JP7143962B1 - LAMINATED PRODUCT, LAMINATED PRODUCTION METHOD, AND LAMINATED DE-INKING METHOD - Google Patents

Abstract

An object of the present invention is to provide a laminate that has excellent physical properties such as scratch resistance as a laminate and that has excellent deinking properties in the recycling treatment of a substrate regardless of the type of active energy ray-curable ink. An object of the present invention is to provide a method for manufacturing the laminate. A laminate having an anchor layer and an ink layer in this order on a non-absorbent substrate, wherein the anchor layer comprises an active energy ray-curable anchor containing a rosin-modified resin and a (meth)acrylate compound. A laminate comprising: a layer obtained by curing an agent with an active energy ray; and wherein the ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray. [Selection figure] None

Description

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

Active energy ray-curing inks and varnishes are more convenient than oxidative polymerization, permeation drying, and hot air drying oil-based inks and varnishes because they cure instantaneously and form strong cured films. It is widely used in the package printing industry, from the characteristic of being non-VOC that does not contain petroleum-based volatile compounds, to beverage and food packaging, pharmaceutical packaging, cosmetic packaging, and general paper containers. in use.

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

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

Energy-saving UV curable inks and varnishes designed to support these new systems tend to switch from general oil-based inks and varnishes in recent years, especially in commercial printing. Performance equivalent to that of oil-based inks and varnishes is required. Among these inks, an increasing number of energy-saving UV curable inks have been certified as "recyclable UV curable inks" with rank A for recyclability.
However, not all UV systems in the market will be replaced by energy-saving UV systems, and there are still many cases where ordinary UV systems (many of which are B-ranked for recyclability) that have a proven track record are still used. 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 facilitate recycling when collecting printed matter, it is extremely difficult and almost impossible to separate printed matter from active energy ray-curable inks and varnishes such as UV-curable inks and varnishes that are not recyclable. It is considered.

Similarly, even if the base material is a non-absorbent base material other than paper, there is an urgent need to develop a technique for facilitating the recycling of the base material. In recent years, UV curing equipment, UV-LED curing equipment, and EB curing equipment, which are less susceptible to heat, have been developed. This is because energy ray irradiation has become possible, and as a result, the number of cases where active energy ray-curable inks and varnishes are used is increasing.

Especially for plastic base materials, marine pollution countermeasures are required among global environmental measures, and development of a plastic recovery system that prevents microplastics that cause marine pollution from flowing out into the ocean is urgently needed. 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 superior in terms of simplicity. If the ink or varnish is not removed from the substrate, the remaining ink or varnish will enter the melting process of the substrate, making it difficult for the substrate to return to its original color, limiting the uses of the recycled substrate. It is highly likely that Therefore, the development of a simple method for detaching additives such as active energy ray-curable inks, varnishes, and adhesives from packaging materials such as plastics will lead to an increase in the efficiency of material recycling.

In addition to flexible packaging materials, active energy ray-curable inks and varnishes can be easily removed from all non-absorbent substrates, including hard plastic substrates such as PET bottle caps, non-woven fabrics, and metals. If the material used as the base material can be easily reused, it will be possible to reduce the use of fossil resources by improving the efficiency of recycling, thereby contributing to the reduction of carbon dioxide.

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

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

JP 2020-090627 A

An object of the present invention is to provide a laminate having excellent physical properties such as scratch resistance as a laminate and excellent deinking properties in the recycling treatment of a substrate regardless of the type of active energy ray-curable ink, and the laminate. and to provide a deinking method for the laminate.

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

That is, the present invention provides a laminate having an anchor layer and an ink layer in this order on a non-absorbent substrate,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with an active energy ray,
It relates to the laminate, wherein the ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray.

The present invention also relates to the laminate having a varnish layer on the ink layer.

In the present invention, the rosin-modified resin is a reaction product of an addition reaction product of a rosin acid (A) and an α,β-unsaturated carboxylic acid or its acid anhydride (B) with a polyol (C). It is related with the said laminated body.

The present invention also provides a laminate having an anchor layer and a varnish layer in this order on a non-absorbent base material (excluding cases in which an ink layer is included between the anchor layer and the varnish layer),
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with an active energy ray,
It relates to the laminate, wherein the varnish layer is a layer obtained by curing an active energy ray-curable varnish with an active energy ray.

In the present invention, the rosin-modified resin is a reaction product of an addition reaction product of a rosin acid (A) and an α,β-unsaturated carboxylic acid or its acid anhydride (B) with a polyol (C). It is related with the said laminated body.

The present invention also provides a method for manufacturing a laminate,
A step of applying an active energy ray-curable anchoring agent containing a rosin-modified resin and a (meth)acrylate compound to a non-absorbing base material and curing with an active energy ray to obtain a laminate having an anchor layer on the base material. 1 and
Step 2 of printing an active energy ray-curable ink on the anchor layer of the laminate having the anchor layer on the non-absorbent base material and curing with an active energy ray to obtain a laminate having an ink layer on the anchor layer. When,
and related to a method for manufacturing a laminate.

Further, in the present invention, an active energy ray-curable varnish is printed on the ink layer of a laminate having an anchor layer and an ink layer on the non-absorbent base material, cured with an active energy ray, and It relates to a method for manufacturing the laminate, including step 3 of obtaining a laminate having a varnish layer on the inside.

The present invention also provides a method for manufacturing a laminate,
A step of applying an active energy ray-curable anchoring agent containing a rosin-modified resin and a (meth)acrylate compound to a non-absorbing base material and curing with an active energy ray to obtain a laminate having an anchor layer on the base material. 1 and
Step 4: Print an active energy ray-curable varnish on the anchor layer of the laminate having the anchor layer on the non-absorbent base material, and cure it with an active energy ray to obtain a laminate having the varnish layer on the anchor layer. When,
and related to a method for manufacturing a laminate.

The present invention also provides a method for deinking a laminate having an anchor layer and an ink layer in this order on a non-absorbent substrate,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with an active energy ray,
The ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray,
It relates to a method of deinking a laminate, wherein the laminate is agitated in an alkaline aqueous solution, the anchor layer is dissolved in the alkaline aqueous solution, and the ink layer is deinked from the non-absorbent substrate.

