WO2022209684A1 - 積層体、印刷物、水系分散液及び積層体の製造方法 - Google Patents

積層体、印刷物、水系分散液及び積層体の製造方法 Download PDF

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Publication number
WO2022209684A1
WO2022209684A1 PCT/JP2022/010431 JP2022010431W WO2022209684A1 WO 2022209684 A1 WO2022209684 A1 WO 2022209684A1 JP 2022010431 W JP2022010431 W JP 2022010431W WO 2022209684 A1 WO2022209684 A1 WO 2022209684A1
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Prior art keywords
laminate
release layer
modified olefin
layer
olefin resin
Prior art date
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Ceased
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PCT/JP2022/010431
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English (en)
French (fr)
Japanese (ja)
Inventor
凌 佐藤
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Yupo Corp
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Yupo Corp
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Publication date
Application filed by Yupo Corp filed Critical Yupo Corp
Priority to EP22779907.9A priority Critical patent/EP4316804A4/en
Priority to JP2023510782A priority patent/JP7549130B2/ja
Priority to US18/284,116 priority patent/US12139588B2/en
Priority to CN202280025510.7A priority patent/CN117120256B/zh
Publication of WO2022209684A1 publication Critical patent/WO2022209684A1/ja
Anticipated expiration legal-status Critical
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
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Definitions

  • the present invention relates to a laminate, a printed matter, an aqueous dispersion, and a method for producing a laminate, and more particularly, to a laminate having a release layer on its surface, and a laminate having a printed layer on the release layer-side surface of the laminate.
  • the present invention relates to a printed matter, an aqueous dispersion for forming the release layer, and a method for producing the laminate.
  • Plastics are used in a wide variety of applications, such as containers and packaging bags. Many plastic products have printed surfaces for information transmission to general consumers and product distribution management. be.
  • Plastic is difficult to decompose in the natural world, and some of it is sorted and collected due to resource conservation, economic efficiency, etc., and is recycled and used as secondary products. However, if plastic products that have undergone printing or the like are mixed in during recycling, the entire recycled product will be colored or partially colored.
  • Patent Document 1 describes a label in which an intermediate layer that removes ink in hot alkaline water is present between an ink layer and a base layer on at least one side of a thermoplastic polymer film.
  • Patent Document 2 describes an article having a detachable surface layer formed of a material that becomes water-swellable or water-soluble by neutralization treatment, and describes treatment with an alkaline aqueous solution. .
  • Patent Document 3 discloses a label in which an alkali-releasing layer is formed on a substrate, and a printed layer is formed on the alkali-releasing layer, or a printed layer is applied via an aluminum deposition layer, wherein the alkali
  • the resin composition used for the release layer contains 20 to 90% by weight of lower alkyl ester units of carboxylic acid having a polymerizable unsaturated group such as acrylic acid as monomer units and 0.5 to 35% by weight of acid component units such as acrylic acid.
  • a random, block and/or graft copolymer containing 0.5 to 30% by weight of crosslinkable component units and 0.05 to 15 parts of a crosslinking agent component per 100 parts of said copolymer. is described.
  • Patent Document 4 discloses a water-based primer composition for forming a detachment primer layer of a printed matter, which consists of a polyester base material, a detachment primer layer, and a printed layer in that order, comprising: (1) a carboxyl group; (2) at least part of the carboxyl groups of the polyurethane resin (A) are neutralized with the amine compound (a-1); and (3) in the polyurethane resin (A) A water-based primer composition having an acid value before reconstitution of 25 to 45 mgKOH/g is described.
  • Japanese Patent Laid-Open No. 11-333952 Japanese Patent Application Laid-Open No. 2001-131484 Japanese Patent Application Laid-Open No. 2002-11819 Japanese Patent Application Laid-Open No. 2017-114930
  • Patent Document 1 is treated with a hot alkaline aqueous solution at 90° C. or higher to remove the ink layer, and the work efficiency during recycling is low.
  • the article having a removable surface layer described in Patent Document 2 also requires heating of the treatment liquid to 70 to 80° C., so the working efficiency during regeneration is low.
  • Ethyl acetate is used as the working solution, and it is necessary to dispose of the wastewater collected after the removal of the printed layer.
