JP2019019256A - Active energy ray-curable overcoat varnish - Google Patents

Abstract

To provide an active energy ray-curable overcoat varnish having high adhesiveness to a printed ink layer, showing excellent glossiness and friction resistance of a cured coating film, having small volume shrinkage occurring when cured, and having high curability that can suppress curling in a recorded matter, and a laminate.SOLUTION: The active energy ray-curable overcoat varnish comprises an amino group-containing styrene (meth)acrylic resin (A), a bi- or tri-functional (meth)acrylate monomer having a cyclic structure (B), and bi- to tetra-functional (meth)acrylate monomer (C) excluding the monomer (B).SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable overcoat varnish that exhibits excellent adhesion, gloss, low curling property and high curability to a substrate and an ink layer.

  In recent years, patterns applied to the surface of various substrates such as film, sheet, plate, etc., or the surface of the substrate by offset printing, gravure printing, screen printing, inkjet printing or electrophotographic printing, etc. By applying an active energy ray-curable overcoat varnish on top of decorations such as patterns, patterns, letters, etc., it is widely used to protect or gloss the surface of the base material itself or the decorative processed surface. Yes. When using an active energy ray-curable overcoat varnish for such surface processing, it is possible to form a film in a short time by applying ultraviolet rays after the overcoat varnish is applied. It is characterized by higher productivity than that. Furthermore, the active energy ray-curable overcoat varnish is a preferable material from the viewpoint of environmental protection because it does not release VOCs such as organic solvents into the atmosphere. Active energy ray curable overcoat varnish is an excellent material that can achieve both high productivity and environmental protection. Replacement is progressing rapidly. Such surface processing is widely used for magazine covers, picture books, posters, printed materials such as calendars, paperware products such as food packaging containers and sanitary products containers, and seal labels, and is familiar to our daily lives. .

  Among them, various film physical properties and various surface treatments have been studied as necessary.Active energy ray-curable overcoat varnish is devised as an oligomer or monomer to be included as a constituent material, or an additive is added. In addition, attempts have been made to impart various functions such as adhesion to a substrate, high glossiness, blocking resistance, and fingerprint resistance.

  For example, Patent Document 1 discloses that one ethylenic group is a hydroxyl group of a copolymer obtained by polymerizing a (meth) acrylate having one or more hydroxyl groups and a monomer having an ethylenically unsaturated group. An ultraviolet curable overprint varnish composition comprising a reactive resin obtained by esterification of a monomer having an unsaturated group and one carboxyl group, a trifunctional or lower reactive diluent, and a photoinitiator. An invention is disclosed in which a cured film having high adhesion, excellent solvent resistance and chemical resistance, and excellent surface gloss can be obtained by using a product.

  Further, in Patent Document 2, an active energy ray-curable varnish is applied to a support substrate, a cosmetic transfer film that can be used repeatedly is superimposed on the coated surface, and then the coating film is cured with active energy rays, A styrene-acrylic resin having a polar functional group, a styrene-acrylic resin having an alkyl side chain having 1 to 18 carbon atoms, a photopolymerizable monomer, and a photopolymerization initiator, used in a surface processing method for peeling a cosmetic transfer film. , An invention is disclosed that comprises a silicone-based and / or polymer-based wax additive, has a high glossiness, suppresses deterioration of glossiness with time, and has good post-processability. .

  Further, Patent Document 3 uses a polymer mainly composed of styrene-acrylic acid ester, has good adhesion to oil-based ink or water-based ink without using a primer, and has little darkening phenomenon due to soaking. An invention relating to an active energy ray-curable overprint varnish composition containing an organic solvent is disclosed.

  However, in the above invention, the adhesion and glossiness of ink layers printed by various printing methods, in particular, the ink layers printed by the electrophotographic method of the toner dispersed in the liquid are insufficient. It has been difficult to obtain an active energy ray-curable overcoat varnish that satisfies the physical properties. Furthermore, the active energy ray curable overcoat varnish has a large volume shrinkage (curing shrinkage) that occurs when it is cured, and has the inherent problem of curling the recorded material, and the need for low curl properties is very high. It was.

