JP2023018605A - Laminate deinking method - Google Patents

Abstract

To provide an easily deinked laminate which is excellent in deinking property in sheet recycling treatment regardless of the kind of active energy ray-curable ink, and a method for manufacturing the laminate; and to provide a method for manufacturing an easily deinked laminate which includes a step 1 of coating an aqueous anchor agent containing an aqueous resin onto a paper base material, drying the anchor agent in an oven, and obtaining a laminate having an anchor layer on the paper base material, and a step 2 of performing printing on the anchor layer of the laminate having the anchor layer on the paper base material by active energy ray-curable ink, curing the ink with active energy rays, and obtaining an easily deinked laminate having an ink layer on the anchor layer.SOLUTION: An easily deinked laminate has an anchor layer and an ink layer in this order on a paper base material, wherein the anchor layer contains an aqueous resin, and the ink layer is a layer obtained by curing active energy ray-curable ink with active energy rays.SELECTED DRAWING: None

Description

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

Active energy ray-curing inks are more convenient than oxidative polymerization, permeation drying, and hot air drying oil-based inks because they cure instantaneously, and they can form strong cured films. In addition, it is widely used in the package printing industry, from beverage and food packaging, pharmaceutical packaging, cosmetic packaging, and general paper containers, due to its non-VOC properties that do not contain petroleum-based volatile compounds. .

Especially in the field of food packaging, 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 is an ideal form of active energy ray curable ink. However, it is difficult to say that it is common because of the large initial capital investment, and ultraviolet (hereinafter also referred to as "UV") curable ink is common in the market.

In recent years, we have introduced an LED curing system that uses a UV-LED light source that is power-saving and suppresses the generation of ozone and heat, and a single metal halide lamp that eliminates the infrared region that generates heat and the ultraviolet region that generates ozone. It is known that there is a gradual transition to energy-saving UV systems used, and energy-saving UV systems in which the number of conventional UV lamps has been reduced from the usual 3-4 lamps to 1 lamp.

Energy-saving UV curable inks designed to support these new systems are becoming more common in commercial printing in recent years as they switch from general oil-based inks. performance is required. In addition, these energy-saving UV curable inks are called “Recyclable U
"V curable ink" has been certified as A rank for recyclability.
However, not all UV systems in the market will be replaced by energy-saving UV systems, and there are still many cases where ordinary UV systems (many of which are B-ranked for recyclability) that have a proven track record are still used. Except for recyclable energy-saving UV curable inks and some recyclable UV curable inks, it is generally considered that UV curable inks are more difficult to recycle than general oil-based inks. In order to facilitate recycling when collecting printed materials, it is considered extremely difficult and almost impossible to separate printed materials of active energy ray-curable inks such as UV-curable inks that are not recyclable. ing.

At paper manufacturing companies, used printing paper is finely pulverized in an alkaline aqueous solution during the deinking process, and then floated on bubbles called flotation using a deinking agent to remove stains due to ink components. I am working on removing it. At this time, if a large amount of undecomposed black component called dirt remains, it becomes difficult to make the paper blank when the paper is made again, which tends to deteriorate the suitability for recycling. In general, the amount of this dirt is said to be greater with UV curable ink than with general oil-based ink. The fibers of the paper break down into small pieces, making it 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 (eg, Patent Document 1) and a method for producing deinked pulp (eg, Patent Document 2) have been proposed. However, these are not intended for UV curable inks, which are considered to be difficult to deink.

In addition, it has been reported that deinking is easy with energy-saving UV ink depending on the ink manufacturing method (for example, Patent Document 3), but there is a drastic improvement in deinking performance of non-recyclable UV curable ink. No solution has been reached.

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

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

JP 2013-221059 JP 2011-080187 JP 2019-098698 JP 2003-119681

An object of the present invention is to provide an easy deinking laminate that has excellent physical properties as a laminate, such as adhesion and scratch resistance, and that has excellent deinking properties in paper recycling processing regardless of the type of active energy ray-curable ink. It is an object of the present invention to provide a body and a method of manufacturing the laminate.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by the laminate and the method for producing the laminate described below, and have completed the present invention.

That is, the present invention provides an easily deinkable laminate having an anchor layer and an ink layer in this order on a paper substrate,
The anchor layer contains an aqueous resin,
It 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.

The present invention also relates to the easily deinkable laminate, wherein the water-based resin contains a water-based acrylic resin.

The present invention also relates to the easily deinkable laminate, wherein the aqueous resin has an acid value of 25 to 300 mgKOH/g.

The present invention also provides a method for producing an easily deinkable laminate,
Step 1 of applying a water-based anchoring agent containing a water-based resin to a paper base material and drying it in an oven to obtain a laminate having an anchor layer on the paper base material;
An easily deinkable laminate having an ink layer on the anchor layer is obtained by printing with an active energy ray-curable ink on the anchor layer of the laminate having the anchor layer on the paper substrate and curing with the active energy ray. Step 2 of obtaining
It relates to a method for manufacturing an easily deinkable laminate.

The present invention also provides a method for deinking a laminate having an anchor layer and an ink layer in this order on a paper substrate,
The anchor layer contains an aqueous resin,
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, wherein 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.

According to the present invention, an easily deinkable laminate that has excellent physical properties as a laminate such as adhesion and scratch resistance and that is excellent in deinking properties in paper recycling processing regardless of the type of active energy ray-curable ink, and A method for producing the laminate could be provided.

The present invention will be described in detail below. It should be noted that the present invention is not limited to the following embodiments, and can be modified in various ways within the spirit of the present invention. In addition, unless otherwise specified, "part" means "mass part" 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, wherein the anchor layer contains a water-based resin and the ink layer is an active energy ray-curable It is an easily deinkable laminate, which is a layer obtained by curing ink with an active energy ray.

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

[Coloring agent]
In the present invention, the ink contains a coloring agent. At least one of pigments and dyes can be used as the colorant. Pigments are preferred from the viewpoint of light resistance.
Pigments that can be used in the present invention are not particularly limited, and known pigments can be used. Both inorganic pigments and organic pigments can be used as the pigment.

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

Organic pigments include soluble azo pigments such as β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic anilide, acetoacetic anilide, and pyrazolone; β-naphthol, β-oxynaphthoic acid Insoluble azo pigments such as anilide, anilide acetoacetate monoazo, disazo anilide acetoacetate, and pyrazolone; copper phthalocyanine blue, halogenated (for example, chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free Phthalocyanine-based pigments such as phthalocyanine; quinacridone-based, dioxazine-based, threne-based (pyranthrone, anthanthrone, indanthrone, anthrapyrimidine, flavanthrone, thioindigo-based, anthraquinone-based, perinone-based, perylene-based, etc.), isoindolinone-based, metal complex-based, quinophthalone-based, and diketopyrrolopyrrole-based polycyclic pigments and heterocyclic pigments;

For more details, see 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 a white pigment, C.I. I. Pigment White 5, 6, 7, 12, 28 and the like.