  • the alkali-releasing label described in Patent Document 3 also uses an organic solvent in the coating liquid for forming the alkali-releasing layer, and no consideration is given to environmental issues.
  • Patent Document 4 uses a water-based coating liquid as the coating liquid for the release layer, and neutralizes at least part of the carboxyl groups of the polyurethane resin (A) contained in the coating liquid.
  • the solubility in water is improved and the primer layer is used as an aqueous solution, but the resulting detachable primer layer has insufficient water resistance.
  • the present invention has been made in view of the above problems, and can be formed with a water-based coating liquid, quickly detached from the substrate during alkali treatment, and has a detachable layer with excellent water resistance.
  • the task is to provide the body.
  • the inventors of the present invention have extensively studied a water-based coating liquid for forming a release layer, and found that a release layer formed from an aqueous dispersion obtained by dispersing a granular alkali-soluble resin in an aqueous medium can be used as a base.
  • the inventors have obtained knowledge that both the improvement of releasability from the material and the improvement of water resistance can be achieved at the same time.
  • the present invention relates to the following (1) to (11).
  • a laminate having a release layer on a base material wherein the release layer comprises a binding portion containing a granular carboxylic acid anhydride-modified olefin resin and a thermoplastic resin having no acid group.
  • the carboxylic anhydride-modified olefin resin has an average particle size of 0.5 to 20 ⁇ m
  • the binding portion has a thickness of 0.25 to 20 ⁇ m
  • the release layer has a substantial acid number of Laminate of 100 KOHmg/m 2 or more.
  • thermoplastic resin is a water-soluble or water-dispersible polymer.
  • thermoplastic resin is a water-soluble or water-dispersible polymer.
  • the present invention it is possible to provide a laminate having a detachable layer that is rapidly detached from a substrate during alkali treatment and has excellent water resistance. Moreover, since the coating liquid is an aqueous dispersion, it is excellent in environmental conservation.
  • FIG. 1 is a cross-sectional view showing the structure of the laminate of the present invention.
  • the laminate 1 of the present invention comprises a release layer 5 on a base material 3, and the release layer 5 comprises a granular carboxylic anhydride-modified olefin resin 11 and an acid group-free and a binding portion 12 comprising a thermoplastic resin.
  • the average particle diameter T a of the carboxylic anhydride-modified olefin resin 11 is 0.5 to 20 ⁇ m
  • the thickness T b of the binding portion 12 is 0.25 to 20 ⁇ m
  • the release layer 5 is Substantial acid value is 100 KOHmg/m 2 or more.
  • the configuration of the desorption layer of the laminate of the present invention can be confirmed by observing the cross section of the laminate including the desorption layer with a scanning electron microscope.
  • the base material 3 on which the release layer 5 is formed is a member constituting an article, and is not particularly limited, but examples thereof include thermoplastic resin moldings, thermosetting resin moldings, non-woven fabrics, and the like. Among them, thermoplastic resin moldings can be preferably used because of their high demand for recycling.
  • thermoplastic resin constituting the thermoplastic resin product is not particularly limited, but examples thereof include polyolefin resins, polyester resins, polyamide resins, polystyrene resins, polyethylene terephthalate resins, polyvinyl chloride resins, polycarbonate resins, and the like.
  • Polyolefin resins include, for example, polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, polyolefin resins are preferable from the viewpoint of adhesion to the release layer.
  • the shape of the substrate is not particularly limited, and examples thereof include a film-like shape, a plate-like shape mainly composed of flat surfaces, and an arbitrary three-dimensional shape combining flat surfaces and curved surfaces. Among them, it is preferable to use a film-like substrate from the viewpoint of handleability.
  • the film-like substrate may be in the form of a roll or sheet.
  • the size of the substrate is not particularly limited.
  • the thickness is preferably 50 ⁇ m or more, more preferably 60 ⁇ m or more, and even more preferably 70 ⁇ m or more, from the viewpoint of obtaining good film strength.
  • the thickness of the substrate is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and even more preferably 100 ⁇ m or less.
