JP2021098770A - Active energy ray-curable ink composition and printed matter of the same - Google Patents

Abstract

To provide an active energy ray-curable ink composition which has good adhesion to various base materials, in particular, is excellent in adhesion to base materials such as polyethylene, polypropylene and polystyrene films, and has chemical resistance of a cured coated film.SOLUTION: An active energy ray-curable ink composition contains a coloring agent, a polymerization initiator, a rosin-modified polyester compound and a (meth)acrylate compound (excluding rosin-modified polyester compound). A ratio of a structural unit derived from rosin in the rosin-modified polyester compound is 40-80 mass% based on the whole structural unit constituting the rosin-modified polyester compound.SELECTED DRAWING: None

Description

The present invention has good adhesion to a wide range of substrates, particularly good adhesion to plastic substrates such as polyethylene, polypropylene, and polystyrene films, and has excellent chemical resistance of cured coating films. The present invention relates to an active energy ray-curable ink composition having a biomass-derived component in the ink composition of 10% by mass or more and a printed matter thereof.

In recent years, active energy ray-curable ink compositions can be cured by irradiating them with active energy rays such as ultraviolet rays, visible rays, and electron beams for a very short time, resulting in high productivity and high coating resistance. It is widely used in fields where durability is required because it is possible.

However, in the active energy ray-curable ink composition, when the base material to be printed is a plastic, the type of plastic, particularly an olefin-based base material such as polyethylene or polypropylene having low polarity, or a polystyrene base material has good adhesion. There is a problem that it cannot be obtained, and various studies have been conducted.

Furthermore, in recent years, as an initiative to reduce the environmental burden, the Japan Organic Resources Association has newly established a biomass mark system, which replaces the raw materials contained in the ink composition with biomass-derived raw materials. It is required to increase the ratio.

However, in the active energy ray-curable ink composition, if the ratio of the biomass-derived raw material is increased, there is a problem that sufficient adhesion to the substrate and coating film resistance cannot be obtained, and various studies have been conducted.

For example, Patent Document 1 (Japanese Patent Laid-Open No. 3-215543) describes a styrene-acrylic acid ester-based copolymer having a nitrogen-containing (meth) acrylic monomer having a weight average molecular weight of 3,000 to 50,000. An active energy ray-curable resin composition containing 10 to 50% by weight and 50 to 90% by weight of a reaction diluent is disclosed. However, although the adhesion to acrylic base materials and polyester base materials is improved to some extent, it is not sufficient, and in particular, olefin-based base materials such as polyethylene and polypropylene having low polarity and polystyrene base materials cannot obtain good adhesion. There was a problem.

For example, Patent Document 2 (Japanese Unexamined Patent Publication No. 8-143635) contains 5 to 95% by weight of rosin epoxy acrylate and 5 to 5 to 50,000 polyurethane resins having a carbon-carbon unsaturated bond group and having a number average molecular weight of 1,000 to 50,000. An active energy ray-curable resin composition containing 95% by weight and 0 to 70% by weight of a reactive diluent is disclosed. However, although the biomass ratio is increased by using the rosin epoxy acrylate, the adhesion is not sufficient, and there is a problem that sufficient adhesion cannot be obtained particularly with a polystyrene base material. Further, since both the rosin epoxy acrylate and the polyurethane resin are monofunctional, there is a problem in coating film resistance.

For example, Patent Document 3 (Japanese Patent Laid-Open No. 2004-339487) discloses an active energy ray-curable resin composition containing a monofunctional polyether-based polymerizable oligomer. However, by using a monofunctional oligomer having a flexible polyether structure, the adhesion to the polyethylene terephthalate base material is improved, but there is a problem in the adhesion of the polystyrene base material. Further, there is a problem that the coating film becomes flexible and the coating film resistance deteriorates. Furthermore, it can be said that it does not use biomass-derived raw materials and is not sufficiently environmentally friendly.

For example, Patent Document 4 (Japanese Unexamined Patent Publication No. 2011-225751) describes 10 to 40% by weight of a polyester resin composed of hydrogenated bisphenol, a diol having a branched alkyl group or ether, and a polybasic acid, and 30 UV curable compounds. UV curable slab printing inks containing up to 75% by weight are disclosed. However, although the adhesion to the polyethylene terephthalate base material is improved, there is a problem in the adhesion to the polystyrene base material. Further, since a monofunctional compound is used as the UV curable compound, there is a problem that sufficient coating film resistance cannot be obtained. Furthermore, it can be said that it does not use biomass-derived raw materials and is not sufficiently environmentally friendly.

For example, Patent Document 5 (Japanese Patent Laid-Open No. 2008-516502) discloses an energy ray-curable ink composition (for newspaper use) containing an acrylate functional group derivative of a natural oil and one or more additional acrylate functional group substances. .. However, although the biomass ratio is increased by using the acrylate functional group derivative of natural oil, there is a problem in adhesion to a plastic base material such as polyethylene, polypropylene, and polystyrene film. In addition, the chemical resistance of the coating film is not at a practical level and has a problem.

Japanese Unexamined Patent Publication No. 3-215543 Japanese Unexamined Patent Publication No. 8-143635 Japanese Unexamined Patent Publication No. 2004-339487 Japanese Unexamined Patent Publication No. 2011-225751 Japanese Patent Application Laid-Open No. 2008-516502

The problem to be solved by the present invention is that it has good adhesion to a wide range of substrates, particularly good adhesion to plastic substrates such as polyethylene, polypropylene, and polystyrene film, and is a cured coating film. It is an object of the present invention to provide an active energy ray-curable ink composition having excellent chemical resistance and having a ratio of biomass-derived components in the ink composition of 10% by mass or more, and a printed matter thereof.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by the following active energy ray-curable ink composition, and have completed the present invention.

That is, the present invention is an active energy ray-curable ink composition containing a colorant, a polymerization initiator, a rosin-modified polyester compound, and a (meth) acrylate compound (except when it is a rosin-modified polyester compound).
The present invention relates to an active energy ray-curable ink composition characterized in that the proportion of structural units derived from rosin in the rosin-modified polyester compound is 40 to 80% by mass with respect to all the structural units constituting the rosin-modified polyester compound.

The present invention also comprises the active energy ray-curable ink composition, wherein the content of the rosin-modified polyester compound is 5 to 30% by mass with respect to the total mass of the active energy ray-curable ink composition.
Regarding.

The present invention also relates to the active energy ray-curable ink composition having a weight average molecular weight of the rosin-modified polyester compound of 1,000 to 10,000.

The present invention also relates to the active energy ray-curable ink composition, wherein the rosin-modified polyester compound is a compound having 2 to 5 (meth) acroyl groups.

The present invention further relates to the above-mentioned active energy ray-curable ink composition containing an inert resin.

The present invention also relates to the active energy ray-curable ink composition in which the content of the inert resin is 1 to 15% by mass with respect to the total mass of the active energy ray-curable ink composition.

Further, in the present invention, the inert resin contains a structural unit derived from styrene.
The present invention relates to the above-mentioned active energy ray-curable ink composition, wherein the ratio of the structural units derived from styrene in the inert resin is 50% by mass or more with respect to all the structural units constituting the inert resin.

Further, the present invention is characterized in that the (meth) acrylate compound contains a (meth) acrylate compound having a heterocyclic structure and / or a (meth) acrylate compound having a bisphenol A structure. Regarding mold ink composition.

