JP7078189B1 - Easy deinking laminate and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an easily deinking laminate having excellent deinking property in a paper recycling process and a method for producing the laminate, regardless of the type of active energy ray-curable ink. SOLUTION: This is an easily deinkable laminated body having an anchor layer and an ink layer in this order on a paper base material, and the anchor layer is an active energy ray containing a rosin-modified resin and a (meth) acrylate compound. An easily deinkable laminate in which a curable anchor agent is cured by an active energy ray and the ink layer is a layer in which an active energy ray curable ink is cured by an active energy ray. [Selection diagram] None

Description

The present invention relates to an easily deinkable laminate and a method for producing the laminate.

Compared to oxidative polymerization type, permeation drying type, and hot air drying type oil-based inks, active energy ray-curable inks have the convenience of being instantly cured and the characteristics of being able to form a strong cured film. It is also widely used in the field of package printing industry, from its non-VOC characteristics that do not contain petroleum-based volatile compounds, to beverage and food packaging applications, pharmaceutical packaging applications, cosmetic packaging applications, and general paper containers. ..

Especially in the food packaging field, as an ideal form of active energy ray-curable ink, an electron beam (hereinafter, also referred to as "EB") curable ink that does not contain a photopolymerization initiator and is safe and secure for the human body and the environment. However, it is hard to say that it is common due to the size of the initial capital investment, and ultraviolet (hereinafter, also referred to as “UV”) curable ink is common in the market.

In recent years, LED curing type systems that use a UV-LED light source that saves power and suppresses the generation of ozone and heat, and one metal halide lamp that eliminates the infrared region where heat is generated and the ultraviolet region where ozone is generated have been introduced. It is known that the energy-saving UV system used and the energy-saving UV system in which the number of conventional UV lamps is reduced from the usual 3 to 4 to one are gradually shifting.

Energy-saving UV curable inks designed to support these new systems have tended to switch from general oil-based inks in recent years in commercial printing, and are equivalent to general oil-based inks in terms of printability and print quality. Performance is required. In addition, these energy-saving UV curable inks are "recyclable U".
An increasing number of "V-curable inks" have been certified as Recyclable A rank.
However, not all UV systems in the market are replaced by energy-saving UV systems, and there are still many cases where ordinary UV systems with a proven track record (many of which are recyclable B rank) are used. UV curable inks are generally considered to be more difficult to recycle than general oil-based inks, except for recyclable energy-saving UV curable inks and some recyclable UV curable inks. In order to simplify recycling when collecting printed matter, it is considered very difficult and almost impossible to separate printed matter of active energy ray-curable ink such as UV curable type that is not recyclable. ing.

At a paper manufacturing company, used printing paper is finely crushed under an alkaline aqueous solution in the deinking process, and then it is removed by floating it in bubbles called flotation using a deinking agent to remove stains caused by ink components. I'm working on removing it. At this time, if a large amount of undecomposed black component called dirt remains, it becomes difficult to make a blank sheet when the paper is made again, and the recycling suitability tends to deteriorate. Generally, it is said that the amount of this dart is larger in UV curable ink than in general oil-based ink, and the more time, temperature, and large amount of deinking agent are used in the deinking process, the more deinking is possible, but paper. As a result, UV systems have become widespread and it has become difficult to recycle paper because the fibers of the ink sticks are broken down into small pieces and it becomes difficult to obtain strength, and the burden of time, power, chemicals, etc. increases. ..

On the other hand, in the field of inkjet ink, a method for producing deinked pulp (for example, Patent Document 1) and a method for producing deinked pulp (for example, Patent Document 2) have been proposed. However, these are not intended for UV curable inks that are difficult to deink.

It has also been reported that deinking is easy with energy-saving UV ink depending on the ink manufacturing method (for example, Patent Document 3), but it is drastic to improve the deinking property of UV curable ink that is not recyclable. It has not been resolved.

In addition, it has been reported that deinking is easy with UV curable ink using a conventional UV system depending on the ink manufacturing method (for example, Patent Document 4), but it is not a general formulation but a dedicated ink. Since it is necessary to use a special raw material such as a resin, there is no one that satisfies all of the ink cost, the physical properties of the ink, and the deinking property.

Therefore, it is desired to establish a printed matter having excellent deinking suitability using a general active energy ray-curable ink, which is expected to be further popularized, and a method for producing the printed matter.

Japanese Patent Application Laid-Open No. 2013-22109 JP 2011-080187 JP-A-2019-098698 Japanese Patent Application Laid-Open No. 2003-119681

The subject of the present invention is an easily deinking laminate which is excellent in physical properties as a laminate such as scratch resistance and is excellent in deinking property in a paper recycling process regardless of the type of active energy ray-curable ink. It is to provide a method of manufacturing a laminated body.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by the following laminate and the method for producing the laminate, and have completed the present invention.

That is, the present invention is an easily deinkable laminated body having an anchor layer and an ink layer in this order on a paper substrate.
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth) acrylate compound with active energy rays.
The present invention relates to an easily deinkable laminate in which the ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray.

Further, in the present invention, the rosin-modified resin is a reaction product of an addition reaction product of a loginic acid (A) and an α, β-unsaturated carboxylic acid or an acid anhydride (B) thereof, and a polyol (C). The present invention relates to the easily deinkable laminate.

Further, the present invention is a method for producing an easily deinkable laminate.
A step of applying an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth) acrylate compound to a paper substrate and curing it with active energy rays to obtain a laminate having an anchor layer on the paper substrate. 1 and
An easily deinkable laminate having an ink layer on the anchor layer is printed on the anchor layer of the laminate having an anchor layer on the paper substrate with active energy ray-curable ink and cured with active energy rays. Step 2 to obtain and
The present invention relates to a method for producing an easily deinkable laminate including.

Further, the present invention is a method for deinking a laminated body, which has an anchor layer and an ink layer in this order on a paper substrate.
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth) acrylate compound with active energy rays.
The ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray.
The present invention relates to a method for deinking a laminate, in which the laminate is stirred in an alkaline aqueous solution, the anchor layer is dissolved in the alkaline aqueous solution, and the ink layer is deinked from a paper substrate.

According to the present invention, an easily deinking laminate having excellent scratch resistance and other physical properties as a laminate and having excellent deinking property in a paper recycling process regardless of the type of active energy ray-curable ink, and the laminate. Was able to provide the manufacturing method of.

Hereinafter, the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the present invention. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

The present invention is an easily deinkable laminate having an anchor layer and an ink layer in this order on a paper substrate, in which the anchor layer contains active energy containing a rosin-modified resin and a (meth) acrylate compound. The line-curable anchoring agent is a layer cured by an active energy ray, and the ink layer is a layer in which an active energy ray-curable ink is cured by an active energy ray, which is an easily deinking laminate.

<Ink layer>
<Active energy ray curable ink>
The active energy ray-curable ink of the present invention (hereinafter, also referred to as “ink”) is characterized by containing a colorant and a (meth) acrylate compound.