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 non-absorbent substrate,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with an active energy ray,
The ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray,
The varnish layer is a layer obtained by curing an active energy ray-curable varnish with an active energy ray,
It relates to a method of deinking a laminate, wherein the laminate is agitated in an alkaline aqueous solution, the anchor layer is dissolved in the alkaline aqueous solution, and the ink layer is deinked from the non-absorbent substrate.

The present invention also provides a method for deinking a laminate having an anchor layer and a varnish layer in this order on a non-absorbent base material (excluding the case where an ink layer is included between the anchor layer and the varnish layer). and
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with an active energy ray,
The varnish layer is a layer obtained by curing an active energy ray-curable varnish with an active energy ray,
It relates to a method of deinking a laminate, wherein the laminate is agitated in an alkaline aqueous solution, the anchor layer is dissolved in the alkaline aqueous solution, and the ink layer is deinked from the non-absorbent substrate.

According to the present invention, a laminate having excellent physical properties as a laminate such as scratch resistance and excellent deinking property in recycling processing of a non-absorbent substrate regardless of the type of active energy ray-curable ink, and the laminate. and a deinking method for the laminate.

The present invention will be described in detail below. It should be noted that the present invention is not limited to the following embodiments, and can be modified in various ways within the spirit of the present invention. In addition, unless otherwise specified, "part" means "mass part" and "%" means "% by mass".

One embodiment of the present invention is a laminate having an anchor layer and an ink layer in this order on a non-absorbent substrate, wherein the anchor layer contains an active energy ray containing a rosin-modified resin and a (meth)acrylate compound. The laminate is a layer in which a curable anchor agent is cured with an active energy ray, and an ink layer is a layer in which an active energy ray curable ink is cured with an active energy ray.

Further, one embodiment of the present invention is a laminate having an anchor layer and a varnish layer in this order on a non-absorbent base material (excluding the case where an ink layer is included between the anchor layer and the varnish layer). The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with an active energy ray, and the varnish layer is an active energy ray-curable varnish, It is a laminate, which is a layer cured with an active energy ray.

<Ink layer>
<Active energy ray-curable ink>
The active energy ray-curable ink (hereinafter also referred to as "ink") used for 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 coloring agent. At least one of pigments and dyes can be used as the colorant. Pigments are preferred from the viewpoint of light resistance.
Pigments that can be used in the present invention are not particularly limited, and known pigments can be used. Both inorganic pigments and organic pigments can be used as the pigment.

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

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

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

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

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

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

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

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

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

In the present invention, the above pigments may be used singly or in combination of two or more.

In the present invention, the pigment can be used at any content as long as the desired density can be reproduced on the surface of the printing substrate, and the content is preferably 5 to 30% by mass based on the total amount of the ink. It is preferably 10 to 25 mass %, more preferably 10 to 25 mass %.

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

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

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

[(Meth)acrylate compound]
(monomer)
2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, β-carboxylethyl (meth)acrylate, 4-tert-butylcyclohequinol (meth)acrylate, tetrahydrofurfuryl acrylates, alkoxylated tetrahydrofurfuryl acrylate, caprolactone (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isoamyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isodecyl (meth)acrylate, 3, 3,5-trimethylcyclohexanol (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (oxyethyl) (meth)acrylate, 1,4-cyclohexanedimethanol (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, benzyl (meth)acrylate, EO-modified (2) nonylphenol acrylate, 2-methyl-2-ethyl-1,3-dioxolane -4-yl) monofunctional (meth)acrylate monomers having one (meth)acryloyl group in the molecule such as methyl acrylate,
1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate Acrylates, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol ( 200) di(meth)acrylate, polyethylene glycol (300) di(meth)acrylate, polyethylene glycol (400) di(meth)acrylate, polyethylene glycol (600) di(meth)acrylate, neopentylglycol hydroxypivalate di(meth)acrylate ) acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO-modified (2) 1,6-hexanediol di(meth)acrylate, PO-modified (2) neopentyl glycol di(meth) Acrylates, (neopentyl glycol-modified) trimethylolpropane di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, EO-modified (4) bisphenol A di(meth)acrylate, PO-modified (4) bisphenol A di( Bifunctional (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, dicyclopentanyl di (meth) acrylate, etc. with two (meth) acryloyl groups in the molecule meth)acrylate monomers,
Trimethylolpropane tri(meth)acrylate, EO-modified (3) trimethylolpropane tri(meth)acrylate, EO-modified (6) trimethylolpropane tri(meth)acrylate, PO-modified (3) trimethylolpropane tri(meth)acrylate , a trifunctional (meth)acrylate monomer having three (meth)acryloyl groups in the molecule such as pentaerythritol tri(meth)acrylate,
Tetrafunctional (meth)acrylate monomers having four acryloyl groups in the molecule such as pentaerythritol tetra(meth)acrylate, EO-modified (4) pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate,
Pentafunctional (meth)acrylate monomers having five (meth)acryloyl groups in the molecule such as dipentaerythritol penta(meth)acrylate,
A hexafunctional (meth)acrylate monomer having six (meth)acryloyl groups in the molecule, such as dipentaerythritol hexa(meth)acrylate, and the like.

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

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

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

Benzophenone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4,4′-bis(diethylamino)benzophenone, 4, 4′-bis(dimethylamino)benzophenone, [4-(methylphenylthio)phenyl]-phenylmethanone, 2-chloro-4phenyl-benzophenone, 1-{4-[(4-benzoylphenylsulfanyl)phenyl]- 2-methyl-2-(4-methylbenzenesulfonyl)propan-1-one, polybutylene glycol bis(4-benzoylphenoxy)acetate and the like.

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

α-Hydroxyalkylphenone compounds include 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxymethoxy)-phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl- Propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], 2,3-dihydro-6-(2-hydroxy-2-methyl-1 -oxopropyl)-1,1,3-trimethyl-3-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenyl]-1H-indene and 2,3-dihydro-5-(2- hydroxy-2-methyl-1-oxopropyl)-1,1,3-trimethyl-3-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenyl]-1H-indene mixture, 2- Hydroxy-1-[4-[4-(2-hydroxy-2-methylpropynyl)benzyl]phenyl]-2-methylpropan-1-one, 2-hydroxy-1-[4-[4-(2-hydroxy -2-methylpropanoyl)phenoxy]phenyl]-2-methylpropan-1-one, 1-[4-(1,1-dimethylethyl)phenyl]-2-hydroxy-2-methylpropan-1-one, etc. is mentioned.