Japanese Patent Laid-Open No. 10-17787 JP 2012-136619 A Japanese Patent Laid-Open No. 5-140500

  The problem to be solved by the present invention is that the adhesion to the printed ink layer is high, the gloss of the cured coating film is excellent, and the volume shrinkage that occurs during curing is small. It is providing the active energy ray hardening-type overcoat varnish and laminated body which have high curability which can suppress.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the adhesive shown below, and have completed the present invention.
That is, the embodiment of the present invention includes an amino group-containing styrene (meth) acrylic resin (A), a 2- to 3-functional (meth) acrylate monomer (B) having a cyclic structure, and 2 other than the monomer (B). An active energy ray-curable overcoat varnish containing a tetrafunctional (meth) acrylate monomer (C).

  Moreover, the embodiment of the present invention is such that the content of the bifunctional to trifunctional (meth) acrylate monomer (B) having the cyclic structure is 15 to 40% by mass in the active energy ray-curable overcoat varnish. It is an energy ray curable overcoat varnish.

  An embodiment of the present invention is the active energy ray-curable overcoat varnish, wherein the ring of the ring structure is an aromatic ring and / or a heterocycle.

  In addition, in the embodiment of the present invention, the active energy ray-curable overtype comprises two or more kinds of the bifunctional to trifunctional (meth) acrylate monomers (B) having the cyclic structure and at least two different cyclic structures. Coat varnish.

Moreover, the embodiment of the present invention is a laminate in which a base material, an ink layer, and the active energy ray-curable overcoat varnish are laminated in this order.

  Further, an embodiment of the present invention is a laminate including a step of printing an ink layer on a substrate, a step of applying the active energy ray-curable overcoat varnish on the ink layer, and a step of irradiating active energy rays. It is a manufacturing method of a body.

  According to the present invention, the active energy which has high adhesion to the printed ink layer, is excellent in gloss and friction resistance of the cured coating film, is small in volume shrinkage upon curing, and can suppress curling of the printed matter. A wire-curable overcoat varnish and a laminate could be provided.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. First, terms used in this specification will be described. “(Meth) acrylate” means at least one of acrylate and / or methacrylate. “(Meth) acryloyl” means acryloyl and / or methacryloyl. The “active energy ray” means an energy ray having a property capable of causing a chemical change such as a chemical reaction on the irradiated material such as ultraviolet rays and electron beams. Unless otherwise specified, “part” means part by mass, and “%” means “% by mass”. Moreover, in the following description, other than “amino group-containing styrene (meth) acrylic resin (A)”, “2- to 3-functional (meth) acrylate monomer (B) having a cyclic structure” and “monomer (B)” The “2- to 4-functional (meth) acrylate monomer (C)” may be abbreviated as “resin (A)”, “monomer (B)”, and “monomer (C)”, respectively.

[Active energy ray-curable overcoat varnish]
One embodiment of the present invention relates to an active energy ray-curable overcoat varnish. The active energy ray-curable overcoat varnish includes a resin (A), a monomer (B), and a monomer (C). The active energy ray-curable overcoat varnish of the present invention can be used for an ink layer and / or a toner layer printed by various printing methods, and in particular, a toner dispersed in a liquid is printed by an electrophotographic method. The toner layer can be suitably used as an overcoat varnish.
Hereinafter, components that are or can be included in the active energy ray-curable overcoat varnish (hereinafter also simply referred to as an overcoat varnish) of the present embodiment will be described.

(Amino group-containing styrene (meth) acrylic resin (A))
The resin (A) used in the present invention can be arbitrarily used as long as it is obtained by a known technique as long as it is a styrene (meth) acrylic resin having at least an amino group. Specifically, an α, β-unsaturated double bond group-containing compound having an amino group, a styrene compound, and a copolymer with an α, β-unsaturated double bond group-containing compound (excluding styrene compounds) And styrene acrylic copolymer having a carboxylic acid group and ethyleneimine reacted (aminoethylated). Preferably, it is a copolymer of an α, β-unsaturated double bond group-containing compound having an amino group, a styrene compound and an α, β-unsaturated double bond group-containing compound (excluding a styrene compound). .