[Colorant]
In the present invention, the ink contains a colorant. As the colorant, at least one of a pigment and a dye can be used. Pigments are preferred from the standpoint of light resistance.
The pigment that can be used in the present invention is not particularly limited, and known pigments can be used. As the pigment, either an inorganic pigment or an organic pigment can be used.

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

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

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

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

As the yellow pigment, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 18, 24, 73, 74, 75, 83, 93, 95, 97, 98, 100, 108, 109, 110, 114, 120, 128, 129, 138, 139, 174, 150, 151, 154, 155, 167, 174, 176, 180, 185, 213 and the like.

Blue or cyan pigments include C.I. I. Pigment Blue 1, 2, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62 and the like.

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

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

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

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

In the present invention, the pigment can be used at any content as long as the desired concentration can be reproduced on the printing paper surface, and is preferably 5 to 30% by mass with respect to the total amount of ink. More preferably, it is 10 to 25% by mass.

[(Meta) acrylate compound]
In the present specification, "(meth) acryloyl", "(meth) acrylic acid", "(meth) acrylate", and "(meth) acryloyloxy" are referred to as "acryloyl and / or", respectively, unless otherwise specified. It means "methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", and "acryloyloxy and / or methacryloyloxy". Further, "PO" represents "propylene oxide" and "EO" represents "ethylene oxide". Further, X of EO-modified (X) and PO-modified (X) represents the number of modified moles of EO and PO, and Y of polyethylene glycol (Y) di (meth) acrylate indicates the approximate molecular weight of the polyethylene glycol portion. ..

The active energy ray-curable ink of the present invention contains a (meth) acrylate compound.
The (meth) acrylate compound that can be used in the present invention is not particularly limited as long as it is a compound having one or more (meth) acryloyl, and includes any form of a monomer, an oligomer, or a polymer.
Here, the "monomer" means a compound having a minimum structural unit for constituting an oligomer or a polymer, and the "oligomer" means a polymer having a structural unit based on 2 to 100 monomers. ..

Specific examples of the (meth) acrylate compound used in the present invention include the compounds shown below.

[(Meta) acrylate compound]
(monomer)
2-Ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, β-carboxyethyl (meth) acrylate, 4-tert-butylcyclohexinol (meth) acrylate, tetrahydrofurfuryl Acrylate, alkoxylated tetrahydrofurfuryl acrylate, caprolactone (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isoamyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isodecyl (meth) acrylate, 3, 3,5-trimethylcyclohexanol (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (oxyethyl) (meth) acrylate, 1,4-Cyclohexanedimethanol (meth) acrylate, cyclic trimethylolpropaneformal (meth) acrylate, benzyl (meth) acrylate, EO-modified (2) nonylphenol acrylate, 2-methyl-2-ethyl-1,3-dioxolan A monofunctional (meth) acrylate monomer having one (meth) acryloyl group in a molecule such as -4-yl) methyl acrylate,
1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-dodecanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol ( 200) Di (meth) acrylate, polyethylene glycol (300) di (meth) acrylate, polyethylene glycol (400) di (meth) acrylate, polyethylene glycol (600) di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) ) Acrylate, Dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, EO-modified (2) 1,6-hexanediol di (meth) acrylate, PO-modified (2) Neopentyl glycol di (meth) Acrylate, (neopentyl glycol-modified) trimethylolpropandi (meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate, EO-modified (4) bisphenol A-di (meth) acrylate, PO-modified (4) bisphenol A-di (4) Bifunctional (meth) acryloyl group having two (meth) acryloyl groups in the molecule such as meta) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol-tricyclodecanedi (meth) acrylate, dicyclopentanyldi (meth) acrylate. Meta) Acrylate monomer,
Trimethylolpropane tri (meth) acrylate, EO-modified (3) trimethylolpropane tri (meth) acrylate, EO-modified (6) trimethylolpropane tri (meth) acrylate, PO-modified (3) trimethylolpropane tri (meth) acrylate , A trifunctional (meth) acrylate monomer having three (meth) acryloyl groups in a molecule such as pentaerythritol tri (meth) acrylate,
A tetrafunctional (meth) acrylate monomer having four acryloyl groups in the molecule, such as pentaerythritol tetra (meth) acrylate, EO-modified (4) pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate.
A pentafunctional (meth) acrylate monomer having five (meth) acryloyl groups in a molecule such as dipentaerythritol penta (meth) acrylate,
Examples thereof include a hexafunctional (meth) acrylate monomer having six (meth) acryloyl groups in a molecule such as dipentaerythritol hexa (meth) acrylate.

(Oligomer)
Among urethane acrylate oligomers such as aliphatic urethane acrylate oligomers and aromatic urethane acrylate oligomers, acrylic ester oligomers, polyester acrylate oligomers, and epoxy acrylate oligomers, those having 1 to 6 (meth) acryloyl groups can be mentioned.
[Other ingredients]
In the present invention, in addition to the above components, the ink is a polymerization initiator, an amine compound, a resin, a polymerization inhibitor, a surface tension adjuster, a wax, an extender pigment, a pigment dispersant, an antifoaming agent, and an ultraviolet absorber, if necessary. , Antioxidants and the like can be contained.

(Polymer initiator)
In the present invention, the ink may contain a polymerization initiator. The polymerization initiator preferably contains a polymerizable initiator for radical polymerization, and more preferably contains a photopolymerization initiator. The polymerization initiator in the present invention is a compound that generates a radical by causing a chemical change through the action of light or the interaction with the electron-excited state of the sensitizing dye. Above all, the polymerization initiator is to be initiated by means of exposure. It is preferable to use a photoradical polymerization initiator from the viewpoint of being able to obtain the above.

In the present invention, the photoradical polymerization initiator is not particularly limited, and known photoradical polymerization initiators can be used. Specific examples thereof include benzophenone compounds, dialkoxyacetophenone compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, thioxanthone compounds and the like. Further, the photopolymerization initiator may be used alone or in combination of two or more.

Examples of benzophenone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4,4'-bis (diethylamino) benzophenone, 4, 4'-bis (dimethylamino) benzophenone, [4- (methylphenylthio) phenyl] -phenylmethanone, 2-chloro-4phenyl-benzophenone, 1- {4-[(4-benzoylphenyl sulfanyl) phenyl]- Examples thereof include 2-methyl-2- (4-methylbenzenesulfonyl) propan-1-one and polybutylene glycolbis (4-benzoylphenoxy) acetate.

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

Examples of the α-hydroxyalkylphenone compound include 1-hydroxy-cyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxymethoxy) -phenyl]. -2-Hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl- Propane-1-one, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2,3-dihydro-6- (2-hydroxy-2-methyl-1) -Oxopropyl) -1,1,3-trimethyl-3- [4- (2-hydroxy-2-methyl-1-oxopropyl) phenyl] -1H-inden and 2,3-dihydro-5- (2-) Hydroxy-2-methyl-1-oxopropyl) -1,1,3-trimethyl-3- [4- (2-hydroxy-2-methyl-1-oxopropyl) phenyl] -1H-inden mixture, 2- Hydroxy-1- [4- [4- (2-hydroxy-2-methylpropynyl) benzyl] phenyl] -2-methylpropan-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy) -2-Methylpropanol) phenoxy] phenyl] -2-methylpropane-1-one, 1- [4- (1,1-dimethylethyl) phenyl] -2-hydroxy-2-methylpropane-1-one, etc. Can be mentioned.

