JP7815865B2 - Rosin-modified resin, active energy ray-curable resin composition, cured product, and laminate - Google Patents

Description

This disclosure relates to rosin-modified resins, active energy ray-curable resin compositions, cured products, and laminates.

Resin compositions that cure with active energy rays such as ultraviolet rays or electron beams (hereinafter referred to as active energy ray-curable resin compositions) contain reactive diluents, resins, photopolymerization initiators, and additives, and are used in a variety of fields as energy-saving industrial materials, including coatings, paints, and printing inks.

In particular, for actinic radiation-curable printing inks, polyfunctional acrylates such as dipentaerythritol hexaacrylate and ditrimethylolpropane tetraacrylate are widely used as reactive diluents due to their excellent curability and film hardness. Diallyl phthalate resins are widely used as binder resins due to their excellent compatibility with polyfunctional acrylates and curability (see paragraph [0009] of Patent Document 1).

Patent No. 5683757

However, diallyl phthalate resin is produced by polymerizing diallyl phthalate monomer, and while it contains polymerizable double bonds, it lacks polar functional groups such as hydroxyl groups or carboxyl groups, limiting its applications. Furthermore, unreacted diallyl phthalate monomer remaining in the resin is a substance of high concern due to its mutagenic potential (see paragraph [0009] of the above-mentioned Patent Document 1). Furthermore, demand for resins made primarily from biomass raw materials has been increasing in recent years.

The problem that this invention aims to solve is to provide a rosin-modified resin that can impart good fluidity, emulsification resistance, and misting resistance.

After extensive research, the inventors discovered that the above problems could be solved by using a rosin-modified resin with a specific composition.

The present disclosure provides the following:
(Item 1)
a structural unit derived from α,β-unsaturated carboxylic acid-modified rosin,
A rosin-modified resin is a reaction product of a resin containing structural units derived from a polyol and structural units derived from a polybasic acid and/or its anhydride with a disproportionated rosin.
(Item 2)
The rosin-modified resin according to the preceding item, which contains structural units derived from hydrogenated rosin.
(Item 3)
An active energy ray-curable resin composition comprising the rosin-modified resin according to any one of the preceding items and poly(meth)acrylate.
(Item 4)
The active energy ray-curable resin composition according to the above item, which is for use in offset ink.
(Item 5)
A cured product of the active energy ray-curable resin composition according to any one of the above items.
(Item 6)
A laminate comprising the cured product described in the above item.

In the present disclosure, one or more of the features described above may be provided in combinations other than those explicitly stated.

The rosin-modified resin of this embodiment can impart good fluidity, emulsification resistance, and misting resistance.

Throughout this disclosure, the range of values for each physical property, content, etc. may be set as appropriate (for example, by selecting from the upper and lower limit values described for each item below). Specifically, when A4, A3, A2, A1 (where A4 > A3 > A2 > A1) are given as examples of the upper and lower limits of the value α, examples of the range of the value α include A4 or less, A3 or less, A2 or less, A1 or more, A2 or more, A3 or more, A1 to A2, A1 to A3, A1 to A4, A2 to A3, A2 to A4, A3 to A4, etc.

[Rosin-modified resin]
The present disclosure provides a structural unit derived from an α,β-unsaturated carboxylic acid-modified rosin,
Provided is a rosin-modified resin, which is a reaction product of a resin (also called an unmodified resin) containing structural units derived from a polyol and structural units derived from a polybasic acid and/or its anhydride, with a disproportionated rosin.

<α,β-unsaturated carboxylic acid modified rosin>
The α,β-unsaturated carboxylic acid modified rosins may be used alone or in combination of two or more.

In this disclosure, α,β-unsaturated carboxylic acid modified rosin means rosin that has been subjected to a cycloaddition reaction.

(rosin)
Rosin is an amber-colored, amorphous resin obtained from pine trees. Rosin is obtained as a mixture.

Examples of rosin-producing pine species include Pinus massoniana, Slash pine (Pinus elliottii), Merkusii pine (Pinus merkusii), Caribbean pine (Pinus caribaea), Loblolly pine (Pinus kesiya), Loblolly pine (Pinus taeda), and Great King pine (Pinus palustris).

Examples of rosin include natural rosin and refined rosin. Natural rosin and refined rosin are collectively referred to as unmodified rosin.

(natural rosin)
Examples of natural rosins include gum rosin, tall oil rosin, and wood rosin.

Natural rosin is produced in countries such as China, Vietnam, Indonesia, and Brazil.

(Refined rosin)
Purified rosin can be obtained by various known purification methods, such as distillation, extraction, recrystallization, and adsorption.

An example of a distillation method is to distill the natural rosin at a temperature of 200 to 300°C under a reduced pressure of 0.01 to 3 kPa.

Examples of extraction methods include dissolving the natural rosin in an alkaline aqueous solution, extracting the insoluble unsaponifiable matter with various organic solvents, and then neutralizing the aqueous layer.

An example of a recrystallization method is to dissolve the natural rosin in an organic solvent as a good solvent, then evaporate the solvent to obtain a concentrated solution, and then add an organic solvent as a poor solvent.

Examples of good solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, chlorinated hydrocarbon solvents such as chloroform, lower alcohols, ketones such as acetone, and acetate esters such as ethyl acetate.

Examples of poor solvents include n-hexane, n-heptane, cyclohexane, and isooctane.

Examples of adsorption methods include contacting molten unmodified rosin or unmodified rosin in solution in an organic solvent with a porous adsorbent.

Examples of porous adsorbents include activated carbon, metal oxides, alumina, zirconia, silica, molecular sieves, zeolites, and microporous clays.

Rosin can be isolated into its constituent components, known as diterpene resin acids. In this disclosure, each diterpene resin acid isolated from rosin is also defined as rosin.

Examples of diterpene resin acids include abietane diterpene resin acids, pimarane diterpene resin acids, dehydro diterpene resin acids, and labdane diterpene resin acids.

Examples of abietane-type diterpene resin acids include abietic acid, neoabietic acid, paraslitric acid, and lepopimaric acid.

Examples of pimarane-type diterpene resin acids include pimaric acid, isopimaric acid, and sandaracopimaric acid.

Examples of dehydro diterpene resin acids include dehydroabietic acid.

Examples of labdane-type diterpene resin acids include communic acid and dihydroagatic acid.

(α,β-unsaturated carboxylic acid or its anhydride)
Examples of α,β-unsaturated carboxylic acids or anhydrides thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, muconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, muconic anhydride, maleic acid half ester, fumaric acid half ester, itaconic acid half ester, 3,4,5,6-tetrahydrophthalic anhydride, etc. Among these, maleic acid, maleic anhydride, and fumaric acid are preferred.