  Examples of the α, β-unsaturated double bond group-containing compound having an amino group include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl ( Acrylic esters such as (meth) acrylate, acrylamides such as N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, etc. These may be used alone or in combination of two or more. Of these, N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate are preferred. The content is determined according to the desired amine value.

  Examples of the styrenic compound include styrene, α-methyl styrene, vinyl styrene, etc., and these may be used alone or in combination of two or more. The content is preferably 10 to 60% by mass.

  As the α, β-unsaturated double bond group-containing compound, various compounds can be used other than the above-mentioned acrylic ester having an amino group and a styrene monomer. For example, methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate Etc., and these 1 type may be used independently and may use 2 or more types together.

  The weight average molecular weight of the resin (A) is preferably 5,000 to 20,000. More preferably, it is 8,000-17,000.

  In this specification, a weight average molecular weight is a polystyrene conversion weight average molecular weight measured by a gel permeation chromatography (hereinafter, GPC) measurement method. The specific measurement of GPC was calculated by comparison with the molecular weight of standard polystyrene using HLC-8020 manufactured by Tosoh Corp. as a device, TSKgel SuperHM-M manufactured by Tosoh Corp. as a column, and tetrahydrofuran as an eluent. .

  The amine value of the resin (A) is preferably 10 to 130 mgKOH / g. More preferably, it is 30-100 mgKOH / g.

  In the present specification, the amine value is a total amine value (mgKOH) measured according to the method of ASTM D2074.

  It is preferable that the glass transition point (henceforth Tg) of resin (A) is 10-100 degreeC. More preferably, it is 20-80 degreeC.

  The glass transition point may be calculated from the glass transition point of the homopolymer of the monomer constituting the resin, or may be measured experimentally. As a method of calculating from the glass transition point of the monomer homopolymer, for example, it is calculated from the formula of FOX. Moreover, as an experimental measurement method, it can be obtained by measuring a DSC curve using a differential scanning calorimeter.

  In the present invention, the content ratio of the resin (A) to the total mass of the overcoat varnish is preferably 5% by mass to 25% by mass, more preferably 10% by mass to 20% by mass.

  Commercially available products of the resin (A) used in the present invention include, for example, a beam set 271MS (weight average molecular weight 10,000, amine value 80 mgKOH / g), beam set 267F (weight average molecular weight 10,000, amine) manufactured by Arakawa Chemical Industries, Ltd. Value 21 mgKOH / g), beam set 255 (weight average molecular weight 10,000, amine value 30 mgKOH / g) and the like.

(2- to 3-functional (meth) acrylate monomer (B) having a cyclic structure)
The content of the monomer (B) with respect to the total mass of the overcoat varnish is preferably 15 to 40% by mass, and more preferably 20 to 35% by mass.

  The monomer (B) used in the present invention is a bi- to tri-functional (meth) acrylate having an aromatic ring, aliphatic hydrocarbon ring, or heterocyclic structure in the molecule. In the present specification, the “n-functional (meth) acrylate monomer” means a monomer having n (meth) acryloyl groups (n is a positive integer). Among these, it is preferable to include any one or more of 2 to 3 functional (meth) acrylates having an aromatic ring or a heterocyclic ring. Furthermore, from the viewpoints of adhesion, friction resistance, and volume shrinkage (curling property) during curing, it is more preferable to use two or more kinds of bi- or tri-functional (meth) acrylates having different cyclic structures in combination, and at least one kind is Among the heterocyclic rings, it is particularly preferable to include a bi- or trifunctional (meth) acrylate having a triazine ring.

  Furthermore, it is preferable to contain 2 to 3 functional (meth) acrylate having an aromatic ring.

  It is preferable that 15 to 90% of content of 2-3 trifunctional (meth) acrylate which has a triazine ring is contained in a monomer (B), More preferably, it is 30 to 70%.