Examples of the α-aminoalkylphenone compound include 2-methyl-1- [4- (methoxythio) -phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-). Morphorinophenyl) -butanone, 1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 1- (9, 9-Dibutyl-9H-Fluoren-2-yl) -2-Methyl-2-morpholin-4-yl-propan-1-one, polyethylene glycol di (β-4- [4- (2-dimethylamino-2) -Benzyl) Butanonylphenyl] piperazine) compound, 2-benzyl-2-dimethylamino-1- (4-piperidinylphenyl) -1-butanone, 1- (biphenyl-4-yl) -2-methyl-2 -Morphorinopropane-1-one, 1- (biphenyl-4-yl) -2-methoxy-2-morpholinopropane-1-one and the like can be mentioned.

Examples of the acylphosphine oxide compound include diphenylacylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphinoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide, and tris (phenyl). (2,4,6-trimethylbenzoyl) phosphinic acid) Polyethylene glycol ester, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, bis (2,4,6-dimethoxybenzoyl) -2,4,4 -Examples include trimethylpentylphosphine oxide.

Examples of the oxime ester compound include 1- [4- (phenylthio) phenyl] octane-1,2-dione, 2-benzoyloxime, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-. Carbazole-3-yl]-, 1- (o-acetyloxime), 3-cyclopentyl-1- (4- (phenylthio) phenyl) propane-1,2-dione-2- (o-benzoyloxime), 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1- (o-acetyloxime), methanone, [8-[[(acetyloxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl] -11- (2-ethylhexyl) -11H-benzo [a] carbazole-5-yl]-, (2,4,6-) Trimethylphenyl), 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propylthioxanthone, 2-chlorothioxanthone, and poly (oxy-). 1,4-Butanjiyl), α- [2-[(9-oxo-9H-thioxanthenyl) oxy] acetyl] -ω-[[2-[(9-oxo-9H-thioxanthenyl) oxy] acetyl] oxy]- , 1,3-di ({α- [1-chloro-9-oxo-9H-thioxanthen-4-yl] oxy} acetylpoly [oxy (1-methylethylene)]) oxy] -2,2-bis ({Α- [1-chloro-9-oxo-9H-thioxanthone-4-yl] oxy} acetylpoly [oxy (1-methylethylene)]) oxymethyl) propane and the like can be mentioned.

The content of the photopolymerization initiator is preferably 1 to 20% by mass, more preferably 5 to 15% by mass, based on the total amount of the ink.

(Amine compound)
In the present invention, the ink may contain an amine compound. The amine compound is not particularly limited, and known amine compounds can be used. By using the amine compound as a component of the active energy ray-curable ink, it is expected to work to enhance the effect of the hydrogen abstraction type photopolymerization initiator.
Specific examples include, for example, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, ethyl 4- (dimethylamino) benzoate, N, N-dihydroxyethylaniline, triethylamine. And N, N-dimethylhexylamine, poly (oxy-1,2-ethandyl, α- [4- (dimethylamino) benzoyl] -ω- [[4- (dimethylamino) benzoyl] oxy]-, bis N, N- [2- (4-dimethylaminobenzoyl) oxyethylene-1-yl] methylamine, poly (oxy-1,2-ethanediyl), α- [4- (dimethylamino) benzoyl] -ω- [[4 -(Dimethylamino) benzoyl] oxy]-, poly [oxy (methyl-1,2-ethandyl), α- [4- (dimethylamino) benzoyl-ω-butoxy-, 2-butoxyethyl-4- (dimethylamino) ) Benzoate, 2- (dimethylamino) ethylbenzoate, etc. As the amine compound, it may be used alone or in combination of two or more.

(resin)
In the present invention, the ink may contain a resin. By containing the resin, the curing shrinkage of the coating film that occurs during curing is alleviated, curling of the base material is suppressed, and the adhesion to the anchoring agent is improved.

The resin may be used alone or in combination of two or more. The resin content is preferably 1 to 20% by mass with respect to the total mass of the ink.

Specifically, as the resin, polyvinyl chloride, (meth) acrylic resin, styrene (meth) acrylic resin, epoxy resin, polyester resin, polyurethane resin, cellulose derivative (for example, ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride- Examples thereof include vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, diallyl phthalate resins, alkyd resins, rosin-modified alkyd resins, petroleum resins, urea resins, synthetic rubbers such as butadiene-acrylic nitrile copolymers. Of these, diallyl phthalate resin and polyester resin are more preferable from the viewpoint of dispersibility.

(Polymerization inhibitor)
In the present invention, the ink may contain a polymerization inhibitor. Specific examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, and N-nitrosophenylhydroxylamine. Examples include aluminum salts.

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

(wax)
In the present invention, the ink may contain wax. By including the wax, the abrasion resistance, the scratch resistance, the blocking prevention property, the slip property, and the scratch resistance can be further improved. The wax is not particularly limited, and known waxes can be used. For example, there are natural waxes and synthetic waxes.
Examples of the natural wax include carnauba wax, wood wax, lanolin, montan wax, paraffin wax, microcrystalline wax and the like.
Examples of the synthetic wax include Fishertropus wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, and the like.

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

(Constitution pigment)
In the present invention, the ink may contain an extender pigment. Examples of the extender pigment include clay, talc, barium sulfate, calcium carbonate, heavy calcium carbonate, barium carbonate, magnesium carbonate, silica, bentonite and the like.

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

Examples of the pigment dispersant include Ajinomoto Fine-Techno Co., Ltd.'s Ajispar series (Ajispar PB821, PB822, PB824, etc.), Lubrizol's Solspers series (Solsperse00, Solsperse32000, Solsperse38500, etc.), and Big Chemie's Disperbic series. (BYK-162, BYK-168, BYK-183, etc.) and the like.

The content of the pigment dispersant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total mass of the ink.

<Anchor layer>
The anchor layer of the laminate of the present invention contains a rosin-modified resin. Such an anchor layer can be obtained by applying an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth) acrylate compound and curing with an active energy ray.

<Active energy ray-curing anchoring agent>
The active energy ray-curable anchoring agent (hereinafter, also referred to as “anchoring agent”) in the present invention includes a rosin-modified resin and a (meth) acrylate compound.

[Rosin modified resin]
The rosin-modified resin in the present invention is a resin containing a rosin-derived skeleton in the resin skeleton. By containing a rosin-derived skeleton, it is possible to suppress curing shrinkage due to UV irradiation during high-speed printing, and it is possible to maintain the smoothness of the dry film, thus improving glossiness and adhesion to the substrate. do. In addition, since the rosin-modified resin has high solubility in the alkali used for deinking and the alkali solubility of the anchor layer is also high, deinking is easy even when an active energy ray-curable ink that is difficult to deink is used. Can be obtained as a laminated body.

