In the polymerizable compound represented by the general formula (1), R ¹ is at least one or more independently selected from organic residues represented by the structural formulas (1) to (7). The polymerizable composition for an active energy ray-curable ink according to any one of [1] and [2], which is an organic residue.

Structural formula (1)

Structural formula (2)

Structural formula (3)

Structural formula (4)

Structural formula (5)

Structural formula (6)

Structural formula (7)

[4] In the polymerizable compound represented by the general formula (1), R ² is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl Glycol, glycerin, trimethylolethane, trimethylolpropane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, brominated bisphenol A, hydrogenated Bisphenol A, bisphenol F, phenol novolak resin, cresol novolak resin, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexyl Or an organic residue derived from a compound selected from the group consisting of -1,2-dicarboxylic acid, phthalic acid, isophthalic acid, and terephthalic acid. The polymerizable composition for active energy ray-curable inks.

[5] A monomer having a radically polymerizable unsaturated group is contained in an amount of 5 to 70% by mass based on the total amount of the polymerizable compound represented by the general formula (1) and the monomer having a radically polymerizable unsaturated group. The polymerizable composition for an active energy ray-curable ink according to any one of [2] to [4].

[6] The active energy ray curing according to any one of [2] to [5], wherein the monomer having a radical polymerizable unsaturated group is a monomer having two or more radical polymerizable unsaturated groups. Polymerizable composition for mold ink.

[7] The polymerizable composition for an active energy ray-curable ink according to any one of [2] to [6], wherein the polymerizable compound is dissolved with a monomer having a radical polymerizable unsaturated group. A polymerizable composition for an active energy ray-curable ink.

[8] An active energy ray-curable ink, which further comprises a radical polymerizable initiator in the polymerizable composition for active energy ray-curable ink according to any one of [1] to [7]. Polymerizable composition.

[9] A printed matter obtained by printing and curing a polymerizable composition for an active energy ray-curable ink according to any one of [1] to [8] on a substrate.

[10] The printed matter according to [9], wherein the substrate is a plastic substrate.

[11] The printed matter according to [10], wherein the plastic substrate is a polyester substrate.

  In addition, "(meth) acrylic acid" described in this specification means acrylic acid and / or methacrylic acid (that is, either acrylic acid or methacrylic acid, or a mixture of both).

  Further, the expression “polymerizable composition for active energy ray-curable ink” described in the present specification refers to not only a composition for an ink consisting of only a polymerizable component but also other components other than the polymerizable component if desired. For example, it is defined to also include a polymerizable composition for an ink that can include additives such as a coloring pigment and a leveling agent.

  Examples of the coloring pigment include phthalocyanine blue, phthalocyanine green, carbon black, titanium white, crystal violet, methyl violet, and triphenylmethane acid dyes. The addition amount of these pigments is desirably 30% by mass or less based on the total amount of the polymerizable components.

  Examples of the leveling agent include silicone compounds such as methylphenyl silicone, dimethylpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, and α- (3-methacryloxypropyl) polydimethylsiloxane. The addition amount of these leveling agents is desirably 5% by mass or less based on the total amount of the polymerizable components.

  If necessary, a thixotropic agent, an antifoaming agent, and the like can be added.

  As described above, according to the present invention, while having the curability and chemical resistance of the polymerizable composition for an active energy ray-curable ink, the curing reaction in the presence of air (oxygen) is hardly inhibited, There is provided a polymerizable composition for an active energy ray-curable ink having good adhesion to a plastic substrate such as a PET film and having a good balance of physical properties.

  Further, according to the present invention, there is provided a printed matter obtained by printing the above-mentioned and the active energy ray-curable ink composition on a substrate and curing the composition.

  Hereinafter, the present invention will be described in more detail. In the following description, “parts” and “%” representing quantitative ratios are based on mass unless otherwise specified.

(The present invention (I))
First, the polymerizable composition for an active energy ray-curable ink of the present invention (I) will be described.

(Polymerizable composition for ink)
The present invention (I) is a polymerizable composition for an active energy ray-curable ink containing the polymerizable compound represented by the general formula (1) as an essential component.

General formula (1)

(Wherein, R ¹ independently represents at least one or more organic residues selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and R ² represents an alcohol compound or a phenol compound. Or an organic residue derived from a carboxylic acid compound, and n represents an integer of 0 to 20. The organic residue further includes a group represented by the general formula (2) and / or the general formula (3). May be substituted.)

General formula (2)

(Wherein, R ¹ independently represents at least one or more organic residues selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n is an integer of 0-20. Represents.)

General formula (3)

(In the formula, R ³ represents either H or CH _3. )

(Active energy ray)
The “active energy ray” described in the present specification refers to an electromagnetic wave having energy capable of activating the compound of the general formula (1). Specific examples of the “active energy ray” include near infrared rays, visible light rays, ultraviolet rays, vacuum infrared rays, X-rays, γ-rays, and electron beams.

(Polymerizable compound)
Next, the polymerizable compound represented by the general formula (1), which is an essential component of the polymerizable composition for an active energy ray-curable ink of the present invention (I), will be described.

(R ¹ group)
In the general formula (1), R ¹ represents an organic residue at least one selected from an alkylene group, a branched alkylene group, a cycloalkylene group, and an aralkylene group.

Specific examples of R ^{1 in} the general formula (1) include linear methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene groups. Alkylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, dicyclopentylene group, cycloalkylene group such as tricyclopentylene group, methylethylene group, etc. Examples thereof include an aralkylene group such as a branched alkylene group, a phenylethylene group, and a 1,2-diphenylethylene group, and an arylene group such as a phenylene group, a naphthylene group, and an anthranylene group. However, it is needless to say that the present invention is not limited to these specific examples.

Among them, R ¹ is preferably ^one having the following structural formulas (1) to (7) from the viewpoints of availability of raw materials and ease of synthesis.

Structural formula (1)

Structural formula (2)

Structural formula (3)

Structural formula (4)

Structural formula (5)

Structural formula (6)

Structural formula (7)

In the general formulas (1) and (2), “R ¹ is each independently” refers to the general formula (1) which is an essential component of the polymerizable composition for an active energy ray-curable ink of the present invention (I). It means that in all the R ¹ in the polymerizable compound represented by the formula, each R ¹ may have a different structure or the same structure. In other words, it means that all of R ¹ may have the same structure, some may have the same structure and others may have different structures, or all may have different structures one by one. I do.

(R ² groups)
R ² in the general formula (1) represents an organic residue derived from an alcohol compound, a phenol compound or a carboxylic acid compound. R ² may further contain a group represented by the general formula (2) and / or the general formula (3).

As used herein, “R ² represents an organic residue derived from an alcohol compound, a phenol compound or a carboxylic acid compound” simply means that R ² is derived only from an alcohol compound, a phenol compound or a carboxylic acid compound. that not only organic residue, an alcohol compound, an organic residue derived from a phenolic compound or carboxylic acid compound need only be included in the R ^2, sulfides such as, alcohol compounds, other than phenol compound or carboxylic acid compound It means that an organic residue derived from the compound may be present in R ² . When R ² is an organic residue derived from a dihydric or higher polyhydric alcohol compound, phenol compound or carboxylic acid compound, as represented by general formula (8), R ^{2 of} general formula (1) May include a group of general formula (2) and / or general formula (3).

General formula (8)

  (I and k each represent an integer of 0 or more, and i + k ≧ 1)

(Alcohol compound)
As the “alcohol compound” here, the following compounds can be exemplified.

