JP7517512B1 - Active energy ray-curable resin composition, method for producing same, and laminate - Google Patents

Abstract

[Problem] The present invention aims to provide an active energy ray-curable composition with improved curability and storage stability, a method for producing said composition, and a laminate using said composition. [Solution] An active energy ray-curable ink containing a urethane (meth)acrylate (A) and a (meth)acrylic compound (B) other than (A), wherein the urethane (meth)acrylate (A) is an active energy ray-curable composition which is a reaction product of a (meth)acrylic compound (a1) having a hydroxyl group, an amine compound (a2) having a hydroxyl group other than (a1), a polyol compound (a3) other than (a1) and (a2), and an isocyanate compound (a4). [Selected Figures] None

Description

The present invention relates to a novel and useful active energy ray-curable resin composition, its manufacturing method, and a laminate.

Active energy ray-curable resin compositions are used in a variety of industrial fields because they instantly change from liquid to solid when irradiated with active energy rays.

In addition, in the printing industry in recent years, the demand for shorter delivery times and environmental friendliness has increased, and instead of the conventional oil-based inks, the use of quick-drying, solvent-free active energy ray-curable inks has expanded. Active energy ray-curable inks contain active energy ray-curable unsaturated compounds such as acrylic ester compounds as components, and instantly cure when exposed to active energy rays, forming a tough film due to the three-dimensional crosslinking of the unsaturated compounds. As they cure instantly, post-processing can be carried out immediately after printing, so active energy ray-curable inks are ideal for use in packaging printing and commercial form printing, where a strong film is required to improve productivity and protect designs.

Binder resins such as diallyl phthalate resins are often used in active energy ray curable inks to impart printability, but most binder resins do not contain (meth)acryloyl groups and therefore do not participate in the formation of three-dimensional crosslinks in the cured film of active energy ray curable inks, resulting in a problem of deteriorating the curability of the ink. The use of urethane (meth)acrylate, a binder resin that contains (meth)acryloyl groups, can solve the problem of ink curability, and urethane (meth)acrylates that contain an amine compound as a reactive component are expected to improve curability and pigment dispersibility.

For example, Patent Document 1 discloses a water-soluble urethane acrylate made from dipentaerythritol acrylate or pentaerythritol acrylate, 2-(dimethylamino)ethanol, and a trifunctional isocyanate compound. However, since the urethane acrylate in Patent Document 1 is water-soluble, no mention is made of the storage stability of the urethane acrylate. Patent Document 2 discloses a polyurethane dispersant having a monofunctional acryloyl group at the end of a long side chain. However, the polyurethane dispersant in Patent Document 2 has a low (meth)acryloyl group concentration, and has little effect on improving curing properties. In printing sites, there is a demand for further productivity improvements and reductions in the amount of active energy radiation exposure, so there is a demand for further improvements in the curing properties of urethane acrylate.

In addition, compared to oil-based inks, active energy ray-curable inks have problems such as poor printability and ink fluidity.

International Publication No. 2021/24842 JP 2013-10963 A

The present invention aims to provide an active energy ray-curable composition with improved curability and storage stability, a method for producing the composition, and a laminate using the composition.

As a result of intensive research, the present inventors have found that an active energy ray-curable resin composition containing a urethane (meth)acrylate having as reaction components a (meth)acrylic compound (a1) having a hydroxyl group, an amine compound (a2) other than (a1) having a hydroxyl group, a polyol compound (a3) other than (a1) and (a2), and an isocyanate compound (a4) is a resin composition with excellent storage stability and curability, and have arrived at the present invention.

That is, the present invention provides an active energy ray-curable composition containing a urethane (meth)acrylate (A) and a polyfunctional (meth)acrylic compound (B) other than (A),
the urethane (meth)acrylate (A) is a reaction product of a (meth)acrylic compound (a1) having a hydroxyl group, an amine compound (a2) having a hydroxyl group other than (a1), a polyol compound (a3) other than (a1) and (a2), and an isocyanate compound (a4) ;
The amine compound (a2) is a tertiary amine,
The present invention relates to an active energy ray-curable composition , wherein the urethane (meth)acrylate (A) has a (meth)acryloyl group concentration in the range of 2.0 to 8.0 mmol/g .

The present invention also relates to the above-mentioned active energy ray-curable composition, characterized in that the (meth)acrylic compound (a1) having a hydroxyl group is at least one selected from the group consisting of pentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, and polypentaerythritol poly(meth)acrylate.

The present invention also relates to the above-mentioned active energy ray-curable composition, characterized in that the polyol compound (a3) contains at least one selected from the group consisting of polyol compounds having 2 to 20 carbon atoms and alkylene oxide-modified polyol compounds having 2 to 20 carbon atoms.

The present invention also relates to the above-mentioned active energy ray-curable composition, characterized in that the polyol compound (a3) is at least one selected from the group consisting of ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol, octanediol, decanediol, glycerin, trimethylolpropane, and pentaerythritol, as well as alkylene oxide modified products thereof.

The present invention also relates to the above active energy ray-curable composition, characterized in that the hydroxyl value of the polyol compound (a3) is 50 to 1850 mg KOH/g.