From the standpoint of emulsifying properties, the amount of α,β-unsaturated carboxylic acid used is preferably 0.5 to 100 parts by mass, and more preferably 0 to 60 parts by mass, per 100 parts by mass of rosin.

The above-mentioned α,β-unsaturated carboxylic acid-modified rosin can be produced by adding an α,β-unsaturated carboxylic acid to rosin melted under heating, and reacting the mixture at a temperature of 160 to 240°C for 1 to 9 hours. The above-mentioned reaction may also be carried out while blowing an inert gas such as nitrogen into a sealed reaction system.

In the cycloaddition reaction, known catalysts such as Lewis acids such as zinc chloride, iron chloride, and tin chloride, and Bronsted acids such as paratoluenesulfonic acid and methanesulfonic acid may be used.

The amount of cycloaddition reaction catalyst used is preferably 0 to 10% by mass relative to the rosin.

The resulting α,β-unsaturated carboxylic acid-modified rosin may contain resin acids derived from unmodified rosin, and the content thereof is preferably less than 25% by mass.

In one embodiment, the α,β-unsaturated carboxylic acid-modified rosin is preferably maleated rosin.

Examples of upper and lower limits for the content of structural units derived from α,β-unsaturated carboxylic acid-modified rosin in 100% by mass of rosin-modified resin include 46, 45, 44, 42, 41, 40, 35, 33, 31, 30, 29, 27, 25, 20, 15, 10, 9, 5, 4, 2, and 1% by mass. In one embodiment, the content is preferably 1 to 46% by mass.

Examples of upper and lower limits for the content of structural units derived from α,β-unsaturated carboxylic acid-modified rosin in 100 mol% of rosin-modified resin include 44, 40, 40, 35, 30, 25, 20, 15, 10, 9, 5, 4, 2, 1, and 0.9 mol%. In one embodiment, the content is preferably 0.9 to 44 mol%.

<Polyol>
In the present disclosure, polyol refers to a compound having two or more hydroxyl groups. The polyols may be used alone or in combination of two or more.

Examples of polyols include diols, triols, and tetraols.

Examples of diols include aliphatic diols, alicyclic diols, and polyalkylene diols.

Examples of aliphatic diols include ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 2-methylpropanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, neopentyl glycol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, methyloctanediol, 1,9-nonanediol, and 1,10-decanediol.

Examples of alicyclic diols include 1,2-cyclopentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptanediol, adamantanediol, and tricyclodecanediol.

Examples of polyalkylene diols include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol.

Examples of triols include glycerin, trimethylolethane, trimethylolpropane, and adamantanetriol.

Examples of tetraols include pentaerythritol, diglycerin, ditrimethylolethane, and ditrimethylolpropane.

Examples of polyols other than those mentioned above include sorbitol, dipentaerythritol, and tripentaerythritol.

Examples of upper and lower limits for the content of structural units derived from polyol in 100% by mass of the rosin-modified resin include 44, 40, 40, 35, 30, 29, 28, 27, 25, 24, 23, 21, 20, 17, 15, 14, 13, 12, 10, 9, 5, 4, 2, and 1% by mass. In one embodiment, the content is preferably 1 to 44% by mass.

Examples of upper and lower limits for the content of structural units derived from polyols in 100 mol% of the rosin-modified resin include 55, 50, 45, 40, 40, 35, 30, 25, 20, 15, 14, 13, 12, 10, 9, 5, 4, 3, and 2.5 mol%. In one embodiment, the content is preferably 2.5 to 55 mol%.

<Polybasic Acid and/or Anhydride Thereof>
The polybasic acids and/or anhydrides thereof may be used alone or in combination of two or more.

Examples of polybasic acids include aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, and aromatic polycarboxylic acids.

Examples of aliphatic polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, and fumaric acid.

Examples of alicyclic polycarboxylic acids include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 4-methylhexahydrophthalic acid, hexahydrophthalic acid, 3,4,5,6-tetrahydrophthalic anhydride, and 1,2,3,6-tetrahydrophthalic anhydride.

Examples of aromatic polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 2,3-naphthalenedicarboxylic acid, and 2,4-naphthalenedicarboxylic acid.

Examples of polybasic acid anhydrides include the anhydrides of the polybasic acids listed above.

The upper and lower limits of the content of structural units derived from polybasic acids and/or their anhydrides in 100% by mass of the rosin-modified resin are, for example, 42, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 5, 4, 2, and 1% by mass. In one embodiment, the content is preferably 1 to 42% by mass.

The upper and lower limits of the content of structural units derived from polybasic acids and/or their anhydrides in 100 mol% of the rosin-modified resin are, for example, 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 5, 4, 2, and 1 mol%. In one embodiment, the content is preferably 1 to 50 mol%.

<Disproportionated rosin>
The disproportionated rosins may be used alone or in combination of two or more.

In this disclosure, disproportionated rosin refers to rosin that has been subjected to a disproportionation reaction. Disproportionation is a modification in which two molecules of rosin react to convert two molecules of abietic acid with conjugated double bonds into one aromatic molecule and the other a molecule with a single double bond.

The above-mentioned disproportionated rosin can be obtained by a method (disproportionation) in which rosin is heated in the presence of a disproportionation catalyst.

Examples of disproportionation catalysts include supported catalysts such as palladium-carbon, rhodium-carbon, and platinum-carbon; metal powders such as nickel and platinum; and various known iodides such as iodine and iron iodide.

The amount of disproportionation catalyst used is preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of rosin.

The reaction temperature for the disproportionation reaction is preferably 100 to 300°C, more preferably 150 to 290°C.

Disproportionated rosin can also be produced by a method in which the disproportionation reaction is followed by the above-mentioned purification.

Examples of upper and lower limits for the content of structural units derived from disproportionated rosin in 100% by mass of rosin-modified resin include 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 7, and 5% by mass. In one embodiment, the content is preferably 5 to 90% by mass.

Examples of upper and lower limits for the content of structural units derived from disproportionated rosin in 100 mol% of rosin-modified resin include 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, and 5 mol%. In one embodiment, the content is preferably 5 to 80 mol%.

The upper and lower limits of the mass ratio of structural units derived from disproportionated rosin to structural units derived from α,β-unsaturated carboxylic acid-modified rosin in the rosin-modified resin (mass of structural units derived from disproportionated rosin/mass of structural units derived from α,β-unsaturated carboxylic acid-modified rosin) are 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3.6, 3.51, 3.5, 2, 1.6, 1.5, 1, 0.9, 0.81, 0.8, 0.79, 0.5, 0.4, 0.3, and 0.22 are examples. In one embodiment, the mass ratio is preferably 0.22 to 90.