Monool compounds such as methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol and t-butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonane Diol, 1,10-decanediol, neopentyl glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedim Nord, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, tricyclo [5.2.1.0 ^2,6] decanedimethanol, bisphenol A Examples thereof include diol compounds such as ethylene oxide adduct and bisphenol A propylene oxide adduct, triol compounds such as glycerin, trimethylolpropane, and trimethylolethane, and tetraol compounds such as pentaerythritol and diglycerin. However, it is needless to say that the present invention is not limited to these specific examples.

(Phenol compound)
Examples of the above-mentioned "phenol compound" include the following compounds.

  Examples thereof include phenol, catechol, resorcinol, hydroquinone, bisphenol A, brominated bisphenol A, bisphenol F, phenol novolak resin, and cresol novolak resin. However, it is needless to say that the present invention is not limited to these specific examples.

(Carboxylic acid compound)
Further, the “carboxylic acid compound” herein includes not only carboxylic acid but also carboxylic acid derivatives (eg, carboxylic acid ester compounds, acid anhydrides, etc.). As the "carboxylic acid compound", the following compounds can be exemplified.

  Acetic acid, propionic acid, butyric acid, benzoic acid, maleic acid, maleic anhydride, fumaric acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic anhydride, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexane Dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, Examples thereof include 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, ester compounds thereof, and acid anhydrides. However, it is needless to say that the present invention is not limited to these specific examples.

(Preferable organic residue contained in R ² )
Among the organic residues contained in R ² , particularly preferred are ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,2, particularly from the viewpoint of easy availability. 6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, Brominated bisphenol A, hydrogenated bisphenol A, bisphenol F, phenol novolak resin, cresol novolak resin, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cycle Hexane dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, phthalic acid, isophthalic acid, and an organic residue derived from terephthalic acid.

(Preferred combination of organic residues)
Preferred combinations of organic residues contained in the general formula (1) and general formula (2) R ¹ and the general formula in (1) of R ^2, R ¹ is a methylene group, an ethylene group, a propylene group , Butylene group, hexylene group, octylene group, cyclopentylene group, cyclohexylene group, dicyclopentylene group, methylethylene group, phenylethylene group, 1,2-diphenylethylene group, phenylene group, at least selected from naphthylene group One or more organic residues, wherein R ² is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, 1,4-butanediol, 1,6 -Hexanediol, 1,8-octanediol , Neopentyl glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, tricyclo [5.2.1.0 ^{2, 6} ] Decane dimethanol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, diglycerin, catechol, bisphenol A, brominated bisphenol A, bisphenol F, phenol novolak Resin, cresol novolak resin, maleic acid, maleic anhydride, fumaric acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic anhydride, 1,3-cyclohexyl Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid It is preferable to include an organic residue derived from at least one member selected from the group consisting of:

Among them, R ¹ is at least one or more organic residues selected from the structural formulas (1) to (7), and R ² is ethylene glycol, propylene glycol, or 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, Bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, brominated bisphenol A, hydrogenated bisphenol A, bisphenol F, phenol novolak resin, cresol novolak resin, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane It contains an organic residue derived from at least one selected from xandicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, phthalic acid, isophthalic acid, and terephthalic acid. preferable.

Structural formula (1)

Structural formula (2)

Structural formula (3)

Structural formula (4)

Structural formula (5)

Structural formula (6)

Structural formula (7)

Of the combinations of organic residues contained in R ¹ and R ² described above, particularly preferred combinations are shown in Table 1 below.

<R ¹ ><R ² >

(Number n)
N in the general formulas (1) and (2) represents an integer of 0 to 20. When n is 21 or more, the molecular weight increases, so that the number of polymerization sites per mass decreases, polymerization tends to be incomplete, and it tends to be difficult to obtain sufficient hardness when cured.

  When n = 0, the polymerizable compound which is an essential component of the polymerizable composition for an active energy ray-curable ink of the present invention (I) contains an allyl ester group. There is a tendency for radical polymerizability to be slightly inferior to the case containing an ether group. Therefore, n is preferably 1 or more.

R ^{2 in the} general formula (1) may further include a group represented by the general formula (2) and / or the general formula (3).

R ¹ and n in the general formula (2) are as described above.

(R ³ groups)
R ³ in the general formula (3) is either H or CH ₃ . When R ³ is H, the polymerizable compound represented by the general formula (1), which is an essential component of the polymerizable composition for an active energy ray-curable ink of the present invention (I), has an acryloyl group. When R ³ is CH ₃ , the polymerizable compound represented by the general formula (1), which is an essential component of the polymerizable composition for an active energy ray-curable ink of the present invention (I), is methacryloyl Group.

  The purpose of introducing an acryloyl group or a methacryloyl group into the polymerizable compound represented by the general formula (1), which is an essential component of the polymerizable composition for an active energy ray-curable ink of the present invention (I), is to increase the curing speed. This is an extremely effective means for increasing the curing speed. However, if the compound belongs to the category of the present invention (I) and has a sufficiently high curing rate, it is not always necessary to introduce an acryloyl group or a methacryloyl group.

  If the structure of the general formula (2) is excessively substituted by the structure of the general formula (3), the polymerization tends to be easily inhibited by oxygen. The number of groups represented by the general formula (3) contained in the polymerizable compound represented by the general formula (1), which is an essential component of the polymerizable composition for an active energy ray-curable ink of the present invention (I), The ratio to the number of groups represented by the general formula (2) is preferably from 0 to 10, more preferably from 0 to 5, and particularly preferably from 0 to 2.

R ³ in the general formula (3) represents either H or CH ₃ . However, the polymerizable compound represented by the general formula (1), which is an essential component of the polymerizable composition for an active energy ray-curable ink of the present invention (I), contains a plurality of polymerizable compounds represented by the general formula (3) in one molecule. When it has a group represented, even if all R ³ contained in one molecule are all H, some of all R ³ contained in one molecule are H, The remainder may be CH ₃ , or all R ³ in one molecule may be all CH ₃ .

  The polymerizable compound represented by the general formula (1), which is an essential component of the polymerizable composition for an active energy ray-curable ink of the present invention (I), has at least one or more general formulas (1) per molecule. What is necessary is just to contain the group represented by this. Therefore, for example, all epoxy groups present in the epoxy compound as a raw material do not need to be the groups represented by the general formula (1), and some epoxy groups may remain.

  For example, when bisphenol A-diglycidyl ether is used as the epoxy compound, one of the two epoxy rings is represented by the general formula (1) even if both of the epoxy rings are groups represented by the general formula (1). And the other may leave the epoxy ring as it is.

  In particular, in the case of an epoxy resin derived from a compound having a large number of hydroxyl groups in one molecule such as a phenol novolak resin, even if all of the epoxy rings are groups represented by the general formula (1), some of them are generally It may be a group represented by the formula (1) and the other part may leave the epoxy ring as it is. Furthermore, both may be mixed as a whole epoxy resin.

(The present invention (II))
Next, the polymerizable composition for an active energy ray-curable ink of the present invention (II) will be described.

  The present invention (II) is a polymerizable composition for an active energy ray-curable ink containing a polymerizable compound represented by the general formula (1) and a monomer having a radical polymerizable unsaturated group as essential components.

  The polymerizable compound represented by the general formula (1), which is an essential component of the polymerizable composition for an active energy ray-curable ink of the present invention (II), is the one described in the present invention (I). .

  The radical-polymerizable unsaturated group-containing monomer, which is an essential component of the polymerizable composition for an active energy ray-curable ink of the present invention (II), is used for adjusting the viscosity of the system.

  "Monomer having a radically polymerizable unsaturated group" is a compound having one or more radically polymerizable unsaturated groups in a molecule, and a compound used for the purpose of adjusting the viscosity of the composition by adding the compound. It is. As described above, in the present specification, in the case of a compound included in the category of the polymerizable compound represented by the general formula (1), for example, a compound having a viscosity that can be used for adjusting the viscosity is used. Is defined as not included in the “monomer having a radically polymerizable unsaturated group”.