The present invention also relates to the above-mentioned active energy ray-curable composition, wherein the amine compound (a2) having a hydroxyl group is an amine compound represented by the following general formula (1):

General formula (1)

R ¹ _x -N- [(R ² O) _z -H] _y

(In the formula, R ¹ represents a linear or branched alkyl group having 1 to 20 carbon atoms,
^R2 represents a linear or branched alkylene group having 2 to 4 carbon atoms.
x represents an integer of 0 to 2, y represents an integer of 1 to 3, and x+y=3.
z represents an integer of 1 to 10.
In addition, when there are two or more [(R ² O)zH] groups, they may be the same or different.

The present invention also relates to the above active energy ray-curable composition, in which the isocyanate compound (a4) is a diisocyanate compound.

The present invention also provides a method for producing the active energy ray-curable composition, comprising the steps of:
The present invention relates to a method for producing an active energy ray-curable composition, comprising a step of reacting a (meth)acrylic compound (a1) having a hydroxyl group, an amine compound (a2) having a hydroxyl group other than (a1), a polyol compound (a3) other than (a1) and (a2), and an isocyanate compound (a4) in a polyfunctional (meth)acrylic compound (B) to obtain a urethane (meth)acrylate (A).

The present invention also relates to a laminate having a cured product of the above-mentioned active energy ray-curable composition on a substrate.

The present invention provides an active energy ray-curable composition with improved curability and storage stability, a method for producing the composition, and a laminate using the composition. This is extremely useful industrially.

The following describes in detail an embodiment of the present invention. However, the present invention is not limited to the embodiment described below, and various modifications are possible without departing from the spirit of the present invention.

The active energy ray-curable resin composition of the present invention contains a urethane (meth)acrylate (A) and a (meth)acrylic compound (B) other than (A), and is characterized in that the urethane (meth)acrylate (A) is a reaction product of a (meth)acrylic compound (a1) having a hydroxyl group, an amine compound (a2) having a hydroxyl group other than (a1), a polyol compound (a3) other than (a1) and (a2), and an isocyanate compound (a4). This makes it possible to combine excellent storage stability and curability.

The content of the urethane (meth)acrylate (A) used in the present invention is preferably 5 to 90% by mass, and more preferably 10 to 80% by mass, based on the total amount of the resin composition, from the viewpoints of storage stability and curing property.

From the viewpoint of improving curability, the (meth)acryloyl group concentration of the urethane (meth)acrylate (A) used in the present invention is preferably in the range of 1.0 to 8.0 mmol/g, and more preferably in the range of 2.0 to 7.0 mmol/g.

((Meth)acrylic compound (a1) having a hydroxyl group)
Examples of the (meth)acrylic compound (a1) having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, polyethylene glycol (meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylates, glycerin poly(meth)acrylate, diglycerin poly(meth)acrylate, trimethylolpropane poly(meth)acrylate, ditrimethylolpropane poly(meth)acrylate, pentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, polypentaerythritol poly(meth)acrylate, etc. These (meth)acrylic compounds (a1) having a hydroxyl group may be used alone or in combination of two or more. Among these, it is preferable to use pentaerythritol polyacrylate, dipentaerythritol polyacrylate, and polypentaerythritol polyacrylate in order to adjust the (meth)acryloyl group concentration of the urethane (meth)acrylate (A) to 1.0 to 8.0 mmol/g.

(Amine compound (a2) having a hydroxyl group other than (a1))
The amine compound (a2) having a hydroxyl group other than (a1) is a compound in which a hydroxyl group in the molecule reacts with an isocyanate group to form a urethane bond.

The amine compound (a2) in the present invention is preferably a compound represented by the following general formula (1).

General formula (1)

R ¹ _x -N- [(R ² O) _z -H] _y

(In the formula, R1 represents a linear or branched alkyl group having 1 to 20 carbon atoms,
R2 represents a linear or branched alkylene group having 2 to 4 carbon atoms.
x represents an integer of 0 to 2, y represents an integer of 1 to 3, and x+y=3.
z represents an integer of 1 to 10.
In addition, when there are two or more [(R ² O) _z —H] groups, they may be the same or different.

From the viewpoint of ease of availability, z in general formula (1) is preferably an integer of 1 to 5, and more preferably 1.

Specific examples of the compound represented by the general formula (1) include amine compounds having one hydroxyl group-containing substituent, such as ethanolamine, propanolamine, and butanolamine;
amine compounds having two hydroxyl group-containing substituents, such as diethanolamine, dipropanolamine, and dibutanolamine;
amine compounds having one substituent having a hydroxyl group and one substituent not having a hydroxyl group, such as N-methylaminoethanol, N-ethylaminoethanol, N-butylaminoethanol, N-methylaminopropanol, N-ethylaminopropanol, N-butylaminopropanol, N-methylaminobutanol, N-ethylaminobutanol, N-butylaminobutanol, and 2-(2-ethylamino)ethoxyethanol;
amine compounds having one substituent having a hydroxyl group and two substituents not having a hydroxyl group, such as N,N-dimethylaminoethanol, N,N-diethylaminoethanol, N,N-dibutylaminoethanol, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-dibutylaminopropanol, N,N-dimethylaminobutanol, N,N-diethylaminobutanol, N,N-dibutylaminobutanol, and 2-(2-diethylamino)ethoxyethanol;
amine compounds having two substituents having a hydroxyl group and one substituent not having a hydroxyl group, such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-tert-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-butyldipropanolamine, N-tert-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N-butyldibutanolamine, N-tert-butyldibutanolamine and N-pentyldibutanolamine;
Examples of the amine compound include amine compounds having three hydroxyl group-containing substituents, such as trimethanolamine, triethanolamine, and tributanolamine.