Examples of α-aminoalkylphenone compounds include 2-methyl-1-[4-(methoxythio)-phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)-butanone, 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 1-(9, 9-dibutyl-9H-fluoren-2-yl)-2-methyl-2-morpholin-4-yl-propan-1-one, polyethylene glycol di(β-4-[4-(2-dimethylamino-2 -benzyl)butanonylphenyl]piperazine)propinate, 2-benzyl-2-dimethylamino-1-(4-piperidinylphenyl)-1-butanone, 1-(biphenyl-4-yl)-2-methyl-2 -morpholinopropan-1-one, 1-(biphenyl-4-yl)-2-methoxy-2-morpholinopropan-1-one and the like.

Examples of acylphosphine oxide compounds include diphenylacylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, tris(phenyl (2,4,6-trimethylbenzoyl)phosphinic acid) polyethylene glycol ester, ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, bis(2,4,6-dimethoxybenzoyl)-2,4,4 -trimethylpentylphosphine oxide and the like.

Oxime ester compounds include 1-[4-(phenylthio)phenyl]octane-1,2-dione, 2-benzoyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H- Carbazol-3-yl]-, 1-(o-acetyloxime), 3-cyclopentyl-1-(4-(phenylthio)phenyl)propane-1,2-dione-2-(o-benzoyloxime), 1- [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-(o-acetyloxime), methanone, [8-[[(acetyloxy)imino] [2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]-, (2,4,6- trimethylphenyl), 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime and the like.

Thioxanthone compounds include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propylthioxanthone, 2-chlorothioxanthone, poly(oxy- 1,4-butanediyl), α-[2-[(9-oxo-9H-thioxanthenyl)oxy]acetyl]-ω-[[2-[(9-oxo-9H-thioxanthenyl)oxy]acetyl]oxy]- , 1,3-di({α-[1-chloro-9-oxo-9H-thioxanthen-4-yl]oxy}acetylpoly[oxy(1-methylethylene)])oxy]-2,2-bis ({α-[1-chloro-9-oxo-9H-thioxantothen-4-yl]oxy}acetylpoly[oxy(1-methylethylene)])oxymethyl)propane and the like.

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

(amine compound)
In the present invention, the ink may contain an amine compound. The amine compound is not particularly limited, and known amine compounds can be used. By using the amine compound as a component of the active energy ray-curable ink, it is expected that the effect of the hydrogen abstraction photopolymerization initiator is enhanced.
Specific examples include N,N-dimethylaniline, N,N-diethyl-aniline, 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-(dimethyl amino)benzoate, 2-(dimethylamino)ethylbenzoate, etc. The amine compound may be used alone or in combination of two or more.

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

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

Specific examples of resins include polyvinyl chloride, (meth)acrylic resin, styrene (meth)acrylic resin, epoxy resin, polyester resin, polyurethane resin, cellulose derivatives (e.g., ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride- Vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, diallyl phthalate resins, alkyd resins, rosin-modified alkyd resins, petroleum resins, urea resins, and synthetic rubbers such as butadiene-acrylonitrile copolymers. Among them, diallyl phthalate resin and polyester resin are more preferable from the viewpoint of dispersibility.

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

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

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

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

(Extender pigment)
In the present invention, the ink may contain an extender. Extender pigments include clay, talc, barium sulfate, calcium carbonate, ground calcium carbonate, barium carbonate, magnesium carbonate, silica, bentonite, and the like.

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

Examples of the pigment dispersant include Ajinomoto Fine-Techno Co., Inc.'s Ajisper series (Ajisper PB821, PB822, PB824, etc.), Lubrizol's Solsperse series (Solsperse00, Solsperse32000, Solsperse38500, etc.), and BYK-Chemie's Disperbik series. (BYK-162, BYK-168, BYK-183, etc.) and the like.

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

<Varnish layer>
<Active energy ray curing varnish>
The active energy ray-curable varnish (hereinafter also referred to as "varnish") used for 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 the active energy ray-curable ink described above, except that substantially no coloring agent is used.

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

<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 a rosin-modified resin and a (meth)acrylate compound.

[Rosin modified resin]
The rosin-modified resin in the present invention is a resin containing a rosin-derived skeleton in the resin skeleton. By containing a rosin-derived skeleton, curing shrinkage due to UV irradiation during high-speed printing can be suppressed, and the smoothness of the dry film can be maintained, improving glossiness and adhesion to the substrate. do. In addition, the rosin-modified resin may have a rosin skeleton in the resin. Even when curable ink is used, it is possible to obtain a laminate that can be easily deinked.

Further, the rosin-modified resin in the present invention is obtained by the Diels-Alder reaction between the organic acid having a conjugated double bond contained in the rosin acids (A) and the α,β-unsaturated carboxylic acid or its acid anhydride (B). compounds, organic acids that do not have a conjugated double bond among rosin acids (A), and other organic acids, and hydroxyl groups possessed by compounds that form an ester bond by reacting a carboxylic acid with a polyol (C) in each A rosin-modified resin that has reacted to form an ester bond is preferred.

[Rosin acids (A)]
The rosin acids (A) used for obtaining the rosin-modified resin in the present invention refer to monobasic acids having a cyclic diterpene skeleton. Represents rosin acid, disproportionated rosin acid, hydrogenated rosin acid, or alkali metal salts of the above compounds, specifically, abietic acid having a conjugated double bond, and its conjugated compound, neoabietic acid, Examples include parastric acid, levopimaric acid, and pimaric acid, isopimaric acid, sandaracopimaric acid, and dehydroabietic acid that do not have a conjugated double bond. Examples of natural resins containing these rosin acids (A) include gum rosin, wood rosin and tall oil rosin.

The amount of the rosin acids (A) used to obtain the rosin-modified resin of the present invention is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, based on the total amount of the resin raw materials. more preferred.
Alkali solubility becomes favorable by making the compounding quantity of rosin acids (A) into 20 mass % or more. By setting the content of the rosin acids (A) to 70% by mass or less, the solubility in the (meth)acrylate compound is improved.

[α,β-unsaturated carboxylic acid or its acid anhydride (B)]
The α,β-unsaturated carboxylic acid or its acid anhydride (B) used for obtaining the rosin-modified resin in the present invention includes maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, isocrotonic acid and the like. are exemplified by the acid anhydrides of In view of reactivity with rosin acids (A), maleic acid or its acid anhydride is preferred.