  Specific examples of the monomer having a radical polymerizable unsaturated group are shown below, but needless to say, the present invention is not limited to these specific examples.

(Monomer having one unsaturated group in the molecule)
Examples of the monomer having one radically polymerizable unsaturated group in a molecule, which is one embodiment of the “monomer having a radically polymerizable unsaturated group”, include the following.

Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl (Meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, diethyleneglycol mono (meth) acrylate, triethyleneglycol Mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, p-tert-butylphenoxyethoxyethyl (meth) ) Acrylate, p-nonylphenoxyethoxyethyl (meth) acrylate, octylphenoxyethoxyethyl (meth) acrylate, dodecylphenoxyethoxyethyl (meth) acrylate-isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, Various (meth) acrylates such as tricyclo [5.2.1.0 ^2,6 ] decanemonomethylol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate;

  Vinyl ethers such as diethylene glycol monovinyl ether, 1,4-butanediol monovinyl ether, triethylene glycol monovinyl ether, hexaethylene glycol monovinyl ether, and 1,4-cyclohexanedimethanol monovinyl ether;

  N-vinylamide compounds such as N-vinylpyrrolidone, N-vinylformamide and N-acryloylmorpholine.

(Monomer having two unsaturated groups in the molecule)
Examples of the monomer having two radically polymerizable unsaturated groups in the molecule include the following.

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalyl hydroxypivalate di (meth) ) Acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di (meth) acrylate, 1,6-hexanediol di ( (T) acrylate, tricyclodecane dimethylol di (meth) acrylate, tricyclodecane dimethylol dicaprolactonate di (meth) acrylate, bisphenol A tetraethylene oxide adduct di (meth) acrylate, bisphenol A polyalkylene oxide adduct Di (meth) acrylate, bisphenol F tetraethylene oxide adduct di (meth) acrylate, bisphenol F polyalkylene oxide adduct di (meth) acrylate, bisphenol S tetraethylene oxide adduct di (meth) acrylate, bisphenol S polyalkylene oxide Adduct di (meth) acrylate, water-added bisphenol A tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol A poly Luylene oxide adduct di (meth) acrylate, water-added bisphenol F tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol F polyalkylene oxide adduct di (meth) acrylate, water-added bisphenol A di (meth) acrylate Water-added bisphenol F di (meth) acrylate, dihydroxybenzene (catechol, resorcin, hydroquinone, etc.) polyalkylene oxide di (meth) acrylate, alkyl dihydroxybenzene polyalkylene oxide di (meth) acrylate, bisphenol A tetraethylene oxide adduct dica Prolactonate di (meth) acrylate bisphenol F tetraethylene oxide adduct dicaprolactonate di (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] Various acrylates such as decane dimethanol di (meth) acrylate, 1,4-cyclohexane dimethanol di (meth) acrylate, and Kayarad R604 (manufactured by Nippon Kayaku Co., Ltd.);

  Fumaric acid esters such as diethyl fumarate, diisobutyl fumarate and di-n-butyl fumarate;

  Vinyl ethers such as diethylene glycol divinyl ether, 1,4-butanediol divinyl ether, triethylene glycol divinyl ether, hexaethylene glycol divinyl ether, and 1,4-cyclohexane dimethanol divinyl ether;

(Monomer having three unsaturated groups in the molecule)
Examples of the monomer having three radically polymerizable unsaturated groups in the molecule include the following.

  Glycerin tri (meth) acrylate, glycerin alkylene oxide tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyalkylene oxide tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, Trimethylolethane tri (meth) acrylate, trimethylolethane polyalkylene oxide tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethylolhexane polyalkylene oxide tri (meth) acrylate, trimethyloloctane tri (meth) acrylate , Trimethyloloctane polyalkylene oxide tri (meth) acrylate, pentaerythritol tri ) Acrylate, trihydroxybenzene (pyrogallol) polyalkylene oxide adduct triacrylate of various (meth) acrylate.

(Monomer having four or more unsaturated groups in the molecule)
Examples of the monomer having four or more radically polymerizable unsaturated groups in the molecule include the following.

  Pentaerythritol tetra (meth) acrylate, pentaerythritol polyalkylene oxide tetra (meth) acrylate, pentaerythritol tetracaprolactonate tetra (meth) acrylate, diglycerin tetra (meth) acrylate, tri (meth) acrylate, diglycerin polyalkylene Oxide tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane polyalkylene oxide tetra (meth) acrylate, ditrimethylolpropanetetracaprolactonate, tetra (meth) acrylate, ditrimethylolethanetetra (meth) Acrylate, ditrimethylolethanepolyalkylene oxide tetra (meth) acrylate, ditrimethylo Butanetetra (meth) acrylate, ditrimethylolbutanepolyalkylene oxide tetra (meth) acrylate, ditrimethylolhexanetetra (meth) acrylate, ditrimethylolhexanepolyalkyleneoxide tetra (meth) acrylate, ditrimethyloloctanetetra (meth) acrylate, ditrimethylol Octane polyalkylene oxide tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol polyalkylene oxide penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol polyalkylene oxide hexa (meth) Acrylate, dipentaerythritol hexacaprolactonate hexa (Meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol polyalkylene oxide hexa (meth) acrylate, tripentaerythritol polyalkylene oxide hepta Various (meth) acrylates such as (meth) acrylate and tripentaerythritol polyalkylene oxide octa (meth) acrylate.

  In addition, "(meth) acrylate" described in this specification means acrylate and / or methacrylate as mentioned above.

  The above-mentioned monomer having a radical polymerizable unsaturated group can be used alone or in combination of two or more kinds. When a vinyl ether compound is used, it is preferable to use it together with a fumaric acid diester.

(Preferred monomer)
Among these monomers having a radically polymerizable unsaturated group, preferred are monomers having two or more radically polymerizable unsaturated groups in the molecule, and more preferably represented by the general formula (1). A monomer having from 2 to 5 radically polymerizable unsaturated groups capable of dissolving a polymerizable compound in a molecule is used.

(Amount of monomer)
The compounding amount of the monomer having a radical polymerizable unsaturated group is preferably 5 to 70% by mass based on all the radical polymerizable compounds. More preferably, it is at most 60% by mass.

  If the monomer having a radically polymerizable unsaturated group is added in an amount exceeding 70% by mass, the curing of the composition of the present invention tends to easily inhibit the radical curing reaction when air (oxygen) is interposed. is there. Further, in a system in which vinyl ether and a fumaric acid ester are used in combination, even when the amount exceeds 70% by mass, the inhibition of the radical curing reaction by air (oxygen) upon curing is relatively small, but in this case, There is a possibility that the solvent resistance may be reduced.

(Temperature during melting)
When dissolving the composition having the composition ratio within the above range, it is preferable to dissolve the composition at 80 ° C. to 120 ° C. in an air stream for 30 minutes to 1 hour. The temperature at this time needs to be lower than the polymerization temperature of the polymerizable compound represented by the general formula (1) and the monomer having a radical polymerizable unsaturated group, and lower than the decomposition temperature.

(The present invention (III))
Next, the present invention (III) will be described in detail.

  The present invention (III) is characterized in that the polymerizable composition for an active energy ray-curable ink according to any one of the present invention (I) and the present invention (II) further contains a radical polymerizable initiator. And a polymerizable composition for an active energy ray-curable ink.

(Radical polymerization initiator)
The radical polymerization initiator used in the present invention (III) is a radical polymerization initiator sensitive to ultraviolet light, visible light, and near infrared light. The radical polymerization initiator that can be used in the present invention is not particularly limited as long as radical polymerization can be initiated by these electromagnetic waves.

