JP7626161B2 - Laminate, manufacturing method of laminate, and deinking method of laminate - Google Patents

Description

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

Compared to oxidative polymerization, penetration drying, and hot air drying oil-based inks and varnishes, active energy ray curing inks and varnishes are convenient because they cure instantly, can form a strong cured film, and are non-VOC, containing no petroleum-based volatile organic compounds (VOCs). As a result, they are widely used in the packaging printing industry for applications ranging from beverage and food packaging, pharmaceutical packaging, and cosmetic packaging, to general paper containers.

In the food packaging field in particular, the ideal form of active energy ray curable ink/varnish would be an electron beam (hereafter referred to as "EB") curable ink, which does not contain photopolymerization initiators and takes into consideration safety and security for humans and the environment. However, due to the large initial capital investment required, this is not common, and ultraviolet ray (hereafter referred to as "UV") curable ink is more prevalent on the market.

In recent years, it is known that there has been a gradual shift to LED curing systems that use UV-LED light sources that are energy-efficient and suppress the generation of ozone and heat, energy-saving UV systems that use a single metal halide lamp that eliminates the infrared range that generates heat and the ultraviolet range that generates ozone, and energy-saving UV systems that reduce the number of UV lamps from the usual three to four to just one.

Energy-saving UV-curable inks and varnishes designed to accommodate these new systems have seen an increasing trend in recent years, particularly in commercial printing, in switching from general oil-based inks and varnishes, and are required to have the same performance as general oil-based inks and varnishes in terms of printability, print quality, etc. Also, an increasing number of these energy-saving UV-curable inks are certified as "recyclable UV-curable inks" with a recyclability rank of A.
However, not all UV systems on the market are being replaced by energy-saving UV systems, and conventional UV systems (many of which are rated B in recyclability) that have a long history are still being used in many cases. UV-curable inks and varnishes are generally considered to be more difficult to recycle than general oil-based inks and varnishes, except for recyclable energy-saving UV-curable inks and some recyclable UV-curable inks. In order to simplify recycling when collecting printed materials, it is considered to be extremely difficult and nearly impossible to separate printed materials printed with non-recyclable UV-curable active energy ray-curable inks and varnishes.

There is also an urgent need to develop methods to make it easier to recycle substrates, even if they are made of materials other than paper. This is because in recent years, UV curing devices, UV-LED curing devices, and EB curing devices that are less susceptible to heat have been developed, and it is now possible to irradiate active energy rays to a degree that does not cause thermal damage to the substrate, even if the substrate is thin. As a result, the use of active energy ray-curable inks and varnishes is increasing.

In particular, measures to combat marine pollution are required as part of global environmental measures for plastic substrates, and there is an urgent need to develop a plastic recovery system that does not allow microplastics, which cause marine pollution, to flow into the ocean. Compared to chemical recycling, in which materials such as plastics are chemically decomposed and reused, material recycling, in which materials are pelletized and reused, is simpler and more convenient. However, if the active energy ray-curable ink/varnish is not removed from the substrate during this process, the remaining ink/varnish will get into the substrate's melting process, making it difficult for the substrate to return to its original color, and there is a high possibility that the uses of the recycled substrate will be limited. Therefore, the development of a simple method for removing additives such as active energy ray-curable ink/varnish and adhesives from packaging materials such as plastics will lead to increased efficiency in material recycling.

Furthermore, if it becomes possible to easily remove active energy ray-curable inks and varnishes from a wide range of substrates, including not only soft packaging materials but also synthetic paper, hard plastic substrates such as PET bottle caps, nonwoven fabrics, and metals, and to reuse the substrate materials, it will be possible to reduce the use of fossil resources by improving the efficiency of recycling, and ultimately contribute to reducing carbon dioxide emissions.

For example, Patent Document 1 discloses an organic solvent-based ink for a detachment layer that can be removed by alkali treatment, a laminate such as a printed matter that uses this ink and includes a detachment layer, 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 easy method for deinking active energy ray-curable inks, which are generally considered to be 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 that use rosin-modified resins.

Therefore, there is a need to develop a printed matter that is excellent in deinking suitability and a method for producing the printed matter when using at least one ink selected from the group consisting of active energy ray-curable inks for offset printing, active energy ray-curable inks for flexographic printing, and active energy ray-curable inks for resin letterpress printing, which are expected to become even more widespread and are considered to have excellent film strength and are difficult to deink.

JP 2020-090627 A Patent No. 7078189

The object of the present invention is to provide a laminate that has excellent physical properties as a laminate, such as scratch resistance, and has excellent deinking properties in the recycling process of a substrate having an ink layer made of an active energy ray-curable ink, and a method for producing the laminate, as well as a method for deinking the laminate.

As a result of extensive research into solving the above problems, the inventors discovered that the above problems can be solved by the laminate and the method for manufacturing the laminate described below, and thus completed the present invention.

That is, the present invention provides a laminate having an anchor layer and an ink layer in this order on a substrate,
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 contains a (meth)acrylate compound having an acid value of 80 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 in which at least one type of ink selected from a volatile organic compound ( VOC) -free active energy ray-curable offset printing ink, a volatile organic compound (VOC) -free active energy ray-curable flexographic printing ink, and a volatile organic compound (VOC)-free active energy ray-curable resin letterpress printing ink is cured with active energy rays.

