Method for manufacturing recorded material and method for manufacturing package

Abstract

To provide a method for producing a printed material having improved blocking resistance and shrink quality.SOLUTION: A method for producing a printed material includes an application step of applying a radiation-curable ink composition onto a shrink film, and a curing step of irradiating the radiation-curable ink composition on the shrink film with radiation to form a cured ink coating, thus obtaining a printed material. The radiation-curable ink composition contains a polymerizable compound whose weighted average glass transition temperature is 20°C to 70°C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a recorded matter and a method for producing a package. [Background technology]

[0002] Inkjet recording is capable of recording high-resolution images using relatively simple equipment and has been rapidly developing in various fields. Among these, inkjet recording on various types of packaging has been studied. Shrink film is one type of film used for packaging, but when inkjet-printed shrink film is used as a label, the ink has low heat resistance, which can lead to dissolution or discoloration of the ink, making it difficult to obtain high-quality printed images. Furthermore, when the shrink film is cured by radiation, the heat generated by the reaction heat during curing can heat the shrink film, resulting in uneven thermal shrinkage during the heating process when the bottle is attached.

[0003] In response to these problems, Patent Document 1 discloses a shrink film for inkjet recording that uses a resin with a predetermined glass transition temperature (Tg), and that has a predetermined heat shrinkage rate when heat-shrunk in hot air at 70°C for 1 minute, and when heat-shrunk in hot air at 70°C for 1 minute and then further heat-shrunk in hot air at 140°C for 1 minute. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-285540 Summary of the Invention [Problem to be solved by the invention]

[0005] Typically, shrink films are heated and shrunk to wrap items such as PET bottles. During this heat shrinkage, problems such as wrinkles may occur in the coating film, depending on the physical properties of the radiation-curable inkjet composition adhered to the shrink film. [Means for solving the problem]

[0006] The method for producing a recorded matter of the present invention comprises an adhering step of adhering a radiation-curable ink composition to a shrink film, and a curing step of irradiating the radiation-curable ink composition adhered to the shrink film with radiation to form a cured coating film and obtain a recorded matter, wherein the weighted average of the glass transition temperatures of the polymerizable compounds contained in the radiation-curable ink composition is 20°C or higher and 70°C or lower.

[0007] The packaging method for a package of the present invention includes a heating step of heating the recorded material obtained by the above-described method for producing a recorded material while the recorded material is used to cover an object to be packaged. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a perspective view showing a serial inkjet device according to an embodiment of the present invention; DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail with reference to the drawings as necessary, but the present invention is not limited to this, and various modifications are possible without departing from the spirit of the present invention. In the drawings, the same elements are given the same reference numerals, and redundant explanations will be omitted. Furthermore, positional relationships such as up, down, left, and right will be based on the positional relationships shown in the drawings unless otherwise specified. Furthermore, the dimensional ratios of the drawings are not limited to those shown in the drawings.

[0010] 1. Manufacturing method of recorded materials The method for producing a recorded matter of this embodiment comprises an attachment step of attaching a radiation-curable ink composition to a shrink film, and a curing step of irradiating the radiation-curable ink composition (hereinafter also simply referred to as "ink composition") attached to the shrink film with radiation to form a cured coating film and obtain a recorded matter, wherein the weighted average of the glass transition temperatures of the polymerizable compounds contained in the radiation-curable ink composition is 20°C or higher and 70°C or lower.

[0011] In a recorded matter obtained by applying an ink composition to a shrink film as a recording medium, the ink composition coating cannot fully follow the heat shrinkage of the shrink film, and wrinkles may occur on the recorded surface of the shrink film after shrinkage. Furthermore, a recorded matter on which an ink composition is recorded on a shrink film is often rolled up for storage, but there is also the problem that the recorded surface and non-recorded surface of the shrink film come into contact with each other when rolled up, and they tend to stick to each other.

[0012] In contrast, in the method for producing a recorded matter of this embodiment, by adjusting the weighted average of the glass transition temperatures of the polymerizable compounds contained in the radiation-curable ink composition, it is possible to further prevent wrinkling in the coating film when the shrink film is heat-shrunk, and to make the film less likely to stick together when rolled up for storage. Hereinafter, preventing wrinkling in the coating film when the film is heat-shrunk is referred to as having excellent "shrink properties," and preventing sticking between the recorded surface and non-recorded surface is referred to as having excellent "blocking resistance."

[0013] Below, each step of the method for producing a recorded matter according to this embodiment will be described in detail, and then the radiation-curable ink composition will be described in detail.

[0014] 1.1.Attachment process In the application step, the radiation-curable ink composition is applied to the shrink film. The application method is not particularly limited, and examples thereof include, in addition to the inkjet method, letterpress printing, intaglio printing, lithographic printing, and stencil printing. Among these, the inkjet method, in which the radiation-curable ink composition is ejected from an inkjet head to be applied to the shrink film, is preferred. More specifically, a pressure-generating means is driven to eject the composition filled in the pressure-generating chamber of the inkjet head from the nozzle. By using the inkjet method, high-quality recorded matter can be obtained more easily. The method for producing a recorded matter of this embodiment will be described below using the inkjet method as an example, but the method for producing a recorded matter of this embodiment is not limited to this method.

[0015] In the inkjet method, an ink composition is ejected from an inkjet head and deposited on a recording medium. More specifically, a pressure generating means may be driven to eject the composition filled in a pressure generating chamber of the inkjet head from a nozzle.

[0016] The inkjet head 10 used in the deposition step includes a line head that performs recording by a line method and a serial head that performs recording by a serial method.