<Monobasic acid>
The rosin-modified resin may optionally contain structural units derived from a monobasic acid. The monobasic acids may be used alone or in combination of two or more.

Examples of monobasic acids include hydrogenated rosin, aromatic monobasic acids, saturated aliphatic monobasic acids, and unsaturated aliphatic monobasic acids.

In this disclosure, "hydrogenated rosin" means rosin that has been subjected to a hydrogenation reaction.

The hydrogen pressure is preferably 2 MPa to 20 MPa, and more preferably 5 MPa to 20 MPa.

The hydrogenation reaction temperature is preferably 100°C to 300°C, and more preferably 150°C to 300°C.

Examples of hydrogenation catalysts include supported catalysts and metal powders.

Examples of supported catalysts include palladium-carbon, rhodium-carbon, ruthenium-carbon, and platinum-carbon.

Examples of metal powders include nickel and platinum. In one embodiment, from the viewpoint of increasing the hydrogenation rate of the unmodified rosin and shortening the hydrogenation time, the hydrogenation catalyst is preferably a palladium, rhodium, ruthenium, or platinum-based catalyst.

Based on 100 parts by mass of rosin, the amount of hydrogenation catalyst used is preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 2 parts by mass.

If necessary, the above hydrogenation can be carried out with the rosin dissolved in a solvent. The solvent used in the hydrogenation reaction (hydrogenation reaction solvent) may be any solvent that is inert to the reaction and easily dissolves the raw materials and products. Examples of hydrogenation reaction solvents include cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, and dioxane. Hydrogenation reaction solvents can be used alone or in combination of two or more.

Based on the non-volatile content of the rosin, the amount of hydrogenation reaction solvent used is preferably 10% by mass or more, and more preferably 10% to 70% by mass.

Examples of aromatic monobasic acids include benzoic acid, methylbenzoic acid, tert-butylbenzoic acid, naphthoic acid, and orthobenzoylbenzoic acid.

Examples of saturated aliphatic monobasic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid, and behenic acid.

Examples of unsaturated aliphatic monobasic acids include crotonic acid, linderic acid, tsuzuic acid, myristoleic acid, palmitoleic acid, undecylenic acid, oleic acid, elaidic acid, gadoleic acid, gondolenic acid, cetoleic acid, erucic acid, brassidic acid, linoelaidic acid, linolenic acid, and arachidonic acid.

Examples of upper and lower limits for the content of structural units derived from monobasic acids in 100% by mass of the rosin-modified resin include 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 5, 4, 2, 1, and 0% by mass. In one embodiment, the content is preferably 0 to 50%, and more preferably 5 to 30% by mass.

Examples of upper and lower limits for the content of structural units derived from monobasic acids in 100 mol% of the rosin-modified resin include 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 5, 4, 2, 1, and 0 mol%. In one embodiment, the content is preferably 0 to 50 mol%, and more preferably 5 to 30 mol%.

<Constituent units other than those listed above: Also called other constituent units>
The rosin-modified resin may contain structural units that do not fall into any of the following categories: structural units derived from an α,β-unsaturated carboxylic acid-modified rosin, structural units derived from a polyol, structural units derived from a polybasic acid and/or anhydride thereof, structural units derived from a disproportionated rosin, and structural units derived from a monobasic acid.

Other structural units include structural units derived from polymerized rosin and structural units derived from alcohols (monools).

In one embodiment, the content of the other structural units is, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, or 0 part by mass, per 100 parts by mass of the rosin-modified resin. Furthermore, the content of the other structural units is, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, or 0 part by mass, per 100 parts by mass of any of the structural units derived from α,β-unsaturated carboxylic acid-modified rosin, structural units derived from polyol, structural units derived from polybasic acids and/or anhydrides thereof, structural units derived from disproportionated rosin, and structural units derived from monobasic acids.

<Physical properties of rosin-modified resin>
The upper and lower limits of the acid value of the rosin-modified resin are exemplified as 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 5, 4, 2, 1, 0.9, 0.5, 0.1 mgKOH/g, etc. In one embodiment, the acid value is preferably 0.1 to 50 mgKOH/g.

Acid value is measured using a method conforming to JIS K5601.

The upper and lower limits of the hydroxyl value of the rosin-modified resin are 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 5, 4, 2, 1, 0.9, 0.5, and 0.1 mgKOH/g. In one embodiment, the hydroxyl value is preferably 0.1 to 150 mgKOH/g.

Hydroxyl value is measured using a method in accordance with JIS K0070.

The upper and lower limits of the weight average molecular weight (Mw) of the above rosin-modified resin are 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 35,000, 34,000, 33,000, 32,000, 31,000, 30,000, 29,000, 2 Examples include 8,000, 27,000, 26,000, 25,000, 24,000, 23,000, 22,000, 21,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, and 1,000. In one embodiment, the weight average molecular weight (Mw) is preferably 1,000 to 100,000, and more preferably 5,000 to 32,000.

Examples of upper and lower limits for the number average molecular weight (Mn) of the rosin-modified resin include 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,750, 1,500, 1,450, 1,400, 1,300, 1,200, 1,100, 1,050, 1,000, 900, 700, and 500. In one embodiment, the number average molecular weight (Mn) is preferably 500 to 10,000, and more preferably 1,000 to 1,500.

The upper and lower limits of the molecular weight distribution (Mw/Mn) of the rosin-modified resin are exemplified as 60, 55, 50, 45, 40, 35, 30, 25, 24, 23, 22, 21, 20, 15, 10, 9, 8, 7, 6, 5, 4, 2, and 1. In one embodiment, the molecular weight distribution (Mw/Mn) is preferably 1 to 60, and more preferably 5 to 25.

The weight-average molecular weight and number-average molecular weight can be determined as polystyrene equivalent values measured in an appropriate solvent by, for example, gel permeation chromatography (GPC). Detailed conditions are exemplified as follows.
Model: Product name "HLC-8320" (manufactured by Tosoh Corporation)
Column: Product name "TSK-GEL" (manufactured by Tosoh Corporation)
Developing solvent, flow rate: tetrahydrofuran, 1.0 mL/min Standard: monodisperse polystyrene Measurement temperature: 40°C
Detector: RI
Polymer concentration: 0.2%

The upper and lower limits of the softening point of the rosin-modified resin are 150, 145, 140, 135, 130, 125, 120, 119, 117, 115, 114, 113, 112, 111, 110, 109, 108, 107, 106, 105, 104, 100, 95, 90, 85, and 80°C. In one embodiment, the softening point is preferably 80 to 150°C, and more preferably 100 to 120°C.

The softening point is measured using a method conforming to JIS K5601.