  • the release layer 5 includes the granular carboxylic anhydride-modified olefin resin 11 and the binding portion 12 containing a thermoplastic resin having no acid group. Since the carboxylic anhydride-modified olefin resin is soluble in alkali, by including a plurality of carboxylic anhydride-modified olefin resins in the desorption layer, the laminate has water resistance and alkali desorption when the laminate is treated with alkali. Can express dissociation. By containing the carboxylic anhydride-modified olefin resin in the form of particles in the release layer, the coating liquid for forming the release layer can be water-based.
  • the carboxylic anhydride-modified olefin resin can be held on the substrate, and a printed layer is provided on the release layer.
  • the adhesiveness is improved during drying, and printability is imparted to the surface of the release layer.
  • a carboxylic anhydride-modified olefin resin is a compound having an acid anhydride group as a functional group.
  • the carboxylic anhydride of the carboxylic anhydride-modified olefin resin used in the present invention is one or more selected from the group consisting of acid anhydrides of ⁇ , ⁇ -unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. and particularly preferably maleic anhydride.
  • the carboxylic anhydride-modified olefin resin used in the present invention is preferably a copolymer of these acid anhydrides and one or a mixture of two or more selected from the group consisting of ethylene, propylene, butene and styrene. Among them, copolymers with isobutene (isobutylene) or styrene are particularly preferred.
  • the acid value when the carboxylic anhydride-modified olefin resin is ring-opened by hydrolysis is preferably 400 KOHmg/g or more.
  • the acid value is 400 KOHmg/g or more, the detachable layer is rapidly detached from the substrate when the laminate is treated with alkali.
  • the acid value is more preferably 500 KOH mg/g or more, more preferably 600 KOH mg/g or more. The following are preferred.
  • Examples of the shape of the granular carboxylic anhydride-modified olefin resin include spherical (perfectly spherical, substantially spherical, ellipsoidal, etc.), polyhedral, rod-like (cylindrical, prismatic, etc.), tabular, irregular shapes, and the like. mentioned. Among them, a spherical shape and a flat shape are preferable from the viewpoint of preventing particles from dropping off from the release layer and from the viewpoint of ink fixability.
  • the carboxylic anhydride-modified olefin resin has an average particle size T a of 0.5 to 20 ⁇ m, depending on the size of the raw carboxylic anhydride-modified olefin resin.
  • T a average particle size
  • the average particle size Ta of the carboxylic anhydride-modified olefin resin is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the ratio of the carboxylic anhydride-modified olefin resin in the release layer is appropriately adjusted according to the acid value when the carboxylic anhydride-modified olefin resin is ring-opened by hydrolysis so that the actual acid value is within the scope of the present invention. Although it may be adjusted, it is preferably 5 to 75% by mass. When the proportion of the carboxylic anhydride-modified olefin resin is 5% by mass or more, the alkali-releasing property tends to be exhibited.
  • the content of the carboxylic anhydride-modified olefin resin in the release layer is more preferably 20% by mass or more, more preferably 40% by mass or more, more preferably 70% by mass or less, and even more preferably 65% by mass or less. .
  • the binding part holds the carboxylic anhydride-modified olefin resin to the base material and also serves to capture the ink and toner printed on the surface of the laminate.
  • the binding portion contains at least a thermoplastic resin having no acid group as a binder resin.
  • thermoplastic resin having no acid group can be used without particular limitation as long as it has no acid group, but a water-soluble polymer or a water-dispersible polymer is preferred.
  • the water-soluble or water-dispersible polymer is cationic.
  • cationic water-dispersible polymers are more preferred.
  • a cationic water-soluble polymer or cationic water-dispersible polymer may be expressed as a cationic water-soluble polymer or water-dispersible polymer.
  • the binding portion is chemically adhered to the ink or toner (specifically, adhesion by ionic bonding) and dispersedly adhered (specifically, Adhesion due to van der Waals force.), and it is presumed that the transferability and adhesion of the ink or toner to the release layer are improved.
  • the water-solubility of the cationic water-soluble polymer should be such that the aqueous medium containing the cationic water-soluble polymer is in a solution state when preparing the coating solution for forming the release layer. .
