JP2023075977A - Method for separating and recovering laminate - Google Patents

Abstract

To provide a method for separating and recovering a laminate that has an excellent releasing property of a printed layer and an adhesive layer, suppresses reattachment of a component detached from a detachable layer, and is suitable for plastic recycling, and a method for producing a high-quality molding material obtained by thermoforming a recovered polyolefin base material.SOLUTION: There is provided a method for separating and recovering a laminate. The method comprises a step of detaching a detachable layer by immersing a laminate comprising at least a polyolefin base layer and a release layer in contact with the polyolefin base layer into a release liquid containing a nonionic surfactant having a value of HLB (Hydrophilic-Lipophilic Balance) of 7 or more to recover a polyolefin base material.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a method for separating and recovering a laminate comprising at least a polyolefin substrate layer and a release layer in contact with the polyolefin substrate layer.

In recent years, packages, plastic bottles, and other plastic products made from plastic film have been discarded or dumped into the ocean as garbage, causing environmental pollution problems. These plastic products are decomposed in seawater to become submicron-sized fragments (microplastics) and float in seawater. When these microplastics are ingested by marine organisms such as fish, they are concentrated in the bodies of the organisms, and there is concern that they may affect the health of seabirds and humans who consume these marine organisms as food.

Examples of the plastic products include multi-layered food packaging packages using plastic films. In such food packaging packages, polyester base material, nylon base material (NY), polypropylene base material ( PP), polyethylene substrates (PE), etc., are used. These film substrates are printed with printing ink, bonded to other film substrates or hot-melt resin substrates via an adhesive or the like, cut and heat-sealed to form a package. However, such a multi-layered food packaging package has a problem that material recycling cannot be performed as it is because a plurality of incompatible different materials are mixed.

Regarding the material recycling of such multilayer packaging materials, for example, in Patent Document 1, surface printing is performed by treating a laminate including a release layer containing a polyurethane resin having a predetermined acid value with an alkaline aqueous solution. Techniques for detaching a printed layer from a laminate having a multi-layer structure as well as a structure have been disclosed.
Patent Document 2 discloses a technique of removing an adhesive layer from a laminate having a multilayer structure by treating a laminate including a polyester polyol-based adhesive having a predetermined acid value with an alkaline aqueous solution. .

Patent Document 3 discloses a technique of removing ink from a film using a washing solution that has a basic pH and contains a cationic or anionic surfactant.

JP 2020-090627 A Japanese Patent Application Laid-Open No. 2020-084130 Japanese Patent Publication No. 2015-520684

However, in the desorption step described in Patent Documents 1 and 2, if the treatment amount of the packaging material with respect to the alkaline aqueous solution is increased in order to improve productivity, the detachability decreases, and furthermore, the detached printed layer and the A problem arises in that the adhesive layer is finely dispersed and re-adheres to the polyolefin substrate. A molding material obtained by recycling such a base material causes deterioration in appearance and physical properties due to coloring.
Further, if the stripping liquid contains the cationic or anionic surfactant described in Patent Document 3, bubbles are generated in the step of immersing the sheet in the stripping liquid and stripping the stripping layer. The generated bubbles entrap the components (especially highly lipophilic components) detached from the detachment layer to form micelles and float on the liquid surface of the detached liquid. On the other hand, since the polyolefin base material with a small specific gravity also floats on the liquid surface of the desorption liquid, the components desorbed from the desorption layer and the polyolefin base material are densely packed on the liquid surface of the desorption liquid, and further the polyolefin base material There is a problem that the re-adhesion to the surface is deteriorated. Note that "re-adhesion" means that the detached layer such as the printed layer or the adhesive layer that has detached from the base material is finely dispersed by stirring and re-adheres to the base material. It causes coloration and deteriorates the properties of recycled materials.
Accordingly, an object of the present invention is to provide a method for separating and recovering a laminate suitable for plastic recycling, in which the printed layer and the adhesive layer are excellent in releasability, and the reattachment of components detached from the detachable layer is suppressed. to provide. Another object of the present invention is to provide a method for producing a high-quality molding material obtained by heat-molding the recovered polyolefin base material.

A method for separating and recovering a laminate according to one aspect of the present invention comprises a laminate comprising at least a polyolefin base layer and a release layer in contact with the polyolefin base layer, and containing a nonionic surfactant having an HLB value of 7 or more. It is characterized by including a step of immersing the polyolefin substrate in a desorption liquid to desorb the desorption layer and recovering the polyolefin base material.

The method for separating and recovering a laminate according to one aspect of the present invention is characterized in that the desorbing liquid is a basic aqueous solution containing a basic compound.

A method for separating and recovering a laminate according to an aspect of the present invention is characterized in that the surfactant contains an alkylene oxide adduct.

The method for separating and recovering a laminate according to an aspect of the present invention is characterized in that the surfactant has an HLB value of 7-20.

A method for separating and recovering a laminate according to an aspect of the present invention is characterized in that the content of the surfactant is 0.1 to 10% by mass based on the mass of the desorbing liquid.

A method for separating and recovering a laminate according to an aspect of the present invention is characterized in that the desorption layer is a layer containing a compound having an acidic group.

A method for separating and recovering a laminate according to an aspect of the present invention is characterized in that the detachable layer includes at least one layer selected from the group consisting of a primer layer, a printed layer and an adhesive layer.

A method for separating and recovering a molding material according to an aspect of the present invention is characterized by melt-kneading the polyolefin base material recovered by the above method for separating and recovering a laminate.

A method for separating and recovering a molded article according to an aspect of the present invention is characterized by heating and molding the molding material obtained by the above-described manufacturing method.

To provide a method for separating and recovering a laminate suitable for plastic recycling, in which the releasability of a printed layer and an adhesive layer is excellent, and reattachment of components detached from the detachable layer is suppressed, according to the present invention. can be done. Further, it is possible to provide a method for producing a high-quality molding material obtained by heat-molding the recovered polyolefin base material.

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 does not exceed the gist thereof. Not limited.

The present invention comprises a step of immersing at least a polyolefin base layer and a laminate having a release layer in contact with the polyolefin base layer in a desorption liquid to remove the release layer and recover the polyolefin base layer. A method for separating and recovering a laminate, comprising: a desorbing liquid containing a nonionic surfactant having an HLB value of 7 or more.

By containing a nonionic surfactant with an HLB value of 7 or more, the stripping liquid promotes stripping of the stripping layer such as the printing layer and the adhesive layer, and further finely dispersed stripping components ( For example, it is possible to suppress redeposition of the detached base material of the highly lipophilic component derived from the detachment layer. As a result, even when a large amount of packaging material is processed, the printed layer and adhesive layer can be easily removed from the packaging material, and the base material without color or stain can be recovered and recycled as a high-quality recycled material.
In addition, since nonionic surfactants suppress the generation of foam compared to anionic or cationic surfactants, both detachability and reattachability can be achieved.

<Separation and recovery method>
In the method for separating and recovering a laminate of the present invention, a laminate comprising at least a polyolefin base layer and a release layer in contact with the polyolefin base layer is separated from the desorbed product containing a nonionic surfactant having an HLB value of 7 or more. It includes a step of recovering the polyolefin substrate layer by immersing it in a liquid to detach the detachable layer.
In the present invention, the term "detachment" means that the base material is detached from the laminate by dissolving or swelling the detachment layer with the detachment liquid, and (1) the detachment layer is dissolved. (2) Even if the detachable layer does not dissolve, it is peeled off due to neutralization, swelling, etc., and the substrate is detached.

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

<Desorption liquid>
The detachment liquid may contain a nonionic surfactant having an HLB value of 7 or more and swell and dissolve the detachment layer. can be selected. Examples of such desorption liquids include water, basic aqueous solutions, acidic aqueous solutions, and fluorine-based solvents. An aqueous solution is preferable from the viewpoint of environmental protection and maintenance of the properties of the recycled material using the recovered polyolefin base material. These desorbed liquids may be heated.
From the viewpoint of removing a urethane-based adhesive layer commonly used in packaging materials, the removing liquid is more preferably a basic aqueous solution containing a basic compound.

[Nonionic surfactant with HLB value of 7 or more]
A nonionic surfactant having an HLB value of 7 or more mainly plays a role of improving the detachability of the detachable layer. This is because the action of the nonionic surfactant with an HLB value of 7 or more facilitates the penetration of the stripping liquid into the stripping layer such as the primer layer, the printing layer, and the adhesive layer, thereby promoting the strippability. It is considered to be for In addition, it is thought that reattachment of finely dispersed printed layers and the like is prevented by adsorption of the desorbed component and the nonionic surfactant having an HLB value of 7 or more on the surface of the base material.
In addition, when the amount of the laminate relative to the desorbing liquid is increased in the separation and recovery, the laminate and the separated base material tend to curl with the desorbed ink pieces involved, and even if they are immersed in the desorbing liquid. However, it is difficult to cleanly remove ink fragments and the like caught in the curl. However, when the desorption liquid contains a nonionic surfactant having an HLB value of 7 or more, the surfactant is adsorbed on the surface of the laminate and the separated base material, thereby suppressing curling. As a result, detachability is improved and reattachment can be suppressed.

The HLB value is an index value related to the affinity of a surfactant for water and oil, and is divided equally by setting the HLB value of a substance having no hydrophilic group to 0 and the HLB value of a substance having only a hydrophilic group to 20. be. The concept of HLB was proposed by William Griffin of the Atlas Powder Company in 1949, and several calculation methods have been proposed.
Formula) HLB = 20 x [(molecular weight of hydrophilic group contained in surfactant)/(molecular weight of surfactant)]
Hydrophilic groups contained in surfactants include, for example, hydroxyl groups and ethyleneoxy groups.

It is important that the HLB value of the nonionic surfactant in the present invention is 7 or more. When the HLB is 7 or more, excellent deinking properties and reattaching properties are exhibited as described above. The HLB value of the nonionic surfactant is preferably 8 or higher, more preferably 10 or higher. The HLB value of the surfactant is preferably 20 or less, more preferably 19 or less, and even more preferably 17 or less. When the HLB value is 20 or less, it is preferable because it is excellent in suppressing foaming.

The nonionic surfactant is not particularly limited as long as it has an HLB value of 7 or more, but is preferably an alkylene oxide adduct to which alkylene oxide (hereinafter also referred to as AO) is added. More preferred are compounds obtained by adding alkylene oxide to alcohols having active hydrogen, compounds obtained by adding alkylene oxide to amines, or compounds obtained by adding alkylene oxide to fatty acids. The addition may be either random addition or block addition. Also, the carbon number of the alkylene oxide is preferably 2 to 4 carbon atoms.
More preferred nonionic surfactants are alcohol-based nonionic surfactants obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an alcohol.