The rosin-modified resin is
an unmodified resin production step in which an α,β-unsaturated carboxylic acid-modified rosin, a polyol, a polybasic acid and/or an anhydride thereof are reacted to obtain an unmodified resin;
The rosin-modified resin is produced by a production method including a rosin-modified resin production step in which an unmodified resin is reacted with a disproportionated rosin to obtain the rosin-modified resin. In the production method, the order of addition of the components is not particularly limited. Furthermore, various known devices (such as an ultrasonic dispersion device) can be used as a dispersion and mixing means.

The above rosin-modified resin can be used as a rosin-modified resin for offset inks.

[Active energy ray-curable resin composition: also referred to as composition]
The present disclosure provides an active energy ray-curable resin composition containing the rosin-modified resin and poly(meth)acrylate.

Examples of upper and lower limits for the rosin-modified resin content per 100% by mass of the composition solids include 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, and 5% by mass. In one embodiment, the content is preferably 5 to 80% by mass.

<Poly(meth)acrylate>
In the present disclosure, poly(meth)acrylate refers to a compound having two or more (meth)acryloyl groups. The poly(meth)acrylates may be used alone or in combination of two or more.

Examples of poly(meth)acrylates include (poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, isocyanurate structure-containing poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate, (poly)alkylene di(alkylene oxide-modified or epoxy-modified) (meth)acrylate, and bisphenol A di(alkylene oxide-modified or epoxy-modified) (meth)acrylate.

<(Poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate>
The (poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (A') or the like.
[In the formula, n is an integer of 0 to 2, and R ^b1′ to R ^{b6 ′} each independently represent a hydrogen atom,
{In the formula, each q is independently an integer of 0 to 16, R ^1′ to R ^3′ are independently a hydrogen atom or an alkyl group, and R ^1′ may be a different group in each unit.}
and
R ^b4' and R ^b5' may be different groups in each structural unit,
In formula (A ^' ),
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^{3 ′} are each independently a hydrogen atom or an alkyl group, and R ^1′ may be a different group in each unit.}
Contains two or more.

In the present disclosure, the phrase "the groups may be different for each structural unit" means, for example, when n is 2 in formula (A'),
This means that R ^b4A and R ^b4B may be different groups, and R ^b5A and R ^b5B may be different groups.

In this disclosure, "(poly)pentaerythritol poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of pentaerythritol poly(meth)acrylate, pentaerythritol polyalkylene oxide-modified (meth)acrylate, pentaerythritol polyepoxy-modified (meth)acrylate, polypentaerythritol poly(meth)acrylate, polypentaerythritol polyalkylene oxide-modified (meth)acrylate, and polypentaerythritol polyepoxy-modified (meth)acrylate."

Examples of pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

Examples of pentaerythritol polyalkylene oxide-modified (meth)acrylates include pentaerythritol di(ethylene oxide-modified (meth)acrylate), pentaerythritol tri(ethylene oxide-modified (meth)acrylate), pentaerythritol tetra(ethylene oxide-modified (meth)acrylate), pentaerythritol di(propylene oxide-modified (meth)acrylate), pentaerythritol tri(propylene oxide-modified (meth)acrylate), and pentaerythritol tetra(propylene oxide-modified (meth)acrylate).

Examples of pentaerythritol polyepoxy-modified (meth)acrylates include pentaerythritol diepoxy (meth)acrylate, pentaerythritol triepoxy (meth)acrylate, and pentaerythritol tetraepoxy (meth)acrylate.

Examples of polypentaerythritol poly(meth)acrylate include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and tripentaerythritol octa(meth)acrylate.

Polypentaerythritol polyalkylene oxide-modified (meth)acrylates include dipentaerythritol di(ethylene oxide-modified (meth)acrylate), dipentaerythritol tri(ethylene oxide-modified (meth)acrylate), dipentaerythritol tetra(ethylene oxide-modified (meth)acrylate), dipentaerythritol penta(ethylene oxide-modified (meth)acrylate), dipentaerythritol hexa(ethylene oxide-modified (meth)acrylate), dipentaerythritol di(propylene Dipentaerythritol tri(propylene oxide modified (meth)acrylate), dipentaerythritol tetra(propylene oxide modified (meth)acrylate), dipentaerythritol penta(propylene oxide modified (meth)acrylate), dipentaerythritol hexa(propylene oxide modified (meth)acrylate), tripentaerythritol di(ethylene oxide modified (meth)acrylate), tripentaerythritol tri(ethylene oxide modified (meth)acrylate acrylate), tripentaerythritol tetra(ethylene oxide modified (meth)acrylate), tripentaerythritol penta(ethylene oxide modified (meth)acrylate), tripentaerythritol hexa(ethylene oxide modified (meth)acrylate), tripentaerythritol hepta(ethylene oxide modified (meth)acrylate), tripentaerythritol octa(ethylene oxide modified (meth)acrylate), tripentaerythritol di(propylene oxide modified (meth)acrylate), tripe Examples include tripentaerythritol tri(propylene oxide-modified (meth)acrylate), tripentaerythritol tetra(propylene oxide-modified (meth)acrylate), tripentaerythritol penta(propylene oxide-modified (meth)acrylate), tripentaerythritol hexa(propylene oxide-modified (meth)acrylate), tripentaerythritol hepta(propylene oxide-modified (meth)acrylate), and tripentaerythritol octa(propylene oxide-modified (meth)acrylate).

Examples of polypentaerythritol polyepoxy-modified (meth)acrylates include dipentaerythritol diepoxy (meth)acrylate, dipentaerythritol triepoxy (meth)acrylate, dipentaerythritol tetraepoxy (meth)acrylate, dipentaerythritol pentaepoxy (meth)acrylate, dipentaerythritol hexaepoxy (meth)acrylate, tripentaerythritol diepoxy (meth)acrylate, tripentaerythritol triepoxy (meth)acrylate, tripentaerythritol tetraepoxy (meth)acrylate, tripentaerythritol pentaepoxy (meth)acrylate, tripentaerythritol hexaepoxy (meth)acrylate, tripentaerythritol heptaepoxy (meth)acrylate, and tripentaerythritol octaepoxy (meth)acrylate.

<(Poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate>
(Poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (B') or the like.
[In the formula, m is an integer of 0 to 2, and R ^b7' to R ^b10' each independently represent a hydrogen atom,
{In the formula, each q is independently an integer of 0 to 16, R ^1′ to R ^3′ are independently a hydrogen atom or an alkyl group, and R ^1′ may be a different group in each unit.}
and
R ^b9′ may be a different group for each structural unit,
In formula (B ^' ),
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^{3 ′} are each independently a hydrogen atom or an alkyl group, and R ^1′ may be a different group in each unit.}
Contains two or more.