  • Cationic water-soluble polymers or water-dispersible polymers that can be used include, for example, (meth)acrylic polymers, urethane-based polymers, ethyleneimine-based polymers having an amino group or an ammonium salt structure, and water-soluble polymers having a phosphonium salt structure.
  • Polymers, polyvinylpyrrolidone, polyvinyl alcohol, and other water-soluble polymers cationized by modification may be mentioned, and one of these may be used alone or two or more of them may be used in combination.
  • a urethane-based polymer is preferable from the viewpoint of releasability of the detachable layer when the laminate is treated with an alkali.
  • a (meth)acrylic polymer or an ethyleneimine polymer having an amino group or an ammonium salt structure is preferable from the viewpoint of ink or toner transferability and adhesion to the release layer.
  • urethane-based polymers include cationic modified urethane resins, cationic ether-based urethane resins, cationic carbonate-based urethane resins, cationic ester-based urethane resins, and other cationic urethane resins.
  • Cationic ester-based urethane resins are preferred from the viewpoint of excellent releasability.
  • a commercial item can also be used as a urethane-type polymer.
  • Commercially available urethane-based polymers include the "Superflex” series from Daiichi Kogyo Seiyaku Co., Ltd., the "WBR” series and the “WEM” series from Taisei Fine Chemicals Co., Ltd., and the like.
  • the glass transition temperature (Tg) of the urethane-based polymer is preferably -30°C or higher, more preferably -10°C or higher, from the viewpoint of improving the releasability during alkali treatment.
  • the glass transition temperature (Tg) is preferably 60°C or lower, more preferably 45°C or lower.
  • the (meth)acrylic polymer or ethyleneimine polymer having an amino group or an ammonium salt structure preferably has a primary to tertiary amino group or an ammonium salt structure. It more preferably has a secondary to tertiary amino group or an ammonium salt structure, and more preferably has a tertiary amino group or an ammonium salt structure.
  • ethyleneimine-based polymers are used in inks or toners used in various printing methods, In particular, since it has a high affinity with the ultraviolet curable ink used in the flexographic printing method, the adhesiveness between the release layer and the ink is improved, which is preferable.
  • ethyleneimine-based polymers include polyethyleneimine, poly(ethyleneimine-urea), ethyleneimine adducts of polyamine polyamides, alkyl modified products thereof, cycloalkyl modified products, aryl modified products, allyl modified products, aralkyl modified products, Examples include benzyl modified products, cyclopentyl modified products, cycloaliphatic hydrocarbon modified products, glycidol modified products, and hydroxides thereof.
  • modifying agents for obtaining modified compounds include methyl chloride, methyl bromide, n-butyl chloride, lauryl chloride, stearyl iodide, oleyl chloride, cyclohexyl chloride, benzyl chloride, allyl chloride, and cyclopentyl chloride.
  • an ethyleneimine-based polymer represented by the following general formula (I) is preferable from the viewpoint of improving the transferability and adhesiveness of the ink or toner used for printing, particularly the UV-curable ink.
  • R 1 and R 2 are each independently a hydrogen atom; a linear or branched alkyl group having 1 to 12 carbon atoms; an alkyl group having an alicyclic structure having 6 to 12 carbon atoms; or represents an aryl group.
  • R 3 is a hydrogen atom; an alkyl group or allyl group having 1 to 18 carbon atoms and optionally containing a hydroxy group; an alkyl group having an alicyclic structure having 6 to 12 carbon atoms and optionally containing a hydroxy group. or represents an aryl group.
  • m represents an integer of 2-6, and n represents an integer of 20-3000.
  • (meth)acrylic polymer or ethyleneimine polymer having an amino group or an ammonium salt structure Commercially available products can also be used as the (meth)acrylic polymer or ethyleneimine polymer having an amino group or an ammonium salt structure.
  • Commercially available (meth)acrylic polymers having an amino group or an ammonium salt structure include “Polyment” manufactured by Nippon Shokubai Co., Ltd., and the like.
  • Commercially available ethyleneimine polymers include "Epomin” manufactured by Nippon Shokubai Co., Ltd. and “Polymin SK" manufactured by BASF.
