JP2023108443A - Easily deinking laminate and manufacturing method thereof - Google Patents

Abstract

To provide an easily deinking laminate with excellent deinkability in paper recycling processing regardless of the type of active energy ray-curable varnish, and a manufacturing method for the laminate.SOLUTION: An easily deinking laminate has an anchor layer and a varnish layer on a paper substrate in this order, where the anchor layer is a layer in which an active energy ray-curable anchor agent containing a rosin modified resin and a (meth)acrylate compound is cured with an active energy ray, and the varnish layer is a layer in which active energy ray-curable varnish is cured with an active energy ray.SELECTED DRAWING: None

Description

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

Active energy ray-curing inks 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. It is used.

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

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 commercial printing in recent years. 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.

At paper manufacturing companies, used printing paper is finely pulverized in an alkaline aqueous solution during the deinking process, and then floated on bubbles called flotation using a deinking agent to remove stains caused by ink components. I am working on removing it. At this time, if a large amount of undecomposed black component called dirt remains, it becomes difficult to make the paper blank when the paper is made again, which tends to deteriorate the suitability for recycling.
On the other hand, transparent varnish does not retain color even if it has low deinking properties, but UV varnish that has formed a film due to the curing reaction, or contaminants that have firmly bonded UV varnish and paper can be recycled. It is known to remain in the paper and weaken the strength of the recycled paper.

In general, the amount of this contaminant is said to be greater in UV curable inks and varnishes than in general oil-based inks and varnishes. However, the fibers of the paper break down into small pieces, making it difficult to obtain strength, and the burden of time, power, and chemicals increases. There is a problem that there is

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

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

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

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

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

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

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

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

The present invention also provides a method for producing an easily deinkable laminate,
A step of applying an active energy ray-curable anchoring agent containing a rosin-modified resin and a (meth)acrylate compound to a paper base material and curing with an active energy ray to obtain a laminate having an anchor layer on the paper base material. 1 and
An easily deinkable laminate having a varnish layer on the anchor layer is obtained by printing with an active energy ray-curable varnish on the anchor layer of the laminate having the anchor layer on the paper substrate and curing with the active energy ray. Step 2 of obtaining
It relates to a method for manufacturing an easily deinkable laminate.

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

According to the present invention, an easily deinkable laminate that has excellent physical properties as a laminate such as scratch resistance and excellent deinking properties in paper recycling processing regardless of the type of active energy ray-curable varnish, and the laminate. We were able to provide a manufacturing method for

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

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

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

[(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 varnish 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) 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. having 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 varnish may optionally contain a polymerization initiator, an amine compound, a resin, a polymerization inhibitor, a surface tension modifier, a wax, an extender pigment, an antifoaming agent, an ultraviolet absorber, and an antioxidant, in addition to the above components. etc. can be contained.

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

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

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

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

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

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

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 varnish.

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

(resin)
In the present invention, the varnish may contain 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 varnish.

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 varnish 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 varnish, from the viewpoint of enhancing the stability of the varnish while maintaining curability.

(wax)
In the present invention, the varnish 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 varnish.

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

<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, since the rosin-modified resin has high solubility in the alkali used for deinking, the alkali solubility of the anchor layer also increases, so even when using an active energy ray-curable varnish that is difficult to deink, deinking is easy. A laminate can be obtained.

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 in the present invention is preferably 20 to 70% by mass, more preferably 30 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, preferably 70 to 180 mol%, relative to the rosin acids (A). is more preferably in the range of , particularly preferably in the range of 80 to 155 mol %. 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 a cyclic diterpene skeleton, such as conjugated linoleic acid, eleostearic acid, parinaric acid, and calendic acid, can be mentioned.

(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 acid anhydrides thereof)
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 30,000, more preferably 3,000 to 15,000. 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 20 to 100 mgKOH/g, more preferably 30 to 100 mgKOH/g, still more preferably 40 to 90 mgKOH/g, and particularly preferably 50 to 80 mgKOH/g. When the acid value of the rosin-modified resin is 20 mgKOH/g or more, the alkali solubility is good, and when it is 100 mgKOH/g or less, the printability is good.