The present invention also relates to the active energy ray-curable ink composition in which the biomass ratio of the active energy ray-curable ink composition is 10% by mass or more.

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

According to the present invention, it has good adhesion to a wide range of substrates, particularly good adhesion to plastic substrates such as polyethylene, polypropylene, and polystyrene film, and excellent chemical resistance of the cured coating film. In addition, it was possible to provide an active energy ray-curable ink composition having a biomass-derived component in the ink composition of 10% by mass or more and a printed matter thereof.

Hereinafter, embodiments for carrying out the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

The terms used herein will be described. "(Meta) acrylate" means acrylate and / or acrylate. The "active energy ray" means an energy ray having a property of causing a chemical change such as a chemical reaction in an irradiated object such as an ultraviolet ray or an electron beam.

<Active energy ray-curable ink composition>
One embodiment of the present invention relates to an active energy ray-curable ink composition. The active energy ray-curable ink composition is an active energy ray-curable ink containing a colorant, a polymerization initiator, a (meth) acrylate compound, and a rosin-modified polyester compound, and has a rosin-derived structure in the rosin-modified polyester compound. The ratio of the units is 40 to 80% by mass with respect to all the structural units constituting the rosin-modified polyester compound.
Hereinafter, the components contained in or may be contained in the active energy ray-curable ink composition of the present embodiment (hereinafter, also simply referred to as “ink composition”) will be described.

[Colorant]
The active energy ray-curable ink composition in the present invention contains a colorant. As the colorant, at least one of a pigment and a dye can be used. Pigments are preferable from the viewpoint of light resistance.
The pigment that can be used in the present invention is not particularly limited, and known pigments can be used. As the pigment, either an inorganic pigment or an organic pigment can be used.

Examples of the inorganic pigment include carbon blacks such as furnace black, lamp black, acetylene black and channel black, iron oxide and titanium oxide.

Examples of the organic pigment include soluble azo pigments such as β-naphthol type, β-oxynaphthoic acid type, β-oxynaphthoic acid type anilide type, acetoacetate anilide type and pyrazolone type; β-naphthol type and β-oxynaphthoic acid. Insoluble azo pigments such as anilide type, acetoacetate anilide type monoazo, acetoacetate anilide type disuazo, pyrazolone type; copper phthalocyanine blue, halogenated (for example, chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal Phthalocyanine pigments such as free phthalocyanine; quinacridone, dioxazine, slene (pirantron, antoanthron, indantron, anthrapyrimidine, flavantron, thioindigo, anthraquinone, perinone, perylene, etc.), isoindolinone, Examples thereof include polycyclic pigments such as metal complex type, quinophthalone type and diketopyrrolopyrrole type, and heterocyclic pigments.

More specifically, C.I. I. In terms of color index, black pigments include C.I. I. Pigment Black 1, 6, 7, 9, 10, 11, 28, 26, 31 and the like.

As the white pigment, C.I. I. Pigment White 5, 6, 7, 12, 28 and the like.

As the yellow pigment, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 18, 24, 73, 74, 75, 83, 93, 95, 97, 98, 100, 108, 109, 110, 114, 120, 128, 129, 138, 139, 174, 150, 151, 154, 155, 167, 180, 185, 213 and the like.

As a blue or cyan pigment, C.I. I. Pigment Blue 1, 2, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62 and the like.

As red or red pigments, C.I. I. Pigment RED 1, 3, 5, 19, 21, 22, 31, 38, 42, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 50, 52, 53: 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 90, 104, 108, 112, 114, 122, 144, 146, 148, 149, 150, 166, 168, 169, 170, 172, 173, 176, 177, 178, 184, 185, 187, 193, 202, 209, 214, 242, 254, 255, 264, 266, 269, C.I. I. Pigment Violet 19 and the like.

As a green pigment, C.I. I. Pigment Green 1, 2, 3, 4, 7, 8, 10, 15, 17, 26, 36, 45, 50 and the like.

As the purple pigment, C.I. I. Pigment Violet 1, 2, 3, 4, 5: 1, 12, 13, 15, 16, 17, 19, 23, 25, 29, 31, 32, 36, 37, 39, 42 and the like.
As the orange pigment, C.I. I. Pigment Orange 13, 16, 20, 34, 36, 38, 39, 43, 51, 61, 63, 64, 74 and the like.

In the present invention, the pigment may be used alone or in combination of two or more.

In the present invention, the pigment can be used at an arbitrary content as long as the desired concentration can be reproduced on the printing paper surface, and is 5 to 30% by mass with respect to the total mass of the ink composition. It is preferable, and more preferably 10 to 25% by mass.

[Polymerization initiator]
The active energy ray-curable ink composition in the present invention contains a polymerization initiator. The polymerization initiator preferably contains a polymerizable initiator for radical polymerization, and more preferably contains a photopolymerization initiator. The polymerization initiator in the present invention is a compound that generates radicals by causing a chemical change through the action of light or the interaction with the electron-excited state of the sensitizing dye. Among them, the polymerization initiator is to initiate polymerization by means of exposure. It is preferable that it is a photoradical polymerization initiator from the viewpoint of being able to carry out.

In the present invention, the photoradical polymerization initiator is not particularly limited, and known photoradical polymerization initiators can be used. Specific examples include benzophenone compounds, dialkoxyacetophenone compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, thioxanthone compounds and the like.

Examples of the benzophenone compound include benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone, and [4- (methylphenylthio). Phenyl] -Phenylmethanone and the like.

Examples of the dialkoxyacetophenone compound include 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, and diethoxyacetophenone.

Examples of the α-hydroxyalkylphenone compound include 1-hydroxy-cyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and 1- [4- (2-hydroxymethoxy) -phenyl. ] -2-Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl -Propane-1-one and the like.

Examples of the α-aminoalkylphenone compound include 2-methyl-1- [4- (methoxythio) -phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4). -Molphorinophenyl) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl-1-butanone and the like can be mentioned.

Examples of the above-mentioned acylphosphine oxide compounds include diphenylacylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Can be mentioned.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone.

In the present invention, the above-mentioned polymerization initiator may be used alone or in combination of two or more.

Among these, from the viewpoint of adhesion and chemical resistance, it is preferable to include an α-aminoalkylphenone-based compound and an acylphosphine oxide-based compound.

In the present invention, the content of the polymerization initiator is preferably 0.5 to 20% by mass, more preferably 5 to 15% by mass, based on the total mass of the ink composition.

[(Meta) acrylate compound]
The active energy ray-curable ink composition in the present invention contains a (meth) acrylate compound. The (meth) acrylate compound is not particularly limited, and known compounds can be used. In the present invention, the "(meth) acrylate compound" means a compound having a minimum structural unit for forming an oligomer or a polymer. Further, "PO" represents "propylene oxide" and "EO" represents "ethylene oxide".

In the present invention, the content of the (meth) acrylate compound is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, based on the total mass of the ink composition.