  Specific examples of the bifunctional to trifunctional (meth) acrylate having an aromatic ring include EO-modified bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, EO-modified bisphenol F diacrylate, and propoxylated bisphenol F. Examples include diacrylate. Among these, EO-modified bisphenol A di (meth) acrylate is preferable. Here, “EO” means ethylene oxide, and “PO” means propylene oxide, which means modified by these.

  Specific examples of the bifunctional to trifunctional (meth) acrylate having an aliphatic hydrocarbon ring include tricyclodecane dimethanol di (meth) acrylate, cyclohexane dimethanol diacrylate, EO-modified hydrogenated bisphenol A di (meth) acrylate, and the like. Is mentioned.

  Examples of the bifunctional to trifunctional (meth) acrylate having a heterocyclic ring include dioxane glycol diacrylate, EO-modified isocyanuric acid diacrylate, and EO-modified isocyanuric acid triacrylate.

(2- to 4-functional (meth) acrylate monomers other than (B) (C))
In the present invention, the content of the monomer (C) with respect to the total mass of the overcoat varnish is preferably 30 to 70% by mass, more preferably 40 to 60% by mass.

  As monomer (C), ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,6- Hexanediol acrylic acid multimeric ester (bifunctional), 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,2-hexadecanediol di (me ) Acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, trimethylol Ethanetri (meth) acrylate, trimethylolhexanetri (meth) acrylate, trimethyloloctanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, and the like can be used. From the viewpoint of reducing the viscosity of the overcoat varnish, those having a viscosity at 25 ° C. of 60 mP · S or less are preferred. Specifically, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,6- Hexanediol acrylic acid multimeric ester, EO-modified trimethylolpropane triacrylate, and 1,9 nonanediol diacrylate are preferred. These are mainly used as reactive diluents. A monomer (C) may be used individually by 1 type, and may use 2 or more types together.

  It is preferable to use at least a bifunctional acrylate and a trifunctional acrylate in combination. From the viewpoint of volume shrinkage during curing, the total amount of trifunctional acrylate and tetrafunctional acrylate in the monomer (C) is preferably 5% by mass or less based on the total mass of the overcoat varnish.

(Other polymerizable compounds)
Other polymerizable compounds other than those described above may be contained as long as the effects of the present invention are not lowered. Specifically, it is preferably 5% by mass or less based on the total mass of the overcoat varnish. Other polymerizable compounds that can be used in the present invention include compounds having at least one α, β-unsaturated double bond group in the molecule, and examples include monomers, oligomers, and polymers.

(Photopolymerization initiator)
As the photopolymerization initiator used in the present invention, as a hydrogen abstraction type, benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl- 4'-methyl-diphenyl sulfide, 2-isopropylthiocisanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, acetophenone / aryl ketone initiator, 4,4'-bis (Diethylanino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, isoamyl p-dimethylaminobenzoate, p-dimethylaminoacetophenone-dialkylaminoaryl ketone initiator, Xanthone, and the like xanthone Part halogen-substituted and multi-ring carbonyl-based initiators.

Further, as a cleavage type photopolymerization initiator, benzoin, benzoin methyl ether, benzoin isopropyl ether, α-acrylbenzoyl benzoin system, benzyl, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, benzylmethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4- Isopropylphenyl-2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 4- (2-acryloyloxyethoxy) phenyl-2-hydroxy-2- Propylke Emissions, and the like diethoxyacetophenone.
The photoinitiator in this invention may be used individually by 1 type, and may use 2 or more types together.

  1-20 mass% is preferable with respect to the total mass of an overcoat varnish, and, as for the content rate of a photoinitiator, 5-15 mass% is more preferable.

(Photopolymerization initiation aid)
The overcoat varnish of the present invention can also contain a photopolymerization initiation assistant.
As photopolymerization initiation aids, triethanolamine, methyldiethanolamine, triisopropanolamine / aliphatic amine, 4,4 ″ -diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Examples thereof include isoamyl dimethylaminobenzoate and dibutylethanolamine.