The rosin-modified resin in the present invention is obtained by a deal alder reaction between an organic acid having a conjugated double bond contained in the loginic acids (A) and an α, β-unsaturated carboxylic acid or an acid anhydride thereof (B). Compounds, organic acids that do not have a conjugated double bond among the logoic acids (A), and other organic acids, and hydroxyl groups of the compound that formed an ester bond by the reaction of the carboxylic acid and the polyol (C) in each. A rosin-modified resin that has reacted to form an ester bond is preferable.

[Rosinic acids (A)]
The rosin-modified resin used to obtain the rosin-modified resin in the present invention refers to a monobasic acid having a cyclic diterpene skeleton. Abietinic acid having a conjugated double bond, and neoavietic acid, which is a conjugated compound thereof, representing a loginic acid, a disproportionated loginic acid, a hydrogenated loginic acid, an alkali metal salt of the compound, or the like. Examples thereof include palatinic acid and levopimaric acid, pimaric acid having no conjugated double bond, isopimaric acid, sandaracopimaric acid, dehydroavietic acid and the like. Moreover, as a natural resin containing these rosin acids (A), gum rosin, wood rosin, tall oil rosin and the like can be mentioned.

The blending amount of the rosin-modified resin used to obtain the rosin-modified resin in the present invention is preferably 20 to 70% by mass, preferably 30 to 60% by mass, based on the total blending amount of the resin raw materials. More preferred.
By setting the blending amount of the rosin acids (A) to 20% by mass or more, the alkali solubility becomes good. By setting the blending amount of the rosin acids (A) to 70% by mass or less, the solubility in the (meth) acrylate compound becomes good.

[Α, β-unsaturated carboxylic acid or acid anhydride thereof (B)]
Examples of the α, β-unsaturated carboxylic acid or its acid anhydride (B) used for obtaining the rosin-modified resin in the present invention include maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, isocrotonic acid and the like. Acid anhydride is exemplified. In view of the reactivity with the rosin acids (A), maleic acid or an acid anhydride thereof is preferable.

The blending amount of the α, β-unsaturated carboxylic acid or the acid anhydride (B) thereof in the present invention is preferably in the range of 60 to 200, preferably 70 to 180 mol% with respect to the loginic acids (A). It is more preferably in the range of 80 to 155 mol%, and particularly preferably in the range of 80 to 155 mol%. When the blending amount of the α, β-unsaturated carboxylic acid or the acid anhydride (B) thereof is adjusted within the above range, it is easy to obtain a rosin-modified resin having excellent friction resistance and adhesion.

[Carboxylic acids other than (A) and (B) (hereinafter also referred to as "other organic acids")]
In order to obtain the rosin-modified resin in the present invention, in addition to the loginic acids (A), α, β-unsaturated carboxylic acid or its acid anhydride (B), other organic acids may be used alone or in combination of two or more. You can also.
The blending amount of the other organic acids is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, based on the total blending amount of the resin raw material.

Specific examples of other organic acids include, but are not limited to, the following.

(Organic monobasic acid)
Aromatic monobasic acids such as benzoic acid, methyl benzoic acid, tertiary butyl benzoic acid, naphthoic acid, orthobenzoyl benzoic acid,
Examples thereof include compounds having a conjugated double bond such as conjugated linoleic acid, eleostearic acid, parinalic acid, and calendic acid but not having a cyclic diterpene skeleton.

(Alicyclic polybasic acid or its acid anhydride)
1,2,3,6-tetrahydrophthalic acid, 3-methyl-1,2,3,6-tetrahydrophthalic acid, 4-methyl-1,2,3,6-tetrahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid Examples thereof include acids, 1,3-cyclohexanedicarboxylic acids, 1,4-cyclohexanedicarboxylic acids, and acid anhydrides thereof.

(Other organic polybasic acids or acid anhydrides thereof)
Alkenyl succinic acid, o-phthalic acid, terephthalic acid, trimellitic acid, pyromerit, such as succinic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, dodecenyl succinic acid, pentadecenyl succinic acid. Acids and their acid anhydrides and the like can be mentioned.

[Polyol (C)]
The polyol (C) is rosin, a compound obtained by a deal alder reaction between an organic acid having a conjugated double bond contained in logonic acids (A) and an α, β-unsaturated carboxylic acid or an acid anhydride thereof (B). Among the acids (A), an organic acid having no conjugated double bond and other organic acids, each of which forms an ester bond by reaction with a carboxylic acid. In order to obtain the rosin-modified resin in the present invention, the polyols described below may be used alone or in combination of two or more. Specific examples of the polyol include, but are not limited to, the following.

(Linear alkylene divalent polyol)
1,2-Etandiol, 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-Nonandiol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16 -Hexadecanediol, 1,2-hexadecanediol, etc.

(Branched alkylene divalent polyol)
2-Methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propane Didiol, 2,4-dimethyl-2,4-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, dimethyloloctane, 2 -Ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2 , 4-diethyl-1,5-pentanediol, etc.

(Cyclic divalent polyol)
1,2-Cycloheptanediol, tricyclodecanedimethanol, 1,2-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol , 1,4-Cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, hydrogenated catechol, hydrogenated resorcin, cyclic alkylene divalent polyol such as hydrogenated hydroquinone; bisphenol A, bisphenol F, bisphenol Aromatic bivalent polyols such as S, catechol, resorcin, hydroquinone and the like.

(Other divalent polyols)
Divalent polyether polyols such as polyethylene glycol (n = 2 to 20), polypropylene glycol (n = 2 to 20), polytetramethylene glycol (n = 2 to 20), polyester polyols and the like.

(Trivalent polyol)
Glycerin, trimethylolpropane, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, hydroxymethylhexanediol, trimethyloloctane, etc.

(Polyol of 4 valence or more)
Linear, branched, and cyclic tetravalent or higher valent polyols such as pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, sorbitol, inositol, and tripentaerythritol.

The rosin-modified resin in the present invention preferably has a weight average molecular weight of 3,000 to 30,000, more preferably 3,000 to 15,000. When the weight average molecular weight is 3,000 to 30,000, the friction resistance and the adhesion are good.

The rosin-modified resin in the present invention preferably has an acid value of 20 to 100 mgKOH / g, more preferably 30 to 100 mgKOH / g, further preferably 40 to 90 mgKOH / g, and particularly preferably 50 to 80 mgKOH / g. When the acid value of the rosin-modified resin is 20 mgKOH / g or more, the alkali solubility is good, and when it is 100 mgKOH / g or less, the printability is good.

The melting point of the rosin-modified resin is preferably 50 ° C. or higher, more preferably 60 to 100 ° C. The melting point can be measured using MeltingPoint M-565 manufactured by BUCHI under the condition of a heating rate of 0.5 ° C./min.

[(Meta) acrylate compound]
As the (meth) acrylate compound contained in the anchoring agent in the present invention, the (meth) acrylate compound described in the above-mentioned active energy ray-curable ink can be used.

[Other ingredients]
In the present invention, the anchoring agent contains silica, alumina, polyethylene wax, defoaming agent, leveling agent, tackifier, preservative, antibacterial agent, rust preventive, etc., if necessary, in addition to the above components. be able to.