[Alcohol-based nonionic surfactant]
Examples of alcohol-based nonionic surfactants include alkylene oxide adducts of primary or secondary alcohols having a total carbon number of 8 to 24, or alkylene oxide adducts of alkylphenols having a total carbon number of 8 to 12. be done. The primary or secondary alcohol having a total carbon number of 8 to 24 may be either saturated or unsaturated.
Examples of primary or secondary alcohols having a total carbon number of 8 to 24 include lauryl alcohol, stearyl alcohol, oleyl alcohol, dodecyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, and myristyl alcohol.
Examples of the alkylene oxide to be added to the alcohol include ethylene oxide, propylene oxide and butylene oxide, and ethylene oxide is preferably essential. The number of moles of alkylene oxide to be added is preferably 1 to 100 mol, more preferably 2 to 50 mol, per 1 mol of alcohol or alkylphenol. It is preferable that it is in the above range because it is particularly excellent in releasability.

[Fatty acid-based nonionic surfactant]
The structure of the fatty acid-based nonionic surfactant is not particularly limited. Examples include oils and fats composed of esters of higher fatty acids and glycerin, and alkylene oxide adducts of mixtures of the above oils and fats and 2 to 10 polyhydric alcohols. The higher fatty acid having 10 to 24 total carbon atoms may be either saturated or unsaturated.
Examples of the higher fatty acids having 10 to 24 carbon atoms in total include saturated higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid; palmitoleic acid, oleic acid, elaidic acid, linoleic acid, unsaturated higher fatty acids such as linolenic acid, erucic acid and ricinoleic acid; Dihydric to decahydric polyhydric alcohols include ethylene glycol, propylene glycol, glycerin, polyglycerin, sorbitol, sorbitan, sucrose and the like. The type and number of moles of alkylene oxide to be added are the same as those described in the section [Alcoholic Nonionic Surfactant] above.

[Amine-based nonionic surfactant]
Amine-based nonionic surfactants include AO adducts of saturated or unsaturated primary or secondary amines having a total carbon number of 8 to 36. Amines include 2-ethylhexylamine, di-2-ethylhexylamine, laurylamine, dilaurylamine, tetradecylamine, ditetradecylamine, hexadecylamine, dihexadecylamine, stearylamine, distearylamine, oleylamine, di and oleylamine. Moreover, the kind of AO and the number of added moles are the same as above.

These nonionic surfactants having an HLB value of 7 or more may be used singly or in combination of two or more. The content of the nonionic surfactant having an HLB value of 7 or more in the desorbed liquid is preferably in the range of 0.1 to 10% by mass, more preferably 0.3, based on the mass of the desorbed liquid. It is in the range of ~5% by mass. When it is 0.1% by mass or more, it is preferable because the deinking property and reattachment property are excellent, and when it is 10% by mass or less, it is preferable from the viewpoint of suppressing foaming.

[Other ingredients]
The stripping liquid may contain components other than the nonionic surfactant having an HLB value of 7 or more within a range that does not impair the effects of the present invention. Examples of such other components include, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, and defoaming agents. can be used as

(Anionic surfactant)
The anionic surfactant is preferably a non-soap surfactant, such as a sulfonate anionic surfactant, a sulfate ester anionic surfactant, a carboxylic acid anionic surfactant, a phosphate ester anionic surfactant. active agents.

[Sulfonic acid-based anionic surfactant]
Examples of the sulfonic acid anionic surfactant include alkylsulfonic acid, alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, alkyldiphenyletherdisulfonic acid, alkylmethyltaurine, sulfosuccinic acid diester, alkylene oxide adduct of sulfonic acid, and these. salt of Specific examples include hexanesulfonic acid, octanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, dinitrobenzenesulfonic acid, and lauryldodecylphenyl ether disulfone. An acid or the like can be used.

[Sulfuric Acid Ester-Based Anionic Surfactant]
Examples of the above-mentioned sulfate ester-based anionic surfactants include sulfate esters (alkyl ether sulfate esters), alkylene oxide adducts of sulfate esters, and salts thereof. Specific examples include lauryl sulfuric acid, myristyl sulfuric acid, polyoxyethylene lauryl ether sulfuric acid, and the like.

[Carboxylic acid-based anionic surfactant]
Examples of the carboxylic acid-based anionic surfactants include alkylcarboxylic acids, alkylbenzenecarboxylic acids, alkylene oxide adducts of carboxylic acids, and salts thereof. Specific examples include lauric acid, myristic acid, palmitic acid, stearic acid, polyoxyethylene lauryl ether acetic acid, and polyoxyethylene tridecyl ether acetic acid.

[Phosphate Ester Anionic Surfactant]
Examples of the phosphate ester-based anionic surfactants include phosphate esters (alkyl ether phosphate esters), alkylene oxide adducts of phosphate esters, and salts thereof. Specific examples include octyl phosphate, lauryl phosphate, tridecyl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, polyoxyethylene octyl ether phosphate, and polyoxyethylene lauryl ether phosphate. etc. can be used.

The anionic surfactant preferably has an alkyl group of 2 to 24 carbon atoms or an alkenyl group of 2 to 24 carbon atoms, more preferably an alkyl group of 8 to 18 carbon atoms. The alkyl group or alkenyl group may be linear or branched.
When the anionic surfactant is an alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide, with ethylene oxide being preferred. The number of moles of alkylene oxide to be added is preferably 1 to 12 mol, more preferably 1 to 8 mol, per 1 mol of alcohol or alkylphenol. It is preferable that it is in the above range because it is particularly excellent in releasability.

Examples of salts constituting the above-mentioned anionic surfactants include metal salts of sodium, potassium, magnesium, calcium and the like. These salts may be used individually by 1 type, and may be used in combination of 2 or more type.
Among them, the anionic surfactant is preferably a sulfonate type or a phosphate type, more preferably an alkyl sulfonate or a polyoxyalkylene alkyl ether sulfonate, from the viewpoint of desorption and reattachment properties. , polyoxyalkylene alkyl ether phosphate, and the like.

(Cationic surfactant)
Examples of cationic surfactants include alkylamine salts and quaternary ammonium salts. Specifically, stearylamine acetate, trimethylyac ammonium chloride, trimethyl tallow ammonium chloride, dimethyldioleyl ammonium chloride, methyloleyl diethanol chloride, tetramethylammonium chloride, laurylpyridinium chloride, laurylpyridinium bromide, laurylpyridinium disulfate, cetylpyridinium bromide. , 4-alkylmercaptopyridine, poly(vinylpyridine)-dodecyl bromide, dodecylbenzyltriethylammonium chloride and the like can be used.

(Amphoteric surfactant)
Examples of amphoteric surfactants include betaine lauryldimethylaminoacetate, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, betaine coconut fatty acid amidopropyldimethylaminoacetate, polyoctylpolyaminoethylglycine, and imidazoline. derivatives.

These other surfactants may be used alone or in combination of two or more. The content of the surfactant in the detached liquid is preferably in the range of 0.1 to 10% by mass, more preferably 0.3, based on the total weight of the detached liquid. It is in the range of ~5% by mass. When it is 0.1% by mass or more, it is preferable because the deinking property and reattachment property are excellent, and when it is 10% by mass or less, it is preferable from the viewpoint of suppressing foaming.

(Antifoaming agent)
Defoamers generally have extremely high lipophilicity and an HLB value in the range of 1-3. When used in combination with a nonionic surfactant having an HLB value of 7 or more, good defoaming properties can be exhibited without reducing detachability and reattachment properties, and foaming due to the surfactant can be suppressed. can be done.
Examples of the antifoaming agent include silicone compounds and non-silicone compounds.

(Silicone-based compound)
Examples of the silicone compound include emulsion type, self-emulsifying type, oil type, oil compound type, and solvent type.
Emulsion type is a silicone antifoaming agent made into an O / W type emulsion by emulsifying a silicone oil compound with an active agent. Examples include “FC2913” and “SILFOAM SE47” manufactured by Wacker Silicone, and “BYK-015” and “BYK-1640” manufactured by BYK-Chemie Japan.
The self-emulsifying type is a silicone-based antifoaming agent containing 100% active ingredients that becomes an emulsion state by diluting and mixing with water. , "SILFOAM SD670" and "SILFOAM SD850" manufactured by Asahi Kasei Wacker Silicone.
The oil type is a 100% silicone oil defoaming agent that does not contain solvents or additives. AK12500” and “BYK-1770” manufactured by BYK-Chemie Japan.
The oil compound type is a silicone antifoaming agent in which silica particles are blended with silicone oil. "PULPSIL22274VP", BYK-Chemie Japan's "BYK-017" and "BYK-018" are mentioned.
The solvent type is a silicone antifoaming agent obtained by dissolving silicone oil in a solvent. and "BYK-025".

(Non-silicone compound)
Examples of the non-silicone compounds include fatty acid ester compounds, urea resin compounds, paraffin compounds, polyoxyalkylene glycol compounds, acrylic ester copolymers, ester polymers, ether polymers, and amide polymers. mineral oil emulsified type, polysiloxane adduct, fluorine compound, vinyl polymer, acetylene alcohol, acrylic polymer, special vinyl polymer, ethylene glycol, higher alcohol (octyl alcohol, cyclohexanol, etc.).

An antifoaming agent may be used individually by 1 type, and may use 2 or more types together. The content of the antifoaming agent in the stripped liquid is preferably in the range of 0.01 to 5% by mass, more preferably in the range of 0.03 to 3% by mass, based on the mass of the stripped liquid. . When it is 0.01% by mass or more, it is excellent in suppressing foaming, and when it is 5% by mass or less, it is excellent in deinking property and reattachment property.
The antifoaming agent is preferably an emulsion-type silicone compound, from the viewpoint that it has good alkali resistance and does not easily reduce the deinking property and reattachment property when combined with the nonionic surfactant having an HLB of 7 or more. It is at least one selected from the group consisting of self-emulsifying silicone compounds and non-silicone compounds.

[Basic compound]
As described above, the stripping solution used in the present invention is preferably a basic aqueous solution containing a basic compound from the viewpoint of stripping the urethane-based adhesive layer that is commonly used in packaging materials.
The basic compound is not particularly limited, and examples thereof include sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH) ₂ ), ammonia, barium hydroxide (Ba(OH) ₂ ), Sodium carbonate _{( Na2CO3} ) is preferably used. More preferably, it is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide.
The content of the basic compound in the basic aqueous solution is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 3 to 15% by mass, based on the mass of the basic aqueous solution. Range. Within the above range, the basic aqueous solution retains sufficient basicity to dissolve or swell the detachable layer, which will be described later, to desorb and recover the polyolefin base material.

The stripping liquid permeates from the end portion of the laminate, contacts the stripping layer, dissolves or swells, and separates the polyolefin base material from the stripping layer. Therefore, in order to proceed with the desorption step efficiently, it is preferable that the laminate is cut or pulverized and the desorption layer is exposed in the cross section when immersed in the desorption liquid. In such a case, the substrate layer can be removed in a shorter time.

The temperature of the desorption liquid when the laminate is immersed is preferably 25 to 120.degree. C., more preferably 30 to 120.degree. C., and particularly preferably 30 to 80.degree. The immersion time in the desorbing 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 desorption liquid used is preferably 5 to 100,000 times, more preferably 10 to 10,000 times the mass of the laminate. is preferably stirred or circulated. The rotation speed is preferably 80-5000 rpm, more preferably 80-4000 rpm.

