JP2018095739A - Ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink that can impart chemical resistance and heat resistance to printed matter in a drying process after printing, and is free of the problems of the increased viscosity of ink and the plate jamming of a printer.SOLUTION: The problem is solved by an ink composition containing a compound containing a furyl group (A) and a compound containing a specific polymerizable functional group (B), a polymerization initiator (C), and a colorant (F).SELECTED DRAWING: None

Description

  The present invention relates to an ink excellent in chemical resistance, heat resistance and residual monomer reduction of printed matter, and excellent in storage stability with time and stability on a printing press.

  In general, when an ink or the like is produced, a binder resin is used for imparting chemical resistance, heat resistance, gloss, substrate adhesion, and the like of the printed material. By using a thermosetting resin as the binder resin, chemical resistance and heat resistance can be imparted to the printed matter in the drying step after printing.

  As a compound that imparts such thermosetting properties, a technique is known in which a compound having a furyl group that performs a Diels-Alder reaction at a relatively low temperature and a compound having a maleimide group are combined (Patent Document 1). Separate the compound with furyl group and the compound with maleimide group into a two-part ink, or if you put one side into the ink and put the other into the adherend, there will be no problems such as thickening of the ink. Chemical resistance and heat resistance can be imparted. However, when preparing a one-component ink combining these compounds, the ink is used because the thermosetting reaction proceeds on the printing press during storage from printing to printing and during printing. There has been a concern that problems such as thickening and plate clogging of the printing press may occur.

In addition, when a compound containing a maleimide group having a substituent as shown in Patent Document 2 is used, the reactivity becomes lower than that of the maleimide group, so that the stability of the ink is increased, but sufficient chemicals for the ink composition are used. There was a problem that tolerance could not be given.

JP 2000-233581 A JP 2014-70162 A

  The present invention has been made in view of the above-described present situation, and can impart chemical resistance and heat resistance to a printed matter in a drying step after printing, and can increase viscosity of ink and plate jam of a printing press. The purpose is to provide ink without problems.

As a result of intensive studies, the present inventors include a compound (A) containing a furyl group, a compound (B) containing a specific polymerizable functional group, and a polymerization initiator (C) in the ink composition. The present inventors have found that the above problems can be solved, and have completed the present invention.
That is, the present invention contains a compound (A) containing a furyl group, a compound (B) containing a polymerizable functional group, a polymerization initiator (C), and a colorant (F).
The compound (B) is a compound containing a group represented by any one of the following formulas [1] to [7] as a polymerizable functional group, or a compound represented by the following formula [8]. The present invention relates to an ink composition.

(In formulas [1] to [7], * represents a bond.)

Further, the present invention is characterized in that the compound (A) containing a furyl group is a polymer (A-1) of a monomer (a) containing a monomer (a-1) containing a furyl group. The present invention relates to the ink composition.

The present invention also relates to an offset ink, a flexographic ink, a gravure ink, or an inkjet ink composed of the ink composition.

  According to the present invention, it is possible to provide an ink that can impart chemical resistance and heat resistance to a printed matter in a drying step after printing, and that does not have a problem of ink thickening or printing plate jamming.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, (meth) acrylate means acrylate and / or methacrylate, and (meth) acrylic acid means acrylic acid and / or methacrylic acid.

<< Curing method and components of ink composition >>
First, combinations of elements constituting the ink composition of the present embodiment will be described. The ink composition of the present embodiment includes, as essential components, a compound (A) containing a furyl group, a compound (B) containing a polymerizable functional group, a polymerization initiator (C), and a colorant (F). The compound (B) is a compound containing a group represented by any one of the following formulas [1] to [7] as a polymerizable functional group, or a compound represented by the following formula [8].

(In formulas [1] to [7], * represents a bond.)

  Formula [1] is an acryloyl group, Formula [2] and Formula [3] are acrylamide groups, Formula [4] and Formula [5] are methacrylamide groups, Formula [6] and Formula [7] are N-vinylamide groups. Yes, the compound represented by the formula [8] is acrylonitrile.

  The ink composition of the present embodiment only needs to satisfy the above-described configuration, and is not limited to an action or a curing process. For example, chemical resistance can be increased by thermal curing. Examples of printing methods including thermal curing include thermal curing after printing, photocuring after printing, thermal curing, photocuring after printing, and simultaneous thermal curing with the heat generated at that time. That is, performing printing while raising the temperature of the substrate to be printed and thermally curing, performing photocuring after performing thermal curing after printing, performing thermal curing by infrared heating after printing, and the like. Among them, in the case of a printing method including photocuring and thermosetting, photocuring is difficult to proceed due to light absorption of the colorant in the ink, but thermal curing proceeds efficiently by including the compound (A) containing a furyl group. Therefore, excellent chemical resistance can be obtained. The effect is presumed as follows.

The reaction in photocuring is radical polymerization by irradiation with active energy rays such as ultraviolet rays. At this stage, most of the polymerizable functional groups in the compound (B) are polymerized, but the reaction rate does not reach 100%. That is widely known. This is one of the reasons why the printed material has insufficient chemical resistance.
The reaction in thermosetting is thermal radical addition by an unreacted polymerizable functional group in the compound (B), an unreacted polymerization initiator (C), and a furyl group in the compound (A). The chemical resistance of the printed matter can be improved.

  In the thermal radical addition reaction, the polymerization initiator (C) is cleaved by heat to generate radicals, radical polymerization of the polymerizable functional group in the compound (B) occurs, and the radical at the polymerization growth terminal is a furyl group. This reaction is presumed to be added to Such a reaction is described in, for example, Non-Patent Document 1 (N. Davidenko et al., “Activity of the Furry Ring in the Free radical Polymerization of Acryal Monomers, Journal. -2766 (1996)) also describes the mechanism.

  The present inventors have an effect of improving the chemical resistance by improving the cross-linking density by a thermal radical addition reaction between the polymerizable functional group and the compound containing a furyl group (A) in the thermosetting step of the ink composition. I found. When the compound (B) is a compound containing a group represented by any of the following formulas [1] to [7] as a polymerizable functional group, or a compound represented by the following formula [8], The derived growth radical is preferable because it easily undergoes an addition reaction to the furyl group.

In addition to the compound (B), a compound containing a polymerizable functional group may be used as long as the object of the invention is not impaired. For example, a compound containing methacryloyloxy group, vinyl group, vinyl ester group, vinyl ether group, allyl ether group, styryl group, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, maleic acid, maleic anhydride , Maleic acid ester, maleic acid amide, and the like.
However, when a compound containing a maleimide group is used, a Diels-Alder reaction of a combination of a furyl group as a diene structure and a maleimide group as a dienophile structure occurs, and the thermal cross-linking progresses effectively and has an effect of improving chemical resistance. Since the reaction proceeds without a catalyst and the temporal stability of the ink composition is lowered, it is preferably not used. As can be seen from the fact that it is shown as a two-component ink composition in JP-A-2000-233581, it is difficult to obtain a one-component ink composition when a compound containing a maleimide group is used.

  In order to improve chemical resistance, the polymerization initiator (C) is preferably used in an amount of 0.01 to 60 parts by mass, more preferably 0.1 to 10 parts by mass, in a total of 100 parts by mass of the solid content of the ink composition. preferable. Further, in the solid content of the ink composition, the ratio of the mass W (A) of the compound (A) containing a furyl group to the mass W (B) of the compound (B) containing a photopolymerizable functional group is W (A ) / W (B) = 95/5 to 5/95.

  Next, each component of the ink composition of this embodiment will be described.

<< Compound containing furyl group (A) >>
The compound (A) containing a furyl group of the present embodiment is presumed to have an effect of imparting chemical resistance to the ink composition by a thermal radical addition reaction in the thermosetting step with the polymerizable functional group in the ink composition. Is done. The compound (A) containing a furyl group is not particularly limited in its structure as long as it contains a furyl group (a group obtained by removing one hydrogen atom from furan). JP 2000-233581, JP 1994-271558, JP 1994-293830, JP 1996-239421, JP 1998-508655, JP 2000-001529, JP 2003-183348, JP 2006-193628, JP Known compounds described in 2007-186684, JP-A 2010-265377, JP-A 2011-170069 and the like can be used, and they may be low-molecular or high-molecular.
Examples of the low molecular weight compound include a monomer containing a furyl group, a compound obtained by reacting a polyfunctional isocyanate and an alcohol containing a furyl group, and the like. In order to increase chemical resistance, a polymer is more preferable, and specific examples include poly (meth) acrylate, polyurethane, polyester, polyamide, polyimide, polycarbonate, polyolefin, polystyrene, polysiloxane, polysiloxane having a furyl group. Examples include ethers, copolymers containing maleic anhydride, epoxy resins, furan resins (condensation polymers of furfuryl alcohol and formaldehyde). These may be used alone, or a mixture may be used. The polymer may be linear, branched or star-shaped, and may be either thermoplastic or thermosetting. In addition, the compound (A) containing a furyl group may further contain a polymerizable functional group.

  The compound (A) containing a furyl group is used in an amount of 5 to 95 parts by mass, out of a total of 100 parts by mass of the solid content of the component obtained by removing the colorant from the ink composition, from the viewpoint of chemical resistance of the ink composition. It is preferably 10 to 70 parts by mass, more preferably 15 to 40 parts by mass.