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

The present invention also provides a method for producing a laminate, comprising the steps of:
A step 1 of applying an active energy ray-curable anchoring agent containing a (meth)acrylate compound onto a substrate and curing the agent with active energy rays to obtain a laminate having an anchor layer on the substrate;
a step 2 of printing at least one ink selected from a volatile organic compound (VOC) -free active energy ray-curable offset printing ink, a volatile organic compound (VOC) -free active energy ray-curable flexographic printing ink, and a volatile organic compound (VOC) -free active energy ray-curable resin letterpress printing ink on the anchor layer of the laminate having an anchor layer on the substrate, and curing the ink 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 producing a laminate, wherein the (meth)acrylate compound contains a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less.

The present invention also relates to a method for producing the above laminate, which further includes step 3 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 substrate, and curing the varnish with active energy rays to obtain a laminate having a varnish layer on the ink layer.

The present invention also provides a method for deinking a laminate having an anchor layer and an ink layer in this order on a substrate, the method comprising the steps of:
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 contains a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less,
the ink layer is a layer obtained by curing, with active energy rays, at least one type of ink selected from a volatile organic compound (VOC) -free active energy ray-curable offset printing ink, a volatile organic compound (VOC) -free active energy ray-curable flexographic printing ink, and a volatile organic compound (VOC ) -free active energy ray-curable resin letterpress printing ink,
The present invention relates to a method for deinking a laminate, in which the laminate is stirred in an alkaline aqueous solution, the anchor layer is dissolved in the alkaline aqueous solution, and the ink layer is deinked from the substrate.

The present invention also provides a method for deinking a laminate having an anchor layer, an ink layer, and a varnish layer on a substrate in this order, comprising the steps of:
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 contains a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less,
the ink layer is a layer obtained by curing, with active energy rays, at least one type of ink selected from a volatile organic compound (VOC) -free active energy ray-curable offset printing ink, a volatile organic compound (VOC) -free active energy ray-curable flexographic printing ink, and a volatile organic compound (VOC ) -free active energy ray-curable resin letterpress printing ink,
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 alkaline aqueous solution, the anchor layer is dissolved in the alkaline aqueous solution, and the ink layer is deinked from the substrate.

The present invention provides a laminate that has excellent physical properties as a laminate, such as scratch resistance, and has excellent deinking properties in the recycling process of a substrate having an ink layer made of an active energy ray-curable ink, as well as a method for producing the laminate, and a method for deinking the laminate.

The present invention will be described in detail below. Note that the present invention is not limited to the following embodiments, and can be modified in various ways within the scope of the invention. In addition, unless otherwise specified, "parts" refers to "parts by mass" and "%" refers to "% by mass."

One embodiment of the present invention is a laminate having an anchor layer and an ink layer in this order on a substrate, the anchor layer being a layer of an active energy ray-curable anchor agent containing a (meth)acrylate compound having an acid value of 20 mg KOH/g or more and 500 mg KOH/g or less, cured with active energy rays, and the ink layer being a layer of an active energy ray-curable ink cured with active energy rays.

One embodiment of the present invention is a laminate having an anchor layer and a varnish layer in this order on a substrate (excluding cases where an ink layer of active energy ray-curable ink cured by active energy rays is included between the anchor layer and the varnish layer), in which the anchor layer is a layer of active energy ray-curable anchor agent containing a (meth)acrylate compound having an acid value of 20 mg KOH/g or more and 500 mg KOH/g or less cured by active energy rays, and the varnish layer is a layer of active energy ray-curable varnish cured by 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.

[Coloring agent]
In the present invention, the ink contains a colorant. As the colorant, at least one of a pigment and a dye can be used. From the viewpoint of light resistance, a pigment is preferred.
The pigment that can be used in the present invention is not particularly limited, and any known pigment can be used. The pigment can be either an inorganic pigment or an organic pigment.

Inorganic pigments include carbon blacks such as furnace black, lamp black, acetylene black, and channel black, as well as iron oxide and titanium oxide.

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

More specifically, in terms of the C.I. Color Index, black pigments include C.I. Pigment Black 1, 6, 7, 9, 10, 11, 28, 26, 31, etc.

White pigments include C.I. Pigment White 5, 6, 7, 12, 28, etc.

Examples of yellow pigments include 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, and 213.

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

Red or crimson 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, 10 8, 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, etc.

Green pigments include C.I. Pigment Green 1, 2, 3, 4, 7, 8, 10, 15, 17, 26, 36, 45, 50, etc.

Examples of purple pigments include C.I. Pigment Violet 1, 2, 3, 4, 5:1, 12, 13, 15, 16, 17, 19, 23, 25, 29, 31, 32, 36, 37, 39, and 42.
Orange pigments include 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 pigment can be used in any content as long as the desired concentration can be reproduced on the surface of the printing substrate, and it is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, based on the total amount of ink.

[(Meth)acrylate compound]
In this specification, unless otherwise specified, "(meth)acryloyl", "(meth)acrylic acid", "(meth)acrylate", and "(meth)acryloyloxy" respectively mean "acryloyl and/or methacryloyl", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", and "acryloyloxy and/or methacryloyloxy". In addition, "PO" stands for "propylene oxide" and "EO" stands for "ethylene oxide". In addition, X in EO-modified (X) and PO-modified (X) represents the number of moles of EO and PO modified, and Y in polyethylene glycol (Y) di(meth)acrylate represents the approximate molecular weight of the polyethylene glycol portion.

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 is a compound having one or more (meth)acryloyl groups, and includes any form of monomer, oligomer, or polymer.
Here, the term "monomer" refers to a compound that is the minimum structural unit for constituting an oligomer or polymer, and the term "oligomer" refers to a polymer having structural units based on 2 to 100 monomers.