After removing the detachable layer from the laminate and recovering the polyolefin base material, the recycled base material can be obtained through the steps of washing and drying the obtained polyolefin base material. The removal rate of the desorption layer on the surface of the substrate is preferably 70% or more, more preferably 80% or more, particularly preferably 90% or more, relative to the area of the desorption layer before desorption.
Further, the obtained recycled base material can be processed into pellets by an extruder or the like and reused as a recycled resin.

<Laminate>
The laminate used in the present invention comprises at least a polyolefin substrate layer and a release layer in contact with the polyolefin substrate layer. The detachment layer in contact with the polyolefin base material is detached by the desorption liquid described above, so that the polyolefin base material can be recovered and recycled.

<Detachment layer>
The stripping layer in the present invention may be a layer that can be stripped from the polyolefin substrate with a known stripping liquid, preferably a layer containing a water-soluble resin or a compound having an acidic group, more preferably an acidic layer. It is a layer containing a compound having a group.
Moreover, since the release layer is a layer in contact with the polyolefin substrate layer, it is preferably at least one layer selected from the group consisting of a primer layer, a printing layer and an adhesive layer. That is, at least one layer selected from the group consisting of a primer layer, a printed layer and an adhesive layer is preferably a layer containing a water-soluble resin or a compound having an acidic group (excluding a water-soluble resin). , more preferably a layer containing a compound having an acidic group. The compound having an acidic group may be a resin or a low-molecular-weight compound. One of these water-soluble resins or compounds having an acidic group may be used alone, or two or more thereof may be used in combination.

At least one layer selected from the group consisting of the primer layer, the printed layer and the adhesive layer is composed of a resin component (hereinafter also referred to as a binder resin) that is a water-soluble resin or a resin having an acidic group. and may contain a binder resin and a low-molecular-weight compound having an acidic group.
Hereinafter, the case where the release layer is a primer layer, a print layer, and an adhesive layer will be described.

[Primer layer]
When the detachable layer is a primer layer, the primer layer is placed in contact with the polyolefin base material and plays a role of detaching the polyolefin base material by dissolution, peeling, or the like with a detachment liquid. The primer layer preferably contains a water-soluble resin or a compound having an acidic group (excluding the water-soluble resin).

(Water-soluble resin)
As the water-soluble resin, any resin that can be swollen or dissolved in water and released from the polyolefin base material may be used. The water may be heated to a temperature of about 25-100°C. Thereby, the primer layer can be removed with water (including warm water).
Such resins can be selected from known resins as long as they do not impair water solubility. polyallylamine resins, water-soluble phenol resins, water-soluble epoxy resins, water-soluble phenoxy resins, water-soluble urea resins, water-soluble melamine resins, polyvinyl alcohol resins, and modified products of these resins. These can be used singly or in combination of two or more. Among them, polyvinyl alcohol (PVA) resin is preferably used from the viewpoint of availability and releasability.
When the water-soluble resin has film-forming properties, the water-soluble resin may be used as the binder resin constituting the primer layer.

Polyvinyl alcohol resins include, in addition to unmodified polyvinyl alcohol, modified polyvinyl alcohol obtained by copolymerizing various monomers during the production of vinyl ester resins and saponifying them, and various types of polyvinyl alcohol obtained by post-modification of unmodified polyvinyl alcohol. Various post-modified polyvinyl alcohols into which functional groups have been introduced may be used. Also, modified polyvinyl alcohol may be post-modified. These modification|denaturation can be performed in the range which does not impair the water-solubility of polyvinyl alcohol resin.
These resins may be used individually by 1 type, and may use 2 or more types together.

Preferable polyvinyl alcohol resins include resins containing structural units having primary hydroxyl groups in side chains and ethylene-modified polyvinyl alcohol resins. Among them, a polyvinyl alcohol resin containing a structural unit having a primary hydroxyl group in a side chain is preferable because of its excellent melt moldability and excellent water solubility. The number of primary hydroxyl groups in these structural units is generally 1-5, preferably 1-2, more preferably 1. Moreover, it is preferable to have a secondary hydroxyl group in addition to the primary hydroxyl group.

The degree of saponification (measured according to JIS K 6726) of the polyvinyl alcohol resin used in the present invention is usually 60 to 100 mol%. In addition, the preferred range of saponification degree varies depending on the modified species. 0.5%. The saponification degree of the side chain 1,2-diol structural unit-containing modified polyvinyl alcohol resin is usually 60 to 99.9 mol%, preferably 65 to 99.8 mol%, more preferably 70 to 99.5 mol%. be. If the degree of saponification is too low, the water solubility tends to decrease. The saponification degree of the ethylene-modified polyvinyl alcohol resin modified with a small amount of ethylene is usually 60 mol % or more, preferably 70 to 99.5 mol %, particularly preferably 75 to 99.0 mol %.
When the degree of saponification is within the above range, the water solubility is excellent and the releasability is improved, which is preferable. Moreover, it is preferable because it is excellent in coatability when forming a primer layer.

The average degree of polymerization of the polyvinyl alcohol resin (measured according to JIS K 6726) is generally 100-3000, preferably 150-2000, more preferably 180-1000, particularly preferably 200-800.

(Compound having an acidic group)
As the compound having an acidic group, a resin having an acidic group or a low-molecular-weight compound having an acidic group may be used. As a result, the primer layer can be removed with the basic aqueous solution described above.

Examples of resins having an acidic group include cellulose resins, urethane resins, polyamide resins, vinyl chloride/vinyl acetate copolymers, ketone resins, polyester resins, and (meth)acrylic resins. Examples of the acidic group include a carboxy group, a phosphoric acid group, a sulfo group, a sulfino group, etc., or an ester or salt thereof.
As the resin having an acidic group, a rosin-modified resin having an acid value such as maleated rosin and fumarated rosin can be used.
In addition, as the resin having an acidic group, a polymerizable monomer having a carboxy group such as itaconic acid, maleic acid, fumaric acid, and cinnamic acid; a polymerizable monomer that is an acid anhydride such as itaconic anhydride and maleic anhydride; Polymerizable monomers having a sulfonic acid group such as styrene; Polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide; Polymerizable monomers having an acidic group such as styrene-(meth)acrylic Resins, radical copolymers such as styrene-(anhydride) maleic acid resins and terpene-(anhydride) maleic acid resins, and acid-modified polyolefin resins can be used.
These may be used individually by 1 type, and may use 2 or more types together.

A low-molecular-weight compound having an acidic group refers to a compound having no molecular weight distribution and having a molecular weight of 1,000 or less. Examples of such compounds include saturated fatty acids such as lauric acid, myristic acid, palmitic acid, margaric acid, and stearic acid; hydroxy acids such as lactic acid, malic acid, and citric acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, and cinnamic acid; oxalic acid, Dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, and maleic acid; tricarboxylic acids such as aconitic acid; oxocarboxylic acids such as pyruvic acid and oxaloacetic acid; carboxylic acid derivatives such as amino acids and nitrocarboxylic acids and acid anhydrides such as trimellitic anhydride and pyromellitic anhydride.
A low-molecular-weight compound having an acidic group can be used in combination with a resin having an acidic group or a known binder resin constituting a known primer layer to form a primer layer.

From the viewpoint of suitability for recoating, the primer layer preferably contains a compound having an acidic group. In addition, from the viewpoint of printability, it is preferable to include a urethane resin having an acidic group, an acrylic resin having an acidic group, and a rosin-modified resin.

[Urethane resin having an acidic group]
The urethane resin having an acidic group is not particularly limited, and for example, a urethane resin obtained by reacting a polyol having an acidic group with a polyisocyanate, or a urethane resin obtained by reacting a polyol with a polyisocyanate, the hydroxyl groups in the urethane resin are acid-modified. and a resin obtained by acid-modifying the amino group in a urethane urea resin obtained by reacting an isocyanate group in a urethane resin obtained by reacting a polyol and a polyisocyanate with a polyamine.
As the urethane resin having an acidic group, a resin obtained by reacting a polyol containing a hydroxy acid and a polyisocyanate may be used. By using a hydroxy acid as a polyol, an acid value derived from a carboxy group can be imparted to the urethane resin, and the releasability can be improved. Further, when the urethane resin having an acidic group has an isocyanate group, a part of the isocyanate group may be reacted with a polyamine to introduce a urea bond to form a urethane urea.

《Polyol》
Polyol is a general term for compounds having at least two hydroxyl groups in one molecule. The number average molecular weight of the polyol is preferably 500-10,000, more preferably 1,000-5,000. The number average molecular weight is calculated from the hydroxyl value of the polyol, and the hydroxyl value refers to the value measured according to 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 polyolefin substrate is improved. When the number average molecular weight is 10,000 or less, the blocking resistance to polyolefin substrates is excellent.

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. Furthermore, the polyol may also include other dimer diols, hydrogenated dimer diols, castor oil-modified polyols, and the like.
That is, the urethane resin preferably contains at least one polyol-derived structural unit selected from the group consisting of polyester polyols, polyether polyols, and polycarbonate polyols. More preferably, it contains a structural unit derived from a polyester polyol, since alkali hydrolysis of the ester bond site of the polyester polyol improves the releasability.
The content of the polyol-derived structural unit is preferably 10 to 75% by mass, more preferably 15 to 70% by mass, still more preferably 20 to 65% by mass, based on the total amount of the urethane resin. The content of polyester polyol-derived structural units is preferably 5% by mass or more, more preferably 30% by mass or more, still more preferably 60% by mass or more, and particularly preferably 80% by mass, based on the total amount of polyol-derived structural units. That's it.

《Hydroxy acid》
The polyols may contain hydroxy acids. The hydroxy acid refers to a compound having both a hydroxyl group, which is an active hydrogen group, and an acidic functional group in one molecule. The acidic functional group refers to a functional group that can be neutralized with potassium hydroxide when measuring the acid value, and specifically includes a carboxy group, a sulfonic acid group, and the like, preferably a carboxy group. As such hydroxy acids, dimethylolalkanoic acids such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid are preferably used.

《Polyisocyanate》
The polyisocyanate is not particularly limited and can be selected from conventionally known polyisocyanates. Preferably, it contains diisocyanates or triisocyanates, more preferably aromatic, aliphatic or cycloaliphatic diisocyanates. These may be used alone or in combination of two or more.

《Polyamine》
Polyamines for forming urethane urea are not particularly limited, and diamine compounds are preferred. In addition, a diamine having a hydroxyl group may be used in that a hydroxyl group can be introduced into the urethane resin.

The acid value of the urethane resin having acidic groups is preferably 15 mgKOH/g or more, more preferably 15 to 70 mgKOH/g, still more preferably 20 to 50 mgKOH/g. When it is 15 mgKOH/g or more, the detachability with a desorbing liquid is favorable, and when it is 70 mgKOH/g or less, it is preferable because substrate adhesion and retort resistance are improved. The hydroxyl value of the urethane resin is preferably 1-35 mgKOH/g, more preferably 10-30 mgKOH/g. When it is 1 mgKOH/g or more, it is preferable because the detachability by the detachment liquid is improved, and when it is 35 mgKOH/g or less, it is preferable because the adhesion to the substrate is improved.