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. 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 varnish can be used.

[Other ingredients]
In the present invention, the anchor agent contains silica, alumina, polyethylene wax, antifoaming agent, leveling agent, tackifier, antiseptic agent, antibacterial agent, antirust agent, etc., in addition to the above components, if necessary. be able to.

<Easy de-inking laminate>
The easily deinkable laminate of the present invention is obtained by printing an active energy ray-curable varnish on an anchor layer obtained by curing an anchor agent applied to a paper base material with active energy rays, and then curing with active energy rays. obtained by

As the method for producing the easily deinkable laminate of the present invention,
Step 1 of applying an active energy ray-curable anchoring agent containing a rosin-modified resin to a paper base material and curing it with an active energy ray to obtain a laminate having an anchor layer on the paper base material;
An easily deinkable laminate having a varnish layer on the anchor layer is obtained by printing with an active energy ray-curable varnish on the anchor layer of the laminate having the anchor layer on the paper substrate and curing with the active energy ray. Step 2 of obtaining
including.

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

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

In the present invention, the method of applying the active energy ray-curable varnish and the method of applying the active energy ray-curable anchoring agent are 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.

<De-inking>
In the present invention, deinking is a process for removing varnish components from so-called waste paper after printing. Specifically, a flotation method is used in which the paper is pulverized in an alkaline aqueous solution, and then the varnish separated from the fibers using a deinking agent is floated and removed by generating fine air bubbles. Fatty acids (soaps), fatty acid derivatives, oil derivatives, higher alcohol derivatives and the like are mainly used as deinking agents. At this time, if a large amount of varnish components remain that have not been completely decomposed, the strength of the paper will be affected when the paper is made again. becomes important.

The deinking agents include deinking agents DI-7020, DI-7027, DI-7250, and DI-767 manufactured by Kao Corporation, DIA-Z series and DIA-Y series manufactured by 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 parts of gum rosin and 14 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. A reaction mixture was obtained. Gas chromatographic mass spectrometry of the reaction mixture then confirmed that the Diels-Alder addition reaction was complete.
Next, 32 parts of benzoic acid, 15 parts of pentaerythritol, 14 parts of glycerin, and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst are added to the above reaction mixture, and the mixture is heated at 240° C. for 8 hours. A dehydration-condensation reaction was carried out over a period of time to obtain a rosin-modified resin 1. The rosin-modified resin 1 had an acid value of 30 and a weight average molecular weight (Mw) of 25,800 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) and 3.5 parts of DiTMPTA were mixed and heated to 100° C. while 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 3)
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 (AC3) was prepared by stirring and mixing.

<Synthesis of rosin-modified resin 2>
45 parts of gum rosin and 16 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. A reaction mixture was obtained. Next, 39 parts of 2-butyl-2-ethyl-1,3-propanediol and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added to the reaction mixture, and the mixture was heated at 240°C. A dehydration-condensation reaction was carried out for 8 hours to obtain a rosin-modified resin 2. The rosin-modified resin 2 had an acid value of 68 and a weight average molecular weight (Mw) of 5,600.
<Preparation of rosin-modified resin varnish 2>
45.0 parts of DPHA, 16.5 parts of TMPTA (EO) and 13.5 parts of DiTMPTA were mixed and heated to 100° C. with stirring. Next, 25.0 parts of rosin-modified resin 2 was mixed and dissolved while being kept at 100° C. to prepare rosin-modified resin varnish 2 .

(Anchor agent 2)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 part of EDB, and 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 (AC2).

(Anchor agent 4)
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 2 were mixed and mixed using a butterfly mixer. An active energy ray-curable anchoring agent (AC4) was prepared by stirring and mixing.

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

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

<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. while stirring. Next, 25.0 parts of petroleum resin PETROTAC 90 was mixed and dissolved while being kept at 100° C. to prepare a petroleum resin varnish.