  As the compound (A) containing a furyl group, it is possible to easily introduce a furyl group, to easily control the amount of furyl group introduced, and to control the printing characteristics of the ink composition by controlling the molecular weight and copolymer composition. The polymer (A-1) is more preferable because it is easy and the glossiness of the ink composition is excellent.

<Polymer containing furyl group (A-1)>
[Structure of Polymer (A-1) Containing Furyl Group and Method for Producing the Same]
The polymer (A-1) containing a furyl group is a polymer obtained by radical polymerization of a monomer having a double bond capable of radical polymerization, and has a structure containing a furyl group. The manufacturing method is
Method [1-1] Method of polymerizing monomer (a) containing monomer (a-1) containing furyl group [1-2] Monomer (a-3) containing reactive functional group And a method of reacting a reactive compound (a-4) containing a furyl group with the obtained polymer (prepolymer).
Method [1-1] is preferred in that the number of synthesis reaction processes can be reduced. The polymer (A-1) may be a homopolymer or a copolymer with another monomer, but the polymer Tg, the viscosity of the photosensitive composition, and the phase with other components. For adjustment of solubility, etc., it is preferable to copolymerize with a monomer other than (a-1) or (a-3).

  Examples of the monomer (a-1) containing a furyl group include monomers represented by the following general formulas [1] to [5], furfuryl vinyl ether, furfuryl allyl ether, and the like. In particular, from the viewpoint that the furyl group concentration in the radical polymer (A-1) containing a furyl group can be easily increased, it is preferable to use the monomer of the general formula [1], and the stability of the monomer itself. It is more preferable to use furfuryl methacrylate in view of the above points and obtaining good polymerizability.

General formula [1]

[Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an oxygen atom or —NH—. ]

General formula [2]

[Wherein R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an oxygen atom, —NH—, or a sulfur atom. ]

General formula [3]

[Wherein R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an oxygen atom, —NH—, or a sulfur atom. ]

General formula [4]

[Wherein R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents an oxygen atom, —NH—, or a sulfur atom. ]

General formula [5]

[Wherein R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents an oxygen atom, —NH—, or a sulfur atom. ]

  Examples of the reactive functional group in the monomer (a-3) containing the reactive functional group used in the method [1-2] include a carboxyl group, an epoxy group, an isocyanate group, and a carboxylic anhydride group. A radical containing a furyl group by reacting these reactive functional groups contained in the polymer with a hydroxyl group, amino group, mercapto group, aldehyde group, etc. in the reactive compound (a-4) containing a furyl group. A polymer (A-1) can be obtained.

  As a monomer (a-3) containing a reactive functional group, the monomer containing a carboxyl group, an epoxy group, an isocyanate group, a carboxylic anhydride group etc. is mentioned, for example.

  As the monomer containing a carboxyl group, (meth) acrylic acid, acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, α- (hydroxymethyl) (meth) acrylic acid, 2- (meth) acryloyl Roxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth) acrylate, Ethylene oxide-modified succinic acid (meth) acrylate, ω-carboxypolycaprolactone (meth) acrylate, p-vinylbenzoic acid, and a monomer obtained by addition reaction of a carboxylic acid anhydride and a monomer containing a hydroxyl group Can be mentioned.

Examples of the carboxylic acid anhydride used for the monomer obtained by addition reaction of the carboxylic acid anhydride and the monomer containing a hydroxyl group include succinic acid anhydride, maleic acid anhydride, itaconic acid anhydride, and phthalic acid. Dicarboxylic anhydrides such as anhydride, glutaric anhydride, dodecenyl succinic anhydride, and chlorendic anhydride;
3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid-1,2-anhydride, 1,3, Aliphatic tricarboxylic anhydrides such as 4-cyclopentanetricarboxylic anhydride;
Benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], trimellitic anhydride chloride [4-chloroformylphthalic acid Anhydride], naphthalenetricarboxylic acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 2,8-naphthalene tricarboxylic acid anhydride, etc.), 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride , 2,3,2′-biphenyltricarboxylic anhydride, 3,4,4′-biphenylmethanetricarboxylic anhydride Such as 3,4,4'-biphenyl sulfonic tricarboxylic acid anhydride and aromatic tricarboxylic acid anhydride and the like.
In addition, when a carboxylic acid anhydride containing two or more acid anhydride groups in one molecule such as tetracarboxylic dianhydride is used for addition reaction with a monomer containing a hydroxyl group, the carboxylic acid anhydride 1 Two or more monomers containing a hydroxyl group are added to a molecule, and two or more radical polymerizable functional groups are contained in one molecule. As a result, the copolymer may be gelled. Therefore, when using a carboxylic acid anhydride containing two or more acid anhydride groups in one molecule, preferably 3 mol% or less of the entire carboxylic acid anhydride. More preferably, it is 2 mol% or less, and it may be preferable not to use it.

Examples of the monomer containing a hydroxyl group used as a monomer obtained by addition reaction of a carboxylic acid anhydride and a monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2 (or 3) Such as hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and ethyl-α-hydroxymethyl acrylate (Meth) acrylates having a hydroxyl group such as alkyl-α-hydroxyalkyl acrylate;
N- such as N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide (Meth) acrylamides having a hydroxyl group such as (hydroxyalkyl) (meth) acrylamide;
Vinyl ethers having a hydroxyl group such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2- (or 3- or 4-) hydroxybutyl vinyl ether;
Examples include allyl ethers having a hydroxyl group such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, and 2- (or 3- or 4-) hydroxybutyl allyl ether.
Monomers obtained by adding alkylene oxide and / or lactone to the above (meth) acrylates having a hydroxyl group, (meth) acrylamides having a hydroxyl group, vinyl ethers having a hydroxyl group, and allyl ethers having a hydroxyl group. Can also be used as a monomer containing a hydroxyl group. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more thereof are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these are used. What added both alkylene oxide and lactone may be used.

  When a structure obtained by addition reaction of a carboxylic acid anhydride and a monomer containing a hydroxyl group is introduced into the polymer (A-1), an addition reaction between the carboxylic acid anhydride and a monomer containing a hydroxyl group is performed. The monomer may be synthesized in advance and used as a monomer (a-2) containing a carboxyl group, or a monomer containing a hydroxyl group and another monomer may be copolymerized in advance. A carboxylic acid anhydride may be added later, but the former method is preferable in that the reaction process of synthesis can be shortened.

  Examples of the monomer containing a carboxylic anhydride group include maleic anhydride, itaconic anhydride, 4-[(2-methacryloyloxyethoxy) carbonyl] phthalic anhydride, and the like.

  As a monomer containing an epoxy group, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycyl diether, 3,4-epoxybutyl (meth) acrylate, 3-methyl- 3,4-epoxybutyl (meth) acrylate, 3-ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5,6-epoxy Hexyl (meth) acrylate, α-ethyl acrylate glycidyl, allyl glycidyl ether, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, N- (3,5 -Dimethyl-4-glycidyl) ben Acrylamide, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α-methyl- p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3 , 4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, 2,4,6 -Triglycidyl Examples include oxymethylstyrene.

  Monomers containing isocyanate groups and block bodies thereof include (meth) acryloyl isocyanate, 2-isocyanatoethyl (meth) acrylate, 2- (meth) acryloyloxyethoxyethyl isocyanate, 1,1- (bis (meth) And acryloyloxymethyl) ethyl isocyanate, m- (meth) acryloylphenyl isocyanate, α, α-dimethyl-4-isopropenylbenzyl isocyanate, and the like.

  Examples of the reactive compound (a-4) containing a furyl group include furfuryl alcohol, furfurylamine, furfuryl mercaptan, furfural, 2-furancarboxylic acid and the like.

  As the monomer (a-3) containing a reactive functional group and the reactive compound (a-4) containing a furyl group, one kind of compound may be used or two or more kinds of compounds may be used in combination.