The urethane resin having an acidic group preferably has a weight average molecular weight of 10,000 to 100,000, more preferably 15,000 to 70,000, still 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 releasability, the drying property of the primer composition, and the suitability for retort resistance are excellent. In addition, the smaller the molecular weight distribution, that is, the sharper the molecular weight distribution, the more uniformly the dissolution and peeling action by the desorption liquid occurs, and the desorption property of the polyolefin base material is improved. The molecular weight distribution is more preferably 5 or less, still more preferably 4 or less. Also, the molecular weight distribution is preferably 1.5 or more, more preferably 1.2 or more.
In the present specification, Mw, Mn and molecular weight distribution (Mw/Mn) are polystyrene equivalent values determined by gel permeation chromatography (GPC).

A urethane resin having an acidic group 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. Within the above range, the adhesiveness to the substrate is excellent.

The number of urethane bonds in the polyurethane resin having an acidic group is preferably 1-3 mmol/g, more preferably 1.5-2 mmol/g. Also, the number of urea bonds is preferably 0 to 3 mmol/g, more preferably 0.2 to 1 mmol/g. Also, the total number of urethane bonds and urea bonds is preferably 1 to 6 mmol/g, more preferably 1.7 to 3 mmol/g.
By setting the number of urethane bonds and the number of urea bonds within the relevant ranges, the releasability and substrate adhesion are improved.

[Acrylic resin having an acidic group]
The acrylic resin having an acidic group includes, for example, a polymer obtained by polymerizing a monomer containing a (meth)acrylic monomer having an acidic group such as (meth)acrylic acid and maleic acid; a (meth)acrylic monomer having a hydroxyl group or a glycidyl group. After polymerizing a monomer containing, the functional group is modified to introduce a carboxyl group (for example, a maleic anhydride-modified resin);
The acid value of the acrylic resin having acidic groups is preferably 50 mgKOH/g or more, more preferably 100 mgKOH/g or more.

[Rosin modified resin]
A rosin-modified resin is a resin prepared using rosin as one of raw materials. Rosin contains a mixture of resin acids such as abietic acid, parastric acid, isopimaric acid, levopimaric acid, etc. These resin acids contain hydrophilic and chemically active carboxyl groups, some of which have conjugated double bonds. Some are prepared. Therefore, polyhydric alcohols and polybasic acids are combined for condensation polymerization, phenolic condensate resol is added to the benzene ring contained in the rosin skeleton, and dienophile maleic anhydride and maleic acid undergo Diels-Alder reaction. Various rosin-modified resins have been prepared by adding a maleic acid or maleic anhydride skeleton by allowing the Various types of such rosin-modified resins are commercially available, and it is also possible to obtain and use them.

Examples of rosin-modified resins include maleated rosin, fumarated rosin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, rosin-modified phenolic resin, rosin-modified alkyd resin, and rosin-modified polyester resin. In the present invention, any rosin-modified resin may be used, but among these, at least one selected from the group consisting of maleic acid, maleic anhydride, fumaric acid and fumaric anhydride in its structure Those containing a portion to be used are preferably used. A resin that "contains a site derived from at least one selected from the group consisting of maleic acid, maleic anhydride, fumaric acid and fumaric anhydride in its structure" means maleic acid and maleic anhydride as part of raw materials. It is prepared using at least one selected from the group consisting of acid, fumaric acid and fumaric anhydride, for example, rosin-modified malein obtained by condensation polymerization of maleic acid or fumaric acid as part of the polybasic acid Acid resins, rosin-modified fumaric acid resins, maleic rosins and fumaric rosins having a structure obtained by adding maleic acid, maleic anhydride, fumaric acid, or fumaric anhydride as a dienophile by Diels-Alder reaction, fumaric rosins, and functional groups contained therein. It means a resin or the like obtained by further polymerizing another chemical species using a group.

The acid value of the rosin-modified resin is preferably 10-400 mgKOH/g, more preferably 100-300 mgKOH/g.

(Other ingredients)
The primer layer may contain a resin other than a water-soluble resin or a compound having an acidic group.
Examples of such resins include cellulose resins, polyamide resins, vinyl chloride resins such as vinyl chloride-vinyl acetate copolymer resins or vinyl chloride-acrylic copolymer resins, ethylene-vinyl acetate copolymer resins, and vinyl acetate resins. , acrylic resin, styrene resin, dammar resin, styrene-acrylic copolymer resin, polyester resin, alkyd resin, terpene resin, phenol-modified terpene resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, polyacetal resin, petroleum resin, and These modified resins can be mentioned. These resins may be used individually by 1 type, and may use 2 or more types together.
Among them, the primer layer preferably contains at least one resin selected from the group consisting of cellulose resins, vinyl chloride resins, rosin resins, and acrylic resins. More preferably, vinyl chloride resin or acrylic resin is included.
The mass ratio of the urethane resin having an acidic group to the other resin (urethane resin having an acidic group:other resin) is preferably 95:5 to 50:50. Within the above range, when the printed layer is peeled off together with the primer layer in a basic aqueous solution, the printed layer is peeled off in the form of a thin film, which facilitates recovery, which is preferable.

The primer layer may contain an extender. Examples of extender pigments include metal oxides such as silica, barium sulfate, kaolin, clay, calcium carbonate, magnesium carbonate, zinc oxide and zirconium oxide. Among them, silica is preferred, and hydrophilic silica is more preferred.
The average particle size of the extender is preferably 0.5-10 μm, more preferably 1-8 μm. The content of the extender pigment in the primer layer is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass. When the average particle size and the content of the extender are within the above ranges, the wettability of the printed layer is improved and the image quality is improved.

The primer layer may be a layer in which the above-described urethane resin having an acidic group is crosslinked with a curing agent. By introducing a crosslinked structure into the primer layer, it is possible to suppress permeation and bleeding of the print layer formed on the primer layer, thereby exhibiting excellent image quality.
Curing agents include, for example, polyisocyanates. The polyisocyanate is not particularly limited and can be selected from conventionally known polyisocyanates, such as aliphatic polyisocyanates and araliphatic polyisocyanates. These may be used alone or in combination of two or more.

The primer layer may further contain known additives. Known additives include, for example, dispersants, wetting agents, adhesion aids, leveling agents, antifoaming agents, antistatic agents, viscosity modifiers, metal chelates, trapping agents, antiblocking agents, wax components other than the above, A silane coupling agent is mentioned.

The thickness of the primer layer is preferably 0.5 to 3.0 μm, more preferably 0.6 to 2.0 μm, still more preferably 0.8 to 1.5 μm, and is formed by a known method. be able to.

[Print layer]
The printed layer is a layer that forms an arbitrary printed pattern for the purpose of decoration, imparting aesthetics, content, expiration date, manufacturer's or seller's indication, etc., and includes a solid printed layer.
When the release layer is a printed layer, the printed layer is placed in contact with the polyolefin base material and plays a role of releasing the polyolefin base material by dissolution, peeling, or the like with a desorption liquid. The print layer preferably contains a water-soluble resin or a compound having an acidic group (excluding the water-soluble resin) and a colorant. Moreover, the method for forming the printed layer is not limited, and it can be formed using a known method.
From the viewpoint of suitability for recoating, the print layer preferably contains a compound containing an acidic group. In addition, from the viewpoint of printability, it is preferable to include a urethane resin having an acidic group, an acrylic resin having an acidic group, and a rosin-modified resin.
The water-soluble resin and the compound having an acidic group, the urethane resin having an acidic group, the acrylic resin having an acidic group, and the rosin-modified resin are the same as (water-soluble resin), (acidic group compound), [Urethane resin having acidic group], [Acrylic resin having acidic group] and [Rosin-modified resin] can be cited.

(coloring agent)
The printing layer may be colored or colorless and contains known colorants used in printing inks and paints. Such coloring agents are not particularly limited, and in addition to inorganic pigments, organic pigments, and dyes, metal powders that impart metallic luster, near-infrared absorbing materials, and ultraviolet absorbing materials may be used.
Examples of inorganic pigments include colored pigments such as titanium oxide, red iron oxide, Prussian blue, ultramarine blue, carbon black and graphite; and extender pigments such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide and talc.
As organic pigments, soluble azo pigments, insoluble azo pigments, azo chelate pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments and the like are preferably used.
It should be noted that the above pigments are not limited to these, and those listed in the generic names of the Color Index can be used as appropriate. Among them, when the removing liquid is a basic aqueous solution, a pigment having alkali resistance that does not dissolve in the basic aqueous solution is preferable. Preventing the elution of the pigment facilitates reuse of the aqueous base solution.
The alkali resistance of a pigment is generally estimated based on the skeleton or structure of the pigment. Pigments with alkali resistance include inorganic pigments, C.I. I. Pigment Blue 15, C.I. I. Pigment Yellow 83 can be mentioned.
When the pigment is titanium oxide, the content of titanium oxide in the printed layer is preferably 20-80 mass %, more preferably 30-75 mass %. In addition, when the pigment is an inorganic pigment other than titanium oxide, an extender pigment, or an organic pigment, the content of each of these pigments in the printed layer is preferably 0.5 to 60% by mass, more preferably 10 to 50% by mass. % by mass.

(Other ingredients)
The printed layer may contain a pigment derivative or a resin-type dispersant as a dispersant for the colorant.
The pigment derivative is a compound in which a substituent is introduced into the skeleton of the pigment, and the content of the pigment derivative is preferably 0.01 to 10% by mass, more preferably 0.05 to 6%, based on the mass of the colorant. % by mass, more preferably 0.1 to 4% by mass. When it is 0.01% by mass or more, the removability of the polyolefin base material is excellent, and when it is 10% by mass or less, reattachment of the printed layer can be suppressed.
The resin-type dispersant adsorbs to the colorant to stabilize the dispersion in printing ink or the like, and can be appropriately selected from known resin-type dispersants. The content of the resin-type dispersant is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, and still more preferably 0.1 to 10% by mass, based on the mass of the colorant. . When it is 0.01% by mass or more, the releasability of the polyolefin substrate is excellent, and when it is 30% by mass or less, the water resistance of the printed layer is excellent.

The printed layer may contain a resin other than a water-soluble resin or a compound containing an acidic group.
Examples of such resins include fibrous materials such as nitrocellulose, cellulose acetate and propionate, chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer, polyester, acrylic, urethane resin and acrylic urethane, Polyamide-based, polybutyral-based, cyclized rubber-based, and chlorinated rubber-based resins can be mentioned. These resins may be used individually by 1 type, and may use 2 or more types together.

The thickness of the printed 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 still more preferably 1 μm or more and 5 μm or less.

