JP2024032644A - Laminate, method for producing laminate, and deinking method for laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that has superior physical properties as the laminate, including scratch resistance, and also has superior deinking properties for recycling a substrate with an ink layer composed of active energy ray-curable ink, and a method for producing the laminate.

SOLUTION: A laminate comprises an anchor layer and an ink layer on a substrate, in this order. The anchor layer is a layer formed by curing an active energy ray-curable anchor agent comprising a (meth) acrylate compound with an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less, as a (meth) acrylate compound, with an active energy ray. The ink layer is a layer formed by curing an active energy ray-curable ink with an active energy ray.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a laminate, a method for manufacturing the laminate, and a method for deinking the laminate.

Active energy ray-curable inks and varnishes are more convenient than oxidative polymerization, permeation drying, and hot air drying oil-based inks and varnishes because they cure instantly and can form strong cured films. The packaging printing industry is widely used in packaging applications such as beverage and food packaging, pharmaceutical packaging, cosmetics packaging, and general paper containers. Widely used in the field of

Especially in the food packaging field, electron beam (hereinafter also referred to as "EB") curing is the ideal form of active energy ray-curable ink and varnish, which does not contain a photopolymerization initiator and is safe and secure for the human body and the environment. One example is mold ink, but it is difficult to say that it is common due to the large initial capital investment, and ultraviolet (hereinafter also referred to as "UV") curable ink is common in the market.

In recent years, LED curing systems that use UV-LED light sources that save power and suppress the generation of ozone and heat, and metal halide lamps that eliminate the infrared region that generates heat and the ultraviolet region that generates ozone, have been introduced. It is known that there is a gradual shift to energy-saving UV systems, such as the energy-saving UV systems used, and energy-saving UV systems that reduce the number of conventional UV lamps from the usual 3 to 4 to 1.

Energy-saving UV-curable inks and varnishes designed to support these new systems have been replaced by general oil-based inks and varnishes in recent years, especially in commercial printing. Performance equivalent to oil-based inks and varnishes is required. In addition, an increasing number of these energy-saving UV curable inks are certified as ``recyclable UV curable inks'' with rank A recyclability.
However, not all UV systems in the market are replaced by energy-saving UV systems, and there are still many cases in which conventional UV systems (many of which have a B rank of recyclability) are still used. UV-curable inks and varnishes are generally considered to be more difficult to recycle than general oil-based inks and varnishes, with the exception of recyclable energy-saving UV-curable inks and some recyclable UV-curable inks. There is. In order to simplify recycling when collecting printed materials, it is extremely difficult and nearly impossible to separate printed materials made with active energy ray-curable inks and varnishes, such as UV-curable types that are not recyclable. It is considered.

Furthermore, even if the base material is a base material other than paper, there is an urgent need to develop a method that facilitates the recycling of the base material. In recent years, UV curing equipment, UV-LED curing equipment, and EB curing equipment that do not apply much heat have been developed. This is because energy ray irradiation has become possible, and as a result, active energy ray-curable inks and varnishes are increasingly being used.

Particularly with respect to plastic base materials, measures against marine pollution are required among global environmental measures, and there is an urgent need to develop a plastic collection system that prevents microplastics, which cause marine pollution, from flowing into the ocean. Compared to chemical recycling, in which plastics and other materials are chemically decomposed and reused, material recycling, in which the materials are made into pellets and reused, is more convenient. If the ink and varnish are not released from the substrate, the remaining ink and varnish will enter the melting process of the substrate, making it difficult for the substrate to return to its original color and limiting the uses of the recycled substrate. There is a high possibility that this will happen. Therefore, developing a simple method for removing additives such as active energy ray-curable inks, varnishes, and adhesives from packaging materials such as plastics will lead to increased efficiency in material recycling.

In addition, active energy ray-curable ink and varnish can be easily removed from all kinds of substrates, including not only soft packaging materials but also synthetic paper, hard plastic substrates such as PET bottle lids, nonwoven fabrics, and metals. If it is possible to easily reuse the base material, it will be possible to improve the efficiency of recycling, reduce the use of fossil resources, and ultimately contribute to reducing the amount of carbon dioxide.

For example, Patent Document 1 discloses an organic solvent-based ink for a release layer that is removable by alkali treatment, a laminate for printed matter containing the release layer using the same, and a method for recycling this laminate. However, the inks that can be removed are limited to inks that use solvents, and there is no simple deinking method for active energy ray-curable inks that are generally solvent-free.

For example, Patent Document 2 discloses a deinking method using an anchor agent for a release layer that can be removed by alkali treatment, but the method is limited to anchors using rosin-modified resins.

For this reason, general active energy ray-curable inks are expected to become more popular, especially active energy ray-curable offset printing inks that have excellent film strength and are difficult to deink, and active energy ray-curable inks for flexographic printing. It is desired to establish a printed matter that has excellent deinking properties when using at least one ink selected from the group consisting of ink and active energy ray-curable resin letterpress printing ink, and a method for producing the printed matter. There is.

JP2020-090627A Patent No. 7078189

An object of the present invention is to provide a laminate that has excellent physical properties as a laminate, such as scratch resistance, and excellent deinking properties in recycling processing of a base material having an ink layer made of an active energy ray-curable ink, and the laminate. It is an object of the present invention to provide a method for manufacturing the laminate, and a method for deinking the laminate.

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

That is, the present invention is a laminate having an anchor layer and an ink layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less,
The present invention relates to a laminate in which the ink layer is a layer obtained by curing active energy ray-curable ink with active energy rays.

The present invention also relates to the above laminate, further comprising a varnish layer on the ink layer.

Further, the present invention provides a laminate having an anchor layer and a varnish layer in this order on a base material (however, an active energy ray-curable ink is applied between the anchor layer and the varnish layer, and an ink layer cured with active energy rays). (excluding cases including),
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less,
The present invention relates to a laminate in which the varnish layer is a layer obtained by curing an active energy ray-curable varnish with active energy rays.

The present invention also provides a method for manufacturing a laminate, comprising:
Step 1: Applying an active energy ray-curable anchor agent containing a (meth)acrylate compound on the base material and curing it with active energy rays to obtain a laminate having an anchor layer on the base material;
Step 2 of printing an active energy ray-curable ink on the anchor layer of the laminate having the anchor layer on the base material and curing it with active energy rays to obtain a laminate having the ink layer on the anchor layer;
including;
The present invention relates to a method for producing a laminate, wherein the (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less.

Further, the present invention further provides the method of printing an active energy ray-curable varnish on the ink layer of the laminate having an anchor layer and an ink layer on the base material, curing it with active energy rays, and applying the varnish on the ink layer. The present invention relates to a method for producing the above-mentioned laminate, which includes step 3 of obtaining a laminate having layers.

The present invention also provides a method for manufacturing a laminate, comprising:
Step 1: Applying an active energy ray-curable anchor agent containing a (meth)acrylate compound on the base material and curing it with active energy rays to obtain a laminate having an anchor layer on the base material;
Step 4 of printing an active energy ray-curable varnish on the anchor layer of the laminate having the anchor layer on the base material and curing it with active energy rays to obtain a laminate having the varnish layer on the anchor layer;
including;
The present invention relates to a method for producing a laminate, wherein the (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less.

