JP2021091476A - Package, and manufacturing method of recycling substrate - Google Patents

Abstract

To provide: a package suitable for plastic recycling, which exhibits excellent substrate adhesiveness that is necessary as a package and exhibits an excellent desorption property of a printing substrate while enabling removal of not only a printing layer on an outer side of the package but also a printing layer on an inner side thereof; and a packaging container thereof.SOLUTION: There is provided a package provided with at least a first substrate, a primer layer for recycling the first substrate obtained by desorbing the first substrate, and a printing layer in this order. The package contains resin (A) in 1 mass% of an aqueous sodium hydroxide solution at 60°C. A primer composition used for forming the primer layer becomes the resin as a binder resin in which a weight average molecular weight (Mw) after immersion for 12 hours becomes 70 mass% or less (Mw before immersion is set to 100 mass%).SELECTED DRAWING: None

Description

The present invention relates to a packaging material containing a recyclable base material and a method for producing a recycled base material.

In recent years, packages made from plastic films, plastic bottles and other plastic products have been disposed of and dumped as garbage in the ocean, which has become a problem of environmental pollution. These plastic products are decomposed in seawater into submicron-sized fragments (microplastics) that float in seawater. When the plastic is ingested by marine organisms such as fish, it is concentrated in the organism. Then, there is a concern that it will affect the health of seabirds and humans who ingest the marine organisms as food. Various efforts have begun to reduce microplastics to remedy these problems.

Examples of the plastic products include food packaging packages using a plastic base material. In the package, various plastic base materials such as polyester (PET) base material, nylon (NY) base material, and polypropylene (PP) base material are used as the film base material. These plastic base materials are subjected to a printing layer with gravure ink, flexographic ink, or other printing ink, and further bonded to a hot-melt resin base material via an adhesive or the like to form a laminated body, and then the laminated body is formed. It is cut and heat-sealed to form a package.

As an attempt to reduce the amount of microplastics, in the above package, (1) the plastic base material is replaced with paper, and (2) the plastic base material is limited to the use of only the same type to simplify recycling (referred to as monomaterialization). , (3) Remove impurities and recycle plastic.

The above (1) is promising in terms of safety and recyclability, but there are many aspects inferior in performance to conventional plastic base materials such as gas barrier property, water vapor barrier property, and water resistance.
In (2) above, a technique for covering the weak points of polyolefin with a functional coating agent such as a barrier coating agent is being developed, but the performance is inferior to that of a conventional plastic base material such as retort suitability and light shielding property. , Replacement with polyolefin is not easy. Further, inks, functional coating agents, adhesives, etc. between polyolefin substrates also have a problem of becoming impurities in recycling polyolefins.

As the above (3), an attempt has been made to remove the printed layer on the outer surface of the package, which becomes an impurity in the recycling process, with an alkaline aqueous solution.
For example, Cited Document 1 discloses a technique in which an undercoat layer made of an acrylic resin or a styrene-maleic acid-based resin is provided on a plastic base material, and a printing layer arranged on the undercoat layer is removed with alkaline water. Further, Patent Document 2 discloses a technique in which an ink using a polyurethane resin or an acrylic resin having an acidic group as a binder resin is printed on the surface, and the printing layer is removed with alkaline water. However, these are techniques that only remove the front printing ink on the outside of the package, and have not yet removed the ink layer in the laminated laminate and peeled the base materials from each other.

In addition to removing the front printing ink layer for plastic recycling, the technology for removing the ink layer in the laminated laminate is an important technology that can be industrially used for environmental protection in promoting plastic recycling. However, the technology that can achieve both of these has not yet been reported.

Japanese Unexamined Patent Publication No. 2001-131484 Japanese Unexamined Patent Publication No. 11-209677

Therefore, the subject of the present invention is that the adhesiveness of the base material required as a packaging material is excellent, and not only the print layer on the outside of the package but also the print layer on the inside can be removed, and the print base material is excellent in detachability. The purpose is to provide packaging materials and packaging containers suitable for plastic recycling.

The present invention is a packaging material provided with at least a first base material, a primer layer for desorbing the first base material and recycling the first base material, and a printing layer in this order.
The primer composition used for forming the primer layer has a weight average molecular weight (Mw) of 70% or less (Mw before immersion) after being immersed in a 1% by mass sodium hydroxide aqueous solution at 60 ° C. for 12 hours as a binder resin. The present invention relates to a packaging material containing a resin (A) that becomes (100%).

Further, the present invention includes at least a first base material, a primer layer for desorbing the first base material and recycling the first base material, a printing layer, and a second base material in this order. It is a packaging material
The primer composition used for forming the primer layer has a weight average molecular weight (Mw) of 70% or less (Mw before immersion) after being immersed in a 1% by mass sodium hydroxide aqueous solution at 60 ° C. for 12 hours as a binder resin. The present invention relates to a packaging material containing a resin (A) that becomes (100%).

Further, in the present invention, the printing ink used for forming the printing layer has a weight average molecular weight (Mw) of 60% or more after being immersed in a 1% by mass sodium hydroxide aqueous solution at 60 ° C. for 12 hours as a binder resin (Mw). The present invention relates to the above-mentioned packaging material containing a resin (B) that becomes (Mw before immersion is 100%).

Further, in the present invention, the primer composition contains 60% by mass or more of the resin (A) in the total amount of the resin components in the primer composition, and
The printing ink relates to the above-mentioned packaging material containing 60% by mass or more of the resin (B) in the total amount of the resin components in the printing ink.

Further, in the present invention, the maximum absorption wavelength in the visible light region (400 to 760 nm) of the aqueous solution after immersing the packaging material cut into 2 cm × 2 cm in 15 g of a 2 mass% sodium hydroxide aqueous solution at 70 ° C. for 2 hours. The present packaging material is characterized by having a transmittance of 75% or more.

The present invention also relates to the above-mentioned packaging material, wherein the primer composition contains a polyurethane resin having an acid value of 15 to 70 mgKOH / g.

A method for producing a recycled base material, which comprises a step of immersing the packaging material in a basic aqueous solution.
The present invention relates to a method for producing a recycled base material, wherein the basic aqueous solution contains 0.5 to 10% by mass of the total basic aqueous solution, and the water temperature of the basic aqueous solution at the time of immersion is 30 to 120 ° C.

INDUSTRIAL APPLICABILITY According to the present invention, the adhesiveness of the base material required as a packaging material is excellent, and not only the print layer on the outside of the package but also the print layer on the inside can be removed, and the print base material is excellent in detachability, which is suitable for plastic recycling. It is possible to provide packaging materials and packaging containers.

The embodiments of the present invention will be described in detail below, but the description of the embodiments or requirements described below is an example of the embodiments of the present invention, and the present invention includes these contents as long as the gist thereof is not exceeded. Not limited.

The packaging material of the present invention is the opposite of a packaging material provided with at least a first base material, a primer layer for desorbing the first base material, and a printing layer in this order, or a primer layer of the printing layer. The primer composition, which is a packaging material having at least a second base material on the side and is used for forming the primer layer, is used as a binder resin after being immersed in a 1% sodium hydroxide aqueous solution at 60 ° C. for 12 hours. It is characterized by containing a resin (A) having an Mw of 70% or less (Mw before immersion is 100%).
In the present invention, "desorption" means that the first base material is desorbed from the packaging material by neutralizing or dissolving the primer layer with a basic aqueous solution and peeling off, and (1) the primer layer is dissolved. When the first base material is desorbed, (2) even if the primer layer is not dissolved, it is peeled off by neutralization, swelling, etc., and the first base material is desorbed. ..
In the packaging material in which the second base material is present, when the first base material is detached, the second base material and the printing layer may be integrated or separate from each other. Good.