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

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

As a 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 an 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 above pigments may be used singly or in combination of two or more.

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

[(Meth)acrylate compound]
In the present specification, "(meth)acryloyl", "(meth)acrylic acid", "(meth)acrylate", and "(meth)acryloyloxy" respectively refer to "acryloyl and/or methacryloyl”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, and “acryloyloxy and/or methacryloyloxy”. Moreover, "PO" represents "propylene oxide", and "EO" represents "ethylene oxide". In addition, X in EO-modified (X) and PO-modified (X) represents the number of modified moles of EO and PO, and Y in polyethylene glycol (Y) di(meth)acrylate indicates the approximate molecular weight of the polyethylene glycol moiety. .

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 groups, and includes monomers, oligomers, and polymers.
Here, "monomer" means a compound of the minimum structural unit for constituting an oligomer or polymer, and "oligomer" means a polymer having structural units based on 2 to 100 monomers. .

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

[(Meth)acrylate compound]
(monomer)
2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, β-carboxylethyl (meth)acrylate, 4-tert-butylcyclohequinol (meth)acrylate, tetrahydrofurfuryl acrylates, 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 trimethylolpropane formal (meth)acrylate, benzyl (meth)acrylate, EO-modified (2) nonylphenol acrylate, 2-methyl-2-ethyl-1,3-dioxolane -4-yl) monofunctional (meth)acrylate monomers having one (meth)acryloyl group in the molecule such as 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 Acrylates, 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, neopentylglycol hydroxypivalate di(meth)acrylate ) 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) Acrylates, (neopentyl glycol-modified) trimethylolpropane di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, EO-modified (4) bisphenol A di(meth)acrylate, PO-modified (4) bisphenol A di( Bifunctional (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, dicyclopentanyl di (meth) acrylate, etc. with two (meth) acryloyl groups in the molecule meth)acrylate monomers,
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 the molecule such as pentaerythritol tri(meth)acrylate,
Tetrafunctional (meth)acrylate monomers having four acryloyl groups in the molecule such as pentaerythritol tetra(meth)acrylate, EO-modified (4) pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate,
Pentafunctional (meth)acrylate monomers having five (meth)acryloyl groups in the molecule such as dipentaerythritol penta(meth)acrylate,
A hexafunctional (meth)acrylate monomer having six (meth)acryloyl groups in the molecule, such as dipentaerythritol hexa(meth)acrylate, and the like.

(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, the ink may contain a polymerization initiator, an amine compound, a resin, a polymerization inhibitor, a surface tension modifier, a wax, an extender pigment, a pigment dispersant, an antifoaming agent, and an ultraviolet absorber, in addition to the above components, if necessary. , antioxidants, and the like.

(Polymerization initiator)
In the present invention, the ink may contain a polymerization initiator. As the polymerization initiator, it is preferable to contain a polymerization initiator for radical polymerization, and it is more preferable to contain a photopolymerization initiator. The polymerization initiator in the present invention is a compound that undergoes a chemical change and generates radicals through the action of light or interaction with the electronically excited state of the sensitizing dye. It is preferably a photoradical polymerization initiator from the viewpoint that it can be.

In the present invention, the photoradical polymerization initiator is not particularly limited, and known ones can be used. Specific examples include benzophenone-based compounds, dialkoxyacetophenone-based compounds, α-hydroxyalkylphenone-based compounds, α-aminoalkylphenone-based compounds, acylphosphine oxide compounds, oxime ester-based compounds, and thioxanthone compounds. Moreover, a photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

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-benzoylphenylsulfanyl)phenyl]- 2-methyl-2-(4-methylbenzenesulfonyl)propan-1-one, polybutylene glycol bis(4-benzoylphenoxy)acetate and the like.

Dialkoxyacetophenone compounds include 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, diethoxyacetophenone and the like.

α-Hydroxyalkylphenone compounds include 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxymethoxy)-phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl- Propan-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-indene 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-indene mixture, 2- Hydroxy-1-[4-[4-(2-hydroxy-2-methylpropynyl)benzyl]phenyl]-2-methylpropan-1-one, 2-hydroxy-1-[4-[4-(2-hydroxy -2-methylpropanoyl)phenoxy]phenyl]-2-methylpropan-1-one, 1-[4-(1,1-dimethylethyl)phenyl]-2-hydroxy-2-methylpropan-1-one, etc. is mentioned.

Examples of α-aminoalkylphenone compounds include 2-methyl-1-[4-(methoxythio)-phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)-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)propinate, 2-benzyl-2-dimethylamino-1-(4-piperidinylphenyl)-1-butanone, 1-(biphenyl-4-yl)-2-methyl-2 -morpholinopropan-1-one, 1-(biphenyl-4-yl)-2-methoxy-2-morpholinopropan-1-one and the like.

Examples of acylphosphine oxide compounds include diphenylacylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 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 -trimethylpentylphosphine oxide and the like.

Oxime ester compounds include 1-[4-(phenylthio)phenyl]octane-1,2-dione, 2-benzoyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H- Carbazol-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-carbazol-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]carbazol-5-yl]-, (2,4,6- trimethylphenyl), 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime and the like.

Thioxanthone compounds include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propylthioxanthone, 2-chlorothioxanthone, poly(oxy- 1,4-butanediyl), 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-thioxantothen-4-yl]oxy}acetylpoly[oxy(1-methylethylene)])oxymethyl)propane and the like.

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 that the effect of the hydrogen abstraction photopolymerization initiator is enhanced.
Specific examples include N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, 4-(dimethylamino)ethyl benzoate, N,N-dihydroxyethylaniline, triethylamine. and N,N-dimethylhexylamine, poly(oxy-1,2-ethanediyl, 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-ethanediyl), α-[4-(dimethylamino)benzoyl-ω-butoxy-, 2-butoxyethyl-4-(dimethylamino ) benzoate, 2-(dimethylamino)ethyl benzoate, etc. The amine compound 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, curing shrinkage of the coating film that occurs during curing is reduced, curling of the base material is suppressed, and adhesion to the anchoring agent is improved.

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

Specific examples of resins include polyvinyl chloride, (meth)acrylic resin, styrene (meth)acrylic resin, epoxy resin, polyester resin, polyurethane resin, cellulose derivatives (e.g., ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride- Vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, diallyl phthalate resins, alkyd resins, rosin-modified alkyd resins, petroleum resins, urea resins, and synthetic rubbers such as butadiene-acrylonitrile copolymers. Among them, 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 polymerization inhibitors 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 enhancing the stability of the ink while maintaining curability.

(wax)
In the present invention, the ink may contain wax. Inclusion of wax can improve friction resistance, scratch resistance, anti-blocking property, slip property, and anti-scratch property. The wax is not particularly limited, and known waxes can be used. For example, there are natural waxes and synthetic waxes.
Natural waxes include, for example, carnauba wax, Japan wax, lanolin, montan wax, paraffin wax, microcrystalline wax and the like.
Synthetic waxes include, for example, Fischer-Tropsch 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.