Among these amine compounds (a2), the use of tertiary amine compounds is preferred because it prevents reactions between amino groups and isocyanate groups, and Michael addition reactions between amino groups and acryloyl groups, and therefore inhibits unintended crosslinking reactions.

The amine compound (a2) may be used alone or in combination of two or more kinds. From the viewpoint of the balance between storage stability and curability, the content of the amine compound (a2) is preferably 5 to 80 mol %, more preferably 10 to 50 mol %, based on the total number of moles of the amine compound (a2) and the polyol compound (a3).

(Polyol compound (a3) other than (a1) and (a2))
As the polyol compound (a3) other than (a1) and (a2), a polyol compound having two or more hydroxyl groups in the molecule can be used. As the polyol compound (a3), a polyol compound having 2 to 20 carbon atoms and an alkylene oxide modified product of a polyol compound having 2 to 20 carbon atoms are preferably used, and the storage stability of the resin composition is improved by using these. As the polyol compound (a3), a polyol compound having a hydroxyl value in the range of 50 to 1850 mgKOH/g is more preferably used, and the curability is improved by using these.

Examples of polyol compounds having 2 to 20 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 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, and the like. linear alkylene dihydric alcohols such as 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16-hexadecanediol, 1,2-hexadecanediol, 1,18-octadecanediol, 1,2-octadecanediol, 1,20-eicosanediol, and 1,2-eicosanediol; neopentyl glycol; and 2-methyl-2,4-pentanediol. , 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-dimethylpentanediol, 2,2-diethyl-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 and branched alkylene dihydric alcohols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptanediol, tricyclodecane dimethanol, bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, hydrogenated bisphenol, and hydrogenated bisphenol S.
Examples of trihydric or higher polyhydric alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, sorbitan, sorbitol, and inositol.
These polyol compounds having 2 to 20 carbon atoms may be used alone or in combination of two or more of them. Among these, it is preferable to use ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, glycerin, trimetrolpropane, pentaerythritol, etc., from the viewpoint of availability.

Examples of the alkylene oxide modified polyol compound having 2 to 20 carbon atoms include alkylene oxide modified compounds such as ethylene oxide modified (EO modified), propylene oxide modified (PO modified), butylene oxide modified (BO modified) on the above-mentioned polyol compound having 3 to 20 carbon atoms. The alkylene oxide modified polyol compound having 2 to 20 carbon atoms may be used alone or in combination of two or more kinds.
Examples of alkylene oxide modified polyol compounds having 2 to 20 carbon atoms include the PEG series (manufactured by Sanyo Chemical Industries, Ltd., polyethylene glycol), the Sannix PP series (manufactured by Sanyo Chemical Industries, Ltd., polypropylene glycol), the PTMG series (manufactured by Mitsubishi Chemical Corporation, polytetramethylene glycol), the Uniox G series (manufactured by NOF Corporation, ethylene oxide modified glycerin), the Sannix GP series (manufactured by Sanyo Chemical Industries, Ltd., propylene oxide modified glycerin), the Sannix TP series (manufactured by Sanyo Chemical Industries, Ltd., propylene oxide modified trimetrol propane), and Wilbride S-753D (manufactured by NOF Corporation, EOPOBO modified glycerin).

(Isocyanate compound (a4))
Examples of the isocyanate compound (a4) include tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like. Examples of the isocyanate include anate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, dimer diisocyanate in which the carboxyl group of a dimer acid is converted to an isocyanate group, Duranate TPA-100 (manufactured by Asahi Kasei Corporation, an isocyanurate compound in which 3 moles of 1,6-hexamethylene diisocyanurate are cyclized), Millionate MR400 (manufactured by Tosoh Corporation, Polymeric MDI), and the like. Among these, diisocyanate compounds are preferred from the viewpoint of reaction control.

(Method for producing urethane (meth)acrylate (A))
A method for producing a reaction product of a (meth)acrylic compound (a1) having one or more hydroxyl groups, an amine compound (a2) having a hydroxyl group, a polyol compound (a3), and an isocyanate compound (a4) will be described.
The reaction of the (meth)acrylic compound (a1) having one or more hydroxyl groups, the amine compound (a2) having a hydroxyl group, the polyol compound (a3), and the isocyanate compound (a4) may be carried out simultaneously, or the (meth)acrylic compound (a1) having one or more hydroxyl groups and the isocyanate compound (a4) may be reacted in advance, and then the amine compound (a2) having a hydroxyl group and the polyol compound (a3) may be reacted.