The present invention also provides a method for deinking a laminate having an anchor layer and an ink layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less,
The ink layer is a layer obtained by curing active energy ray-curable ink with active energy rays,
The present invention relates to a method for deinking a laminate, in which the laminate is stirred in an aqueous alkaline solution, the anchor layer is dissolved in the aqueous alkaline solution, and the ink layer is deinked from the base material.

The present invention also provides a method for deinking a laminate having an anchor layer, an ink layer, and a varnish layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less,
The ink layer is a layer obtained by curing active energy ray-curable ink with active energy rays,
The varnish layer is a layer obtained by curing an active energy ray-curable varnish with active energy rays,
The present invention relates to a method for deinking a laminate, in which the laminate is stirred in an aqueous alkaline solution, the anchor layer is dissolved in the aqueous alkaline solution, and the ink layer is deinked from the base material.

The present invention also provides a laminate having an anchor layer and a varnish layer in this order on a base material (however, an active energy ray-curable ink is applied between the anchor layer and the varnish layer and is cured with active energy rays). A deinking method (excluding cases where an ink layer is included),
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less,
The varnish layer is a layer obtained by curing an active energy ray-curable varnish with active energy rays,
The present invention relates to a method for deinking a laminate, in which the laminate is stirred in an aqueous alkaline solution, the anchor layer is dissolved in the aqueous alkaline solution, and the ink layer is deinked from the base material.

According to the present invention, a laminate having excellent physical properties as a laminate such as scratch resistance and excellent deinking properties in recycling processing of a base material having an ink layer made of an active energy ray-curable ink, and production of the laminate. It was possible to provide a method and a method for deinking the laminate.

The present invention will be explained in detail below. Note that the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the spirit thereof. Further, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

One embodiment of the present invention is a laminate having an anchor layer and an ink layer in this order on a base material, wherein the anchor layer is a (meth)acrylate compound, and the (meth)acrylate compound has an acid value of 20 mg KOH. The ink layer is a layer in which an active energy ray-curable anchor agent containing a (meth)acrylate compound of 500 mgKOH/g or more is cured with active energy rays, and the ink layer is a layer in which an active energy ray-curable ink is cured with active energy rays. It is a laminate that is a hardened layer.

Further, an embodiment of the present invention provides a laminate having an anchor layer and a varnish layer in this order on a base material (however, an active energy ray-curable ink is applied between the anchor layer and the varnish layer). (excluding cases where the anchor layer contains an ink layer cured with The varnish layer is a layered product in which the varnish layer is a layer obtained by curing an active energy ray-curable varnish with active energy rays.

<Ink layer>
<Active energy ray curable ink>
The active energy ray-curable ink (hereinafter also referred to as "ink") used in the ink layer of the present invention 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 pigments and dyes can be used. From the viewpoint of light resistance, pigments are preferred.
The pigment that can be used in the present invention is not particularly limited, and any known pigment can be used. As the pigment, both inorganic pigments and organic pigments can be used.

Examples of inorganic pigments 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 anilide type, acetoacetate anilide type, pyrazolone type; β-naphthol type, β-oxynaphthoic acid type Insoluble azo pigments such as anilide series, acetoacetate anilide monoazo, acetoacetate anilide disazo, and pyrazolone series; copper phthalocyanine blue, halogenated (e.g. chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free Phthalocyanine pigments such as phthalocyanine; quinacridone series, dioxazine series, threne series (pyranthrone, anthrone, indanthrone, anthrapyrimidine, flavanthrone, thioindigo series, anthraquinone series, perinone series, perylene series, etc.), isoindolinone series, metals Examples include polycyclic pigments and heterocyclic pigments such as complex pigments, quinophthalone pigments, and diketopyrrolopyrrole pigments.

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

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

As a yellow pigment, C. 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.

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

Red or red pigments include C. 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. Pigment Violet 19 and the like.

As a green pigment, C. 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. 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. 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 alone or in combination of two or more.

In the present invention, the above-mentioned pigment can be used in any content as long as the desired concentration can be reproduced on the surface of the printing substrate, and the content may be 5 to 30% by mass based on the total amount of the ink. Preferably, it is more preferably 10 to 25% by mass.

[(meth)acrylate compound]
In this specification, "(meth)acryloyl", "(meth)acrylic acid", "(meth)acrylate", and "(meth)acryloyloxy" each 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 represents the approximate molecular weight of the polyethylene glycol moiety. .

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

[(meth)acrylate compound]
(monomer)
2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, β-carboxylethyl (meth)acrylate, 4-tert-butylcyclohexyl (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-Cyclohexane dimethanol (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, benzyl (meth)acrylate, EO-modified (2) nonylphenol acrylate, 2-methyl-2-ethyl-1,3-dioxolane Monofunctional (meth)acrylate monomers having one (meth)acryloyl group in the 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 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, hydroxypivalic acid neopentyl glycol 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)acrylate Acrylate, (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(meth)acrylate, Difunctional (meth)acrylate, cyclohexanedimethanol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, dicyclopentanyl di(meth)acrylate, etc., which have two (meth)acryloyl groups in the molecule. meth)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 , trifunctional (meth)acrylate monomers 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, and ditrimethylolpropane tetra(meth)acrylate;
Pentafunctional (meth)acrylate monomers having five (meth)acryloyl groups in the molecule, such as dipentaerythritol penta(meth)acrylate;
Examples include hexafunctional (meth)acrylate monomers having six (meth)acryloyl groups in the molecule, such as dipentaerythritol hexa(meth)acrylate.

(oligomer)
Examples include urethane acrylate oligomers such as aliphatic urethane acrylate oligomers and aromatic urethane acrylate oligomers, acrylic ester oligomers, polyester acrylate oligomers, and epoxy acrylate oligomers having 1 to 6 (meth)acryloyl groups.

[Other ingredients]
In the present invention, in addition to the above-mentioned components, the ink may optionally contain a polymerization initiator, an amine compound, a resin, a polymerization inhibitor, a surface tension regulator, a wax, an extender, a pigment dispersant, an antifoaming agent, and an ultraviolet absorber. , an antioxidant, an antistatic agent, etc.

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

In the present invention, the photoradical polymerization initiator is not particularly limited, and any known one can be used. Specific examples include benzophenone compounds, dialkoxyacetophenone compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, and thioxanthone compounds. Further, the photopolymerization initiators 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-benzoylphenylsulfanyl)phenyl]- Examples include 2-methyl-2-(4-methylbenzenesulfonyl)propan-1-one and polybutylene glycol bis(4-benzoylphenoxy) acetate.

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

Examples of 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- mixture of hydroxy-2-methyl-1-oxopropyl)-1,1,3-trimethyl-3-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenyl]-1H-indene, 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. can be 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-based compounds include diphenylacyl phenylphosphine 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.

Examples of 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.

Examples of 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 Examples include ({α-[1-chloro-9-oxo-9H-thioxanthoten-4-yl]oxy}acetylpoly[oxy(1-methylethylene)])oxymethyl)propane.