(Extender pigment)
In the present invention, the ink may contain an extender. Extender pigments include clay, talc, barium sulfate, calcium carbonate, ground 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 pigment dispersibility. The pigment dispersant is not particularly limited, and known pigment dispersants 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, nitrogen-containing heterocycles 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 are more preferable because good pigment dispersibility can be easily obtained.

Examples of the pigment dispersant include Ajinomoto Fine-Techno Co., Inc.'s Ajisper series (Ajisper PB821, PB822, PB824, etc.), Lubrizol's Solsperse series (Solsperse 24000, Solsperse 32000, Solsperse 38500, etc.), and BYK-Chemie's Disperbik 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, relative to the total mass of the ink.

<Anchor layer>
The anchor layer of the laminate of the present invention contains an aqueous resin. Such an anchor layer can be obtained by coating an aqueous anchor agent containing an aqueous resin and drying it.

[Aqueous anchoring agent]
The aqueous anchoring agent in the present invention contains water and an aqueous resin.

[Aqueous resin]
Examples of water-based resins in the present invention include water-based acrylic resins, water-based urethane resins, and water-based polyester resins. Among them, it is preferable to use a water-based acrylic resin and a water-based urethane resin, and it is particularly preferable to use a water-based acrylic resin.

[Water-based acrylic resin]
Aqueous acrylic resins have acrylic monomer constitutional units. Furthermore, acrylic resins obtained by copolymerizing styrene-based monomers, maleic acid-based monomers, etc. are also preferable. The acrylic resin preferably has a carboxyl group and is made water-soluble in the presence of an emulsifier and/or a basic compound.

Preferred examples of the acrylic monomer include alkyl esters of (meth)acrylic acid, alkylamides of (meth)acrylic acid, and hydroxyalkyl esters of (meth)acrylic acid. The alkyl group constituting the alkyl ester or the like preferably has 1 to 18 carbon atoms.

Examples of suitable styrene-based monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, and the like. Preferred maleic acid-based monomers include maleic anhydride and maleic acid. and may be an alkyl ester having 1 to 18 carbon atoms, an alkylamide having 1 to 18 carbon atoms, or a hydroxyalkyl ester having 2 to 4 carbon atoms. Furthermore, the water-based acrylic resin used in the present invention may further contain, as a reactive component, a known monomer generally used as a reactive component for water-based acrylic resins other than the above.

Using these reaction components, an acrylic resin can be produced by a known production method, a method using a known emulsifier or a protective colloid of a polymer, or introducing a carboxyl group into the molecule and using a basic compound. It can be made aqueous by the method of neutralization. As the basic compound, an amine compound is preferred, and ammonia is preferably used. The aqueous acrylic resin is preferably an aqueous emulsion, more preferably a core-shell type acrylic emulsion, and preferably has a core/shell ratio of 10:90 to 70:30.

The acid value of the water-based acrylic resin is preferably 25-300 mgKOH/g. This is because the acid value provides a good water-soluble resin and improves the deinking properties of the UV ink. The water-based acrylic resin preferably has a glass transition temperature of -50 to 150°C, more preferably -30 to 100°C. This is because the glass transition temperature range improves the adhesion to the substrate. Further, the weight average molecular weight of the aqueous acrylic resin is preferably 5,000 to 700,000, more preferably 8,000 to 500,000, and further preferably 8,000 to 200,000. preferable.

(Synthesis method)
The water-based acrylic resin is appropriately produced by a known method. For example, the method described in JP-A-2011-144332 can be used as appropriate.

[Aqueous polyurethane resin]
The water-based polyurethane resin has an acid value to be neutralized, and preferably has an acid value of 25-65 mgKOH/g. Also, the glass transition temperature is preferably -50 to 100°C. Here, the glass transition temperature means the maximum value of Tan δ in dynamic viscoelasticity measurement.

The water-based polyurethane resin may be in the form of a polyurethane resin synthesized from a polyol, a hydroxy acid and a polyisocyanate, or a urethane prepolymer having an isocyanate group at the end synthesized from a polyol, a hydroxy acid and a polyisocyanate and chain-extended with a polyamine. A preferred embodiment is a polyurethane resin containing polyurethane urea.

Water-based polyurethane resins and polyurethane urea resins are water soluble by introducing ionic groups such as carboxyl groups and sulfone groups into the resin and neutralizing it using a basic compound when reacting polyol and polyisocyanate. I am letting A carboxyl group is preferable as the ionic group from the viewpoint of water resistance.

(polyol)
The above polyols do not include hydroxy acids, which will be described later. Suitable polyols include, but are not limited to, polyester polyols, polyether polyols, polylactone polyols, polycarbonate polyols, polyolefin polyols, dimer diols, and hydrogenated dimer diols. These polyols may be used alone or in combination of two or more. The water-based polyurethane resin preferably contains structural units composed of at least one polyol selected from polyester polyols, polyether polyols and polycarbonate polyols. The polyol preferably has a number average molecular weight of 500-5000.

(polyether polyol)
Suitable polyether polyols include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, and copolymers thereof. It is preferable that the structural unit consisting of these is an aqueous polyurethane resin. The aqueous polyurethane resin preferably contains a structural unit derived from polyethylene glycol, preferably 0.1 to 25% by mass, more preferably 2 to 15% by mass, based on the total mass of the aqueous polyurethane resin. It is more preferable to contain up to 10% by mass.

(polyester polyol)
The above polyester polyol preferably has a constitutional unit composed of a diol containing a dibasic acid and a branched diol. As the dibasic acid, sebacic acid, adipic acid, succinic acid and the like can be suitably used, and the branched diol refers to a form in which at least one of the hydrogen atoms on the carbon atoms of the alkylene glycol has a substituent. Specifically, it is selected from propylene glycol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and 2-methyl-1,3-propanediol. 50% by mass or more of the total mass of diols. In addition, embodiment of polyester polyol is not limited to these.

(polycarbonate polyol)
The above-mentioned polycarbonate polyol is not limited by the production method or the type of diol constituting the polycarbonate polyol, but a polycondensate obtained by transesterification reaction between a diol composed of alkylene glycol and a carbonate compound is preferably exemplified. The polycarbonate polyol is preferably an alicyclic and/or aliphatic polycarbonate diol.

Examples of the diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, and neopentyl. Glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decane Diol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butynediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, polypropylene Glycol, dipropylene glycol and the like are suitable, and these can be used alone or in combination of two or more. A polycarbonate polyol having a diol structure having a branched structure such as 3-methyl-1,5-pentanediol is preferred.
The carbonate compound includes, but is not limited to, dialkyl carbonate, diaryl carbonate, or alkylene carbonate. Specific examples of carbonate compounds include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and dibutyl carbonate, diaryl carbonates such as diphenyl carbonate, and alkylene carbonates such as ethylene carbonate.