The ratio [(a1')/(a4')] of the number of moles (a1') of hydroxyl groups contained in the (meth)acrylic compound (a1) having one or more hydroxyl groups to the number of moles (a4') of isocyanate groups contained in the isocyanate compound (a4) is preferably in the range of 0.2 to 0.6. When [(a1')/(a4')] is in the range of 0.2 to 0.6, the molecular weight of the urethane (meth)acrylate (A) becomes favorable, and the flowability is improved.

The reaction proceeds without a catalyst, but a catalyst can also be used. Examples of catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline, and metal catalysts such as tin, zinc, aluminum, and zirconium, with tin 2-ethylhexanoate being preferred from the viewpoint of reactivity.
Although the reaction can be carried out in a solvent as necessary, it can also be carried out in a (meth)acrylic compound (B) described below, which is preferable because it can omit the step of dissolving the urethane (meth)acrylate (A) in the (meth)acrylic compound and the step of removing the solvent.

The molecular weight of the urethane (meth)acrylate (A) is preferably in the range of 2,000 to 30,000 in terms of weight average molecular weight from the viewpoint of storage stability.
In the present invention, the weight average molecular weight was measured by gel permeation chromatography (HLC-8320) manufactured by Tosoh Corporation. A calibration curve was prepared using a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel Super HM-M columns (manufactured by Tosoh Corporation) were used. 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.

In addition, the number of (meth)acryloyl groups contained in the urethane (meth)acrylate (A) is preferably 4 to 50 per molecule from the viewpoint of curability, and more preferably 7 to 30 per molecule.

((Meth)acrylic compound (B))
The content of the (meth)acrylic compound (B) used in the ink of the present invention is 10 to 90 mass % relative to the total amount of the resin composition, more preferably 15 to 85 mass %, and even more preferably 20 to 80 mass %.

The (meth)acrylic compound (B) is not particularly limited, and examples thereof include monofunctional (meth)acrylic compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, and acryloylmorpholine;
Bifunctional (meth)acrylic compounds such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (n=2-20), propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate (n=2-20), alkane (having 4-12 carbon atoms) glycol di(meth)acrylate, alkane (having 4-12 carbon atoms) glycol ethylene oxide adduct (2-20 moles) di(meth)acrylate, alkane (having 4-12 carbon atoms) glycol propylene oxide adduct (2-20 moles) di(meth)acrylate, hydroxypivalyl hydroxypivalate di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, bisphenol A ethylene oxide adduct (2-20 moles) di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, and hydrogenated bisphenol A ethylene oxide adduct (2-20 moles) di(meth)acrylate;
trifunctional (meth)acrylic compounds such as glycerin tri(meth)acrylate, glycerin ethylene oxide adduct (3 to 30 mol) tri(meth)acrylate, glycerin propylene oxide adduct (3 to 30 mol) tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide adduct (3 to 30 mol) tri(meth)acrylate, and trimethylolpropane propylene oxide adduct (3 to 30 mol) tri(meth)acrylate;
Pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide adduct (4-40 mol) tetra(meth)acrylate, pentaerythritol propylene oxide adduct (4-40 mol) tetra(meth)acrylate, diglycerol tetra(meth)acrylate, pentaerythritol ethylene oxide adduct (4-40 mol) tetra(meth)acrylate, pentaerythritol propylene oxide adduct (4-40 mol) tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate (meth)acrylic compounds having 4 or more functionalities, such as tetrafunctional or higher (meth)acrylic acid compounds, such as tetrafunctional or higher (meth)acrylic acid compounds, ditrimethylolpropane ethylene oxide adduct (4 to 40 mol) tetra(meth)acrylate, ditrimethylolpropane propylene oxide adduct (3 to 30 mol) tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol ethylene oxide adduct (6 to 60 mol) hexa(meth)acrylate, and dipentaerythritol propylene oxide adduct (6 to 60 mol) hexa(meth)acrylate;
(meth)acrylate compounds such as polyester (meth)acrylate, urethane (meth)acrylate other than (A), and epoxy (meth)acrylate;
and mixtures thereof.
Among these, it is preferable to use a difunctional or higher (meth)acrylic compound from the viewpoint of curability. Also, the proportion of the difunctional or higher (meth)acrylic compound in the total amount of (B) is preferably 40 to 100 mass% from the viewpoint of curability.

The active energy ray-curable ink of the present invention can use active energy ray-curable compounds other than (B) depending on the required properties of the cured film.

Vinyl compounds can be used as active energy ray-curable compounds other than (B), such as styrene, N-vinylpyrrolidone, and divinylbenzene.

In the active energy ray-curable resin composition of the present invention, a photopolymerization initiator can be used as necessary.
The photopolymerization initiator includes a photocleavage type initiator and a hydrogen abstraction type polymerization initiator.

Photocleavable initiators include α-(dimethyl)aminoalkylphenone compounds and α-morpholinoalkylphenone compounds.

More specifically, examples of α-(dimethyl)amino alkylphenone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and examples of α-morpholino alkylphenone compounds include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one. These may be used alone or in combination of two or more kinds.