Examples of other monomers that can be used as the monomer (a) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2,2,4-trimethylcyclohexyl (meth) acrylate, 4-t-butyl Cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxye Ru (meth) acrylate, tricyclo- [5.2.1.0 (2,6)]-decanyl (meth) acrylate, tricyclo- [5.2.1.0 (2,6)]-decanyloxyethyl Aliphatic monomers such as (meth) acrylates;
Aromatic monomers such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, rosin acrylate;
(Meth) acrylic acid 2- (1,3-dioxobutoxy) ethyl, (meth) acrylic acid 2- (1,3-dioxobutoxy) propyl, (meth) acrylic acid 3- (1,3-dioxo Butoxy) propyl, (meth) acrylic acid 2- (1,3-dioxobutoxy) butyl, (meth) acrylic acid 3- (1,3-dioxobutoxy) butyl, (meth) acrylic acid 4- (1, Monomers containing an active methylene group such as 3-dioxobutoxy) butyl;
Oxetane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, 1,4-dioxaspiro [4,5] deca 2-yl) methyl (meth) acrylate, 2-methacryloyloxy-γ-butyrolactone, 3-methacryloyloxy-γ-butyrolactone, 5-methacryloyloxy-2,6-norbornanecarbolactone, β-methacryloyloxy-β-methyl Includes heterocyclic rings such as -δ-valerolactone, β-methacryloyloxy-β-methyl-γ-butyrolactone, 2- (1-methacryloyloxy) ethyl-4-butanolide, N- (meth) acryloyloxyethyl hexahydrophthalimide Monomer;
Polyalkylene glycols such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, and ethoxypolypropylene glycol (meth) acrylate A monomer comprising:
(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, isobutyl (meth) acrylamide, t-butyl Unsubstituted or N-substituted (meth) acrylamides such as (meth) acrylamide, t-octyl (meth) acrylamide, 2-hydroxyethyl acrylamide, diacetone (meth) acrylamide, acryloylmorpholine;
Nitriles such as (meth) acrylonitrile;
Polymerizable oligomers such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, and one-end methacryloylated polyethylene glycol;
Styrenes such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, vinyltoluene, indene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate and vinyl propionate;
N-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide;
2-phosphonooxyethyl (meth) acrylate, 2-phosphonooxypropyl (meth) acrylate, 3-phosphonooxypropyl (meth) acrylate, 4-phosphonooxybutyl (meth) acrylate, 5-phosphonooxypentyl (Meth) acrylate, 6-phosphonooxyhexyl (meth) acrylate, 8-phosphonooxyoctyl (meth) acrylate, 10-phosphonooxydecyl (meth) acrylate, 12-phosphonooxide decyl (meth) acrylate, phospho Nooxypolyethylene glycol mono (meth) acrylate, phosphonooxypolypropylene glycol mono (meth) acrylate, 3-chloro-2-phosphonooxypropyl (meth) acrylate, 2- (meth) acryloyloxyethylphenyl acid Monomer containing Sufeto, 2- (meth) acryloyloxyethyl -p- methoxyphenyl acid phosphate phosphonooxy group and the like;
Monomers containing phosphono groups such as 2-phosphonoethyl (meth) acrylate and 5-phosphonopentyl (meth) acrylate;
Vinyl sulfonic acid, 2-sulfoethyl (meth) acrylate, 2-sulfo-1-propyl (meth) acrylate, 1-sulfo-2-propyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, 1-sulfo-2 -Butyl (meth) acrylate, 3-sulfo-2-butyl (meth) acrylate, 3-bromo-2-sulfo-2-propyl (meth) acrylate, 3-methoxy-1-sulfo-2-propyl (meth) acrylate , 4-((meth) acryloylamino) benzenesulfonic acid, N- (1,1-dimethyl-2-sulfoethyl) (meth) acrylamide, ((meth) acrylamide) methanesulfonic acid, 2-((meth) acrylic Amide) ethanesulfonic acid, 3-((meth) acrylamido) propane-1-sulfonic acid Monomers comprising 2- (meth) acrylamide-2-methylpropane sulfonic acid, 4-styrenesulfonic acid, 4- (prop-1-en-2-yl) sulfonic acid group, such as benzenesulfonic acid;
N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 1- (t-butylamino) ethyl (meth) acrylate, 2- (t-butylamino) ethyl (meth) acrylate , 1,2,6,6-tetramethylpiperidin-4-yl (meth) acrylate, N- (2,2,6,6-tetramethylpiperidinyl) (meth) acrylamide-containing single monomer body;
Examples thereof include a monomer containing a carboxyl group, a monomer containing an epoxy group, a monomer containing an isocyanate group, a monomer containing a carboxylic anhydride group, and a monomer containing a hydroxyl group.

The mass average molecular weight (Mw) of the polymer (A-1) is preferably 2000 to 70000, and more preferably 4000 to 50000. This is because when the weight average molecular weight is 2000 or more, the chemical resistance of the ink composition is excellent, and when the weight average molecular weight is 70000 or less, the ink composition tends to have a low viscosity and printing is easy.
In addition, the weight average molecular weight in this embodiment is a value obtained by gel permeation chromatography (GPC) and converted to polystyrene. More specifically, the values obtained by the measurement methods described in Examples described later are shown.

[Reaction process when producing polymer (A-1) containing furyl group]
The polymer (A-1) containing a furyl group can be produced by the methods [1-1] to [1-2] described above. Polymerization process as a process common to these methods Process modification of polymerizing monomer (a-1) containing monomer (a-1) containing a furyl group or monomer (a-3) containing a reactive functional group Process Reactive compound (a-4) or carboxylic acid anhydride containing a furyl group to the reactive functional group introduced into the prepolymer by copolymerizing the monomer (a-3) containing a reactive functional group Since there are steps for reacting the products, each step will be described.

(Polymerization process)
Polymerization of the monomer (a) containing the furyl group-containing monomer (a-1) or the reactive functional group-containing monomer (a-3) can be carried out by a known method. That is, it can be carried out by optionally mixing the monomer (a) with a polymerization initiator and heating. The polymerization temperature is 40 to 150 ° C, preferably 50 to 120 ° C.

In the polymerization, 0.001 to 15 parts by mass of a polymerization initiator can be arbitrarily used with respect to 100 parts by mass of the monomer (a).
As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Dicarbonate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide And diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

During the polymerization, a chain transfer agent may be used for the purpose of adjusting the molecular weight. 0.001-15 mass parts chain transfer agent can be arbitrarily used with respect to 100 mass parts of monomers (a).
The chain transfer agent is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and a known chain transfer agent can be used. For example, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid , Thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, butylthioglycolate, etc .; dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, tetramethylthiuram disulfide, tetraethylthiuram Disulfides such as disulfide and tetrabutylthiuram disulfide; carbon tetrachloride, methylene chloride, Halogenated hydrocarbons such as Moform, bromotrichloroethane, carbon tetrabromide, ethylene bromide; secondary alcohols such as isopropanol, glycerin; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, Potassium hypophosphite), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, and salts thereof (sodium hydrogensulfite, potassium hydrogensulfite, sodium dithionite, potassium dithionite, metabisulfite) Lower oxides such as sodium sulfite and potassium metabisulfite) and salts thereof; and allyl alcohol, 2-ethylhexyl thioglycolate, α-methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, anisole, etc. Can be mentioned. These may be used alone or in combination of two or more.

In the polymerization, an organic solvent can be used as a polymerization solvent.
As an organic solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethoxydiethylene glycol, 3-methoxy-1-butanol and the like are used. However, it is not limited to these. These polymerization solvents may be used as a mixture of two or more kinds, but are preferably used for final use.

(Modification process)
A reactive compound (a-4) or a carboxylic acid anhydride containing a furyl group in the reactive functional group introduced into the prepolymer by copolymerizing the monomer (a-3) containing a reactive functional group In the step of reacting, it is preferable to select appropriate reaction conditions depending on the combination of the reactive functional group introduced into the prepolymer and the reactive functional group in the compound used for modification, and each example will be described. .

  In the case of a combination of a hydroxyl group or amino group and an isocyanate group, the reaction proceeds by adding no catalyst or an appropriate catalyst and heating. Suitable catalysts include, for example, amines such as triethylamine, tributylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, and salts thereof, tetrabutyl titanate, dibutyltin dilaurate, tin octylate. And metal salts and complexes.

  In the case of a combination of a hydroxyl group or amino group and an acid anhydride group, it is preferable to add a base catalyst or an amine catalyst and react at 0 to 100 ° C.

  In the case of a combination of a mercapto group or amino group and an epoxy group, it is preferable to react at 0 to 100 ° C. with no catalyst or a base catalyst added.

  In the case of a combination of a carboxyl group and an epoxy group, a base catalyst or a quaternary ammonium catalyst is preferably added and reacted at 60 to 110 ° C.

<< Compound containing polymerizable functional group (B) >>
The compound (B) containing a polymerizable functional group of this embodiment is a compound containing no furyl group and containing an acryloyl group, a compound containing a (meth) acrylamide group, a compound containing an N-vinylamide group, and acrylonitrile. If any one of them is included, the structure is not particularly limited, and they can be used alone or in combination of two or more. It can be low or high molecular, and it can be used separately or in combination according to the viscosity, printability, print hardness, adhesion, and resolution required for the ink composition. The ratio can be adjusted.
From the viewpoint of chemical resistance of the printed material, a compound or acrylonitrile containing an acryloyl group, (meth) acrylamide group or N-vinylamide group having good reactivity with the compound (A) is used. Different functional groups as the polymerizable functional group, for example, an acryloyl group and an acrylamide group may be contained in one compound, or a compound having one kind of functional group may be mixed and used.

  The ratio of the compound (A) containing a furyl group and the compound (B) containing a polymerizable functional group is effective for both photocuring and thermosetting to improve the chemical resistance of the photosensitive composition. The number of moles of furyl group is preferably 0.01 to 2 with respect to the number of moles 1 of the functional group. Use of 0.01 or more tends to cause thermal curing due to a furyl group and tends to improve chemical resistance. Use of 2 or less facilitates radical polymerization of a photopolymerizable functional group at the stage of photocuring. There is a tendency to improve chemical resistance.

<Low molecular weight compound (B) containing a polymerizable functional group>
Among the compounds (B) containing a polymerizable functional group, examples of the low molecular weight include monofunctional or polyfunctional monomers or oligomers. The molecular weight is preferably less than 2000.