(polyisocyanate)
Suitable polyisocyanates include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. These may be trimers to form an isocyanurate ring structure.
Aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate and the like.
Aliphatic diisocyanates include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and lysine diisocyanate.
Alicyclic diisocyanates include cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, and norbornane diisocyanate. , m-tetramethylxylylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, and dimer diisocyanate obtained by converting the carboxyl group of dimer acid to an isocyanate group.
Among them, at least one selected from trimers of tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, bis(isocyanatomethyl)cyclohexane, hexamethylene diisocyanate and hexamethylene diisocyanate is preferable. These polyisocyanates can be used alone or in combination of two or more.

(hydroxy acid)
The hydroxy acid can utilize, but is not limited to, carboxyl-containing polyols. For example, dimethylolalkanoic acids such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, and the like are suitable. These can be used alone or in combination of two or more. A hydroxy acid is used in the production process of an aqueous polyurethane resin, and its carboxyl group is introduced into the resulting polyurethane resin to have an acid value. Unreacted carboxyl groups are neutralized and rendered aqueous.

(polyamine)
Compounds that can be used as the polyamine include various known amines such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-Hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, and dimer diamine obtained by converting the carboxyl group of dimer acid to amino group. etc. are preferably mentioned, and these can be used alone or in combination of two or more.

(Reaction terminator)
A reaction terminator can also be used in combination with the above polyamine. Examples of such reaction terminator include dialkylamines such as di-n-dibutylamine, monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri(hydroxymethyl)aminomethane, 2-amino -amines having a hydroxyl group such as 2-ethyl-1,3-propanediol, N-di-2-hydroxyethylethylenediamine, N-di-2-hydroxyethylpropylenediamine, N-di-2-hydroxypropylethylenediamine; Furthermore, monoamine amino acids such as glycine, alanine, glutamic acid, taurine, aspartic acid, aminobutyric acid, valine, aminocaproic acid, aminobenzoic acid, aminoisophthalic acid, and sulfamic acid are included.

(Neutralizer)
To make the polyurethane resin water-soluble, it is preferable to neutralize the carboxyl groups in the resin with a basic compound. Basic compounds include sodium hydroxide, potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N,N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine and the like, and these are one or two or more used in combination with Ammonia is preferred from the viewpoint of water resistance of printed matter, residual odor, and the like.

(Synthesis method)
Polyurethane resins are appropriately produced by known methods. Examples thereof include an acetone method using an organic solvent that is inert to isocyanate and hydrophilic, and a non-solvent synthesis method that does not use any solvent. For example, the method described in JP-A-2013-234214 can be used as appropriate.

[Other ingredients]
In addition to the above components, the water-based anchoring agent in the present invention may optionally contain silica, alumina, polyethylene wax, antifoaming agents, leveling agents, tackifiers, preservatives, antibacterial agents, antirust agents, and the like. can be done.

<Easy de-inking laminate>
The easily deinkable laminate of the present invention is obtained by printing an active energy ray-curable ink on an anchoring agent applied to a paper substrate and curing with an active energy ray.

As the method for producing the easily deinkable laminate of the present invention,
Step 1 of applying a water-based anchoring agent containing a water-based resin to a paper base material and drying it in an oven to obtain a laminate having an anchor layer on the paper base material;
An easily deinkable laminate having an ink layer on the anchor layer is obtained by printing with an active energy ray-curable ink on the anchor layer of the laminate having the anchor layer on the paper substrate and curing with the active energy ray. Step 2 of obtaining
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 a known one can be used, but it is preferable to use an active energy ray-curable varnish or a water-based varnish, and it is particularly preferable to use an active energy ray-curable varnish. .

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

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

The active energy ray source is not particularly limited, and known sources can be used. Specifically, LEDs (light emitting diodes) such as mercury lamps, xenon lamps, metal hydride lamps, excimer lamps, ultraviolet light emitting diodes (UV-LED), ultraviolet laser diodes (UV-LD), EB (electron beam) irradiation equipment , gas and solid-state lasers.

In the present invention, the method of printing the aqueous anchoring agent is not particularly limited, and known methods can be used. Specific examples include gravure printing, flexographic printing, and the like.

<De-inking>
In the present invention, deinking is a process for removing ink components from so-called waste paper that has been printed. Specifically, a flotation method is used in which the paper is finely pulverized in an alkaline aqueous solution, and then the ink separated from the fibers using a deinking agent is floated and removed by generating fine air bubbles. Fatty acids (soaps), fatty acid derivatives, oil derivatives, higher alcohol derivatives and the like are mainly used as deinking agents. At this time, if there are many black components (dirt) that could not be completely decomposed, it will affect the blankness when the paper is made again. The area of foreign matter and the number of large foreign matter are important.

As deinking agents, deinking agents DI-7020, DI-7027, DI-7250, and DI-767 manufactured by Kao Corporation, DIA-Z series and DIA-Y series manufactured by Nisshin Chemical Co., Ltd., and Lion Specialty Chemicals Co., Ltd. Riptor series etc. are available.

The evaluation of printed matter is based on the JIS P8208 Pulp - Debris measurement method, and the degree of whiteness is measured using a whiteness meter or the like. There are methods such as using a microscope 3D scanner dedicated measurement device (SCAN-MARK 800, Spec*Scan 2000, etc.) equipped with dirt counter software. Based on these, the degree of deinking was determined from the degree of whiteness and the number of remaining inks.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is by no means limited by the following examples. In the examples and comparative examples, "parts" and "%" represent "mass parts" and "mass%", respectively.

<Synthesis of acrylic emulsion>
A core/shell type acrylic emulsion was synthesized for use as an aqueous anchoring agent.

(Synthesis example 1)
100 parts of isopropyl alcohol was charged into a four-necked flask purged with nitrogen gas, the temperature was raised to 80 to 82° C., and 38.0 parts of styrene, 2.0 parts of acrylic acid, and 6.5 parts of methyl methacrylate were charged to a dropping funnel. A mixture of 0 part and 1.0 part of benzoyl peroxide was added dropwise over 2 hours. After the dropwise addition, 0.5 part of benzoyl peroxide was added, and the reaction was further continued for 2 hours. The temperature was lowered to 40° C., and dimethylethanolamine and ion-exchanged water were added. Thereafter, the temperature of the reaction flask was raised to 80-82° C. and stripping was carried out to finally obtain a water-soluble resin with a solid content of 30%.
To the water-soluble resin obtained above, 10 parts of ion-exchanged water was charged in a reaction flask, the temperature was raised to 80° C. to 82° C., 2 parts of potassium persulfate were added, and 24.6 parts of styrene and 2-ethylhexyl were added. A mixture of 21.0 parts of acrylate and 8.4 parts of butyl acrylate was added dropwise over 2 hours. After completion of dropping, 0.2 part of potassium persulfate was added and reacted for 2 hours. The solid content of the acrylic emulsion (resin 1) thus obtained was 40%. The theoretical acid value was 16 mgKOH/g.