  • the lower limit of the weight average molecular weight of the (meth)acrylic polymer or ethyleneimine polymer having an amino group or an ammonium salt structure is 10, from the viewpoint of improving adhesion to substrates and adhesion to ink and the like. 000 is preferred, and 20,000 is more preferred.
  • the upper limit of the weight average molecular weight is preferably 1,000,000, more preferably 500,000.
  • thermoplastic resin that does not have an acid group In order for a thermoplastic resin that does not have an acid group to work as a binder, it must have an appropriate level of adhesiveness. If the glass transition temperature (Tg) of the thermoplastic resin that does not have an acid group is too low, the surface of the laminate becomes sticky, and the phenomenon of blocking, in which the stacked laminates stick to each other, tends to occur frequently. -30°C or higher is preferred. In addition, if the glass transition temperature (Tg) of the thermoplastic resin having no acid group is too high, the thermoplastic resin having no acid group becomes too hard, and the base material, carboxylic acid anhydride-modified olefin resin, ink, etc. It is preferable that the glass transition temperature (Tg) is 80° C.
  • the glass transition temperature (Tg) of the thermoplastic resin having no acid group is more preferably ⁇ 10° C. or higher in order to function well as a binder, and the upper limit is more preferably 60° C. or lower.
  • the temperature is preferably 45° C. or lower, and more preferably 45° C. or lower.
  • the thermoplastic resin having no acid group is preferably contained in the binding portion at a rate of 60% by mass or more.
  • the content of the thermoplastic resin having no acid group in the binding portion is 60% by mass or more, the adhesion of the ink or toner to the release layer is improved.
  • the content of the thermoplastic resin having no acid group in the binding portion is more preferably 65% by mass or more, more preferably 70% by mass or more, and the upper limit is not particularly limited, and even 100% by mass. However, it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.
  • the binding portion may contain a component other than the thermoplastic resin having no acid group within a range that does not impair the effects of the present invention.
  • Other components include, for example, silane coupling agents, antistatic agents, cross-linking accelerators, anti-blocking agents, pH adjusters, antifoaming agents, dispersants, wetting agents, emulsifiers, thickeners, anti-settling agents, dripping agents.
  • the ratio of the binding portion in the release layer is preferably 25 to 95% by mass.
  • the carboxylic anhydride-modified olefin resin can be retained without falling off from the base material, and when it is 95% by mass or less, the carboxylic anhydride-modified olefin resin has alkali-releasing properties. does not interfere with
  • the binder content in the release layer is more preferably 30% by mass or more, more preferably 35% by mass or more, and more preferably 80% by mass or less, further preferably 60% by mass or less.
  • the thickness Tb of the binding portion is 0.25 to 20 ⁇ m.
  • the thickness Tb of the binding portion is more preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, more preferably 15 ⁇ m or less, and still more preferably 10 ⁇ m or less.
  • the thickness T b (T b /T a ) of the binding portion relative to the average particle diameter T a of the granular carboxylic anhydride-modified olefin resin is preferably 0.1 times or more.
  • the thickness T b (T b /T a ) of the binding portion relative to the average particle diameter T a of the granular carboxylic anhydride-modified olefin resin is more preferably 0.2 times or more, more preferably 0.5 times or more. From the viewpoint of the alkali solubility of the release layer, it is preferably 3 times or less, more preferably 2 times or less. It is more preferably 1.2 times or less because the release layer has better alkali solubility.
  • the desorption layer preferably has a substantial acid value of 100 KOHmg/m 2 or more.
  • “Substantial acid value” is calculated from the actual amount of the carboxylic anhydride-modified olefin resin contained in the desorption layer and the acid value of the carboxylic anhydride-modified olefin resin per unit area of the desorption layer. refers to the acid number of
  • the basis weight of the release layer is X (g/m 2 )
  • the content of the carboxylic anhydride-modified olefin resin in the release layer is Y (% by mass)
  • the ring-opening of the carboxylic anhydride-modified olefin resin by hydrolysis When the acid value of is Z (mg KOH/g), the actual acid value of the desorption layer is represented by the following formula.
  • Substantial acid number (KOHmg/m 2 ) X x 0.01 Y x Z
  • the acid value when the carboxylic anhydride-modified olefin resin is ring-opened by hydrolysis is JIS K 0070-1992 "Acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter test of chemical products It can be measured by the neutralization titration method of "Method”.