In the packaging material, the primer layer is dissolved and peeled off with a basic aqueous solution or the like, so that the first base material is detached and the first base material can be separated and recovered. Therefore, the packaging material of the present invention corresponds to the packaging material used for separating and recovering the first base material.
The present invention will be described in detail below, but these are examples of embodiments of the present invention, and the present invention is not limited to these contents as long as the gist thereof is not exceeded.

<Primer layer and primer composition for desorbing the first substrate>
The primer layer in the present invention is formed from the primer composition, is arranged in contact with the first base material, and is a layer for desorbing the first base material by dissolution / peeling using a basic aqueous solution or the like. As a binder resin, the resin (A) has a weight average molecular weight (Mw) of 70% or less (Mw before immersion is 100%) after being immersed in a 1% by mass sodium hydroxide aqueous solution at 60 ° C. for 12 hours. Contains. When the primer composition contains the resin (A), the molecular weight is lowered in the basic aqueous solution, the primer layer is easily swollen and dissolved, and the desorption property by the basic aqueous solution is improved.

<Resin (A)>
The resin (A) is not particularly limited and can be selected from conventionally known resins, and may be used alone or in combination of two or more.
The resin (A) is preferably contained in an amount of 60% by mass or more, more preferably 80% by mass or more, based on the total amount of the resin components constituting the primer layer.
Examples of the resin skeleton of the resin (A) include urethane resin, cellulose resin, polyester resin, amino resin, polylactic acid, and the like, and urethane resin is preferable because it has good laminating suitability.

[Urethane resin]
The acid value of the urethane resin is preferably 15 mgKOH / g or more, more preferably 15 to 70 mgKOH / g, and even more preferably 20 to 50 mgKOH / g. When it is 15 mgKOH / g or more, the molecular weight of the resin tends to decrease in the basic aqueous solution, and the desorption property by the basic aqueous solution becomes good. Therefore, when it is 70 mgKOH / g or less, the substrate adhesiveness and retort resistance It is preferable because the property is good.
The hydroxyl value of the urethane resin is preferably 1 to 35 mgKOH / g, more preferably 10 to 30 mgKOH / g. When it is 1 mgKOH / g or more, it is preferable because the desorption property by a basic aqueous solution is good, and when it is 35 mgKOH / g or less, it is preferable because the substrate adhesiveness is good.
Both the hydroxyl value and the acid value are values measured according to JIS K0070.

The weight average molecular weight of the urethane resin is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, and even more preferably 15,000 to 50,000.
The molecular weight distribution (Mw / Mn) of the urethane resin is preferably 6 or less. Mw represents the weight average molecular weight and Mn represents the number average molecular weight. When the molecular weight distribution is 6 or less, the influence caused by the excessive high molecular weight component, the unreacted component, the side reaction component and other low molecular weight components can be avoided, and the desorption property and the drying property of the primer composition can be avoided. Good retort resistance.

Further, the smaller the molecular weight distribution, that is, the sharper the molecular weight distribution, the more uniformly the dissolution / peeling action of the basic aqueous solution occurs and the detachability of the first base material is improved, which is preferable. The molecular weight distribution is more preferably 5 or less, still more preferably 4 or less. Further, the molecular weight distribution is preferably 1.5 or more, more preferably 1.2 or more.
Mw, Mn and the molecular weight distribution (Mw / Mn) are polystyrene-equivalent values obtained by gel permeation chromatography (GPC).
When the molecular weight distribution and the acid value are within the above ranges, not only the desorption property by the basic aqueous solution but also the drying property, the substrate adhesiveness and the retort resistance of the primer composition are improved, which is preferable.

The urethane resin may have an amine value. When the urethane resin has an amine value, the amine value is preferably 0.1 to 20 mgKOH / g, more preferably 1 to 10 mgKOH / g. When it is within the above range, the adhesiveness to the base material becomes good, which is preferable.

The urethane resin is not particularly limited, and is preferably a resin obtained by reacting a polyol, a hydroxy acid and a polyisocyanate, for example. By using a hydroxy acid, an acid value can be imparted to the urethane resin, and desorption property can be improved. More preferably, it is a resin obtained by reacting a resin obtained by reacting a polyol, a hydroxy acid and a polyisocyanate with a polyamine.

(Polyol)
Polyol is a general term for compounds having at least two hydroxyl groups in one molecule, and does not contain hydroxy acids, which will be described later.
The number average molecular weight of the polyol is preferably 500 to 10,000, more preferably 1,000 to 5,000. The number average molecular weight referred to here is calculated from the hydroxyl value of the polyol, and the hydroxyl value is a value measured by JISK0070. When the number average molecular weight of the polyol is 500 or more, the flexibility of the primer layer is excellent and the adhesion to the first substrate is improved. When the number average molecular weight is 10,000 or less, the blocking resistance to the first substrate is excellent when there is a winding step after forming the primer layer.

The polyol is not particularly limited, and more preferably, at least one polyol selected from the group consisting of polyester polyols, polyether polyols, and polycarbonate polyols is used. Further, the polyol may also contain other dimer diols, hydrogenated dimer diols, castor oil-modified polyols and the like.
The urethane resin in the present invention more preferably contains a constituent unit derived from at least one polyol selected from the group consisting of polyester polyols and polycarbonate polyols, and has a desorption property because the molecular weight tends to decrease in a basic aqueous solution. improves.
The content of the constituent unit derived from the polyol is preferably 10 to 75% by mass, more preferably 15 to 70% by mass, and further preferably 20 to 65% by mass with respect to the total amount of the urethane resin.

[Polyester polyol]
Examples of the polyester polyol include a polyester polyol composed of a condensate of a dibasic acid and a diol; a polyester polyol composed of a polylactone polyol which is a ring-opening polymer of a cyclic ester compound; and a polyester diol is preferable. The polyester polyol can be used alone or in combination of two or more.
Dibasic acids include adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, glutaric acid, 1 , 4-Cyclohexyldicarboxylic acid, dimeric acid, hydrogenated dimeric acid and the like, with adipic acid or succinic acid being preferred.

Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol (hereinafter referred to as propylene glycol), 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, and 1,6-. Hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethyl Pentandiol 2,4-diethyl-1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether , 2-Monoglycerin ether, dimerdiol, hydrogenated dimerdiol and the like.

As the polyester diol, a condensate of a dibasic acid and a diol having a branched structure may be used. It is preferable to use a diol having a branched structure because the adhesion to the plastic base material and the retort resistance can be improved.
The diol having a branched structure is preferably a diol having a structure in which at least one hydrogen atom of the alkylene glycol is substituted with an alkyl group, and is, for example, 1,2-propanediol, 1,3-butanediol, or 2-methyl. -1,3-propanediol, neopentyl glycol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,5-hexanediol, 2-methyl-1,4-pentanediol, 2, 4-Diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,3-pentane Diol, 2,2,4-trimethyl-1,6-hexanediol can be mentioned. Of these, at least one selected from the group consisting of 1,2-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, and 2-butyl-2-ethyl-1,3-propanediol is preferable. Therefore, 1,2-propanediol or 3-methyl-1,5-pentanediol is preferably used.

As the raw material of the polyester polyol, a polyol having 3 or more hydroxyl groups and a polyunsaturated carboxylic acid having 3 or more carboxyl groups may be used in combination.
Preferable examples of the cyclic ester compound include α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone.