[0017] In the line method using a line head, for example, an inkjet head having a width equal to or greater than the recording width of the recording medium is fixed to the inkjet device. The recording medium is then moved in the sub-scanning direction (the longitudinal direction of the recording medium, the transport direction), and ink droplets are ejected from the nozzles of the inkjet head in conjunction with this movement to record an image on the recording medium.

[0018] In the serial method using a serial head, for example, an inkjet head is mounted on a carriage that can move in the width direction of the recording medium. The carriage is then moved in the main scanning direction (the horizontal or width direction of the recording medium), and ink droplets are ejected from the nozzle openings of the head in conjunction with this movement, thereby recording an image on the recording medium.

[0019] In the application step, the amount of radiation-curable ink composition applied to the shrink film is such that the maximum thickness of the cured coating is preferably 7.5 μm or less, more preferably 5 μm or less, and even more preferably 1.0 to 5.0 μm. By ensuring that the maximum thickness of the cured coating is 7.5 μm or less, the coating thickness becomes thinner when the recorded material is wound up in the lamination step described below, which tends to reduce the volume of the roll and further improve storage efficiency. Furthermore, by ensuring that the maximum thickness of the cured coating is 1.0 μm or more, the coating is more likely to wrinkle during heat shrinkage, making the present invention particularly useful.

[0020] In this embodiment, a shrink film refers to a film that has the property of shrinking by 10% or more in at least one direction when heated to 80° C., preferably by 15% or more, more preferably by 20% or more, and even more preferably by 30% or more. The higher the shrinkage rate of a shrink film, the more likely it is that the coating film will wrinkle during heat shrinkage, making the present invention particularly useful.

[0021] The shrinkage percentage of a shrink film when heated to 80°C can be calculated using the following formula. The shrinkage percentage can be measured in any direction, and in this embodiment, it is sufficient that the shrinkage percentage in at least one direction in which the film shrinks the most is within the above range. A stretched film obtained by stretching an unstretched film to orient the resin in the stretching direction has the property that, when heated, the stress due to molecular orientation is relieved and the film shrinks to the dimensions before stretching. The shrinkage percentage and direction can be adjusted by the stretching step described below, and the shrinkage direction is not particularly limited and may be the machine direction, the width direction, or both. Shrinkage rate (%) = (length before shrinkage - length after shrinkage) / length before shrinkage

[0022] The resin constituting the shrink film is not particularly limited, but examples thereof include polyolefin resins, polyester resins, polystyrene resins, and polyvinyl chloride resins. One example of a polyester resin constituting the shrink film is a resin obtained by condensation polymerization of a dicarboxylic acid component and a polyhydric alcohol component.

[0023] The dicarboxylic acid component is not particularly limited, but examples thereof include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene-1,4- or -2,6-dicarboxylic acid, and 5-sodium sulfoisophthalic acid; ester-forming derivatives of aromatic dicarboxylic acids such as dialkyl esters and diaryl esters; and aliphatic dicarboxylic acids such as dimer acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, oxalic acid, and succinic acid.

[0024] In addition, oxycarboxylic acids such as p-oxybenzoic acid, and polycarboxylic acids such as trimellitic anhydride and pyromellitic anhydride may also be used.

[0025] The polyhydric alcohol component is not particularly limited, but examples thereof include alkylene glycols such as ethylene glycol, diethylene glycol, dimer diol, propylene glycol, triethylene glycol, 1,4-butanediol, neopentyl glycol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,9-nonanediol, and 1,10-decanediol; ethylene oxide adducts of bisphenol compounds or derivatives thereof; trimethylolpropane, glycerin, pentaerythritol, polyoxytetramethylene glycol, and polyethylene glycol.

[0026] In addition, polyhydric alcohols such as trimethylolpropane, trimethylolethane, glycerin, diglycerin, and pentaerythritol may also be used.

[0027] The polystyrene resin is not particularly limited, but examples thereof include polystyrene, poly(alkylstyrenes) such as poly(p-, m-, or o-methylstyrene), poly(2,4-, 2,5-, 3,4-, or 3,5-dimethylstyrene), and poly(p-tertiarybutylstyrene), poly(halogenated styrenes) such as poly(p-, m-, or o-chlorostyrene), poly(p-, m-, or o-bromostyrene), poly(p-, m-, or o-fluorostyrene), and poly(o-methyl-p-fluorostyrene), and poly(p-, m-, or o-chlorostyrene). Examples of suitable styrene-based copolymers include poly(halogen-substituted alkylstyrenes) such as poly(methylstyrene), poly(alkoxystyrenes) such as poly(p-, m-, or o-methoxystyrene) and poly(p-, m-, or o-ethoxystyrene), poly(carboxyalkylstyrenes) such as poly(p-, m-, or o-carboxymethylstyrene), poly(alkyl ether styrenes) such as poly(p-vinylbenzyl propyl ether), poly(alkylsilylstyrenes) such as poly(p-trimethylsilylstyrene), and even poly(vinylbenzyl dimethoxyphosphide).

[0028] The shrink film may contain a rubber component, and examples of such rubber components include, but are not limited to, rubber in which the butadiene moiety of a styrene-butadiene block copolymer is partially or completely hydrogenated, styrene-butadiene copolymer rubber, styrene-isoprene block copolymer, rubber in which the butadiene moiety of a styrene-isoprene block copolymer is partially or completely hydrogenated, methyl acrylate-butadiene-styrene copolymer rubber, methyl methacrylate-alkyl acrylate-butadiene-styrene copolymer rubber, etc.