  0.1-5 mass% is preferable with respect to the total mass of overcoat varnish, and, as for the content rate of a photoinitiation adjuvant, 0.5-3 mass% is more preferable.

(Other ingredients)
A leveling agent, an antistatic agent, a surfactant, an antifoaming agent, a polymerization inhibitor, an ultraviolet absorber, a wax, a slipping agent and the like can be added to the overcoat varnish of the present invention as necessary.

  The overcoat varnish of the present invention preferably contains substantially no solvent. “Substantially” means 5% or less, preferably 3% or less.

(Product laminate and its manufacturing method)
The laminate of the present invention has an overcoat layer obtained by curing the active energy ray-curable overcoat varnish of the present invention on an ink layer printed on a substrate.
The laminate includes at least one overcoat layer on the surface of an ink layer printed on a substrate by a printing method such as electrophotographic printing, inkjet printing, screen printing, flexographic printing, offset printing, and gravure printing. Formed.
The ink layer of the laminate of the present invention is preferably printed by electrophotographic printing.
The overcoat layer of the present invention may be formed on a part of the ink layer or on the entire surface of the ink layer. The overcoat layer may be formed on a portion where the ink layer is not printed.
The thickness of the overcoat layer in the laminate of the present invention is preferably 1 to 10 μm, and more preferably 3 to 7 μm.

  The method for producing a laminate of the present invention includes a step of printing an ink layer on a substrate by electrophotographic printing, a step of applying the active energy ray-curable overcoat varnish of the present invention on the ink layer, and the active energy. It is preferable to include a step of curing the wire curable overcoat varnish.

  There is no restriction | limiting in particular as a base material, A well-known thing can be used. Specifically, art paper, coated paper, coated paper such as cast paper, high quality paper, medium quality paper, non-coated paper such as newspaper paper, synthetic paper such as YUPO, PET (polyethylene terephthalate), PP (polypropylene) ) And OPP (biaxially oriented polypropylene).

  The process of printing the ink layer in electrophotographic printing is not particularly limited and can be arbitrarily selected from known methods. In a preferred embodiment, printing is performed using Indigo (registered trademark), a digital printer manufactured by Hewlett-Packard Company. The ink layer is preferably printed by electrophotographic printing with electrostatic ink containing at least a colorant, an ethylene acrylic resin binder and a liquid dispersion medium.

There are no particular restrictions on the application of the active energy ray-curable overcoat varnish, and any known method can be used. Specific examples include a roll coater, a rod coater, a blade, a wire bar, a doctor knife, a spin coater, a screen coater, a gravure coater, an offset gravure coater, and a flexo coater.
Moreover, you may heat at the time of coating as needed.

  The step of curing the active energy ray-curable overcoat varnish of the present invention is performed by irradiating ultraviolet rays (light) from a light source. In this step, the photopolymerization initiator contained in the active energy ray-curable overcoat varnish is decomposed by irradiation with ultraviolet rays to generate initiation species such as radicals, acids and bases, and the polymerization reaction of the polymerizable compound Promoted by the function of the starting species. Or in this process, the polymerization reaction of a polymeric compound starts by irradiation of an ultraviolet-ray.

  There is no restriction | limiting in particular as a light source, A well-known thing can be used. Specifically, a mercury lamp, a xenon lamp, a metal halide lamp, an LED (light emitting diode) such as an ultraviolet light emitting diode (UV-LED), and an ultraviolet laser diode (UV-LD) can be used as the light source.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these.