In this disclosure, "(poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of trimethylolpropane poly(meth)acrylate, trimethylolpropane polyalkylene oxide-modified (meth)acrylate, trimethylolpropane polyepoxy-modified (meth)acrylate, polytrimethylolpropane poly(meth)acrylate, polytrimethylolpropane polyalkylene oxide-modified (meth)acrylate, and polytrimethylolpropane polyepoxy-modified (meth)acrylate."

Examples of trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate and trimethylolpropane tri(meth)acrylate.

Examples of trimethylolpropane polyalkylene oxide-modified (meth)acrylates include trimethylolpropane di(ethylene oxide-modified (meth)acrylate), trimethylolpropane tri(ethylene oxide-modified (meth)acrylate), trimethylolpropane di(propylene oxide-modified (meth)acrylate), and trimethylolpropane tri(propylene oxide-modified (meth)acrylate).

Examples of trimethylolpropane polyepoxy-modified (meth)acrylates include trimethylolpropane diepoxy (meth)acrylate and trimethylolpropane triepoxy (meth)acrylate.

Examples of polytrimethylolpropane poly(meth)acrylate include ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate.

Examples of polytrimethylolpropane polyalkylene oxide-modified (meth)acrylates include ditrimethylolpropane di(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane tri(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane tetra(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane di(propylene oxide-modified (meth)acrylate), ditrimethylolpropane tri(propylene oxide-modified (meth)acrylate), and ditrimethylolpropane tetra(propylene oxide-modified (meth)acrylate).

Examples of polytrimethylolpropane polyepoxy-modified (meth)acrylates include ditrimethylolpropane diepoxy (meth)acrylate, ditrimethylolpropane triepoxy (meth)acrylate, and ditrimethylolpropane tetraepoxy (meth)acrylate.

<(Poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate>
The (poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (C') or the like.
[In the formula, p represents an integer of 0 to 7, and R ^b11′ to R ^{b14 ′} each independently represent a hydrogen atom,
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^3′ each independently represent a hydrogen atom or an alkyl group, and R ^1′ may be a different group in each unit.}
and
R ^b13′ may be a different group for each structural unit,
In formula (C ^' ),
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^{3 ′} are each independently a hydrogen atom or an alkyl group, and R ^1′ may be a different group in each unit.}
Contains two or more.

In this disclosure, "(poly)glycerin poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of glycerin poly(meth)acrylate, glycerin polyalkylene oxide-modified (meth)acrylate, glycerin polyepoxy-modified (meth)acrylate, polyglycerin poly(meth)acrylate, polyglycerin polyalkylene oxide-modified (meth)acrylate, and polyglycerin polyepoxy-modified (meth)acrylate."

Examples of glycerin poly(meth)acrylate include glycerin di(meth)acrylate and glycerin tri(meth)acrylate.

Examples of glycerin polyalkylene oxide-modified (meth)acrylates include glycerin di(ethylene oxide-modified (meth)acrylate), glycerin tri(ethylene oxide-modified (meth)acrylate), glycerin di(propylene oxide-modified (meth)acrylate), and glycerin tri(propylene oxide-modified (meth)acrylate).

Examples of glycerin polyepoxy-modified (meth)acrylates include glycerin diepoxy (meth)acrylate and glycerin triepoxy (meth)acrylate.

Examples of polyglycerin poly(meth)acrylates include diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, triglycerin di(meth)acrylate, triglycerin tri(meth)acrylate, triglycerin tetra(meth)acrylate, and triglycerin penta(meth)acrylate.

Polyglycerin polyalkylene oxide-modified (meth)acrylates include diglycerin di(ethylene oxide-modified (meth)acrylate), diglycerin tri(ethylene oxide-modified (meth)acrylate), diglycerin tetra(ethylene oxide-modified (meth)acrylate), triglycerin di(ethylene oxide-modified (meth)acrylate), triglycerin tri(ethylene oxide-modified (meth)acrylate), triglycerin tetra(ethylene oxide-modified (meth)acrylate), triglycerin penta(ethylene oxide-modified (meth)acrylate) Examples of the triglyceride include diglycerin di(propylene oxide-modified (meth)acrylate), diglycerin tri(propylene oxide-modified (meth)acrylate), diglycerin tetra(propylene oxide-modified (meth)acrylate), triglycerin di(propylene oxide-modified (meth)acrylate), triglycerin tri(propylene oxide-modified (meth)acrylate), triglycerin tetra(propylene oxide-modified (meth)acrylate), and triglycerin penta(propylene oxide-modified (meth)acrylate).

Examples of polyglycerin polyepoxy-modified (meth)acrylates include diglycerin diepoxy (meth)acrylate, diglycerin triepoxy (meth)acrylate, diglycerin tetraepoxy (meth)acrylate, triglycerin diepoxy (meth)acrylate, triglycerin triepoxy (meth)acrylate, triglycerin tetraepoxy (meth)acrylate, and triglycerin pentaepoxy (meth)acrylate.

<Isocyanurate Structure-Containing Poly(Alkylene Oxide-Modified or Epoxy-Modified) (Meth)acrylate>
The isocyanurate structure-containing poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (D') or the like.
wherein R ^b15′ to R ^{b17 ′} each independently represent a hydrogen atom,
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^3′ each independently represent a hydrogen atom or an alkyl group, and R ^1′ may be a different group in each unit.}
and in formula (D ^' ),
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^{3 ′} are each independently a hydrogen atom or an alkyl group, and R ^1′ may be a different group in each unit.}
Contains two or more.

In this disclosure, "isocyanurate structure-containing poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of isocyanurate structure-containing poly(meth)acrylate, isocyanurate structure-containing polyalkylene oxide-modified (meth)acrylate, and isocyanurate structure-containing polyepoxy-modified (meth)acrylate."

Examples of isocyanurate structure-containing poly(meth)acrylates include isocyanuric acid di(meth)acrylate and isocyanuric acid tri(meth)acrylate.

Examples of the isocyanurate structure-containing polyalkylene oxide-modified (meth)acrylate include isocyanuric acid di(ethylene oxide-modified (meth)acrylate) and isocyanuric acid tri(ethylene oxide-modified (meth)acrylate).

Examples of the isocyanurate structure-containing polyepoxy-modified (meth)acrylate include isocyanuric acid diepoxy-modified (meth)acrylate and isocyanuric acid triepoxy-modified (meth)acrylate.

<(Poly)alkylene di(alkylene oxide-modified or epoxy-modified) (meth)acrylate>
The (poly)alkylene di(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (E') or the like.
wherein R ^b18′ to R ^{b19 ′} are each independently
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^{3 ′} are each independently a hydrogen atom or an alkyl group, and R ^1′ may be a different group in each unit.}
and
R ^b20′ is an alkylene group, and r is an integer of 1 or more.