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

<Production of acrylic 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. while stirring. Next, 25.0 parts of an acrylic resin S-6100 was mixed and dissolved while being kept at 100° C. to prepare an acrylic resin varnish.

(Anchor agent 7)
10.0 parts of TMPTA (EO), 18.0 parts of DiTMPTA, 7.0 parts of DPHA, 5.0 parts of 4MBP, 2.0 parts of TPO, 1.0 parts of EDB, and acrylic 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 (AC7).

(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 polyester acrylate oligomer 57.0 parts of PS-4500 were mixed and mixed by stirring using a butterfly mixer to prepare an active energy ray-curable anchoring agent (AC8).

(Anchor agent 9)
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 an epoxy acrylate oligomer 57.0 parts of EBECRYL 3700 were mixed and mixed by stirring using a butterfly mixer to prepare an active energy ray-curable anchoring agent (AC9).

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

(Anchor agent 11)
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 chlorinated polyester 57.0 parts of an acrylate oligomer (PHOTOMER 5028: manufactured by IGM RESINS) was mixed and mixed with stirring using a butterfly mixer to prepare an active energy ray-curable anchoring agent (AC11).

<Varnish production example>
<Preparation of oil-based resin varnish>
(Manufacturing example of rosin-modified phenolic resin)
In a reaction vessel, 54.3 parts of gum rosin, 30.8 parts of tert-butylphenol and 9.4 parts of 92% by weight of paraformaldehyde in a xylene solvent are reacted in the presence of sodium hydroxide catalyst at 100°C for 4 hours, A phenolic resin from which moisture was removed was added dropwise at 150° C. and reacted for 2 hours. Further, 5.4 parts of glycerin was added, and 0.1 part of calcium oxide was used as a catalyst for reaction at 250° C. for 15 hours. In the meantime, the rosin phenol resin was able to be obtained by taking it out one by one.

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

(Varnish production example 1 (oil-based varnish) (varnish other than active energy ray-curable varnish))
69.0 parts of rosin-modified phenolic resin varnish, 30.0 parts of soybean oil, 0.5 parts of MK dryer, and 0.5 parts of drying inhibitor CP were mixed, stirred and mixed using a butterfly mixer, and then rolled with three rolls. A varnish was prepared by dispersing the particles so that the maximum particle size was 7.5 μm or less.
(Varnish production example 2 (UV varnish 1) (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.

(Varnish production example 3 (UV varnish 2) (active energy ray-curable varnish))
6.0 parts TMPTA (EO), 13.0 parts DiTMPTA, 7.0 parts DPHA, 2.0 parts TPO, 6.0 parts 184, 1.0 parts EDB, 3.0 parts filler and 62.0 parts of MIRAMER PS-4500, 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 a varnish.

(Varnish production example 4 (LED varnish) (active energy ray-curable varnish))
6.0 parts TMPTA (EO), 13.0 parts DiTMPTA, 7.0 parts DPHA, 7.0 parts TPO, 1.0 parts DETX, 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.

(Varnish production example 5 (UV flexon varnish) (active energy ray-curable varnish))
36.0 parts TMPTA (EO), 10.0 parts DiTMPTA, 7.0 parts DPHA, 5.0 parts 184, 2.0 parts TPO, 1.0 parts EDB, using a butterfly mixer After stirring and mixing, the mixture was dispersed by a disper to prepare a varnish. After that, 39.0 parts of TMPTA (EO) was added and stirred and mixed using a butterfly mixer to prepare a varnish.

(Varnish production example 6 (EB varnish) (active energy ray-curable varnish))
9.0 parts of TMPTA (EO), 13.0 parts of DiTMPTA, 7.0 parts of DPHA, 3.0 parts of filler, and 68.0 parts of diallyl phthalate resin varnish are mixed and stirred using a butterfly mixer. After mixing, the mixture was dispersed with three rolls so that the maximum particle size was 7.5 μm or less to prepare a varnish.