(Radical polymerization initiator sensitive to visible light or ultraviolet light)
Specific examples of the radical polymerization initiator sensitive to visible light or ultraviolet light include, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1,2-benzyl-2-methylamino-1- (4-morpholinophenyl) butanone, 1,2-hydroxy-2-methyl-1- Acetophenone or a derivative thereof such as phenylpropan-1-one; benzophenone or a derivative thereof such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4-trimethylsilylbenzophenone or 4-benzoyl-4′-methyldiphenylsulfide; benzoin , Benzoi Benzoin or its derivatives such as ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin isopropyl ether, methylphenylglyoxylate, benzoin dimethyl ketal, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-di Chlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2 6-dichlorobenzoyl) -4-biphenylylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzo) Yl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-chlorophenylphosphine oxide, bis (2,6- Dichlorobenzoyl) -2,4-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -decylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-octylphenylphosphine oxide, bis (2 , 6-Dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphenyl Phosphine oxide, bis (2,6-di Roll-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis ( 2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-phenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4- Biphenylylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxybiphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2-naphthylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-meth Kill-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methalkyl-1-naphthoyl) -4-methoxyphenylphosphine oxide, bis (2-methacryl-1-naphthoyl) -4-biphenylylphosphine Oxide, bis (2-chloro-1-naphthoyl) -2,5-dimethylphenylylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,6-trimethylpentylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide and the like.

(Polymerization initiator sensitive to visible light)
Specific examples of the polymerization initiator sensitive to visible light include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl). -Phenyl) titanium (trade name: IRGACURE784, manufactured by Ciba Specialty Chemicals Co., Ltd.).

(Polymerization initiator sensitive to visible light and / or near infrared light)
Specific examples of the polymerization initiator sensitive to visible light and / or near infrared light include visible light and / or near infrared light represented by the general formula (4) having photosensitivity in the visible light or near infrared light region. A combination of the absorbing cationic dye and the boron-based compound of the general formula (5) is exemplified.

General formula (4)
D ⁺ · A ^-
(In the formula, D ⁺ represents a cationic dye having absorption in the near-infrared light region, and A ⁻ represents various anions.)

General formula (5)

(In the formula, Z ⁺ represents an arbitrary cation, and R ^{4 to} R ⁷ each independently represent an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group. , A heterocyclic group, a halogen atom, a substituted alkyl group, a substituted aryl group, a substituted allyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group)

(Cationic dye)
The cationic dye of the general formula (4) of the present invention is a dye having an absorption in an arbitrary wavelength range usually from 400 nm to 2000 nm, and preferably from 500 nm to 1500 nm.

(Cation)
Preferred cations (D ⁺ ) of the present invention include, for example, methine, polymethine, indoline, cyanine, xanthene, oxazine, thiazine, diarylmethane, triarylmethane, and cations of pyrylium-based cationic dyes. Representative examples of such cationic dyes include cations represented by structural formulas (9) to (22).

Structural formula (9)

Structural formula (10)

Structural formula (11)

Structural formula (12)

Structural formula (13)

Structural formula (14)

Structural formula (15)

Structural formula (16)

Structural formula (17)

Structural formula (18)

Structural formula (19)

Structural formula (20)

Structural formula (21)

Structural formula (22)

(Counter anion A ^-)
A ⁻ which is a counter anion is an arbitrary anion, and a 4-coordinate boron anion represented by the general formula (6) is particularly preferable.

General formula (6)

(Wherein, R ^{8 to} R ¹¹ each independently represent an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom, a substituted alkyl group, a substituted aryl group, Represents a substituted allyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group)

  Specific examples of the above counter ion include n-butyl triphenyl boron ion, n-octyl triphenyl boron ion, triphenylsilyl triphenyl boron ion, di-n-dodecyl diphenyl boron ion, tetraphenyl boron ion, and tri-n -Butyl (dimethylphenylsilyl) boron ion; and more specifically, the anion described in the specification of JP-A-6-75374.

In the boron-based catalyst represented by the general formula (5), specific examples of the four-coordinate boron ion as an anion include n-butyltriphenylboron ion, n-octyltriphenylboron ion, triphenyl Silyl triphenyl boron ion, n-butyl trianisyl boron ion, n-butyl tri (p-fluorophenyl) boron ion, n-butyl tri (p-trifluoromethylphenyl) boron ion, di-n-dodecyl diphenyl boron ion, tetra Examples include phenyl boron ion, triphenyl naphthyl boron ion, tetrabutyl boron ion, and tri-n-butyl (dimethylphenylsilyl) boron ion. The cation (Z ⁺ ) described in the formula is a quaternary ammonium cation or a quaternary pyridinium cation represented by the general formula (7), a quaternary quinolinium cation, a diazonium cation, a tetrazolium cation, or a phosphonium cation. , (Oxo) sulfonium cations, metal cations such as sodium, potassium, lithium, magnesium, and calcium; organic oxygen cations such as flavylium and pyranium salts; carbon cations such as tropylium and cyclopropylium; and halogenium cations such as iodonium Examples include ions, arsenic, cobalt, chromium, palladium, titanium, tin, cations of metal compounds such as antimony, and the like, which are described in detail in JP-A-6-75374. These cationic dyes and boron-based catalysts can be used alone or in combination of two or more.

General formula (7)

(Wherein, R ^{12 to} R ¹⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a substituted alkyl group, a substituted aryl group, a substituted allyl group , A substituted aralkyl group, a substituted alkenyl group or a substituted alkynyl group)

  These radical polymerization initiators used in polymerization by near infrared rays, visible light rays or ultraviolet rays can be used alone or in combination of two or more as necessary.

(Quantity ratio of radical polymerization initiator)
These radical polymerization initiators may be blended in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of all polymerizable components in the polymerizable composition for active energy ray-curable ink of the present invention. Preferably, it is more preferably 0.1 part by mass and 7 parts by mass, and further preferably 0.5 part by mass to 5 parts by mass. If the amount ratio of the radical polymerization initiator is less than 0.01 parts by mass, the curing of the composition may be insufficient. On the other hand, it is economically undesirable to add more than 10 parts by mass of the radical polymerization initiator.

(Photosensitizer)
In the polymerizable composition for an active energy ray-curable ink described in the present invention (I) to the present invention (III), a photosensitizer may be added if necessary.

  Photosensitizers that can be used in the present invention include amines, ureas, sulfur compounds, nitrile compounds, phosphorus compounds, nitrogen compounds, chlorine compounds and the like, but needless to say, those compounds are not limited to these compounds. Absent.

(Gelling agent)
Moreover, in the polymerizable composition for active energy ray-curable inks according to the present invention (I) to (III), a gelling agent may be added if necessary.