(Synthesis example 1 of amino group-containing styrene (meth) acrylic resin (A))
In a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, a condenser, and a stirrer, 90.1 parts of methyl ethyl ketone (MEK) was charged and replaced with nitrogen gas. The reaction vessel was heated to 110 ° C., 33.0 parts of N, N-dimethylamino methacrylate, 57.0 parts of styrene, 10.0 parts of butyl acrylate, and 2,2′-azobis (2 -A methylpropionate) dimethyl (Wako Pure Chemical Industries, Ltd. product: V-601) 9.0% mixture was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropping, the reaction was further carried out at 110 ° C. for 3 hours, 0.9 part of V-601 was added, and the reaction was carried out at 110 ° C. for 1 hour. Thereafter, MEK was removed under reduced pressure to obtain amino group-containing styrene acrylic resin 1 (weight average molecular weight 9800, amine value 118 mgKOH / g).

(Synthesis Examples 2 to 4 of amino group-containing styrene (meth) acrylic resin (A))
Amino group-containing styrene (meth) acrylic resins 2 to 4 were obtained in the same manner as in Synthesis Example 1 except that the monomers and amounts described in Table 1 were changed. The weight average molecular weight and amine value were as described in Table 2.

(Comparative resin synthesis examples 1-2)
Comparative resin 1 and comparative resin 2 were obtained in the same manner as in Synthesis example 1, except that the raw materials and amounts described in Table 2 were changed. The weight average molecular weight and amine value were as described in Table 2.

Abbreviations in Tables 1 and 2 are as follows. The numerical values in Tables 1 and 2 represent “parts” unless otherwise specified, and blanks indicate that they are not blended.
DM: N, N-dimethylaminoethyl methacrylate St: styrene BA: butyl acrylate 2-HEA: 2-ethylhexyl acrylate BMA: butyl methacrylate CHMA: cyclohexyl methacrylate MMA: methyl methacrylate

(How to create an overcoat varnish)
The materials described in Tables 3 to 5 were mixed, and the overcoat varnishes of Examples 1 to 24 and Comparative Examples 1 to 9 were obtained by stirring at 50 ° C. for 30 minutes. In addition, unless otherwise indicated, the numerical value in Tables 3-5 represents a "part", and the blank represents that it has not mix | blended.

Abbreviations in Tables 3 to 5 are as follows.
(Amino group-containing styrene (meth) acrylic resin (A))
Beam set 271MS: Arakawa Chemical Industries amino group-containing styrene acrylic resin, weight average molecular weight 10,000, amine value 80 mgKOH / g
Beam set 255: Arakawa Chemical Industries, Ltd. amino group-containing styrene acrylic resin, weight average molecular weight 10,000, amine value 30 mgKOH / g
(Comparative resin)
-Joncryl 611: a carboxylic acid-modified styrene acrylic resin manufactured by BASF, weight average molecular weight 8100, amine value 0 mgKOH / g
Joncryl 804: hydroxyl group-modified styrene acrylic resin, weight average molecular weight 12500, amine value 0 mgKOH / g

(2- to 3-functional (meth) acrylate monomer (B) having a cyclic structure in the molecule)
NK ester A-DCP: manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester (registered trademark) A-DCP, tricyclodecane dimethanol diacrylate, HBPE-4: manufactured by Daiichi Kogyo Seiyaku, New Frontier (registered trademark) HBPE- 4. Ethylene oxide (EO) modified hydrogenated bisphenol A diacrylate photomer 4028: manufactured by iGM, Photomer (registered trademark) 4028, EO modified bisphenol A diacrylate Aronix M-315: manufactured by Toagosei Co., Ltd., Aronix (registered trademark) ) M-315, a mixture of isocyanuric acid EO-modified diacrylate and isocyanuric acid EO-modified triacrylate. 3 to 13% content of isocyanuric acid EO-modified diacrylate
・ Aronix M-215: manufactured by Toa Gosei Co., Ltd., Aronix (registered trademark) M-215, isocyanuric acid EO-modified diacrylate ・ Fancryl FA-731A: manufactured by Hitachi Chemical Co., Ltd., Funcryl FA-731A, Tris (2-acryloyloxy) Ethyl) isocyanurate