In the present invention, the amount of the α,β-unsaturated carboxylic acid or its acid anhydride (B) is preferably in the range of 60 to 200 mol%, preferably 70 to 180 mol%, relative to the rosin acids (A). A range of mol % is more preferred, and a range of 80 to 160 mol % is particularly preferred. When the blending amount of the α,β-unsaturated carboxylic acid or its acid anhydride (B) is adjusted within the above range, it is easy to obtain a rosin-modified resin excellent in friction resistance and adhesion.

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

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

(organic monobasic acid)
aromatic monobasic acids such as benzoic acid, methyl benzoic acid, tertiary butyl benzoic acid, naphthoic acid, and orthobenzoyl benzoic acid;
Compounds having a conjugated double bond but not having a cyclic diterpene skeleton, such as conjugated linoleic acid, eleostearic acid, parinaric acid, and calendic acid, can be mentioned.

(fatty acid)
Flaxseed oil fatty acid, tung oil fatty acid, castor oil fatty acid, soybean oil fatty acid, tall oil fatty acid, bran oil fatty acid, palm oil fatty acid, coconut oil fatty acid, dehydrated castor oil fatty acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearin acid, isostearic acid, oleic acid, linoleic acid, linolenic acid and the like.

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

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

[Polyol (C)]
Polyol (C) is a compound obtained by a Diels-Alder reaction between an organic acid having a conjugated double bond contained in rosin acids (A) and α,β-unsaturated carboxylic acid or its acid anhydride (B), rosin An ester bond is formed by reaction with a carboxylic acid in an organic acid having no conjugated double bond among acids (A) and other organic acids. In order to obtain the rosin-modified resin of the present invention, the following polyols can be used singly or in combination of two or more. Specific examples of polyols include, but are not limited to:

(Linear alkylene dihydric polyol)
1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1 ,6-hexanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1, 9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16 - hexadecanediol, 1,2-hexadecanediol, and the like.

(Branched alkylene dihydric polyol)
2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propane diol, 2,4-dimethyl-2,4-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, dimethyloloctane, 2 -ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2 , 4-diethyl-1,5-pentanediol and the like.

(Cyclic dihydric polyol)
1,2-cycloheptanediol, tricyclodecanedimethanol, 1,2-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol , 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, hydrogenated catechol, hydrogenated resorcinol, hydrogenated hydroquinone and other cyclic alkylene dihydric polyols; bisphenol A, bisphenol F, bisphenol aromatic dihydric polyols such as S, catechol, resorcinol and hydroquinone;

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

(Trivalent polyol)
glycerin, trimethylolpropane, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, hydroxymethylhexanediol, trimethyloloctane and the like;

(Tetravalent or higher polyol)
Linear, branched and cyclic tetravalent or higher polyols such as pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, sorbitol, inositol and tripentaerythritol.

The rosin-modified resin in the present invention preferably has a weight average molecular weight of 3,000 to 50,000, more preferably 3,000 to 30,000. When the weight-average molecular weight is 3,000 to 30,000, the abrasion resistance and adhesion are improved.

The rosin-modified resin in the present invention preferably has an acid value of 10 to 100 mgKOH/g, more preferably 20 to 100 mgKOH/g, even more preferably 30 to 90 mgKOH/g. When the acid value of the rosin-modified resin is 10 mgKOH/g or more, the alkali solubility is good, and when it is 100 mgKOH/g or less, the printability is good.

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

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

[Other ingredients]
In the present invention, the anchoring agent may include silica, alumina, antifoaming agents, leveling agents, tackifiers, preservatives, antibacterial agents, antirust agents, etc., adhesion aids, polymerization initiators, etc., in addition to the above components, if necessary. agents, amine compounds, polymerization inhibitors, waxes, extenders, pigment dispersants, ultraviolet absorbers, antioxidants, antistatic agents, and the like.

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

(Polymerization inhibitor)
The polymerization inhibitor contained in the anchoring agent in the present invention can be used by adding the polymerization inhibitor by a conventional method. From the viewpoint of not inhibiting the curability, the amount of the polymerization inhibitor is preferably 3% by mass or less based on the total mass of the active energy ray-curable coating varnish, and is in the range of 0.01 to 1% by mass. It is even more preferred to use

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, cupferron, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N-(3 -oxyanilino-1,3-dimethylbutylidene)aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methylethylketoxime, and cyclohexanone oxime.
In particular, 2,2,6,6-tetraalkylpiperidine derivatives and 2,2,6, which are compounds having two hydrocarbon groups each at the 2-position and the 6-position on the piperidine ring (four in total). 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 on the printing press 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 in which an anchoring agent applied to a non-absorbing base material is cured with active energy rays, and cured with active energy rays. obtained by
In this embodiment, an additional varnish layer may be provided over the ink layer. The varnish used for the varnish layer is not particularly limited, and a known one can be used, but it is preferable to use an active energy ray-curable varnish or a water-based varnish, and it is particularly preferable to use an active energy ray-curable varnish. .

As a method for manufacturing the laminate of this embodiment,
Step 1 of applying an active energy ray-curable anchoring agent containing a rosin-modified resin to a non-absorbing base material and curing with an active energy ray to obtain a laminate having an anchor layer on a paper base material;
An easily deinkable laminate having an ink layer on the anchor layer, which is printed with an active energy ray-curable ink on the anchor layer of the laminate having the anchor layer on the non-absorbent base material and cured with an active energy ray. Step 2 of obtaining
including.

Further, in the production method of this embodiment, an active energy ray-curable varnish is further printed on the ink layer of the laminate having the anchor layer and the ink layer on the non-absorbent base material, and the active energy ray is applied to the ink layer. A step 3 of curing to obtain a laminate having a varnish layer on the ink layer may be included.

In one embodiment, the laminate of the present invention is obtained by printing an active energy ray-curable varnish on an anchor layer in which an anchoring agent applied to a non-absorbing base material is cured with active energy rays, and cured with active energy rays. obtained by

As a method for manufacturing the laminate of this embodiment,
Step 1 of applying an active energy ray-curable anchoring agent containing a rosin-modified resin to a non-absorbing base material and curing with an active energy ray to obtain a laminate having an anchor layer on a paper base material;
Step 4: Print an active energy ray-curable varnish on the anchor layer of the laminate having the anchor layer on the non-absorbent base material, and cure it with an active energy ray to obtain a laminate having the varnish layer on the anchor layer. When,
including.