(Synthesis Examples 2-7)
In Synthesis Examples 2 to 7, polymerization was carried out in the same manner as in Synthesis Example 1 except for the blending of the monomers, to obtain Resins 2 to 7, which are acrylic emulsions. Table 1 shows the formulation of these monomers.

<Synthesis of water-based urethane resin>
A water-based urethane resin was synthesized for use as a water-based anchoring agent.

(Synthesis Example 8)
Poly(3-methyl-1,5-pentaneadipate)diol 103.3 having a number average molecular weight of 400 was prepared while introducing nitrogen gas in a reactor equipped with a thermometer, stirrer, reflux condenser and nitrogen gas inlet. 24.2 parts of polyethylene glycol having a number average molecular weight of 2000, 15.1 parts of 2,2-dimethylolpropionic acid and 138.2 parts of isophorone diisocyanate were reacted in 200 parts of methyl ethyl ketone for 6 hours at the boiling point to obtain a terminal isocyanate prepolymer. After cooling to 40° C., 100 parts of acetone was added to obtain a solvent solution of a terminal isocyanate prepolymer. Next, to a mixture of 14.4 parts of 2-hydroxyethylethylenediamine, 4.8 parts of isophoronediamine and 400 parts of acetone, 580.9 parts of the resulting isocyanate-terminated prepolymer solution was gradually added at room temperature. A reaction was carried out at 50° C. for 3 hours to obtain a solvent-type polyurethane resin solution. Next, 9.8 parts of 28% aqueous ammonia and 700 parts of deionized water were gradually added to the solvent-type polyurethane resin solution to neutralize it, and then the total amount of methyl ethyl ketone and acetone was distilled off under azeotropic conditions. After removing the solvent, water was added to adjust the viscosity to obtain an aqueous urethane resin (resin 8) having an acid value of 21 mgKOH/g, a solid content of 30%, a viscosity of 780 mPa·s and a weight average molecular weight of 20,000.

(Synthesis Example 9)
Poly(3-methyl-1,5-pentaneadipate)diol having a number average molecular weight of 400 was added at 82.5 while introducing nitrogen gas in a reactor equipped with a thermometer, stirrer, reflux condenser and nitrogen gas inlet. 24.2 parts of polyethylene glycol having a number average molecular weight of 2000, 35.9 parts of 2,2-dimethylolpropionic acid and 138.2 parts of isophorone diisocyanate were subjected to a boiling point reaction in 200 parts of methyl ethyl ketone for 6 hours to obtain a terminal isocyanate prepolymer. After cooling to 40° C., 100 parts of acetone was added to obtain a solvent solution of a terminal isocyanate prepolymer. Next, to a mixture of 14.4 parts of 2-hydroxyethylethylenediamine, 4.8 parts of isophoronediamine and 400 parts of acetone, 580.9 parts of the resulting isocyanate-terminated prepolymer solution was gradually added at room temperature. A reaction was carried out at 50° C. for 3 hours to obtain a solvent-type polyurethane resin solution. Next, 9.8 parts of 28% aqueous ammonia and 700 parts of deionized water were gradually added to the solvent-type polyurethane resin solution to neutralize it, and then the total amount of methyl ethyl ketone and acetone was distilled off under azeotropic conditions. After removing the solvent, water was added to adjust the viscosity to obtain a water-based urethane resin (resin 9) having an acid value of 50 mgKOH/g, a solid content of 30%, a viscosity of 1000 mPa·s and a weight average molecular weight of 25,000.

<Synthesis of oil-based urethane resin>
(Synthesis Example 10)
130 parts of a polyester polyol which is a condensate of 3-methyl-1,5-pentanediol having a number average molecular weight of 2000 and adipic acid in a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 18.2 parts of neopentyl glycol, 101.4 parts of isophorone diisocyanate, 0.03 parts of stannous 2-ethylhexylate and 62.6 parts of ethyl acetate were charged and reacted at 90° C. for 3 hours under a stream of nitrogen to obtain ethyl acetate. 125.7 parts were added and cooled to obtain 438.0 parts of a solvent solution of terminal isocyanate prepolymer. Then, to a mixture of 43.8 parts of isophoronediamine, 1.24 parts of di-n-butylamine, 301.7 parts of ethyl acetate and 210 parts of isopropyl alcohol, 438.0 parts of the resulting terminal isocyanate prepolymer was gradually added at room temperature. and then reacted at 50° C. for 1 hour. Then, after adding 5.3 parts of isophorone diisocyanate to adjust the viscosity, the solid content was adjusted to 30% with a solvent obtained by mixing ethyl acetate/isopropyl alcohol at a mass ratio of 7/3, and the acid value was 0 mgKOH/g. A polyurethane resin (resin 10) having a viscosity of 800 mPa·s and a mass average molecular weight of 35,000 was obtained.

<Preparation of anchor agent>
(Anchor agent 1)
99.0 parts of the acrylic emulsion (resin 1) obtained in Synthesis Example 1 (40% solid) and 1.0 part of polyethylene wax (Chemipearl W500 manufactured by Mitsui Chemicals, Inc.) were added, and the mixture was stirred for 10 minutes with a disper to form an aqueous solution. An anchoring agent (AC1) was obtained.

(Anchor agents 2 to 9)
Aqueous anchoring agents (AC2) to (AC9) were obtained by blending resins 2 to 9 in the same manner as in anchoring agent 1.

(Anchor agent 10)
Oil-based urethane resin obtained in Synthesis Example 10 (Resin 10) 79.0 parts (30% solid), ethyl acetate 10.0 parts, isopropyl alcohol 10.0 parts, polyethylene wax (Chemipearl W500 manufactured by Mitsui Chemicals, Inc.)1. 0 part was added and stirred with a disper for 10 minutes to obtain an oily anchoring agent (AC10).

(Anchor agent 11)
20.0 parts of TMPTA (EO), 60.0 parts of DiTMPTA, 10.0 parts of DPHA, 6.0 parts of 4MBP, 3.0 parts of TPO, and 1.0 parts of EDB were mixed, and butterfly A UV flexo acrylic anchoring agent (AC11) was prepared by stirring and mixing using a mixer.

<Preparation of active energy ray-curable resin varnish>
65.0 parts of DPHA, 6.5 parts of TMPTA (EO), and 3.5 parts of DiTMPTA were mixed and heated to 100° C. with stirring. Next, 25.0 parts of a diallyl phthalate resin was mixed and dissolved while being kept at 100° C. to prepare a diallyl phthalate resin varnish.

(Anchor agent 12)
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 parts of EDB, and resin varnish 57.0 parts were mixed and stirred and mixed using a butterfly mixer to prepare a UV offset acrylic anchor agent (AC12).