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 any known amine compound can be used. By using an amine compound as a component of an active energy ray-curable ink, it is expected that it will work to enhance the effect of a hydrogen abstraction type photopolymerization initiator.
Specific examples include 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-ethanediyl, α-[4-(dimethylamino)benzoyl]-ω-[[4-(dimethylamino)benzoyl]oxy]-, bisN, 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)ethylbenzoate, etc. The amine compound may be used alone, or two or more types may be used in combination.

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

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

Specific examples of the resin include polyvinyl chloride, (meth)acrylic resin, styrene (meth)acrylic resin, epoxy resin, polyester resin, polyurethane resin, cellulose derivatives (for example, ethyl cellulose, cellulose acetate, nitrocellulose), and vinyl chloride. Examples include vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, diallyl phthalate resin, alkyd resin, rosin-modified alkyd resin, petroleum resin, urea resin, and synthetic rubber such as butadiene-acrylonitrile copolymer. Among these, diallyl phthalate resin and polyester resin are more preferred 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 based on the total mass of the ink, from the viewpoint of increasing the stability of the ink while maintaining curability.

(wax)
In the present invention, the ink may contain wax. Including wax can improve friction resistance, scratch resistance, anti-blocking properties, slip properties, and anti-scratch properties. There are no particular restrictions on the wax, and any known wax can be used. For example, natural waxes and synthetic waxes.
Examples of natural waxes include carnauba wax, Japanese wax, lanolin, montan wax, paraffin wax, and microcrystalline wax.
Examples of synthetic waxes include Fischer-Trops wax, polyethylene wax, polypropylene wax, and polytetrafluoroethylene wax.

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

(Extender pigment)
In the present invention, the ink may contain an extender pigment. Extender pigments 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 pigment dispersibility. There are no particular limitations on the pigment dispersant, and any known pigment dispersant can be used. Among these, resin-type pigment dispersants having a basic functional group are preferred, and examples of the basic functional group include primary, secondary, or tertiary amino groups, and 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 the Ajisper series (Ajisper PB821, PB822, PB824, etc.) manufactured by Ajinomoto Fine-Techno Co., Ltd., the Solspers series (Solsperse 00, Solsperse 32000, Solsperse 38500, etc.) manufactured by Lubrizol, Inc., and the Disperbic series manufactured by Byk Chemie, Inc. (BYK-162, BYK-168, BYK-183, etc.).

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.

The active energy ray-curable ink in the present application is at least one ink selected from active energy ray-curable offset printing inks, active energy ray-curable flexo printing inks, and active energy ray-curable resin letterpress printing inks. It is preferable that This is because these inks have high film strength among active energy ray-curable inks and are difficult to deink, and the effects of the present invention are particularly noticeable.

<Varnish layer>
<Active energy ray curable varnish>
The active energy ray-curable varnish (hereinafter also referred to as "varnish") used in the varnish layer of the present invention is characterized by containing a (meth)acrylate compound.

The material used for the varnish in the present invention is the same as that of the active energy ray-curable ink described above, except that a colorant is not substantially used.

<Anchor layer>
The anchor layer of the laminate of the present invention can be obtained by applying an active energy ray-curable anchor agent containing a (meth)acrylate compound with an acid value of 20 mgKOH/g to 500 mgKOH/g and curing it with active energy rays. can.

<Active energy ray-curable anchor agent>
The active energy ray-curable anchor agent (hereinafter also referred to as "anchor agent") in the present invention includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less.

[(meth)acrylate compound]
The (meth)acrylate compound contained in the anchor agent in the present invention has the same meaning as the (meth)acrylate compound described in the active energy ray-curable ink described above.

[(Meth)acrylate compound with acid value of 20 mgKOH/g or more and 500 mgKOH/g or less]
The active energy ray-curable anchor agent in the present invention contains, as a (meth)acrylate compound, a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less.
By including a (meth)acrylate compound with an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less, the anchor layer is easily separated (peeled off, dissolved, etc.) from the base material during deinking.
The acid value of the (meth)acrylate compound having an acid value of 20 to 500 mgKOH/g is preferably 50 to 450 mgKOH/g, more preferably 80 to 400 mgKOH/g, and particularly preferably 100 to 350 mgKOH/g.

The content of the (meth)acrylate compound with an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less is preferably 15 to 90% by mass, and 20 to 80% by mass based on the total amount of the active energy ray-curable anchor agent. The content is more preferably from 25 to 75% by weight, even more preferably from 30 to 70% by weight. When the content of the (meth)acrylate compound with an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less is 15% by mass or more, the deinking property is good, and when it is 90% by mass or less, the scratch resistance is good. .

Specifically, the (meth)acrylate compounds with an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less include MIRAMER SC6632 and MIRAMER SC6640 manufactured by MIWON, DPV27 and DPV28 manufactured by Negami Kogyo Co., Ltd., and EBECRYL11 and (ACA) manufactured by Daicel Allnex. Z200M, (ACA) Z230AA, (ACA) Z250, (ACA) Z251, (ACA) Z254F, (ACA) Z300, (ACA) Z320, β-CEA, Taisei Fine Chemical Co., Ltd. 8KQ-2001, PH-9001, etc. Can be mentioned.

[Other ingredients]
In the present invention, the anchoring agent may include silica, alumina, antifoaming agents, leveling agents, tackifiers, preservatives, antibacterial agents, rust preventives, etc., adhesion aids, polymerization initiators, etc. in addition to the above-mentioned components as necessary. It can contain agents, amine compounds, polymerization inhibitors, waxes, extender pigments, pigment dispersants, ultraviolet absorbers, antioxidants, antistatic agents, and the like.

(Polymerization initiator, amine compound, extender pigment, pigment dispersant)
The polymerization initiator, amine compound, wax, extender pigment, and pigment dispersant that the anchor agent in the present invention can have are the polymerization initiator, amine compound wax, amine compound wax, Extender pigments and pigment dispersants can be used.

(Polymerization inhibitor)
The polymerization inhibitor contained in the anchor agent in the present invention can be added and used by a conventional method. From the viewpoint of not inhibiting curability, the amount of the polymerization inhibitor is preferably 3% by mass or less, based on the total mass of the anchor agent, and more preferably in the range of 0.01 to 1% by mass. preferable.

Specific examples of usable polymerization inhibitors include (alkyl)phenol, hydroquinone, catechol, resorcinol, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N-(3 -oxyanilino-1,3-dimethylbutylidene) aniline oxide, dibutyl cresol, cyclohexanone oximucresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, and cyclohexanone oxime.
In particular, 2,2,6,6-tetraalkylpiperidine derivatives and 2,2,6, selected from hindered amine systems such as 6-tetramethylpiperidine derivatives, 1-alkyl-2,2,6,6-tetramethylpiperidine derivatives or 1-hydro-2,2,6,6-tetramethylpiperidine derivatives It is preferred to use one or more compounds, which can inhibit the curing reaction in printing machines and provide excellent storage stability.