Specific examples of the (meth) acrylate compound include 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, β-carboxyethyl (meth) acrylate, and 4-tert. -Butylcyclohexinol (meth) acrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, caprolactone (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isoamyl (meth) acrylate, 2-phenoxyethyl ( Meta) acrylate, isodecyl (meth) acrylate, 3,3,5-trimethylcyclohexanol (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Dicyclopentenyl (oxyethyl) (meth) acrylate, 1,4-cyclohexanedimethanol (meth) acrylate, cyclic trimethylpropanformal (meth) acrylate, benzyl (meth) acrylate, EO-modified (2) nonylphenol acrylate, 2 -Methyl-2-ethyl-1,3-dioxolan-4-yl) monofunctional (meth) acrylate compounds such as methyl acrylate and acryloylmorpholin,
1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-dodecanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol ( 200) Di (meth) acrylate, polyethylene glycol (300) di (meth) acrylate, polyethylene glycol (400) di (meth) acrylate, polyethylene glycol (600) di (meth) acrylate, neopentyl glycol di (meth) hydroxypivalate ) Acrylate, Dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, EO modified (2) 1,6-hexanediol di (meth) acrylate, PO modified (2) Neopentyl glycol di (meth) Acrylate, (neopentyl glycol modified) trimethylolpropandi (meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate, EO modified (4) bisphenol A di (meth) acrylate, PO modified (4) bisphenol A di (4) Meta) acrylates, cyclohexanedimethanol di (meth) acrylates, dimethylol-tricyclodecanedi (meth) acrylates, dicyclopentanyldi (meth) acrylates, tris (2-hydroxyethyl) isocyanurate di (meth) acrylates, etc. Bifunctional (meth) acrylate compound,
Trimethylolpropane tri (meth) acrylate, EO-modified (3) trimethylolpropane tri (meth) acrylate, PO-modified (3) trimethylolpropane tri (meth) acrylate, ε-caprolactone-modified tris- (2-acryloxyethyl) Trifunctional (meth) acrylate compounds such as isocyanurate, tri (meth) acrylate ethoxylated isocyanurate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and pentaerythritol tri (meth) acrylate,
Tetrafunctional (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate,
Dipentaerythritol Penta (meth) acrylate and other pentafunctional (meth) acrylate compounds,
Examples thereof include hexafunctional (meth) acrylate compounds such as dipentaerythritol hexa (meth) acrylate.
The "n-functional (meth) acrylate compound" means a (meth) acrylate compound having n (meth) acryloyl groups.

Further, as the (meth) acrylate compound, urethane acrylate, polyester acrylate (excluding rosin-modified polyester compound), epoxy acrylate and the like can also be used.

Urethane acrylate is, for example, one obtained by reacting diisocyanate with (meth) acrylates having a hydroxyl group, or an isocyanate group-containing urethane prepolymer obtained by reacting a polyol and polyisocyanate under a condition of excess isocyanate group. Some are obtained by reacting with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under a condition of excess hydroxyl group can be obtained by reacting with (meth) acrylates having an isocyanate group.

The polyester acrylate can be obtained, for example, by reacting a polyester polycarboxylic acid obtained by polycondensing a polybasic acid and a polyhydric alcohol with a hydroxyl group-containing (meth) acrylate or the like.

Examples of the epoxy acrylate include those in which the glycidyl group of the epoxy resin is esterified with (meth) acrylic acid to use the functional group as the (meth) acrylate group, and the (meth) acrylic acid addition to the bisphenol A type epoxy resin. , There are (meth) acrylic acid additives to novolak type epoxy resin.

In the present invention, the above (meth) acrylate compound may be used alone or in combination of two or more.

Among these, it is preferable to contain a 2 to 4 functional (meth) acrylate compound from the viewpoint of adhesion and chemical resistance.

Among the above 2 to 4 functional (meth) acrylate compounds, it is more preferable to include a (meth) acrylate compound having a heterocyclic structure.
Specific examples of the 2 to 4-functional (meth) acrylate compound having a heterocyclic structure include dioxane glycol diacrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate. Examples include tri (meth) acrylate.

The content of the (meth) acrylate compound having a heterocyclic structure is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, based on the total mass of the ink composition.

When a monofunctional (meth) acrylate compound is contained, it is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the ink composition from the viewpoint of chemical resistance. preferable.

When a penta-functional or higher functional (meth) acrylate compound is contained, it is preferably 25% by mass or less, preferably 15% by mass or less, based on the total mass of the ink composition from the viewpoint of adhesion. More preferred.

[Rosin-modified polyester compound]
The rosin-modified polyester compound contained in the active energy ray-curable ink composition in the present invention has a rosin-modified polyester compound in which the ratio of structural units derived from rosin (hereinafter, also referred to as “rosin content”) in the rosin-modified polyester compound is high. It is characterized in that it is 40 to 80% by mass with respect to all the structural units constituting the above.

In the present invention, the rosin-modified polyester compound is not particularly limited as long as the ratio of the structural units derived from rosin is 40 to 80% by mass with respect to all the structural units constituting the rosin-modified polyester compound, and known ones are used. be able to. For example, the following rosin-modified polyester resin and the like can be mentioned.
-A compound in which a conjugated logonic acid and an ethylenically unsaturated double bond-containing compound having a carboxy group are subjected to a deal alder addition reaction, and further, a carboxy group of the reaction compound and a hydroxyl group of the polyol are esterified.
-The conjugated logonic acid and the ethylenically unsaturated double bond-containing compound having a carboxy group are subjected to a deal alder addition reaction, and further, the ethylenically unsaturated double bond-containing compound having a carboxy group and a carboxy group of the reaction compound is subjected to the addition reaction. A compound obtained by reacting a carboxy group with a hydroxyl group of a polyol (see JP-A-2018-150469).
-The conjugated logonic acid and the ethylenically unsaturated double bond-containing compound having a carboxy group are subjected to a deal alder addition reaction, and further, the carboxy group of the reaction compound is reacted with the hydroxyl group of the polyol, and then the compound remains. A compound obtained by adding an epoxy group of an ethylenically unsaturated double bond-containing compound having an epoxy group to an existing hydroxyl group and / or carboxy group.
-The conjugated logonic acid and the ethylenically unsaturated double bond-containing compound having a carboxy group are subjected to a deal alder addition reaction, and further, the carboxy group of the reaction compound is reacted with the hydroxyl group of the polyol, and then the compound remains. A compound obtained by addition-reacting an existing hydroxyl group with a carboxy group of an ethylenically unsaturated double bond-containing compound having a carboxy group and / or an isocyanate group of an ethylenically unsaturated double bond-containing compound having an isocyanate group.
-The conjugated logonic acid and the ethylenically unsaturated double bond-containing compound having a carboxy group are subjected to a deal alder addition reaction, and further, the carboxy group of the reaction compound and the ethylenically unsaturated double bond-containing compound having a hydroxyl group are subjected to. A compound obtained by esterifying a hydroxyl group (see JP-A-2007-56185).
-Esterylation reaction of conjugated loginate with polyol, and further, ethylenically unsaturated double bond having a hydroxyl group of the reaction compound, a carboxy group of an ethylenically unsaturated double bond-containing compound having a carboxy group, and an epoxy group. A compound obtained by addition-reacting one or more selected from the group consisting of an epoxy group of a contained compound and an isocyanate group of an ethylenically unsaturated double bond-containing compound having an isocyanate group.
-A compound obtained by subjecting a conjugated rosin acid and an ethylenically unsaturated double bond-containing compound to a Diels-Alder addition reaction.
-The conjugated logonic acid and an ethylenically unsaturated double bond-containing compound (excluding those having a carboxy group) are subjected to a deal alder addition reaction, and the carboxy group of the reaction compound and the hydroxyl group of the polyol are esterified. Compound (see Japanese Patent Application Laid-Open No. 2000-080326).
-The conjugated logonic acid and an ethylenically unsaturated double bond-containing compound (excluding those having a carboxy group) are subjected to a deal alder addition reaction, and further, an esterification reaction is carried out between the carboxy group of the reaction compound and the hydroxyl group of the polyol. After that, a compound obtained by addition-reacting an epoxy group of an ethylenically unsaturated double bond-containing compound having an epoxy group to the remaining hydroxyl group and / or carboxy group.
-The conjugated logonic acid and an ethylenically unsaturated double bond-containing compound (excluding those having a carboxy group) are subjected to a deal alder addition reaction, and further, an esterification reaction is carried out between the carboxy group of the reaction compound and the hydroxyl group of the polyol. After that, the carboxy group of the ethylenically unsaturated double bond-containing compound having a carboxy group and / or the isocyanate group of the ethylenically unsaturated double bond-containing compound having an isocyanate group are added to the remaining hydroxyl groups by addition reaction. Compound.