Examples of the compound containing an acryloyl group represented by the formula [1] include a furyl group among those exemplified as the monomer (a) used in synthesizing the radical polymer (A-1) containing the furyl group. An acryloyl monomer excluding the monomer (a-1) containing
ω-carboxy-polycaprolactone monoacrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxypropyl succinic acid, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol acrylate Monofunctional acrylates such as 2-hydroxy-3-phenoxypropyl acrylate;
Bifunctional acrylates such as ethylene glycol diacrylate, EO-modified bisphenol A diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane diacrylate Kind;
Trifunctional acrylates such as trimethylolpropane triacrylate, pentaerythritol triacrylate;
Examples thereof include tetra- or higher functional acrylates such as pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol decaacrylate, and pentapentaerythritol dodecaacrylate.
Moreover, the polyfunctional acrylate obtained by making polyfunctional isocyanate and the acrylate monomer containing a hydroxyl group react can be mentioned as a low molecular weight thing among the compounds (B) containing a photopolymerizable functional group.
As polyfunctional isocyanate,
Tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, tolidine isocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, isopropylidenebis Bifunctional isocyanates such as (cyclohexyl isocyanate), 3- (2′-isocyanatocyclohexyl) propyl isocyanate, dianisidine isocyanate, diphenyl ether diisocyanate, dimer isocyanate, and tetramethylxylylene diisocyanate;
Trifunctional isocyanates such as lysine triisocyanate, tris (isocyanatophenyl) methane, tris (isocyanatophenyl) thiophosphate;
Biuret, uretdione, isocyanurate, adduct body, etc. of the above isocyanates are exemplified.
When reacting a polyfunctional isocyanate with an acrylate monomer containing a hydroxyl group, other polyols such as low molecular weight polyfunctional alcohols and polyesters, polyethers, polycarbonates, polyacryls, polyolefins, etc. May be used in combination.
Furthermore, epoxy acrylates obtained by reacting an epoxy resin with an acrylate monomer containing a carboxyl group or reacting a phenol resin with an acrylate monomer containing an epoxy group can be mentioned.

  As the compound containing a (meth) acrylamide group represented by the formulas [2] to [5], for example, as the monomer (a) used when synthesizing the radical polymer (A-1) containing the furyl group. Among those exemplified, (meth) acrylamides having a hydroxyl group, unsubstituted or N-substituted (meth) acrylamides, N- [3- (dimethylamino) propyl] (meth) acrylamide, N, N′-methylenebis (meta) ) Acrylamide, N, N′-hexamethylenebis (meth) acrylamide, N, N ′-{[(2- (meth) acrylamide-2-[(3- (meth) acrylamidepropoxy) methyl] propane-1,3 -Diyl) bis (oxy)] bis (propane-1,3-diyl)} di (meth) acrylamide, N, N ', N "-tri (meth) acryl Ilediethylenetriamide, N, N′-di (meth) acryloyl-4,7,10-trioxa-1,13-tridecanediamine, N, N ′, N ″, N ′ ″-tetra (meth) acryloyl Examples include triethylenetetraamine.

  Examples of the compound containing an N-vinylamide group represented by the formula [6] or [7] include N-vinyl-2-pyrrolidone, N-vinylcaprolactam, N-vinylacetamide, N-vinylformamide, N-vinyl lactamide, N -Vinyltetrahydrophthalamide, N-methyl-N-vinylacetamide, 2-acetamidoacrylic acid and the like.

<High molecular weight compound (B) containing a polymerizable functional group>
A polymer may be used for the compound (B) containing a polymerizable functional group. For example, poly (meth) acrylates, polyurethanes, polyesters, polyamides, polyimides, polycarbonates, polyolefins, polystyrenes, polysiloxanes, polyethers, copolymers containing maleic anhydride, those in which polymerizable functional groups are introduced into epoxy resins, etc. These can be used alone or in admixture. The polymer may be any of linear, branched, star-shaped, etc., and may be thermoplastic or thermosetting.

  When the compound (B) containing a polymerizable functional group has a high molecular weight, the weight average molecular weight (Mw) is preferably 2000 to 50000, more preferably 4000 to 30000. This is because when the Mw is 2000 or more, the chemical resistance of the ink composition tends to be good, and when it is 50000 or less, the viscosity becomes low and printing becomes easy.

  Poly (meth) acrylates are preferred because the printability of the ink composition can be easily controlled by controlling the molecular weight and copolymer composition, and the color gamut of the printed matter of the ink composition is excellent. The poly (meth) acrylate may contain a structure derived from a comonomer other than (meth) acrylate. Further, the polymerizable functional group is preferably a group represented by any one of the above formulas [1] to [7] from the viewpoint of chemical resistance.

  The method for introducing the polymerizable functional group into the compound (B) is not particularly limited. For example, the carboxyl group, the hydroxyl group, the mercapto group, the amino group, and the active methylene group in the prepolymer, the epoxy group, the isocyanate group, and the aldehyde group. A method of reacting a monomer containing, and a method of utilizing the reverse combination. There are no particular restrictions on the prepolymer, and acrylic, urethane, polyester, polyolefin, polyether, natural rubber, block copolymer rubber, silicone, and other polymers can be used.

When an acrylic type is used as the prepolymer, the following methods [B-1] to [B-3] are preferable as the method for introducing the polymerizable functional group.
Method [B-1] Method of reacting a part or all of the carboxyl groups in the (meth) acrylic copolymer containing a carboxyl group with an epoxy group in a monomer containing an epoxy group [B-2 Method for reacting an epoxy group in a (meth) acrylic copolymer containing an epoxy group with a carboxyl group in a monomer containing a carboxyl group [B-3] (meth) acrylic containing a hydroxyl group Method for reacting hydroxyl group in copolymer with isocyanate group or acid anhydride group in monomer containing isocyanate group or carboxylic acid anhydride group

  The steps common to the above methods include a polymerization step for obtaining a prepolymer and a modification step for introducing a polymerizable functional group, both of which are radical polymers (A-1) containing a furyl group. It can be manufactured in the same process as that for manufacturing.

A monomer containing a carboxyl group, an epoxy group or a hydroxyl group used for polymerization of a prepolymer and a monomer containing an epoxy group, a carboxyl group, an isocyanate group or a carboxylic acid anhydride group used for modification are a furyl group. Among those mentioned for the radical polymer (A-1) containing, a furyl group can be used.

  In the modification step of introducing a polymerizable functional group into the prepolymer, a gas having a polymerization inhibiting effect may be introduced into the reaction system during the reaction, or a polymerization inhibitor may be added. By introducing a gas having a polymerization inhibition effect into the reaction system or adding a polymerization inhibitor, gelation during the addition reaction can be prevented.

  Examples of the gas having an effect of inhibiting radical polymerization include a gas containing oxygen that does not enter the explosion range of the substance in the system, for example, air, a mixed gas of air and nitrogen, and the like.

  As the radical polymerization inhibitor, known ones can be used, and are not particularly limited. For example, hydroquinone, methoquinone, 2,6-di-t-butylphenol, 2,2′-methylenebis (4-methyl- 6-t-butylphenol), phenothiazine and the like. These polymerization inhibitors may be used alone or in combination of two or more. As an amount of the polymerization inhibitor to be used, 0.005 to 5 parts by mass is preferable, 0.03 to 3 parts by mass is more preferable, and 0.05 to 3 parts by mass with respect to a total of 100 parts by mass of the solid content in the reaction system. Most preferred is 1.5 parts by weight. This is because if the polymerization inhibitor is 0.005 parts by mass or more, a polymerization inhibition effect is easily obtained, while if it is 5 parts by mass or less, the photocuring property and thermosetting property of the ink composition are difficult to decrease. Moreover, it is more preferable to use a gas having a polymerization inhibiting effect in combination with the polymerization inhibitor because the amount of the polymerization inhibitor to be used can be reduced or the polymerization inhibiting effect can be enhanced.

<< Polymerization initiator (C) >>
As a polymerization initiator (C) of this embodiment, a photoinitiator (C1) and a thermal polymerization initiator (C2) are mentioned.
<Photopolymerization initiator (C1)>
The structure of the photopolymerization initiator (C1) of the present embodiment is particularly limited as long as radicals are generated by ultraviolet irradiation and are used for initiating polymerization of polymerizable functional groups in the ink composition. It is not a thing. When photocuring is performed during printing, a photopolymerizable initiator (C1) is used to start curing. On the other hand, even in the case of an ink composition that does not undergo photocuring during printing, a compound that is generally known as a photopolymerization initiator can also have a function as a thermal polymerization initiator during heat curing. In both the printing method to be performed and the printing method in which photocuring is not performed, chemical resistance can be imparted by adding the photopolymerization initiator (C1) when the printed matter is thermally cured.