<Laminated body>
In one embodiment of the laminate of the present invention, an active energy ray-curable ink is printed on an anchor layer in which an anchor agent coated on a base material is cured with active energy rays, and then cured with active energy rays. obtained by.
In this embodiment, a varnish layer may be further provided on the ink layer. The varnish used for the varnish layer is not particularly limited and any known varnish 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 method for manufacturing the laminate of this embodiment is as follows:
An active energy ray-curable anchor agent containing a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less is applied to the base material, and the active energy ray curable anchor agent is applied as a (meth)acrylate compound. Step 1 of curing to obtain a laminate having an anchor layer on the base material;
Step 2 of printing an active energy ray-curable ink on the anchor layer of the laminate having the anchor layer on the base material and curing it with active energy rays to obtain a laminate having the ink layer on the anchor layer;
including.

Further, in the manufacturing method of this embodiment, an active energy ray-curable varnish is further printed on the ink layer of the laminate having an anchor layer and an ink layer on the base material, and is cured with active energy rays. , may include step 3 of obtaining a laminate having a varnish layer on the ink layer.

In one embodiment of the laminate of the present invention, an active energy ray-curable varnish is printed on an anchor layer in which an anchor agent coated on a base material is cured with active energy rays, and then cured with active energy rays. obtained by.

The method for manufacturing the laminate of this embodiment is as follows:
An active energy ray-curable anchor agent containing a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less is applied to the base material, and the active energy ray curable anchor agent is applied as a (meth)acrylate compound. Step 1 of curing to obtain a laminate having an anchor layer on the base material;
Step 4 of printing an active energy ray-curable varnish on the anchor layer of the laminate having the anchor layer on the base material and curing it with active energy rays to obtain a laminate having the varnish layer on the anchor layer;
including.

The base material is not particularly limited, and any known material can be used. Specifically, polypropylene (PP) (including synthetic paper), polyethylene (PE), polyethylene terephthalate (PET), plastic substrates with inorganic vapor deposited layers such as aluminum, silica, and alumina, aluminum foil, and polyvinyl chloride. (PVC), polystyrene (PS), nylon, cellophane, metal sheet, paper (excluding synthetic paper), etc., and non-absorbent substrates are preferred. Various additives such as an antistatic agent, an antifogging agent, and an ultraviolet inhibitor may be used in the base material.

In the present invention, the active energy ray curable ink can be printed using any known method, including offset printing using an active energy ray curable offset printing ink, active energy ray curable resin letterpress printing ink, etc. It is suitably used in resin letterpress printing using active energy ray-curable flexographic printing ink.

In the present invention, the method for printing the active energy ray-curable varnish is not particularly limited, and any known method can be used. Specifically, roll coaters, gravure coaters, flexo coaters, air doctor coaters, blade coaters, air knife coaters, squeeze coaters, impregnation coaters, transfer roll coaters, kiss coaters, curtain coaters, cast coaters, spray coaters, die coaters, and offset printing. , resin letterpress printing, gravure printing, flexo printing, etc.

In the present invention, the method of applying the active energy ray-curable anchor agent is not particularly limited, and any known method can be used. Specifically, roll coaters, gravure coaters, flexo coaters, air doctor coaters, blade coaters, air knife coaters, squeeze coaters, impregnation coaters, transfer roll coaters, kiss coaters, curtain coaters, cast coaters, spray coaters, die coaters, and offset printing. , resin letterpress printing, gravure printing, flexo printing, etc.

There are no particular restrictions on the active energy ray source, 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-LEDs), ultraviolet laser diodes (UV-LDs), and EB (electron beam) irradiation equipment. , gas/solid-state lasers, etc.

<Deinking>
In the present invention, deinking is a process for removing ink and varnish components from printed substrates.

(Ink component removal process using alkaline aqueous solution)
The process for forming the laminate is, for example, in a treatment tank containing an alkaline aqueous solution, in which the ink layer and the varnish layer are removed by contacting the laminate with an alkaline aqueous solution.

(alkaline aqueous solution)
In the present invention, the alkaline aqueous solution is an aqueous solution containing an alkaline compound, and preferably contains the alkaline compound in an amount of 0.5 to 10% by mass of the entire aqueous solution, more preferably 1 to 5% by mass. The alkaline compounds mentioned above are not particularly limited, but include sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH) ₂ ammonia, barium hydroxide (Ba(OH) ₂ ), and sodium carbonate. Preferred examples include (Na ₂ CO ₃ ), etc. NaOH and/or KOH are preferred.

(Ink/varnish component removal process)
The mechanism by which the ink layer and varnish layer can be detached from the laminate due to contact between the alkaline aqueous solution and the laminate is presumed to be that the presence of the resin allows the alkaline aqueous solution to be released from the surface of the anchor layer and/or the cross section of the laminate. This is because the anchor layer is dissolved by penetration. After applying an anchor layer on the base material and printing an ink layer or varnish layer, the laminate that is shaped into a packaging container through a bag-making process is not cut or crushed before or during the recycling process. It is preferable that the cross section of the laminate is exposed to the aqueous alkaline solution.

It is preferable that the laminate and the alkaline aqueous solution are brought into contact with each other while being stirred. The stirring means is not particularly limited, and includes known stirring equipment such as general dispers, radial flow turbine blades, axial flow turbine blades, paddle blades, propeller blades, anchor blades, and high shear mixers. For example, in the case of a 2L flask scale, the stirring rotational speed is preferably 100 to 350 rpm, depending on the shape and size of the stirring blade. The stirring time is preferably 15 minutes or more and 24 hours or less.

(Base material recovery process)
The recycled base material manufacturing method of the present invention includes a step of recovering the base material after removing the ink layer and the varnish layer from the laminate. The process of recovering the base material involves, after treating the laminate with an alkaline aqueous solution, separating and recovering the base material from a treatment tank containing a mixture of the alkaline aqueous solution, pieces of peeled ink and varnish layers, and the base material. It is preferable that the base material can be obtained with high purity. The method for recovering the base material is not particularly limited, and for example, separation and recovery based on the size difference between the base material and the pieces of the ink layer or varnish layer is preferable, and separation and recovery based on the difference in specific gravity is also preferable. Alternatively, separation and recovery can be carried out as appropriate by a combination of these, but it is preferable to include a separation and recovery process based on specific gravity differences, and more preferably to use a separation and recovery process based on specific gravity differences and a separation and recovery process based on size differences. .
In addition, in the separation and collection step based on the difference in specific gravity, it is preferable to collect only the base material that floats on the alkaline aqueous solution in the treatment tank. Further, it is preferable that impurity components in the alkaline aqueous solution and fragments of the ink layer or varnish layer settle out, so that separation from the base material is easy and only the base material can be recovered with higher accuracy. Therefore, the physical properties and transparency of the base material recycled after collection are improved. The separation method based on the difference in specific gravity may be a conventionally known method, such as one using a fluidized bed or a centrifugal separator.

After the ink layer and varnish layer are detached from the laminate and the base material is recovered, a recycled base material can be obtained through the steps of washing and drying the base material. At this time, it is preferable that all contaminants, including detached ink layer and varnish layer fragments, adhere to the recycled base material as much as possible. The obtained recycled base material can be processed into pellets using an extruder or the like and reused as recycled resin. The use of the recycled resin is not limited, and it may be processed into a colorless and transparent film, or it may be processed into a molded product with a colorant added thereto.