The conjugated loginate used to obtain the rosin-modified polyester compound of the present invention is a loginic acid having a conjugated double bond. As used herein, the term "rosin acids" means organic monobasic acids having a cyclic diterpene skeleton and derivatives thereof. The rosin acids may be, for example, rosin acid, disproportionated rosin acid, hydrogenated rosin acid, and alkali metal salts of these compounds. Further, the "conjugated double bond" means a bond in which a plurality of double bonds are alternately connected with a single bond in between. However, the conjugated double bond of the π-electron conjugated system contained in the aromatic compound is not included. That is, the "conjugated rosin acid" described in the present specification means the above-mentioned rosin acids excluding hydrogenated rosin acid having no conjugated double bond.

Specific examples of the conjugated rosin acid include abietic acid and its conjugated compounds, neo-abietic acid, palastolic acid, and levopimaric acid. In addition, examples of natural resins containing these conjugated rosins include gum rosin, wood rosin, and tall oil rosin. Generally, the above natural resin contains a conjugated loginate (A1) and a loginic acid having no conjugated double bond, but even if these natural resins are used in the production of the rosin-modified resin (A). No problem, rosin acids having no conjugated double bond in the natural resin act as a monobasic acid and are incorporated into the resin.

The α, β-unsaturated dicarboxylic acid or an acid anhydride thereof that can be used to obtain the rosin-modified polyester compound of the present invention is not particularly limited, and known ones can be used. Specific examples thereof include maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, isocrotonic acid and the like, or acid anhydrides thereof. Of these, maleic acid or an acid anhydride thereof is preferable from the viewpoint of reactivity with conjugated rosin acid.

The polyol that can be used to obtain the rosin-modified polyester compound of the present invention is not particularly limited, and known ones can be used.
Specifically, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, which are linear alkylene dihydric alcohols, 1 , 2-Pentanediol, 1,5-Pentanediol, 1,6-Hexanediol, 1,2-Hexanediol, 1,5-Hexanediol, 2,5-Hexanediol, 1,7-Heptanediol, 1, 8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14 -Tetradecanediol, 1,2-tetradecanediol, 1,16-hexadecanediol, 1,2-hexadecanediol, etc.
Bifurcated alkylene dihydric alcohols 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl -2,4-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, dimethylol octane, 2-ethyl-1,3- Hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1, 5-Pentanediol etc.
Cyclic alkylene dihydric alcohols 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptandiol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated Bisphenol F, hydrogenated bisphenol S, hydrogenated catechol, hydrogenated resorcin, hydrogenated hydroquinone, etc.
Further, a polyether polyol such as polyethylene glycol (n = 2 to 20), polypropylene glycol (n = 2 to 20), polytetramethylene glycol (n = 2 to 20), and a dihydric alcohol such as polyester polyol.
Glycerin, Trimethylol Propane, Pentaerythritol, 1,2,6-Hexanetriol, 3-Methylpentane-1,3,5-Triol, Hydroxymethylhexanediol, Trimethyloloctane, Diglycerin, Ditrimethylolpropane, Dipentaeryth Examples thereof include trihydric or higher alcohols such as linear, branched and cyclic polyhydric alcohols such as lithol, sorbitol, inositol and tripentaerythritol.
The above-mentioned polyol may be used alone or in combination of two or more. Of these, a dihydric alcohol is preferable because a resin structure with few branches is preferable from the viewpoint of the flexibility of the coating film.

The ethylenically unsaturated double bond-containing compound that can be used to obtain the rosin-modified polyester compound of the present invention is not particularly limited, and known compounds can be used.
Specifically, examples of the ethylenically unsaturated double bond-containing compound having a carboxy group include acrylic acid, methacrylic acid, β-carboxyethyl (meth) acrylate, maleic acid, fumaric acid, citraconic acid, itaconic acid, and crotonic acid. , Isocrotonic acid, cinnamic acid, 2,4-hexadienonic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenic acid, 7-octenoic acid, 2-ethyl-3-butenoic acid, 4 -Methyl-4-pentenoic acid, 5-methyl-5-hexenoic acid, 6-methyl-6-heptenoic acid, 3-propyl-3-butenoic acid, 3- (2-propenyl) benzoic acid, 3-vinylbenzoic acid , 4-Vinylbenzoic acid and acid anhydrides thereof.

Examples of the ethylenically unsaturated double bond-containing compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , 2-Hydroxy-3-phenoxypropyl acrylate, pentaerythritol (meth) triacrylate, dipentaerythritol penta (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, ethyl-α-hydroxymethyl acrylate, N- (2-) Hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl Examples thereof include vinyl ether, 2-hydroxyethylallyl ether, 3-hydroxypropylallyl ether, 4-hydroxybutylallyl ether and the like. Further, the ethylenically unsaturated double bond-containing compound obtained by adding an alkylene oxide and / or lactone to the above-mentioned ethylenically unsaturated double bond-containing compound also has a hydroxyl group in the method of the present invention. It can be used as an unsaturated double bond-containing compound.
Among them, from the viewpoint of the flexibility of the coating film, a resin structure having few branches is preferable, so an ethylenically unsaturated double bond-containing compound having two or less hydroxyl groups is preferable, and a (meth) acrylate having two or less hydroxyl groups is preferable. Compounds are more preferred.

Examples of the ethylenically unsaturated double bond-containing compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl allyl ether, and 2,3-epoxy-2-methylpropyl (meth). Acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 4-vinyl-1-cyclohexene-1,2-epoxide, glycidyl cinnamate, 1,3-butadiene monoepoxiside, celloxide 2000 (manufactured by Daicel Chemical Industry Co., Ltd.), etc. Can be mentioned.

Examples of the ethylenically unsaturated double bond-containing compound having an isocyanate group include 2-isocyanatoethylacrylate, 2-isocyanatoethyl methacrylate, 2- (2-acryloyloxyethyloxy) ethyl isocyanate, and 2- (2-methacryloyl). Oxyethyloxy) ethyl isocyanate and the like can be mentioned.
Further, a compound obtained by reacting a part of the isocyanate group of the polyisocyanate with the hydroxyl group of the (meth) acrylate compound having a hydroxyl group can also be used as the ethylenically unsaturated double bond-containing compound having an isocyanate group.