<Example of manufacturing ink for varnish coloring>
(Manufacture of oil-based ink for varnish coloring)
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 triple roll so that the maximum particle size was 7.5 μm or less to prepare an oil-based varnish coloring ink.

(Manufacture of active energy ray-curable ink for varnish coloring)
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 active energy ray-curable ink for varnish coloring was prepared by dispersing the particles so that the particle size was 7.5 μm or less.

Explanations of notations for materials used in the examples are as follows.
[Coloring agent]
- 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 EBECRYL 3700: manufactured by Allnex Belgium, EBECRYL 3700, epoxy acrylate oligomer EBECRYL 2221: manufactured by Allnex Belgium, EBECRYL 2221, urethane acrylate Oligomer PHOTOMER 5028: IGM RESINS, PHOTOMER 5028, chlorinated 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 ・ S-6100: Daido Chemical Industry Co., Ltd., Daikarak S-6100 , acrylic 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: Chemmark Chemical Co., Ltd., CHEMARK DETX, 2,4-diethylthioxanthone ・184: IGM RESINS Co., Ltd., Omnirad184, 1-hydroxy-cyclohexylphenyl ketone [amine compound]
・ EDB: CHEMARK EDB manufactured by Chemmark Chemical Co., ethyl-4-(dimethylamino) benzoate [metal dryer]
・MK Dryer: Toyo Ink Co., Ltd., MK Dryer [drying inhibitor]
・Drying inhibitor CP: Drying inhibitor CP manufactured by Toyo Ink Co., Ltd.
[Aluminum gelling agent]
・ ALCH: Kawaken Fine Chemicals Co., Ltd., ALCH, aluminum ethyl acetate diisopropylate [others]
・Soybean oil fatty acid normal butyl ester: SFB2, manufactured by Toshin Oil Co., Ltd.

Examples 1-10, Comparative Examples 1-9
<Printing of anchoring agent on substrate>
In Examples 1 to 4, 7 to 10, and Comparative Examples 1 to 8, an RI tester (simple printing machine manufactured by Akira Seisakusho Co., Ltd.) was used, and the anchor agent shown in Table 1 was applied to one side of the substrate with an ink gauge of 0.25 mL. was applied by printing. After that, the coating film was cured with an ultraviolet curing device (160 W/cm methhalide lamp) manufactured by iGraphics Co., Ltd. at a conveyor speed of 30 m/min to prepare a laminate having an anchor layer on the substrate.
In Examples 5 and 6, a bar coater (No. 4, manufactured by Yasuda Seiki Co., Ltd.) was used, and the anchor agent shown in Table 1 was applied onto the base material by the coater. After that, the coating film was cured with an ultraviolet curing device (160 W/cm methhalide lamp) manufactured by iGraphics Co., Ltd. at a conveyor speed of 30 m/min to prepare a laminate having an anchor layer on the substrate.