Examples of deinking agents include deinking agents DI-7020, DI-7027, DI-7250, and DI-767 manufactured by Kao Corporation, DIA-Z series and DIA-Y series manufactured by Nissin Chemical Co., Ltd., and deinking agents manufactured by Lion Specialty Chemicals. Liptor series etc. are available.

EXAMPLES The present invention will be specifically explained by showing Examples and Comparative Examples below. However, the present invention is not limited in any way by the following examples. In addition, in Examples and Comparative Examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

(Anchor agent 1)
Mix 40.0 parts of SC6640, 30.0 parts of SC6632, 22.0 parts of DiTMPTA, 5.0 parts of 4MBP, 2.0 parts of TPO, and 1.0 parts of EDB, and use a butterfly mixer. An active energy ray-curable anchor agent (AC1) was prepared by stirring and mixing.

(Anchor agent 2)
Active energy was obtained by mixing 80.0 parts of SC6640, 12.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, and 1.0 parts of EDB, and stirring and mixing using a butterfly mixer. A line-curable anchor agent (AC2) was prepared.

(Anchor agent 3)
15.0 parts of SC6632, 65.0 parts of TMPTA (EO), 12.0 parts of DiTMPTA, 5.0 parts of 4MBP, 2.0 parts of TPO, and 1.0 parts of EDB were mixed, and a butterfly mixer was used. An active energy ray-curable anchor agent (AC3) was prepared by stirring and mixing using a .

(Anchor agent 4)
40.0 parts of SC6632, 40.0 parts of TMPTA (EO), 12.0 parts of DiTMPTA, 5.0 parts of 4MBP, 2.0 parts of TPO, and 1.0 parts of EDB were mixed, and a butterfly mixer was used. An active energy ray-curable anchor agent (AC4) was prepared by stirring and mixing using the following method.

(Anchor agent 5)
Mix 90.0 parts of SC6640, 2.0 parts of TMPTA (EO), 5.0 parts of 4MBP, 2.0 parts of TPO, and 1.0 parts of EDB, and stir and mix using a butterfly mixer. An active energy ray-curable anchor agent (AC5) was prepared.

(Anchor agent 6)
5.0 parts of SC6632, 75.0 parts of TMPTA (EO), 12.0 parts of DiTMPTA, 5.0 parts of 4MBP, 2.0 parts of TPO, and 1.0 parts of EDB were mixed, and a butterfly mixer was used. An active energy ray-curable anchor agent (AC6) was prepared by stirring and mixing using the following method.

(Anchor agent 7)
Mix 70.0 parts of TMPTA (EO), 22.0 parts of DiTMPTA, 5.0 parts of 4MBP, 2.0 parts of TPO, and 1.0 parts of EDB, and stir and mix using a butterfly mixer. An active energy ray-curable anchor agent (AC7) was prepared.

<Preparation of 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 mixture was heated to 100° C. with stirring. Next, 25.0 parts of diallyl phthalate resin was mixed and dissolved while keeping the mixture at 100° C. to produce a diallyl phthalate resin varnish.

<Ink production example>

(Ink production example 1 (UV ink 1) (active energy ray curable offset printing ink, active energy ray curable resin letterpress printing ink))
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, 3.0 parts of 379, DEABP 1.5 parts of DETX, 1.0 parts of EDB, and 47.0 parts of diallyl phthalate resin varnish were mixed, stirred and mixed using a butterfly mixer, and then mixed with three rolls until the maximum An ink was prepared by dispersing the particles so that the particle size was 7.5 μm or less.

(Ink production example 2 (UV ink 2) (active energy ray-curable offset printing ink, active energy ray-curable resin letterpress printing ink))
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, 3.0 parts of 379, DEABP Mix 1.5 parts of DETX, 1.5 parts of DETX, 1.0 parts of EDB, and 47.0 parts of MIRAMER PS-4500, stir and mix using a butterfly mixer, and then mix with three rolls to the maximum. An ink was prepared by dispersing the particles so that the particle size was 7.5 μm or less.

(Ink production example 3 (LED ink) (active energy ray-curable offset printing ink, active energy ray-curable resin letterpress printing ink))
17.0 parts of RAVEN 1080 Ultra, 3.0 parts of BA-2550, 6.0 parts of TMPTA (EO), 10.0 parts of DiTMPTA, 7.0 parts of DPHA, 3.0 parts of 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 were mixed, and a butterfly mixer was used. After stirring and mixing using a 3-roll roller, the mixture was dispersed to a maximum particle size of 7.5 μm or less to prepare an ink.

(Ink production example 4 (UV flexographic ink) (active energy ray-curable flexographic printing ink))
15.0 parts of RAVEN 1080 Ultra, 1.0 parts of BA-2550, 16.0 parts of TMPTA (EO), 5.0 parts of DiTMPTA, 7.0 parts of DPHA, 3.0 parts of 379, DEABP 2.0 parts of 4MBP, 2.5 parts of DETX, 1.0 parts of EDB, and 6.0 parts of Solsperse 24000 were stirred and mixed using a butterfly mixer, and then mixed with three rolls. An ink was prepared by dispersing the particles so that the maximum particle size was 7.5 μm or less. Thereafter, 39.0 parts of TMPTA (EO) was added and mixed using a butterfly mixer to prepare an ink.

(Ink production example 5 (UV ink yellow) (active energy ray curable offset printing ink, active energy ray curable resin letterpress printing ink))
15.0 parts of Permanent Yellow BHS, 6.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 3.0 parts of 379, 1.5 parts of DEABP, 1 part of DETX .5 parts of EDB, 1.0 parts of EDB, and 47.0 parts of diallyl phthalate resin varnish were mixed, stirred and mixed using a butterfly mixer, and then passed through three rolls until the maximum particle size was 7.5 μm or less. An ink was prepared by dispersing it as follows.

(Ink production example 6 (UV ink red) (active energy ray curable offset printing ink, active energy ray curable resin letterpress printing 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 were mixed, stirred and mixed using a butterfly mixer, and then processed with three rolls until the maximum particle size was 7.5 μm or less. An ink was prepared by dispersing it so that

(Ink production example 7 (UV indigo) (active energy ray-curable offset printing ink, active energy ray-curable resin letterpress printing ink))
Heliogen Blue 20.0 parts of D7088, 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, 1 part of DETX .5 parts of EDB, 1.0 parts of EDB, and 47.0 parts of diallyl phthalate resin varnish were mixed, stirred and mixed using a butterfly mixer, and then passed through three rolls until the maximum particle size was 7.5 μm or less. An ink was prepared by dispersing it as follows.

(Ink production example 9 (EB ink black) (active energy ray-curable offset printing ink, active energy ray-curable resin letterpress printing ink))
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. After stirring and mixing using a butterfly mixer, the ink was prepared by dispersing with three rolls so that the maximum particle size was 7.5 μm or less.

<Preparation of oil-based resin varnish>
(Production example of rosin modified phenolic resin)
In a reaction vessel, 54.3 parts of gum rosin 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 phenol resin from which water had been removed was added dropwise at 150°C and reacted for 2 hours. Furthermore, 5.4 parts of glycerin was added, and the mixture was reacted at 250° C. for 15 hours using 0.1 part of calcium oxide as a catalyst. During this time, rosin phenol resin could be obtained by sequentially taking out the resin.