Examples of the ethylenically unsaturated double bond-containing compound other than the above include the above-mentioned ethylenically unsaturated double bond-containing compound having a carboxy group, an ethylenically unsaturated double bond-containing compound having a hydroxyl group, and ethylene having an epoxy group. An ethylenically unsaturated double bond-containing compound other than the sex-unsaturated double bond-containing compound and the ethylenically unsaturated double bond-containing compound having an isocyanate group can be used, and specifically, 2-ethylhexyl (specifically, 2-ethylhexyl ( Meta) acrylate, 4-tert-butylcyclohexanol (meth) acrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isoamyl (meth) acrylate, 2-phenoxyethyl (Meta) acrylate, isodecyl (meth) acrylate, 3,3,5-trimethylcyclohexanol (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentanyl (meth) Acrylate, dicyclopentenyl (oxyethyl) (meth) acrylate, cyclic trimethylolpropanformal (meth) acrylate, benzyl (meth) acrylate, EO-modified (2) nonylphenol acrylate, 2-methyl-2-ethyl-1,3- Monofunctional (meth) acrylate compounds such as dioxolan-4-yl) methyl acrylate and acryloyl morpholine,
1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-dodecanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol ( 200) Di (meth) acrylate, polyethylene glycol (300) di (meth) acrylate, polyethylene glycol (400) di (meth) acrylate, polyethylene glycol (600) di (meth) acrylate, dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, EO modified (2) 1,6-hexanediol di (meth) acrylate, PO modified (2) neopentyl glycol di (meth) acrylate, dimethylol tricyclodecanedi (meth) acrylate , EO modified (4) bisphenol A di (meth) acrylate, PO modified (4) bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol-tricyclodecanedi (meth) acrylate, dicyclopenta Bifunctional (meth) acrylate compounds such as nildi (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, EO-modified (3) trimethylolpropane tri (meth) acrylate, PO-modified (3) trimethylolpropane tri (meth) acrylate, ε-caprolactone-modified tris- (2-acryloxyethyl) Trifunctional (meth) acrylate compounds such as isocyanurate, tri (meth) acrylate ethoxylated isocyanuric acid,
Tetrafunctional (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate,
Hexa-functional (meth) acrylate compounds such as dipentaerythritol hexa (meth) acrylate,
Examples thereof include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, butyl vinyl ether, ethyl vinyl ether, 1-hexene, allyl acetate, allyl cyanide, vinyl cyanide, vinyl cyclohexane, vinyl methyl ketone, acetylene and ethynyl toluene. ..
Among them, from the viewpoint of the flexibility of the coating film, a resin structure having few branches is preferable, so a compound having 2 to 4 ethylenically unsaturated double bonds is preferable, and a 2 to 4 functional (meth) acrylate is more preferable.

The ethylenically unsaturated double bond-containing compound may be used alone or in combination of two or more.

The rosin content of the rosin-modified polyester compound is more preferably 40 to 60% by mass from the viewpoint of pencil hardness.

The weight average molecular weight (hereinafter, also referred to as Mw) of the rosin-modified polyester compound is preferably 1,000 to 10,000, and more preferably 2,000 to 8,000.

In the present invention, Mw was measured by gel permeation chromatography (hereinafter referred to as "GPC"). The specific measurement method of GPC is as follows. A calibration curve was prepared from a standard polystyrene sample using HLC-8020 manufactured by Tosoh Corporation. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M (manufactured by Tosoh Corporation) were used as the column. The measurement was performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C.

From the viewpoint of adhesion, the content of the rosin-modified polyester compound is preferably 5 to 30% by mass, more preferably 15 to 30% by mass, based on the total mass of the active energy ray-curable ink composition.

In the present invention, the rosin-modified polyester compound preferably has an acryloyl group. Having an acryloyl group further improves chemical resistance. The number of acryloyl groups contained in the rosin-modified polyester compound is preferably 2 to 5, and more preferably 2 to 4.

[Inert resin]
The active energy ray-curable ink composition in the present invention preferably further contains an inert resin (excluding the above-mentioned rosin-modified polyester compound). By including the inert resin, the adhesion to the base material is further improved. In the present invention, the "inert resin" means a compound having no reactive group.

The content of the inert resin is preferably 1 to 15% by mass, more preferably 3 to 15% by mass, and 5 to 15% by mass with respect to the total mass of the ink composition. Is particularly preferable.

From the viewpoint of adhesion, the Mw of the inert resin is preferably 5,000 to 30,000, more preferably 10,000 to 20,000.

The inert resin is not particularly limited, and known ones can be used. Specific examples include polyvinyl chloride, poly (meth) acrylic resin, polystyrene resin, styrene (meth) acrylic resin, epoxy resin, polyester resin, polyurethane resin, cellulose derivative (for example, ethyl cellulose, cellulose acetate, nitrocellulose), chloride. Examples thereof include vinyl-vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, diallyl phthalate resins, alkyd resins, rosin-modified alkyd resins, petroleum resins, urea resins, and synthetic rubbers such as butadiene-acrylic nitrile copolymers. Above all, from the viewpoint of adhesion, the ratio of styrene-derived structural units in the inert resin (hereinafter, also referred to as “styrene content”) is 50% by mass or more with respect to all the structural units constituting the inert resin. A (meth) acrylic resin is preferable, and a styrene (meth) acrylic resin having a styrene content of 60% or more is more preferable.

[Other ingredients]
In addition to the above components, the active energy ray-curable ink composition of the present invention contains extender pigments, pigment dispersants, other polymerizable compounds, sensitizers, and waxes, as long as the effects of the present invention do not deteriorate. , Polymerization inhibitor, surface tension modifier, antifoaming agent, ultraviolet absorber, antioxidant and the like can be contained.

(Pigment dispersant)
In the present invention, the ink composition preferably contains a pigment dispersant in order to improve the pigment dispersibility. The pigment dispersant is not particularly limited, and a known pigment dispersant can be used. Among them, a resin-type pigment dispersant having a basic functional group is preferable, and examples of the basic functional group include a nitrogen-containing heterocycle such as a primary, secondary or tertiary amino group, pyridine, pyrimidine, and pyrazine. it can.
Further, as the skeleton constituting the resin-type pigment dispersant, a fatty acid amine skeleton and / or a urethane skeleton is more preferable because good pigment dispersibility can be easily obtained.

Examples of the pigment dispersant include Ajinomoto Fine-Techno Co., Ltd.'s Ajispar series (Ajispar PB821, PB822, PB824, etc.), Lubrizol's Solspers series (Solsperse24000, Solsperse32000, Solsperse38500, etc.), and Big Chemie's Disperbic. It can be obtained from series (BYK-162, BYK-168, BYK-183, etc.).

The content of the pigment dispersant is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the ink composition.

(Other polymerizable compounds)
A polymerizable compound other than the (meth) acrylate compound (hereinafter, referred to as “other polymerizable compound”) can be contained. Examples of other polymerizable compounds include compounds having a polymerizable group such as an allyl group, a vinyl group, a vinyl ether group, and an internal double bond group (maleic acid, etc.) in the molecule.

(Sensitizer)
In the present invention, the ink composition may also contain a sensitizer in order to improve the curability. The sensitizer is not particularly limited, and a known sensitizer can be used. Specifically, triethanolamine, methyldiethanolamine, triisopropanolamine, aliphatic amines, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, dibutylethanolamine, 4, Examples thereof include 4-bis (dimethylamino) benzophenone.

The content of the polymerization initiator is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, based on the total mass of the ink composition.