[0029] The shrink film is preferably a stretched film. The stretching treatment may be either uniaxial stretching or biaxial stretching. The stretching method is not particularly limited, but examples include a method having a stretching step in which an unstretched film is stretched 2.0 to 8.0 times, preferably 2.5 to 6.0 times, in the direction to impart shrinkability in a temperature range of Tg-20°C to Tg+40°C, based on the glass transition temperature (Tg) of the resin constituting the shrink film. After the stretching step, the film may be heat-treated at a temperature of 50 to 110°C while being stretched 0 to 15% or relaxed 0 to 15%.

[0030] 1.2.Curing process In the curing step, the radiation-curable ink composition attached to the shrink film is irradiated with radiation to form a cured coating film, thereby obtaining a recorded product. When irradiated with radiation, a polymerization reaction of the polymerizable compound is initiated, curing the ink composition and forming a coating film. If a polymerization initiator is present, it generates active species (initiating species) such as radicals, acids, and bases, and the polymerization reaction of the monomer is promoted by the function of these initiating species. Furthermore, if a photosensitizer is present, it absorbs radiation and becomes excited, and upon contact with the polymerization initiator, it promotes the decomposition of the polymerization initiator, thereby achieving a more rapid curing reaction.

[0031] Examples of the radiation include ultraviolet light, infrared light, visible light, and X-rays. The radiation source is provided downstream of the inkjet head and irradiates the ink composition with the radiation. The radiation source is not particularly limited, but examples thereof include ultraviolet light-emitting diodes. Use of such a radiation source can reduce the size and cost of the device. Because ultraviolet light-emitting diodes as an ultraviolet light source are small, they can be installed inside the inkjet device.

[0032] For example, ultraviolet light-emitting diodes can be attached to a carriage (at both ends along the medium width direction and / or on the medium transport direction side) on which an inkjet head that ejects the radiation-curable inkjet composition is mounted. Furthermore, due to the composition of the radiation-curable inkjet composition described above, it is possible to achieve low-energy, high-speed curing.

[0033] 1.3.Lamination process The method for producing a recorded matter in this embodiment may further include a lamination step of stacking the obtained recorded matter so that the recorded side to which the radiation curable ink composition is attached faces the non-recorded side to which the radiation curable ink composition is not attached. Such a lamination step may be performed by winding up the long recorded matter into a roll.

[0034] In industrial applications, recorded materials are usually wound into rolls, and when the recorded material is wound into a roll, the recorded side with the ink coating and the backside are pressed together inside the roll and stored in this state. In such a state, blocking is a particular problem. For this reason, the present invention is particularly useful.

[0035] 2. Packaging method for package The packaging method of the present embodiment includes a heating step of heating the recorded matter obtained as described above while covering the object to be packaged with the recorded matter, whereby the recorded matter covering the object to be packaged undergoes thermal shrinkage, and the object can be packaged by this shrinkage.

[0036] At this time, the recorded surface may be in contact with the packaged object, or the non-recorded surface may be in contact with the packaged object.

[0037] The conditions for the heating step are not particularly limited, but the heating temperature is preferably 70 to 180° C., more preferably 80 to 150° C., and even more preferably 90 to 150° C. The heating time is preferably 3 to 90 seconds, more preferably 5 to 60 seconds, and even more preferably 10 to 30 seconds.

[0038] 3. Radiation-curable ink composition The radiation-curable ink composition of this embodiment is cured by irradiation with radiation. Examples of radiation include ultraviolet light, electron beams, infrared light, visible light, and X-rays. As the radiation, ultraviolet light is preferred because radiation sources are readily available and widely used, and materials suitable for curing by ultraviolet radiation are readily available and widely used.

[0039] The components contained in the radiation-curable ink composition of this embodiment are not particularly limited, but examples include polymerizable compounds, polymerization initiators, polymerization inhibitors, sensitizers, surfactants, colorants, and dispersants. The ink composition does not need to contain all of these components, and may contain only some of them. Below, the components that can be contained in the radiation-curable inkjet composition of this embodiment will be described.

[0040] 3.1. Polymerizable compounds In this embodiment, a polymerizable compound is generally defined as a compound having a polymerizable unsaturated bond. The polymerizable compound may include a monofunctional monomer having one polymerizable functional group and a polyfunctional monomer having multiple polymerizable functional groups. The polymerizable compound may be used alone or in combination of two or more.

[0041] The weighted average glass transition temperature of the polymerizable compound contained in the radiation-curable ink composition is 20 to 70°C, preferably 25 to 65°C, more preferably 30 to 60°C, and even more preferably 35 to 60°C. When the weighted average glass transition temperature is 20°C or higher, blocking resistance is further improved. Furthermore, when the weighted average glass transition temperature is 20°C or higher, curability also tends to be further improved. Furthermore, when the weighted average glass transition temperature is 70°C or lower, shrink properties are further improved.

[0042] The "glass transition temperature of the polymerizable compound" means the glass transition temperature of a homopolymer of the polymerizable compound. The weighted average glass transition temperature of the polymerizable compound can be adjusted by the glass transition temperature of the homopolymer of the polymerizable compound used and the content mass ratio of the polymerizable compound used.

[0043] Here, a method for calculating the weighted average of the glass transition temperatures of the homopolymers in the polymerizable compound will be described. The weighted average of the glass transition temperatures of the homopolymers is called Tg All The glass transition temperature of the homopolymer of each polymerizable compound is Tg N The content mass ratio of the polymerizable compound is X N (wt%). N is a number starting from 1 depending on the type of polymerizable compound contained in the radiation-curable inkjet ink composition. For example, when three types of polymerizable compounds are used, Tg1, Tg2, and Tg3 are obtained. The weighted average Tg of the glass transition temperatures of homopolymers All is the glass transition temperature Tg of the homopolymer calculated for each polymerizable compound. N and the mass ratio X N Therefore, the following equation (1) holds true: Tg All =ΣTg N ×X N ···(1)

[0044] The glass transition temperature of a homopolymer of a polymerizable compound can be measured by differential scanning calorimetry (DSC) in accordance with JIS K 7121. For example, a measuring device such as a DSC6220 manufactured by Seiko Electronics Co., Ltd. can be used, and a sample can be prepared by polymerizing a monomer to such an extent that the glass transition temperature of the homopolymer becomes constant.