<Easy deinking laminate>
In the easily deinkable laminate of the present invention, an active energy ray-curable ink is printed on an anchor layer obtained by applying an anchor agent coated on a paper substrate and cured by the active energy ray, and the ink is cured by the active energy ray. Obtained by.

As a method for producing an easily deinkable laminate of the present invention,
Step 1 of applying an active energy ray-curable anchor agent containing a rosin-modified resin to a paper substrate and curing it with active energy rays to obtain a laminate having an anchor layer on the paper substrate.
An easily deinkable laminate having an ink layer on the anchor layer is printed on the anchor layer of the laminate having an anchor layer on the paper substrate with active energy ray-curable ink and cured with active energy rays. Step 2 to obtain and
including.

The easily deinkable laminate of the present invention may further have a varnish layer on the ink layer. The varnish used for the varnish layer is not particularly limited, and known ones can be used, but it is preferable to use an active energy ray-curable varnish or an aqueous varnish, and it is particularly preferable to use an active energy ray-curable varnish. ..

The paper substrate is not particularly limited, and known ones can be used. Specific examples thereof include coated paper such as art paper, coated paper and cast paper, non-coated paper such as high-quality paper, medium-quality paper and newspaper paper, and synthetic paper such as YUPO paper.

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

The active energy radiation source is not particularly limited, and a known source can be used. Specifically, LED (light emitting diode) such as mercury lamp, xenon lamp, metal hydride lamp, excimer lamp, ultraviolet light emitting diode (UV-LED), ultraviolet laser diode (UV-LD), EB (electron beam) irradiation device. , Gas / solid-state laser, etc.

In the present invention, the method for applying the active energy ray-curable anchoring agent is not particularly limited, and a known method can be used. Specifically, roll coater, gravure coater, flexo coater, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, transfer roll coater, kiss coater, curtain coater, cast coater, spray coater, die coater, offset printing. , Gravure printing, flexographic printing, etc.

<Ink removal>
In the present invention, deinking is a process for removing ink components from so-called used paper that has already been printed. Specifically, a flotation method is used in which the paper is finely crushed in an alkaline aqueous solution and then the ink separated from the fibers by using a deinking agent is floated and removed by generating fine bubbles. As the deinking agent, fatty acids (soap), fatty acid derivatives, oil and fat derivatives, higher alcohol derivatives and the like are mainly used. At this time, if a large amount of black components (also called dirt) that could not be decomposed remain, it will affect the blanking of the paper when it is made again, so it is a guideline for confirming the suitability for recycling. The area of miscellaneous items and the number of large recycles are important.

As the deinking agent, Kao Corporation deinking agents DI-7020, DI-7827, DI-7250, DI-767, Nissin Chemical Co., Ltd. DIA-Z series, DIA-Y series, Lion Specialty Chemicals Co., Ltd. Lyptor series etc. are available.

For the evaluation of printed matter, the whiteness is measured using a whiteness meter or the like according to the JIS P8208 pulp-porosity measuring method, and the principle of the miscellaneous matter is to judge the remaining ink by the hue difference of the image captured by the scanner of the personal computer. There are measuring methods such as using a measuring device (SCAN-MARK 800, Spec * Scan2000, etc.) dedicated to a microscope 3D scanner equipped with dirt counter software. Based on these, the degree of deinking was determined from the whiteness and the number of remaining inks.

Examples and comparative examples are shown below, and the present invention will be specifically described. However, the present invention is not limited to the following examples. In the examples and comparative examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

<Synthesis of rosin-modified resin 1>
A four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer is charged with 25 parts of gum rosin and 14 parts of maleic anhydride, and heated at 180 ° C. for 1 hour while blowing nitrogen gas. To obtain a reaction mixture. Then, by gas chromatograph mass spectrometry of the reaction mixture, it was confirmed that the Diels-Alder addition reaction was completed.
Next, 32 parts of benzoic acid, 15 parts of pentaerythritol, 14 parts of glycerin, and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added to the above reaction mixture, and 8 parts at 240 ° C. A dehydration condensation reaction was carried out over time to obtain a rosin-modified resin 1. The acid value of the rosin-modified resin 1 was 30, and the weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 25,800.
<Creation of rosin-modified resin varnish 1>
65.0 parts of DPHA, 6.5 parts of TMPTA (EO), and 3.5 parts of DiTMPTA were mixed, and the temperature was raised while stirring to 100 ° C. Next, 25.0 parts of the rosin-modified resin 1 was mixed and dissolved while keeping the temperature at 100 ° C. to prepare a rosin-modified resin varnish 1.

(Anchor agent 1)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and rosin-modified resin. 57.0 parts of varnish 1 was mixed, and the mixture was stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC1).

(Anchor agent 3)
Mix 62.0 parts of TMPTA (EO), 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and 30.0 parts of rosin-modified resin varnish 1 and use a butterfly mixer. The active energy ray-curable anchoring agent (AC3) was prepared by stirring and mixing.

<Synthesis of rosin-modified resin 2>
A four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer is charged with 45 parts of gum rosin and 16 parts of maleic anhydride, and heated at 180 ° C. for 1 hour while blowing nitrogen gas. To obtain a reaction mixture. Next, 39 parts of 2-butyl-2-ethyl-1,3-propanediol and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added to the above reaction mixture at 240 ° C. A dehydration condensation reaction was carried out for 8 hours to obtain a rosin-modified resin 2. The acid value of the rosin-modified resin 2 was 68, and the weight average molecular weight (Mw) was 5,600.
<Creation of rosin-modified resin varnish 2>
45.0 parts of DPHA, 16.5 parts of TMPTA (EO) and 13.5 parts of DiTMPTA were mixed and heated to 100 ° C. with stirring. Next, 25.0 parts of the rosin-modified resin 2 was mixed and dissolved while keeping the temperature at 100 ° C. to prepare a rosin-modified resin varnish 2.

(Anchor agent 2)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and rosin-modified resin. 57.0 parts of varnish 2 was mixed, and the mixture was stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC2).

(Anchor agent 4)
Mix 62.0 parts of TMPTA (EO), 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and 30.0 parts of rosin-modified resin varnish 2, and use a butterfly mixer. The active energy ray-curable anchoring agent (AC4) was prepared by stirring and mixing.

<Making diallyl phthalate resin varnish>
65.0 parts of DPHA, 6.5 parts of TMPTA (EO), and 3.5 parts of DiTMPTA were mixed, and the temperature was raised while stirring to 100 ° C. Next, 25.0 parts of diallyl phthalate resin Daiso Dup A was mixed and dissolved while keeping the temperature at 100 ° C. to prepare a diallyl phthalate resin varnish.

(Anchor agent 5)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and resin varnish. 57.0 parts were mixed, and the mixture was stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC5).

<Making petroleum resin varnish>
65.0 parts of DPHA, 6.5 parts of TMPTA (EO), and 3.5 parts of DiTMPTA were mixed, and the temperature was raised while stirring to 100 ° C. Next, 25.0 parts of petroleum resin Petrotac 90 were mixed and dissolved while keeping the temperature at 100 ° C. to prepare a petroleum resin varnish.