[Adhesive layer]
When the release layer is an adhesive layer, the adhesive layer is placed in contact with the polyolefin substrate and plays a role of releasing the polyolefin substrate by dissolution, peeling, or the like with a release liquid. The adhesive layer preferably contains a compound having an acidic group (excluding a water-soluble resin). Since the adhesive layer contains a resin having an acidic group or a low-molecular-weight compound having an acidic group, the adhesive layer can be removed using the basic aqueous solution described above.
For the compound having an acidic group, the resin having an acidic group, and the low-molecular-weight compound having an acidic group, the description of (compound having an acidic group) in the section [Primer layer] described above can be used.
Moreover, the method for forming the adhesive layer is not limited, and it can be formed using a known method.

The adhesive layer is a cured product of an adhesive containing a polyester polyol having an acidic group and at least one polyisocyanate selected from the group consisting of aliphatic polyisocyanates and araliphatic polyisocyanates, from the viewpoint of releasability. may be The cured product corresponds to a resin having an acidic group.
Further, the adhesive layer is a cured product of an adhesive containing polyester polyol, at least one polyisocyanate selected from the group consisting of aliphatic polyisocyanate and araliphatic polyisocyanate, and a low-molecular-weight compound having an acidic group. may be

(polyester polyol)
The polyester polyol only needs to have an acidic group, and can be appropriately selected from known polyester polyols. By containing such a polyester polyol, when a basic aqueous solution is used as the removing liquid, the presence of an ester bond having a high affinity with a basic compound improves the removing property, which is preferable. Polyester polyols may be used alone or in combination of two or more.

Polyester polyol is not particularly limited, but polyester polyol obtained by reacting a carboxy group component and a hydroxyl group component; ring-opening of lactones such as polycaprolactone, polyvalerolactone, poly(β-methyl-γ-valerolactone) A polyester polyol obtained by polymerization; is preferably used.
Examples of the carboxy group component include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, phthalic anhydride, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and Examples include dibasic acids such as maleic acid and itaconic anhydride, dialkyl esters thereof, and mixtures thereof.
Examples of the hydroxyl group component include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, butylene glycol, neopentyl glycol, trimethylolpropane, glycerin, 1,6-hexanediol, and 1,4-butanediol. , 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, 1,9-nonanediol, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether Diols such as glycols, polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, polyurethane polyols, or mixtures thereof.
The carboxy group component and the hydroxyl group component may be used in combination of two or more.

The polyester polyol may be a polyester urethane polyol obtained by reacting the hydroxyl groups in the polyol with a polyisocyanate. The presence of urethane bonds in the polyester polyol exhibits excellent heat resistance and adhesiveness.
Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. is mentioned.

Moreover, the polyester polyol may be an acid anhydride-modified product obtained by reacting the hydroxyl groups in the polyol with an acid anhydride. Thereby, a carboxy group, which is an acidic group, can be introduced into the polyester polyol.
Acid anhydrides include, for example, pyromellitic anhydride, mellitic anhydride, trimellitic anhydride, and trimellitic ester anhydride. Examples of trimellitate anhydrides include ethylene glycol bis-anhydro trimellitate and propylene glycol bis-anhydro trimellitate.

The acid value of the polyester polyol is preferably 5.0 mgKOH/g or more, more preferably 10.0 mgKOH/g or more. Moreover, the acid value of the polyester polyol is preferably 100 mgKOH/g or less, more preferably 80 mgKOH/g or less. When the acid value of the polyester polyol is within the above range, the basic aqueous solution permeates and decomposes when the polyester polyol is brought into contact with a desorption liquid, which is a basic aqueous solution, thereby exhibiting better desorption properties.
When the adhesive contains a plurality of polyester polyols, the acid value of the entire polyester polyol can be obtained from the acid value of each polyester polyol and its mass ratio.

The number average molecular weight (Mn) of the polyester polyol is preferably 3,000 to 25,000, more preferably 5,000 to 20,000, particularly preferably 7,000 to 15,000. When the number average molecular weight of the polyester polyol is 3,000 or more, not only coatability but also sufficient retort suitability can be exhibited, and when it is 20,000 or less, not only coatability but also releasability is improved. preferred because

The polyester polyol component may be used in combination with a plurality of polyester polyol components in order to satisfy various physical properties required for the packaging material. Furthermore, a polyester polyol having a number average molecular weight of less than 3,000 may be included in order to improve adhesion to the substrate.
The content of the polyester polyol having a number average molecular weight of less than 3,000 is preferably 0 to 30% by weight, more preferably 0 to 20% by weight, based on the total weight of the polyester polyol. Retort resistance can be maintained as it is 30% by mass or less.

(Other polyols)
The adhesive constituting the adhesive layer may contain polyol other than polyester polyol. Polyols that may be contained other than polyester polyols are not particularly limited, and examples thereof include polycarbonate polyols, polycaprolactone polyols, polyether polyols, polyolefin polyols, acrylic polyols, silicone polyols, castor oil-based polyols, and fluorine-based polyols. .

(polyisocyanate)
The polyisocyanate to be combined with the polyester polyol described above to form the adhesive layer is preferably at least one selected from the group consisting of known aliphatic polyisocyanates and araliphatic polyisocyanates.

Aliphatic polyisocyanates include, for example, acyclic aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, and 1,2-butylene diisocyanate; 1,4-cyclohexane diisocyanate, Alicyclic diisocyanates such as 1,3-cyclohexane diisocyanate and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (hereinafter referred to as isophorone diisocyanate); allophanate type, nurate type, biuret type derived from the above diisocyanates , adduct-type derivatives, or polyisocyanates such as complexes thereof;
The derivative is preferably a nurate type or an adduct type, more preferably an adduct type. As the aliphatic polyisocyanate, a polyisocyanate derived from hexamethylene diisocyanate (hereinafter also referred to as HDI) is preferable because it facilitates ensuring a good balance between detachability and laminate physical properties.

Examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis( 1-isocyanate-1-methylethyl)benzene or mixtures thereof; allophanate type, nurate type, biuret type, adduct type derivatives derived from the above araliphatic diisocyanates, or complexes thereof Polyisocyanate;

(Other polyisocyanates)
The adhesive may contain other polyisocyanates other than the aliphatic polyisocyanate and the araliphatic polyisocyanate within a range that does not impair the effects of the present invention. Examples of such polyisocyanates include aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate; and polyisocyanates such as derivatives of the above diisocyanates and complexes thereof.

The mixing ratio of the polyol and polyisocyanate may be such that the molar ratio (NCO/OH) of the isocyanate groups of the polyisocyanate to the hydroxyl groups in the polyol is 0.3 to 10.0. It is preferably 0.3 to 7.0, more preferably 0.5 to 5.0.

(Other ingredients)
The adhesive layer contains silane coupling agents, phosphorus oxyacids or derivatives thereof, leveling agents, antifoaming agents, reaction accelerators, inorganic fillers (for example, silica, alumina, mica, talc, aluminum flakes, glass flakes, etc.). ), layered inorganic compounds, stabilizers (e.g., antioxidants, heat stabilizers, ultraviolet absorbers, hydrolysis inhibitors), rust inhibitors, thickeners, plasticizers, antistatic agents, lubricants, antiblocking agents, It may contain a coloring agent, a filler, a crystal nucleating agent, a catalyst for adjusting the curing reaction, and the like.

<Polyolefin base material layer>
The laminate used in the present invention has a polyolefin base material layer. Since the polyolefin base material has a small specific gravity and floats on the liquid surface of the desorption liquid, the components desorbed from the desorption layer (especially highly lipophilic components) tend to reattach, but the HLB value is 7 or more. By using a detachment liquid containing an active agent, it is possible to achieve both detachability and reattachability.
Examples of polyolefin substrate layers include plastic substrates such as polyethylene (PE) and biaxially oriented polypropylene (OPP), as well as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene. (HDPE), acid-modified polyethylene, unoriented polypropylene (CPP), acid-modified polypropylene, copolymerized polypropylene.
The thickness of the polyolefin base material layer is not particularly limited, and may be appropriately selected according to the application. It is preferably 5 to 200 μm, more preferably 10 to 150 μm.

<Structure of laminate>
The laminate in the present invention only needs to have a partial structure including at least a polyolefin base layer and a release layer in contact with the polyolefin base layer, and may further have other layers.
The laminate may have a base material layer other than the polyolefin base material. Examples of such substrates include polyester resins, polyamide resins, polystyrene resins, vinyl chloride resins, vinyl acetate resins, ABS resins, acrylic resins, acetal resins, polycarbonate resins, polyvinyl alcohol resins, cellulose plastics, and aluminum foil. , metal deposition layers such as aluminum, and metal oxide deposition layers such as silica and alumina.
The thickness of the aluminum foil is often used in the range of 3 to 50 μm from an economical point of view. In addition, since the aluminum foil, the aluminum vapor deposition layer and the alumina vapor deposition layer are dissolved in the basic aqueous solution and desorbed, they function as a desorption layer and can separate the adjacent polyolefin resin.

Specific examples of the laminate include the following configurations.
(1) A laminate comprising a polyolefin substrate layer and a printed layer in this order, wherein the printed layer is a release layer.
(2) A laminate comprising a polyolefin substrate layer, a primer layer and a printed layer in this order, wherein the primer layer is a release layer.
(3) A laminate comprising a first substrate layer, a printed layer, an adhesive layer and a second substrate layer in this order, wherein at least one of the printed layer and the adhesive layer is removed. A laminate, which is a release layer and a base material in contact with the release layer is a polyolefin base material.
(4) A laminate comprising a first base layer, a primer layer, a printed layer, an adhesive layer and a second base layer in this order, wherein at least one of the primer layer and the adhesive layer A laminate in which a layer is a release layer and a base material in contact with the release layer is a polyolefin base material.
(5) A laminate comprising a first substrate layer, an adhesive layer, and a second substrate layer in this order, wherein the adhesive layer is a release layer, and at least one substrate is a polyolefin group. A laminate that is a material.
(6) A laminate comprising a first substrate layer, a vapor deposition layer, a printed layer, an adhesive layer, and a second substrate layer in this order, wherein at least one of the vapor deposition layer and the adhesive layer A laminate in which a layer is a release layer and a base material in contact with the release layer is a polyolefin base material.

Examples of the laminate structure of the present invention are shown below, but the present invention is not limited thereto. In addition, in the following configuration, the "base material layer" does not have to be a single layer, and may be a laminate in which a plurality of base materials are laminated.
・Polyolefin substrate layer/removable printed layer ・Polyolefin substrate layer/removable primer layer/printed layer ・Polyolefin substrate layer/removable printed layer/removable adhesive layer/polyolefin substrate layer ・Polyolefin substrate layer/ Releasable primer layer/Printed layer/Releasable adhesive layer/Polyolefin substrate layer/Releasable adhesive layer/Printed layer/Releasable adhesive layer/Polyolefin substrate layer/Polyolefin substrate layer/Releasable adhesive layer/Polyolefin group Material layer/Polyolefin base layer/Release primer layer/Printing layer/Release adhesive layer/Vapor deposition layer/Polyolefin base layer

<Method for manufacturing molding material>
A molding material can be produced by melt-kneading the polyolefin base material recovered by the separation and recovery method described above. The method for producing the molding material of the present invention preferably includes steps 1 to 3 below. When the molding material contains a masterbatch, the following step 4 may be further included.
(Step 1) A step of crushing the laminate and immersing it in a desorption liquid to remove the polyolefin base material from the laminate (Step 2) A step of washing the polyolefin base material obtained in Step 1 with water ( Step 3) Step of melt-kneading the polyolefin base material obtained in step 2 to obtain a recycled resin (Step 4) Step of mixing the masterbatch with the recycled resin obtained in step 3

The method of crushing the packaging material in step 1 is not particularly limited, and examples thereof include methods using a jaw crusher, impact crusher, cutter mill, stamp mill, ring mill, roller mill, jet mill, and hammer mill.
Step 2 may further include a drying step as needed. Through step 2, a recycled base material (also referred to as a recycled plastic base material) can be obtained.