[0045] The content of the polymerizable compound is preferably 55 to 85% by mass, more preferably 60 to 80% by mass, and even more preferably 65 to 75% by mass, relative to the total amount of the ink composition. When the content of the polymerizable compound is within the above range, blocking resistance, shrink properties, or curability tend to be further improved.

[0046] 3.1.1. Monofunctional Monomers The monofunctional monomer is not particularly limited, and examples thereof include nitrogen-containing monofunctional monomers, aromatic group-containing monofunctional monomers, monofunctional monomers having an alicyclic structure, etc. Furthermore, other monofunctional monomers may be contained instead of or in addition to these, as necessary.

[0047] The content of the monofunctional monomer is preferably 50% by mass or more, more preferably 60 to 95% by mass, even more preferably 65 to 90% by mass, and particularly preferably 70 to 85% by mass, based on the total amount of the polymerizable compounds. When the content of the monofunctional monomer is 50% by mass or more, shrink properties tend to be further improved. Furthermore, when the content of the monofunctional monomer is 95% by mass or less, blocking resistance tends to be further improved.

[0048] Examples of monofunctional monomers are shown below, but the monofunctional monomers in this embodiment are not limited to the following.

[0049] 3.1.1.1. Nitrogen-containing monofunctional monomers The polymerizable compound preferably contains a nitrogen-containing monofunctional monomer, which tends to further improve the hardness of the resulting coating film and further improve the blocking resistance.

[0050] The nitrogen-containing monofunctional monomer is not particularly limited, and examples thereof include nitrogen-containing monofunctional vinyl monomers such as N-vinylcaprolactam (n-VC), N-vinylformamide, N-vinylcarbazole, N-vinylacetamide, vinylmethyloxazolidinone (VMOX), and N-vinylpyrrolidone; nitrogen-containing monofunctional acrylate monomers such as acryloylmorpholine (ACMO); and nitrogen-containing monofunctional acrylamide monomers such as (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, diacetone acrylamide, N,N-dimethyl(meth)acrylamide, and dimethylaminoethyl acrylate benzyl chloride quaternary salt.

[0051] Among these, it is preferable to contain either a nitrogen-containing monofunctional vinyl monomer or a nitrogen-containing monofunctional acrylate monomer, more preferably a monomer having a nitrogen-containing heterocyclic structure such as vinylmethyloxazolidinone, acryloylmorpholine, or N-vinylcaprolactam, and even more preferably vinylmethyloxazolidinone. By containing such a nitrogen-containing monofunctional monomer, the viscosity of the ink composition tends to be further reduced, thereby further improving the ejection stability. Furthermore, by containing such a nitrogen-containing monofunctional monomer, the blocking resistance, shrink properties, or curability tends to be further improved. Furthermore, since vinylmethyloxazolidinone is a monomer with low viscosity at room temperature, by containing vinylmethyloxazolidinone, the ejection stability tends to be further improved.

[0052] The content of the nitrogen-containing monofunctional monomer is preferably 15 to 45% by mass, more preferably 20 to 40% by mass, and even more preferably 25 to 35% by mass, relative to the total amount of the ink composition. When the content of the nitrogen-containing monofunctional monomer is within the above range, blocking resistance, shrink properties, or curability tend to be further improved.

[0053] 3.1.1.2. Aromatic group-containing monofunctional monomers The aromatic group-containing monofunctional monomer is not particularly limited, but examples thereof include phenoxyethyl (meth)acrylate (PEA), benzyl (meth)acrylate, alkoxylated 2-phenoxyethyl (meth)acrylate, ethoxylated nonylphenyl (meth)acrylate, alkoxylated nonylphenyl (meth)acrylate, p-cumylphenol EO-modified (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.

[0054] Among these, phenoxyethyl (meth)acrylate and benzyl (meth)acrylate are preferred, phenoxyethyl (meth)acrylate is more preferred, and phenoxyethyl acrylate (PEA) is even more preferred. By using such aromatic group-containing monofunctional monomers, the solubility of the polymerization initiator tends to be further improved, and the curability of the ink composition tends to be further improved. In particular, when an acylphosphine oxide-based polymerization initiator or a thioxanthone-based polymerization initiator is used, the solubility tends to be improved.

[0055] The content of the aromatic group-containing monofunctional monomer is preferably 25 to 55 mass %, more preferably 30 to 50 mass %, and even more preferably 35 to 45 mass %, relative to the total amount of the ink composition. When the content of the aromatic group-containing monofunctional monomer is within the above range, blocking resistance, shrink properties, and curability tend to be further improved.

[0056] 3.1.1.3. Monofunctional monomers with alicyclic structures The monofunctional monomer having an alicyclic structure is not particularly limited, but examples thereof include monomers having a monocyclic hydrocarbon group such as tert-butylcyclohexanol (meth)acrylate (TBCHA), 3,3,5-trimethylcyclohexyl (meth)acrylate (TMCHA), and 2-(meth)acrylic acid-1,4-dioxaspiro[4,5]dec-2-ylmethyl; monomers having an unsaturated polycyclic hydrocarbon group such as dicyclopentenyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate; and monomers having a saturated polycyclic hydrocarbon group such as dicyclopentanyl (meth)acrylate and isobornyl (meth)acrylate (IBXA).