[Polycarbonate polyol]
As the polycarbonate polyol, those containing an aliphatic polycarbonate polyol are preferable. The number average molecular weight of the polycarbonate polyol is preferably 500 to 5,000, more preferably 800 to 4,000, and even more preferably 1,000 to 3,000.

The aliphatic polycarbonate polyol preferably contains a structural unit derived from an aliphatic diol such as a substituted or unsubstituted alkylene glycol, and the method for producing the aliphatic polycarbonate polyol is not limited, but the aliphatic diol and the carbonate compound are used. It is preferably a polycondensate produced by an ester exchange reaction.

The aliphatic diol preferably has 4 to 10 carbon atoms, and for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and the like. 2-Methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl -1,8-octanediol, 1,10-decanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butinediol, 2,2,4-trimethyl-1,3-pentane Examples thereof include diol, 1,4-cyclohexanedimethanol, diethylene glycol, polypropylene glycol, dipropylene glycol and the like. The substituent contained in the aliphatic diol is preferably an alkyl group having 10 or less carbon atoms. These aliphatic diols can be used alone or in combination of two or more.

The carbonate compound is not particularly limited, and examples thereof include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and dibutyl carbonate; diaryl carbonates such as diphenyl carbonate; and alkylene carbonates such as ethylene carbonate. Since it becomes a polycondensate in the transesterification reaction with the aliphatic diol and is replaced, the structure of the carbonate compound is not limited, and a compound having good reactivity may be appropriately selected.

The polycarbonate polyol is preferably liquid at 25 ° C. By using a liquid polycarbonate polyol as a raw material for a polyurethane resin, flexibility and elasticity are given to the primer layer, adhesion to a base material is improved, and retort suitability and blocking resistance are improved.
Examples of such a liquid polycarbonate polyol include an alkylene glycol having an odd number of carbon atoms and having a linear structure and an alkylene glycol having an even number of carbon atoms and having a linear structure (linear diol) as an aliphatic diol component. , Or an aliphatic polycarbonate polyol using an alkylene glycol (branched diol) having an alkyl substituent and the like.

It is preferable that the aliphatic polycarbonate polyol contains a structural unit derived from a branched diol having a tertiary carbon as an aliphatic diol component because the desorption property and the blocking resistance are improved.
Examples of the branched diol having a tertiary carbon include 1,2-propanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octane. Examples thereof include diols, 2,2,4-trimethyl-1,3-pentanediol, and 3-methyl-1,5-pentanediol is preferable.
More preferably, a linear diol and a branched diol having a tertiary carbon are used in combination, and an aliphatic polycarbonate polyol using 1,6-hexanediol and 3-methyl-1,5-pentanediol is used. Especially preferable.
The mass ratio (linear diol: branched diol having tertiary carbon) to the total mass of the aliphatic polycarbonate polyol is preferably 70:30 to 5:95, and more preferably 50:50 to 10:90.

(Hydroxy acid)
The hydroxy acid in the present invention refers to a compound having both a hydroxyl group as an active hydrogen group and an acidic functional group in one molecule.
The acidic functional group indicates a functional group that can be neutralized with potassium hydroxide when measuring the acid value, and specific examples thereof include a carboxyl group and a sulfonic acid group, and a carboxyl group is preferable. Since the probability that the acidic group reacts with the isocyanate group is low, the acid value can be maintained even when a hydroxyl group-containing urethane resin is used.
The hydroxy acid is not particularly limited, and for example, dimethylolalkanoic acid such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid is preferably used. These can be used alone or in combination of two or more.

(Polyisocyanate)
The polyisocyanate is not particularly limited and can be selected from conventionally known polyisocyanates, preferably containing diisocyanate or triisocyanate, and more preferably containing aromatic, aliphatic or alicyclic diisocyanate. These may be used alone or in combination of two or more.

Examples of aromatic, aliphatic or alicyclic diisocyanates include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, and 4,4'-dibenzylisocyanate. , Dimethyldiphenylmethane diisocyanate, tetramethyldiphenylmethane diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, o-xylylene diisocyanate and 2,4-tolylene diisocyanate, Aromatic diisocyanates such as 2,6-tolylene diisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Alibo diisocyanates such as: cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methyl Examples thereof include cyclohexanediisocyanate, m-tetramethylxylylene diisocyanate, and alicyclic diisocyanate such as dimerged isocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group.

Among them, from the viewpoint of reactivity, preferably from isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate. At least one selected from the group of The diisocyanate is also preferably a triisocyanate having a trimer structure such as an isocyanurate structure.

(Polyamine)
The polyamine in the present invention is not particularly limited, and is preferably a diamine compound.
Examples of the diamine compound include ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, and dimerdiamine obtained by converting the carboxyl group of dimer acid into an amino group. These can be used alone or in combination of two or more.
More preferably, hydroxyl groups such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. It is a diamine having. By using a diamine having a hydroxyl group, a certain amount of the hydroxyl group can remain unreacted, and the hydroxyl value can be introduced into the urethane resin.

Amino acids can be used as the diamine compound. Amino acid refers to a compound having both an amino group and an acidic functional group in one molecule, and examples thereof include glutamine, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid, and diaminobenzenesulfonic acid. Since the acidic group has a low probability of reacting with the isocyanate group, the acid value can be maintained in the polyurethane resin.

When reacting the polyamine, a polymerization inhibitor may be used in combination. Examples of the polymerization terminator include dialkylamine compounds such as di-n-dibutylamine; monoethanolamine, diethanolamine, butanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, and the like. Compounds such as 2-amino-2-ethyl-1,3-propanediol, N-di-2-hydroxyethylethylenediamine, N-di-2-hydroxyethylpropylenediamine, N-di-2-hydroxypropylethylenediamine Amine compounds having; examples include monoamine-type amino acid compounds such as glycine, alanine, glutamic acid, taurine, aspartic acid, aminobutyric acid, valine, aminocaproic acid, aminobenzoic acid, aminoisophthalic acid, sulfamic acid. In order to introduce the hydroxyl value into the polyurethane resin, it is preferable to use an amine compound having a hydroxyl group.
When the hydroxyl group-containing urethane resin is contained, the mass ratio of the hydroxyl group-containing urethane resin to the other resin in the primer composition (hydroxyl group-containing urethane resin: the other resin in the primer composition) is preferably 95: 5 to 5. 50:50. Within the above range, when the print layer is peeled off together with the primer layer in the basic aqueous solution, the print layer is peeled off in a thin film state, which is preferable because recovery is easy.

[Manufacturing of urethane resin]
As described above, the urethane resin is more preferably a resin obtained by reacting a polyol, a hydroxy acid and a polyisocyanate with a urethane prepolymer having an isocyanate group at the terminal, and further reacting a polyamine to extend the chain. In this case, in the reaction of the polyol, the hydroxy acid and the polyisocyanate (hereinafter referred to as the urethanization step), the functional group molar ratio (NCO / OH) of the polyisocyanate and the polyol and the hydroxy acid is preferably 1.05 to 3. It is .0, more preferably 1.1 to 2.8. The functional group molar ratio (amino group / NCO) of the isocyanate group of the urethane prepolymer and the amino group of the polyamine is preferably 0.7 to 1.3.

The number of urethane bonds of the polyurethane resin is preferably 1 to 3 mmol / g, and more preferably 1.5 to 2 mmol / g. The number of urea bonds in the polyurethane resin is preferably 0 to 3 mmol / g, more preferably 0.2 to 1 mmol / g. The total number of urethane bonds and urea bonds is preferably 1 to 6 mmol / g, more preferably 1.7 to 3 mmol / g.
It is preferable to set the number of urethane bonds and the number of urea bonds in the corresponding ranges because desorption and substrate adhesiveness are improved.