In the melt-kneading process in step 3, various additives are added as necessary, and after mixing with a Henschel mixer, tumbler, disper, etc., kneader, roll mill, super mixer, Henschel mixer, Shugi mixer, vertical granulator, high Speed mixer, furmatrix, ball mill, steel mill, sand mill, vibration mill, attritor, batch kneader such as Banbury mixer, twin screw extruder, single screw extruder, rotor type twin screw kneader, etc. Refers to mixing or dispersing. As a result, a recycled resin, which is a resin composition, is obtained. The shape of the recycled resin is not particularly limited, and may be in the form of pellets, powder, granules, or beads. The melt-kneading step preferably uses a twin-screw extruder.

[Master Badge]
The molding material of the present invention can further contain a masterbatch. The masterbatch is not particularly limited as long as it is compatible with the recycled resin, and generally a mixture of a thermoplastic resin such as polyethylene resin or polypropylene resin and a colorant kneaded can be used. The thermoplastic resin contained in the masterbatch may be used alone or in combination of two or more.
The masterbatch in the present invention may contain alkali metal, alkaline earth metal or zinc metallic soap, hydrotalcite, nonionic surfactant, cationic surfactant, anionic surfactant, as long as the effects of the present invention are not impaired. amphoteric surfactants, antistatic agents, flame retardants such as halogen-based, phosphorus-based or metal oxides, lubricants such as ethylenebisalkylamide, antioxidants, ultraviolet absorbers and fillers.

<Molded body>
A molded article can be obtained by heat-molding the molding material obtained by the manufacturing method described above. The thermoforming method is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, and compression molding.
The molding material produced using the polyolefin base material recovered by the separation and recovery method of the present invention is of high quality because the printed layer and the adhesive layer are detached and the reattachment of the detached components is suppressed. It can be used in various fields such as home electric appliances, stationery, automobile parts, toys, sporting goods, medical materials, and building and construction materials.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples. Parts and % in the present invention represent parts by mass and % by mass unless otherwise specified.

<Molecular weight and molecular weight distribution>
Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were measured by GPC (gel permeation chromatography), and were obtained as converted molecular weights using polystyrene as a standard substance. 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 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, hydroxyl value>
Acid value and hydroxyl value were measured according to the method described in JIS K 0070 (1992).

<Production of primer composition and printing ink resin>
[Synthesis Example 1-1] (Polyurethane resin P1)
While introducing nitrogen gas in a reactor equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer, PPA (consisting of a polycondensate of propylene glycol and adipic acid, having a number average molecular weight of 2, 000 polyester polyol) 152.2 parts, PPG (a polyether polyol having a number average molecular weight of 2,000 consisting of polypropylene glycol) 15.2 parts, BD (1,4-butanediol) 13.6 parts, IPDI (isophorone 99.8 parts of diisocyanate) and 200 parts of NPAC (n-propyl acetate) were charged and reacted at 90° C. for 5 hours to obtain a urethane prepolymer solution having terminal isocyanate groups.
Then, a mixture of 19.2 parts of AEA (2-(2-aminoethylamino) ethanol) and 350 parts of IPA (isopropyl alcohol) was added dropwise over 60 minutes at room temperature, followed by reaction 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, resulting in polyurethane resin P1 having a solid content concentration of 30%, a weight average molecular weight of 27,000, Mw/Mn = 3.1, and an acid value of 0.0 mgKOH/g. A solution of

[Synthesis Example 1-2] (Polyurethane Resin P2)
A solution of polyurethane resin P2 was obtained in the same manner as in Synthesis Example 1-1, except that the raw materials and charged amounts shown in Table 1 were used.

[Synthesis Example 1-3] (Polyurethane Resin P3)
108.6 parts of PPA, PEG (consisting of polyethylene glycol, number average molecular weight 2, 000 polyether polyol), 28.3 parts of DMPA (2,2-dimethylolpropanoic acid), 105.7 parts of IPDI, and 200 parts of NPAC, and reacted at 90° C. for 5 hours. , a prepolymer solution having terminal isocyanate groups was obtained.
Then, a mixture of 16.7 parts of AEA and 150 parts of IPA was added dropwise at room temperature over 60 minutes, and then 10.0 parts of 28% aqueous ammonia and 690 parts of ion-exchanged water were gradually added to the resin. was water-solubilized by neutralizing the carboxyl group of
Next, NPAC and IPA were distilled off under reduced pressure to obtain an aqueous solution of polyurethane resin P3 having a solid concentration of 30%, a weight average molecular weight of 32,000, Mw/Mn of 3.3, and an acid value of 39.3 mgKOH/g. However, the acid value in P3 is the value before neutralization.

Abbreviations in Table 1 are shown below.
PPA: a polyester polyol with a number average molecular weight of 2,000 consisting of a polycondensate of propylene glycol and adipic acid PPG: a polyether polyol with a number average molecular weight of 2,000 consisting of polypropylene glycol PEG: a number average molecular weight consisting of polyethylene glycol 2,000 polyether polyols DMPA: 2,2-dimethylolpropanoic acid BD: 1,4-butanediol IPDI: isophorone diisocyanate NPAC: normal propyl acetate AEA: 2-(2-aminoethylamino) ethanol IPA: isopropyl alcohol

[Synthesis Example 1-4] (Acrylic resin P4)
70 parts of styrene, 23 parts of acrylic acid, 7 parts of 2-hydroxyethyl methacrylate, EA while introducing nitrogen gas in a reactor equipped with a reflux condenser, a dropping funnel, a gas inlet tube, a stirrer, and a thermometer. (Ethyl acetate) 40 parts and IPA 40 parts were charged, the temperature was raised to 90° C., 1 part of AIBN (azobisisobutyronitrile) and 15 parts of EA were added to carry out a polymerization reaction for 4 hours, and further AIBN was added to 0.1. and 3 parts of EA were added and allowed to react for 2 hours to obtain an acrylic resin solution.
EA is added to the obtained acrylic resin solution to adjust the solid content, and the acrylic resin P4 having a solid content concentration of 30%, a weight average molecular weight of 27,000, an acid value of 179.1 mgKOH / g, and a hydroxyl value of 30.2 mgKOH / g. A solution was obtained.

<Composition for Primer Layer Formation>
[Production Example 1-1] (Primer Composition S1)
87 parts of the polyurethane resin P2 solution, 5 parts of EA, 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) were stirred and mixed using a disper to form a primer composition. I got the product S1.

[Production Examples 1-2 to 6] (Primer Compositions S2 to S6)
Primer compositions S2 to S6 were obtained in the same manner as in Production Example 1-1, except that the raw materials and compounding ratios shown in Table 2 were changed.

Abbreviations in Table 2 are shown below.
Maleated rosin solution: Malquied No. manufactured by Arakawa Chemical Co., Ltd. 32 (acid value 130 mg KOH / g, solid content concentration 100% product) diluted with ethyl acetate to a solid content concentration of 30% PVA solution: Kuraray Co., Ltd. Kuraray Poval 5-88 (saponification degree 86.5 to 89.0% ) 15% solids concentration aqueous solution curing agent solution: HDI-TMP adduct (Asahi Kasei Duranate P301-75E, solids concentration 75%) diluted with ethyl acetate to a solids concentration of 50%

<Production of printing ink>
[Production Example 2-1] (Printing ink R1)
Indigo pigment P. B. 10 parts of 15 (CI Pigment Blue 15), 0.2 parts of Synergist 2100 (BYK-SYNERGIST 2100 manufactured by BYK-Chemie Japan), 0.5 parts of BYK-142 (DISPERBYK-142 manufactured by BYK-Chemie Japan), 24.3 parts of polyurethane resin P1 solution, 5 parts of PVC (vinyl chloride-vinyl acetate copolymer resin (Solbin TAO manufactured by Nisshin Chemical Co., Ltd., solid content 30%, EA solution)), 10 parts of EA, and 10 parts of IPA were mixed and stirred. , using a sand mill as a bead mill, dispersion treatment was performed for 20 minutes. Thereafter, 20 parts of the polyurethane resin P1 solution, 10 parts of EA, and 10 parts of IPA were mixed and stirred to obtain printing ink R1. Table 3 shows the total blending amount of the blending during dispersion and the post-blending.

[Production Examples 2-2 to 4] (Printing Inks R2 to 4)
Printing Inks R2 to R4 were obtained in the same manner as in Ink Production Example 2-1, except that the raw materials and blending ratios shown in Table 3 were used. The blending amount in Table 3 is the sum of the blending at the time of dispersion and the post-blending. In Production Examples 2-3 and 4, 29.3 parts of the resin solution was used at the time of dispersion, and 20 parts of the resin solution was used at the time of post-blending.

Abbreviations in Table 3 are shown below.
P. B. 15: C.I. I. Pigment Blue 15
Synergist 2100: BYK-SYNERGIST 2100 made by Big Chemie Japan
BYK-142: DISPERBYK-142 made by Big Chemie Japan
Maleated rosin solution: Malquied No. manufactured by Arakawa Chemical Co., Ltd. 32 (acid value 130 mg KOH / g, solid content concentration 100% product) diluted with ethyl acetate to a solid content concentration of 30% PVC solution: Vinyl chloride - vinyl acetate copolymer resin (manufactured by Nisshin Chemical Solbin TAO, solid content 30%, EA solution)
EA: ethyl acetate IPA: isopropyl alcohol

<Production of polyol used for adhesive>
[Synthesis Example 2-1] (polyester polyol B1)
124 parts of ethylene glycol, 212 parts of neopentyl glycol, 368 parts of 1,6-hexanediol, 645 parts of isophthalic acid and adipine were placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank and nitrogen gas inlet tube. 36 parts of acid and 265 parts of sebacic acid were charged, and the temperature was raised to 250° C. while stirring under a nitrogen stream to carry out an esterification reaction. After a predetermined amount of water was distilled and the reaction was continued until the acid value became 5 or less, the pressure was gradually reduced, and the deglycol reaction was performed at 1 mmHg or less for 5 hours to obtain a polyester polyol. After that, 35 parts of isophorone diisocyanate was gradually added and reacted at 150° C. for about 2 hours to obtain a polyester polyurethane polyol. 12.0 parts of ethylene glycol bis-anhydrotrimellitate was added to 100 parts of this polyester polyurethane polyol, reacted at 180° C. for about 2 hours, and then diluted with ethyl acetate until the solid content concentration reached 50%. A solution of partially acid-modified polyester polyol B1 having an average molecular weight of 9,000 and an acid value of 30.3 mgKOH/g was obtained.