[0057] Among these, isobornyl (meth)acrylate, tert-butylcyclohexanol acrylate, and trimethylcyclohexyl (meth)acrylate are preferred, and isobornyl acrylate is more preferred. By using such monofunctional monomers having an alicyclic structure, blocking resistance, shrink properties, or curability tend to be further improved.

[0058] The content of the monofunctional monomer having an alicyclic structure is preferably 15 to 45 mass %, more preferably 20 to 40 mass %, and even more preferably 25 to 35 mass %, relative to the total amount of the ink composition. When the content of the monofunctional monomer having an alicyclic structure is within the above range, blocking resistance, shrink properties, or curability tend to be further improved.

[0059] 3.1.2. Polyfunctional Monomers The polyfunctional monomer is not particularly limited, but examples thereof include vinyl group-containing (meth)acrylates and polyfunctional (meth)acrylates. Note that the polyfunctional monomer is not limited to the above.

[0060] The content of the polyfunctional monomer is preferably 5 to 40% by mass or more, more preferably 10 to 30% by mass or more, and even more preferably 15 to 20% by mass, based on the total amount of the polymerizable compounds. When the content of the polyfunctional monomer is 5% by mass or more, blocking resistance tends to be further improved. Furthermore, when the content of the polyfunctional monomer is 40% by mass or less, shrink properties tend to be further improved.

[0061] Examples of polyfunctional monomers are given below, but the polyfunctional monomers in this embodiment are not limited to the following.

[0062] 3.1.2.1. Vinyl group-containing (meth)acrylates The vinyl group-containing (meth)acrylate is not particularly limited, but examples thereof include compounds represented by the following formula (I): By including such a vinyl group-containing (meth)acrylate, blocking resistance, shrink properties, or curability tend to be further improved. H2C=CR 1 -CO-OR 2 -O-CH=CH-R 3 (I) (In the formula, R 1 is a hydrogen atom or a methyl group, and R2 is a divalent organic residue having 2 to 20 carbon atoms, and R 3 is a hydrogen atom or a monovalent organic residue having 1 to 11 carbon atoms.

[0063] In the above formula (I), R 2 Examples of the divalent organic residue having 2 to 20 carbon atoms represented by the formula (I) include a linear, branched, or cyclic alkylene group having 2 to 20 carbon atoms, which may be substituted; an alkylene group having 2 to 20 carbon atoms and having an oxygen atom via an ether bond and / or an ester bond in its structure, which may be substituted; and a divalent aromatic group having 6 to 11 carbon atoms, which may be substituted. Among these, alkylene groups having 2 to 6 carbon atoms, such as an ethylene group, an n-propylene group, an isopropylene group, and a butylene group, and alkylene groups having 2 to 9 carbon atoms and having an oxygen atom via an ether bond in its structure, such as an oxyethylene group, an oxy-n-propylene group, an oxyisopropylene group, and an oxybutylene group, are preferred. Furthermore, from the viewpoint of further reducing the viscosity of the ink composition and further improving the curability of the ink composition, R 2 is an alkylene group having 2 to 9 carbon atoms and having an oxygen atom by an ether bond in the structure, such as an oxyethylene group, an oxy-n-propylene group, an oxyisopropylene group, or an oxybutylene group, and more preferred are compounds having a glycol ether chain.

[0064] In the above formula (I), R 3 Suitable monovalent organic residues having 1 to 11 carbon atoms and represented by the formula (I) are linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms, which may be substituted, and aromatic groups having 6 to 11 carbon atoms, which may be substituted. Among these, alkyl groups having 1 to 2 carbon atoms, such as methyl or ethyl groups, and aromatic groups having 6 to 8 carbon atoms, such as phenyl and benzyl groups, are preferably used.

[0065] When each of the above organic residues is a group that may be substituted, the substituent is divided into a group containing carbon atoms and a group not containing carbon atoms. First, when the above substituent is a group containing carbon atoms, the carbon atom is counted in the number of carbon atoms of the organic residue. Examples of the group containing carbon atoms include, but are not limited to, a carboxyl group and an alkoxy group. Next, examples of the group not containing carbon atoms include, but are not limited to, a hydroxyl group and a halo group.

[0066] Specific examples of the compound of formula (I) include, but are not limited to, 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 1-methyl-3-vinyloxypropyl (meth)acrylate, 1-vinyloxymethylpropyl (meth)acrylate, 2-methyl-3-vinyloxypropyl (meth)acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth)acrylate, ) 3-vinyloxybutyl acrylate, 1-methyl-2-vinyloxypropyl (meth)acrylate, 2-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, 3-vinyloxymethylcyclohexylmethyl (meth)acrylate, 2-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, m-vinyloxymethylphenyl (meth)acrylate Methyl, o-vinyloxymethylphenylmethyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-(vinyloxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxy)propyl (meth)acrylate, 2-(vinyloxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxy)propyl (meth)acrylate, 2-(vinyloxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate (meth)acrylate 2-(vinyloxyethoxyisopropoxy)ethyl, (meth)acrylate 2-(vinyloxyisopropoxyethoxy)ethyl, (meth)acrylate 2-(vinyloxyisopropoxyisopropoxy)ethyl, (meth)acrylate 2-(vinyloxyethoxyethoxy)propyl, (meth)acrylate 2-(vinyloxyethoxyisopropoxy)propyl, (meth)acrylate 2-(vinyloxyisopropoxyethoxy)propyl, (meth)acrylate 2-(vinyloxyisopropoxyisopropoxy)propyl, (meth)acrylate 2-(vinyloxyisopropoxyisopropoxy)propyl,2-(vinyloxyethoxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate ethyl, 2-(isopropenoxyethoxy)ethyl (meth)acrylate, 2-(isopropenoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenoxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenoxyethoxyethoxyethoxy)ethyl (meth)acrylate, polyethylene glycol monovinyl ether (meth)acrylate, and polypropylene glycol monovinyl ether (meth)acrylate. Of these specific examples, 2-(2-vinyloxyethoxy)ethyl acrylate is particularly preferred because it allows the ink composition to have a good balance between curability and viscosity. In this embodiment, 2-(2-vinyloxyethoxy)ethyl acrylate is also referred to as VEEA.