  Examples of the gelling agent include an aluminum complex compound. Cyclic aluminum compounds such as cyclic aluminum oxide octate (Algomer 800 manufactured by Kawaken Fine Chemical Co., Ltd.) and cyclic aluminum oxide stearate (Algomer 1000S manufactured by Kawaken Fine Chemical Co., Ltd.), etc. Ken Fine Chemicals AIPD)

, Aluminum-sec-butyrate (ASPD manufactured by Kawaken Fine Chemical Co., Ltd.)
, Aluminum isopropylate-mono-sec-butyrate (AMD manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum alkyl acetates, for example, aluminum di-n-butoxide-ethyl acetoacetate (Chopepe-Al-EB2 manufactured by Hope Pharmaceutical Co., Ltd.), aluminum Di-iso-butoxide-methylacetoacetate (Chopepe-Al-MB12 manufactured by Hope Pharmaceutical Co., Ltd.), aluminum-di-iso-butoxide-ethylacetoacetate (Chopepe-Al-EB102 manufactured by Hope Pharmaceutical Co., Ltd.), aluminum-di-iso- Butoxide-ethyl acetoacetate (Chope-Al-EB2 manufactured by Hope Pharmaceutical Co., Ltd.), aluminum-di-iso-propoxide-ethyl acetoacetate (Chlop manufactured by Hope Pharmaceutical Co., Ltd.) e-Al-EP12, Kawaken Fine Chemical's ALch), Aluminum-Tris (acetylacetonate) (Kawaken Fine Chemical's ALCH-TR), Aluminum-Tris (acetylacetoacetate) (Kawaken Fine Chemical's aluminum chelate) -A), aluminum-bis (ethylacetylacetonate) -monoacetylacetonate (aluminum chelate D manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum chelate M (manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum chelate NB-15 (manufactured by Hope Pharmaceutical Co., Ltd.) ), Kelope S (Hope Pharmaceutical Co., Ltd.), Kelope ACS-2 (Hope Pharmaceutical Co., Ltd., Liquid Olive AOO (Hope Pharmaceutical Co., Ltd.), and Liquid Olive AOS (Hope Pharmaceutical Co., Ltd.). (Manufactured by NOF Corporation), Rumi bromide oleate, aluminum naphthaldehyde sulfonate, aluminum urate, aluminum acetylacetonate, and the like.

  These gelling agents can be used in the range of 0.1 to 10 parts by mass based on 100 parts by mass of the varnish. Other gelling agents such as cyclic dipeptides, bisamides such as ethylene bis (12-hydroxyoctadecanoic acid) amide, which can gel an organic liquid, Al-Mg-hydroxycaprylate, and Al-Mg-hydroxy myristate , Al-Mg-hydroxypalmitate, Al-Mg-hydroxybehenate and the like in the form of a powdery aluminum-magnesium compound. Furthermore, AIP, ASB, AIE-M, ASE-M, OAO, OAO-EF, OAO-HT, Cyco-Gel, Ketalin, Ketalin-II, Ketalin-III, TRI-HLP-49, P-95, KHD, ATC -30, OASMS, OAS / 607, ALAC, AO-L47 (all manufactured by Chattem Chemicals, Inc.). Further, organic titanates such as tetraisopropyl titanate, tetra n-butyl titanate, tetramethoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium lactate, and titanium lactate ethyl ester are exemplified. Further, organic zirconium and the like such as zirconium-tetrabutoxide, zirconium acetylacetone, zirconium acetylacetone, zirconium acetylacetone, acetylacetone zirconium butoxide, and ethyl zirconium butoxide acetoacetate are exemplified.

(Optional component)
In the polymerizable compositions for active energy ray-curable inks of the present invention (I) to (III), in order to enhance the suitability as a printing ink, other optional components, for example, represented by the general formula (1) Any compound having a radically polymerizable unsaturated group that does not belong to the polymerizable compound to be produced and does not belong to a monomer having a radically polymerizable unsaturated group, or any resin that does not have a radically polymerizable unsaturated group. It can be used as appropriate.

  Representative examples of these optional components include epoxy (meth) acrylate, urethane (meth) acrylate, polyester acrylate, diallyl phthalate resin, amino resin, alkyd resin, and hydrocarbon resin.

(Epoxy (meth) acrylate)
Epoxy (meth) acrylate is also called a vinyl ester resin, and is generally formed by a ring-opening reaction between a compound having an epoxy group represented by an epoxy resin and a carboxyl group of a carboxyl compound such as (meth) acrylic acid. Polymerizable unsaturated group formed by a ring-opening reaction between a resin having a functional unsaturated group or a compound having a carboxyl group and an epoxy group of a polymerizable unsaturated compound having an epoxy group in a molecule such as glycidyl (meth) acrylate Is a resin having the following properties.

  P161 The resin described in “(ii) Epoxy acrylate”, etc., and its production is carried out by a known method.

  Examples of the epoxy resin used as a raw material of the epoxy (meth) acrylate include bisphenol A diglycidyl ether and its high molecular weight homolog, glycidyl ether of bisphenol A alkylene oxide adduct, bisphenol F diglycidyl ether and its high molecular weight homolog, bisphenol F Examples include glycidyl ethers of alkylene oxide adducts, and novolak-type polyglycidyl ethers.

  Further, the epoxy (meth) acrylate referred to herein is defined to include a rosin-modified epoxy (meth) acrylate and a fatty acid-modified epoxy (meth) acrylate.

  However, in the present specification, even if a compound belonging to the category of the polymerizable compound represented by the general formula (1) belongs to the category of the epoxy (meth) acrylate described above, It is defined as not included in acrylate.

(Polyester (meth) acrylate)
Polyester (meth) acrylate is a polyester having a terminal carboxyl group obtained from a saturated polycarboxylic acid and / or an unsaturated polycarboxylic acid and a polyhydric alcohol, and an α, β-unsaturated carboxylic acid ester group. A (meth) acrylate obtained by reacting an epoxy compound containing a, a saturated polycarboxylic acid and / or an unsaturated polycarboxylic acid and a polyester having a carboxyl group at a terminal obtained from a polyhydric alcohol with a hydroxyl group-containing acrylate. (Meth) acrylic acid is obtained by reacting (meth) acrylic acid with a (meth) acrylate obtained by reacting, a polyester having a hydroxyl group at a terminal obtained from a saturated polycarboxylic acid and / or an unsaturated polycarboxylic acid and a polyhydric alcohol. (Meth) acrylates and the like; (Published September 20, 1988)

  P160 The resin described in “(i) Polyester acrylate” and the like, and its production is performed by a known method.

(Saturated polycarboxylic acid)
Examples of the saturated polycarboxylic acid include polycarboxylic acids having no polymerizable unsaturated group, such as phthalic acid, isophthalic acid, terephthalic acid, adipic acid, and sebacic acid. Examples of the unsaturated polycarboxylic acid include dicarboxylic acids having an active unsaturated group, such as fumaric acid, maleic acid, fumaric anhydride, and itaconic acid.

(Polyhydric alcohol component)
Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2- Polyvalents such as methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A Alcohol.

  However, in the present specification, those belonging to the category of the polymerizable compound represented by the general formula (1) may be polyester (meth) even if they belong to the category of the polyester (meth) acrylate described above. It is defined as not included in acrylate.

(Urethane (meth) acrylate)
Urethane (meth) acrylate is a (meth) acrylate containing a terminal isocyanate group and a hydroxyl group by reacting an alcohol having one or more hydroxyl groups in one molecule with a compound having two or more isocyanate groups in one molecule. And a (meth) acrylate obtained by reacting a (meth) acrylate containing an isocyanate group with an alcohol containing one or more hydroxyl groups in one molecule, and New Material Handbook (Maruzen Co., Ltd., issued on September 20, 1988) P161 "(iii) Urethane acrylate" section, etc., and its production method is carried out by a known method. .

  Specific examples of the alcohol having one or more hydroxyl groups in one molecule used as a raw material of urethane (meth) acrylate include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, 1,2- Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane- Examples thereof include 1,4-dimethanol, an alkylene oxide adduct of bisphenol A, a polyester having a terminal hydroxyl group obtained from a saturated dicarboxylic acid and / or an unsaturated dicarboxylic acid and a polyhydric alcohol.