As the photopolymerization initiator (C1), an initiator having light absorption with a wavelength of 380 nm to 410 nm is preferably used. For example, acylphosphine oxide, α-aminoacetophenone, benzophenone, and thioxanthone initiators are used. Is mentioned. By using these initiators, the curing proceeds efficiently to the deep part of the ink coating, and even when two or more colors are printed in layers, it is sufficiently cured, without wrinkles and tack, and after curing. The amount of residual components such as initiators and monomers in the printed material is reduced.
Examples of initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, oligo (2-Hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethyl Amino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2- [4- (methylthiobenzoyl)]-2- (4-morpholinyl) Propane, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl Phenyl} -2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, [4- [4-methylphenyl] thio] phenyl] phenylmethanone, 4- (dimethylamino) ethyl benzoate, 1- [ 4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 4,4′-bis- (dimethylamino) benzophenone, 4,4′-diethylaminobenzophenone, 1- [4- (4-Benzoylphenylsulfanyl) phenyl] -2-methyl-2-[(4-methylphenyl) sulfonyl] propan-1-one, (methylimino) diethane-2,1-diyl (4-dimethylamibenzoate) ) And the like.
Further, in order to improve the curability when photocuring, a sensitizer may be used in combination.

<Thermal polymerization initiator (C2)>
The structure of the thermal polymerization initiator (C2) of the present embodiment is particularly limited as long as radicals are generated by heat and used for initiating polymerization of polymerizable functional groups in the ink composition. is not. By adding the thermal polymerization initiator (C2), chemical resistance can be imparted when the printed matter is thermally cured.
As the thermal polymerization initiator (C2), polymerization initiators such as azo compounds and organic peroxides mentioned in the polymerization step of the compound (A) can be used as long as the temporal stability of the ink composition is not impaired. .

<< Colorant (F) >>
The colorant (F) of this embodiment is not particularly limited, and organic or inorganic pigments and dyes can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance are preferable, and organic pigments are usually used, but are not limited thereto.

<Pigment>
The pigment that can be used in the present invention is not particularly limited, and examples thereof include a soluble azo pigment, an insoluble azo pigment, a phthalocyanine pigment, a halogenated phthalocyanine pigment, a quinacridone pigment, an isoindolinone pigment, an isoindoline pigment, a perylene pigment, and a perinone. Pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, etc.
A more specific example is indicated by the generic name of the color index.
Blue pigments such as Pigment Black 7, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 22, Pigment Blue 60, or Pigment Blue 64;
Green pigments such as CI Pigment Green 7, Pigment Green 36, or Pigment Green 58;
Pigment Red 9, Pigment Red 48, Pigment Red 49, Pigment Red 52, Pigment Red 53, Pigment Red 57, Pigment Red 97, Pigment Red 122, Pigment Red 123, Pigment Red 144, Pigment Red 146, Pigment Red 149, Pigment Red 166, Pigment Red 168, Pigment Red 177, Pigment Red 178, Pigment Red 179, Pigment Red 180, Pigment Red 185, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Red 215, Pigment Red 216, Pigment Red 217, Pigment Red 220, Pigment Head 221, Pigment Red 223, Pigment Red 224, Pigment Red 226, Pigment Red 227, Pigment Red 228, Pigment Red 238, Pigment Red 240, Pigment Red 242, a red pigment such as Pigment Red 254 or Pigment Red 255;
A purple pigment such as Pigment Violet 19, Pigment Violet 23, Pigment Violet 29, Pigment Violet 30, Pigment Violet 37, Pigment Violet 40, or Pigment Violet 50;
Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 20, Pigment Yellow 24, Pigment Yellow 74, Pigment Yellow 83, Pigment Yellow 86, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 109, Pigment Yellow 110, Pigment Yellow 117, Pigment Yellow 120, Pigment Yellow 125, Pigment Yellow 128, Pigment Yellow 137, Pigment, Yellow 138, Pigment Yellow 139, Pigment Yellow 147, Pigment Yellow 148, Pigment Yellow 150, Pigment Yellow 151 , Pigment Yellow 153, Pigment I Low 154, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 168, Pigment Yellow 180, Pigment Yellow 185, or yellow pigments such as CI Pigment Yellow 213;
Pigment Orange 13, Pigment Orange 36, Pigment Orange 37, Pigment Orange 38, Pigment Orange 43, Pigment Orange 51, Pigment Orange 55, Pigment Orange 59, Pigment Orange 61, Pigment Orange 64, Pigment Orange 71, or Pigment Orange 74, etc. Orange pigment; or
Examples thereof include brown pigments such as Pigment Brown 23, Pigment Brown 25, and Pigment Brown 26.

As for carbon black, any carbon black such as neutral, acidic, or basic can be used.

<Dye>
As the colorant used in the ink, a dye may be used in addition to the pigment, and in particular, Food Red 3, 3: 1, 7, 9, 17, 17: 1, Food Blue 2, 2: 1, Food Yellow. 3, Food Black 1, 2, Food Brown 3, etc. are preferable from the viewpoint of safety.

In order to ensure a sufficient color gamut of the printed material, the amount of the colorant added is preferably 10 to 55% by weight in the solid content of the ink composition.

<< Other materials >>
The ink composition of the present embodiment can further contain the following materials as long as the object of the invention is not impaired.

<Liquid medium>
In order to improve handling when printing the ink composition, a liquid medium such as an organic solvent may be used. For example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, benzene, toluene, ethylbenzene , Xylene, cyclohexane, hexane, octane, dichloromethane, chloroform, dimethylformamide, dimethylacetamide, acetonitrile, dimethylsulfoxide and the like.
These organic solvents can be used alone or in combination of two or more, but are preferably used for final use.
As the liquid medium, water can be used for water-based inks, and active energy ray-curable monomers can be used for active energy ray-curable inks.

<Dispersing aid>
When the pigment is dispersed in a dye carrier such as a resin and / or a solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, an ink composition in which the pigment is dispersed in a resin and / or solvent using the dispersion aid is used. If it is, a printed matter excellent in gloss and hue can be obtained.
The dispersion aid is preferably used in an amount of 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the pigment.

The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and acts to stabilize the dispersion of the pigment on the dye carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based, JP 2009-255063 dispersing agent and the like are used according, it may be used alone or in admixture of two or more thereof.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate;
Cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts;
Examples include alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline, and these can be used alone or in admixture of two or more.

The pigment derivative is a compound in which a substituent is introduced into an organic pigment, and this organic pigment also includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called pigments. Examples of the pigment derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

<Other resins>
The photosensitive composition of this embodiment may contain the other resin which does not contain any of a furyl group and a polymeric functional group as needed. For example, a thermoplastic resin and a thermosetting resin are mentioned.
Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like.
Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, a phenol resin, and β-hydroxyalkylamide described in JP2012-198527. Etc.

<Other materials>
If necessary, a polyfunctional thiol or amine compound for promoting photocuring, a curing agent for promoting thermosetting, an ultraviolet absorber for stabilizing the ink composition, a polymerization inhibitor, Storage stabilizers, light stabilizers, antioxidants, etc., surface tension modifiers for improving printability, surfactants, etc., inorganic fillers for improving the adhesion and friction resistance of printed matter, and adhesion imparting You may add additives, such as an agent. These additives can be added in any amount as long as the purpose of the ink composition is not impaired.

<< Method for Producing Ink Composition >>
The ink composition of the present embodiment includes a compound (A) containing a furyl group, a compound (B) containing a polymerizable functional group, a polymerization initiator (C), a colorant (F), and as necessary. It can be prepared by mixing and stirring with other components.
A pigment dispersion is obtained by finely dispersing a colorant such as a pigment or a dye in a pigment carrier such as a resin and / or a solvent using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. The compound (A) containing a furyl group in the pigment dispersion, the compound (B) containing a polymerizable functional group, and a polymerization initiator (C)
If necessary, it can be produced by mixing and stirring an organic solvent and other components. In addition, the ink composition containing two or more pigments may be a mixture of each pigment dispersion separately dispersed in a dye carrier and / or a solvent, or may be mixed with each pigment and dyed simultaneously. You may disperse | distribute finely in a support | carrier and / or a solvent.
The compound (A) containing a furyl group and the compound (B) containing a polymerizable functional group may be used as a dye carrier when producing a pigment dispersion.

<< Use of ink composition >>
The ink composition of the present embodiment can be used for various ink-jet inks such as organic solvent-based, water-based, and active energy ray-curable inks, and various inks used for gravure printing, offset printing, flexographic printing, screen printing, and the like. it can.
The ink composition of the present embodiment has a good balance between the stability of the ink composition and the curability, so that the inkjet discharge stability and the on-machine stability at the time of printing are high, and the printed matter has excellent chemical resistance and friction resistance. Can be obtained.

  There are no particular limitations on the printing substrate, but plastic substrates such as soft vinyl chloride, hard vinyl chloride, polystyrene, polystyrene foam, polymethyl methacrylate (PMMA), polypropylene, polyethylene, polyethylene terephthalate (PET), polycarbonate, and mixtures thereof Or, modified products, paper substrates such as fine paper, art paper, coated paper and cast coated paper, and metal substrates such as glass and stainless steel can be used.

The embodiments of the present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by mass”, and “%” represents “% by mass”.
Further, in the following examples, the molecular weight of the resin is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography), and GPC-8020 manufactured by Tosoh Corporation uses tetrahydrofuran as the eluent. Used three TSKgelSuperHM-M (manufactured by Tosoh Corporation), and measured at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C.
IR measurement was performed using SpectrumOne manufactured by PerkinElmer.
In the present specification, the nonvolatile content means a value calculated from the sample mass after heating / the sample mass before heating when 1 g of the sample is heated at 200 ° C. for 10 minutes. However, in the case of a commercial product, a value calculated based on a method specified by the manufacturer may be adopted. In this specification, solid content and non-volatile content are synonymous.