The non-absorbent base material is not particularly limited, and known ones can be used. Specifically, polypropylene (PP), polyethylene (PET), polyethylene terephthalate (PET), aluminum, silica, plastic substrates having inorganic deposition layers such as alumina, aluminum foil, polyvinyl chloride (PVC), polystyrene ( PS), nylon, cellophane, metal sheets, etc. Various additives such as antistatic agents, antifogging agents, and UV inhibitors may be used in the substrate.

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

In the present invention, the method of printing the active energy ray-curable varnish is not particularly limited, and known methods can be used. Specifically, roll coater, gravure coater, flexo coater, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, transfer roll coater, kiss coater, curtain coater, cast coater, spray coater, die coater, offset printing , gravure printing, flexographic printing, and the like.

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

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

<De-inking>
In the present invention, deinking is a process for removing ink and varnish components from a printed non-absorbent substrate.

(Ink component removal step with alkaline aqueous solution)
For example, the laminate is formed in a process of contacting with an alkaline aqueous solution in a treatment tank containing an alkaline aqueous solution to remove an ink layer or a varnish layer.

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

(Ink and varnish component removal process)
The mechanism by which the ink layer and the varnish layer can be detached from the laminate by contacting the above-mentioned alkaline aqueous solution with the laminate is presumed to be that the presence of the above-mentioned resin causes the alkali aqueous solution to detach from the surface of the anchor layer and/or the cross-section of the laminate. This is because the penetration dissolves the anchor layer. After coating an anchor layer on a non-absorbent base material, printing an ink layer or varnish layer, and then going through the bag-making process, etc., the laminate that is in the form of a packaging container is cut or pulverized before or during the recycling process. It is preferable that the laminate is brought into contact with the alkaline aqueous solution in a state in which the cross section of the laminate is exposed.

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 dispersers, 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 2 L flask scale, the stirring rotation 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 step)
The recycled base material production method of the present invention includes a step of recovering the non-absorbent base material after removing the ink layer and the varnish layer from the laminate. The process of recovering the non-absorbent base material is, after treatment of the laminate with the alkaline aqueous solution, the non-absorbent base material from the treatment tank in which the alkaline aqueous solution, the peeled ink layer and varnish layer fragments, the non-absorbent base material, etc. are mixed. It is a process of separating and recovering the material, and it is preferable to obtain a non-absorbent base material with high purity. The method for recovering the non-absorbent base material is not particularly limited, and for example, separation and recovery based on the size difference between fragments of the non-absorbent base material and the ink layer or varnish layer is preferred, and separation and recovery based on the difference in specific gravity is also preferred. Alternatively, it is possible to appropriately separate and recover by a combination thereof, etc., but it is preferable to include a separation and recovery step based on the difference in specific gravity, and more preferably, a separation and recovery step based on the difference in specific gravity and a separation and recovery step based on the size difference are used in combination. .
In the separation and recovery step based on the difference in specific gravity, it is preferable to recover only the base material that floats on the alkaline aqueous solution in the treatment tank. Moreover, it is preferable if the impurity components in the alkaline aqueous solution and the fragments of the ink layer and the varnish layer are sedimented, so that the separation from the non-absorbent base material is easy and only the non-absorbent base material can be collected more accurately. Therefore, the physical properties and transparency of the non-absorbent base material recycled after recovery are improved. The method of separation based on the difference in specific gravity may be a conventionally known method, and may be a method using a fluidized bed, a centrifugal separator, or the like.

After removing the ink layer and varnish layer from the laminate and recovering the non-absorbent base material, the non-absorbent base material is washed with water and dried to obtain a recycled non-absorbent base material. At this time, it is preferable that all contaminants including fragments of the detached ink layer and varnish layer adhere to the recycled non-absorbent substrate as little as possible. The obtained recycled non-absorbent base material can be processed into pellets using an extruder or the like and reused as a recycled resin. Applications of the recycled resin are not limited, and it may be processed into a colorless and transparent film, or may be processed into a molded product to which a coloring agent is added.

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

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

<Synthesis of rosin-modified resin 1>
25.0 parts of gum rosin and 13.0 parts of maleic anhydride are charged in a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, and the mixture is heated at 180°C for 1 hour while blowing in nitrogen gas. The reaction mixture was obtained by heating over . Gas chromatographic mass spectrometry of the reaction mixture then confirmed that the Diels-Alder addition reaction was complete.
Next, 38.0 parts of benzoic acid, 18.0 parts of pentaerythritol, 9.0 parts of glycerin, and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst are added to the reaction mixture. Then, a dehydration-condensation reaction was carried out at 240° C. for 9 hours to obtain a rosin-modified resin 1. The rosin-modified resin 1 had an acid value of 36 and a weight average molecular weight (Mw) of 27,200 in terms of polystyrene measured by GPC.
<Preparation of rosin-modified resin varnish 1>
65.0 parts of DPHA, 6.5 parts of TMPTA (EO), 3.0 parts of DiTMPTA, and 0.5 parts of Polystop 7300P were mixed and heated to 100° C. with stirring. Next, 25.0 parts of rosin-modified resin 1 was mixed and dissolved while being kept at 100° C. to prepare rosin-modified resin varnish 1 .

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

(Anchor agent 2)
62.0 parts of TMPTA (EO), 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 parts of EDB, and 30.0 parts of rosin-modified resin varnish 1 were mixed and mixed using a butterfly mixer. An active energy ray-curable anchoring agent (AC2) was prepared by stirring and mixing.

(Anchor agent 3)
95.0 parts of the anchoring agent 1 and 5.0 parts of the additive 1 were mixed immediately before printing to prepare an anchoring agent (AC3).

(Anchor agent 4)
Immediately before printing, 95.0 parts of the anchoring agent 1 and 5.0 parts of the additive 2 were mixed to prepare an anchoring agent (AC4).