The number of urethane bonds is a value represented by the following formula (3) when (number of NCO moles / number of OH moles)> 1 in the urethanization reaction step, and (number of NCO moles / number of OH moles) ≤ 1. In the case, it is a value represented by the following equation (4).
Formula (3): Number of urethane bonds (mmol / g) = Total number of moles of hydroxyl groups (mmol) / Total mass of solids (g)
Formula (4): Number of urethane bonds (mmol / g) = Total number of moles of isocyanate groups (mmol) /
Total solid mass (g)
In the formulas (3) and (4), the total number of moles of hydroxyl groups represents the total number of moles of hydroxyl groups of the polyol and hydroxyic acid used in the urethanization step, and the total solid content is the total number of non-volatile components of the polyurethane resin. It represents the mass, and the total number of moles of isocyanate groups represents the total number of moles of isocyanate groups contained in the polyisocyanate.

The urea bond number is a value applied to those subjected to the urethanization reaction under the condition of (NCO molar number / OH molar number)> 1.
The urea bond number is a value represented by the following formula (5) when (number of moles of amino groups / number of moles of NCO)> 1 in the urea conversion reaction step (number of moles of amino groups / number of moles of NCO) ≤ 1. In the case of, it is a value represented by the following equation (6).
Formula (5): Number of urea bonds (mmol / g) = [total number of moles of isocyanate groups (mmol) -total number of moles of hydroxyl groups (mmol)] / total solid content (g)
Formula (6): Number of urea bonds (mmol / g) = total number of moles of amino groups (mmol) / total mass of solids (g)
In the formulas (5) and (6), the total number of moles of isocyanate groups represents the total number of moles of isocyanate groups contained in the polyisocyanate used in the urethanization step, and the total number of moles of hydroxyl groups is the polyol used in the urethanization step and the number of moles of hydroxyl groups. The total number of moles of hydroxyl groups contained in hydroxyic acid and the like is represented by the total number of moles of amino groups, and the total number of moles of amino groups represents the total number of moles of primary and / or secondary amino groups of the polyamine used in the ureation reaction step. The mass represents the total mass of the non-volatile components of the polyurethane resin.

[Cellulose resin]
Examples of the cellulose resin include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkyl cellulose, and carboxyalkyl cellulose. Examples of the alkyl group optionally contained in the cellulose resin include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group and the like. The alkyl group may have a substituent. Of these, cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferred. The weight average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 200,000.

[Other resins]
The primer layer may further contain a resin other than the resin (A).
Other resins include resins having a weight average molecular weight (Mw) greater than 70% by mass after being immersed in a 1% by mass sodium hydroxide aqueous solution at 60 ° C. for 12 hours (Mw before immersion is 100% by mass). Yes, for example, vinyl chloride resin such as urethane resin, polyamide resin, vinyl chloride-vinyl acetate copolymer resin or vinyl chloride-acrylic copolymer resin, rosin resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, Acrylic resin, styrene resin, dammar resin, styrene-maleic acid copolymer resin, styrene-acrylic copolymer resin, polyester resin, alkyd resin, terpene resin, phenol-modified terpene resin, ketone resin, cyclized rubber, rubber chloride, butyral, Examples thereof include polyacetal resins, petroleum resins, and modified resins thereof. These resins may be used alone or in admixture of two or more.
Above all, the primer layer preferably contains at least one resin selected from the group consisting of urethane resin, vinyl chloride resin, rosin resin, acrylic resin and styrene-maleic acid copolymer resin. It is still preferable that the resin is at least one selected from the group consisting of vinyl chloride-based resins, styrene-maleic acid copolymer resins, and rosin-based resins. The vinyl chloride resin has excellent compatibility when a urethane resin is used as the main resin, and is preferably used for the purpose of imparting coating film strength. Further, more preferably, it is particularly preferable to use a rosin-based resin, a dibasic acid-modified resin of rosin, a styrene maleic acid copolymer resin, and an acrylic resin containing acrylic acid and methacrylic acid in combination. By using these resins together, the hydrophilicity of the primer layer is improved, which is advantageous for desorption.

[Other ingredients]
The primer layer may further contain other components other than the resin.
The primer layer preferably contains an extender pigment from the viewpoint of improving the film strength, improving the optical properties, and improving the fluidity of the primer composition.
Examples of the extender pigment include metal oxides such as silica, barium sulfate, kaolin, clay, calcium carbonate, magnesium carbonate, zinc oxide, and zirconium oxide. These are used to improve fluidity, film strength, optical properties, and image quality when overprinting printing inks. Of these, the use of silica and barium sulfate is preferable. When it is silica, it is preferably hydrophilic. In the case of barium sulfate, it is preferably precipitated barium sulfate. The extender pigment preferably has an average particle size of 0.5 to 10 μm, and more preferably 1 to 8 μm. The extender pigment is preferably contained in an amount of 0.5 to 30% by mass, and more preferably 1 to 25% by mass in the total amount of the ink. Further, silica is preferably 1 to 5% by mass, and barium sulfate is preferably 10 to 25% by mass.
Further, known additives may be added. Known additives include dispersants, wetting agents, adhesion aids, leveling agents, defoaming agents, antistatic agents, viscosity modifiers, curing agents, metal chelates, trapping agents, blocking inhibitors, and wax components other than the above. , Silane coupling agent and the like. In addition, the primer composition preferably contains an antifogging agent, a hydrophilic agent, and an antistatic agent as additives. The antifogging agent, hydrophilic agent, and antistatic agent may include those conventionally known as additives to be added to a general film or coating agent for the purpose of imparting antifogging property, hydrophilicity, and antistatic property. it can. Specific preferred examples include glycerin fatty acid ester, phosphoric acid ester, and quaternary ammonium salt.
Other components may be blended with the resin (A) in advance, or may be added when the resin (A) is blended.

<Manufacturing of primer composition>
The primer composition can be produced by dissolving and / or dispersing at least the resin (A) in an organic solvent, and may contain the above-mentioned other components, if necessary.
Examples of the organic solvent include aromatic organic solvents such as toluene and xylene; ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester organic solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate. Known organic solvents such as alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; glycol ether-based solvents such as ethylene glycol monopropyl ether and propylene glycol monomethyl ether; Alternatively, two or more types can be mixed and used.

The solid content concentration in the primer composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. Further, the content of the resin (A) in the primer composition is preferably 0.5 to 50% by mass, more preferably 5 to 30% by mass. Optimal printability can be obtained within the above range.
The viscosity of the primer composition is preferably 20 to 500 mPa · s, more preferably 30 to 300 mPa · s, because appropriate printability can be obtained in the printing process. The viscosity of the primer composition can be appropriately adjusted depending on the content of the resin (A), the content of other components described later, and the like.
As the primer layer, the primer composition can be formed on the first substrate by a known printing device or coating device. The viscosity of the primer composition depends on the printing apparatus or coating apparatus used, and can be adjusted with the organic solvent or the like.

<First base material>
The first base material is a recyclable base material, and examples thereof include a plastic base material on a film or a sheet that is generally used as a packaging material, and a laminated body in which these are laminated may be used.
Examples of the plastic base material include a film of a thermoplastic resin and a thermosetting resin, and a film of a thermoplastic resin is preferable. Examples of the thermoplastic resin include polyolefin resins, polyester resins, polyamide resins, polystyrene resins, vinyl chloride resins, vinyl acetate resins, ABS resins, acrylic resins, acetal resins, polycarbonate resins, and fibrous plastics.