  • the actual acid number is 400 KOHmg/m 2 or more.
  • the upper limit is not particularly limited, but if the actual acid number is too large, the amount of alkali required for the alkali desorption treatment increases. /m 2 or less is more preferable, and 1500 KOHmg/m 2 or less is even more preferable.
  • the shape of the laminate of the present invention conforms to the shape of the base material, and is not particularly limited. Any shape is included. Among them, a film form is preferred from the viewpoint of ease of handling and moldability.
  • the laminate of the present invention includes a step of forming a release layer by applying an aqueous dispersion for forming a release layer onto a substrate and drying the coating.
  • the aqueous dispersion used for the production of the laminate contains a granular carboxylic anhydride-modified olefin resin and a thermoplastic resin having no acid group, the carboxylic anhydride-modified olefin resin and the thermoplastic resin having no acid group, It can also be prepared by dissolving or dispersing optional components in an aqueous solvent, if necessary.
  • the aqueous solvent may be water, or may contain water as a main component and water-soluble organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, toluene, and xylene. Having water as the main component means that 50% by mass or more of the whole is water. The use of an aqueous solvent facilitates process control and is preferable from the viewpoint of safety.
  • the carboxylic anhydride-modified olefin resin, the thermoplastic resin having no acid group, and any other components are as described above, and preferred ones are also the same.
  • the content of the carboxylic anhydride-modified olefin resin in the solid content of the aqueous dispersion is preferably 5 to 75% by mass. When the content of the carboxylic anhydride-modified olefin resin is within the above range, it is possible to achieve both alkali elimination property and adhesion.
  • the carboxylic anhydride-modified olefin resin content in the solid content of the aqueous dispersion is more preferably 20% by mass or more, more preferably 40% by mass or more, and more preferably 70% by mass or less, and 65% by mass or less. is more preferred.
  • thermoplastic resin having no acid group in the solid content of the aqueous dispersion may be blended so that the content of the carboxylic anhydride-modified olefin resin falls within the above range.
  • the desorption layer when the desorption layer is formed, the desorption layer has a substantial acid value of 100 KOHmg/m 2 or more.
  • the content of the carboxylic anhydride-modified olefin resin it is necessary to adjust the content of the carboxylic anhydride-modified olefin resin, adjust the acid value when the carboxylic anhydride-modified olefin resin is ring-opened by hydrolysis, and the like. mentioned.
  • the aqueous dispersion preferably has a viscosity of 5 to 200 mPa ⁇ s at 20° C. when the solid content concentration is 20% by mass. If the viscosity is too low, the dispersion in the water-based dispersion tends to precipitate, and aggregates tend to occur, which may prevent uniform coating of the release layer. On the other hand, if the viscosity is too high, it may not be possible to stably apply a low coating amount.
  • the viscosity of the aqueous dispersion is more preferably 15 mPa ⁇ s or more, more preferably 20 mPa ⁇ s or more, and more preferably 150 mPa ⁇ s or less, further preferably 120 mPa ⁇ s or less. The viscosity was measured with a Brookfield viscometer at a rotation speed of 60 rpm.
  • the application of the aqueous dispersion and the drying of the coating film may be performed in-line or off-line in accordance with the molding of the substrate.
  • Coating devices such as a die coater, bar coater, roll coater, lip coater, gravure coater, spray coater, blade coater, reverse coater, and air knife coater can be used to apply the aqueous dispersion.
  • the amount of the water-based dispersion applied can be appropriately adjusted in consideration of the thickness of the desorption layer after drying, the concentration of the ingredients, and the like.
  • a drying device such as a hot air blower or an infrared dryer can be used to dry the coating film. Drying may be performed at room temperature or by heating. When heating, the temperature is preferably 40 to 200°C, more preferably 60 to 150°C.
  • thermoplastic resin that does not have an acid group melts and forms a film, forming a detachable layer in which the carboxylic anhydride-modified olefin resin is retained on the base material.
  • the printed matter of the present invention comprises a printed layer on the release layer of the laminate of the present invention, and is obtained by forming the printed layer on the release layer.