Specific examples of the (meth)acrylate compounds 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-carboxyethyl (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, ) 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-dioxolan-4-yl) methyl acrylate, and other monofunctional (meth)acrylate monomers having one (meth)acryloyl group in the molecule;
1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol (200) di(meth)acrylate, polyethylene glycol (300) di(meth)acrylate, polyethylene glycol (400) di(meth)acrylate, polyethylene glycol (600) di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate , dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO-modified (2) 1,6-hexanediol di(meth)acrylate, PO-modified (2) neopentyl glycol di(meth)acrylate, (neopentyl glycol-modified) trimethylolpropane di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, EO-modified (4) bisphenol A di(meth)acrylate, PO-modified (4) bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and other bifunctional (meth)acrylate monomers having two (meth)acryloyl groups in the molecule;
Trifunctional (meth)acrylate monomers having three (meth)acryloyl groups in the molecule, such as 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, and pentaerythritol tri(meth)acrylate;
Pentaerythritol tetra(meth)acrylate, EO-modified (4) tetrafunctional (meth)acrylate monomers having four acryloyl groups in the molecule, such as 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;
and hexafunctional (meth)acrylate monomers having six (meth)acryloyl groups in the molecule, such as dipentaerythritol hexa(meth)acrylate.

(Oligomer)
Examples of the oligomer 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, the ink may contain, if necessary, in addition to the above-mentioned components, a polymerization initiator, an amine compound, a resin, a polymerization inhibitor, a surface tension adjuster, a wax, an extender pigment, a pigment dispersant, an antifoaming agent, an ultraviolet absorber, an antioxidant, an antistatic agent, and the like.

(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 contains a photopolymerization initiator. The polymerization initiator in the present invention is a compound that undergoes a chemical change through the action of light or through interaction with the electronically excited state of the sensitizing dye to generate radicals or cations, and among these, a photoradical polymerization initiator is preferable from the viewpoint of being able to initiate polymerization by exposure to light.

In the present invention, the photo-radical polymerization initiator is not particularly limited, and known ones 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. The photo-polymerization initiator may be used alone or in combination of two or more kinds.

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, etc.

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

Examples of α-hydroxyalkylphenone compounds include 1-hydroxy-cyclohexyl phenyl 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- Examples include a mixture of 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 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, 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, and 1-[4-(1,1-dimethylethyl)phenyl]-2-hydroxy-2-methylpropan-1-one.

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-morpholino Examples include phosphine-4-yl-propan-1-one, polyethylene glycol di(β-4-[4-(2-dimethylamino-2-benzyl)butanonylphenyl]piperazine)propionate, 2-benzyl-2-dimethylamino-1-(4-piperidinylphenyl)-1-butanone, 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, and 1-(biphenyl-4-yl)-2-methoxy-2-morpholinopropan-1-one.

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)phenylphosphineate, and bis(2,4,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

Oxime ester compounds include 1-[4-(phenylthio)phenyl]octane-1,2-dione, 2-benzoyl oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyl oxime), 3-cyclopentyl-1-(4-(phenylthio)phenyl)propane-1,2-dione-2-(o-benzoyl oxime), 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, etc.

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

The content of the photopolymerization initiator is preferably 1 to 20% by mass, and 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. There is no particular limitation on the amine compound, and any known amine compound 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 type photopolymerization initiator can be enhanced.
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]-, 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, and the like. The amine compounds may be used alone or in combination of two or more kinds.

(resin)
In the present invention, the ink may contain a resin, which reduces the cure shrinkage of the coating film that occurs during curing, suppresses curling of the substrate, and improves adhesion to the anchoring agent.

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

Specific examples of resins include polyvinyl chloride, (meth)acrylic resins, styrene (meth)acrylic resins, epoxy resins, polyester resins, polyurethane resins, 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 these, diallyl phthalate resins and polyester resins are more preferred from the viewpoint of dispersibility.

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

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

(wax)
In the present invention, the ink may contain wax. By containing wax, it is possible to improve the abrasion resistance, scratch resistance, blocking prevention, smoothness, and scratch prevention. There is no particular limitation on the wax, and any known wax can be used. For example, natural wax and synthetic wax can be used.
Examples of natural waxes include carnauba wax, Japan wax, lanolin, montan wax, paraffin wax, and microcrystalline wax.
Examples of synthetic waxes include Fischer-Tropsch wax, polyethylene wax, polypropylene wax, and polytetrafluoroethylene wax.

The wax content 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, such as clay, talc, barium sulfate, calcium carbonate, ground calcium carbonate, barium carbonate, magnesium carbonate, silica, or bentonite.

(Pigment Dispersant)
In the present invention, the ink preferably contains a pigment dispersant in order to improve the pigment dispersibility. There is no particular limitation on the pigment dispersant, and any known pigment dispersant can be used. Among them, a resin-type pigment dispersant having a basic functional group is preferable, and examples of the basic functional group include a primary, secondary, or tertiary amino group, and nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine.
Further, as the skeleton constituting the resin-type pigment dispersant, a fatty acid amine skeleton and/or a urethane skeleton are more preferable since 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 Solsperse series (Solsperse 00, Solsperse 32000, Solsperse 38500, etc.) manufactured by Lubrizol, and the Disperbyk series (BYK-162, BYK-168, BYK-183, etc.) manufactured by BYK-Chemie.

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

The active energy ray curable ink in this application is preferably at least one type of ink selected from active energy ray curable ink for offset printing, active energy ray curable ink for flexographic printing, and active energy ray curable ink for resin letterpress printing. These inks have high film strength among active energy ray curable inks and are difficult to deink, and are inks in which the effects of the present invention are particularly pronounced.