In this disclosure, "(poly)alkylene di(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of alkylene di(meth)acrylate, alkylene dialkylene oxide-modified (meth)acrylate, alkylene diepoxy-modified (meth)acrylate, polyalkylene di(meth)acrylate, polyalkylene dialkylene oxide-modified (meth)acrylate, and polyalkylene diepoxy-modified (meth)acrylate."

Examples of alkylene di(meth)acrylates include 1,2-ethylenediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

Alkylene dialkylene oxide-modified (meth)acrylates include 1,2-ethylenediol di(ethylene oxide-modified (meth)acrylate), 1,3-propanediol di(ethylene oxide-modified (meth)acrylate), 1,4-butanediol di(ethylene oxide-modified (meth)acrylate), 1,5-pentanediol di(ethylene oxide-modified (meth)acrylate), 1,6-hexanediol di(ethylene oxide-modified (meth)acrylate), 1,7-heptanediol di(ethylene oxide-modified (meth)acrylate), 1,8-octanediol di(ethylene oxide-modified (meth)acrylate), 1,9-nonanediol di(ethylene oxide-modified (meth)acrylate), 1,10-decanediol di(ethylene oxide-modified (meth)acrylate), neopentyl glycol di(ethylene oxide-modified (meth)acrylate), acrylate), 1,2-ethylenediol di(propylene oxide-modified (meth)acrylate), 1,3-propanediol di(propylene oxide-modified (meth)acrylate), 1,4-butanediol di(propylene oxide-modified (meth)acrylate), 1,5-pentanediol di(propylene oxide-modified (meth)acrylate), 1,6-hexanediol di(propylene oxide-modified (meth)acrylate), 1,7-heptanediol di(propylene oxide-modified (meth)acrylate), 1,8-octanediol di(propylene oxide-modified (meth)acrylate), 1,9-nonanediol di(propylene oxide-modified (meth)acrylate), 1,10-decanediol di(propylene oxide-modified (meth)acrylate), neopentyl glycol di(propylene oxide-modified (meth)acrylate), etc.

Examples of alkylene diepoxy-modified (meth)acrylates include 1,2-ethylenediol diepoxy (meth)acrylate, 1,3-propanediol diepoxy (meth)acrylate, 1,4-butanediol diepoxy (meth)acrylate, 1,5-pentanediol diepoxy (meth)acrylate, 1,6-hexanediol diepoxy (meth)acrylate, 1,7-heptanediol diepoxy (meth)acrylate, 1,8-octanediol diepoxy (meth)acrylate, 1,9-nonanediol diepoxy (meth)acrylate, 1,10-decanediol diepoxy (meth)acrylate, and neopentyl glycol diepoxy (meth)acrylate.

Examples of polyalkylene di(meth)acrylates include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate.

Examples of polyalkylene dialkylene oxide-modified (meth)acrylates include diethylene glycol di(ethylene oxide-modified (meth)acrylate), dipropylene glycol di(ethylene oxide-modified (meth)acrylate), triethylene glycol (ethylene oxide-modified (meth)acrylate), and tripropylene glycol (ethylene oxide-modified (meth)acrylate).

Examples of polyalkylene diepoxy-modified (meth)acrylates include diethylene glycol diepoxy (meth)acrylate, dipropylene glycol diepoxy (meth)acrylate, triethylene glycol diepoxy (meth)acrylate, and tripropylene glycol diepoxy (meth)acrylate.

<Bisphenol A di(alkylene oxide-modified or epoxy-modified) (meth)acrylate>
Bisphenol A di(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by formula (F') or the like.
[In the formula, R ^b21′ to R ^{b22 ′} are each independently
{In the formula, q is an integer of 0 to 16, R ^1′ to R ^{3 ′} are each independently a hydrogen atom or an alkyl group, and R ^1′ may be a different group in each unit.}
It is.]

In this disclosure, "bisphenol A di(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of bisphenol A di(meth)acrylate, bisphenol A dialkylene oxide-modified (meth)acrylate, and bisphenol A diepoxy-modified (meth)acrylate."

Examples of bisphenol A dialkylene oxide-modified (meth)acrylates include bisphenol A di(ethylene oxide-modified (meth)acrylate) and bisphenol A di(propylene oxide-modified (meth)acrylate).

Examples of upper and lower limits for the poly(meth)acrylate content based on 100% by mass of the solids content of the composition include 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, and 20% by mass. In one embodiment, the content is preferably 20 to 99% by mass.

<Photopolymerization initiator>
In one embodiment, the active energy ray-curable resin composition may contain a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more kinds.

The photopolymerization initiator is not particularly limited, and various known initiators can be used. Examples of photopolymerization initiators include benzophenone, o-benzoylbenzoic acid methyl ester, p-dimethylaminobenzoic acid ester, p-dimethylacetophenone, thioxanthone, alkylthioxanthone, and amines.

Commercially available photopolymerization initiators include Omnirad 1173, Omnirad 651, Omnirad 184, Omnirad 907, Omnirad 2959, Omnirad 127, Omnirad 369, Omnirad 369E, Omnirad 379, Omnirad 379EG, Omnirad TPO, and Omnirad 819 (all manufactured by IGM Resins).

Examples of upper and lower limits for the photopolymerization initiator content per 100% by mass of the composition solids include 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 2, 1, and 0% by mass. In one embodiment, the content is preferably 0 to 50% by mass.

If ionizing radiation other than ultraviolet light is used as the active energy ray, it is not necessary to add a photopolymerization initiator.

<Sensitizer>
In one embodiment, the active energy ray-curable resin composition may contain a sensitizer. The sensitizer may be used alone or in combination of two or more kinds.

Sensitizers include unsaturated ketones such as benzophenones, chalcones, and dibenzalacetone, 1,2-diketones such as benzil and camphorquinone, benzoins, fluorenes, naphthoquinones, anthraquinones, xanthenes, thioxanthenes, xanthones, thioxanthones, coumarins, ketocoumarins, cyanines, merocyanines, and polymethine dyes such as oxonols, acridines, azines, thiazines, oxazines, indolines, azulenes, and azulenite. Examples include ruthenium complexes, squarylium complexes, porphyrins, tetraphenylporphyrins, triarylmethanes, tetrabenzoporphyrins, tetrapyrazinoporphyrazines, phthalocyanines, tetraazaporphyrazines, tetraquinoxalylporphyrazines, naphthalocyanines, subphthalocyanines, pyrylium complexes, thiopyrylium complexes, tetraphyrins, annulenes, spiropyrans, spirooxazines, thiospiropyrans, metal arene complexes, and organic ruthenium complexes.