<Ink manufacturing example>
<Preparation of oil-based resin varnish>
(Manufacturing example of rosin-modified phenolic resin)
In a reaction vessel, 54.3 parts of gum rosin, 30.8 parts of tert-butylphenol and 9.4 parts of 92% by weight of paraformaldehyde in a xylene solvent are reacted in the presence of sodium hydroxide catalyst at 100°C for 4 hours, A phenolic resin from which moisture was removed 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. In the meantime, the rosin phenol resin was able to be obtained by taking it out one by one.

(Manufacturing example of rosin-modified phenolic resin varnish)
Next, 45.0 parts of the rosin-modified phenol resin as a binder resin, 44.0 parts of soybean oil, and 10 soybean oil fatty acid normal butyl ester were added to a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer. 0 part and 1.0 part of ALCH were heated and stirred at 190° C. for 1 hour to obtain a rosin-modified phenolic resin varnish.

(Ink production example 1 (oil-based ink black))
17.0 parts of RAVEN 1080 Ultra, 3.0 parts of BA-2550, 59.0 parts of rosin-modified phenolic resin varnish, 20.0 parts of soybean oil, 0.5 parts of MK dryer, and 0.5 parts of drying inhibitor CP. The mixture was stirred and mixed using a butterfly mixer, and then dispersed with a three-roll roll so that the maximum particle size was 7.5 μm or less to prepare an ink.

(Ink production example 2 (UV ink black 1))
17.0 parts RAVEN 1080 Ultra, 3.0 parts BA-2550, 6.0 parts TMPTA (EO), 13.0 parts DiTMPTA, 7.0 parts DPHA, 3.0 parts 379, DEABP 1.5 parts of DETX, 1.5 parts of EDB, and 47.0 parts of diallyl phthalate resin varnish were mixed and mixed by stirring using a butterfly mixer. An ink was prepared by dispersing the particles so that the particle size was 7.5 μm or less.

(Ink production example 3 (UV ink black 2))
17.0 parts RAVEN 1080 Ultra, 3.0 parts BA-2550, 6.0 parts TMPTA (EO), 13.0 parts DiTMPTA, 7.0 parts DPHA, 3.0 parts 379, DEABP 1.5 parts, 1.5 parts of DETX, 1.0 parts of EDB, and 47.0 parts of MIRAMER PS-4500 were mixed, stirred and mixed using a butterfly mixer, and then three rolls were used to maximum An ink was prepared by dispersing the particles so that the particle size was 7.5 μm or less.

(Ink production example 4 (high sensitivity black ink))
17.0 parts RAVEN 1080 Ultra, 3.0 parts BA-2550, 6.0 parts TMPTA (EO), 10.0 parts DiTMPTA, 7.0 parts DPHA, 3.0 parts 379, TPO 2.0 parts of DEABP, 2.5 parts of 4MBP, 2.5 parts of DETX, 1.0 parts of EDB, and 44.0 parts of diallyl phthalate resin varnish are mixed, and a butterfly mixer was stirred and mixed using , and dispersed with a triple roll so that the maximum particle size was 7.5 μm or less to prepare an ink.

(Ink production example 5 (UV flexographic ink))
15.0 parts RAVEN 1080 Ultra, 1.0 parts BA-2550, 16.0 parts TMPTA (EO), 5.0 parts DiTMPTA, 7.0 parts DPHA, 3.0 parts 379, DEABP 2.0 parts of 4MBP, 2.5 parts of 4MBP, 2.5 parts of DETX, 1.0 parts of EDB, and 6.0 parts of Solsperse 24000, after stirring and mixing using a butterfly mixer, with three rolls An ink was prepared by dispersing the particles so that the maximum particle size was 7.5 μm or less. After that, 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))
15.0 parts Permanent Yellow BHS, 6.0 parts TMPTA (EO), 18.0 parts DiTMPTA, 7.0 parts DPHA, 3.0 parts 379, 1.5 parts DEABP, 1 part DETX .5 parts, 1.0 part of EDB, and 47.0 parts of diallyl phthalate resin varnish are mixed, stirred and mixed using a butterfly mixer, and then the maximum particle size becomes 7.5 μm or less with three rolls. Ink was prepared by dispersing as follows.

(Ink Production Example 7 (UV red ink))
20.0 parts of Permanent Rubine L5B-01, 6.0 parts of TMPTA (EO), 13.0 parts of DiTMPTA, 7.0 parts of DPHA, 3.0 parts of 379, 1.5 parts of DEABP, DETX 1.5 parts of EDB, 1.0 parts of EDB, and 47.0 parts of diallyl phthalate resin varnish are mixed, stirred and mixed using a butterfly mixer, and the maximum particle size is 7.5 μm or less with three rolls. Ink was prepared by dispersing so that

(Ink production example 8 (UV ink indigo))
20.0 parts Heliogen Blue D7088, 6.0 parts TMPTA(EO), 13.0 parts DiTMPTA, 7.0 parts DPHA, 3.0 parts 379, 1.5 parts DEABP, 1 part DETX .5 parts, 1.0 part of EDB, and 47.0 parts of diallyl phthalate resin varnish are mixed, stirred and mixed using a butterfly mixer, and then the maximum particle size becomes 7.5 μm or less with three rolls. Ink was prepared by dispersing as follows.

(Ink production example 9 (EB ink black))
17.0 parts of RAVEN 1080 Ultra, 3.0 parts of BA-2550, 6.0 parts of TMPTA (EO), 13.0 parts of DiTMPTA, 7.0 parts of DPHA, and 54 parts of diallyl phthalate resin varnish 0 part, and stirred and mixed using a butterfly mixer, and then dispersed with a three-roll roll so that the maximum particle size becomes 7.5 μm or less to prepare an ink.