[Synthesis Example 2-2] (polyester polyol B2)
58 parts of ethylene glycol, 412 parts of diethylene glycol, 343 parts of neopentyl glycol, 517 parts of isophthalic acid, and 393 parts of adipic acid are charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank and nitrogen gas inlet tube. , the temperature was raised to 250° C. with stirring under a nitrogen stream to carry out an esterification reaction. After a predetermined amount of water was distilled and the reaction was continued until the acid value became 5 or less, the pressure was gradually reduced, and the deglycol reaction was performed at 1 mmHg or less for 5 hours to obtain a polyester polyol. 4.0 parts of trimellitic anhydride was added to 100 parts of this polyester polyol, reacted at 180° C. for about 2 hours, and then diluted with ethyl acetate to a solid content concentration of 50%, resulting in a number average molecular weight of 2,000. , and an acid value of 23.5 mg KOH/g, a solution of partially acid-modified polyester polyol B2 was obtained.

[Synthesis Example 2-3] (polyester polyol B3)
188 parts of ethylene glycol, 316 parts of neopentyl glycol, 179 parts of 1,6-hexanediol, 315 parts of terephthalic acid and isophthalic acid were added to a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank and nitrogen gas inlet tube. 315 parts of acid, 64 parts of adipic acid, and 323 parts of sebacic acid were charged, and the temperature was raised to 250° C. while stirring under a nitrogen stream to carry out an esterification reaction. After a predetermined amount of water was distilled and the reaction was continued until the acid value became 5 or less, the pressure was gradually reduced, and the deglycol reaction was performed at 1 mmHg or less for 5 hours to obtain a polyester polyol. After that, 8.5 parts of isophorone diisocyanate was gradually added and reacted at 150° C. for about 2 hours to obtain a polyester polyurethane polyol. 0.4 part of trimellitic anhydride was added to 100 parts of this polyester polyurethane polyol, reacted at 180° C. for about 2 hours, and then diluted with ethyl acetate until the solid content concentration reached 50%. 500 and an acid value of 2.2 mg KOH/g, a solution of partially acid-modified polyester polyol B3 was obtained.

<Adjustment of polyisocyanate>
[Preparation Example 1] (Polyisocyanate C1)
Coronate 2785 (biuret-type polyisocyanate derived from hexamethylene diisocyanate, manufactured by Tosoh Corporation) was diluted with ethyl acetate to adjust the solid content concentration to 50% and NCO% = 9.6%, and a solution of polyisocyanate C1 was prepared. Obtained.

[Preparation Example 2] (Polyisocyanate C2)
Takenate D-110NB (trimethylolpropane adduct type polyisocyanate derived from xylylene diisocyanate (hereinafter referred to as XDI), manufactured by Mitsui Chemicals, Inc.) was diluted with ethyl acetate to give a solid content of 50% and NCO% = 7.9. % to obtain a solution of polyisocyanate C2.

<Manufacture of adhesive>
[Production Example 3-1] (Adhesive D1)
90 parts of the polyester polyol B1 solution, 10 parts of the polyester polyol B2 solution and 8 parts of the polyisocyanate C1 solution were blended, and EA was added to prepare an adhesive solution having a solid concentration of 30%.

[Production Examples 3-2 to 4] (Adhesives D2 to 4)
Solutions of adhesives D2 to 4 were obtained in the same manner as in Production Example 3-1, except that the raw materials and formulations were changed to those shown in Table 4.

Abbreviations in Table 4 are shown below.
Maleated rosin solution: Malquied No. manufactured by Arakawa Chemical Co., Ltd. 32 (acid value 130 mgKOH/g, solid concentration 100% product) diluted with ethyl acetate to a solid concentration of 30%

<Production of laminate>
A method for manufacturing a laminate will be described below. In addition, the primer composition and the printing ink were each prepared using a mixed solvent of EA/IPA (mass ratio: 70/30) so that the viscosity would be 15 seconds (25°C, Zahn Cup #3 (manufactured by Rigosha)). was used after diluting to Also, the thickness of the primer layer and the printed layer were each adjusted to be about 1.5 μm.

[Production Example 4-1] (Laminate L1)
The diluted primer composition S1 and printing ink R1 were printed in this order on OPP (corona-treated oriented polypropylene film, thickness 20 μm) using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, and printed at 50° C. After drying, a laminate L1 having a structure of polyolefin substrate layer (OPP)/release primer layer (S1)/printing layer (R1) was obtained.

[Production Examples 4-2 to 7] (Laminates L2 to 7)
Laminates L2 to L7 were obtained in the same manner as in Production Example 4-1, except that the substrate and primer composition were changed as shown in Table 5.

[Production Example 4-8] (Laminate L8)
A diluted printing ink R2 is printed on OPP using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, and dried at 50° C. to form a polyolefin substrate layer (OPP)/release printing layer (R2 ) was obtained.

[Production Examples 4-9 to 11] (Laminates L9 to 11)
Laminates L9 to L11 were obtained in the same manner as in Production Examples 4-8, except that the base material and printing ink were changed as shown in Table 5.

[Production Example 4-12] (Laminate L12)
Adhesive D1 is applied to OPP using a dry laminating machine so that the coating amount after drying is 2 g / m ² and dried, then laminated with CPP (unstretched polypropylene film thickness 50 μm), CPP / D1 / OPP A laminate having the structure of was obtained.
Next, the diluted primer composition S1 and printing ink R1 are printed on the OPP of the laminate obtained above 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. Thus, a laminate L12 having a configuration of polyolefin substrate layer (CPP)/release adhesive layer (D1)/polyolefin substrate layer (OPP)/release primer layer (S1)/printed layer (R1) was obtained. rice field.

[Production Example 4-13] (Laminate L13)
Adhesive D1 is applied to OPP using a dry laminating machine so that the coating amount after drying is 2 g / m ² , dried, and then laminated with CPP to obtain a laminate having a structure of CPP / D1 / OPP. rice field.
Next, on the OPP of the laminate obtained above, diluted printing ink R2 is printed using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, dried at 50 ° C., and the polyolefin base layer ( CPP)/releasable adhesive layer (D1)/polyolefin substrate layer (OPP)/printed layer (R2) to obtain a laminate L13.

[Production Example 4-14] (Laminate L14)
For OPP, diluted primer composition S1 and printing ink R1 are printed in this order using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, and dried at 50 ° C. to obtain OPP / S1 / R1. A laminate having the following structure was obtained.
Next, on the printed layer of the obtained laminate, the adhesive D1 is applied using a dry laminator so that the coating amount after drying is 2 g / m ² and dried, and then laminated with CPP to form a polyolefin base. A laminate L14 having a structure of material layer (OPP)/removable primer layer (S1)/printing layer (R1)/removable adhesive layer (D1)/polyolefin substrate layer (CPP) was obtained.

[Production Examples 4-15 to 22] (Laminates L15 to 22)
Laminates L15 to L22 were obtained in the same manner as in Production Examples 4-14, except that the substrate, primer composition and adhesive were changed to those shown in Table 5.

[Production Example 4-23] (Laminate L23)
A diluted printing ink R2 was printed on OPP using a gravure printing machine equipped with a gravure plate having a plate depth of 30 μm, and dried at 50° C. to obtain a laminate having the structure OPP/R2.
Next, on the printed layer of the obtained laminate, the adhesive D1 is applied using a dry laminator so that the coating amount after drying is 2 g / m ² and dried, and then laminated with CPP to form a polyolefin base. A laminate L25 having a structure of material layer (OPP)/releasable printed layer (R2)/releasable adhesive layer (D1)/polyolefin substrate layer (CPP) was obtained.

[Production Examples 4-24 to 28] (Laminates L24 to 28)
Laminates L24 to L28 were obtained in the same manner as in Production Examples 4-23, except that the substrate, diluted printing ink and adhesive were changed to those shown in Table 5.

[Production Example 4-29] (Laminate L29)
Adhesive D1 is applied to OPP using a dry laminator so that the coating amount after drying is 2 g / m ² and dried, and then laminated with CPP to form a polyolefin base layer (OPP) / release adhesive layer. A laminate L29 having a structure of (D1)/polyolefin substrate layer (CPP) was obtained.

[Production Examples 4-30 to 31] (Laminates L30 to 31)
Laminates L30 to L31 were obtained in the same manner as in Production Example 4-29, except that the content of the adhesive was changed as shown in Table 5.

[Production Example 4-32] (Laminate L32)
Adhesive D4 was applied to PET (polyethylene terephthalate film, thickness 12 μm) using a dry laminator so that the coating amount after drying was 2 g/m ² , dried, and then laminated with NY (nylon film, thickness 15 μm). Furthermore, on NY, after applying and drying the adhesive D1 using a dry laminator so that the coating amount after drying is 2 g / m ² , it is laminated with CPP, and the base layer (PET) / adhesive A laminate L32 having a structure of layer (D4)/base layer (NY)/releasable adhesive layer (D1)/polyolefin base layer (CPP) was obtained.

[Production Example 4-33] (Laminate L33)
The diluted printing ink R1 was printed on PET in this order using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, and dried at 50° C. to obtain a laminate having a structure of PET/R1. rice field.
Next, on the printed layer of the obtained laminate, an adhesive D4 was applied using a dry laminator so that the coating amount after drying was 2 g/m ^{2 ,} dried, and then laminated with NY. Furthermore, on NY, after applying and drying the adhesive D1 using a dry laminating machine so that the coating amount after drying is 2 g / m ² , it is laminated with CPP, and the base layer (PET) / printing layer A laminate L33 having a configuration of (R1)/adhesive layer (D4)/base layer (NY)/release adhesive layer (D1)/polyolefin base layer (CPP) was obtained.

[Production Example 4-34] (Laminate L34)
Adhesive D4 was applied to PET using a dry laminator so that the coating amount after drying was 2 g/m ² , dried, and then laminated with NY. Furthermore, after applying and drying the adhesive D1 using a dry laminator on NY so that the coating amount after drying is 2 g / m ² , it is laminated with CPP, and the configuration of PET / D4 / NY / D1 / CPP A laminate was obtained.
Next, the diluted primer composition S1 and printing ink R1 are printed on PET of the obtained laminate in this order using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, and dried at 50 ° C. Then, printed layer (R1) / removable primer layer (S1) / substrate layer (PET) / adhesive layer (D4) / substrate layer (NY) / removable adhesive layer (D1) / polyolefin substrate A laminate L34 having a structure of layers (CPP) was obtained.

[Comparative Production Example 4-1] (Laminate LL1)
Primer composition S1 and printing ink R1 are printed on PET in this order using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, dried at 50 ° C., and the substrate layer (PET) / stripping A laminate LL1 having a configuration of a release primer layer (S1)/printing layer (R1) was obtained.