<Varnish printing>
The varnish was evaluated using a mixture of varnish-coloring inks, since it is difficult to evaluate a varnish that does not contain a coloring agent.
In Examples 1 to 7 and 9 and Comparative Examples 2 to 8, the laminate having the anchor layer on the prepared base material was coated with an ink gauge of 0.25 mL using an RI tester, and each varnish shown in Table 1 was coated with varnish. After applying a mixture of 2% active energy ray-curable ink for coloring, the coating film is cured under the conditions of a conveyor speed of 30 m/min with an UV curing device (160 W/cm methhalide lamp) manufactured by Eye Graphics. to obtain a laminate having an anchor layer and a varnish layer on the substrate in this order.
In Example 8, the laminated body having the anchor layer on the prepared base material was mixed with 2% active energy ray-curable ink for coloring varnish with LED varnish using an ink gauge of 0.25 mL using an RI tester. After coating, the varnish 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 100 m/min, and an anchor layer and a varnish layer are formed in this order on the substrate. A laminate having
In Example 10, the laminate having the anchor layer on the prepared base material was mixed with EB varnish and 2% active energy ray-curable ink for varnish coloring with an ink gauge of 0.25 mL using an RI tester. Then, using a low-energy electron beam irradiation apparatus manufactured by ESI Co., Ltd. (applied voltage 175 KV, oxygen concentration 50 ppm, nitrogen-substituted atmosphere), 30 KGy electron beams are irradiated to cure the varnish, and the varnish is cured on the substrate. A laminate having an anchor layer and a varnish layer in this order was obtained.
In Comparative Example 1, an oil-based varnish (a varnish other than an active energy ray-curable varnish) was applied to a laminate having an anchor layer on a prepared base material using an RI tester with an ink gauge of 0.25 mL. After coating with a mixture of 2% ink, the varnish was cured by standing at room temperature for 24 hours to obtain a laminate having an anchor layer and a varnish layer on the substrate in this order.
In Comparative Example 9, using an RI tester, a mixture of UV varnish 1 and 2% active energy ray-curable ink for varnish coloring was applied directly to the base material with an ink gauge of 0.25 mL, and then exposed to ultraviolet rays manufactured by Eye Graphics Co., Ltd. The varnish was cured with a curing device (160 W/cm 2 methhalide lamp) at a conveyor speed of 30 m/min to obtain a laminate having a varnish layer on the substrate.

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

<Evaluation of laminate>
(Evaluation of scratch resistance)
The laminate was evaluated by rubbing the varnish layer with a cotton cloth. 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 to the varnish layer 〇 △ : The surface of the varnish layer is rubbed △ : The middle part of the varnish layer is rubbed △× : The bottom of the varnish layer is rubbed × : The coating film of the varnish layer disappears

<Evaluation of de-inking property>
After aging the laminates of Examples 1 to 10 and Comparative Examples 1 to 9 for one week at 60° C., they were stored for 10 days under an environment of room temperature of 23±1° C. and humidity of 50±2%. Then, it was cut to 10 cm×10 cm, immersed in a 1.0±0.1% sodium hydroxide aqueous solution, and pulled out after 10 hours.
After pulling up, the area ratio of the colored portion was visually measured. It can be judged that the smaller the colored area ratio, the better the deinking property. The evaluation criteria are as shown below, and ◯, ◯Δ, and Δ are practically preferable.
Evaluation of colored area ratio ○: Very good de-inking property (0% or more to less than 10%)
〇△ : Good de-inking property (10% or more to less than 25%)
△: De-inking is normal (25% or more to less than 40%)
△×: Poor deinkability (40% or more to less than 60%)
×: Very poor de-inking property (60% or more)

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

Claims (4)

An easily deinkable laminate having an anchor layer and a varnish layer in this order on a paper substrate,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with an active energy ray,
The easily deinkable laminate, wherein the varnish layer is a layer obtained by curing an active energy ray-curable varnish with an active energy ray. 2. The rosin-modified resin according to claim 1, which 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). Easily deinkable laminate. A method for manufacturing an easily deinkable laminate, comprising:
A step of applying an active energy ray-curable anchoring agent containing a rosin-modified resin and a (meth)acrylate compound to a paper base material and curing with an active energy ray to obtain a laminate having an anchor layer on the paper base material. 1 and
An active energy ray-curable varnish is applied onto the anchor layer of the laminate having the anchor layer on the paper base material and cured with an active energy ray to obtain an easily deinkable laminate having a varnish layer on the anchor layer. Step 2 of obtaining
A method for producing an easily deinkable laminate, comprising: A deinking method for a laminate having an anchor layer and a varnish layer in this order on a paper substrate,
The anchor layer is a layer obtained by curing an active energy ray-curable anchor agent containing a rosin-modified resin and a (meth)acrylate compound with 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 stirred in an alkaline aqueous solution, the anchor layer is dissolved in the alkaline aqueous solution, and the varnish layer is deinked from the paper substrate.