(Example of manufacturing rosin modified phenolic resin varnish)
Next, in a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 45.0 parts of the rosin-modified phenol resin as a binder resin, 44.0 parts of soybean oil, and 10 parts of soybean oil fatty acid n-butyl ester were added. 0 part of ALCH 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 10 (oil-based ink) (ink other than active energy ray-curable ink))
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, 0.5 parts of drying inhibitor CP. After stirring and mixing using a butterfly mixer, the mixture was dispersed using three rolls so that the maximum particle size was 7.5 μm or less to prepare an ink.

(Varnish production example 1 (UV varnish) (active energy ray curable varnish for offset printing, active energy ray curable varnish for resin letterpress printing))
6.0 parts of TMPTA (EO), 13.0 parts of DiTMPTA, 7.0 parts of DPHA, 6.0 parts of 184, 2.0 parts of TPO, 1.0 parts of EDB, 3.0 parts of filler. , and 62.0 parts of diallyl phthalate resin varnish were mixed, stirred and mixed using a butterfly mixer, and then dispersed using three rolls so that the maximum particle size was 7.5 μm or less to prepare a varnish.

The description of the notation of the materials used in the examples is as follows.
[Colorant]
・Permanent Yellow BHS: Manufactured by Clariant, Permanent Yellow BHS (C.I.Pigment Yellow 174)
・Permanent Rubine L5B-01: Manufactured by Clariant, Permanent Rubine L5B-01 (C.I.Pigment Red 57:1)
・HELIOGEN BLUE D7088: Made by BASF, HELIOGEN BLUE D7088 (C.I.Pigment Blue 15:3)
・Raven 1080 Ultra: Made by Bilra Carbon, Raven 1080 Ultra Powder (C.I.Pigment Black 7)
・BA-2550: Manufactured by Morimura Shoji Co., Ltd., Alkaline Blue Toner BA-2550 (C.I.Pigmen
t Blue 61)
[Extender pigment]
・Filler: Made by Matsumura Sangyo Co., Ltd., High Filler #5000PJ, Talc [(meth)acrylate compound]
・SC6640: Manufactured by MIWON, MIRAMER SC6640 (acid value: 255mgKOH/g)
・SC6632: Manufactured by MIWON, MIRAMER SC6632 (acid value: 190mgKOH/g)
・TMPTA (EO): manufactured by BASF, LAROMER LR8863, trimethylolpropane ethylene oxide modified triacrylate ・DiTMPTA: manufactured by Daicel Allnex, 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: Osaka Soda Co., Ltd., Daiso Dapp A
[Photopolymerization initiator]
・379: Manufactured by IGM RESINS, Omnirad379, 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone/TPO: Chemark Chemical Co., Ltd., CHEMARK TPO, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide/DEABP: Chemark Chemical Co., Ltd., CHEMARK DEABP, 4,4'-bis(dimethylamino)benzophenone/4MBP: Soho Jitsugyo Co., Ltd. Manufactured by SB-PI 712
・DETX: Chemark Chemical Co., Ltd., CHEMARK DETX, 2,4-diethylthioxanthone ・184: IGM RESINS Co., Ltd., Omnirad184, 1-hydroxy-cyclohexylphenyl ketone [amine compound]
・EDB: Chemark Chemical Co., Ltd., CHEMARK EDB, ethyl-4-(dimethylamino)benzoate [pigment dispersant]
Solsperse24000: Manufactured by Lubrizol, Solsperse24000
[Metal dryer]
・MK dryer: manufactured by Toyo Ink Co., Ltd., MK dryer [drying inhibitor]
・Drying inhibitor CP: manufactured by Toyo Ink Co., Ltd., drying inhibitor CP
[Aluminum gelling agent]
・ALCH: Manufactured by Kawaken Fine Chemical Co., Ltd., ALCH, aluminum ethyl acetate diisopropylate [other]
・Soybean oil fatty acid normal butyl ester: manufactured by Toshin Yushi Co., Ltd., SFB2
・Soybean oil: Manufactured by Nisshin Oilio Group Co., Ltd.: Soybean white squeezed oil

<Printing of anchor agent on base material>
Examples 1 to 12, 14 to 27, and Comparative Examples 2 and 3 were prepared using an RI tester (a simple printing machine manufactured by Mei Seisakusho Co., Ltd. (for printing offset printing inks, flexo printing inks, and resin letterpress printing inks). The anchoring agent was applied by printing on one side of the base material listed in Table 1 with an ink gauge of 0.25 mL using a printing machine capable of printing. Thereafter, the coating film was cured using an ultraviolet curing device (160 W/cm metal halide lamp) manufactured by Eye Graphics at a conveyor speed of 30 m/min to produce a laminate having an anchor layer on the base material.
In Example 13, the anchor agents shown in Table 1 were applied onto the base materials shown in Table 1 using a bar coater (No. 4, manufactured by Yasuda Seiki Co., Ltd.). Thereafter, the coating film was cured using an ultraviolet curing device (160 W/cm metal halide lamp) manufactured by Eye Graphics at a conveyor speed of 30 m/min to produce a laminate having an anchor layer on the base material.

<Ink and varnish printing>
In Examples 1 to 22, 24, and Comparative Example 2, after printing each sample ink shown in Table 1 with an ink gauge of 0.25 mL using an RI tester on the produced laminate having an anchor layer on the base material, The printed matter is cured using an ultraviolet curing device (160 W/cm metal halide lamp) manufactured by Eye Graphics at a conveyor speed of 30 m/min to form a laminated film having an anchor layer and an ink layer in this order on the base material. I got a body.
In addition, in Example 23, after printing LED ink with an ink gauge of 0.25 mL using an RI tester on the produced laminate having an anchor layer on the base material, the printed matter was printed using an ultraviolet curing device manufactured by I-Graphics Co., Ltd. The ink was cured using a 160 W/cm metal halide lamp) at a conveyor speed of 100 m/min to obtain a laminate having an anchor layer and an ink layer on the base material in this order.
In addition, in Example 25, after printing EB ink with an ink gauge of 0.25 mL using an RI tester on the produced laminate having an anchor layer on the base material, the printed matter was manufactured using a low-energy electron beam manufactured by ESI Co., Ltd. The ink is cured by irradiating the ink with an electron beam of 30 KGy using an irradiation device (pressure voltage 175 KV, oxygen concentration 50 ppm, nitrogen-substituted atmosphere) to form a laminate having an anchor layer and an ink layer in this order on the base material. Obtained.
In addition, in Example 26, using an RI tester, a UV varnish in which 2 parts of UV ink 1 was mixed in advance with an ink gauge of 0.25 mL was printed on the produced laminate having an anchor layer on the base material, and then the printed matter was printed. The coating film was cured using an ultraviolet curing device (160 W/cm metal halide lamp) manufactured by Eye Graphics at a conveyor speed of 30 m/min to form a laminate having an anchor layer and a varnish layer in this order on the base material. Obtained.
In addition, in Example 27, after printing UV ink 1 with an ink gauge of 0.25 mL using an RI tester on the produced laminate having an anchor layer on the base material, the printed matter was printed using an ultraviolet curing device manufactured by I-Graphics. (160 W/cm metal halide lamp) at a conveyor speed of 30 m/min, and after printing UV varnish using an RI tester with an ink gauge of 0.25 mL, the printed matter was manufactured by I-Graphics Co., Ltd. The coating film was cured using an ultraviolet curing device (160 W/cm metal halide lamp) at a conveyor speed of 30 m/min to obtain a laminate having an anchor layer, an ink layer, and a varnish layer in this order on the base material. .
In addition, in Comparative Example 3, after printing oil-based ink (ink other than active energy ray-curable ink) with an ink gauge of 0.25 mL using an RI tester on the laminate having an anchor layer on the prepared base material, The ink was cured by being left at room temperature for 24 hours to obtain a laminate having an anchor layer and an ink layer in this order on the base material.
In addition, in Comparative Example 1, after printing oil-based black ink (ink other than active energy ray-curable ink) directly on the base material listed in Table 1 with an ink gauge of 0.25 mL using an RI tester, it was left at room temperature for 24 hours. The ink was left to harden to obtain a laminate having an ink layer on the base material.