(Anchor agent 6)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and resin varnish. 57.0 parts were mixed, and the mixture was stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC6).

<Making acrylic resin varnish>
65.0 parts of DPHA, 6.5 parts of TMPTA (EO), and 3.5 parts of DiTMPTA were mixed, and the temperature was raised while stirring to 100 ° C. Next, 25.0 parts of acrylic resin S-6100 was mixed and dissolved while keeping the temperature at 100 ° C. to prepare an acrylic resin varnish.

(Anchor agent 7)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and acrylic resin varnish. Was mixed in 57.0 parts and stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC7).

(Anchor agent 8)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and polyester acrylate oligomer. 57.0 parts of PS-4500 was mixed, and the mixture was stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC8).

(Anchor agent 9)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and epoxy acrylate oligomer. 57.0 parts of EBECRYL 3700 was mixed, and the mixture was stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC9).

(Anchor agent 10)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and urethane acrylate oligomer. 57.0 parts of EBECRYL 2221 was mixed, and the mixture was stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC10).

(Anchor agent 11)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and chlorinated polyester. An active energy ray-curable anchor agent (AC11) was prepared by mixing 57.0 parts of an acrylate oligomer (PHOTOMER 5028: manufactured by IGM RESINS) and stirring and mixing using a butterfly mixer.

<Ink manufacturing example>
<Making oil-based resin varnish>
(Example of manufacturing rosin-modified phenolic resin)
In a reaction vessel, 54.3 parts of gumrosin was previously reacted with 30.8 parts of tertiary butylphenol and 9.4 parts of 92% by weight paraformaldehyde in a xylene solvent at 100 ° C. for 4 hours under a sodium hydroxide catalyst. The water-removed phenol resin was added dropwise at 150 ° C. and reacted for 2 hours. Further, 5.4 parts of glycerin was added, and 0.1 part of calcium oxide was used as a catalyst for reaction at 250 ° C. for 15 hours. During that time, the rosin phenol resin could be obtained by sequentially taking out the resin.

(Example of manufacturing rosin-modified phenolic resin varnish)
Next, in a stirrer, a reflux cooler with a water separator, and a four-necked flask with a thermometer, 45.0 parts of the rosin-modified phenolic resin, 44.0 parts of soybean oil, and 10 parts of soybean oil fatty acid normal butyl ester were placed as binder resins. A rosin-modified phenolic resin varnish was obtained by heating and stirring 0 part and 1.0 part of ALCH at 190 ° C. for 1 hour.

(Ink Production Example 1 (Oil Ink) (Ink other than active energy ray-curable ink))
RAVEN 1080 Ultra 17.0 parts, BA-2550 parts 3.0 parts, rosin-modified phenolic resin varnish 59.0 parts, soybean oil 20.0 parts, MK dryer 0.5 parts, drying inhibitor CP 0.5 parts. The ink was mixed, stirred and mixed using a butterfly mixer, and then dispersed in three rolls so that the maximum particle size was 7.5 μm or less to prepare an ink.

(Ink Production Example 2 (UV Ink Ink 1) (Active Energy Ray Curable Ink))
RAVEN 1080 Ultra 17.0 copies, BA-2550 copies 3.0 copies, TMPTA (EO) 6.0 copies, DiTMPTA 13.0 copies, DPHA 7.0 copies, 379 3.0 copies, DEABP 1.5 parts, DETX 1.5 parts, EDB 1.0 parts, and diallyl phthalate resin varnish 47.0 parts, stir and mix using a butterfly mixer, and then roll up to 3 rolls. The ink was prepared by dispersing so that the particle size was 7.5 μm or less.

(Ink Production Example 3 (UV Ink 2) (Active Energy Ray Curable Ink))
RAVEN 1080 Ultra 17.0 copies, BA-2550 copies 3.0 copies, TMPTA (EO) 6.0 copies, DiTMPTA 13.0 copies, DPHA 7.0 copies, 379 3.0 copies, DEABP 1.5 parts, DETX 1.5 parts, EDB 1.0 parts, and MIRAMER PS-4500 47.0 parts, stir and mix using a butterfly mixer, and then roll up to 3 rolls. Inks were prepared by dispersing them so that the particle size was 7.5 μm or less.

(Ink manufacturing example 4 (LED ink ink) (active energy ray curable ink))
RAVEN 1080 Ultra 17.0 copies, BA-2550 copies 3.0 copies, TMPTA (EO) 6.0 copies, DiTMPTA 10.0 copies, DPHA 7.0 copies, 379 3.0 copies, TPO 2.0 parts, DEABP 2.0 parts, 4MBP 2.5 parts, DETX 2.5 parts, EDB 1.0 parts, and diallyl phthalate resin varnish 44.0 parts, butterfly mixer After stirring and mixing using the above, ink was prepared by dispersing in three rolls so that the maximum particle size was 7.5 μm or less.

(Ink Production Example 5 (UV Flexo Ink) (Active Energy Ray Curable Ink))
RAVEN 1080 Ultra 15.0 copies, BA-2550 copies 1.0 copies, TMPTA (EO) 16.0 copies, DiTMPTA 5.0 copies, DPHA 7.0 copies, 379 3.0 copies, DEABP 2.0 parts, 4MBP 2.5 parts, DETX 2.5 parts, EDB 1.0 parts, and Solspecte24000 6.0 parts, after stirring and mixing using a butterfly mixer, in 3 rolls. The ink was prepared by dispersing so that the maximum particle size was 7.5 μm or less. Then, 39.0 parts of TMPTA (EO) was added and stirred and mixed using a butterfly mixer to prepare an ink.

(Ink Production Example 6 (UV Ink Yellow) (Active Energy Ray Curable Ink))
Permanent Yellow BHS 15.0 copies, TMPTA (EO) 6.0 copies, DiTMPTA 18.0 copies, DPHA 7.0 copies, 379 3.0 copies, DEABP 1.5 copies, DETX 1 copy After mixing 5.5 parts, 1.0 part of EDB, and 47.0 parts of diallyl phthalate resin varnish and stirring and mixing using a butterfly mixer, the maximum particle size becomes 7.5 μm or less with 3 rolls. Ink was prepared by dispersing in the above manner.

(Ink Production Example 7 (UV Ink Red) (Active Energy Ray Curable Ink))
Permanent Rubine L5B-01 20.0 copies, TMPTA (EO) 6.0 copies, DiTMPTA 13.0 copies, DPHA 7.0 copies, 379 3.0 copies, DEABP 1.5 copies, DETX 1.5 parts, EDB 1.0 part, and diallyl phthalate resin varnish 47.0 parts, and after stirring and mixing using a butterfly mixer, the maximum particle size is 7.5 μm or less on three rolls. The ink was prepared by dispersing so as to be.

(Ink Production Example 8 (UV Indigo) (Active Energy Ray Curable Ink))
Heliogen Blue D7088 20.0 parts, TMPTA (EO) 6.0 parts, DiTMPTA 13.0 parts, DPHA 7.0 parts, 379 parts 3.0 parts, DEABP 1.5 parts, DETX 1 part After mixing 5.5 parts, 1.0 part of EDB, and 47.0 parts of diallyl phthalate resin varnish and stirring and mixing using a butterfly mixer, the maximum particle size becomes 7.5 μm or less with 3 rolls. Ink was prepared by dispersing in the above manner.