Furthermore, examples of hydrogen abstraction type polymerization initiators include dialkylbenzophenone compounds and thioxanthone compounds.

More specifically, examples of dialkylaminobenzophenone compounds include 4,4'-dialkylaminobenzophenones such as 4,4'-bis-(dimethylamino)benzophenone and 4,4'-bis-(diethylamino)benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide. The dialkylaminobenzophenone compounds may be used alone or in combination of two or more types. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy-N,N,N-trimethyl-1-propanamine hydrochloride, and the like. These may be used alone or in combination of two or more types.

Sensitizers include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 2,3,4-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-(1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl)benzophenone, methyl-o-benzoylbenzoate, [4-(methylphenylthio)phenyl]phenylmethanone, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy- Examples include 2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymer, diethoxyacetophenone, dibutoxyacetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether. These may be used alone or in combination of two or more.

A radical polymerization inhibitor may be added to the active energy ray-curable resin composition of the present invention.
Examples of the radical polymerization inhibitor include (alkyl)phenols, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cupferron, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N-(3-oxyanilino-1,3-dimethylbutylidene)aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, and cyclohexanone oxime.

Other additives may be used in the active energy ray-curable resin composition of the present invention as necessary. Examples include extender pigments, inorganic fine particles, leveling agents, defoamers, waxes, and film-forming aids.

The method of applying the active energy ray-curable resin composition of the present invention is not particularly limited, and is appropriately selected according to the shape of the substrate, the pattern of the printed layer to be formed, the area of the printed layer to be formed, etc. Examples of application methods include inkjet printing, gravure printing, offset printing, screen printing, roll coating, bar coating, spin coating, air spraying, airless spraying, and immersion and pulling up, and two or more of these methods may be combined.

There are no particular limitations on the substrate, and any material can be used, such as paper, plastic, stickers, labels, and metal, with paper being preferred.

In the present invention, there is no particular limitation on the method of curing the active energy ray-curable resin composition with active energy rays, and any known source of active energy rays can be used. Specific examples include mercury lamps, xenon lamps, metal hydride lamps, LEDs (light-emitting diodes) such as ultraviolet light-emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs), electron beams, and gas/solid-state lasers.

(Active energy ray curable ink)
The active energy ray-curable composition of the present application can be suitably used in active energy ray-curable inks.

The active energy ray curable ink is prepared with a composition consisting of 0-30% by mass of pigment, 5-40% by mass of urethane (meth)acrylate (A), 20-80% by mass of (meth)acrylic compound (B), 0-30% by mass of resin, 0-20% by mass of photopolymerization initiator and/or sensitizer, and 0-10% by mass of other additives based on the total mass of the ink.

Pigments can be added as colorants to active energy ray curable inks. If no pigment is added, the ink becomes a transparent varnish, but if a pigment is added, the ink becomes colored.

Pigments include inorganic and organic pigments. Inorganic pigments include yellow lead, zinc yellow, Prussian blue, barium sulfate, cadmium red, titanium oxide, zinc oxide, red iron oxide, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, and red iron oxide. Organic pigments include soluble azo pigments such as β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetate anilide, and pyrazolone, and insoluble azo pigments such as β-naphthol, β-oxynaphthoic acid anilide, acetoacetate anilide monoazo, acetoacetate anilide disazo, and pyrazolone. Various known and publicly used pigments can be used, including phthalocyanine pigments such as zo pigments, copper phthalocyanine blue, halogenated (chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine, and metal-free phthalocyanine; quinacridones, dioxazines, threnes (pyranthrone, anthanthrone, indanthrone, anthrapyrimidine, flavanthrone, thioindigo, anthraquinone, perinone, perylene, etc.); isoindolinones, metal complexes, and quinophthalones, as well as other polycyclic and heterocyclic pigments.

In the active energy ray curable ink, a resin can be used as required.
Resins that can be used in the present invention are not particularly limited, and examples thereof include diallyl orthophthalate resin, diallyl isophthalate resin, diallyl terephthalate resin, polyester resin, polyvinyl chloride, poly(meth)acrylic acid ester, epoxy resin, polyurethane resin, petroleum (based) resin, cellulose derivatives (e.g., ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride-vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, polyamide resin, polyvinyl acetal resin, butadiene-acrylonitrile copolymer, etc. These resins can be used alone or in combination of two or more.

Wax may also be added as an additive for imparting abrasion resistance, anti-blocking properties, smoothness, and scratch resistance.
Examples of waxes include natural waxes such as carnauba wax, Japan wax, lanolin, montan wax, paraffin wax, and microcrystalline wax, and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and silicone compounds.

Additives such as ultraviolet absorbers, infrared absorbers, and antibacterial agents can also be added depending on the required performance.

The active energy ray curable ink may be produced in the same manner as conventional active energy ray curable inks. For example, ink composition components such as the pigment, urethane (meth)acrylate (A), (meth)acrylic compound (B), polymerization inhibitor, photopolymerization initiator and sensitizer, and other additives are produced at a temperature between room temperature and 100°C using a kneader, triple roll mill, attritor, sand mill, gate mixer, or other milling, mixing, and adjustment machine.