(2- to 4-functional (meth) acrylate monomers other than (B))
・ Biscoat 230D: manufactured by Osaka Organic Chemical Industry Co., Ltd., biscoat # 230D, 1,6-hexanediol acrylic acid multimeric ester (bifunctional)
SR508: Arkema, SR508, dipropylene glycol diacrylate TPGDA: Daicel Ornex, TPGDA, tripropylene glycol diacrylate ND-DA: Daiichi Kogyo Seiyaku, New Frontier (registered trademark) ND- DA, 1,9-nonanediol diacrylate, Laromar LR8863: manufactured by BASF, Laromer (registered trademark) LR8863, EO-modified trimethylolpropane triacrylate (trifunctional)
SR355NS: Arkema, SR355NS, ditrimethylolpropane tetraacrylate

(Other polymerizable compounds)
NK ester LA: Shin Nakamura Chemical Co., Ltd., NK ester (registered trademark) LA, lauryl acrylate (monofunctional)
Aronix M-101A: manufactured by Toa Gosei Co., Ltd., Aronix (registered trademark) M-215, phenol EO-modified acrylate (monofunctional)
・ Fancryl FA-513AS: manufactured by Hitachi Chemical Co., Ltd., fancryl FA-513AS, dicyclopentanyl acrylate ・ CN968: manufactured by Sartomer, aromatic urethane acrylate (hexafunctional)
Laromar DPHA: manufactured by BASF, Laromer (registered trademark) DPHA, dipentaerythritol hexaacrylate

(Photopolymerization initiator)
SB-PI712: manufactured by Sort, SB-PI712, 4-methylbenzophenone, Dido UV cure 174: manufactured by Daido Kasei Kogyo, Dido UV cure 174, 1-hydroxycyclohexyl phenyl ketone

(Photopolymerization initiation aid)
Amino alcohol MDA: manufactured by Nippon Emulsifier Co., Ltd., amino alcohol MDA, N-methyldiethanolamine)

(Other ingredients)
TEGO AIREX 920: manufactured by Evonik, TEGO (registered trademark) AIREX 920, antifoaming agent)

The obtained overcoat varnish was evaluated for performance by the following method.
(How to create a test piece)
An ink layer is solid-printed on a coated paper as a base material using Indigo 30000 manufactured by HP of an electrophotographic printing machine using electrostatic ink dispersed in a liquid, and 0 is printed on the entire surface using an RI tester. The overcoat varnish was developed in a 5 ml volume. Thereafter, the overcoat varnish was cured by color development at a conveyor speed of 30 m / min, a mercury lamp of 160 W / cm, and a distance between the recorded material and the mercury lamp of 5 cm, and a recorded material for testing was prepared.

(Adhesion)
A 12 mm wide adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd.) is applied to the surface where the overcoat varnish is developed using the test recorded material created by the above method, and the tape is peeled off at 90 ° to the recorded material. The peeled surface of the recorded material was evaluated according to the following criteria. It is evaluated that the level is 3 or more and there is no practical problem.
5: No peeling at all 4: The peeling area of the coating film is 1% or more and less than 5% 3: The peeling area of the coating film is 5% or more and less than 20% 2: The peeling area of the coating film is 20% or more and less than 60% 1: Coating More than 60% of film peeling area

(Glossy)
Gloss value at 60 ° reflection angle of the surface where the overcoat varnish was developed with the gloss meter GM-26D manufactured by Murakami Color Research Laboratory using the test recorded material created by the above method (based on JIS Z 8741) Was measured. It is evaluated that the level is 3 or more and there is no practical problem.
5:80 or more 4:60 or more and less than 80 3:40 or more and less than 60 2:20 or more and less than 40 1:20

(Yellowing)
The b ^* value in the CIE 1976 L ^* a ^* b ^* color space of the surface on which the overcoat varnish was developed was measured with the X-Rite eXact using the test recorded material prepared by the above method. It is evaluated that the level is 3 or more and there is no practical problem.
5: Less than 0.5 4: 0.5 or more and less than 1.0 3: 1.0 or more and less than 1.5 2: 1.5 or more and less than 2.0 1: 2.0 or more