Specific examples of sensitizers include 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-dimethylaminobenzal)cyclohexanone, 2,6-bis(4-dimethylaminobenzal)-4-methylcyclohexanone, Michler's ketone, 4,4-bis(dimethylamino)chalcone, 4,4-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylvinylene)-isonaphthothiazole, 1,3-bis(4-dimethylaminobenzal)acetone, 1,3-carbonyl-bis(4-diethylaminobenzal)acetone, 3,3-carbonyl Examples include ruby-bis(7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine; p-dimethylaminobenzoic acid alkyl esters such as p-dimethylaminobenzoic acid methyl ester, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid butyl ester, p-dimethylaminobenzoic acid butoxyethyl ester, and p-dimethylaminobenzoic acid isoamyl ester; and p-diethylaminobenzoic acid alkyl esters such as p-diethylaminobenzoic acid methyl ester, p-diethylaminobenzoic acid ethyl ester, and p-diethylaminobenzoic acid isoamyl ester. Other examples include thioxanthones such as thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone, and benzophenones such as 4,4'-bis-(diethylamino)benzophenone.

Commercially available sensitizers include Omnirad EMK and Omnirad DETX (both manufactured by IGM Resins).

Examples of upper and lower limits for the sensitizer content per 100% by mass of the solids content of the composition include 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.5, and 0.1% by mass. In one embodiment, the content is preferably 0 to 50% by mass.

<Pigments>
In one embodiment, the active energy ray-curable resin composition may contain a pigment. The pigment may be used alone or in combination of two or more kinds.

Pigments include white pigments such as titanium oxide, zinc oxide, white lead, lithopone, and antimony oxide; black pigments such as aniline black, iron black, and carbon black; yellow pigments such as yellow lead, yellow iron oxide, titanium yellow, Hansa Yellow (10G, 5G, 3G, and others), disazo yellow, benzidine yellow, and permanent yellow; orange pigments such as chrome vermilion, permanent orange, Balkan fast orange, and indanthrene brilliant orange; brown pigments such as iron oxide, permanent brown, and para brown; red iron oxide, cadmium red, antimony vermilion, permanent red, rhodamine lake, alizarin lake, thioindigo red, PV carmine, monolight fast red, and quinacridone. Examples include red pigments such as phosphorus-based red pigments; purple pigments such as cobalt purple, manganese purple, fast violet, methyl violet lake, indanthrene brilliant violet, and dioxazine violet; blue pigments such as ultramarine, Prussian blue, cobalt blue, alkali blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, copper phthalocyanine blue, indanthrene blue, and indigo; green pigments such as chrome green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malachite green lake, phthalocyanine green, and polychlorobromo copper phthalocyanine; as well as various fluorescent pigments and metal powder pigments.

Examples of upper and lower limits for the pigment content based on 100% by mass of the composition solids include 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 2, 1, and 0% by mass. In one embodiment, the content is preferably 0 to 70% by mass.

<Gelling agent>
In one embodiment, the active energy ray-curable resin composition may contain a gelling agent. The gelling agents may be used alone or in combination of two or more.

Examples of gelling agents include aluminum-based gelling agents, titanium-based gelling agents, and zirconium-based gelling agents.

Examples of aluminum-based gelling agents include aluminum octylate, aluminum stearate, aluminum ethylate, aluminum isopropylate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetylacetate, aluminum dibutoxide monoacetylacetate, and aluminum triacetylacetate.

Examples of titanium-based gelling agents include tetraisopropyl titanate, tetraoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, and titanium lactate.

Examples of zirconium-based gelling agents include zirconium tetrabutoxide, zirconium acetylacetone, and ethyl acetoacetate zirconium butoxide.

Examples of upper and lower limits for the gelling agent content based on 100% by mass of the composition solids include 20, 15, 10, 5, 4, 2, 1, and 0% by mass. In one embodiment, the content is preferably 0 to 20% by mass.

<Polymerization inhibitor>
In one embodiment, the active energy ray-curable resin composition may contain a polymerization inhibitor. The polymerization inhibitor may be used alone or in combination of two or more kinds.

Examples of polymerization inhibitors include quinone-based polymerization inhibitors, monoalkylphenol-based polymerization inhibitors, amine-based polymerization inhibitors, and nitrosamine-based polymerization inhibitors.

Examples of quinone polymerization inhibitors include methoquinone, hydroquinone, methoxyhydroquinone, and benzoquinone.

Examples of monoalkylphenol polymerization inhibitors include 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2-t-butyl-4,6-dimethylphenol, and 2,4,6-tri-t-butylphenol.

Examples of amine-based polymerization inhibitors include alkylated diphenylamine, phenothiazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine.

Examples of nitrosamine polymerization inhibitors include N-nitrosophenylhydroxylamine ammonium salt, 2,4-dinitrophenol, and 2-methyl-N-nitrosoaniline.

Examples of upper and lower limits for the content of the polymerization inhibitor based on 100% by mass of the solids content of the composition include 5, 4, 3, 2, 1, 0.9, 0.7, 0.5, 0.4, 0.3, 0.2, 0.1, and 0% by mass. In one embodiment, the content is preferably 0 to 5% by mass, and more preferably 0 to 3% by mass.

<Organic solvent>
In one embodiment, the composition may contain an organic solvent. The organic solvent may be used alone or in combination of two or more kinds.

Examples of organic solvents include ketone solvents such as methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, and cyclohexanone; aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate; ester solvents such as ethyl acetate, butyl acetate, methyl cellosolve acetate, and cellosolve acetate; petroleum-based solvents such as Solvesso #100 and Solvesso #150 (both trade names, manufactured by ExxonMobil Corporation); haloalkane solvents such as chloroform; and amide solvents such as dimethylformamide.

Examples of upper and lower limits for the organic solvent content per 100% by mass of the composition include 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 2, 1, and 0% by mass. In one embodiment, the content is preferably 0 to 90% by mass.

<Additives>
The composition may contain, as an additive, an agent that does not fall into any of the above-mentioned rosin-modified resin, poly(meth)acrylate, photopolymerization initiator, sensitizer, pigment, gelling agent, polymerization inhibitor, and organic solvent.

Examples of additives include surface conditioners, antifoaming agents, photosensitizers, antioxidants, light stabilizers, and polymerization inhibitors.

In one embodiment, the content of the additives is, for example, less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, or 0 part by weight, per 100 parts by weight of the composition. Also, for example, the content of any of the rosin-modified resin, poly(meth)acrylate, photopolymerization initiator, pigment, gelling agent, polymerization inhibitor, and organic solvent is, for example, less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, or 0 part by weight, per 100 parts by weight of the composition.