More specifically, polyolefin resin films such as polyethylene (PE), biaxially stretched polypropylene (OPP); polyester resin films such as polyethylene terephthalate, polyethylene naphthalate (PEN), polylactic acid (PLA); Polyethylene resin film such as nylon 6, poly-p-xylylene adipamide (MXD6 nylon); polycarbonate resin film; polyacrylic nitrile resin film; polyimide resin film; these multilayers (eg, nylon 6 / MXD6 / Nylon 6, nylon 6 / polyethylene-vinyl alcohol copolymer / nylon 6), a mixture; and the like are used. Among them, those having mechanical strength and dimensional stability are preferable.
The thickness of the plastic film is preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less, and further preferably 10 μm or more and 50 μm or less.

The first base material may be a gas barrier base material, for example, a plastic base material having an inorganic vapor deposition layer such as aluminum, silica, or alumina; a plastic base material having an organic layer such as polyvinyl alcohol; and the like.
Commercially available products of a plastic substrate having an inorganic vapor deposition layer include, for example, "GL FILM" (manufactured by Toppan Printing Co., Ltd.) in which an inorganic vapor deposition layer such as alumina is laminated on a plastic substrate, and IB-FILM (large). (Made by Nippon Printing Co., Ltd.) and the like. Since aluminum and alumina have solubility in a basic aqueous solution, they can be dissolved in a desorption step described later and only the plastic base material can be recycled.

From the viewpoint of reuse as a recycled base material, the first base material preferably contains a polyolefin resin film such as polyethylene and biaxially stretched polypropylene.

When the first base material is a laminated body, it is preferable that the base materials are laminated via an adhesive layer. The method for forming the adhesive layer is not limited, and a known adhesive can be used to form the adhesive layer by a known method.
The first base material may be a plastic base material coated with or kneaded with additives such as an antistatic agent, an antifogging agent, and an ultraviolet protection agent, or the surface of the base material may be corona-treated or kneaded. Those treated with low temperature plasma can also be used.
In particular, a plastic film having an antifogging property in which an antifogging agent is applied or kneaded on a polypropylene base material or the like has high hydrophilicity of the base material itself, which is advantageous in desorption.

<Print layer>
The printing layer in the present invention is a layer provided in contact with the primer layer on the side opposite to the first base material of the primer layer, and is a layer for decoration, imparting aesthetics, contents, expiration date, manufacturer or seller. It is a clear layer for the purpose of protecting the layer forming an arbitrary print pattern and / or the layer forming a print pattern and giving a design property such as gloss for the purpose of displaying a solid print. Including layers. The printing layer can be provided, for example, between the primer layer and the adhesive layer, and may be provided on the entire surface or a part of the primer layer.
The printing layer can be formed by using a conventionally known pigment or dye, if necessary, and may be formed by using a printing ink containing the pigment or dye, and the forming method is not particularly limited. The print layer may be formed of a single layer or a plurality of layers.
The thickness of the printing layer is preferably 0.1 μm or more and 100 μm or less, more preferably 0.1 μm or more and 10 μm or less, and further preferably 1 μm or more and 5 μm or less.

Examples of the printing ink for forming the printing layer include printing inks containing a medium such as a pigment, a binder resin, a solvent, or water. The binder resin contains a resin (B) having a Mw of 60% or more after being immersed in a 1% by mass sodium hydroxide aqueous solution at 60 ° C. for 12 hours (Mw before immersion is 100%). When the printing ink contains the resin (B), it is possible to prevent the printing layer from being dissolved or finely dispersed in the basic aqueous solution, and the printing layer can be easily recovered. For example, fiber materials such as nitrocellulose and cellulose acetate propionate, chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer, polyester, acrylic, styrene, rosin, polyurethane and acrylic urethane, polyamide. A system, a polybutylal system, a cyclized rubber system, a chloride rubber system, or a binder in which they are appropriately used can be used. Among them, polyamide resin, cellulose resin, polyurethane resin, acrylic resin, rosin resin, styrene resin, and vinyl chloride resin are suitable for ensuring the physical properties of the coating film of the printing layer. Further, it is also preferable to use a dibasic acid-modified resin of rosin, which is a rosin-based resin, a styrene maleic acid copolymer resin, and an acrylic resin containing acrylic acid and methacrylic acid in combination. The hydrophilicity of the plastic is improved, and the compatibility with the alkaline aqueous solution is improved, which is advantageous for the desorption property.

[Pigment]
The packaging material containing the printing layer used in the present invention is cut into 2 cm × 2 cm and immersed in 15 g of a 2 mass% sodium hydroxide aqueous solution at 70 ° C. for 2 hours in the visible light region (400 to 760 nm) of the aqueous solution. ) The transmittance at the maximum absorption wavelength is preferably 75% or more. A major factor in lowering the transmittance is that the ink pigment contained in the printing layer elutes into the sodium hydroxide aqueous solution. Recycled packaging materials are generally colored and are often used for applications where coloring is not a problem. However, if an uncolored recycled base material is obtained, the range of applications will be expanded. It is expected. It is meaningful to satisfy the regulation of the transmittance, which is an index of whether or not the recycled base material is colored.
In order for the pigment to satisfy the regulation of the transmittance, it is necessary that the pigment has alkali resistance. The alkali resistance of pigments can be roughly estimated from the pigment skeleton and structure. It can be said that those derived from dyes that dissolve in an alkaline aqueous solution and those that decompose in an alkaline aqueous solution do not have alkali resistance.
Further, even if the pigment itself has alkali resistance, the auxiliary component contained in the pigment may lower the transmittance, which is also not preferable in the application in which coloring is a problem.
For example, as an alkali-resistant pigment, an inorganic pigment, P.I. B. 15, P.I. Y. 83 and the like can be mentioned.

The method of applying the printing ink is not particularly limited, and the printing ink can be applied by a method such as a gravure coating method, a flexographic coating method, a roll coating method, a bar coating method, a die coating method, a curtain coating method, a spin coating method, or an inkjet method. .. The printed layer can be formed by leaving it as it is or, if necessary, by blowing air, heating, drying under reduced pressure, irradiating with ultraviolet rays, or the like.

<Second base material>
The packaging material of the present invention has a form in which the printing layer is located on the uppermost side of the packaging material when the first base material is on the lower side, but if necessary, a protective layer or the like is provided on the upper side of the printing layer. It may be provided. Further, the second base material may be present on the upper side of the print layer.
The second base material may be, for example, the base material mentioned in the above-mentioned first base material or a sealant base material, and may be a laminated body in which these are laminated. The second base material is preferably a sealant base material and contains polyolefin. The second base material may have a vapor-deposited film of silica, alumina, or the like.
Examples of the sealant base material include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE) and other polyethylene, acid-modified polyethylene, unstretched polypropylene (CPP), and acid-modified polypropylene. Examples thereof include copolymerized polypropylene, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene- (meth) acrylic acid copolymer, and ionomer.
From the viewpoint of recyclability, the second base material is the first base material low-density polyethylene, polyethylene such as linear low-density polyethylene or high-density polyethylene, acid-modified polyethylene, unstretched polypropylene, acid-modified polypropylene, and copolymerization. Polyethylene and other polyolefins are preferred.
From the viewpoint of retort resistance, polypropylene is preferable, and from the viewpoint of heat sealability, unstretched polypropylene is preferable.