Note that the base materials used in the examples are as follows.
・PP: Manufactured by Okamoto Co., Ltd., polypropylene sheet ・PE: Manufactured by Futamura Chemical Co., Ltd., Taiko FC
・PET: Manufactured by Toyobo Co., Ltd., Reshine Aluminum vapor deposition: Manufactured by Gojo Paper Co., Ltd., SPECIALITIES
・Aluminum foil: Manufactured by Toyo Aluminum Co., Ltd., Leadmax ・Synthetic paper: Manufactured by Yupo Corporation, New Yupo FGS
・PVC: Made by Lintec Corporation, PVC80CP
・PS: Manufactured by Oishi Sangyo Co., Ltd., Styrophane nylon: Manufactured by Unitika Co., Ltd., Emblem Cellophane: Manufactured by Futamura Chemical Co., Ltd., PL
・Metal: Made by Nippon Steel Corporation, ET2.8 tin plate

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

<Evaluation of laminate>

(Evaluation of scratch resistance)
The produced laminate was evaluated by rubbing the ink surface with a cotton cloth. It can be judged that the less abrasion occurs, the better the scratch resistance is. The evaluation criteria are as shown below, and 〇, 〇△, and △ are practically preferred.
〇: No rubbing on the printed surface with ink spread 〇△: Rubbing up to the surface layer of the printed surface with ink spread △: Rubbing up to the middle part of the printed surface with ink spread △×: Printing with colored ink spread Rubbing to the bottom of the surface ×: The coating film on the printed surface on which the ink was spread is lost.

(Evaluation of adhesion)
Adhesive tape (Cellotape (registered trademark, manufactured by Nichiban Co., Ltd., 18 mm width) was applied to the ink surface of the produced laminate, and peeled off in a 90-degree vertical direction. Based on the ratio of the peeled area of the ink film from the anchor layer, the base material The adhesion to was evaluated. 〇, 〇△, △ are practically preferred.
〇: No peeling of the anchor layer from the base material 〇△: Peeling of the anchor layer from the base material is less than 10% △: Peeling of the anchor layer from the base material is 10% or more and less than 30% △×: Base material The anchor layer peels off from the base material by 30% or more and less than 70%. ×: The anchor layer peels off from the base material by 70% or more.

<Evaluation of deinking performance>
The produced laminates of Examples 1 to 27 and Comparative Examples 1 to 3 were aged at 60°C for one week, and then stored for an additional 10 days at a room temperature of 23±1°C and a humidity of 50±2%. Thereafter, it was cut into 30 x 30 mm pieces and 90 g of each sample was used in the test.

<Evaluation of deinking properties of laminate>
Into a 2L flask, add 1.5L of 30°C warm water, 11mL of 3.75% sodium hydroxide aqueous solution, and 11mL of deinking agent (DI-7027, manufactured by Kao Corporation) diluted to 1.5%. A sample was added and stirred at 300 rpm for 20 minutes. Two minutes after the start of stirring, the sample adhering to the lid was washed away into the tank with a small amount of water. After the desorption was completed, the base material was taken out, and it was visually evaluated to see how much of the area of each 30 x 30 mm area was covered with the ink.
〇: Ink has come off from 95% or more of the base material △: Ink has come off from 90% or more but less than 95% of the base material ×: Ink has come off from less than 90% of the base material

It can be judged that the products are practical if they are rated as ○, ○△, or △ in the three evaluations of scratch resistance, adhesion, and deinking performance.

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

That is, the present invention is a laminate having an anchor layer and an ink layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound with an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less,
The ink layer contains at least one type of ink selected from active energy ray-curable offset printing inks, active energy ray-curable flexo printing inks, and active energy ray-curable resin letterpress printing inks. The present invention relates to a laminate, which is a layer cured with.

The present invention also provides a method for manufacturing a laminate, comprising:
Step 1: Applying an active energy ray-curable anchor agent containing a (meth)acrylate compound on the base material and curing it with active energy rays to obtain a laminate having an anchor layer on the base material;
On the anchor layer of the laminate having the anchor layer on the base material, an active energy ray-curable offset printing ink, an active energy ray-curable flexo printing ink, and an active energy ray-curable resin letterpress printing ink are applied. Step 2 of printing at least one selected ink and curing with active energy rays to obtain a laminate having an ink layer on the anchor layer;
including;
The present invention relates to a method for manufacturing a laminate, wherein the (meth)acrylate compound has an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less.

The present invention also provides a method for deinking a laminate having an anchor layer and an ink layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound with an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less,
The ink layer contains at least one ink selected from active energy ray-curable offset printing inks, active energy ray-curable flexo printing inks, and active energy ray-curable resin letterpress printing inks. It is a layer hardened with
The present invention relates to a method for deinking a laminate, in which the laminate is stirred in an aqueous alkaline solution, the anchor layer is dissolved in the aqueous alkaline solution, and the ink layer is deinked from the base material.

That is, the present invention is a laminate having an anchor layer and an ink layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less,
An active energy ray-curable offset printing ink in which the ink layer does not contain a volatile organic compound , an active energy ray-curable flexo printing ink that does not contain a volatile organic compound , and an active energy ray-curable ink that does not contain a volatile organic compound. The present invention relates to a laminate, which is a layer formed by curing at least one type of ink selected from line-curable resin letterpress printing inks with active energy rays.

The present invention also provides a method for manufacturing a laminate, comprising:
Step 1: Applying an active energy ray-curable anchor agent containing a (meth)acrylate compound on the base material and curing it with active energy rays to obtain a laminate having an anchor layer on the base material;
On the anchor layer of the laminate having the anchor layer on the base material, an active energy ray-curable offset printing ink that does not contain volatile organic compounds , an active energy ray-curable flexographic printing ink that does not contain volatile organic compounds. , and at least one type of ink selected from active energy ray-curable resin letterpress printing inks that do not contain volatile organic compounds is printed and cured with active energy rays to form a laminate having an ink layer on the anchor layer. Step 2 of obtaining
including;
The present invention relates to a method for manufacturing a laminate, wherein the (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less.