Explanations of notations for materials used in the examples are as follows.
[Coloring agent]
・Permanent Yellow BHS: Permanent Yellow BHS (CI Pigment Yellow 174) manufactured by Clariant
・Permanent Rubine L5B-01: Permanent Rubine L5B-01 (C.I.Pigment Red 57:1) manufactured by Clariant
・HELIOGEN BLUE D7088: manufactured by BASF, HELIOGEN BLUE D7088 (C. Pigment Blue 15:3)
- Raven 1080 Ultra: Raven 1080 Ultra Powder (CI Pigment Black 7) manufactured by Bilra Carbon
・ BA-2550: Alkaline Blue Toner BA-2550 (C.I.Pigmen) manufactured by Morimura Shoji Co., Ltd.
t Blue 61)
[(Meth)acrylate compound]
・TMPTA (EO): manufactured by BASF, LAROMER LR8863, trimethylolpropane ethylene oxide-modified triacrylate ・DiTMPTA: manufactured by Daicel Ornex, EBECRYL1142, ditrimethylolpropane tetraacrylate ・DPHA: manufactured by MIWON, MIRAMER M600, dipentaerythritol Hexaacrylate PS-4500: manufactured by MIWON, MIRAMER PS-4500, polyester acrylate oligomer [resin]
・ Diallyl phthalate resin: Daiso Dap A manufactured by Osaka Soda Co., Ltd. (acid value 2 to 3 mg KOH / g)
[Photoinitiator]
379: IGM RESINS, Omnirad 379, 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone TPO: Chemmark Chemical Co., CHEMARK TPO, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide DEABP: Chemmark Chemical Co., CHEMARK DEABP, 4,4'-bis (dimethylamino) benzophenone 4MBP: Soho Jitsugyosha Made by SB-PI 712
・DETX: CHEMARK DETX manufactured by Chemmark Chemical Co., 2,4-diethylthioxanthone [amine compound]
EDB: CHEMARK EDB manufactured by Chemmark Chemical Co., ethyl-4-(dimethylamino) benzoate [pigment dispersant]
Solsperse24000: manufactured by Lubrizol, Solsperse24000,
[Metal dryer]
・MK Dryer: Toyo Ink Co., Ltd., MK Dryer [drying inhibitor]
・Drying inhibitor CP: Drying inhibitor CP manufactured by Toyo Ink Co., Ltd.
[Aluminum gelling agent]
・ ALCH: Kawaken Fine Chemicals Co., Ltd., ALCH, aluminum ethyl acetate diisopropylate [others]
・Soybean oil fatty acid normal butyl ester: SFB2, manufactured by Toshin Oil Co., Ltd.

Examples 1-18, Comparative Examples 1-7
<Printing of anchoring agent on substrate>
In Examples 1 to 18 and Comparative Examples 1 and 4, a bar coater (No. 4, manufactured by Yasuda Seiki Co., Ltd.) was used to apply the anchoring agent shown in Table 2 onto the substrate. Then, it was dried in an oven at 160 degrees for 10 minutes to produce a laminate having an anchor layer on the substrate.
In Comparative Example 5, a bar coater (No. 4, manufactured by Yasuda Seiki Co., Ltd.) was used to apply the anchor agent shown in Table 2 onto the substrate. After that, the coating film was cured with an ultraviolet curing device (160 W/cm methhalide lamp) manufactured by iGraphics Co., Ltd. under the conditions of a conveyor speed of 30 m/min to prepare a laminate having an anchor layer on the substrate.
In Comparative Example 6, an RI tester (simple printing machine manufactured by Akira Seisakusho Co., Ltd.) was used to apply an anchoring agent to one side of the substrate with an ink gauge of 0.25 mL. After that, the coating film was cured with an ultraviolet curing device (160 W/cm methhalide lamp) manufactured by iGraphics Co., Ltd. under the conditions of a conveyor speed of 30 m/min to prepare a laminate having an anchor layer on the substrate.

<Ink printing>
In Examples 1 to 12, 15 to 18, and Comparative Examples 4 to 6, sample inks shown in Table 2 were printed using an RI tester with an ink gauge of 0.25 mL on the laminate having the anchor layer on the prepared base material. After that, the printed material was cured with an ultraviolet curing device (160 W/cm methhalide lamp) manufactured by Eye Graphics Co., Ltd. under the conditions of a conveyor speed of 30 m/min, and an anchor layer and an ink layer were formed on the substrate in this order. was obtained.
In Example 13, the laminate having the anchor layer on the prepared base material was printed with the sample ink shown in Table 2 with an ink gauge of 0.25 mL using an RI tester, and then the printed material was subjected to UV irradiation manufactured by Eye Graphics. The ink was cured with a curing device (160 W/cm 2 methhalide lamp) at a conveyor speed of 100 m/min to obtain a laminate having an anchor layer and an ink layer on the substrate in this order.
In Example 14, the laminate having the anchor layer on the prepared base material was printed with the sample ink shown in Table 2 using an RI tester with an ink gauge of 0.25 mL. The ink is cured by irradiating 30 KGy electron beams using an energy electron beam irradiation device (pressurized voltage 175 KV, oxygen concentration 50 ppm, nitrogen-substituted atmosphere) to laminate an anchor layer and an ink layer on the substrate in this order. got a body
In Comparative Example 1, the sample ink shown in Table 2 was printed on the laminate having the anchor layer on the prepared base material with an ink gauge of 0.25 mL using an RI tester, and then left at room temperature for 24 hours to remove the ink. After curing, a laminate having an anchor layer and an ink layer in this order on the substrate was obtained.
In Comparative Examples 2 and 3, after printing the sample inks shown in Table 2 directly on the base material with an ink gauge of 0.25 mL using an RI tester, the developed product was subjected to an ultraviolet curing device (160 W/cm2) manufactured by Eye Graphics Co., Ltd. The ink was cured with a halide lamp) at a conveyor speed of 30 m/min to obtain a laminate having an ink layer on the substrate.
In Comparative Example 7, using an RI tester, the sample inks shown in Table 2 were printed directly on the substrate with an ink gauge of 0.25 mL. A laminate having

The obtained laminate was evaluated for performance by the following method. Table 2 shows the results.

<Evaluation of laminate>
(residual solvent)
The residual solvent in the resulting laminate was evaluated.
The laminates of Examples 1 to 18 and Comparative Examples 1 to 7 were heated in a closed Erlenmeyer flask at 80° C. for 30 minutes to evaporate the solvent, and the volatile solvent was analyzed by gas chromatography (GC-4000, manufactured by GL Sciences). confirmed the quantity.
[Evaluation criteria]
◯: The total amount of residual solvent was less than 0.5 mg/m ² .
○△: The total amount of residual solvent was 0.5 mg/m ² or more and less than 1 mg/m ² .
Δ: The total amount of residual solvent was 1 mg/m ² or more and less than 2 mg/m ² .
Δx: The total amount of residual solvent was 2 mg/m ² or more and less than 3 mg/m ² .
x: The total amount of residual solvent was 3 mg/m ² or more.
◯, ◯Δ, and Δ are practically preferable.

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

(Evaluation of adhesion)
Adhesive tape (Cellotape (registered trademark), 18 mm width, manufactured by Nichiban Co., Ltd.) was attached to the ink surface of the laminate prepared, and peeled off in the vertical direction at 90 degrees. The adhesion to was evaluated. ◯, ◯Δ, and Δ are practically preferable.
○: No peeling of ink film from anchor layer ○△: Less than 10% of ink film peeling from anchor layer △: More than 10% and less than 30% of ink film peeling from anchor layer △×: Anchor layer The peeling of the ink film from the anchor layer is 30% or more and less than 70% ×: 70% or more of the ink film is peeled off from the anchor layer

<Evaluation of de-inking property>
The laminates of Examples 1 to 18 and Comparative Examples 1 to 7 thus produced were aged at 60° C. for 1 week and then stored for 10 days under an environment of room temperature of 23±1° C. and humidity of 50±2%. After that, it was cut to 30×30 mm and 58 g of each was used as a sample for the test.