  • the printing layer is a layer composed of characters, images, etc. formed with printing ink or toner.
  • the printed layer is located on the surface of the laminate of the present invention on the release layer side, and may cover at least a part of the surface of the release layer, or may cover the entire area.
  • various printing methods such as offset printing, inkjet method, electrophotographic (laser) method, thermal recording method, and thermal transfer method can be used. can be used.
  • alkaline aqueous solutions examples include sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonia water, barium hydroxide, and calcium hydroxide.
  • the concentration of the alkaline aqueous solution may be appropriately adjusted according to the printing form of the printed matter, processing time, etc., but it is preferably used in the range of 0.5 to 15% by mass, more preferably 1 to 5% by mass.
  • concentration of the alkaline aqueous solution is within the above range, the alkaline aqueous solution can maintain sufficient alkalinity for desorption, and is also suitable for penetrating through the printed matter and the cross section of the laminate laminate to be compatible with the desorption layer. Therefore, the ink can be detached in a shorter time.
  • the concentration of the alkaline aqueous solution is 5% or less from the viewpoint of environmental protection and waste liquid handling in the recycling process.
  • the amount of the alkaline aqueous solution used is preferably 100 to 1,000,000 times the mass of the printed matter or laminate. When the amount of the alkaline aqueous solution used is 100 times or more with respect to the mass of the printed matter or laminate, a sufficient alkali desorption effect of the release layer can be obtained. It is preferably 1,000,000 times the amount or less because the release effect does not change.
  • the amount of the alkaline aqueous solution used is more preferably 200 times or more, more preferably 300 times or more, and more preferably 10,000 times or less with respect to the mass of the printed matter or laminate. A double amount or less is more preferable.
  • the temperature of the alkaline aqueous solution during the treatment is preferably room temperature to 90° C., specifically, it is preferably 20° C. or higher, more preferably 30° C. or higher, and 70° C. from the viewpoint of treatment efficiency. It is more preferably 65° C. or less, particularly preferably 60° C. or less.
  • the method of contacting the printed matter or laminate with the alkaline aqueous solution is not particularly limited, but from the viewpoint of the efficiency of the alkali desorption treatment, immersion in the alkaline aqueous solution is preferable.
  • immersion in the alkaline aqueous solution By immersing in the alkaline aqueous solution, the printed matter or the laminate as a whole comes into contact with the alkaline aqueous solution, so that the treatment can be performed efficiently.
  • the immersion time may be appropriately adjusted according to the printing form of the printed material, preferably 1 minute to 24 hours, more preferably 1 minute to 12 hours.
  • the concentration of the alkaline aqueous solution is preferably 0.5 to 15% by mass
  • the immersion temperature is preferably 30 to 70° C.
  • the immersion time is 1 to 12%. Time is preferred.
  • the concentration of the alkaline aqueous solution is preferably 1 to 15% by mass
  • the immersion temperature is preferably 30 to 70° C.
  • the immersion time is 1 to 12 hours. is preferred.
  • the product is washed with water and dried to obtain an article from which the printed matter has been removed (deinked).
  • the removal rate of the printed layer is preferably 90% or higher, more preferably 95% or higher, still more preferably 98% or higher.
  • the printed matter or laminate may be pulverized and agitated by circulating washing.
  • a printed material having a printed layer on the surface (release layer side surface) of the laminate is obtained by removing the printed layer in an alkaline aqueous solution, washing with water and drying to obtain a recycled base material.
  • the recycled base material is a thermoplastic resin, it can be recycled into pellets by an extruder for use.
  • Substantial acid number (KOHmg/m 2 ) X x 0.01 Y x Z (In the above formula, X is the basis weight (g/m 2 ) of the release layer, Y is the content (% by mass) of the carboxylic anhydride-modified olefin resin in the release layer, and Z is the content of the carboxylic anhydride-modified olefin resin. acid value (KOHmg/g).)
  • the laminate obtained in each example and comparative example was cut into an A2 size (420 mm ⁇ 594 mm), and a design including a design was offset printed on the release layer surface.