<< Production Example >>
<Production of Compound (A) Containing Furyl Group>
[Production Example 1]
Put 90.0 parts of ethylene glycol monobutyl ether acetate into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, and heat to 60 ° C. while injecting nitrogen gas into the vessel. And a mixture of 50.0 parts of furfuryl methacrylate, 50.0 parts of methyl methacrylate and 2.5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 2 hours to carry out the polymerization reaction. . After completion of the dropwise addition, the mixture was further reacted at 60 ° C. for 1 hour, and then 0.5 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 10.0 parts of ethylene glycol monobutyl ether acetate. After that, stirring was continued at the same temperature for 3 hours, and then cooled to room temperature. A compound solution A1 containing a furyl group having a nonvolatile content of 50% was obtained. The weight average molecular weight was 50000.

[Production Example 2]
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube, 69.3 parts of ethylene glycol monobutyl ether acetate and Desmodur Z4470BA (IPDI isocyanurate, 70% non-volatile content of butyl acetate solution manufactured by Sumika Bayer) NCO group content 11.9%) 102.3 parts, furfuryl alcohol 28.4 parts, dibutyltin dilaurate 0.20 parts, and heated to 80 ° C. while injecting nitrogen gas into the container, Stirring was continued for a period of time, and IR measurement was performed to confirm that the target product was produced, and then the mixture was cooled to room temperature. A compound solution A2 containing a furyl group having a nonvolatile content of 50% was obtained.

[Production Example 3]
The compound was synthesized in the same manner as in Production Example 1 except that the solvent was changed from ethylene glycol monobutyl ether acetate to n-propyl acetate to obtain a compound solution A3 having a furyl group.

[Production Example 4]
A reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube was charged with 160.2 parts of xylene, and the temperature was raised until the internal temperature reached 125 to 130 ° C. Next, a liquid mixture comprising 40.2 parts of furfuryl methacrylate, 11.5 parts of styrene, 34.2 parts of methacrylic acid, 14.1 parts of α-methylstyrene and 6.3 parts of di-tert-butyl peroxide was added from a dropping funnel. After dropping over 4 hours, the polymerization reaction was completed by keeping at the same temperature for 3 hours. The temperature was further raised to 180 ° C., and xylene was completely removed under reduced pressure to obtain a copolymer having a weight average molecular weight of 13,000. Ammonia water and deionized water were added to the obtained copolymer to obtain a compound solution A4 containing a furyl group having a pH of 8.3 and a nonvolatile content of 30%.

[Comparative Production Example 1]
Resin 1 was obtained by synthesizing in the same manner as in Production Example 1 except that furfuryl methacrylate was changed to tetrahydrofurfuryl methacrylate. This compound does not contain a furyl group.

<Production of Compound (B) Containing Polymerizable Functional Group>
[Production Example 5]
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube, 70.8 parts of ethylene glycol monobutyl ether acetate and Desmodur Z4470BA (IPDI isocyanurate, 70% non-volatile butyl acetate solution manufactured by Sumika Bayer) NCO group content 11.9%) 97.2 parts, 2-hydroxyethyl acrylate 32.0 parts, dibutyltin dilaurate 0.20 part, methoquinone 0.01 part, and nitrogen gas and dry air in the container The mixture was heated to 80 ° C. while injecting the mixed gas, stirred for 8 hours, and IR measurement was performed to confirm that the target product was produced, and then the mixture was cooled to room temperature. A compound solution B1 containing an acryloyl group as a polymerizable functional group having a nonvolatile content of 50% was obtained.

[Production Examples 6 and 7]
A compound solution B2 containing an acrylamide group and a compound solution B3 containing a methacrylamide group were obtained in the same manner as in Production Example 3 except that the types and amounts of the raw materials were changed as shown in Table 1.

[Comparative Production Example 2]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, 67.4 parts of 2,3-dimethylmaleic anhydride, 0.01 part of methoquinone, and 50.0 parts of ethanol were added. While blowing a mixed gas of nitrogen gas and dry air, a mixed solution of 32.6 parts of 2-amino-1-ethanol and 50.0 parts of ethanol was dropped from a dropping device over 2 hours at room temperature. After completion of the dropwise addition, the reaction was carried out by heating at 85 ° C. for 4 hours, followed by cooling to room temperature. The precipitated solid was collected by filtration and dried under reduced pressure to obtain a precursor.
In a reaction vessel equipped with a stirrer, thermometer, dripping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 50 parts of precursor, 0.01 part of methoquinone, 1000.0 parts of toluene are placed, and nitrogen gas and dry air are added. The reaction vessel was refluxed at 110 ° C. for 5 hours while blowing the mixed gas, and water produced was removed. After cooling at 0 ° C. for 2 hours, the precipitated solid was collected by filtration, washed with hexane, and dried under reduced pressure to obtain N- (2-hydroxyethyl) -2,3-dimethylmaleimide: HEMI.
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas introduction tube, 74.6 parts of ethylene glycol monobutyl ether acetate and Desmodur Z4470BA (IPDI isocyanurate, 70% non-volatile content butyl acetate solution manufactured by Sumika Bayer) NCO group content 11.9%) 84.8 parts, 40.6 parts HEMI, 0.20 parts dibutyltin dilaurate, 0.01 parts methoquinone, and inject a mixed gas of nitrogen gas and dry air into the container. Then, the mixture was heated to 80 ° C., stirred for 8 hours, and IR measurement was performed to confirm that the target product was produced, followed by cooling to room temperature. A compound solution B4 containing a maleimide group having a substituent with a nonvolatile content of 50% was obtained.

Abbreviations in Table 1 are shown below.
FMA: furfuryl methacrylate MMA: methyl methacrylate THFMA: tetrahydrofurfuryl methacrylate St: styrene MAA: methacrylic acid αMS: α-methylstyrene Z4470BA: Desmodur Z4470BA (IPDI isocyanurate, butyl acetate having a nonvolatile content of 70%) Solution, NCO group content 11.9%)
FA: furfuryl alcohol HEA: 2-hydroxyethyl acrylate HEAAm: N- (2-hydroxyethyl) acrylamide HEMAm: N- (2-hydroxyethyl) methacrylamide HEMI: N- (2-hydroxyethyl) -2,3- Dimethylmaleimide V65: 2,2′-azobis (2,4-dimethylvaleronitrile)
Perbutyl D: Di-tert-butyl peroxide DBTDL: Dibutyltin dilaurate MQ: Metoquinone BGAc: Tylene glycol monobutyl ether acetate AcOPr: n-propyl acetate

<< Inkjet ink >>
<Manufacture of pigment dispersion>
[Production Example 8]
Dispersant PB821 (Ajinomoto Fine Techno Co., Ltd., a basic dispersant of a condensate of a polyallylamine and a polyester having a free carboxylic acid, 14 parts by weight of ethylene glycol monobutyl ether acetate with 46 parts of ethylene glycol monobutyl ether acetate. Dissolve and add 40 parts of colorant carbon black (Raven 1060UP manufactured by Columbian), stir and mix for about 30 minutes with a high speed mixer until uniform, and then 1 hour per 1 kg of mill base in a 0.6 L horizontal sand mill. Dispersion was performed to obtain Pigment Dispersion 1.

[Production Examples 9 to 14]
Pigment dispersions 2 to 7 were obtained in the same manner as in Production Example 8, except that the colorant was changed as shown in Table 2.

Abbreviations in Table 2 are shown below.
CB: Carbon black PY150: Pigment yellow 150
PY154: Pigment Yellow 154
PY83: Pigment Yellow 83
PV19: Pigment Violet 19
PR122: Pigment Red 122
PR146: Pigment Red 146
PB821: manufactured by Ajinomoto Fine Techno Co., Ltd. Basic dispersant of a condensate of polyallylamine and polyester having a free carboxylic acid Weight average molecular weight 45000 Acid value 18 Amine value 8
BGAc: Ethylene glycol monobutyl ether acetate

<Manufacture of inkjet ink>
[Example 1]
10.0 parts of pigment dispersion 1, 7.6 parts of compound solution A1, 2.0 parts of trimethylolpropane triacrylate, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -0.2 parts of ON and 80.2 parts of ethylene glycol monobutyl ether acetate were uniformly stirred and mixed, and then filtered through a 1 µm filter to obtain an inkjet ink.

[Examples 2 to 15, Comparative Examples 1 to 4]
The pigment dispersion, the compound (A) containing a furyl group, the compound (B) containing a polymerizable functional group, a photopolymerization initiator (C1), a thermal polymerization initiator (C2), and other materials are changed as shown in Table 3. Except having carried out, it carried out similarly to Example 1, and obtained the inkjet ink of Examples 2-15 and Comparative Examples 1-4.

Abbreviations in Table 3 are shown below.
TMPTA: trimethylolpropane triacrylate ACMO: acryloylmorpholine NVP: N-vinylpyrrolidone AN: acrylonitrile TMPTMA: trimethylolpropane trimethacrylate BMI-5100: 3,3′-dimethyl-5,5′-diethyl-4,4′- Diphenylmethane bismaleimide Irg907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one AIBN: 2,2′-azobisisobutyronitrile: V-60 (manufactured by Wako Pure Chemical Industries, Ltd.) )
BGAc: Ethylene glycol monobutyl ether acetate

<Evaluation of inkjet ink>
Using the obtained ink, the alcohol resistance and stability were evaluated by the following methods. The results are shown in Table 3.