[0067] The content of the vinyl group-containing (meth)acrylate is preferably 1.0 to 10% by mass, more preferably 2.0 to 8.0% by mass, and even more preferably 4.0 to 6.0% by mass, relative to the total amount of the ink composition. When the content of the vinyl group-containing (meth)acrylate is within the above range, blocking resistance, shrink properties, and curability tend to be further improved.

[0068] 3.1.2.2. Multifunctional (meth)acrylates The polyfunctional (meth)acrylate is not particularly limited, and examples thereof include dipropylene glycol di(meth)acrylate (DPGDA), diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol dimethacrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, EO (ethylene oxide) adduct di(meth)acrylate of bisphenol A, PO (propylene oxide) di(meth)acrylate of bisphenol A, and the like. Examples of the acrylate include bifunctional (meth)acrylates such as ethylene oxide adduct di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate; and trifunctional or higher polyfunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin propoxy tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, and caprolactam-modified dipentaerythritol hexa(meth)acrylate.

[0069] Among these, dipropylene glycol diacrylate (DPGDA) is more preferable. By using such a polyfunctional (meth)acrylate, the curability and abrasion resistance tend to be further improved, and the viscosity tends to be further reduced.

[0070] The content of the polyfunctional (meth)acrylate is preferably 2.5 to 17.5 mass %, more preferably 5.0 to 15 mass %, and even more preferably 7.5 to 12.5 mass %, relative to the total amount of the ink composition. When the content of the polyfunctional (meth)acrylate is within the above range, curability tends to be further improved and viscosity tends to be further reduced.

[0071] 3.2.Polymerization initiator The polymerization initiator is not particularly limited as long as it is a photopolymerization initiator that generates active species upon irradiation with radiation, and examples thereof include known polymerization initiators such as acylphosphine oxide-based polymerization initiators, alkylphenone-based polymerization initiators, titanocene-based polymerization initiators, and thioxanthone-based polymerization initiators. Among these, acylphosphine oxide-based polymerization initiators and thioxanthone-based polymerization initiators are preferred, with acylphosphine oxide-based polymerization initiators being more preferred. Use of such polymerization initiators tends to further improve the curability of the composition. The polymerization initiators may be used alone or in combination of two or more.

[0072] The content of the polymerization initiator relative to the total amount of the ink composition is preferably 2.5 to 17.5% by mass, more preferably 5 to 15% by mass, and even more preferably 7.5 to 12.5% ​​by mass. When the content of the polymerization initiator is within the above range, the curability of the composition tends to be further improved.

[0073] The acylphosphine oxide polymerization initiator is not particularly limited, but examples thereof include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0074] Commercially available acylphosphine oxide polymerization initiators such as these are not particularly limited, but examples thereof include Omnirad 819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), IRGACURE 1800 (a mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 1-hydroxycyclohexylphenyl ketone in a mass ratio of 25:75), and Speedcure TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide).

[0075] 3.3.Sensitizers The sensitizer is not particularly limited, but examples thereof include thioxanthone compounds, such as thioxanthone, diethylthioxanthone, isopropylthioxanthone, and chlorothioxanthone.

[0076] Commercially available thioxanthone polymerization initiators include, but are not limited to, Speedcure DETX (2,4-diethylthioxanthen-9-one), Speedcure ITX (2-isopropylthioxanthone) (both manufactured by Lambson Chemical), and KAYACURE DETX-S (2,4-diethylthioxanthone) (manufactured by Nippon Kayaku Co., Ltd.).

[0077] The content of the sensitizer is preferably 0.5 to 7.5 mass %, more preferably 1.5 to 5.0 mass %, and even more preferably 2.5 to 3.5 mass %, relative to the total amount of the ink composition. When the content of the sensitizer is within the above range, the curability of the composition tends to be further improved.

[0078] 3.4. Polymerization inhibitors Examples of the polymerization inhibitor include, but are not limited to, p-methoxyphenol, hydroquinone monomethyl ether (MEHQ), 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, hydroquinone, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-butylphenol), and 4,4'-thiobis(3-methyl-6-t-butylphenol), hindered amine compounds, 2,2,6,6-tetramethylpiperidinyl-1-oxyl, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (LA-7RD), and derivatives of 2,2,6,6-tetramethylpiperidinyl-1-oxyl.

[0079] The content of the polymerization inhibitor is preferably 0.1 to 0.7% by mass, and more preferably 0.2 to 0.5% by mass, relative to the total amount of the ink composition. When the content of the polymerization inhibitor is within the above range, the storage stability of the ink composition tends to be further improved.

[0080] 3.5.Surfactants The surfactant is not particularly limited, but examples thereof include acetylene glycol surfactants, fluorine-based surfactants, and silicone-based surfactants.

[0081] The acetylene glycol surfactant is not particularly limited, but examples thereof include alkylene oxide adducts of 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7-diol, and alkylene oxide adducts of 2,4-dimethyl-5-decyne-4-ol and 2,4-dimethyl-5-decyne-4-ol.