<Synthesis of rosin-modified resin 2>
44.0 parts of gum rosin and 16.0 parts of maleic anhydride are charged in a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, and heated at 180°C for 1 hour while blowing nitrogen gas. The reaction mixture was obtained by heating over . Next, 39.0 parts of 2-butyl-2-ethyl-1,3-propanediol and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added to the above reaction mixture, and A dehydration-condensation reaction was carried out at °C for 8 hours to obtain a rosin-modified resin 2. The rosin-modified resin 2 had an acid value of 72 and a weight average molecular weight (Mw) of 5,200.
<Preparation of rosin-modified resin varnish 2>
45.0 parts of DPHA, 16.5 parts of TMPTA (EO), 13.0 parts of DiTMPTA, and 0.5 parts of Polystop 7300P were mixed and heated to 100° C. with stirring. Next, 25.0 parts of rosin-modified resin 2 was mixed and dissolved while being kept at 100° C. to prepare rosin-modified resin varnish 2 .

(Anchor agent 5)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and a rosin modified resin 57.0 parts of varnish 2 was mixed and stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchoring agent (AC5).
<Synthesis of rosin-modified resin 3>
45.0 parts of gum rosin and 13.0 parts of maleic anhydride are charged into a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, and the mixture is heated at 180°C for 1 hour while blowing nitrogen gas. The reaction mixture was obtained by heating over . Next, 4.0 parts of 1,4-cyclohexanedimethanol, 19.0 parts of neopentyl glycol, 6.0 parts of trimethylolpropane, and p-toluenesulfonic acid monohydrate as a catalyst are added to the above reaction mixture. After adding 0.1 part of the product and conducting dehydration condensation reaction at 240° C. for 6 hours, 12 parts of tall oil fatty acid was added and dehydration condensation reaction was conducted for 3 hours to obtain Resin 3. Resin 3 had an acid value of 55 and an Mw of 7,800.
<Preparation of rosin-modified resin varnish 3>
45.0 parts of DPHA, 16.5 parts of TMPTA (EO), 13.0 parts of DiTMPTA, and 0.5 parts of Polystop 7300P were mixed and heated to 100° C. with stirring. Next, 25.0 parts of rosin-modified resin 3 was mixed and dissolved while being kept at 100° C. to prepare rosin-modified resin varnish 3 .

(Anchor agent 6)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and a rosin modified resin 57.0 parts of varnish 3 was mixed and stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchoring agent (AC6).

<Production 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 to 100° C. with stirring. Next, 25.0 parts of diallyl phthalate resin Daiso Dup A (resin 4) was mixed and dissolved while being kept at 100° C. to prepare a diallyl phthalate resin varnish.

(Anchor agent 7)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 parts of EDB, and diallyl phthalate resin 57.0 parts of varnish was mixed, and the mixture was stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchoring agent (AC7).

<Production of petroleum resin varnish>
65.0 parts of DPHA, 6.5 parts of TMPTA (EO), and 3.5 parts of DiTMPTA were mixed and heated to 100° C. with stirring. Next, 25.0 parts of petroleum resin PETROTAC 90 (resin 5) was mixed and dissolved while being kept at 100° C. to prepare a petroleum resin varnish.

(Anchor agent 8)
10.0 parts TMPTA (EO), 18.0 parts DiTMPTA, 7.0 parts DPHA, 5.0 parts 4MBP, 2.0 parts TPO, 1.0 parts EDB, and petroleum resin varnish was mixed with 57.0 parts, and stirred and mixed using a butterfly mixer to prepare an active energy ray-curable anchoring agent (AC8).

<Ink manufacturing example>

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

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

(Ink production example 3 (LED ink black) (active energy ray-curable ink))
17.0 parts RAVEN 1080 Ultra, 3.0 parts BA-2550, 6.0 parts TMPTA (EO), 10.0 parts DiTMPTA, 7.0 parts DPHA, 3.0 parts 379, TPO 2.0 parts of DEABP, 2.5 parts of 4MBP, 2.5 parts of DETX, 1.0 parts of EDB, and 44.0 parts of diallyl phthalate resin varnish are mixed, and a butterfly mixer was stirred and mixed using , and dispersed with a triple roll so that the maximum particle size was 7.5 μm or less to prepare an ink.

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

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

(Ink production example 6 (UV red ink) (active energy ray-curable ink))
20.0 parts of Permanent Rubine L5B-01, 6.0 parts of TMPTA (EO), 13.0 parts of DiTMPTA, 7.0 parts of DPHA, 3.0 parts of 379, 1.5 parts of DEABP, DETX 1.5 parts of EDB, 1.0 parts of EDB, and 47.0 parts of diallyl phthalate resin varnish are mixed, stirred and mixed using a butterfly mixer, and the maximum particle size is 7.5 μm or less with three rolls. Ink was prepared by dispersing so that

(Ink production example 7 (UV ink indigo) (active energy ray-curable ink))
20.0 parts Heliogen Blue D7088, 6.0 parts TMPTA(EO), 13.0 parts DiTMPTA, 7.0 parts DPHA, 3.0 parts 379, 1.5 parts DEABP, 1 part DETX .5 parts, 1.0 part of EDB, and 47.0 parts of diallyl phthalate resin varnish are mixed, stirred and mixed using a butterfly mixer, and then the maximum particle size becomes 7.5 μm or less with three rolls. Ink was prepared by dispersing as follows.

(Ink production example 9 (EB ink black) (active energy ray-curable 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 0 part, and stirred and mixed using a butterfly mixer, and then dispersed with a three-roll roll so that the maximum particle size becomes 7.5 μm or less to prepare an ink.
<Preparation of oil-based resin varnish>
(Manufacturing example of rosin-modified phenolic resin)
In a reaction vessel, 54.3 parts of gum rosin, 30.8 parts of tert-butylphenol and 9.4 parts of 92% by weight of paraformaldehyde in a xylene solvent are reacted in the presence of sodium hydroxide catalyst at 100°C for 4 hours, A phenolic resin from which moisture was removed was added dropwise at 150° C. and reacted for 2 hours. Further, 5.4 parts of glycerin was added, and 0.1 part of calcium oxide was used as a catalyst for reaction at 250° C. for 15 hours. In the meantime, the rosin phenol resin was able to be obtained by taking it out one by one.

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

(Ink production example 1 (oil-based ink) (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. The mixture was stirred and mixed using a butterfly mixer, and then dispersed with a three-roll roll so that the maximum particle size was 7.5 μm or less to prepare an ink.