[Stability]
Immediately after ink preparation, the ink was adjusted to 25 ° C., and the initial viscosity was measured with a TVE25L viscosity system manufactured by Toki Sangyo Co., Ltd. 20 mL of the ink was placed in a screw tube bottle (capacity: about 20 mL), sealed, and allowed to stand in a 70 ° C. environment for 1 week, and then the viscosity was measured in the same manner to evaluate the temporal stability. The evaluation criteria at this time are as follows.
○: Increase in viscosity after aging test is less than 10% compared to initial viscosity △: Increase in viscosity after aging test is 10% or more and less than 15% compared to initial viscosity ×: Increase in viscosity after aging test More than 15% compared to the initial viscosity

[Alcohol resistance]
The ink was printed on a non-treated polyvinyl chloride resin sheet (Metamark MD5) with a large-format inkjet printer Color Painter 64S (manufactured by Seikoai Infotech) at a printing rate of 100%. (Tester Sangyo Model AB301) was evaluated. As evaluation conditions, one drop of a solution diluted with ethanol / water = 70/30 was dropped on a test piece (gold width 3), and 50 reciprocations were performed at a load of 200 g. The evaluation criteria at this time are as follows.
○: The ink was not peeled off at all. Δ: The printing surface was discolored or part of the ink was peeled off. X: The ink was peeled off and the substrate was seen more than half.

As shown in Table 3, in Examples 1 to 15, both stability and alcohol resistance were good.
Examples 1 to 15 including any one of a compound containing an acryloyl group, a compound containing an acrylamide group, a compound containing a methacrylamide group, a compound containing an N-vinylamide group, and acrylonitrile as the compound (B) containing a polymerizable functional group All of them had good alcohol resistance, but Comparative Example 2, which did not contain these compounds and used a compound containing a methacryloyloxy group, had insufficient alcohol resistance. Comparative Example 3 using a compound containing a maleimide group had insufficient stability. Moreover, the comparative example 4 which uses the compound containing the maleimide group which has a substituent was inadequate in alcohol resistance.
In Example 8 using A2 in which the compound (A) containing a furyl group is a low molecule, alcohol resistance is slightly inferior, but in Examples 1 to 7 and 9-15 using A1 which is a polymer, alcohol resistance is used. Was excellent. In Comparative Example 1 in which the compound (A) containing a furyl group was not used, the alcohol resistance was insufficient.
Although Example 9 using a thermal-polymerization initiator (C2) was a little inferior to Examples 1-8 and 10-15, alcohol resistance was equivalent.

<< gravure ink >>
<Manufacture of gravure ink>
Example 16
C. I. 12 parts of Pigment Yellow 14 and Ajisper PB821 (Ajinomoto Fine Techno Co., Ltd., a basic dispersant of a condensate of polyallylamine and a polyester having a free carboxylic acid, weight average molecular weight 45000, acid value 18, amine value 8) n-propyl acetate 1.8 parts of a dispersant solution diluted to 40% solids (6 parts with respect to 100 parts of pigment), 0.6 parts of the following azo acid derivative (5 parts with respect to 100 parts of pigment), n-propyl acetate / Isopropyl alcohol mixed solvent (weight ratio 72/28) 10 parts by stirring and mixing, and kneading with a sand mill, then 14 parts of a compound solution A1 containing a furyl group, 3.5 parts of trimethylolpropane triacrylate, 2-methyl- 1.1 parts of 1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 56.8 parts of the mixed solvent were mixed. As a result, yellow / raw ink (G-1) was obtained. To 100 parts of the obtained yellow / raw ink (G-1), 50 parts of a toluene / isopropyl alcohol mixed solvent (weight ratio 90/10) was added and mixed as a diluent solvent to obtain yellow / diluted ink (G-2). It was.
Azo-based acidic derivative: represented by the following general formula [11].
General formula [11]
P- (SO ₃ H)
[Wherein P is an azo pigment residue. ]

[Comparative Example 5]
A raw ink (X-1) and a diluted ink (X-2) of Comparative Example 4 were obtained in the same manner as in Example 16 except that the resin 1 was used instead of the compound solution A1 containing a furyl group.

<Evaluation of gravure ink>
Using the obtained ink, the residual amounts of raw inks G-1 and X-1 of Example 16 and Comparative Example 5 were evaluated as a measure of storage stability over time. For the gravure diluted inks G-2 and X-2, separation and precipitation, on-machine stability (plate fog), and retort suitability were evaluated as measures of storage stability with time and chemical resistance, respectively. The evaluation results are shown in Table 4.

[Amount of residue]
The gravure printing ink was stored at 40 ° C. for 2 weeks, filtered through a nylon filter cloth (350 mesh), and the amount of residue was visually evaluated. The evaluation criteria at this time are as follows.
A: Almost no residue and good.
○: There is only a small amount of residue, which is generally good.
X: The residue is very much and a large lump is formed.

[Separation]
After the gravure diluted ink was stored at 40 ° C. for 2 weeks, the density difference between the supernatant and the supernatant of the liquid was evaluated from the ink adhesion property by inserting a spatula. The evaluation criteria at that time are as follows.
A: The diluted ink adheres at a uniform concentration, and the concentration in the liquid is uniform and good.
○: Diluted ink adheres with very slight density unevenness but is generally good.
Δ: Diluted ink adheres to the spatula in a striped pattern, and the concentration in the liquid is not uniform.
X: There is a large density difference between the upper and lower sides of the diluted ink, and since the liquid surface is transparent, it hardly adheres to the spatula.

[Precipitation]
After storing the gravure diluted ink at 40 ° C. for 2 weeks, the amount of precipitate was visually evaluated from scraping the bottom with a spatula. The evaluation criteria at that time are as follows.
(Double-circle): There is no deposit and it is good.
○: There is no obvious precipitate, but the concentration at the bottom is slightly high and thick.
X: A large amount of hard precipitate is generated on the entire bottom surface.

[Stability on board (plate cover)]
An NBR (nitrile butadiene rubber) rubber hardness 80Hs impression cylinder, a blade thickness of 60 μm (base material thickness 40 μm, one side ceramic layer thickness 10 μm), a chrome hardness 1050 Hv made by Toyo Prepress Co., Ltd. An electronic engraving plate (stylus angle of 120 degrees, 250 lines / inch) and gravure diluted ink are set in a gravure printing machine (manufactured by Fuji Machine Industry Co., Ltd.), with a doctor pressure of 2 kg / cm ² and a rotation speed of 100 m / min. After the plate was idled for 60 minutes, it was printed on the corona-treated surface of a single-sided corona-treated PET film “E-5100 (manufactured by Toyobo Co., Ltd.)” at a printing speed of 100 m / min with a printing pressure of 2 kg / cm ² and hot air at 60 ° C. And dried to obtain a printed matter. During printing, a viscosity controller is used to appropriately replenish each dilution solvent to maintain a certain viscosity. The evaluation criteria at that time are as follows.
A: No ink transfer was observed in the non-image area.
○: Ink transfer was slightly observed in the non-image area.
X: Ink transfer was observed over the entire non-image area.

[Retort aptitude]
Using a dry laminating machine (Fuji Kikai Kogyo Co., Ltd.), the printed matter, aluminum foil, and CPP film “ZK-93K” (Toray Synthetic Film Co., Ltd.) prepared by the above method are used for dry laminating adhesive TM. A laminate was obtained using -250HV / CAT-RT86 (manufactured by Toyo Morton Co., Ltd.). A laminate is cut into 20 × 12 cm, and a bag is made by heat-sealing three sides (temperature: 190 ° C., pressure: 2 kgf, time: 1 second), and 1: 1: 1 soup (ketchup: vinegar: An evaluation sample was prepared by filling water = weight ratio 1: 1: 1) and heat-sealing the remainder. The sample was subjected to a retort treatment at 120 ° C./30 minutes using a retort sterilizer (Flavor Ace, manufactured by Nisaka Seisakusho). Thereafter, the presence or absence of delamination was visually evaluated, and the adhesive strength was measured and evaluated. The evaluation criteria at that time are as follows.
○: There is no delamination and the adhesive strength is generally good.
○ △: Good with no delamination, although the adhesive strength is slightly reduced, but is generally good.
X: Delamination occurs and the adhesive strength is greatly reduced.

As shown in Table 4, Example 16 includes a compound (A) containing a furyl group, a compound containing an acryloyl group among compounds (B) containing a polymerizable functional group, and a photopolymerizable initiator (C1). Residue amount, separation, precipitation, on-machine stability and retort suitability were all good.
Since Comparative Example 5 did not contain the compound (A) containing a furyl group, the retort resistance was insufficient.