Printing methods for active energy ray-curable inks include lithographic printing (normal lithographic printing using dampening water and waterless lithographic printing not using dampening water), letterpress printing, intaglio printing, and stencil printing, with lithographic printing being preferred.

The present invention will be described in more detail below with reference to examples, but the following examples do not limit the scope of the invention. In the present invention, "parts" means "parts by mass" and "%" means "% by mass."

(Production Example 1)
Into a four-neck flask equipped with a stirrer, a cooler, a thermometer, and a gas inlet tube, 67.1 parts of MIRAMER M500 (a mixture with (meth)acrylic compound (B)) as a (meth)acrylic compound (a1) having a hydroxyl group, 11.1 parts of toluene-2,4-diisocyanate as an isocyanate compound (a4), 11.5 parts of MIRAMER M600 and 5.0 parts of LAROMER LR8863 as (meth)acrylic compound (B), 0.01 part of tin 2-ethylhexanoate as a catalyst, and 0.2 parts of tert-butylhydroquinone as a polymerization inhibitor were placed, and the mixture was reacted at 100° C. for 1 hour while blowing in air with stirring. Next, 0.5 parts of N-methyldiethanolamine as an amine compound (a2) having a hydroxyl group other than (a1) and 4.6 parts of Sannix GP-250 as a polyol compound (a3) other than (a1) and (a2) were added, and the mixture was further reacted at 110° C. for 5 hours to obtain a resin composition 1. The value of [(a1')/(a4')] in this reaction was 0.5, and the acrylic group concentration of the obtained urethane acrylate (A) was 6.43 mmol/g.

(Production Examples 2 to 45, 47)
Resin compositions 2 to 45 and 47 were obtained in the same manner as in Production Example 1, except that the raw materials were changed according to the composition in Table 1.

(Manufacture Example 46)
Into a four-neck flask equipped with a stirrer, a cooler, a thermometer, and a gas inlet tube was added 66.8 parts of MIRAMER M500 (a mixture with (meth)acrylic compound (B)) as a (meth)acrylic compound (a1) having a hydroxyl group, 0.7 parts of N-butyldiethanolamine as an amine compound (a2) having a hydroxyl group other than (a1), 4.6 parts of Sannix GP-250 as a polyol compound (a3) other than (a1) and (a2), 11.1 parts of toluene-2,4-diisocyanate as an isocyanate compound (a4), 11.6 parts of MIRAMER M600 as a (meth)acrylic compound (B), and LAROMER 5.0 parts of LR8863, 0.01 parts of tin 2-ethylhexanoate as a catalyst, and 0.2 parts of tertiary butyl hydroquinone as a polymerization inhibitor were added, and air was blown in with stirring to carry out a reaction at 110°C for 5 hours to obtain Resin Composition 46. The value of [(a1')/(a4')] in this reaction was 0.5, and the acrylic group concentration of the obtained urethane acrylate (A) was 6.40 mmol/g.

(Manufacture example 48)
Stirrer, cooler, thermometer, 66.8 parts of MIRAMER M500 (mixture with (meth)acrylic compound (B)) as (meth)acrylic compound (a1) having a hydroxyl group in a four-neck flask equipped with a gas inlet tube, 11.1 parts of toluene-2,4-diisocyanate as isocyanate compound (a4), 11.6 parts of MIRAMER M600 as (meth)acrylic compound (B) and 5.0 parts of LAROMER LR8863, 0.01 parts of tin 2-ethylhexanoate as a catalyst, 0.2 parts of tertiary butyl hydroquinone as a polymerization inhibitor, and reacted for 1 hour at 100 ° C. while blowing air into the mixture. Next, 5.3 parts of Sannix GP-250 was added as a polyol compound (a3) other than (a1) and (a2), and the mixture was further reacted at 110 ° C. for 5 hours to obtain a resin composition 48. In this reaction, the value of [(a1')/(a4')] was 0.5, and the acrylic group concentration of the resulting urethane acrylate (A) was 6.40 mmol/g.

(Manufacture Example 49)
A stirrer, a cooler, a thermometer, and a gas inlet tube were added to a four-neck flask containing 66.3 parts of MIRAMER M500 (a mixture with (meth)acrylic compound (B)) as the (meth)acrylic compound (a1), 11.0 parts of toluene-2,4-diisocyanate as the isocyanate compound (a4), 11.9 parts of MIRAMER M600 as the (meth)acrylic compound (B) and 5.0 parts of LAROMER LR8863, 0.01 parts of tin 2-ethylhexanoate as a catalyst, and 0.2 parts of tertiary butyl hydroquinone as a polymerization inhibitor, and the mixture was stirred and reacted at 100 ° C. for 1 hour. Next, 5.6 parts of N,N-dimethylethanolamine was added as an amine compound (a2) having a hydroxyl group other than (a1), and the mixture was further reacted at 110 ° C. for 5 hours to obtain a resin composition 49. In this reaction, the value of [(a1')/(a4')] was 0.5, and the acrylic group concentration of the resulting urethane acrylate (A) was 6.3.5 mmol/g.