(wax)
In the present invention, the ink composition preferably contains wax in order to improve abrasion resistance, blocking prevention property, slip property, and scratch resistance. The wax is not particularly limited, and known waxes can be used. For example, there are natural waxes and synthetic waxes.
Examples of natural waxes include carnauba wax, wood wax, lanolin, montan wax, paraffin wax, microcrystalline wax and the like.
Examples of the synthetic wax include Fishertropus wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, and polyamide wax silicone compound.

The content of the wax is preferably 0.1 to 5% by mass with respect to the total mass of the ink composition.

(Polymerization inhibitor)
In the present invention, a polymerization inhibitor can be used in the ink composition in order to improve storage stability. As the polymerization inhibitor, hindered phenol-based compounds, phenothiazine-based compounds, hindered amine-based compounds, and phosphorus-based compounds are particularly preferably used.
Specific examples thereof include 4-methoxyphenol, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, and aluminum salts of N-nitrosophenylhydroxylamine. ..
Among them, it is preferable to contain a hindered phenol-based compound and / or a phenothiazine-based compound, and more preferably 2,6-di-t-butyl-4-methylphenol and phenothiazine are contained.

The content of the polymerization inhibitor is preferably 0.01 to 2% by mass with respect to the total mass of the ink from the viewpoint of improving the storage stability while maintaining the curability.

In the present invention, it is preferable that the ink composition does not substantially contain an organic solvent from the viewpoint of reducing the environmental load. The term "substantially free" means less than 3% by mass, more preferably less than 1% by mass, based on the total mass of the ink composition.

(Biomass degree)
The Japan Organic Resources Association defines the degree of biomass as follows.

Biomass degree = ("dry weight of used biomass" ÷ "dry weight of product") x 100

Biomass mark certification requires a biomass degree of 10% or more.
In the present invention, the means for achieving a biomass degree of 10% or more is not particularly limited except that it contains a rosin-modified polyester compound, and a known method can be used.

<Printed matter>
The printed matter in the present invention is obtained by printing the above active energy ray-curable ink composition on a substrate. The base material is not particularly limited, and known materials can be used. Specifically, coated paper such as art paper, coated paper, cast paper, high-quality paper, medium-quality paper, non-coated paper such as newspaper, synthetic paper such as YUPO paper, PET (polyethylene terephthalate), PP ( Examples thereof include plastic films such as (polypropylene) and OPP (biaxially stretched polypropylene). Above all, good adhesion can be obtained for polyethylene, polypropylene, and polystyrene films.

In the present invention, the method for printing the active energy ray-curable ink composition is not particularly limited, and a known method can be used. Specific examples include offset printing, flexographic printing, gravure printing, and screen printing.

In the present invention, the method for curing the active energy ray-curable ink composition is not particularly limited, and a known method can be used. Specifically, it can be cured by irradiating with α-rays, γ-rays, electron beams, X-rays, ultraviolet rays, visible light, infrared light and the like. Among them, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable. The peak wavelength of ultraviolet rays is preferably 200 to 600 nm, more preferably 350 to 420 nm.

The active energy radiation source is not particularly limited, and a known one can be used. Specific examples thereof include mercury lamps, xenon lamps, metal hydride lamps, ultraviolet light emitting diodes (UV-LEDs), LEDs (light emitting diodes) such as ultraviolet laser diodes (UV-LD), and gas / solid state lasers.

Examples and comparative examples will be shown below, and the present invention will be described in more detail. However, the present invention is not limited thereto. In the examples and comparative examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

The details of the various measurements performed in the following examples are as follows.
(Weight average molecular weight)
The weight average molecular weight was measured by gel permeation chromatography (HLC-8320) manufactured by Tosoh Corporation. The calibration curve was prepared from a standard polystyrene sample. Further, tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M (manufactured by Tosoh Corporation) were used as the columns. The measurement was performed under the conditions of a flow rate of 0.6 mL / min, an injection volume of 10 μL, and a column temperature of 40 ° C.
(Rosin content)
The rosin content was determined by the following formula.

Rosin content = ("dry weight of rosin used" ÷ "dry weight of resin") x 100

[Rosin-modified polyester compound A]
A four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 48.1 parts of abietic acid and 15.6 parts of maleic anhydride, and 1 at 180 ° C. while blowing nitrogen gas. The reaction mixture was obtained by heating over time. Then, as described above, gas chromatograph mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was completed.
Next, 7.3 parts of bisphenol A, 4.7 parts of octanediol, 13.3 parts of 2,2-dimethyl-1,3propanediol, and 2-hydroxyethyl acrylate 11. 1 part and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours. The number of (meth) acroyl groups was 48.1% with a rosin content. The rosin-modified polyester compound A of 3 was obtained. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 4500.

[Rosin-modified polyester compound B]
A four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 47.0 parts of abietic acid and 15.2 parts of maleic anhydride, and 1 at 180 ° C. while blowing nitrogen gas. The reaction mixture was obtained by heating over time. Then, as described above, gas chromatograph mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was completed.
Next, 7.1 parts of bisphenol A, 4.5 parts of octanediol, 12.9 parts of 2,2-dimethyl-1,3propanediol and 13.2 parts of glycidyl acrylate were added to the above reaction mixture. 0.1 part of p-toluenesulfonic acid monohydrate was added as a catalyst, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours. The rosin content was 47.0% and the number of (meth) acroyl groups was 3. The rosin-modified polyester compound B of the above was obtained. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 6200.

[Rosin-modified polyester compound C]
A four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 47.0 parts of abietic acid and 15.2 parts of maleic anhydride, and 1 at 180 ° C. while blowing nitrogen gas. The reaction mixture was obtained by heating over time. Then, as described above, gas chromatograph mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was completed.
Next, 7.1 parts of bisphenol A, 4.5 parts of octanediol, 12.9 parts of 2,2-dimethyl-1,3propanediol and 2-acryloyloxyethyl isothia were added to the reaction mixture. 13.2 parts of nalto and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours at a rosin content of 47.0% (). Meta) A rosin-modified polyester compound C having 3 acryloyl groups was obtained. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 3500.

[Rosin-modified polyester compound D]
In a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 50.2 parts of abietic acid and 18.2 parts of ditrimethylolpropane tetraacrylate were charged, and 180 parts were blown with nitrogen gas. The reaction mixture was obtained by heating at ° C. for 1 hour. Then, as described above, gas chromatograph mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was completed.
Next, 9.5 parts of bisphenol A, 6.0 parts of 1,4-cyclohexanedimethanol, 4.3 parts of 2,2-dimethyl-1,3 propanediol and glycidyl acrylate were added to the above reaction mixture. 11.8 parts and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours at a rosin content of 50.2% (meth). ) A rosin-modified polyester compound D having 2 acroyl groups was obtained. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 7600.

[Rosin-modified polyester compound E]
In a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 50.3 parts of abietic acid and 18.2 parts of ditrimethylolpropane tetraacrylate were charged, and 180 parts were blown with nitrogen gas. The reaction mixture was obtained by heating at ° C. for 1 hour. Then, as described above, gas chromatograph mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was completed.
Next, in the above reaction mixture, 9.5 parts of bisphenol A, 6.0 parts of 1,4-cyclohexanedimethanol, 4.3 parts of 2,2-dimethyl-1,3 propanediol and 2- 11.7 parts of acryloyloxyethyl isocyanate and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours to obtain a rosin content of 50. A rosin-modified polyester compound E having 2 (meth) acryloyl groups was obtained at 2%. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 2100.