<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 materials used in the varnish of the present invention are the same as those in the active energy ray-curable ink described above, except that substantially no colorant is 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 having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less, and curing it with active energy rays.

<Active energy ray curable anchoring agent>
The active energy ray-curable anchor agent (hereinafter also referred to as "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.

[(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 explained in the above-mentioned active energy ray-curable ink.

[(Meth)acrylate compound having an 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 the (meth)acrylate compound, a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less.
By containing a (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less, the anchor layer becomes easier to separate (peel off, dissolve, etc.) from the substrate during deinking.
The acid value of the (meth)acrylate compound having an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less 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 (meth)acrylate compounds with an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less is preferably 15 to 90 mass%, more preferably 20 to 80 mass%, even more preferably 25 to 75 mass%, and particularly preferably 30 to 70 mass%, of the total amount of active energy ray-curable anchor agent. When the content of (meth)acrylate compounds with an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less is 15 mass% or more, the deinking property is good, and when it is 90 mass% or less, the scratch resistance is good.

Specific examples of (meth)acrylate compounds with an acid value of 20 mgKOH/g or more and 500 mgKOH/g or less include MIWON's MIRAMER SC6632 and MIRAMER SC6640, Negami Chemical Industries, Ltd.'s DPV27 and DPV28, Daicel-Allnex's EBECRYL11, (ACA)Z200M, (ACA)Z230AA, (ACA)Z250, (ACA)Z251, (ACA)Z254F, (ACA)Z300, (ACA)Z320, β-CEA, and Taisei Fine Chemical's 8KQ-2001 and PH-9001.

[Other ingredients]
In the present invention, the anchor agent may contain, if necessary, in addition to the above-mentioned components, silica, alumina, an antifoaming agent, a leveling agent, a tackifier, a preservative, an antibacterial agent, an antirust agent, an adhesion aid, a polymerization initiator, an amine compound, a polymerization inhibitor, wax, an extender pigment, a pigment dispersant, an ultraviolet absorber, an antioxidant, an antistatic agent, and the like.

(Polymerization initiators, amine compounds, extender pigments, pigment dispersants)
The polymerization initiator, amine compound, wax, extender pigment, and pigment dispersant that can be contained in the anchor agent in the present invention can be the polymerization initiator, amine compound wax, extender pigment, and pigment dispersant explained in the above-mentioned active energy ray-curable ink, respectively.

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

Specific examples of usable polymerization inhibitors include (alkyl)phenols, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cupferron, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N-(3-oxyanilino-1,3-dimethylbutylidene)aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, and cyclohexanone oxime.
In particular, it is preferable to use one or more compounds selected from hindered amines such as 2,2,6,6-tetraalkylpiperidine derivatives, 2,2,6,6-tetramethylpiperidine derivatives, 1-alkyl-2,2,6,6-tetramethylpiperidine derivatives, and 1-hydro-2,2,6,6-tetramethylpiperidine derivatives, which are compounds having two hydrocarbon groups each at the 2-position and the 6-position on the piperidine ring (four in total), and these can inhibit the curing reaction in a printing machine and provide excellent storage stability.

<Laminate>
In one embodiment, the laminate of the present invention is obtained by printing an active energy ray-curable ink on an anchor layer obtained by applying an anchor agent to a substrate and curing the ink with active energy rays, and then curing the ink with active energy rays.
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 a water-based varnish, and it is particularly preferable to use an active energy ray-curable varnish.

The method for producing the laminate of this embodiment includes the following steps:
A step 1 of applying 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 to a substrate, and curing the agent with active energy rays to obtain a laminate having an anchor layer on the substrate;
A step 2 of printing an active energy ray curable ink on the anchor layer of the laminate having an anchor layer on the substrate, and curing the ink with active energy rays to obtain a laminate having an ink layer on the anchor layer;
Includes.

The manufacturing method of this embodiment may further include step 3 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 substrate, and curing the varnish with active energy rays to obtain a laminate having a varnish layer on the ink layer.

In one embodiment, the laminate of the present invention is obtained by printing an active energy ray-curable varnish onto an anchor layer in which an anchor agent has been applied to a substrate and cured with active energy rays, and then curing the varnish with active energy rays.

The method for producing the laminate of this embodiment includes the following steps:
A step 1 of applying 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 to a substrate, and curing the agent with active energy rays to obtain a laminate having an anchor layer on the substrate;
A step 4 of printing an active energy ray curable varnish on the anchor layer of the laminate having an anchor layer on the substrate and curing the varnish with active energy rays to obtain a laminate having a varnish layer on the anchor layer;
Includes.

There are no particular limitations on the substrate, and any known substrate can be used. Specific examples include polypropylene (PP) (including synthetic paper), polyethylene (PE), polyethylene terephthalate (PET), plastic substrates having inorganic vapor deposition layers such as aluminum, silica, and alumina, aluminum foil, polyvinyl chloride (PVC), polystyrene (PS), nylon, cellophane, metal sheets, and paper (excluding synthetic paper). Non-absorbent substrates are preferred. Various additives such as antistatic agents, anti-fogging agents, and ultraviolet protection agents may be used in the substrate.

In the present invention, the method of printing the active energy ray curable ink can be any known method, but it is preferably used for offset printing using an active energy ray curable offset printing ink, resin letterpress printing using an active energy ray curable resin letterpress printing ink, and flexographic printing using an 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. Specific examples include 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, offset printing, resin letterpress printing, gravure printing, and flexo printing.