<< Active energy ray-curable offset ink >>
<Manufacture of active energy ray-curable offset ink>
[Example 17]
Compound solution A3 containing furyl group 10 parts in advance, diallyl phthalate resin (molecular weight 50000) 5 parts, dipentaerythritol penta (hexa) acrylate mixture (mixing ratio is dipentaerythritol pentaacrylate: dipentaerythritol hexaacrylate = 15 %: 85%) was kept at an upper limit temperature of 100 ° C. and heated and mixed to evaporate the solvent in A3 and simultaneously dissolve. 60 parts of this lysate, 10 parts 2-benzyl-2-dimethylamino-1- (morpholinophenyl) -butan-1-one, 20 parts phthalocyanine blue, N-2- (aminoethyl) -3-aminopropyl Mix 2 parts of trimethoxysilane, stir and mix using a butterfly mixer, disperse so that the maximum particle size is 7.5 μm or less with 3 rolls, and use a spread meter to achieve a certain viscosity standard To prepare an active energy ray-curable offset ink (U-1).

[Comparative Example 6]
An active energy ray-curable offset ink (U-2) of Comparative Example 5 was obtained in the same manner as in Example 17 except that 10 parts of diallyl phthalate resin was used without using the compound solution A3 containing a furyl group.

<Evaluation of active energy ray-curable offset ink>
PP (Idemitsu Super Pure Ray SG140) and PET (Mitsubishi Resin Deacrail A2012) are coated with a predetermined amount of ink using an RI tester (simple print transfer device), and then with a 160 W / cm ² metal halide lamp. Irradiation was performed at a predetermined irradiation amount to produce a print sample. Print samples were used to evaluate water resistance adhesion and film strength. The evaluation results are shown in Table 5.

[Water-resistant adhesion]
The print sample was immersed in a TOMY autoclave BS-325 at 120 ° C. for 40 minutes, and then the adhesion with PP and PET was evaluated by a cellophane tape peeling test according to the following criteria.
5: No peeling at all 4: Adhesion test part less than 10% peeling 3: Adhesion test part 50% or more peeling 2: Adhesion test part 80% or more peeling 1: All peeling

[Coating strength]
The print sample was rubbed with MEK, and the number of rubs was confirmed. For a film having sufficient film strength, it is assumed that there is no rub-off 50 times or more and that the film strength is strong, and if it is less than that, the film strength is sequentially inferior.

As shown in Table 5, Example 17 includes a compound (A) containing a furyl group, a compound containing an acryloyl group among compounds (B) containing a polymerizable functional group, and a photopolymerizable initiator (C1). The water resistance adhesion and the film strength were all good.
Since Comparative Example 6 did not include the compound (A) containing a furyl group, the water resistance adhesion and the film strength were insufficient.

<< Flexo ink >>
<Manufacture of other resins>
[Production Example 15]
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, 159.4 parts of xylene were added, and the temperature was raised to 125 to 130 ° C. while injecting nitrogen gas into the vessel. A mixture of 59.1 parts of styrene, 20.4 parts of acrylic acid, 20.4 parts of α-methylstyrene and 6.3 parts of di-tert-butyl peroxide was added dropwise over 4 hours, and then kept at the same temperature for 3 hours. The polymerization reaction was completed. The temperature was further raised to 180 ° C., and xylene was completely removed under reduced pressure to obtain a copolymer having a weight average molecular weight of 12,000. Ammonia water and deionized water were added to the obtained copolymer to obtain a resin aqueous solution 1 having a pH of 8.6 and a solid content of 30%.

[Production Example 16]
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, 159.4 parts of xylene were added, and the temperature was raised to 125 to 130 ° C. while injecting nitrogen gas into the vessel. A mixture of 31.5 parts of styrene, 10.5 parts of acrylic acid, 0.5 part of α-methylstyrene and 6.3 parts of di-tert-butyl peroxide was added dropwise over 4 hours, and then kept at the same temperature for 3 hours. The polymerization reaction was completed. The temperature was further raised to 180 ° C., and xylene was completely removed under reduced pressure to obtain a copolymer. Ammonia water and deionized water were added to the obtained copolymer to obtain a resin aqueous solution having a pH of 8.3 and a solid content of 30%. To this resin aqueous solution, 47.5 parts of styrene, 0.5 part of butyl acrylate and 1.0 part of ammonium persulfate were added dropwise over 1 hour with stirring to obtain an acrylic emulsion 1 having a nonvolatile content of 45%.

<Manufacture of pigment dispersion>
[Aqueous Pigment Dispersion I]
Phthalocyanine blue pigment 45.0%
Resin aqueous solution 1 10.0%
Polyoxyethylene polyoxypropylene block polymer (nonionic activator (a))
(Molecular weight 8350, ethylene oxide addition in total molecule 80%) 2.0%
2,4,7,9-tetramethyl-5-decyne-4,7-diol (nonionic active agent)
(B)) 1.0%
Silicone defoamer 0.1%
41.9% deionized water
Total 100.0%
After mixing, stirring and mixing, the mixture was dispersed with a sand mill until the particle size became 10 μm or less with a grind gauge to obtain an aqueous pigment dispersion I.

<Manufacture of varnish composition>
[Varnish composition i]
Compound solution A4 containing furyl group 30.0%
Trimethylolpropane triacrylate 4.8%
2,2-Dimethoxy-1,2-diphenylethane-1-one 1.2%
Acrylic emulsion 1 33.3%
Polyethylene wax 4.0%
Silicone defoamer 0.2%
Deionized water 26.5%
Total 100.0%
And varnish composition i was obtained by stirring with a disper.

[Varnish composition ii]
Resin aqueous solution 1 50.0%
Acrylic emulsion 1 33.3%
Polyethylene wax 4.0%
Silicone defoamer 0.2%
Deionized water 12.5%
Total 100.0%
And varnish composition ii was obtained by stirring with a disper.
<Manufacture of flexo ink>
[Example 18]
Ink composition 1 was obtained by adding 40.0 parts of aqueous pigment dispersion I in 60.0 parts of varnish composition i, and stirring with a disper.

[Comparative Example 7]
Ink composition 2 was obtained in the same manner as in Example 18 except that varnish composition ii was used instead of varnish composition i.

<Evaluation of flexographic ink>
Using the prepared ink, the stability over time, re-dissolvability, water resistance, overcoat resistance, and friction resistance were evaluated by the following methods. The evaluation results are shown in Table 6.

[Stability over time]
The viscosity was measured by measuring the number of seconds with a 25 ° C. Zahn cup # 4 on the day of preparation of the ink composition. After the ink composition was stored at 40 ° C. for 30 days, the viscosity of the ink composition returned to 25 ° C. was measured to confirm an increase in viscosity. The evaluation criteria at that time are as follows.
◎: Within 3 seconds ○: Within 10 seconds △: Within 30 seconds ×: More than 30 seconds

[Resolubility]
The ink composition was applied to a glass plate with a bar coater # 4 and air-dried with a dryer for 3 seconds, and then the ink was applied to the coating film. The evaluation criteria at that time are as follows.
◎: 1 second or less ○: 5 seconds or less △: 5 seconds or more and 10 seconds or less ×: 10 seconds or more

[water resistant]
The ink composition was applied to a glass plate with a bar coater # 4 and air-dried with a dryer for 3 seconds, and then water was poured into the coating film. The evaluation criteria at that time are as follows.
◎: 20 seconds or more ○: 10 seconds or more and 20 seconds or less Δ: 10 seconds or less ×: 1 second or less

[Repeatability]
Evaluation of overprinting suitability using a flexo proofing machine. Leveling, trapping and squeezing properties were evaluated. The evaluation criteria at that time are as follows.
◎: The above three items are all good ○: The above two items are good △: There are defective items ×: All are defective

[Abrasion resistance]
A printed matter was prepared using a hand proofer, and the appearance was evaluated by rubbing 100 times with a load of 500 g against high-quality paper using a Gakushin type friction resistance tester. The evaluation criteria at that time are as follows.
◎: No color fading ○: Slightly colored on high-quality paper △: Clear color on high-quality paper ×: Scratches on printed matter

As shown in Table 6, Example 18 contains a compound (A) containing a furyl group, a compound containing an acryloyl group among compounds (B) containing a polymerizable functional group, and a photopolymerizable initiator (C1). In addition, water resistance, overcoat resistance, and friction resistance were all good.
Since the comparative example 7 does not contain the compound (A) containing a furyl group, the water resistance, the overcoat resistance, and the friction resistance were insufficient.

The ink composition of the present embodiment can be used as long as it is cured by heat. The organic solvent-based inkjet ink, organic solvent-based gravure ink, active energy ray-curable offset ink, and water-based flexographic ink described above. In addition to ink, it can also be used in various inks used for organic solvent-based, water-based, active energy ray-curable ink jet printing, gravure printing, offset printing, flexographic printing, screen printing, and the like.

Claims (3)

A compound (A) containing a furyl group, a compound (B) containing a polymerizable functional group, a polymerization initiator (C), and a colorant (F),
The compound (B) is a compound containing a group represented by any one of the following formulas [1] to [7] as a polymerizable functional group, or a compound represented by the following formula [8]. Ink composition.

(In formulas [1] to [7], * represents a bond.) The compound (A) containing a furyl group is a polymer (A-1) of a monomer (a) containing a monomer (a-1) containing a furyl group. Ink composition. An offset ink, flexographic ink, gravure ink, or inkjet ink comprising the ink composition according to claim 1 or 2.