  Examples of the hydroxyl group-containing (meth) acrylate used as a raw material of urethane (meth) acrylate include 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. ) Acrylate, 4-hydroxybutyl (meth) acrylate, 2-methacryloyloxyethyl-2-hydroxybutyl phthalate and the like. Examples of the (meth) acrylate containing an isocyanate group used as a raw material of urethane (meth) acrylate include 2- (meth) acryloyloxyethyl isocyanate and (meth) acryloyl isocyanate. Compounds having two or more isocyanate groups in one molecule used as a raw material of urethane (meth) acrylate include methylene diphenyl diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, tetramethyl Xylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, hydride of xylylene diisocyanate, hexamethylene diisocyanate, norbornene diisocyanate, a polymer of methylene diphenyl diisocyanate, dianisidine diisocyanate, diphenyl ether diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, triisocyanate phenyl Thiophosphate Examples include lysine diisocyanate methyl ester, lysine triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, a dimer of tolylene diisocyanate, and methylcyclohexane diisocyanate. .

  However, in the present specification, even if the compounds belonging to the category of the polymerizable compound represented by the general formula (1) belong to the category of the urethane (meth) acrylate described above, It is defined as not included in acrylate.

(Diallyl phthalate resin)
The diallyl phthalate resin is a DAP prepolymer obtained by partially polymerizing a diallyl phthalate (hereinafter referred to as DAP) monomer synthesized from allyl alcohol or allyl chloride and sodium phthalate or phthalic anhydride. Include ortho, iso and tele structural isomers, and prepolymers have similar isomers. For details, see “Plastic Encyclopedia (Asakura Shoten Co., Ltd., issued March 1, 1992) P258“ 1.6. "Diallyl phthalate resin", and the like, and its production method is carried out by a known method.

(Alkyd resin)
The alkyd resin is a resin obtained by a condensation reaction between a polybasic acid and a polyhydric alcohol, and is described in detail in "Plastic Encyclopedia (Asakura Shoten Co., Ltd., published on March 1, 1992) P210 1.4.1. And the like, and its production method is performed by a known method.

(Amino resin)
The amino resin is a curable resin formed by a reaction between an aldehyde and a compound having an amino group (—NH ₂ ), and is described in detail in “Polymer Dictionary (Maruzen Co., Ltd., issued on September 20, 1994), p. 35”. And the like. The resin is described in “Amino Resin” and the like, and its production method is performed by a known method. In this specification, a benzoguanamine-aldehyde resin is also defined as being included in the amino resin.

(Hydrocarbon resin)
Hydrocarbon resins are low molecular weight thermoplastic polymers that are obtained from cracked petroleum fractions, turpentine oil, coal tar and various pure monomers, including coumarone-indene resin, petroleum Resins, terpene resins, etc., and are described in detail in "Polymer Dictionary (published by Maruzen Co., Ltd., September 20, 1994) P642" Hydrocarbon Resin "". This is performed by a known method.

(Polymerization inhibitor)
The polymerizable compositions for active energy ray-curable inks of the present invention (I) to (III) may optionally contain a polymerization inhibitor in order to prevent thermal polymerization during production and maintain storage stability. Can be blended. A composition containing such a polymerization inhibitor is preferable from the viewpoint of prevention of thermal polymerization and storage stability.

  Typical examples of the polymerization inhibitor include (alkyl) phenol, hydroquinone, catechol, resorcinol, p-methoxyphenol, t-butylcatechol, pyrogallol, phenothiazine, p-benzoquinone, nitrosobenzene, and 2,5-diphenyl. -Tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperon, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino-1,3-dimethylbutylidene) aniline Oxides, dibutyl cresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, cyclohexanone oxime and the like can be mentioned. The amount of these polymerization inhibitors is preferably 1 part by mass or less based on 100 parts by mass of all polymerizable components.

(Printing method)
The method of use or use of the polymerizable composition for an active energy ray-curable ink of the present invention having the above-described structure is not particularly limited. For example, as a printing method, the polymerizable composition for an active energy ray-curable ink of the present invention can be employed for, for example, screen printing, offset printing, gravure printing, intaglio printing, and the like.

  When the polymerizable composition for an active energy ray-curable ink of the present invention is used for printing, generally, at room temperature to 100 ° C., a pigment, a radical polymerizable compound, a radical polymerization inhibitor if necessary, a radical polymerizable initiator The components of the printing ink composition such as a sensitizer and / or a sensitizer and other additives are added to the polymerizable composition for an active energy ray-curable ink of the present invention, and a kneader, a three-roll, an attritor, a sand mill, and a gate are added. A printing ink can be produced by mixing using a mixer or the like, mixing, and an adjusting machine.

(Pigment)
Examples of the pigment include an inorganic pigment and an organic pigment. Inorganic pigments such as yellow lead, zinc yellow, navy blue, barium sulfate, cadmium red, titanium oxide, zinc white, petal, alumina white, calcium carbonate, ultramarine blue, carbon black, graphite, aluminum powder, red iron oxide, etc. Are soluble azo pigments such as β-naphthol type, β-oxynaphthoic acid type, β-oxynaphthoic acid type anilide type, acetoacetic anilide type, pyrazolone type, β-naphthol type, β-oxynaphthoic acid type anilide type, Insoluble azo pigments such as acetoacetate anilide monoazo, acetoacetate anilide disazo and pyrazolone, phthalocyanine pigments such as copper phthalocyanine blue, halogenated (chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine , Quinacridone , Dioxazine-based, sulene-based (pyranthrone, anthantrone, indanthrone, anthrapyrimidine, flavantron, thioindigo, anthraquinone, perinone, perylene, etc.), isoindolinone, metal complex, quinophthalone, etc. Various publicly known pigments such as formula pigments and heterocyclic pigments can be used.

(Additive)
Further, other additives can be used in the polymerizable composition for an active energy ray-curable ink, if necessary. For example, anti-friction agents, anti-blocking agents, slip agents, anti-scratch agents, antifoaming agents, carnauba wax, wood wax, lanolin, montan wax, paraffin wax, natural wax such as microcrystalline wax, Fischer-Trops wax, Examples thereof include synthetic waxes such as polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and silicone compounds.

  The polymerizable composition for an active energy ray-curable ink of the present invention can be suitably used as an overcoating agent for the purpose of protecting the surface of a printed matter, imparting gloss, and the like.

(The present invention (IV))
Next, the present invention (IV) will be described in detail.

  The present invention (IV) is a printed matter obtained by printing and curing a polymerizable composition for an active energy ray-curable ink according to any one of the present invention (I) to the present invention (III) on a substrate.

  As described above, the polymerizable composition for an active energy ray-curable ink of the present invention can be used for, for example, a screen printing ink, an offset printing ink, a gravure printing ink, an intaglio printing ink, or the like. Furthermore, the polymerizable composition for an active energy ray-curable ink of the present invention can be used not only for color printing, but also for color printing such as yellow, red, indigo, and black, as well as a transparent overprint varnish (commonly referred to as “printing varnish”). OP varnish).

  When the polymerizable composition for an active energy ray-curable ink of the present invention is used as a screen printing ink, for example, it is printed on a substrate to a thickness of about 10 to 30 μm by a screen printing method, and then irradiated with an active energy ray. By curing, a cured layer using the polymerizable composition for an active energy ray-curable ink of the present invention can be formed.

(Printed matter)
Active energy ray-curable prints include foam prints, various book prints, various packaging prints such as carton paper, various plastic prints, stickers, label prints, art prints, metal prints (art prints, beverage can prints, canned foods) Etc.), especially when printed or coated on a plastic substrate, has a remarkable effect compared to other polymerizable compositions for active energy ray-curable printing inks. Demonstrate.

(Plastic substrate)
In the present invention, the term "plastic substrate" refers to a substrate whose surface to be printed is made of plastic. Specific examples of the plastic substrate described above include a polyethylene substrate, a polypropylene substrate, a polystyrene substrate, a polyvinyl chloride substrate, a polyester substrate, an acrylic substrate, a urethane substrate, and a polycarbonate. Substrates made of these and substrates whose surfaces have been treated may be mentioned. Further, it can also be used for a laminated steel sheet to which a polyethylene film, a polypropylene film, a polyvinyl chloride film, a polyester film, an acrylic film is bonded, a coated paper coated with an acrylic resin or a urethane resin, and the like.