In the present invention, the method for applying the active energy ray-curable anchor agent is not particularly limited, and any known method can be used. Specific examples include 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, offset printing, resin letterpress printing, gravure printing, and flexo printing.

There are no particular limitations on the source of active energy rays, and any known source can be used. Specific examples include mercury lamps, xenon lamps, metal hydride lamps, excimer lamps, LEDs (light-emitting diodes) such as ultraviolet light-emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs), EB (electron beam) irradiation devices, and gas and solid-state lasers.

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

(Ink component removal process using alkaline aqueous solution)
The laminate is, for example, brought into contact with an alkaline aqueous solution in a treatment tank containing the alkaline aqueous solution, thereby removing the ink layer and the varnish layer.

(Alkaline aqueous solution)
In the present invention, the alkaline aqueous solution is an aqueous solution containing an alkaline compound, and the alkaline compound is preferably contained in an amount of 0.5 to 10 mass % of the entire aqueous solution, and more preferably 1 to 5 mass %. The alkaline compound is not particularly limited, but suitable examples include sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH) ₂ ammonia, barium hydroxide (Ba(OH) ₂ ), sodium _carbonate ( _Na2CO3 ), etc. Preferred are NaOH and/or KOH.

(Ink and varnish component removal process)
The mechanism by which the ink layer or varnish layer can be detached from the laminate by contacting the alkaline aqueous solution with the laminate is assumed to be that the presence of the resin allows the alkaline aqueous solution to penetrate through the surface of the anchor layer and/or the cross section of the laminate, dissolving the anchor layer. After the anchor layer is applied to the substrate and the ink layer or varnish layer is printed, the laminate that has been made into a packaging container through a bag making process or the like is preferably cut or crushed in the recycling process or before, so that the laminate comes into contact with the alkaline aqueous solution in a state where the cross section of the laminate is exposed.

It is preferable to bring the laminate into contact with the alkaline aqueous solution while stirring. There are no particular limitations on the stirring means, and examples include known stirring equipment such as a general disperser, radial flow turbine blade, axial flow turbine blade, paddle blade, propeller blade, anchor blade, and high shear mixer. For example, in the case of a 2-L flask scale, the stirring rotation speed is preferably 100 to 350 rpm, although it depends on the shape and size of the stirring blade. The stirring time is preferably 15 minutes or more and 24 hours or less.

(Substrate recovery process)
The method for producing a recycled substrate of the present invention includes a step of recovering the substrate after the ink layer or varnish layer is removed from the laminate. The step of recovering the substrate refers to a step of separating and recovering the substrate from a treatment tank in which the alkaline aqueous solution, the peeled ink layer or varnish layer fragments, and the substrate are mixed after the laminate is treated with an alkaline aqueous solution, and it is preferable to obtain the substrate with high purity. The method for recovering the substrate is not particularly limited, and for example, separation and recovery based on the size difference between the substrate and the ink layer or varnish layer fragments is preferable, and separation and recovery based on the specific gravity difference is also preferable. Alternatively, separation and recovery can be appropriately performed by a combination of these, but it is preferable to include a separation and recovery step based on the specific gravity difference, and more preferably, a separation and recovery step based on the specific gravity difference and a separation and recovery step based on the size difference are used in combination.
In addition, in the separation and recovery process based on the specific gravity difference, it is preferable to recover only the substrate floating in the alkaline aqueous solution in the treatment tank. It is also preferable if impurity components in the alkaline aqueous solution and fragments of the ink layer and varnish layer settle, which makes it easy to separate from the substrate and allows only the substrate to be recovered more accurately. Therefore, the physical properties and transparency of the substrate recycled after recovery are improved. The method of separation based on the specific gravity difference may be a conventionally known method, such as one using a fluidized bed or one using a centrifuge.

After the ink layer and varnish layer are detached from the laminate and the substrate is recovered, the substrate is washed with water and dried to obtain a recycled substrate. In this case, it is preferable that the recycled substrate is as free of any contaminants as possible, including fragments of the detached ink layer and varnish layer. The recycled substrate obtained can be processed into pellets using an extruder or the like and reused as recycled resin. There are no restrictions on the use of the recycled resin, and it may be processed into a colorless and transparent film, or into a molded product with added colorants.

Available deinking agents include DI-7020, DI-7027, DI-7250, and DI-767 manufactured by Kao Corporation, the DIA-Z series and DIA-Y series manufactured by Nissin Chemical Industry Co., Ltd., and the Riptor series manufactured by Lion Specialty Chemicals.

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

(Anchoring agent 1)
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 part of EDB were mixed and stirred using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC1).

(Anchoring agent 2)
80.0 parts of SC6640, 12.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, and 1.0 part of EDB were mixed and stirred using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC2).

(Anchoring 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 part of EDB were mixed and stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC3).

(Anchoring agent 4)
An active energy ray-curable anchor agent (AC4) was prepared by mixing 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 part of EDB and stirring the mixture using a butterfly mixer.

(Anchoring agent 5)
90.0 parts of SC6640, 2.0 parts of TMPTA (EO), 5.0 parts of 4MBP, 2.0 parts of TPO, and 1.0 part of EDB were mixed and stirred using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC5).

(Anchoring Agent 6)
An active energy ray-curable anchor agent (AC6) was prepared by mixing 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 part of EDB and stirring the mixture using a butterfly mixer.

(Anchoring agent 7)
70.0 parts of TMPTA (EO), 22.0 parts of DiTMPTA, 5.0 parts of 4MBP, 2.0 parts of TPO, and 1.0 part of EDB were mixed and stirred using a butterfly mixer to prepare an active energy ray-curable anchor agent (AC7).