[0082] The fluorine-based surfactant is not particularly limited, but examples thereof include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkyl amine oxide compounds.

[0083] Examples of silicone surfactants include polysiloxane compounds, polyester-modified silicones, and polyether-modified organosiloxanes. Examples of polyester-modified silicones include BYK-347, 348, BYK-UV3500, 3510, and 3530 (all manufactured by BYK Additives & Instruments). Examples of polyether-modified silicones include BYK-3570 (manufactured by BYK Additives & Instruments).

[0084] The content of the surfactant is preferably 0.1 to 1.0% by mass, and more preferably 0.2 to 0.8% by mass, relative to the total mass of the ink composition. When the content of the surfactant is within this range, the wettability of the ink composition tends to be further improved.

[0085] 3.6.Colorants The ink composition according to this embodiment may further contain a coloring material. By containing a coloring material, the ink composition according to this embodiment can be used as a colored ink composition. The coloring material can be at least one of a pigment and a dye.

[0086] As inorganic pigments, carbon blacks (CI (Colour Index Generic Name) Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide can be used.

[0087] Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye chelates (for example, basic dye chelates, acid dye chelates, etc.); dye lakes (basic dye lakes, acid dye lakes), nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments.

[0088] Although this can be changed appropriately depending on the type of ink desired, the total content of coloring materials is preferably 0.5 to 15% by mass, more preferably 1.0 to 10% by mass, and even more preferably 1.5 to 5.0% by mass, relative to the total amount of ink composition. Note that the ink composition according to this embodiment may be a clear ink that does not contain coloring materials or that contains coloring materials to an extent that coloring is not intended (for example, 0.1% by mass or less).

[0089] The dye is not particularly limited, but examples thereof include acid dyes such as CI Acid Yellow, CI Acid Red, CI Acid Blue, CI Acid Orange, CI Acid Violet, and CI Acid Black; basic dyes such as CI Basic Yellow, CI Basic Red, CI Basic Blue, CI Basic Orange, CI Basic Violet, and CI Basic Black; direct dyes such as CI Direct Yellow, CI Direct Red, CI Direct Blue, CI Direct Orange, CI Direct Violet, and CI Direct Black; reactive dyes such as CI Reactive Yellow, CI Reactive Red, CI Reactive Blue, CI Reactive Orange, CI Reactive Violet, and CI Reactive Black; and disperse dyes such as CI Disperse Yellow, CI Disperse Red, CI Disperse Blue, CI Disperse Orange, CI Disperse Violet, and CI Disperse Black. The above dyes may be used alone or in combination of two or more.

[0090] 3.7.Other Ingredients The radiation-curable ink jet composition according to this embodiment may further contain additives such as coloring materials such as pigments and dyes, and dispersants for pigments and the like, as needed.

[0091] 4. Inkjet device As an example of an inkjet device, a perspective view of a serial printer is shown in Fig. 1. As shown in Fig. 1, the serial printer 20 includes a conveying unit 220 and a recording unit 230. The conveying unit 220 conveys the recording medium F fed to the serial printer to the recording unit 230, and ejects the recording medium after recording outside the serial printer. Specifically, the conveying unit 220 has feed rollers and conveys the fed recording medium F in the sub-scanning direction T1.

[0092] The recording unit 230 also includes an inkjet head 231 that ejects a composition onto the recording medium F sent from the conveying unit 220, a radiation source 232 that irradiates the deposited ink composition with radiation, a carriage 234 that carries these, and a carriage movement mechanism 235 that moves the carriage 234 in the main scanning directions S1 and S2 of the recording medium F.

[0093] In the case of a serial printer, an inkjet head 231 having a length smaller than the width of the recording medium is provided, and the head moves to perform recording in multiple passes (multi-pass). In addition, in a serial printer, the head 231 and radiation source 232 are mounted on a carriage 234 that moves in a predetermined direction, and the head moves in conjunction with the movement of the carriage, thereby ejecting the composition onto the recording medium. In this way, recording is performed in two or more passes (multi-pass). A pass is also called a main scan. A sub-scan is performed to transport the recording medium between passes. In other words, main scans and sub-scans are performed alternately.

[0094] Although FIG. 1 shows an embodiment in which the radiation source is mounted on a carriage, the present invention is not limited to this, and the radiation source may be one that is not mounted on a carriage.

[0095] Furthermore, the inkjet device of this embodiment is not limited to the serial printer, but may be the line printer described above. [Example]

[0096] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples.

[0097] 1. Preparation of ink composition The ink compositions of each example were obtained by placing the components in a mixing tank, mixing and stirring, and filtering through a 5 μm membrane filter so as to obtain the composition shown in Table 1. The numerical values ​​for each component shown in each example in the table represent wt % unless otherwise specified.

[0098] [Table 1]

[0099] The abbreviations and product ingredients used in Table 1 are as follows: [Polymerizable compound] (monofunctional monomer) VMOX (vinylmethyloxazolidinone, manufactured by BASF) ACMO (KJ Chemicals Co., Ltd., acryloylmorpholine) n-VC (ISP Japan, N-vinylcaprolactam) PEA (Phenoxyethyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) IBXA (Osaka Organic Chemical Industry, Ltd., isobornyl acrylate) (polyfunctional monomer) VEEA (Nippon Shokubai Co., Ltd., 2-(2-vinyloxyethoxy)ethyl acrylate) DPGDA (dipropylene glycol diacrylate, manufactured by Sartomer Corporation) [Polymerization inhibitor] LA-7RD (ADEKA Corporation trade name, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl) MEHQ (product name "p-methoxyphenol", manufactured by Kanto Chemical Co., Ltd., hydroquinone monomethyl ether) [Polymerization initiator] Omnirad 819 (IGM Resins, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) Speedcure TPO (LAMBSON, 2,4,6-trimethylbenzoyldiphenylphosphine oxide) [Sensitizer] Speedcure DETX (LAMBSON, 2,4-diethylthioxanthen-9-one) [Surfactant] BYK-UV3500 (BYK Additives & Instruments, silicone surfactant) [Dispersion] Dispersant: Solsperse 36000 (Lubrizol, polymer dispersant) Black pigment: carbon black