[Rosin-modified polyester compound F]
A four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 48.4 parts of abietic acid and 14.1 parts of pentaeslitol tetraacrylate, and while blowing nitrogen gas, The reaction mixture was obtained by heating at 180 ° C. for 1 hour. Then, as described above, gas chromatograph mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was completed.
Next, 9.1 parts of bisphenol A, 5.8 parts of 1,4-cyclohexanedimethanol, 22.6 parts of 2-acryloyloxyethyl isocyanate, and p-toluene as a catalyst were added to the above reaction mixture. 0.1 part of sulfonic acid monohydrate was added and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours to obtain a rosin-modified polyester compound F having a rosin content of 48.4% and a (meth) acryloyl group number of 4. .. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 4100.

[Rosin-modified polyester compound G]
In a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 51.5 parts of abietic acid and 16.7 parts of maleic anhydride were charged, and while blowing nitrogen gas, 1 at 180 ° C. The reaction mixture was obtained by heating over time. Then, as described above, gas chromatograph mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was completed.
Next, 12.2 parts of 1,4-cyclohexanedimethanol, 6.2 parts of octanediol, and 13.3 parts of 2,2-dimethyl-1,3propanediol were added to the reaction mixture as catalysts. 0.1 part of p-toluenesulfonic acid monohydrate was added, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours. A rosin-modified polyester compound G having a rosin content of 51.5% and a (meth) acroyl group of 0 was used. Got The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 4300.

[Rosin-modified polyester compound H]
In a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 59.9 parts of abietic acid and 17.4 parts of pentaeslitol tetraacrylate were charged, and 180 parts were blown with nitrogen gas. The reaction mixture was obtained by heating at ° C. for 1 hour. Then, as described above, gas chromatograph mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was completed.
Next, 22.6 parts of bisphenol A and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added to the above reaction mixture, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours. A rosin-modified polyester compound H having a rosin content of 59.9% and a (meth) acroyl group of 0 was obtained. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 4900.

[Rosin-modified polyester compound I]
A four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 44.5 parts of abietic acid and 14.4 parts of maleic anhydride, and 1 at 180 ° C. while blowing nitrogen gas. The reaction mixture was obtained by heating over time. Then, as described above, gas chromatograph mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was completed.
Next, in the above reaction mixture, 6.7 parts of bisphenol A, 4.3 parts of octanediol, 6.1 parts of 2,2-dimethyl-1,3propanediol, and 23 parts of 2-hydroxyethyl acrylate were added. Nine parts and 0.1 part of p-toluenesulfonic acid monohydrate were added as a catalyst, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours. The number of (meth) acroyl groups was 44.5% with a rosin content. The rosin-modified polyester compound I of No. 7 was obtained. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 5000.

[Rosin-modified polyester compound J]
A four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 49.3 parts of abietic acid and 16.0 parts of maleic anhydride, and 1 at 180 ° C. while blowing nitrogen gas. The reaction mixture was obtained by heating over time. Then, as described above, gas chromatograph mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was completed.
Next, in the above reaction mixture, 4.4 parts of pentaesritol, 7.4 parts of bisphenol A, 4.8 parts of octanediol, and 2,2-dimethyl-1,3propanediol 6. 8 parts, 11.3 parts of 2-hydroxyethyl acrylate, and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours. A rosin-modified polyester compound J having a rosin content of 49.3% and a (meth) acroyl group number of 3 was obtained. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 4500.

[Rosin-modified polyester compound K]
A four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 48.1 parts of abietic acid and 15.6 parts of maleic anhydride, and 1 at 180 ° C. while blowing nitrogen gas. The reaction mixture was obtained by heating over time. Then, as described above, gas chromatograph mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was completed.
Next, 7.3 parts of bisphenol A, 4.7 parts of octanediol, 13.3 parts of 2,2-dimethyl-1,3propanediol and 2-hydroxyethyl acrylate were added to the above reaction mixture. 11.1 parts and 0.1 part of p-toluenesulfonic acid monohydrate were added as a catalyst, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours to obtain a rosin content of 48.1% (meth). A rosin-modified polyester compound K having 3 acroyl groups was obtained. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 15,000.

[Rosin-modified polyester compound L]
In a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 36.8 parts of abietic acid, 11.9 parts of maleic anhydride, and 10.5 parts of 1,4-cyclohexanedicarboxylic acid were placed. The reaction mixture was obtained by heating at 180 ° C. for 1 hour while charging and blowing nitrogen gas. Then, as described above, gas chromatograph mass spectrometry of the reaction mixture confirmed that the Diels-Alder addition reaction was completed.
Next, 13.9 parts of bisphenol A, 12.7 parts of 2,2-dimethyl-1,3propanediol and 14.1 parts of 2-hydroxyethyl acrylate were added to the reaction mixture as catalysts. 0.1 part of p-toluenesulfonic acid monohydrate was added, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours. The rosin-modified polyester compound L having a rosin content of 36.8% and a (meth) acroyl group number of 2 was used. Got The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 4000.

[Rosin-modified polyester compound M]
83.1 parts of abietic acid, 6.2 parts of pentaesylitol, and 10.6 parts of 2-hydroxyethyl acrylate in a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer. A part and 0.1 part of p-toluenesulfonic acid monohydrate were added as a catalyst, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours. The rosin content was 83.1% and the number of (meth) abietic groups was 2. The rosin-modified polyester compound M of the above was obtained. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 2100.

[Polyester compound N]
16.7 parts of maleic anhydride, 10.5 parts of 1,4-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedi in a four-necked flask equipped with a stirrer, a reflux cooler with a water separator, and a thermometer. 40.9 parts of methanol, 13.2 parts of 2-hydroxyethyl acrylate, and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added, and a dehydration condensation reaction was carried out at 230 ° C. for 12 hours. A polyester compound N having a (meth) acroyl group number of 2 was obtained with a rosin content of 0%. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 4300.

[Inert resin A]
In a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 100 parts of toluene was charged, the temperature was raised to 80 ° C. under a nitrogen stream, and 100 parts of styrene and 3 parts of benzoyl peroxide were dissolved in advance. The dissolved solution was added dropwise over 3 hours. Benzoyl peroxide 0. After adding 5 parts and continuing the reaction for another 2 hours, the solvent was removed and pumped out. An inert resin A having a styrene content of 100% was obtained. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 9500.

Inactive resins B to K were obtained in the same manner as inactive resin A except that the raw materials and amounts shown in Table 1 were used.

[Rogin Crocodile A]
In a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 29.9 parts of Miramar M3130 and 0.1 parts of hydroquinone were charged, and the temperature was raised to 110 ° C. in the atmosphere. 70.0 parts of the modified polyester compound A was gradually added and dissolved to obtain rosin varnish A.

Rosin varnishes B to M and varnish N were obtained in the same manner as for rosin varnish A except that the raw materials and amounts shown in Table 2 were used.

[Method for producing ink composition 1 having active energy ray curability]
As a colorant, 20.0 parts of LIONOL BLUE FG-7400-G, 1.0 part of azisper PB821, 26.9 parts of Aronix M-315 as a (meth) acrylate compound, 35.0 parts of rosin varnish A, Add 10.0 parts of inert resin A, 2.5 parts of Omnirad379EG, 2.5 parts of Chemrk DEABP, 2.0 parts of KAYACURE DETX-S, and 0.1 part of hydroquinone as a polymerization initiator, and fly. The ink composition 1 was prepared by stirring and mixing using a mixer and dispersing in three rolls so that the maximum particle size was 15 μm or less to have a biomass degree of 11.8%.