<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 heated with stirring to 100° C. Then, 25.0 parts of diallyl phthalate resin was mixed and dissolved while maintaining the temperature at 100° C. to prepare a diallyl phthalate resin varnish.

<Ink manufacturing example>

(Ink Production Example 1 (UV Ink 1) (Active Energy Ray Curable Offset Printing Ink, Active Energy Ray Curable Resin Letterpress Printing Ink))
An ink was prepared by mixing 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, 1.5 parts of DEABP, 1.5 parts of DETX, 1.0 part of EDB, and 47.0 parts of diallyl phthalate resin varnish and stirring the mixture using a butterfly mixer. The mixture was then dispersed using a three-roll mill so that the maximum 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, 1.5 parts of DEABP, 1.5 parts of DETX, 1.0 part of EDB, and 47.0 parts of MIRAMER PS-4500 were mixed and stirred and mixed using a butterfly mixer, and then dispersed using a three-roll mill so that the maximum particle size was 7.5 μm or less to prepare an ink.

(Ink Production Example 3 (LED Ink) (Active Energy Ray Curable Offset Printing Ink, Active Energy Ray Curable Resin Letterpress Printing Ink))
An ink was prepared by mixing 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, 2.0 parts of TPO, 2.0 parts of DEABP, 2.5 parts of 4MBP, 2.5 parts of DETX, 1.0 part of EDB, and 44.0 parts of diallyl phthalate resin varnish and stirring the mixture using a butterfly mixer. The mixture was then dispersed using a three-roll mill so that the maximum particle size was 7.5 μm or less.

(Ink Production Example 4 (UV Flexographic Ink) (Active Energy Ray Curable Flexographic Printing Ink))
15.0 parts of RAVEN 1080 Ultra, 1.0 part of BA-2550, 16.0 parts of TMPTA (EO), 5.0 parts of DiTMPTA, 7.0 parts of DPHA, 3.0 parts of 379, 2.0 parts of DEABP, 2.5 parts of 4MBP, 2.5 parts of DETX, 1.0 part of EDB, and 6.0 parts of Solsperse 24000 were mixed and stirred using a butterfly mixer, and then dispersed with a three-roll mill so that the maximum particle size was 7.5 μm or less to prepare an ink. Then, 39.0 parts of TMPTA (EO) were added and mixed and stirred using a butterfly mixer to prepare an ink.

(Ink Production Example 5 (Yellow UV Ink) (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, 1.5 parts of DETX, 1.0 part of EDB, and 47.0 parts of diallyl phthalate resin varnish were mixed and stirred using a butterfly mixer, and then dispersed using a three-roll mill so that the maximum particle size was 7.5 μm or less to prepare an ink.

(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, 1.5 parts of DETX, 1.0 part of EDB, and 47.0 parts of diallyl phthalate resin varnish were mixed and stirred using a butterfly mixer, and then dispersed using a three-roll mill so that the maximum particle size was 7.5 μm or less to prepare an ink.

(Ink Production Example 7 (UV Ink Blue) (Active Energy Ray Curable Offset Printing Ink, Active Energy Ray Curable Resin Letterpress Printing Ink))
20.0 parts of Heliogen Blue 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, 1.5 parts of DETX, 1.0 part of EDB, and 47.0 parts of diallyl phthalate resin varnish were mixed and stirred using a butterfly mixer, and then dispersed using a three-roll mill so that the maximum particle size was 7.5 μm or less to prepare an ink.

(Ink Production Example 9 (EB 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), 13.0 parts of DiTMPTA, 7.0 parts of DPHA, and 54.0 parts of diallyl phthalate resin varnish were mixed and stirred using a butterfly mixer, and then dispersed using a three-roll mill so that the maximum particle size was 7.5 μm or less, to prepare an ink.

<Preparation of oil-based resin varnish>
(Example of rosin modified phenolic resin production)
In a reaction vessel, 54.3 parts of gum rosin was reacted with 30.8 parts of tertiary butylphenol and 9.4 parts of 92% by weight paraformaldehyde in a xylene solvent under sodium hydroxide catalyst at 100°C for 4 hours, and the phenolic resin from which moisture had been removed was added dropwise at 150°C and reacted for 2 hours. 5.4 parts of glycerin was then added, and the reaction was continued for 15 hours at 250°C using 0.1 part of calcium oxide as a catalyst. During this time, the mixture was successively removed to obtain a rosin phenolic resin.

(Example of rosin modified phenolic resin varnish production)
Next, 45.0 parts of the rosin-modified phenolic resin as a binder resin, 44.0 parts of soybean oil, 10.0 parts of soybean oil fatty acid normal butyl ester, and 1.0 part of ALCH were placed in a four-neck flask equipped with a stirrer, a reflux condenser equipped with a water separator, and a thermometer, and 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, and 0.5 parts of drying inhibitor CP were mixed and stirred using a butterfly mixer, and then dispersed using a three-roll mill 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 part of EDB, 3.0 parts of filler, and 62.0 parts of diallyl phthalate resin varnish were mixed and stirred using a butterfly mixer, and then dispersed using a three-roll mill so that the maximum particle size was 7.5 μm or less to prepare a varnish.