The thickness of the second base material is not particularly limited, and is preferably 10 μm or more and 150 μm or less, and more preferably 20 μm or more and 70 μm or less in consideration of processability to the packaging container or heat sealability. By providing the second base material with irregularities having a height difference of about several μm, slipperiness and tearability of the packaging material can be imparted.
The method of laminating the second base material is not particularly limited, and for example, the printed surface of the laminated film having the first base material, the primer layer and the printing layer and the second base material are bonded to each other by using a laminating adhesive. A method of laminating the resin; a method of melting the resin constituting the second base material, extruding the resin onto the printing layer, and cooling and solidifying the resin; and the like can be mentioned.

The following is an example of the structure of the packaging material of the present invention, but the present invention is not limited thereto. As described above, the first base material and the second base material may be a laminate in which a plurality of base materials are laminated.
-First base material / primer layer / printing layer-first base material (laminate) / primer layer / printing layer-first base material / primer layer / printing layer / adhesive layer / second base material -First base material / primer layer / printing layer / adhesive layer / second base material (laminate)

<Packaging container>
The packaging material of the present invention can be used alone by being processed into a bag shape, a tubular shape, or the like, but can be used as a packaging container in combination with other packaging materials.
Since at least a part of the packaging container is made of the packaging material, a packaging container in which the first base material mainly used as a printing base material can be recycled can be obtained from the packaging material portion. Be done.
The type and use of the packaging material of the present invention and the packaging container are not particularly limited, but can be suitably used for, for example, food containers, detergent containers, cosmetic containers, pharmaceutical containers, and the like. The shape of the packaging container is not limited, and it can be molded into a shape according to the contents, and is preferably used for a pouch or the like.

<Recycled base material manufacturing method>
The method for producing a recycled base material of the present invention includes at least a first base material, a primer layer for desorbing the first base material, and a printing layer in this order, and the primer layer is used as a binder resin at 60 ° C. Contains the resin (A) having a Mw of 70% by mass or less after being immersed in the 1% by mass sodium hydroxide aqueous solution for 12 hours (Mw before immersion is 100% by mass), and is in contact with the first base material. A packaging material provided with the primer layer and a printing layer provided on the side opposite to the first base material of the primer layer, or a packaging container formed of the packaging material. The step of immersing in a basic aqueous solution is included.

Since the object of the present invention is to obtain the first base material after desorption as a recycled base material / recycled base material, it is preferable to remove as much primer layer as possible from the first base material. is there. Specifically, it is preferable that at least 50% by mass or more of the 100% by mass of the primer layer is desorbed in the area and film thickness direction. It is more preferable that 60% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more are desorbed.

The basic compound used in the basic aqueous solution is not particularly limited, and is, for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) ₂ ), ammonia, barium hydroxide (Ba (Ba). OH) ₂ ) and sodium carbonate (Na ₂ CO ₃ ) are preferably used, but are not limited thereto. More preferably, it is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide.
The basic aqueous solution preferably contains a basic compound in an amount of 0.5 to 20% by mass, more preferably 1 to 15% by mass, and particularly preferably 3 to 15% by mass, based on the total amount of the basic aqueous solution. When the concentration is within the above range, the basic aqueous solution can retain sufficient basicity to exfoliate the primer layer by dissolution or swelling to desorb the first base material.

The basic aqueous solution permeates from the end portion of the packaging material or the packaging container, contacts the primer layer, dissolves or swells, and separates the first base material from the primer layer. Therefore, in order to efficiently proceed with the desorption step, it is preferable that the packaging material or the packaging container is in a state where the primer layer is exposed on the cross section when the packaging material or the packaging container is cut or crushed and immersed in a basic aqueous solution. In such a case, the first base material layer can be desorbed in a shorter time.

The temperature of the basic aqueous solution when the packaging material is immersed is preferably 25 to 120 ° C, more preferably 30 to 120 ° C, and particularly preferably 30 to 80 ° C. The immersion time in the basic aqueous solution is preferably 1 minute to 24 hours, more preferably 1 minute to 12 hours, and preferably 1 minute to 6 hours. The amount of the basic aqueous solution used is preferably 1 to 1,000,000 times the mass of the packaging material, and it is preferable to stir or circulate the basic aqueous solution in order to improve the desorption efficiency. The rotation speed is preferably 80 to 250 rpm, more preferably 80 to 200 rpm.

A recycled base material can be obtained through a step of peeling the primer layer together with the printing layer from the packaging material, removing and recovering the first base material, and then washing and drying the first base material with water. The removal rate of the print layer on the surface of the first base material is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more, based on the area of the print layer before desorption.

Therefore, according to the present invention, the step of immersing the packaging material or the packaging container in the basic aqueous solution, the step of dissolving or peeling the primer layer from the packaging material or the packaging container to remove the first base material, the first step. A recycled base material of the first base material can be obtained by going through a step of recovering the base material and a step of washing and drying the first base material with water. Further, the obtained recycled base material can be processed into pellets by an extruder or the like and reused as a recycled resin.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, parts and% in the present invention represent parts by mass and% by mass.

(Molecular weight and molecular weight distribution)
The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were measured by GPC (gel permeation chromatography) and determined as converted molecular weights using polystyrene as a standard substance. The measurement conditions are shown below.
GPC device: Showa Denko Shodex GPC-104
Column: The following columns were connected in series and used.
Showa Denko Shodex LF-404 2 pieces Showa Denko Shodex LF-G
Detector: RI (Differential Refractometer)
Measurement conditions: Column temperature 40 ° C
Eluent: tetrahydrofuran Flow rate: 0.3 mL / min

(Acid value)
In the following, the acid value was measured according to the method described in JIS K0070 (1992).

(Mw change rate after mixing with NaOH aqueous solution)
A sample obtained by mixing a resin solution and a 1 wt% sodium hydroxide aqueous solution at a mass ratio of 1/1 was heated in an oven at 60 ° C. for 12 hours, diluted with tetrahydrofuran, filtered, and then the molecular weight was measured by GPC. The Mw change rate of the sample was calculated when the Mw of the resin was 100%.

<Manufacturing of resin for primer composition>
[Synthesis Example 1] (Polyurethane resin P1)
PC (3-methyl-1,5-pentanediol and 1,6-hexanediol) while introducing nitrogen gas in a reactor equipped with a reflux cooling tube, a dropping funnel, a gas introduction tube, a stirrer, and a thermometer. 142.4 parts of a polycondensate having a molar ratio of dimethyl carbonate and 9/1/10, a polycarbonate polyol having a number average molecular weight of 2,000, and PPG (a polyether having a number average molecular weight of 2,000 consisting of polyethylene glycol). 14.2 parts of polyol), DMPA (2,2-dimethylolpropanoic acid), 28.7 parts, 101.3 parts of IPDI (isophorone diisocyanate), 200 parts of NPAC (normal propyl acetate) were charged, and the temperature was 90 ° C. for 5 hours. The reaction was carried out to obtain a urethane prepolymer solution having an isocyanate group at the terminal.
Next, a mixture of 13.4 parts of AEA (2- (2-aminoethylamino) ethanol) and 350 parts of IPA (isopropyl alcohol) was added dropwise at room temperature over 60 minutes, and then reacted at 70 ° C. for 3 hours. To obtain a polyurethane resin solution.
NPAC was added to the obtained polyurethane resin solution to adjust the solid content, and the polyurethane resin P1 having a solid content concentration of 30%, a mass average molecular weight of 31,000, Mw / Mn = 3.5, and an acid value of 40.0 mgKOH / g. Solution was obtained.