The present invention also provides a method for deinking a laminate having an anchor layer and an ink layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less,
An active energy ray-curable offset printing ink in which the ink layer does not contain a volatile organic compound , an active energy ray-curable flexo printing ink that does not contain a volatile organic compound , and an active energy ray-curable ink that does not contain a volatile organic compound. A layer obtained by curing at least one type of ink selected from line-curable resin letterpress printing inks with active energy rays,
The present invention relates to a method for deinking a laminate, in which the laminate is stirred in an aqueous alkaline solution, the anchor layer is dissolved in the aqueous alkaline solution, and the ink layer is deinked from the base material.

The present invention also provides a method for deinking a laminate having an anchor layer, an ink layer, and a varnish layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound with an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less,
An active energy ray-curable offset printing ink in which the ink layer does not contain a volatile organic compound, an active energy ray-curable flexo printing ink that does not contain a volatile organic compound, and an active energy ray-curable ink that does not contain a volatile organic compound. A layer obtained by curing at least one type of ink selected from line-curable resin letterpress printing inks with active energy rays,
The varnish layer is a layer obtained by curing an active energy ray-curable varnish with active energy rays,
The present invention relates to a method for deinking a laminate, in which the laminate is stirred in an aqueous alkaline solution, the anchor layer is dissolved in the aqueous alkaline solution, and the ink layer is deinked from the base material.

That is, the present invention is a laminate having an anchor layer and an ink layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less,
The ink layer includes an active energy ray-curable offset printing ink that does not contain volatile organic compounds (VOC) , an active energy ray-curable flexographic printing ink that does not contain volatile organic compounds (VOC), and a volatile organic compound (VOC) -free active energy ray-curable offset printing ink. The present invention relates to a laminate, which is a layer obtained by curing at least one type of ink selected from active energy ray-curable resin letterpress printing inks that do not contain compounds (VOC) with active energy rays.

The present invention also provides a method for manufacturing a laminate, comprising:
Step 1: Applying an active energy ray-curable anchor agent containing a (meth)acrylate compound on the base material and curing it with active energy rays to obtain a laminate having an anchor layer on the base material;
On the anchor layer of the laminate having the anchor layer on the base material, an active energy ray-curable offset printing ink that does not contain volatile organic compounds (VOC) , an active energy ray that does not contain volatile organic compounds (VOC). At least one ink selected from a curable flexographic printing ink and an active energy ray-curable resin letterpress printing ink that does not contain volatile organic compounds (VOC) is printed and cured with active energy rays to form an anchor layer. Step 2 of obtaining a laminate having an ink layer thereon;
including;
The present invention relates to a method for manufacturing a laminate, wherein the (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less.

The present invention also provides a method for deinking a laminate having an anchor layer and an ink layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less,
The ink layer includes an active energy ray-curable offset printing ink that does not contain volatile organic compounds (VOC) , an active energy ray-curable flexographic printing ink that does not contain volatile organic compounds (VOC), and a volatile organic compound (VOC) -free active energy ray-curable offset printing ink. A layer obtained by curing at least one type of ink selected from active energy ray-curable resin letterpress printing inks that do not contain compounds (VOC) with active energy rays,
The present invention relates to a method for deinking a laminate, in which the laminate is stirred in an aqueous alkaline solution, the anchor layer is dissolved in the aqueous alkaline solution, and the ink layer is deinked from the base material.

The present invention also provides a method for deinking a laminate having an anchor layer, an ink layer, and a varnish layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less,
The ink layer includes an active energy ray-curable offset printing ink that does not contain volatile organic compounds (VOC) , an active energy ray-curable flexographic printing ink that does not contain volatile organic compounds (VOC), and a volatile organic compound (VOC) -free active energy ray-curable offset printing ink. A layer obtained by curing at least one type of ink selected from active energy ray-curable resin letterpress printing inks that do not contain compounds (VOC) with active energy rays,
The varnish layer is a layer obtained by curing an active energy ray-curable varnish with active energy rays,
The present invention relates to a method for deinking a laminate, in which the laminate is stirred in an aqueous alkaline solution, the anchor layer is dissolved in the aqueous alkaline solution, and the ink layer is deinked from the base material.

Claims (9)

A laminate having an anchor layer and an ink layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less,
The laminate, wherein the ink layer is a layer obtained by curing active energy ray-curable ink with active energy rays. The laminate according to claim 1, further comprising a varnish layer on the ink layer. A laminate having an anchor layer and a varnish layer in this order on a base material (excluding cases where an active energy ray-curable ink is included between the anchor layer and the varnish layer, and an ink layer cured by active energy rays) ) and
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less,
A laminate, wherein the varnish layer is a layer obtained by curing an active energy ray-curable varnish with active energy rays. A method for manufacturing a laminate, comprising:
Step 1: Applying an active energy ray-curable anchor agent containing a (meth)acrylate compound on the base material and curing it with active energy rays to obtain a laminate having an anchor layer on the base material;
Step 2 of printing an active energy ray-curable ink on the anchor layer of the laminate having the anchor layer on the base material and curing it with active energy rays to obtain a laminate having the ink layer on the anchor layer;
including;
A method for manufacturing a laminate, wherein the (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less. Furthermore, an active energy ray-curable varnish is printed on the ink layer of the laminate having an anchor layer and an ink layer on the base material, and cured with active energy rays, thereby producing a laminate having a varnish layer on the ink layer. The method for manufacturing a laminate according to claim 4, comprising step 3 of obtaining. A method for manufacturing a laminate, comprising:
Step 1: Applying an active energy ray-curable anchor agent containing a (meth)acrylate compound on the base material and curing it with active energy rays to obtain a laminate having an anchor layer on the base material;
Step 4 of printing an active energy ray-curable varnish on the anchor layer of the laminate having the anchor layer on the base material and curing it with active energy rays to obtain a laminate having the varnish layer on the anchor layer;
including;
A method for manufacturing a laminate, wherein the (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less. A method for deinking a laminate having an anchor layer and an ink layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less,
The ink layer is a layer obtained by curing active energy ray-curable ink with active energy rays,
A method for deinking a laminate, in which the laminate is stirred in an aqueous alkaline solution, the anchor layer is dissolved in the aqueous alkaline solution, and the ink layer is deinked from the base material. A method for deinking a laminate having an anchor layer, an ink layer, and a varnish layer in this order on a base material,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less,
The ink layer is a layer obtained by curing active energy ray-curable ink with active energy rays,
The varnish layer is a layer obtained by curing an active energy ray-curable varnish with active energy rays,
A method for deinking a laminate, in which the laminate is stirred in an aqueous alkaline solution, the anchor layer is dissolved in the aqueous alkaline solution, and the ink layer is deinked from the base material. A laminate having an anchor layer and a varnish layer in this order on a base material (provided that an active energy ray-curable ink is included between the anchor layer and the varnish layer, and an ink layer cured by active energy rays is included) A deinking method (excluding
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a (meth)acrylate compound with active energy rays,
The (meth)acrylate compound includes a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less,
The varnish layer is a layer obtained by curing an active energy ray-curable varnish with active energy rays,
A method for deinking a laminate, in which the laminate is stirred in an aqueous alkaline solution, the anchor layer is dissolved in the aqueous alkaline solution, and the ink layer is deinked from the base material.