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

Add 1350 mL of room temperature purified water to a 2 L pulper, re-disintegrate with the concentrated sample for 1 minute, transfer the sample from the 2 L pulper to a 10 L bucket, add warm water of 30 ° C. ± 2 ° C. and dilute to 5.4 kg. Among them, 4.3 kg was fractionated, and J.I. TAPPI No. 39-compliant floatator manufactured by Kyokuto Shinko Co., Ltd. SF-2
5, stirring was performed for 10 minutes under conditions of a screw rotation speed of 1500 rpm and an air supply rate of 4 L/min.

The sample in the flotator tank was recovered, 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.

A wet paper was prepared using a 150-mesh wire netting machine (φ160 mm, manufactured by Kumagai Riki Kogyo Co., Ltd.) defined by JIS P8222, sandwiched between filter papers, and dehydrated by pressing for 5 minutes at a pressure of 410 kPa. After that, it was dried at a surface temperature of 90° C. for 4 minutes using a rotary drum dryer. The weight after drying was adjusted to 60 g, and 5 sheets of recycled paper were produced.

Contaminants such as metal flakes apparently not derived from the ink were removed from the obtained five sheets of recycled paper.

Performance evaluation of the obtained recycled paper was performed by the following method. Table 1 shows the results.

<Evaluation of ISO whiteness>
The ISO whiteness of the produced recycled paper was evaluated using ColorTouch PC manufactured by Technidyne. The measured value was the average value of the obtained 5 sheets.
It can be judged that the higher the ISO whiteness, the better the deinking property. The evaluation criteria are as shown below, and ◯ and Δ are practically preferable.
○: Whiteness is very high (80 to 100)
△: Whiteness is high (70 to 79)
×: Low whiteness (0 to 69)

<Evaluation of the total area of foreign matter>
The recycled paper thus produced was collected by Dirt Counter Apogee System Inc. ^Spec * ^{Scan 2000 manufactured} by ^JIS P8208 Pulp It was carried out according to the foreign matter measurement method. The measured value was the average value of the obtained 5 sheets.
It can be judged that the smaller the area of foreign substances, the better the deinking property. The evaluation criteria are as shown below, and ◯, ◯Δ, and Δ are practically preferable.
Evaluation of the total area of contaminants (mm ² /m ² ) ◯: Very good deinking property (less than 15 mm ² /m ² )
〇△: Good de-inking property (15 mm ² /m ² or more and less than 20 mm ² /m ² )
△: Deinking is normal (20 mm ² /m ² or more and less than 40 mm ² /m ² )
Δ×: Poor deinking property (40 mm ² /m ² or more and less than 60 mm ² /m ² )
x: Very poor de-inking property (60 mm ² /m ² or more)

<Evaluation of number of contaminants (0.3 mm ² or more)>
The recycled paper thus produced was collected by Dirt Counter Apogee System Inc. Using a Spec*Scan 2000 manufactured by Sanyo Denki, the number of contaminants of 0.3 mm ² or more (pieces/167 cm ² ) was measured according to JIS P8208 pulp-contaminant measuring method. The measured value was the average value of the obtained 5 sheets.
It can be judged that the less the number of impurities, the better the deinking property. The evaluation criteria are as shown below, and ◯ is practically preferable.
○: Very good de-inking property (0 pieces)
△×: Poor de-inking property (1 to 2 pieces)
×: very poor de-inking property (3 or more)

Comprehensive evaluation of the above three deinking properties, ISO whiteness, foreign matter area, foreign matter number, all three evaluations that are practically preferable are judged to have good deinking property, If all of the evaluations are 0, 0, △, and Δ, and are practically preferable, it is judged to have good de-inking properties, and the others are judged to have poor de-inking properties.
〇: Good de-inking property △: De-inking property ×: Poor de-inking property

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

That is, the present invention provides an easily deinkable laminate having an anchor layer and an ink layer in this order on a paper substrate,
The anchor layer contains an aqueous resin,
The water-based resin contains one or more selected from the group consisting of water-based acrylic resins and water-based urethane resins,
The aqueous resin has an acid value of 25 to 300 mgKOH/g,
It 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.

The present invention also provides a method for producing an easily deinkable laminate,
Step 1 of applying a water-based anchoring agent containing a water-based resin to a paper base material and drying it in an oven to obtain a laminate having an anchor layer on the paper base material;
An easily deinkable laminate having an ink layer on the anchor layer is obtained by printing with an active energy ray-curable ink on the anchor layer of the laminate having the anchor layer on the paper substrate and curing with the active energy ray. Step 2 of obtaining
including
The water-based resin contains one or more selected from the group consisting of water-based acrylic resins and water-based urethane resins,
The present invention relates to a method for producing an easily deinkable laminate, wherein the aqueous resin has an acid value of 25 to 300 mgKOH/g .

The present invention also provides a method for deinking a laminate having an anchor layer and an ink layer in this order on a paper substrate,
The anchor layer contains an aqueous resin,
The water-based resin contains one or more selected from the group consisting of water-based acrylic resins and water-based urethane resins,
The aqueous resin has an acid value of 25 to 300 mgKOH/g,
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, wherein 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.

That is, the present invention is a method for deinking a laminate,
Step 1 of obtaining a laminate having an anchor layer on the paper substrate by applying a water-based anchoring agent containing a water-based resin to the paper substrate and drying it in an oven;
An easily deinkable laminate having an ink layer on the anchor layer is obtained by printing with an active energy ray-curable ink on the anchor layer of the laminate having the anchor layer on the paper substrate and curing with the active energy ray. Step 2 of obtaining
A laminate manufactured from a manufacturing method comprising
The water-based resin contains one or more selected from the group consisting of water-based acrylic resins and water-based urethane resins,
The aqueous resin has an acid value of 25 to 300 mgKOH/g,
The present invention relates to a method for deinking a laminate, wherein 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.

Claims (5)

An easily deinkable laminate having an anchor layer and an ink layer in this order on a paper substrate,
The anchor layer contains an aqueous resin,
An easily deinkable laminate, wherein the ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray. 2. The easily deinkable laminate according to claim 1, wherein the water-based resin comprises a water-based acrylic resin. 3. The easily deinkable laminate according to claim 1, wherein the aqueous resin has an acid value of 25 to 300 mgKOH/g. A method for manufacturing an easily deinkable laminate, comprising:
Step 1 of applying a water-based anchoring agent containing a water-based resin to a paper base material and drying it in an oven to obtain a laminate having an anchor layer on the paper base material;
An easily deinkable laminate having an ink layer on the anchor layer is obtained by printing with an active energy ray-curable ink on the anchor layer of the laminate having the anchor layer on the paper substrate and curing with the active energy ray. Step 2 of obtaining
A method for producing an easily deinkable laminate, comprising: A deinking method for a laminate having an anchor layer and an ink layer in this order on a paper substrate,
The anchor layer contains an aqueous resin,
The ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray,
A method for deinking a laminate, wherein 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.