[Synthetic Examples 2-7, Comparative Synthesis Example 1] (Polyurethane Resins P2 to P7, PP1)
Solutions of polyurethane resins P2 to P7 and PP1 were obtained by the same method as in Synthesis Example 1 except that the raw materials and the amount charged shown in Table 1 were used.

The abbreviations in Table 1 are shown below.
-PC: Polycondensate having a molar ratio of 3-methyl-1,5-pentanediol, 1,6-hexanediol and dimethyl carbonate of 9/1/10, a polycarbonate polyol having a number average molecular weight of 2,000-PMPA : Polyester polyol having a number average molecular weight of 2,000 consisting of a polycondensate of 3-methyl-1,5-pentanediol and adipic acid ・ PPA: A polycondensate of propylene glycol and adipic acid having a number average molecular weight of 2, 000 polyester polyols ・ PPG: polyether polyols with a number average molecular weight of 2,000 consisting of polyethylene glycol ・ DMPA: 2,2-dimethylolpropanoic acid ・ BD: 1,4-butanediol ・ IPDI: isophorone diisocyanate ・ NPAC: Normal propyl acetate ・ AEA: 2- (2-aminoethylamino) ethanol ・ IPA: isopropyl alcohol In addition, the above synthesis examples 2 to 7 and comparative synthesis example 1 have Mw / Mn and mass average molecular weight shown in Table 1. As described above, the synthesis conditions such as the dropping amount, dropping speed, temperature control and stirring speed were adjusted.

<Composition for forming a primer layer>
[Production Example 1] (Primer composition S1)
87 parts of polyurethane resin P1 solution, 5 parts of EA (ethyl acetate), 5 parts of IPA, and 3 parts of silica particles (P-73 manufactured by Mizusawa Chemical Co., Ltd .: hydrophilic silica particles having an average particle diameter of 3.8 μm) are stirred and mixed using a disper. Then, the primer composition S1 was obtained.

[Production Examples 2 to 12, Comparative Production Examples 1 to 2] (Primer Compositions S2 to S12, SS1 to SS2)
Primer compositions S2 to S12 and SS1 to SS2 were obtained by the same method as in Production Example 1 except that the raw materials and blending ratios shown in Table 2 were used.

The abbreviations in Table 2 are shown below. -P8 solution: Nitrocellulose resin solution (nitrocellulose solid content 30% solution with nitrogen content 11.5% by mass and mass average molecular weight 30,000) Mw change rate: 69%
-P9 solution: Nitrocellulose resin (same as P8) / Alkid resin (Hutakid 133-60 manufactured by Hitachi Chemical Co., Ltd.) (mixed solution with solid content weight ratio of 70:30, mass average molecular weight 20000, solid content 30% by weight toluene solution) Mw change rate: 65%
-PP2 solution: Styrene-acrylic copolymer resin with a weight average molecular weight of 40,000 and an acid value of 60 mgKOH / g (solid content 30% solution) Mw change rate: 95%
-PP4 solution: Rosin-maleic acid resin solution (rosin-maleic acid modified resin solution with solid content concentration of 30% and acid value of 200 mgKOH / g) Mw change rate: 85%
-Silica particles: P-73 manufactured by Mizusawa Chemical Co., Ltd. (hydrophilic silica particles with an average particle diameter of 3.8 μm)
-Hydrophilic agent A: Glycerin mono 12-hydroxystearate

<Ink manufacturing>
[Ink Production Example 1] (Printing Ink R1)
20 parts of PP1 solution, 5 parts of PP3 solution, 10 parts of indigo pigment, 10 parts of ethyl acetate, and 10 parts of isopropanol were mixed and stirred, and dispersed treatment was performed for 20 minutes using a sand mill as a bead mill. Then, 25 parts of the PP1 solution, 10 parts of ethyl acetate, and 10 parts of isopropanol were mixed and stirred to obtain printing ink R1.

[Ink Production Examples 2 to 7] (Printing Ink R2 to 8)
Printing inks R2 to 8 were obtained by the same method as in Ink Production Example 1 except that the raw materials and blending ratios shown in Table 3 were used.

The abbreviations in Table 3 are shown below.
-PP3 solution: Vinyl chloride-vinyl acetate copolymer resin solution (Solvine TAO manufactured by Nissin Chemical Co., Ltd .: Solid content 30% by mass ethyl acetate solution-Indigo pigment: CI Pigment Blue 15
-Yellow pigment: C.I. I. Pigment Yellow 83
-Red pigment: C.I. I. Pigment Red 57: 1

<Manufacturing of packaging materials>
[Example 1 (1)] (Front printed matter L1 (1))
The primer composition S1 and the printing ink R1 were each diluted with a mixed solvent of EA / IPA (mass ratio 70/30) at 25 ° C. of Zahn Cup # 3 (manufactured by Rigo Co., Ltd.) for 15 seconds.
The diluted primer composition S1 and printing ink R1 were printed on PET (corona-treated polyethylene terephthalate substrate, thickness 12 μm) in this order using a gravure printing machine equipped with a gravure plate having a plate depth of 30 μm, and the temperature was 50 ° C. The printed matter L1 (1), which is composed of the first base material layer (PET) / primer layer (S1) / printed layer (R1), was obtained.

[Examples 2 (1) to 20 (1), Comparative Examples 1 (1) to 4 (1)] (Front printed matter L2 (1) to L20 (1), LL2 (1) to LL4 (1))
By the same method as that of the printed matter L1 (1) except that the primer composition and the printing ink shown in Table 4 were used, the printed matter L2 (1) to L20 (1) and the printed matter LL2 (1) to LL4 (1). ) Was obtained.

[Comparative Example 1 (1)] (Front printed matter LL1 (1))
The printing ink R1 was diluted with a mixed solvent of EA / IPA (mass ratio 70/30) at 25 ° C. of Zahn Cup # 3 (manufactured by Rigo Co., Ltd.) for 15 seconds.
The diluted printing ink R1 was printed on PET (corona-treated polyethylene terephthalate substrate, thickness 12 μm) using a gravure printing machine equipped with a gravure plate having a plate depth of 30 μm, dried at 50 ° C., and first. A printed matter LL1 (1), which is composed of a base material layer (PET) / a printed layer (R1), was obtained.

[Example 1 (2)] (laminated laminate L1 (2))
The primer composition S1 and the printing ink R1 were each diluted with a mixed solvent of EA / IPA (mass ratio 70/30) at 25 ° C. of Zahn Cup # 3 (manufactured by Rigo Co., Ltd.) for 15 seconds.
The primer composition S1 and the printing ink R1 were printed on OPP (corona-treated stretched polypropylene substrate film thickness 20 μm) in this order using a gravure printing machine equipped with a gravure plate having a plate depth of 30 μm, and dried at 50 ° C. Then, a laminate having the composition of the first base material layer (OPP) / primer layer (S1) / printing layer (R1) was obtained.
Next, an adhesive A (polyester urethane adhesive "TM250HV / CAT-RT86L-60" manufactured by Toyo Morton Co., Ltd.) was applied onto the printed layer of the obtained laminate using a dry laminating machine, and the amount applied after drying was 2 g / After coating and drying to m ² , it is bonded to CPP (non-stretched polypropylene base material, thickness 30 μm) to form a first base material layer (OPP) / primer layer (S1) / printing layer (R1) /. A laminated laminate L1 (2) having an adhesive layer / a second base material layer (CPP) was obtained.