(Production Examples 50 and 51)
Resin compositions 50 and 51 were obtained in the same manner as in Production Example 49, except that the raw materials were changed according to the composition in Table 1.

Details of the materials listed in Table 1 are given below.
(Meth)acrylic compound (a1)
ARONIX M306: manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate/pentaerythritol tetraacrylate = 70/30 (mass ratio) MIRAMER M500: manufactured by Bigen Specialty Chemical Co., Ltd., a mixture of dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate = 50/50 (mass ratio) Viscoat #802: manufactured by Osaka Organic Chemical Industry Co., Ltd., polypentaerythritol polyacrylate HEA: manufactured by Osaka Organic Chemical Industry Co., Ltd., 2-hydroxyethyl acrylate 4-HBA: manufactured by Osaka Organic Chemical Industry Co., Ltd., 4-hydroxybutyl acrylate polyol compound (a3)
PEG-300: Sanyo Chemical Industries, Ltd., polyethylene glycol Sannix PP-600: Sanyo Chemical Industries, Ltd., polypropylene glycol PTMG-250: Mitsubishi Chemical Corporation, polytetramethylene glycol Uniox G-450: NOF Corp., ethylene oxide modified glycerin Sannix GP-250: Sanyo Chemical Industries, Ltd., propylene oxide modified glycerin Sannix TP-400: Sanyo Chemical Industries, Ltd., propylene oxide modified trimetrol propane Wilbride S-753D: NOF Corp., EOPOBO modified glycerin Newpol BP-2P: Sanyo Chemical Industries, Ltd., propylene oxide modified bisphenol A
Newpol BPE-20T: ethylene oxide modified bisphenol A, manufactured by Sanyo Chemical Industries, Ltd.
Sannix PP-1200: manufactured by Sanyo Chemical Industries, Ltd., polypropylene glycol-isocyanate compound (a4)
Duranate TPA-100: manufactured by Asahi Kasei Corporation, an isocyanurate compound (meth)acrylic compound (B) obtained by cyclizing 3 moles of 1,6-hexamethylene diisocyanurate
MIRAMER M600: Dipentaerythritol hexaacrylate manufactured by Bigen Specialty Chemical Co., Ltd. LAROMER LR8863: Ethylene oxide modified trimethylolpropane triacrylate manufactured by BASF Corporation Polymerization inhibitor TBHQ: Tertiary butyl hydroquinone

(Examples 1 to 47, Comparative Examples 1 to 4)
According to the composition in Table 2, resin compositions 1 to 51 and an initiator were mixed to obtain active energy ray curable compositions of Examples 1 to 47 and Comparative Examples 1 to 4. The obtained active energy ray curable compositions were evaluated for storage stability and MEK (methyl ethyl ketone) rubbing evaluation, and the results are also shown in Table 2.

<Storage stability evaluation>
The active energy ray curable composition was left to stand in a sealed container at 60° C. for one week. After stirring, the mixture was filtered through a 80-mesh metal mesh, and the amount of aggregates on the mesh was visually evaluated. ◎, ○, and △ are practical levels.
(Evaluation criteria)
⊚: No agglomerates at all.
A: A small number of small aggregates are present.
Δ: Small aggregates are present.
×: Large aggregates are present.

<MEK rubbing evaluation>
An active energy ray curable composition was applied to a corona-treated PET substrate (Mitsubishi Chemical Corporation, A-PET sheet, Novaclear A2012, thickness 0.25 mm) using an RI tester (simple paint developer), and cured using a high-pressure mercury lamp (output: 96 W/cm, lamp distance: 10 cm, conveyor speed: 100 m/min, number of passes: 1). The UV-cured film was rubbed back and forth with a cotton swab soaked in MEK, and the number of times the cotton swab was rubbed back and forth when the UV-cured film was damaged was used as the basis for the evaluation. ◎, ○, and △ are practical levels.
(Evaluation criteria)
◎: 200 times or more ○: 100 times or more but less than 200 times △: 50 times or more but less than 100 times ×: Less than 50 times

From Examples 1 to 47, it was found that the resin composition of the present invention contains the amine compound (a2) and the polyol compound (a3), which makes it possible to control the reactivity of the (meth)acryloyl group, and has excellent storage stability and MEK rubbing properties.

(Examples 48 to 96, Comparative Examples 5 to 8)
According to the compositions in Table 3, the active energy ray curable inks of Examples 48 to 96 and Comparative Examples 5 to 8 were obtained by milling in a three-roll mill. The "printability" and "fluidity" of the obtained active energy ray curable inks were examined. The results are also shown in Table 3.

<Method of Evaluating Printability>
Isopropyl alcohol and purified water were used to prepare an 8% concentration aqueous isopropyl alcohol solution. The active energy ray curable ink was left in the 8% concentration aqueous isopropyl alcohol solution for 30 seconds, and the degree of ink scattering during that time was evaluated. The less the ink scattered in the 8% concentration aqueous isopropyl alcohol solution, the better the printability (staining during printing) was judged to be, and the evaluation was made on the following four-point scale. ◎, ○, and △ are practical levels.
(Evaluation criteria)
◎: Ink does not scatter in the aqueous solution even after 30 seconds. ◯: Ink scatters in the aqueous solution in 20 to 30 seconds. △: Ink scatters in the aqueous solution in 10 to 20 seconds. ×: Ink scatters in the aqueous solution in less than 10 seconds.