[Method for producing ink compositions 2-33 having active energy ray curability]
Ink compositions 2-33 were obtained in the same manner as ink composition 1 except that the raw materials and amounts shown in Tables 3 to 7 were changed. Unless otherwise specified, the numerical values represent "parts by mass", and the blanks indicate that they are not blended.

The abbreviations in Tables 3 to 7 are as follows.
[Pigment]
-LIONOL BLUE FG-7400-G: manufactured by Toyo Color Co., Ltd., C.I. I. Pigment Blue 15: 3
[Dispersant]
Azisper PB821: A comb-shaped dispersant containing a basic functional group, manufactured by Ajinomoto Fine-Techno Co., Ltd. [(meth) acrylate compound]
-Aronix M-315: Toa Synthetic Co., Ltd., Tris (2-hydroxyethyl) isocyanurate triacrylate-Evecryl 1142: Dicell Orcnex Co., Ltd., Ditrimethylolpropane Tetraacrylate Miramar M220: Toyo Chemicals Co., Ltd. Propropylene Glycol Diacrylate Miramar M3130: Toyo Chemicals Co., Ltd., Trimethylolpropane EO Modified Triacrylate Miramar M340: Toyo Chemicals Co., Ltd., Pentaerythritol Triacrylate Miramar M600: Toyo Chemicals Co., Ltd., Dipentaerythritol Hexaacrylate [Polymerization initiator]
Omnirad379EG: iGM RESINS, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl-1-butanone, Chemark DEABP: Sort, 4, , 4'-bis (diethylamino) benzophenone, KAYACURE DETX-S: manufactured by Nippon Kayaku Co., Ltd., 2,3-diethylthioxanthone
[Polymerization inhibitor]
・ Hydroquinone: Made by Ube Industries, Ltd., Hydroquinone

The obtained ink composition was evaluated by the following method. Examples 1 to 32 and Comparative Examples 1 to 9 are shown in Table 8.

[How to create a test sample]
Using an RI tester (manufactured by Tester Sangyo Co., Ltd.), the obtained ink composition was used as a base material, Denka styrene sheet (manufactured by Denka Co., Ltd.), PET sheet (manufactured by Mineron Kasei Kogyo Co., Ltd.), and PP filler sheet (manufactured by Mineron Kasei Kogyo Co., Ltd.) A solid image was printed on Zeon Kasei Co., Ltd.) with a filling amount of 0.25 ml. Then, the ink composition was cured with a conveyor speed of 60 m / min, an LED lamp (“XP-9” manufactured by Air Motion System Co., Ltd., an irradiation distance of 10 mm, and an output of 70%) to prepare a test sample. The RI tester is a testing machine that prints ink on paper or film, and can adjust the amount of ink transfer and the printing pressure.

[Adhesion]
Adhesive tape (cellotape manufactured by Nichiban Co., Ltd. (registered trademark) 18 mm width) is attached to the print layer of the test sample prepared by the above method, peeled vertically, and the adhesion to the base material is determined from the ratio of the peeled area of the ink film. evaluated. A level of 3 or higher is evaluated as having no problem in practical use.
5: No ink film peeling 4: Ink film peeling is less than 10% 3: Ink film peeling is 10% or more and less than 30% 2: Ink film peeling is 30% or more and less than 70% 1: Ink film Is peeled off by 70% or more

[Pencil hardness]
The pencil hardness of the coating film of the test sample prepared by the above method was measured according to "JIS K 5600-5-4 (1 999 9)". A level of 3 or higher is evaluated as having no problem in practical use.
5: Pencil hardness is 2H or more 4: Pencil hardness is H or more 3: Pencil hardness is B or more 2: Pencil hardness is 2B or more 1: Pencil hardness is 3B or less

[chemical resistance]
The coating film of the test sample prepared by the above method was rubbed 100 times with a cotton swab soaked in 99.5% ethanol, and the number of times the substrate was exposed was evaluated. A level of 3 or higher is evaluated as having no problem in practical use.
5: 100 times or more 4:75 times or more 3:50 times or more 2:25 times or more 1:24 times or less

As shown in Table 8, an active energy ray-curable ink containing a colorant, a polymerization initiator, a rosin-modified polyester compound, and a (meth) acrylate compound (except when it is a rosin-modified polyester compound). Example 1 is an active energy ray-curable ink characterized in that the proportion of structural units derived from rosin in the rosin-modified polyester compound is 40 to 80% by mass with respect to all the structural units constituting the rosin-modified polyester compound. ~ 32 were all good in adhesion, pencil hardness, and chemical resistance without any problem in practical use.
Comparative Examples 1 to 3 and Comparative Examples 7 to 9 in which the ratio of the rosin-derived structural units was 40% by mass or less with respect to all the structural units constituting the rosin-modified polyester compound had poor adhesion, and the rosin-derived structure was obtained. Comparative Examples 4 to 6 in which the ratio of the units was 80% by mass or more with respect to all the structural units constituting the rosin-modified polyester compound were poor in pencil hardness and chemical resistance.

Claims (11)

An active energy ray-curable ink composition comprising a colorant, a polymerization initiator, a rosin-modified polyester compound, and a (meth) acrylate compound (except when it is a rosin-modified polyester compound).
An active energy ray-curable ink composition, wherein the proportion of structural units derived from rosin in the rosin-modified polyester compound is 40 to 80% by mass with respect to all the structural units constituting the rosin-modified polyester compound. The active energy ray-curable ink composition according to claim 1, wherein the content of the rosin-modified polyester compound is 5 to 30% by mass with respect to the total mass of the active energy ray-curable ink composition. Stuff. The active energy ray-curable ink composition according to claim 1 or 2, wherein the rosin-modified polyester compound has a weight average molecular weight of 1,000 to 10,000. The active energy ray-curable ink composition according to any one of claims 1 to 3, wherein the rosin-modified polyester compound is a compound having 2 to 5 (meth) acroyl groups. The active energy ray-curable ink composition according to any one of claims 1 to 4, further comprising an inert resin. The active energy ray-curable ink composition according to claim 5, wherein the content of the inert resin is 1 to 15% by mass with respect to the total mass of the active energy ray-curable ink composition. Stuff. The inert resin contains a structural unit derived from styrene and contains.
The active energy ray-curable type according to claim 5 or 6, wherein the ratio of the structural units derived from styrene in the inert resin is 50% by mass or more with respect to all the structural units constituting the inert resin. Ink composition. The active energy ray-curable ink composition according to claim 7, wherein the inert resin is a polystyrene resin or a styrene (meth) acrylic resin. The active energy ray-curable ink composition according to any one of claims 1 to 8, wherein the (meth) acrylate compound contains a (meth) acrylate compound having a heterocyclic structure. The active energy ray-curable ink composition according to any one of claims 1 to 9, wherein the plant component-derived component ratio (biomass ratio) of the active energy ray-curable ink composition is 10% by mass or more. A printed matter obtained by printing the active energy ray-curable ink composition according to any one of claims 1 to 10 on a substrate and curing the active energy ray-curable ink composition.