[Comparative Example 1 (2)] (Laminated Laminated Body LL1 (2))
The printing ink R1 was diluted with a mixed solvent of EA / IPA (mass ratio 70/30) at 25 ° C. of Zahn Cup # 3 (manufactured by Rigo Co., Ltd.) for 15 seconds.
Printing ink R1 was printed on OPP (corona-treated stretched polypropylene base material, thickness 20 μm) using a gravure printing machine equipped with a gravure plate having a plate depth of 30 μm, dried at 50 ° C., and the first base material. A laminate having a layer (OPP) / printed layer (R1) configuration was obtained.
Next, an adhesive A (polyester urethane adhesive "TM250HV / CAT-RT86L-60" manufactured by Toyo Morton Co., Ltd.) was applied onto the printed layer of the obtained laminate using a dry laminating machine, and the amount applied after drying was 2 g / After coating and drying to m ² , it is bonded to CPP (non-stretched polypropylene base material, thickness 30 μm) to form a first base material layer (OPP) / printing layer (R1) / adhesive layer / second. LL1 (2), which is a laminated laminate having the composition of the base material layer (CPP) of the above, was obtained.

[Examples 2 (2) to 20 (2), Comparative Examples 2 (2) to 4 (2)] (laminated laminates L2 (2) to L20 (2), LL2 (2) to LL4 (2))
Laminated laminates L2 (2) to L20 (2) and LL2 (2) to LL4 (2) by the same method as the laminated laminate L1 (2) except that the primer composition and printing ink shown in Table 4 were used. ) Was obtained.

<Evaluation of packaging materials>
The following evaluation was performed on the obtained packaging material. The results are shown in Table 4.

<Evaluation of detachability in printed matter>
The obtained printed matter is cut into 2 cm × 2 cm, immersed in 50 g of a 2% sodium hydroxide (NaOH) aqueous solution, stirred at a liquid temperature of 50 ° C. and a rotation speed of 150 rpm, washed with water and dried, and then a PET substrate. The peelability of the printed layer from the above was evaluated.
5 (excellent): The printed layer is peeled from the 100% PET film within 20 minutes of stirring.
4 (Good): The printed layer peeled off from the 100% PET film within 1 hour over 20 minutes of stirring.
3 (Yes): The print layer is peeled from the PET film by 80% or more and 100% or less within 12 hours over 1 hour of stirring.
2 (impossible): 20% or more and less than 80% of the print layer is peeled from the PET film after 12 hours of stirring. 1 (inferior): Less than 20% of the printed layer peeled off from the PET film after 12 hours of stirring.
3, 4 and 5 are ranges in which there is no practical problem.

<Evaluation of detachability in laminated laminate>
The obtained laminated laminate was cut into 2 cm × 2 cm, immersed in 50 g of a 2% sodium hydroxide (NaOH) aqueous solution, stirred at 50 ° C., washed with water and dried, and then the pattern layer was peeled off from the OPP film. Was evaluated.
5 (excellent): The printing layer, adhesive layer, etc. are peeled off from the 100% OPP film within 20 minutes of stirring.
4 (Good): The printing layer, adhesive layer, etc. were peeled off from the 100% OPP film within 1 hour over 20 minutes of stirring.
3 (Yes): The printing layer, adhesive layer, etc. are peeled off from the OPP film by 80% or more and 100% or less within 12 hours over 1 hour of stirring.
2 (impossible): 20% or more and less than 80% of the printing layer, adhesive layer, etc. are peeled from the OPP film in 12 hours of stirring.
1 (inferior): Less than 20% of the printing layer, adhesive layer, etc. peeled off from the OPP film in 12 hours of stirring. 3, 4 and 5 are ranges in which there is no practical problem.

<Evaluation of base material adhesiveness (tape adhesiveness) in printed matter>
With respect to the obtained printed matter, a cellophane tape (12 mm width) manufactured by Nichiban Co., Ltd. was attached on the printing layer, the tape was slowly peeled off, and the degree of peeling of the ink film when the tape was rapidly peeled off from the middle was evaluated.
5 (excellent): The ink film does not peel off at all even if it is peeled off rapidly.
4 (Good): The ink film in an area of less than 25% of the rapidly peeled part is peeled off.
3 (Yes): The ink film in an area of 25% or more and less than 75% of the rapidly peeled portion is peeled off.
2 (impossible): The ink film in an area of 75% or more of the rapidly peeled part is peeled off, or a part of the ink film is peeled off in the slowly peeled part.
1 (inferior): The ink film on the slowly peeled part is completely peeled off.
3, 4 and 5 are ranges in which there is no practical problem.

(Transmittance)
The obtained laminated laminate was cut into a size of 2 cm × 2 cm, immersed in 15 g of a 2% NaOH aqueous solution, and stirred at a liquid temperature of 70 ° C. and a rotation speed of 150 rpm for 2 hours. The solution portion of the sample was taken out and placed in a measurement cell, and the transmittance at the maximum absorption wavelength in the visible light region (400 to 760 nm) was measured with an ultraviolet visible spectrophotometer (V-560 manufactured by JASCO Corporation).
The higher the transmittance, the more transparent the pellets can be obtained when the film is regenerated into a pellet-shaped recycled base material, and the more the coloration of the NaOH aqueous solution is suppressed, so that the NaOH aqueous solution can be easily reused.

From the above evaluation results, if the packaging material is made of the primer composition of the present invention and the printing ink, the ink and the like can be easily desorbed from the base material in the alkaline aqueous solution in the packaging material having the front printing structure and the laminated structure. It was shown that a good quality recycled base material can be obtained.

Claims (7)

A packaging material provided with at least a first base material, a primer layer for desorbing the first base material and recycling the first base material, and a printing layer in this order.
The primer composition used for forming the primer layer has a weight average molecular weight (Mw) of 70% or less (Mw before immersion) after being immersed in a 1% by mass sodium hydroxide aqueous solution at 60 ° C. for 12 hours as a binder resin. A packaging material containing a resin (A) that becomes (100%). A packaging material provided with at least a first base material, a primer layer for desorbing the first base material and recycling the first base material, a printing layer, and a second base material in this order. ,
The primer composition used for forming the primer layer has a weight average molecular weight (Mw) of 70% or less (Mw before immersion) after being immersed in a 1% by mass sodium hydroxide aqueous solution at 60 ° C. for 12 hours as a binder resin. A packaging material containing a resin (A) that becomes (100%). The printing ink used to form the printing layer has a weight average molecular weight (Mw) of 60% or more after being immersed in a 1% by mass sodium hydroxide aqueous solution at 60 ° C. for 12 hours as a binder resin (Mw before immersion is 100). The packaging material according to claim 1 or 2, which contains a resin (B) to be (%). The primer composition contains 60% by mass or more of the resin (A) in the total amount of the resin in the primer composition, and
The packaging material according to any one of claims 1 to 3, wherein the printing ink contains 60% by mass or more of the resin (B) in the total amount of the resin components in the printing ink. A 2 cm x 2 cm piece of packaging material is immersed in 15 g of a 2 mass% sodium hydroxide aqueous solution at 70 ° C. for 2 hours, and the transmittance of the aqueous solution in the visible light region (400 to 760 nm) at the maximum absorption wavelength is 75. The packaging material according to any one of claims 1 to 4, wherein the content is% or more. The packaging material according to any one of claims 1 to 5, wherein the primer composition contains a polyurethane resin having an acid value of 15 to 70 mgKOH / g. A method for producing a recycled base material, which comprises a step of immersing the packaging material according to any one of claims 1 to 6 in a basic aqueous solution.
A method for producing a recycled base material, wherein the basic aqueous solution contains 0.5 to 10% by mass of the total basic aqueous solution, and the water temperature of the basic aqueous solution at the time of immersion is 30 to 120 ° C.