<Method of evaluating liquidity>
Measurements were made using the spreadmeter method in accordance with the JIS K5701:2000 fluidity measurement method, observing over time the property of ink sandwiched between two horizontally placed parallel plates spreading concentrically under the weight of the loaded plates (115 grams), and rating the ink spread diameter [mm] after 60 seconds on the following four-point scale: ◎, ○, and △ are practical levels.
(Evaluation criteria)
◎: 34.0 mm or more ○: 32.0 mm or more, less than 34.0 mm △: 30.0 mm or more, less than 32.0 mm ×: less than 30.0 mm

Details of the materials listed in Table 3 are given below.
Pigment LIONOL YELLOW 1315: LIONOL YELLOW 1315, manufactured by Toyo Color Co., Ltd.
Photopolymerization initiator Omnirad 379EG: manufactured by iGM RESINS, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one KAYACURE DETX-S: manufactured by Nippon Kayaku Co., Ltd., 2,4-diethylthioxanthone

Examples 48 to 96 of the present invention were evaluated as having good "printability" and "fluidity", while Comparative Example 5 did not contain the amine compound (a2), and therefore the ink dispersibility was reduced, resulting in poor fluidity.
In Comparative Examples 6 to 8, since the urethane (meth)acrylate (A) did not contain the polyol compound (a3), the polarity of the ink was increased, and the printability was deteriorated.
From these findings, it was found that the present invention can provide an active energy ray-curable ink that is excellent in printability and flowability and can eliminate problems during printing.

The resin composition of the present invention can have both storage stability and curing reactivity to active energy rays by reacting a polyol compound and an amine compound having a hydroxyl group with many acrylic compounds, and can become a film having a highly crosslinked structure after curing. Therefore, it is also useful for various printing inks, paints, coating agents, photoresists, etc. other than those specifically described.

Claims (9)

An active energy ray-curable composition comprising a urethane (meth)acrylate (A) and a polyfunctional (meth)acrylic compound (B) other than (A),
the urethane (meth)acrylate (A) is a reaction product of a (meth)acrylic compound (a1) having a hydroxyl group, an amine compound (a2) having a hydroxyl group other than (a1), a polyol compound (a3) other than (a1) and (a2), and an isocyanate compound (a4), and is a reaction product of a hydroxyl group of the (meth)acrylic compound (a1) having a hydroxyl group, a hydroxyl group of the amine compound (a2) having a hydroxyl group other than (a1), and a hydroxyl group of the polyol compound (a3) other than (a1) and (a2), and an isocyanate group of the isocyanate compound (a4);
The amine compound (a2) is a tertiary amine,
An active energy ray-curable composition, comprising a urethane (meth)acrylate (A) having a (meth)acryloyl group concentration in the range of 2.0 to 8.0 mmol/g. The active energy ray curable composition according to claim 1, characterized in that the (meth)acrylic compound (a1) having a hydroxyl group is at least one selected from the group consisting of pentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, and polypentaerythritol poly(meth)acrylate. The active energy ray-curable composition according to claim 1, characterized in that the polyol compound (a3) contains at least one selected from the group consisting of polyol compounds having 2 to 20 carbon atoms and alkylene oxide-modified polyol compounds having 2 to 20 carbon atoms. The active energy ray curable composition according to claim 1, characterized in that the polyol compound (a3) is at least one selected from the group consisting of ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol, octanediol, decanediol, glycerin, trimethylolpropane, pentaerythritol, and alkylene oxide modified products thereof. The active energy ray-curable composition according to claim 1, characterized in that the hydroxyl value of the polyol compound (a3) is 50 to 1850 mg KOH/g. 2. The active energy ray-curable composition according to claim 1, wherein the amine compound (a2) having a hydroxyl group is an amine compound represented by the following general formula (1):

General formula (1)

R ¹ _x -N- [(R ² O) _z -H] _y


(In the formula, R ¹ represents a linear or branched alkyl group having 1 to 20 carbon atoms,
^R2 represents a linear or branched alkylene group having 2 to 4 carbon atoms.
x represents an integer of 0 to 2, y represents an integer of 1 to 3, and x+y=3.
z represents an integer of 1 to 10.
In addition, when there are two or more [(R ² O)zH] groups, they may be the same or different. The active energy ray-curable composition according to claim 1, wherein the isocyanate compound (a4) is a diisocyanate compound. A method for producing the active energy ray-curable composition according to claim 1, comprising the steps of:
A method for producing an active energy ray-curable composition, comprising a step of reacting a (meth)acrylic compound (a1) having a hydroxyl group, an amine compound (a2) having a hydroxyl group other than (a1), a polyol compound (a3) other than (a1) and (a2), and an isocyanate compound (a4) in a polyfunctional (meth)acrylic compound (B) to obtain a urethane (meth)acrylate (A). A laminate having a substrate and a cured product of the active energy ray-curable composition according to any one of claims 1 to 7.