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

Explanations of notations for materials used in the examples are as follows.
[Coloring agent]
・Permanent Yellow BHS: Permanent Yellow BHS (CI Pigment Yellow 174) manufactured by Clariant
・Permanent Rubine L5B-01: Permanent Rubine L5B-01 (C.I.Pigment Red 57:1) manufactured by Clariant
・HELIOGEN BLUE D7088: manufactured by BASF, HELIOGEN BLUE D7088 (CI Pigment Blue 15:3)
- Raven 1080 Ultra: Raven 1080 Ultra Powder (CI Pigment Black 7) manufactured by Bilra Carbon
・ BA-2550: Alkaline Blue Toner BA-2550 (C.I.Pigmen) manufactured by Morimura Shoji Co., Ltd.
t Blue 61)
[Extender Pigment]
・Filler: High Filler #5000PJ manufactured by Matsumura Sangyo Co., Ltd., talc [(meth)acrylate compound]
・TMPTA (EO): manufactured by BASF, LAROMER LR8863, trimethylolpropane ethylene oxide-modified triacrylate ・DiTMPTA: manufactured by Daicel Ornex, EBECRYL1142, ditrimethylolpropane tetraacrylate ・DPHA: manufactured by MIWON, MIRAMER M600, dipentaerythritol Hexaacrylate PS-4500: manufactured by MIWON, MIRAMER PS-4500, polyester acrylate oligomer [resin]
・ Daiso Dap A: Osaka Soda Co., Ltd., Daiso Dap A, diallyl phthalate resin ・ Petrotac 90: Tosoh Corporation, Petrotac 90, petroleum resin [photoinitiator]
379: IGM RESINS, Omnirad 379, 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone TPO: Chemmark Chemical Co., CHEMARK TPO, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide DEABP: Chemmark Chemical Co., CHEMARK DEABP, 4,4'-bis (dimethylamino) benzophenone 4MBP: Soho Jitsugyosha Made by SB-PI 712
・DETX: CHEMARK DETX manufactured by Chemmark Chemical Co., 2,4-diethylthioxanthone ・184: Omnirad184 manufactured by IGM RESINS Co., 1-hydroxy-cyclohexylphenyl ketone [amine compound]
EDB: CHEMARK EDB manufactured by Chemmark Chemical Co., ethyl-4-(dimethylamino) benzoate [pigment dispersant]
Solsperse24000: manufactured by Lubrizol, Solsperse24000
[Polymerization inhibitor]
Polystop 7300P: Polystop 7300P manufactured by Hakuto Sangyo Co., Ltd.
[Metal dryer]
・MK Dryer: Toyo Ink Co., Ltd., MK Dryer [drying inhibitor]
・Drying inhibitor CP: Drying inhibitor CP manufactured by Toyo Ink Co., Ltd.
[Aluminum gelling agent]
・ ALCH: Kawaken Fine Chemicals Co., Ltd., ALCH, aluminum ethyl acetate diisopropylate [others]
・Soybean oil fatty acid normal butyl ester: SFB2, manufactured by Toshin Oil Co., Ltd.
・ Additive 1: manufactured by Tosoh Corporation, Coronate HX, modified polyisocyanate ・ Additive 2: manufactured by Nippon Shokubai Co., Ltd., Chemitite PZ-33, aziridine-based cross-linking agent

<Printing of anchoring agent on substrate>
In Examples 1 to 13, 15 to 31, and Comparative Examples 2 to 4, an RI tester (simple printing machine manufactured by Akira Seisakusho Co., Ltd.) was used to anchor one side of the substrate shown in Table 1 with an ink gauge of 0.25 mL. The agent was applied by printing. After that, the coating film was cured with an ultraviolet curing device (160 W/cm metal halide lamp) manufactured by Eye Graphics Co., Ltd. under the conditions of a conveyor speed of 30 m/min to prepare a laminate having an anchor layer on the base material.
In Example 14, a bar coater (No. 4, manufactured by Yasuda Seiki Co., Ltd.) was used, and the anchor agents shown in Table 1 were applied onto the substrates shown in Table 1 with the coater. After that, the coating film was cured with an ultraviolet curing device (160 W/cm methhalide lamp) manufactured by iGraphics Co., Ltd. under the conditions of a conveyor speed of 30 m/min to prepare a laminate having an anchor layer on the substrate.

<Ink and varnish printing>
In Examples 1 to 26 and 28 and Comparative Examples 2 and 3, each sample ink shown in Table 1 was printed on the prepared laminate having an anchor layer on the substrate using an RI tester with an ink gauge of 0.25 mL. After that, the printed material is cured with an ultraviolet curing device (160 W/cm methhalide lamp) manufactured by Eye Graphics Co., Ltd. under the conditions of a conveyor speed of 30 m/min, and an anchor layer and an ink layer are formed in this order on the substrate. A laminate having
In Example 27, the laminated body having the anchor layer on the prepared base material was printed with LED ink using an RI tester with an ink gauge of 0.25 mL, and then the printed material was subjected to an ultraviolet curing device manufactured by Eye Graphics ( 160 W/cm 2 methhalide lamp) and a conveyor speed of 100 m/min to cure the ink to obtain a laminate having an anchor layer and an ink layer on the substrate in this order.
In Example 29, the laminate having the anchor layer on the prepared base material was printed with EB ink using an RI tester with an ink gauge of 0.25 mL, and then the printed material was printed with a low-energy electron beam manufactured by ESI Co., Ltd. Using an irradiation device (pressurized voltage 175 KV, oxygen concentration 50 ppm, nitrogen-substituted atmosphere), 30 KGy of electron beam is irradiated to cure the ink to obtain a laminate having an anchor layer and an ink layer on the substrate in this order. rice field.
In Example 30, a laminate having an anchor layer on the prepared base material was printed with UV varnish obtained by mixing 2 parts of UV ink black 1 in advance with an ink gauge of 0.25 mL using an RI tester. The coating film was cured with an ultraviolet curing device (160 W/cm methhalide lamp) manufactured by Eye Graphics Co., Ltd. under the conditions of a conveyor speed of 30 m/min, and a laminate having an anchor layer and a varnish layer on the base material in this order was obtained. Obtained.
In Example 31, the laminate having the anchor layer on the prepared base material was printed with UV ink 1 using an RI tester with an ink gauge of 0.25 mL, and then the printed material was printed using an ultraviolet curing device manufactured by Eye Graphics. (160 W / cm methhalide lamp), the coating film is cured under the conditions of a conveyor speed of 30 m / min, and using an RI tester, UV varnish is printed with an ink gauge of 0.25 mL. The coating film was cured with an ultraviolet curing device (160 W/cm 2 methhalide lamp) manufactured by the company at a conveyor speed of 30 m/min to obtain a laminate having an anchor layer and a varnish layer on the substrate in this order.
In Comparative Example 4, the laminate having the anchor layer on the prepared base material was printed with an oil-based ink (ink other than the active energy ray-curable ink) using an RI tester with an ink gauge of 0.25 mL. The ink was cured by standing at room temperature for 24 hours to obtain a laminate having an anchor layer and an ink layer in this order on the substrate.
In Comparative Example 1, an RI tester was used to print oil-based black ink (ink other than active energy ray-curable ink) directly on the base material shown in Table 1 with an ink gauge of 0.25 mL, and then at room temperature for 24 hours. The ink was cured by standing to obtain a laminate having an ink layer on the substrate.