(Ink Production Example 9 (EB Ink) (Active Energy Ray Curable Ink))
RAVEN 1080 Ultra 17.0 parts, BA-2550 parts 3.0 parts, TMPTA (EO) 6.0 parts, DiTMPTA 13.0 parts, DPHA 7.0 parts, and diallyl phthalate resin varnish 54 parts. After mixing 0 parts and stirring and mixing using a butterfly mixer, the ink was prepared by dispersing the ink on three rolls so that the maximum particle size was 7.5 μm or less.

The description of the notation of the materials used in the examples is as follows.
[Colorant]
-Permanent Yellow BHS: Made by Clariant, Permanent Yellow BHS (CI Pigment Yellow 174)
-Permanent Ruby L5B-01: manufactured by Clariant, Permanent Ruby L5B-01 (CI Pigment Red 57: 1).
HELIOGEN BLUE D7088: BASF, HELIOGEN BLUE D7088 (CI Pigment Blue 15: 3)
Raven 1080 Ultra: Made by Billa Carbon, Raven 1080 Ultra Powder (CI Pigment Black 7)
BA-2550: Alkaline Blue Toner BA-2550 (CI Pigmen) manufactured by Morimura Brothers, Inc.
tBlue 61)
[(Meta) acrylate compound]
-TMPTA (EO): BASF, LAROMER LR8863, trimethylolpropane ethylene oxide-modified triacrylate-DiTMPTA: Dicel Ornex, EBECRYL1142, dimethylolpropane tetraacrylate-DPHA: MIWON, MIRAMER M600, dipentaerythritol Hexaacrylate / PS-4500: MIWON, MIRAMER PS-4500, Polyester acrylate oligomer / EBECRYL 3700: Ornex / Belgium, EBECRYL 3700, Epoxy acrylate oligomer / EBECRYL 2221: Ornex / Belgium, EBECRYL 2221, urethane acrylate Oligomer PHOTOMER 5028: manufactured by IGM RESINS, PHOTOMER 5028, chlorinated polyester acrylate oligomer [resin]
・ Die Sodap A: Made by Osaka Soda Co., Ltd., Die Sodap A, Dialyl phthalate resin ・ Petrotac 90: Tosoh Co., Ltd., Petrotac 90, Petroleum resin ・ S-6100: Daido Kasei Kogyo Co., Ltd., Daika Rack S-6100 , Acrylic resin [photopolymerization initiator]
379: Omnirad 379, 1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone TPO: manufactured by IGM RESINS. Chemark Chemical, CHEMARK TPO, 2,4,6-trimethylbenzoyl-diphenylphosphinoxide DEABP: Chemark Chemical, CHEMARK DEABP, 4,4'-bis (dimethylamino) benzophenone, 4MBP: Soho Kogyo Co., Ltd. Made by SB-PI 712
DETX: Chemark Chemical, CHEMARK DETX, 2,4-diethylthioxanthone [amine compound]
-EDB: CHEMARK EDB, manufactured by Chemark Chemical, ethyl-4- (dimethylamino) benzoate [pigment dispersant]
Solspecte24000: Lubrizol, Solspesse24000,
[Metal dryer]
・ MK dryer: MK dryer manufactured by Toyo Ink Co., Ltd. [Drying inhibitor]
・ Drying inhibitor CP: Made by Toyo Ink Co., Ltd., Drying inhibitor CP
[Aluminum gelling agent]
・ ALCH: Kawaken Fine Chemical Co., Ltd., ALCH, Aluminum Ethyl Acetate Diisopropylate [Others]
・ Soybean oil fatty acid normal butyl ester: manufactured by Toshin Oil & Fat Co., Ltd., SFB2

Examples 1 to 13, Comparative Examples 1 to 11
<Printing of anchoring agent on the base material>
In Examples 1 to 4, 7 to 13, and Comparative Examples 1 to 8, an RI tester (a simple printing machine manufactured by Ming Seisakusho Co., Ltd.) was used, and an anchor agent was printed on one side of the base material with an ink gauge of 0.25 mL. Applied. Then, the coating film was cured under the condition of a conveyor speed of 30 m / min with an ultraviolet curing device (160 W / cm metal halide lamp) manufactured by Eye Graphics Co., Ltd. to prepare a laminate having an anchor layer on the substrate.
Further, in Examples 5 and 6, a bar coater (No. 4, manufactured by Yasuda Seiki Co., Ltd.) was used, and the anchoring agent shown in Table 1 was applied onto the substrate by the coater. Then, the coating film was cured under the condition of a conveyor speed of 30 m / min with an ultraviolet curing device (160 W / cm metal halide lamp) manufactured by Eye Graphics Co., Ltd. to prepare a laminate having an anchor layer on the substrate.

<Printing of ink>
In Examples 1 to 7, 10 to 13, and Comparative Examples 2 to 8, each sample ink shown in Table 1 was applied to a laminate having an anchor layer on the prepared substrate by using an RI tester and using an ink gauge of 0.25 mL. After printing, the printed matter is cured with an ultraviolet curing device (160 W / cm metahalide lamp) manufactured by Eye Graphics Co., Ltd. under the condition of a conveyor speed of 30 m / min, and the anchor layer and the ink layer are formed on the substrate. A laminate having the order was obtained.
Further, in Example 8, a RI tester was used to print LED ink ink on a laminate having an anchor layer on the prepared base material with an ink gauge of 0.25 mL, and then the printed matter was printed with an ultraviolet curing device manufactured by Eye Graphics Co., Ltd. The ink was cured under the condition of a conveyor speed of 100 m / min with a 160 W / cm metal halide lamp) to obtain a laminate having an anchor layer and an ink layer on the substrate in this order.
In Example 9, an RI tester was used to print EB ink ink on a laminate having an anchor layer on the prepared substrate with an ink gauge of 0.25 mL, and then the printed matter was printed with a low-energy electron beam manufactured by ESI Co., Ltd. Using an irradiation device (pressurized voltage 175 KV, atmosphere substituted with nitrogen at an oxygen concentration of 50 ppm), an electron beam of 30 KGy was irradiated to cure the ink, and a laminate having an anchor layer and an ink layer on the substrate was obtained in this order. rice field.
Further, in Comparative Example 1, oil-based ink ink (ink other than active energy ray-curable ink) was printed on the laminated body having an anchor layer on the prepared substrate using an RI tester with an ink gauge of 0.25 mL. The ink was cured by leaving it at room temperature for 24 hours to obtain a laminate having an anchor layer and an ink layer on the substrate in this order.
In Comparative Examples 9 and 10, each sample ink shown in Table 1 was printed directly on the substrate with an ink gauge of 0.25 mL using an RI tester, and then the developed material was subjected to an ultraviolet curing device (160 W / cm) manufactured by Eye Graphics. The ink was cured under the condition of a conveyor speed of 30 m / min with a metahalide lamp) to obtain a laminate having an ink layer on a substrate.
In Comparative Example 11, oil-based black ink (ink other than active energy ray-curable ink) was printed directly on the substrate using an RI tester with an ink gauge of 0.25 mL, and then left at room temperature for 24 hours to cure the ink. A laminate having an ink layer on the substrate was obtained.