Abbreviations in Table 5 are shown below.
OPP: corona-treated oriented polypropylene film, thickness 20 μm
PE: linear low-density polyethylene film, thickness 50 μm
CPP: unstretched polypropylene film, thickness 50 μm
PET: polyethylene terephthalate film, thickness 12 μm
NY: nylon film, thickness 15 μm

<Production of desorbed liquid>
[Production Example 5-1] (Treatment Liquid A1)
1 part of POE alkyl ether A (polyoxyethylene lauryl ether, POE addition number: 4, HLB: 9.7) as a surfactant, BYK-1650 as an antifoaming agent (manufactured by BYK-Chemie Japan, silicone emulsion type antifoaming agent , solid content concentration 27.5%), 2 parts of sodium hydroxide and 96.9 parts of water were blended and stirred with a disper to obtain treatment liquid A1.

[Production Examples 5-2 to 18, Comparative Production Examples 5-1 to 3] (Treatment Liquids A2 to 18, AA1 to 3)
Treatment solutions A2 to 18 and AA1 to 3 were obtained in the same manner as in Production Example 5-1, except that the composition was changed to that shown in Table 6.

Abbreviations in Table 6 are shown below.
(Nonionic surfactant)
POE alkyl ether A: polyoxyethylene (POE) lauryl ether, POE addition number: 4, HLB: 9.7
POE alkyl ether B: POE lauryl ether, POE addition number; 12, HLB; 15.3
POE alkyl ether C: POE stearyl ether, POE addition number: 12, HLB: 13.9
POE alkyl ether D: POE stearyl ether, POE addition number: 50, HLB: 17.8
POE alkyl ether E: POE oleyl ether, POE addition number; 6, HLB; 10.0
POE alkyl ether F: POE oleyl ether, POE addition number: 13, HLB: 13.6

(Nonionic surfactant)
POE acetylenediol A: POE addition number; 1.3, HLB; 4.0
POE acetylenediol B: POE addition number; 3.5, HLB; 8.0
POE acetylene diol C: POE addition number; 10, HLB; 13
POE acetylene diol D: POE addition number; 30, HLB; 17

(Anionic surfactant)
POE lauryl ether phosphate: POE addition number; 4, HLB; 10.0

(Antifoaming agent)
BYK-018: manufactured by BYK-Chemie Japan, silicone-based oil compound type, solid concentration >97%

<Separation and recovery of laminate>
[Example 1-1]
200 g of the treatment liquid A1 and 8 g of a 1 cm×1 cm sample of the packaging material L1 were placed in a 1000 mL stainless steel beaker and stirred at 70° C. and 2000 rpm. The following evaluations were performed on the state of separation and collection of the laminate.

[Examples 1-2 to 72, Comparative Examples 1 to 13]
In addition, the separation and recovery state of the laminate was evaluated in the same manner as in Example 1-1 except that the materials listed in Tables 7-1 to 7-4 were used.
The results are shown in Tables 7-1 to 7-4 (Table 7 below).

<Evaluation of laminate>
(effervescent)
10 minutes after the start of stirring, the stirring was temporarily interrupted, and the height of the liquid surface (above the bubbles) was visually observed and evaluated according to the following criteria. The height of 450 mL refers to the volume scale indicated on the beaker, and the larger the number, the higher the liquid level, that is, the more bubbles are generated.
A (excellent): The height of the liquid surface (above the bubbles) during stirring is less than 450 mL B (Good): The height of the liquid surface (above the bubbles) during stirring is 450 mL or more and less than 600 mL C (Good): During stirring The height of the liquid level (above the bubbles) is 600 mL or more and less than 900 mL D (impossible): The height of the liquid level (above the bubbles) during stirring is 900 mL or more

(Substrate Separability)
For laminates having adhesive layers using releasable adhesives D1 to D3, the substrates were sampled at 15 minutes, 30 minutes, and 1 hour after the start of stirring, washed with water, and dried. Thirty substrates were randomly selected from the obtained substrates, and the thickness of the substrates was measured. Based on the thickness of the base material, it was determined whether the laminate was separated between the adhesive layers using the adhesives D1 to D3, and evaluation was made according to the following criteria.
A (excellent): 15 minutes after the start of stirring, all 30 sheets are substrates after separation.
B (good): 30 minutes after the start of stirring, all 30 substrates are separated substrates.
C (Possible): One hour after the start of stirring, all 30 substrates were separated substrates.
D (impossible): 1 hour after the start of stirring, the base material before separation is mixed.

(Removability of printed layer)
For the laminate comprising a detachable primer layer and/or detachable printed layer on a polyolefin substrate, and the laminate LL1, the substrate was sampled at 15 minutes, 30 minutes, and 1 hour after the start of stirring, and washed with water. Dried. From the obtained substrate, 10 polyolefin substrates printed with the detachable primer layer and/or the detachable printed layer after separation were sampled, and the removal rate of the printed layer was visually confirmed and evaluated according to the following criteria. . As for the laminate LL1, the PET base material was collected and evaluated.
A (excellent): 90% or more of the printed layer was peeled off from the substrate 15 minutes after the start of stirring.
B (good): 90% or more of the printed layer peeled off from the base material 30 minutes after the start of stirring.
C (Possible): 90% or more of the printed layer peeled off from the substrate after 1 hour from the start of stirring.
D (impossible): 90% or more of the printed layer did not peel off from the substrate after 1 hour from the start of stirring.

(Removability of adhesive)
For laminates having adhesive layers using releasable adhesives D1 to D3, the substrates were sampled at 15 minutes, 30 minutes, and 1 hour after the start of stirring, washed with water, and dried. From the obtained base material, 10 samples of the sealant base material after separation were sampled, and the presence or absence of the absorption peak of the adhesive was confirmed using FT-IR for a total of 30 places, 3 places on the front and back sides of each sealant base material, Evaluation was made according to the following criteria.
A (excellent): Absorption peaks of the adhesive are not observed at 25 or more of 30 locations on the substrate 15 minutes after the start of stirring.
B (Good): Absorption peaks of the adhesive are not observed at 25 or more of 30 locations on the substrate 30 minutes after the start of stirring.
C (acceptable): Absorption peaks of the adhesive are not observed at 25 or more of 30 locations on the base material after 1 hour from the start of stirring.
D (impossible): Absorption peaks of the adhesive are observed at 6 or more of 30 locations on the base material 1 hour after the start of stirring.

(Reattachment of printed layer)
When it was confirmed that 90% or more of the printed layer had been detached from the base material in the detachability evaluation of the printed layer, the material was stirred for an additional hour, then the detached base material was collected, washed with water, and dried. From the obtained substrate, 10 polyolefin substrates printed with a desorption primer layer and / or a desorption printing layer after separation are sampled, and the obtained 10 substrates are stacked and measured with a spectrophotometer (X- Color values L ^* _x , a ^* _x , and b ^* _x were measured with X-rite eXact manufactured by rite.
On the other hand, even when it was confirmed that 90% or more of the printed layer had detached from the base material, the detached base material was recovered in the same manner, and 10 base materials were stacked to determine the color values L ^* _y and a. ^* _y and b ^* _y were measured.
The color difference ΔE before and after stirring for 1 hour was determined by the following formula, and the reattachment property was evaluated according to the following criteria.
(Formula) ΔE=((L ^* _x −L ^* _y ) ² +(a ^* _x −a ^* _y ) ² +(b ^* _x −b ^* _y ) ² ) ^1/2
A (excellent): ΔE is less than 3 B (good): ΔE is 3 or more and less than 10 C (acceptable): ΔE is 10 or more and less than 20 D (improper): other than A to C

(Reattachment of Adhesive Layer)
In the detachability evaluation of the adhesive layer, from the time when the absorption peak of the adhesive was not confirmed at 25 or more locations out of 30, after stirring for an additional hour, the detached base material was collected, washed with water, and dried. . Ten sealant substrates after separation were sampled from the obtained substrates, and the presence or absence of absorption peaks of the adhesive was confirmed using FT-IR for a total of 30 locations (3 front and back surfaces) of each sealant substrate.
A (excellent): Less than 5 locations where absorption peaks of the adhesive were confirmed.
B (good): 5 or more but less than 8 locations where absorption peaks of the adhesive were confirmed.
C (Possible): 8 or more but less than 10 locations where absorption peaks of the adhesive were confirmed.
D (impossible): 10 or more locations where absorption peaks of the adhesive were confirmed.

<Production of recycled film and evaluation of transmittance>
[Example 2-1]
A 1 cm×1 cm sample of packaging material L14 was immersed in treatment liquid A1 and stirred at 70° C. for 2 hours. After recovering the released OPP and CPP base materials, washing with water and drying, the mixture of OPP and CPP base materials is extruded at 200° C. with a single-screw extruder, and pelletized through a pelletizing process to obtain recycled resin pellets. got The recycled resin was extruded at 200° C. using a T-die film molding machine to produce a recycled film having a thickness of 40 μm.
Regarding the coloration of the recycled film, the total light transmittance was measured using a haze meter (manufactured by Nippon Denshi Kogyo Co., Ltd., SH7000) and evaluated according to the following criteria.
A (excellent): total light transmittance of 70% or more B (good): total light transmittance of 50% or more and less than 70% C (acceptable): total light transmittance of 30% or more and less than 50% D (improper): Total light transmittance less than 30%

[Examples 2-2 to 18, Comparative Examples 2-1 to 2]
A recycled film was produced and evaluated in the same manner as in Example 2-1, except that the packaging material and treatment liquid were changed to those shown in Table 8. Table 8 shows the results.

From the above evaluation results, the treatment liquid of the present invention can easily detach the printed layer and the adhesive layer from the packaging material even when the processing amount of the packaging material is large, and reattach the printed layer and the adhesive layer. It was shown that a high-quality recycled base material with little coloration can be obtained, and a high-quality molding material with little coloration can be obtained.

Claims (9)

A laminate comprising at least a polyolefin base layer and a release layer in contact with the polyolefin base layer is immersed in a release liquid containing a nonionic surfactant having an HLB value of 7 or more to remove the release layer. A method for separating and recovering a laminate, comprising a step of recovering a polyolefin base material with a 2. The method for separating and recovering a laminate according to claim 1, wherein the desorbing liquid is a basic aqueous solution containing a basic compound. 3. The method for separating and recovering a laminate according to claim 1, wherein the surfactant contains an alkylene oxide adduct. The method for separating and recovering a laminate according to any one of claims 1 to 3, wherein the surfactant has an HLB value of 7 to 20. The method for separating and recovering a laminate according to any one of claims 1 to 4, wherein the content of the surfactant is 0.1 to 10% by mass based on the mass of the desorbing liquid. The method for separating and recovering a laminate according to any one of claims 1 to 5, wherein the desorption layer is a layer containing a compound having an acidic group. The method for separating and recovering a laminate according to any one of claims 1 to 6, wherein the release layer includes at least one layer selected from the group consisting of a primer layer, a printed layer and an adhesive layer. A method for producing a molding material, comprising melt-kneading a polyolefin base material recovered by the method for separating and recovering a laminate according to any one of claims 1 to 7. A method for producing a molded article, which comprises thermoforming the molding material obtained by the production method according to claim 8 .