The substrates used in the examples are as follows.
・ PP1: Polypropylene sheet manufactured by Okamoto Co., Ltd. ・ PP2: Novatec PP manufactured by Japan Polypropylene Corporation
・ PE1: Taiko FC manufactured by Futamura Chemical Co., Ltd.
・ PE2: Novatec HD manufactured by Japan Polyethylene 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/nylon: manufactured by Unitika Ltd., emblem ・ cellophane: manufactured by Futamura Chemical Co., Ltd., PL
・Metal: ET2.8/2.8T2.5B manufactured by Nippon Steel Corporation

The obtained laminate was evaluated for performance by the following method. Table 1 shows the results.

<Evaluation of laminate>

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

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

<Evaluation of de-inking property>
The laminates of Examples 1 to 31 and Comparative Examples 1 to 4 thus produced were aged at 60° C. for 1 week and then stored for 10 days under an environment of room temperature of 23±1° C. and humidity of 50±2%. After that, it was cut to 30×30 mm, and 90 g of each was used as a sample for the test.

<Evaluation of de-inking property of laminate>
In a 2 L flask, 1.5 L of warm water at 30° C., 11 mL of 3.75% sodium hydroxide aqueous solution, and 11 mL of deinking agent (manufactured by Kao Corporation DI-7027) diluted to 1.5% are added. A sample was added and stirred at 300 rpm for 20 minutes. After 2 minutes from the start of stirring, the sample adhering to the lid was washed into the tank with a small amount of water. After the detachment was completed, the substrate was taken out, and how much area in each 30×30 mm was covered with ink was visually evaluated.
〇: Ink is detached from 99% or more of the base material. 〇△: Ink is detached from 95% or more and less than 99% of the base material. ×: Ink is detached from less than 90% of the substrate

It can be judged that practical use is obtained when the three evaluations of scratch resistance, adhesion, and deinking are 0, 0 Δ, and Δ.

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

Claims (11)

A laminate having an anchor layer and an ink layer in this order on a non-absorbent substrate,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with an active energy ray,
The laminate, wherein the ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray. 2. The laminate according to claim 1, further comprising a varnish layer on the ink layer. Claim 1 or 2, wherein the rosin-modified resin is a reaction product of an addition reaction product of a rosin acid (A) and an α,β-unsaturated carboxylic acid or its acid anhydride (B) with a polyol (C). Laminate as described. A laminate having an anchor layer and a varnish layer in this order on a non-absorbent substrate (excluding the case where an ink layer is included between the anchor layer and the varnish layer),
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with an active energy ray,
The laminate, wherein the varnish layer is a layer obtained by curing an active energy ray-curable varnish with an active energy ray. 5. The rosin-modified resin according to claim 4, which is a reaction product of an addition reaction product of rosin acids (A) and an α,β-unsaturated carboxylic acid or its acid anhydride (B) with a polyol (C). laminate. A method for manufacturing a laminate,
A step of applying an active energy ray-curable anchoring agent containing a rosin-modified resin and a (meth)acrylate compound to a non-absorbing base material and curing with an active energy ray to obtain a laminate having an anchor layer on the base material. 1 and
Step 2 of printing an active energy ray-curable ink on the anchor layer of the laminate having the anchor layer on the non-absorbent base material and curing with an active energy ray to obtain a laminate having an ink layer on the anchor layer. When,
A method of manufacturing a laminate, comprising: Furthermore, an active energy ray-curable varnish is printed on the ink layer of the laminate having the anchor layer and the ink layer on the non-absorbent base material, and cured with an active energy ray to form a varnish layer on the ink layer. 7. The method for producing a laminate according to claim 6, comprising step 3 of obtaining the laminate. A method for manufacturing a laminate,
A step of applying an active energy ray-curable anchoring agent containing a rosin-modified resin and a (meth)acrylate compound to a non-absorbing base material and curing with an active energy ray to obtain a laminate having an anchor layer on the base material. 1 and
Step 4: Print an active energy ray-curable varnish on the anchor layer of the laminate having the anchor layer on the non-absorbent base material, and cure it with an active energy ray to obtain a laminate having the varnish layer on the anchor layer. When,
A method of manufacturing a laminate, comprising: A deinking method for a laminate having an anchor layer and an ink layer in this order on a non-absorbent substrate,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with an active energy ray,
The ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray,
A method of deinking a laminate, wherein the laminate is agitated in an alkaline aqueous solution, the anchor layer is dissolved in the alkaline aqueous solution, and the ink layer is deinked from the non-absorbent substrate. A deinking method for a laminate having an anchor layer, an ink layer, and a varnish layer in this order on a non-absorbent substrate,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with an active energy ray,
The ink layer is a layer obtained by curing an active energy ray-curable ink with an active energy ray,
The varnish layer is a layer obtained by curing an active energy ray-curable varnish with an active energy ray,
A method of deinking a laminate, wherein the laminate is agitated in an alkaline aqueous solution, the anchor layer is dissolved in the alkaline aqueous solution, and the ink layer is deinked from the non-absorbent substrate. A method for deinking a laminate having an anchor layer and a varnish layer in this order on a non-absorbent substrate (excluding cases where an ink layer is included between the anchor layer and the varnish layer),
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with an active energy ray,
The varnish layer is a layer obtained by curing an active energy ray-curable varnish with an active energy ray,
A method of deinking a laminate, wherein the laminate is agitated in an alkaline aqueous solution, the anchor layer is dissolved in the alkaline aqueous solution, and the ink layer is deinked from the non-absorbent substrate.