  In this specification, the above-described laminated steel sheet and coated paper are also defined as being included in the plastic substrate (because their surfaces to be printed are made of plastic).

  Among these plastic substrates, when a polyester substrate such as a PET substrate, a polybutylene terephthalate substrate, or a polytrimethylene terephthalate substrate is used, the present invention (I) and the present invention ( The polymerizable composition for active energy ray-curable ink according to II) or the present invention (III) exhibits good adhesion to a substrate.

  The method for producing the printed matter of the present invention (IV) is not particularly limited, and for example, the following method can be exemplified.

  The polymerizable composition for an active energy ray-curable ink of the present invention (I), (II) or (III) is applied on a substrate according to a usual printing method, for example, paper, film or sheet. And then harden by irradiating with active energy rays.

  Among the active energy rays, as a light source for curing with visible light or ultraviolet light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, a halogen lamp, a xenon lamp, a tungsten lamp, a gallium lamp, and a carbon arc A lamp, an incandescent lamp, a fluorescent lamp, an excimer lamp, a laser, or the like can be used. Among these light sources, a high-pressure mercury lamp and a metal halide lamp are particularly preferred. Standard curing conditions are a line speed of 5 m / min to 80 m / min per lamp by an ultraviolet irradiation device using a high-pressure mercury lamp or a metal halide lamp having an output of 80 W / cm to 300 W / cm.

  The curing method using an electron beam does not necessarily require the use of a radical polymerization initiator. Examples of the electron beam that can be used include a Cockroft-Walton type, a Van de Graaff type or a resonance transformer type, and an electron beam having an energy in the range of 50 keV to 1000 keV, preferably 100 keV to 300 keV is used. it can.

  Next, the present invention will be described with reference to examples, but the present invention is not limited to the examples.

  Various physical properties were measured as follows. 1) Measurement of acid value It was measured by the test method of acid value described in JIS K0070.

  The conversion, yield, and purity of the reaction were determined by using a calibration curve prepared in advance and quantifying each component by an absolute calibration curve method using a high-performance liquid chromatograph. The column used was Showdex (registered trademark) F-411A (manufactured by Showa Denko KK), the solvent was 1% by mass aqueous phosphoric acid / methanol = 7/3, the flow rate was 1.0 ml / min, and the detection device was SPD-10AVvp. The peak of each component was detected at 210 nm using (manufactured by Shimadzu Corporation).

(Production Example 1-1) Synthesis of monoallyloxyethyl fumarate (hereinafter abbreviated as “H-BAF”)

  500 g (5.10 mol) of maleic anhydride, 573 g (5.61 mol) of ethylene glycol monoallyl ether, and 0.05 g of hydroquinone monomethyl ether were charged into a 2 liter flask, and the reaction solution was stirred with a magnetic stirrer under a nitrogen stream. And heated to 50 ° C. in an oil bath. After 24 hours, the heating was stopped and the flask was cooled. When the reaction solution was analyzed by high performance liquid chromatography, the conversion of maleic anhydride was 95%.

  Further, 499.54 g of the above reaction solution was charged into a 2 liter flask equipped with a reflux device, 215.07 g of toluene, 4.99 g of concentrated hydrochloric acid (1% by mass based on the raw material), and 0.25 g of hydroquinone monomethyl ether. Under a nitrogen stream, the reaction solution was heated at 140 ° C. in an oil bath while stirring with a magnetic stirrer to reflux toluene. After 3 hours, heating was stopped and the flask was cooled. To the reaction solution was added 500 ml of toluene, and the mixture was filtered to remove insolubles. To remove the hydrochloric acid, 500 ml of water was added to the filtrate, and the mixture was separated with a separating funnel. The toluene layer was concentrated by an evaporator to obtain 428 g of the target H-BAF. The yield based on maleic anhydride was 90%.

(Production Example 2-1) Synthesis of Sample A In a 1-liter flask, 400.4 g (2.0 mol) of H-BAF, Adekaresin (registered trademark) EP-4100G (bisphenol A diglycidyl ether, epoxy equivalent 185, Asahi Denka Kogyo ( 374.0 g, N, N-dimethylaminoethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) 8.00 g, IRGANOX1010 (pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate] and 0.4 g of Ciba Specialty Chemicals Co., Ltd.) and heated to 110 ° C. in an oil bath while stirring the reaction solution with a magnetic stirrer under a nitrogen stream. After 6 hours, heating was stopped and the flask was cooled. This compound is referred to as "Sample A". Sample A had an acid value of 6.5 mg KOH / g.

(Production Example 2-2) Synthesis of Sample B In a 1-liter flask, 200.2 g (1.0 mol) of H-BAF, 72.1 g (1.0 mol) of acrylic acid, and Adeka Resin (registered trademark) EP-4100G (bisphenol A Glycidyl ether, epoxy equivalent 185, 374.0 g of Asahi Denka Kogyo Co., Ltd., 10.0 g of N, N-dimethylaminoethyl methacrylate (Kyoeisha Chemical Co., Ltd.), IRGANOX1010 (pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate], 0.4 g of Ciba Specialty Chemicals Co., Ltd.) and stirring the reaction mixture under a nitrogen stream while stirring with a magnetic stirrer. Heated to 110 ° C. in bath. After 5 hours, heating was stopped and the flask was cooled. This compound is referred to as "Sample B". Sample B had an acid value of 0.5 mg KOH / g.

(Production Example 2-3) Synthesis of Sample C In a 1-liter flask, 400.4 g (2.0 mol) of H-BAF, Adekaresin (registered trademark) EP-4080E (hydrogenated bisphenol A diglycidyl ether, epoxy equivalent 214, Asahi Denka) 446.0 g, manufactured by Kogyo Co., Ltd., 6.26 g of TPP-Zc (benzyltriphenylphosphonium chloride, manufactured by Hokuko Chemical Industry Co., Ltd.), IRGANOX (registered trademark) 1010 (pentaerythrityl-tetrakis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate] and 0.4 g of Ciba Specialty Chemicals Co., Ltd.), and stir the reaction solution with a magnetic stirrer under a nitrogen gas stream in an oil bath. Heated to 100 ° C. This compound is referred to as "Sample C". Sample C had an acid value of 0.7 mg KOH / g.

(Production Example 2-4) Synthesis of Sample D In a 1-liter flask, 400.4 g (2.0 mol) of H-BAF and Adekaresin (registered trademark) EP-4088S (tricyclo [5.2.1.0 ^2,6 ] de) were added. Candimethanol diglycidyl ether, epoxy equivalent 178, 446.0 g, manufactured by Asahi Denka Kogyo Co., Ltd., 6.26 g of TPP-Zc (benzyltriphenylphosphophosphonium chloride, manufactured by Hokuko Chemical Co., Ltd.), IRGANOX1010 (pentaerythrityl) 0.4 g of -tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals Co., Ltd.) and charged with a magnetic stirrer under nitrogen flow. While stirring, the mixture was heated to 100 ° C. in an oil bath. This compound is referred to as "Sample D". The acid value was 12.3 mgKOH / g.

(Production Example 2-5) Synthesis of Sample E In a 1-liter flask, 400.4 g (2.0 mol) of H-BAF, Adekaresin (registered trademark) EP-4085S (1,4-cyclohexanedimethanol diglycidyl ether, epoxy equivalent 146) Asahi Denka Kogyo Co., Ltd.) 292 g, TPP-Zc (benzyltriphenylphosphonium chloride, Hokuko Chemical Co., Ltd.) 5.12 g, IRGANOX (registered trademark) 1010 (pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate], 0.4 g of Ciba Specialty Chemicals Co., Ltd.), and the reaction solution was stirred with a magnetic stirrer under a nitrogen stream while an oil bath was used. To 100 ° C. This compound is referred to as "Sample E". The acid value of this sample E was 12.3 mgKOH / g.