[0100] 2. Evaluation Method 2.1. Curability The radiation-curable ink composition obtained above was applied to a PET film using a bar coater to a thickness of 10 μm (as the thickness of the cured film). 2 The irradiation energy [mJ / cm ] was measured until the sample became tack-free. 2 ] is the irradiance [mW / cm ] on the irradiated surface irradiated by the light source. 2 ] was measured and calculated by multiplying this by the duration of irradiation [s].

[0101] The irradiation intensity was measured using a UV intensity meter UM-10 and a light receiving unit UM-400 (both manufactured by KONICA MINOLTA SENSING, INC.). The tack-free state was judged based on the following criteria: whether the ink adhered to the cotton swab or whether the cured ink on the recording medium was scratched. The cotton swabs used were Johnson cotton swabs manufactured by Johnson & Johnson. The swabs were rubbed back and forth 10 times, with a rubbing force of 100 g.

[0102] Based on the irradiation energy when the coating became tack-free, the curability was evaluated according to the following evaluation criteria. (Evaluation criteria) A: Tack-free energy 150mJ / cm 2 less than B: Tack-free energy 150mJ / cm 2 More than 250mJ / cm 2 less than C: Tack-free energy 250mJ / cm 2 End

[0103] Blocking Using an inkjet printer "PX-G5000" (product name, manufactured by Seiko Epson Corporation), a solid pattern image was printed on a recording medium, PET film "Bonset" (product name, manufactured by Takiron CI), at room temperature and normal pressure, with a recording resolution of 600 dpi x 600 dpi and a droplet weight of 20 ng, i.e., with a dot generation rate of 50%, to obtain a printed sample with a film thickness of 5 μm.

[0104] The solid pattern image is an image in which dots are recorded for all pixels, which are the minimum recording unit area defined by the recording resolution. While the above printing was performed, ultraviolet light was irradiated from a UV-LED in an ultraviolet irradiation device mounted next to the carriage, and a recorded product was obtained in which a cured film of the ink composition with a thickness of 5 μm was formed on the recording medium.

[0105] The recorded matter obtained as described above was rolled up with the cured film facing inward and processed into a cylindrical shape. This recorded matter was placed around a container (glass bottle) to be packaged that had been preheated in a thermostatic oven, and left to stand in the thermostatic oven at 90°C for 10 seconds to shrink the recorded matter and make it adhere tightly to the container.

[0106] In the packaging of the packaged item described above, the recorded material was shrunk and brought into close contact with the packaged item. The presence or absence of sticking was evaluated by visually observing whether or not any traces of the cured film adhering to the container had been transferred, and the blocking resistance was evaluated according to the following evaluation criteria. (Evaluation criteria) A: The cured film does not stick to the container. B: The cured film is slightly stuck to the container. C: The cured film is stuck to the container (peeling off).

[0107] 2.2.Shrink characteristics The packaging of the packaged object prepared for the evaluation of blocking resistance was visually observed for the occurrence of wrinkles after shrinkage, and the shrink properties were evaluated according to the following evaluation criteria. (Evaluation criteria) A: No wrinkles in the cured film B: There are some wrinkles in the cured film C: Large wrinkles in the cured film [Explanation of symbols]

[0108] 20... serial printer, 220... transport unit, 230... recording unit, 231... inkjet head, 232... radiation source, 234... carriage, 235... carriage moving mechanism, F... recording medium, S1, S2... main scanning direction, T1... sub-scanning direction

Claims

1. a step of adhering the radiation curable ink composition to a shrink film; a curing step of irradiating the radiation-curable ink composition attached to the shrink film with radiation to form a cured coating film and obtain a recorded product; a lamination step of stacking the recorded matter so that the recording surface to which the radiation curable ink composition is adhered faces the non-recording surface to which the radiation curable ink composition is not adhered, the weighted average of the glass transition temperatures of the polymerizable compounds contained in the radiation-curable ink composition is 20°C or higher and 70°C or lower; A method for producing recorded materials.

2. the polymerizable compound contains a nitrogen-containing monofunctional monomer; A method for producing the recorded matter according to claim 1.

3. the nitrogen-containing monofunctional monomer comprises vinylmethyloxazolidinone; A method for producing the recorded matter according to claim 2.

4. the content of the monofunctional monomer in the radiation-curable ink composition is 50% by mass or more relative to the total amount of the polymerizable compound; A method for producing the recorded matter according to any one of claims 1 to 3.

5. In the application step, the radiation-curable ink composition is applied to the shrink film so that the maximum film thickness of the cured coating film is 5 μm or less. A method for producing the recorded matter according to any one of claims 1 to 4.

6. The laminating step is carried out by winding the recorded matter into a roll. A method for producing the recorded matter according to claim 1.

7. In the adhesion step, the radiation curable ink composition is ejected from an inkjet head and adhered to the shrink film. A method for producing the recorded matter according to any one of claims 1 to 6.

8. The method includes a heating step of heating a packaged object while the packaged object is covered with the recorded matter obtained by the method for producing a recorded matter according to any one of claims 1 to 7. Packaging method for the package.

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