The performance of the obtained laminate was evaluated by the following method. The results are shown in Table 1.

<Evaluation of laminated body>

(Evaluation of scratch resistance)
The ink surface was rubbed and evaluated using a cotton cloth using the prepared laminate. It can be judged that the less the rubbing is, the better the scratch resistance is. The evaluation criteria are as shown below, and 〇, 〇 △, and Δ are practically preferable.
〇: No rubbing on the printed surface where the ink is spread 〇 △: Rubbing to the surface layer of the printed surface where the ink is spread △: Rubbing to the middle part of the printed surface where the ink is spread △ ×: Printing with the ink spread Rubbing to the bottom of the surface ×: The coating on the printed surface where the ink is spread disappears

<Evaluation of deinkability>
The prepared laminates of Examples 1 to 13 and Comparative Examples 1 to 11 were aged at 60 ° C. for 1 week, and then stored in an environment of room temperature 23 ± 1 ° C. and humidity 50 ± 2% for another 10 days. Then, it was cut into 30 × 30 mm, and 58 g of each was used as a sample for the test.

A deinking agent (DI-manufactured by Kao Corporation) diluted to 1.5 L of warm water at 30 ° C., 7 mL of 3.75% sodium hydroxide aqueous solution (0.5% of paper), and 1.5% of 2 L pulper. After adding 7 mL (0.2% of paper) of 7027), a sample was added, and the mixture was stirred at 3000 rpm for 20 minutes. Two minutes after the start of stirring, the sample adhering to the lid was rinsed into the tank with a small amount of water. After completion of disaggregation, the sample was concentrated to 625 g using a 150 mesh wire mesh.

1350 mL of purified water at room temperature was added to 2 L pulper, and the sample was re-dissociated together with the concentrated sample for 1 minute. The sample was transferred from the 2 L pulper to a 10 L bucket, warm water at 30 ° C. ± 2 ° C. was added, and the mixture was diluted to 5.4 kg. Of that, 4.3 kg was separated and J. TAPPI No. With SF-25 manufactured by Far East Promotion Co., Ltd., which is a 39-compliant floatator, stirring was performed for 10 minutes under the conditions of a screw rotation speed of 1500 rpm and an air supply amount of 4 L / min.

The sample in the floatator tank was collected, water was added to the sample to dilute the total amount to 8 kg, and then an aluminum sulfate solution was added to adjust the pH to 5.0 to 5.6.

Wet paper was prepared using a 150-mesh wire mesh using a hand-squeezing machine (φ160 mm, manufactured by Kumagai Riki Kogyo Co., Ltd.) specified by JIS P8222, sandwiched between filter papers, and pressed at a pressure of 410 kPa for 5 minutes to dehydrate. Then, using a rotary drum dryer, the surface temperature was 90 ° C. for 4 minutes. The weight after drying was adjusted to 60 g, and 5 recycled papers were prepared.

From the obtained 5 recycled papers, impurities such as metal pieces that were apparently not derived from the ink were removed.

The performance of the obtained recycled paper was evaluated by the following method. The results are shown in Table 1.

<Evaluation of ISO whiteness>
The recycled paper produced was evaluated for ISO whiteness using a Color Touch PC manufactured by Technidiyne. The measured value was the average value of the obtained 5 sheets.
It can be determined that the higher the ISO whiteness, the better the deinking property. The evaluation criteria are as shown below, and 〇 and Δ are practically preferable.
〇: Very high whiteness (80-100)
Δ: High whiteness (70 to 79)
×: Whiteness is low (0 to 69)

<Evaluation of total area of miscellaneous goods>
Regarding the produced recycled paper, the dirt counter Apogee System Inc. Use Spec * Scan 2000 to measure the total area of impurities of 0.05 mm ² or more (mm ² / m ² ) and the number of impurities of 0.3 mm ² or more (pieces / 167 cm ² ). The procedure was carried out according to the method for measuring foreign matter. The measured value was the average value of the obtained 5 sheets.
It can be judged that the smaller the area of the foreign matter, the better the deinking property. The evaluation criteria are as shown below, and 〇, 〇 △, and Δ are practically preferable.
Evaluation of total area of foreign matter (mm ² / m ² ) 〇: Very good deinking property (less than 15 mm ² / m ² )
〇 △: Good deinking property (15 mm ² / m ² or more and less than 20 mm ² / m ² )
Δ: Deinking property is normal (20 mm ² / m ² or more and less than 40 mm ² / m ² )
△ ×: Poor deinkability (40 mm ² / m ² or more and less than 60 mm ² / m ² )
×: Very poor deinking property (60 mm ² / m ² or more)

<Evaluation of the number of today's miscellaneous items (0.3 mm ² or more)>
Regarding the produced recycled paper, the dirt counter Apogee System Inc. The number of contaminants (pieces / 167 cm ² ) of 0.3 mm ² or more was measured using Spec * Scan 2000 manufactured by JIS P8208 pulp-complex measurement method. The measured value was the average value of the obtained 5 sheets.
It can be judged that the smaller the number of foreign substances, the better the deinking property. The evaluation criteria are as shown below, and 〇 is practically preferable.
〇: Very good deinking property (0 pieces)
△ ×: Poor deinkability (1-2 pieces)
×: Very poor deinking property (3 or more)

Based on the above three evaluations related to deinkability, ISO whiteness, area of contaminants, number of contaminants, and all three evaluations that are practically preferable are judged to have good deinkability. Those with all evaluations of only 〇, 〇 △, and Δ, which are practically preferable, are judged to have deinkability, and the others are judged to have poor deinkability.
〇: Good deinking property △: Deinking property ×: Poor deinking property

From the above, it was found that the easily deinkable laminate of the present invention has deinkability while having print quality such as scratches required in the market.

Claims (4)

An easily deinkable laminate having an anchor layer and an ink layer in this order on a paper substrate.
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth) acrylate compound with active energy rays.
An easily deinkable laminate in which the ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray. 13. Easy deinking laminate. It is a method for manufacturing an easily deinkable laminate,
A step of applying an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth) acrylate compound to a paper substrate and curing it with active energy rays to obtain a laminate having an anchor layer on the paper substrate. 1 and
An easily deinkable laminate having an ink layer on the anchor layer is printed on the anchor layer of the laminate having an anchor layer on the paper substrate with active energy ray-curable ink and cured with active energy rays. Step 2 to obtain and
A method for producing an easily deinkable laminate including. A method of deinking a laminated body having an anchor layer and an ink layer in this order on a paper substrate.
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth) acrylate compound with active energy rays.
The ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray.
A method of deinking a laminate, in which the laminate is stirred in an alkaline aqueous solution, the anchor layer is dissolved in the alkaline aqueous solution, and the ink layer is deinked from the paper substrate.