  • an offset printing machine (trade name: SM102, manufactured by Heidelberg) and oxidation polymerization type sheet-fed process ink (trade name: Fusion G (black, indigo, red, yellow), manufactured by DIC) were used.
  • the pattern was printed in four colors of black, indigo, red and yellow, and the density of each color was 100%. Specifically, 1,000 sheets were continuously printed at a speed of 8,000 sheets/hour under an environment of a temperature of 23° C. and a relative humidity of 50% to obtain an offset printed material.
  • This three-layer structure laminate was introduced into a tenter oven, heated to 150° C., and stretched 8 times in the horizontal direction using a tenter. Then, it was heat-set (annealed) at 165° C., further cooled to 60° C., and the edge portions were slit to obtain a thermoplastic resin film having a thickness of 110 ⁇ m as a substrate (1).
  • Example 1 "Isoban-04" (trade name) manufactured by Kuraray Co., Ltd. was used as the isobutylene-maleic anhydride copolymer and pulverized with a bead mill to obtain tabular particles having an average particle diameter (D50) of 3.6 ⁇ m. . 20 parts of a cation-modified urethane resin (Daiichi Kogyo Seiyaku Co., Ltd. "Superflex 620” (trade name) is mixed with 100 parts of the pulverized isobutylene maleic anhydride copolymer particles, and the solid content concentration is 20% by mass.
  • D50 average particle diameter
  • Superflex 620 (trade name) is mixed with 100 parts of the pulverized isobutylene maleic anhydride copolymer particles, and the solid content concentration is 20% by mass.
  • Example 2 A dispersion was prepared in the same manner as in Example 1 except that 150 parts of the cation-modified urethane resin was used, and a laminate was prepared using the obtained dispersion.
  • Example 3 A dispersion was prepared in the same manner as in Example 1 except that 900 parts of the cation-modified urethane resin was used, and a laminate was prepared using the obtained dispersion.
  • Example 4 Example 1 except that the pulverization conditions of isobutylene-maleic anhydride copolymer "Isoban-04" (trade name) manufactured by Kuraray Co., Ltd. were changed to obtain tabular particles having an average particle diameter (D50) of 13.8 ⁇ m. A dispersion was prepared in the same manner as in , and a laminate was prepared using the obtained dispersion.
  • Isoban-04 trademark of isobutylene-maleic anhydride copolymer manufactured by Kuraray Co., Ltd.
  • Example 5 A dispersion was prepared in the same manner as in Example 4 except that 150 parts of the cation-modified urethane resin was used, and a laminate was prepared using the obtained dispersion.
  • Example 6 A dispersion was prepared in the same manner as in Example 4 except that 900 parts of the cation-modified urethane resin was used, and a laminate was prepared using the obtained dispersion.
  • Example 7 A dispersion was prepared and obtained in the same manner as in Example 1, except that a styrene maleic anhydride copolymer (Polyscope "XIRAN 1000P" (trade name)) was used instead of the isobutylene maleic anhydride copolymer. A laminate was produced using the dispersion.
  • a styrene maleic anhydride copolymer Polyscope "XIRAN 1000P" (trade name)
  • Example 8 A dispersion was prepared in the same manner as in Example 7 except that 150 parts of the cation-modified urethane resin was used, and a laminate was prepared using the obtained dispersion.
  • Example 1 A dispersion was prepared in the same manner as in Example 7 except that 900 parts of the cation-modified urethane resin was used, and a laminate was prepared using the obtained dispersion.
  • Example 2 A laminate was produced in the same manner as in Example 1, except that the cation-modified urethane resin was not used and an isobutylene-maleic anhydride copolymer neutralized with ammonia was dissolved in water and used.
  • Examples 1 to 8 all had a print layer removal rate of 95% or more when alkali treated at 40 ° C. for 20 minutes, and even when alkali treated at 20 ° C. for 20 minutes. A removal rate of 70% or more was found to be excellent in detachability. On the other hand, in Comparative Example 1, 70% or more was removed when alkali treatment was performed at 40° C. for 20 minutes, but removal was insufficient when alkali treatment was performed at 20° C. for 20 minutes. In addition, although the detachability of Comparative Example 2 by alkali treatment was good, the water resistance of the detachment layer was insufficient.

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