The descriptions of the materials used in the examples are as follows:
[Coloring agent]
・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: Alkaline Blue Toner BA-2550 (C.I. Pigment), manufactured by Morimura Shoji Co., Ltd.
t Blue 61)
[Extender pigment]
Filler: Matsumura Sangyo Co., Ltd., High Filler #5000PJ, talc [(meth)acrylate compound]
SC6640: MIWON Corporation, MIRAMER SC6640 (acid value: 255 mg KOH / g)
SC6632: MIWON Corporation, MIRAMER SC6632 (acid value: 190 mg KOH / g)
TMPTA (EO): BASF Corporation, LAROMER LR8863, trimethylolpropane ethylene oxide modified triacrylate DiTMPTA: Daicel Allnex Corporation, EBECRYL1142, ditrimethylolpropane tetraacrylate DPHA: MIWON Corporation, MIRAMER M600, dipentaerythritol hexaacrylate PS-4500: MIWON Corporation, MIRAMER PS-4500, polyester acrylate oligomer [resin]
Diallyl phthalate resin: manufactured by Osaka Soda Co., Ltd., Daiso DAP A
[Photopolymerization initiator]
379: Omnirad 379, manufactured by IGM RESINS, 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; TPO: CHEMARK TPO, manufactured by Chemark Chemical Co.; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; DEABP: CHEMARK DEABP, manufactured by Chemark Chemical Co.; 4,4'-bis(dimethylamino)benzophenone; 4MBP: SB-PI 712, manufactured by Soho Jitsugyo Co.
DETX: CHEMARK DETX, 2,4-diethylthioxanthone, manufactured by Chemark Chemical Co. 184: Omnirad 184, 1-hydroxy-cyclohexyl phenyl ketone, manufactured by IGM RESINS [amine compound]
EDB: Chemark Chemical Co., CHEMARK EDB, ethyl 4-(dimethylamino)benzoate [pigment dispersant]
Solsperse 24000: Solsperse 24000 manufactured by Lubrizol
[Metal dryer]
MK Dryer: MK Dryer [drying inhibitor] manufactured by Toyo Ink Co., Ltd.
Drying retardant CP: Drying retardant CP manufactured by Toyo Ink Co., Ltd.
[Aluminum gelling agent]
ALCH: ALCH, aluminum ethyl acetate diisopropylate, manufactured by Kawaken Fine Chemicals Co., Ltd. [Others]
Soybean oil fatty acid normal butyl ester: SFB2, manufactured by Toshin Yushi Co., Ltd.
・Soybean oil: Nisshin Oillio Group Co., Ltd.: White refined soybean oil

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

<Ink and varnish printing>
In Examples 1 to 22, 24, and Comparative Example 2, the prepared laminate having an anchor layer on a substrate was printed with each sample ink shown in Table 1 using an RI tester with an ink gauge of 0.25 mL, and then the printed matter was cured with an ultraviolet curing device (160 W/cm metal halide lamp) manufactured by iGraphics Co., Ltd. at a conveyor speed of 30 m/min to form a coating film, thereby obtaining a laminate having an anchor layer and an ink layer in this order on the substrate.
In Example 23, LED ink was printed with an ink gauge of 0.25 mL using an RI tester on the prepared laminate having an anchor layer on a substrate, and the ink was then cured on the printed matter with an ultraviolet curing device (160 W/cm metal halide lamp) manufactured by iGraphics Co., Ltd. at a conveyor speed of 100 m/min to obtain a laminate having an anchor layer and an ink layer in this order on the substrate.
In Example 25, the prepared laminate having an anchor layer on a substrate was printed with EB ink using an RI tester with an ink gauge of 0.25 mL, and the printed matter was then irradiated with an electron beam of 30 KGy using a low-energy electron beam irradiation device manufactured by ESI Corporation (voltage of 175 KV, nitrogen-substituted atmosphere with an oxygen concentration of 50 ppm) to harden the ink, thereby obtaining a laminate having an anchor layer and an ink layer in this order on the substrate.
In Example 26, a laminate having an anchor layer on a substrate was printed with a UV varnish prepared by mixing two parts of UV ink 1 with an ink gauge of 0.25 mL using an RI tester, and the coating was then cured with an ultraviolet curing device (160 W/cm metal halide lamp) manufactured by iGraphics Co., Ltd. at a conveyor speed of 30 m/min to obtain a laminate having an anchor layer and a varnish layer in that order on the substrate.
In Example 27, the prepared laminate having an anchor layer on a substrate was printed with UV ink 1 at an ink gauge of 0.25 mL using an RI tester, and the printed matter was cured to form a coating film at a conveyor speed of 30 m/min using an ultraviolet curing device manufactured by iGraphics (160 W/cm metal halide lamp). Further, using an RI tester, UV varnish was printed at an ink gauge of 0.25 mL, and the printed matter was cured to form a coating film at a conveyor speed of 30 m/min using an ultraviolet curing device manufactured by iGraphics (160 W/cm metal halide lamp). Thus, a laminate having an anchor layer, an ink layer, and a varnish layer in this order on a substrate was obtained.
In addition, in Comparative Example 3, an oil-based ink (an ink other than an active energy ray-curable ink) was printed with an ink gauge of 0.25 mL using an RI tester on the prepared laminate having an anchor layer on a substrate, and the ink was then left to stand at room temperature for 24 hours to cure, thereby obtaining a laminate having an anchor layer and an ink layer in this order on the substrate.
In Comparative Example 1, an oil-based black ink (an ink other than an active energy ray-curable ink) was printed directly onto the substrate shown in Table 1 using an RI tester with an ink gauge of 0.25 mL, and then the ink was left to stand at room temperature for 24 hours to cure, thereby obtaining a laminate having an ink layer on the substrate.