The above composition can be produced by dispersing and mixing the above rosin-modified resin and poly(meth)acrylate, as well as, if necessary, a photopolymerization initiator, pigment, gelling agent, polymerization inhibitor, organic solvent, and additives, using any of a variety of known means.

The order in which the components are added is not particularly limited. Furthermore, various known devices (such as emulsifying dispersers and ultrasonic dispersers) can be used as dispersion and mixing means.

The above-mentioned active energy ray-curable resin composition can be used as an active energy ray-curable resin composition for offset ink.

[Cured product]
The present disclosure provides a cured product of the active energy ray-curable resin composition.

Examples of curing conditions include those described below.

[Laminate]
The present disclosure provides a laminate comprising the above-described cured product.

In one embodiment, the laminate comprises a cured product laminated on a substrate.

Any of the known substrates can be used without particular limitation. Examples of substrates include paper (art paper, cast-coated paper, form paper, PPC paper, fine-quality coated paper, kraft paper, polyethylene-laminated paper, glassine paper, etc.) and plastic substrates (polyolefin, polycarbonate, polymethacrylate, polyester, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin, etc.).

Examples of coating methods (printing methods) include offset printing, flexographic printing, screen printing, bar coater coating, Mayer bar coating, air knife coating, gravure coating, etc. The amount of coating is not particularly limited, but the mass after drying is preferably about 0.1 to 30 g/ ^m2 , and more preferably about 1 to 20 g/ ^m2 .

Examples of curing means include electron beams or ultraviolet light. Examples of ultraviolet light sources include high-pressure mercury lamps, xenon lamps, metal halide lamps, and UV-LEDs.

When using a high-pressure mercury lamp, the curing conditions (light intensity, light source placement, and conveying speed) are preferably a conveying speed of approximately 5 to 50 m/min for one lamp with a light intensity of approximately 80 to 160 W/cm.

The present invention will be described in detail below through examples and comparative examples. However, the description of the preferred embodiment above and the following examples are provided for illustrative purposes only and are not intended to limit the present invention. Therefore, the scope of the present invention is not limited to the embodiments or examples specifically described in this specification, but is limited only by the claims. Furthermore, in each example and comparative example, numerical values such as parts and percentages are by mass unless otherwise specified.

Example 1
23 parts of rosin and 7 parts of maleic acid were placed in a reaction vessel equipped with a stirrer, a reflux condenser with a water divider, and a thermometer, and stirred at 180° C. for 1 hour to obtain 30 parts of maleated rosin.
Thereafter, 50 parts of disproportionated rosin, 14 parts of trimethylolpropane, and 8 parts of succinic acid were added and reacted at 270° C. for 24 hours with stirring to obtain a rosin-modified resin.

Unless otherwise noted, the examples and comparative examples other than Example 1 were carried out in the same manner as Example 1, with the exception of the changes shown in the table below.

The rosin-modified resins produced were evaluated as follows:

20 parts of the rosin-modified resin of Example 1 and 30 parts of ditrimethylolpropane tetraacrylate as a poly(meth)acrylate were mixed. Next, 25 parts of ditrimethylolpropane tetraacrylate, 8 parts of a photopolymerization initiator (product name "Omnirad 369" manufactured by IGM Resins B.V.), 1 part of a photosensitizer (product name "Omnirad EMK" manufactured by IGM Resins B.V.), 1 part of a photosensitizer (product name "Omnirad DETX" manufactured by IGM Resins B.V.), and 15 parts of black ink pigment (MA-100 manufactured by Mitsubishi Chemical) were added and milled using three rollers to prepare an active energy ray-curable resin composition.

<Liquidity>
1.30 mL of the active energy ray-curable resin composition was placed on a glass plate tilted at 60°, and the flow of the active energy ray-curable resin composition after leaving it for 30 minutes was measured. The evaluation criteria were as follows:
○: 30 mm or more ×: less than 30 mm

<Emulsification resistance>
30.0 g of each ink was added to 30.0 g of water and emulsified using a Homo Disper (device name: "T.K. HOMO DISPER", manufactured by Primix Corporation) at a rotation speed of 3,000 rpm. From the sample separated into an ink phase (solid) and an aqueous phase (liquid), water in the aqueous phase was sampled and its weight (g) was measured. The emulsification rate (%) was calculated using Equation 1.
(Formula 1) Emulsification rate (%) = [(amount of water added (30.0 g)) - (weight of water collected after emulsification)} / (amount of ink added (30.0 g))] x 100
○: 55% or less ×: More than 55%

<Misting resistance>
A 13 cm x 21 cm piece of OHP film was attached to the wall below the roller of the incometer, and after adjusting the roller temperature to 40°C, 2.6 mL of the active energy ray-curable resin composition was placed on the roller. The roller was rotated at 1200 rpm for 2 minutes, and the mass of the active energy ray-curable resin composition attached to the film was weighed. The evaluation criteria were as follows:
○: 100 mg or less ×: More than 100 mg

Evaluation Examples Thermal Stability Thermal stability was evaluated according to the following methods and criteria.
A varnish composition was prepared by charging 40 parts of rosin-modified resin, 60 parts of ditrimethylolpropane tetraacrylate, and 0.10 parts of methoquinone into a reaction vessel equipped with a stirrer and a condenser, and stirring at 120°C for 1 hour. The composition was transferred to a sealable glass container and stored at 80°C, and evaluated based on the time it took for the E-type viscosity to increase by 20% or more.
○: 24 hours or more ×: Less than 24 hours

Claims (6)

a structural unit derived from α,β-unsaturated carboxylic acid-modified rosin,
A rosin-modified resin which is a reaction product of a resin comprising structural units derived from a polyol and structural units derived from a polybasic acid and/or anhydride thereof with a disproportionated rosin,
the α,β-unsaturated carboxylic acid is maleic acid;
the polyol is trimethylolpropane;
the polybasic acid and/or anhydride thereof is succinic acid;
the content of the structural unit derived from the polyol in 100% by mass of the rosin-modified resin is 10% by mass to 20% by mass,
the content of the structural units derived from the polybasic acid and/or anhydride thereof in 100% by mass of the rosin-modified resin is 5% by mass to 15% by mass;
The rosin-modified resin, wherein the content of the structural units derived from the disproportionated rosin in 100% by mass of the rosin-modified resin is 45% by mass to 55% by mass. The rosin-modified resin according to claim 1, which contains structural units derived from hydrogenated rosin. An active energy ray-curable resin composition comprising the rosin-modified resin according to claim 1 or 2 and poly(meth)acrylate. The active energy ray-curable resin composition according to claim 3, which is for use in offset ink. A cured product of the active energy ray-curable resin composition according to claim 3 or 4. A laminate comprising the cured product according to claim 5 .