(Abrasion resistance)
Gakushin type friction fastness tester load 500g 500 times using the recorded material for testing created by the above method. Paper: A surface on which the overcoat varnish of the recorded material was developed by conducting a friction resistance test on high-quality paper. The wounds that occurred were evaluated. It is evaluated that the level is 3 or more and there is no practical problem.
5: No scratch 4: Scratch area 0% or more and less than 10% 3: Scratch area 10% or more and less than 30% 2: Scratch area 30% or more and less than 50% 1: Scratch area 50% that's all

(Curl property)
For curling, overcoat varnish was applied to 50 μm-treated OPP (biaxially oriented polypropylene film) with bar coater # 3, conveyor speed was 30 m / min, mercury lamp was 160 W / cm, and distance between recorded material and lamp was 5 cm. I made a record. The obtained recorded matter was cut into 10 cm × 10 cm, placed on a horizontal plane, the distance from the horizontal plane to the four corners of the recorded matter was measured, and evaluated according to the following criteria. A level of 3 or more is a practical level.
5: Less than 4 mm 4: 4 mm or more and less than 6 mm 3: 6 mm or more and less than 8 mm 2: 8 mm or more and less than 10 mm 1: 10 mm or more

(Curable)
For curability, the overcoat varnish was applied onto the coated paper using a bar coater # 3, and the recorded material was allowed to pass under conditions of a conveyor speed of 10 m / min, a mercury lamp of 128 W / cm, and a distance between the recorded material and the lamp of 5 cm. The number of passes until the tack disappears from the surface was evaluated. It is evaluated that the level is 3 or more and there is no practical problem.
5: 1 times 4: 2 times 3: 3 times 2: 4 times 1: 5 times or more

  Similar results were obtained for ink layers printed by offset printing and gravure printing. According to the present invention, an active energy ray curable overcoat varnish is used, and an ink layer printed by various printing methods, particularly an electrostatic ink dispersed in a liquid, is highly applied to an ink layer printed by electrophotographic printing. It has become possible to provide a laminate having adhesiveness and further having high gloss, high friction resistance, and low curl.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the active energy ray-curable overcoat varnish shown below, and have completed the present invention.
That is, the embodiment of the present invention includes an amino group-containing styrene (meth) acrylic resin (A), a 2- to 3-functional (meth) acrylate monomer (B) having a cyclic structure, and 2 other than the monomer (B). An active energy ray-curable overcoat varnish containing a tetrafunctional (meth) acrylate monomer (C) ,
The 2 to 3 functional (meth) acrylate monomer (B) having the cyclic structure includes a 2 to 3 functional (meth) acrylate monomer having a heterocyclic ring and a 2 to 3 functional (meth) acrylate monomer having an aromatic ring. This is an active energy ray-curable overcoat varnish .

Claims (6)

  Amino group-containing styrene (meth) acrylic resin (A), a 2- to 3-functional (meth) acrylate monomer (B) having a cyclic structure, and a 2- to 4-functional (meth) acrylate monomer (C) other than the monomer (B) And an active energy ray-curable overcoat varnish.    2. The active energy ray-curable overcoat according to claim 1, wherein the content of the bifunctional to trifunctional (meth) acrylate monomer (B) having the cyclic structure is 15 to 40% by mass in the active energy ray-curable overcoat varnish. Coat varnish.   The active energy ray-curable overcoat varnish according to claim 1 or 2, wherein the ring of the cyclic structure is an aromatic ring and / or a heterocyclic ring.   The active energy ray curing according to any one of claims 1 to 3, comprising two or more kinds of the bi- to tri-functional (meth) acrylate monomer (B) having the cyclic structure, wherein at least two kinds of cyclic structures are different. Type overcoat varnish.   The laminated body in which the base material, the ink layer, and the active energy ray hardening-type overcoat varnish of any one of Claims 1-4 were laminated | stacked in this order.   The process of printing an ink layer on a base material, The process of apply | coating the active energy ray hardening-type overcoat varnish of any one of Claims 1-4 on the said ink layer, and the process of irradiating an active energy ray. The manufacturing method of the laminated body containing.