The substrates used in the examples are as follows:
PP: Polypropylene sheet manufactured by Okamoto Corporation PE: Taiko FC manufactured by Futamura Chemical Co., Ltd.
PET: Reshine, manufactured by Toyobo Co., Ltd. Aluminum vapor deposition: SPECIALITIES, manufactured by Gojo Paper Co., Ltd.
Aluminum foil: Leadmax, manufactured by Toyo Aluminum Co., Ltd. Synthetic paper: New Yupo FGS, manufactured by Yupo Corporation
PVC: PVC80C P, manufactured by Lintec Corporation
・PS: Manufactured by Oishi Sangyo Co., Ltd., Styrophane and nylon: Manufactured by Unitika Ltd., Emblem and cellophane: Manufactured by Futamura Chemical Co., Ltd., PL
Metal: ET2.8 tinplate, manufactured by Nippon Steel Corporation

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 laminate was evaluated by rubbing the ink surface with cotton cloth. The less rubbing, the better the scratch resistance. The evaluation criteria are as shown below, with ◯, ◯△, and △ being practically preferable.
〇: No rubbing on the printed surface where the ink has been spread. 〇△: Rubbing down to the surface of the printed surface where the ink has been spread. △: Rubbing down to the middle part of the printed surface where the ink has been spread. △×: Rubbing down to the bottom part of the printed surface where the ink has been spread. ×: The coating on the printed surface where the ink has been spread is gone.

(Evaluation of Adhesion)
An adhesive tape (Nichiban Cellotape (registered trademark) 18 m) was applied to the ink surface of the laminate.
The adhesiveness to the substrate was evaluated based on the ratio of the area of the anchor layer that was peeled off from the substrate .
◯: No peeling of the anchor layer from the substrate. ◯△: Less than 10% of the anchor layer peeled off from the substrate. △: Peeling of the anchor layer from the substrate is 10% or more and less than 30%. △×: Peeling of the anchor layer from the substrate is 30% or more and less than 70%. ×: 70% or more of the anchor layer peeled off from the substrate.

<Evaluation of deinking ability>
The laminates of Examples 1 to 27 and Comparative Examples 1 to 3 were aged at 60° C. for one week, and then stored for another 10 days in an environment of room temperature 23±1° C. and humidity 50±2%. Then, they were cut into pieces of 30×30 mm, and 90 g of each piece was used as a sample for testing.

<Evaluation of deinking properties of laminate>
A 2L flask was charged with 1.5L of 30°C hot water, 11mL of 3.75% aqueous sodium hydroxide solution, and 11mL of a deinking agent diluted to 1.5% (DI-7027 manufactured by Kao Corporation), followed by the addition of the sample and stirring 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 removal was complete, the substrate was removed and the extent to which the area of each 30 x 30 mm was covered with ink was visually evaluated.
○: Ink has come off from 95% or more of the substrate. △: Ink has come off from 90% to less than 95% of the substrate. ×: Ink has come off from less than 90% of the substrate.

Products that are rated 〇, 〇△, or △ for scratch resistance, adhesion, and deinking are considered to be practical.

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

Claims (6)

A laminate having an anchor layer and an ink layer in this order on a substrate,
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 contains a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less,
the content of the (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less is 5 to 40 mass% based on the total amount of the active energy ray-curable anchor agent,
A laminate, in which the ink layer is a layer obtained by curing, with active energy rays, at least one type of ink selected from an active energy ray-curable offset printing ink containing no volatile organic compounds (VOCs) and an active energy ray-curable resin letterpress printing ink containing no volatile organic compounds (VOCs) (excluding the case where the (meth)acrylate compound in the anchor agent contains urethane acrylate). 2. The laminate of claim 1, except when the substrate is a shrink plastic substrate. A method for producing a laminate, comprising the steps of:
A step 1 of applying an active energy ray-curable anchoring agent containing a (meth)acrylate compound onto a substrate and curing the agent with active energy rays to obtain a laminate having an anchor layer on the substrate;
a step 2 of printing at least one ink selected from an active energy ray-curable offset printing ink containing no volatile organic compounds (VOCs) and an active energy ray-curable resin letterpress printing ink containing no volatile organic compounds (VOCs) on the anchor layer of the laminate having an anchor layer on the substrate, and curing the ink with active energy rays to obtain a laminate having an ink layer on the anchor layer;
Including,
The (meth)acrylate compound contains a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less, and the content of the (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less is 5 to 40 mass % in the total amount of the active energy ray-curable anchor agent (excluding the case where the (meth)acrylate compound in the anchor agent contains a urethane acrylate). The method for producing a laminate according to claim 3, except when the substrate is a shrink plastic substrate. A method for deinking a laminate having an anchor layer and an ink layer on a substrate in this order, comprising the steps of:
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 contains a (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less,
the content of the (meth)acrylate compound having an acid value of 80 mgKOH/g or more and 500 mgKOH/g or less is 5 to 40 mass% based on the total amount of the active energy ray-curable anchor agent,
the ink layer is a layer obtained by curing at least one ink selected from an active energy ray-curable offset printing ink containing no volatile organic compounds (VOCs) and an active energy ray-curable resin letterpress printing ink containing no volatile organic compounds (VOCs) with active energy rays;
A method for deinking a laminate, in which the laminate is stirred in an alkaline aqueous solution, the anchor layer is dissolved in the alkaline aqueous solution, and the ink layer is deinked from the substrate (excluding the case where the (meth)acrylate compound in the anchor agent contains urethane acrylate). The method for deinking a laminate according to claim 5, except when the substrate is a shrink plastic substrate.