(Production Example 2-6) Synthesis of Sample F In a 300 ml flask, 48.39 g (0.290 mol) of H-BAF, Araldite ECN (registered trademark) 1273 (cresol novolak type epoxy resin, epoxy equivalent 214, manufactured by Asahi Chiba Corporation) ) 51.70 g, toluene 43.42 g, DMP-30 (2,4,6-tris (dimethylaminomethyl) phenol, manufactured by Wako Pure Chemical Industries, Ltd.) 0.50 g, and hydroquinone monomethyl ether 0.02 g. The reaction solution was heated to 100 ° C. in an oil bath while stirring with a magnetic stirrer under a nitrogen stream. After 22 hours, heating was stopped and the flask was cooled. Analysis of this reaction solution by high performance liquid chromatography revealed that 0.92 g of H-BAF as the raw material remained, and that the conversion of H-BAF was 98.1%. This compound is referred to as "Sample F".

(Production Example 2-7) Synthesis of sample G In a 300 ml flask, 12.90 g (0.064 mol) of H-BAF, 4.63 g (0.064 mol) of acrylic acid, and Araldite ECN (registered trademark) 1273 (cresol novolac epoxy resin) 30.75 g, epoxy equivalent 214, manufactured by Asahi Ciba Co., Ltd.), toluene 48.24 g, DMP-30 (2,4,6-tris (dimethylaminomethyl) phenol, manufactured by Wako Pure Chemical Industries, Ltd.) 49 g and hydroquinone monomethyl ether 0.02 g were charged, and the reaction solution was heated to 100 ° C. in an oil bath while stirring with a magnetic stirrer under a nitrogen stream. After 13 hours, heating was stopped and the flask was cooled. Analysis of this reaction solution by high performance liquid chromatography revealed that 0.06 g of H-BAF as the raw material and 1.21 g of acrylic acid remained. The conversion of H-BAF was 99.5%, and the conversion of acrylic acid was 76.0%. This compound is referred to as "sample G".

(Production Example 2-8) Synthesis of Sample H In a 1-liter flask, 200.2 g (1.0 mol) of H-BAF, 114.1 g (1.0 mol) of allyl glycidyl ether, 6.89 g of triethyl methacryloyloxyethyl ammonium chloride, 6.89 g of IRGANOX (Registered trademark) 1010 (pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals Co., Ltd.). The reaction solution was heated to 110 ° C. in an oil bath while stirring with a magnetic stirrer. After 20 hours, heating was stopped and the flask was cooled. This compound is referred to as "sample H". The acid value of this sample H was 10.0 mgKOH / g.

(Examples 1 to 7, Comparative Examples 1 and 2)
Each component shown in Table 2 was mixed and kneaded with a three-roll mill to obtain a polymerizable composition for an active energy ray-curable ink of the present invention or a comparative example. Tests were conducted on the curability and adhesion of these polymerizable compositions for active energy ray-curable inks.

The prepared polymerizable composition was screen-printed on an untreated PET film having a thickness of 1 mm using a 150-mesh screen made of Tetron, and irradiated with an integrated ultraviolet ray of 600 mJ / cm ² by a 120 W / cm metal halide lamp. , Printed matter was created. In the obtained printed matter, it was confirmed visually that the screen was well reproduced on the PET film.

Curability: The cured state of the ink surface of the printed matter was checked with a finger.
：: There is no tack at all.
Δ: tackiness.
×: Not cured.

  Adhesion: The adhesion of the printed matter was evaluated according to the cross-cut method (JIS K 5600-5-6). However, the test results were classified into the following three types (in this evaluation, even if one cross-cut portion has some peeling, as long as the cross-cut portion has not actually peeled off, “peel-off” Has not been determined.)

：: 5 or less of 100 cross-cut parts peeled off.
Δ: 35 or less of 100 cross-cut parts peeled off.
X: The cross-cut part which peeled exceeded 35 pieces out of 100 pieces.

  Further, the “adhesiveness” was also evaluated in accordance with the JIS evaluation criteria. In this JIS evaluation, the test results were classified into the following three types.

  A: Even if no peeling of the cross-cut portion occurs, or even if a small peel-off occurs, the influence of the cross-cut portion clearly does not exceed 5% of the total cross-cut area.

  B: In the crosscut portion, the influence of peeling or chipping exceeds 5% of the total crosscut area, but does not exceed 35%.

  C: In the cross-cut portion, the influence of peeling or chipping exceeds 35% of the total cross-cut area.

Table 2 shows the evaluation results.
The expression “parts” in Table 2 means “parts by mass”.

Claims (11)

A polymerizable composition for an active energy ray-curable ink, comprising a polymerizable compound represented by the general formula (1).
General formula (1)

(Wherein, R ¹ independently represents at least one or more organic residues selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and R ² represents an alcohol compound or a phenol compound. Or an organic residue derived from a carboxylic acid compound, and n represents an integer of 0 to 20. The organic residue further includes a group represented by the general formula (2) and / or the general formula (3). May be substituted.)
General formula (2)

(Wherein, R ¹ independently represents at least one or more organic residues selected from the group consisting of an alkylene group, a branched alkylene group, a cycloalkylene group, an aralkylene group and an arylene group, and n is an integer of 0-20. Represents.)
General formula (3)

(In the formula, R ³ represents either H or CH _3. )   A polymerizable composition for an active energy ray-curable ink, comprising a polymerizable compound represented by the general formula (1) and a monomer having a radical polymerizable unsaturated group. In the polymerizable compound represented by the general formula (1), R ¹ is independently at least one or more organic residues selected from the organic residues represented by the structural formulas (1) to (7). The polymerizable composition for an active energy ray-curable ink according to claim 1, wherein:
Structural formula (1)

Structural formula (2)

Structural formula (3)

Structural formula (4)

Structural formula (5)

Structural formula (6)

Structural formula (7)

In the polymerizable compound represented by the general formula (1), R ² is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin , Trimethylolethane, trimethylolpropane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, brominated bisphenol A, hydrogenated bisphenol A, Bisphenol F, phenol novolak resin, cresol novolak resin, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexene- The active energy according to any one of claims 1 to 3, wherein the active energy is an organic residue derived from a compound selected from the group consisting of 2,2-dicarboxylic acid, phthalic acid, isophthalic acid and terephthalic acid. A polymerizable composition for a line-curable ink.   A monomer having a radical polymerizable unsaturated group is contained in an amount of 5 to 70% by mass based on the total amount of the polymerizable compound represented by the general formula (1) and the monomer having a radical polymerizable unsaturated group. The polymerizable composition for an active energy ray-curable ink according to claim 2.   The polymerizable material for an active energy ray-curable ink according to any one of claims 2 to 5, wherein the monomer having a radical polymerizable unsaturated group is a monomer having two or more radical polymerizable unsaturated groups. Composition.   The active energy ray-curable ink according to any one of claims 2 to 6, wherein the polymerizable compound is dissolved with a monomer having a radical polymerizable unsaturated group. Polymerizable composition for ink.   The polymerizable composition for an active energy ray-curable ink according to any one of claims 1 to 7, further comprising a radical polymerizable initiator. .   A printed matter obtained by printing and curing a polymerizable composition for an active energy ray-curable ink according to any one of claims 1 to 8.   The printed material according to claim 9, wherein the substrate is a plastic substrate.   The printed material according to claim 10, wherein the plastic substrate is a polyester substrate.