JP5403266B2 - Packaging sheet - Google Patents

Description

  The present invention relates to a packaging sheet, for example, a press-through pack sheet for pharmaceutical packaging (hereinafter referred to as “PTP sheet”), a pack sheet for food packaging, and the like.

  In general, pharmaceuticals are often taken continuously or left untreated. In such a case, most users of the medicine forget the purchase time of the medicine.

  In addition, in pharmacies, it is difficult for a pharmacist to recognize the expiration date of a medicine from the notation written on a packaging container such as a PTP sheet, so it is extremely difficult for the pharmacist to properly inform the user of the expiration date of the medicine. . In recent years, information such as a production lot is printed on a packaging sheet such as a PTP sheet, but the information is extremely difficult to see due to various restrictions. In addition, if the PTP sheet is divided at the printing location, the information cannot be read.

  Under such circumstances, there is a concern that the user may take a medicinal product that is less effective and delay the treatment of the user.

  In response to such a problem, in the past, “First, when the PTP sheet is sandwiched between mounts so that the medicine cannot be removed from the PTP sheet, the user can remove the mount and remove the medicine from the PTP sheet. "PTP sheet package with indicator showing elapsed time" has been proposed (for example, JP 2009-143591A).

JP 2009-143591 A

  However, if a PTP sheet package is required in addition to the PTP sheet in order to add the indicator function, additional capital investment is required and the product cost is increased, which is not economically preferable. Note that this can also occur for food packaging.

  The subject of this invention is providing the packaging sheet with an indicator function which can be manufactured using the existing packaging sheet manufacturing equipment as it is.

(1)
A packaging sheet according to one aspect of the present invention includes a first sheet, a second sheet, and a third sheet. The “packaging sheet” here is, for example, a press-through pack sheet for drug packaging, a pack sheet for food packaging, or the like. The first sheet has a recess. The “recessed portion” used here means a pocket forming portion for accommodating a packaging object. The second sheet is in close contact with the first sheet so as to cover the opening of the recess. At least one of the first sheet and the second sheet has a time-dependent color change layer. Here, at least one of the first sheet and the second sheet may be formed only of the time-dependent color change layer. Further, the time-dependent color change layer may be designed so that characters and figures are raised when a target management time elapses. The temporal color change layer is formed of a temporal color change material whose color and / or color tone changes over time. The “time-dependent color changing layer” referred to here may be one that changes at least one of its color and tone by reacting with oxygen, carbon dioxide, moisture, etc. in the air, At least one of the color and the color tone may be changed by gradually evaporating the object, or at least one of the color and the color tone may be changed by being exposed to light. The third sheet has a blocking property against a specific substance or light. And this 3rd sheet | seat is closely_contact | adhered to the surface on the opposite side to the contact surface of a sheet | seat which has a time-dependent color change layer so that peeling is possible. Here, the “contact surface” means a contact surface between the first sheet and the second sheet.

  A packaging sheet including such a color-changing layer with time can be produced using an existing multilayer packaging sheet production apparatus as it is. Therefore, this packaging sheet has an indicator function and can be manufactured by using existing packaging sheet manufacturing equipment as it is.

(2)
In the packaging sheet according to one aspect of the present invention, the temporal color change layer may be formed over the entire surface of the sheet having the temporal color change layer.

  Such a packaging sheet can improve a user's recognition property with respect to the color change of a time-dependent color change layer.

(3)
The packaging sheet which concerns on 1 aspect of this invention WHEREIN: It is preferable that a time-dependent color change layer is provided in a recessed part at least. In such a case, the third sheet is in close contact with at least the surface on the opposite side of the inner bottom surface of the recess.

  The concave portion is usually made of a transparent material so that the object to be packaged can be visually recognized, and is the portion that is most easily noticeable to the human eye. For this reason, such a packaging sheet can tell a user the expiration date and expiration date of a packaging target object efficiently.

(4)
In the packaging sheet according to (3) above, it is preferable that the color-changing material with time changes from transparent to opaque.

  In such a packaging sheet, the packaging object can be changed from being visible to being invisible. For this reason, with such a packaging sheet, it is possible to more efficiently convey to the user the expiration date or expiration date of the packaging object.

(5)
In the packaging sheet according to one aspect of the present invention, the temporal color change material may be designed such that at least one of color and color tone changes with time due to oxidation. In such a case, the third sheet is formed from a material having oxygen barrier properties.

  The color-change materials with time as described above are widely known and easily available. For this reason, this packaging sheet can be formed easily.

(6)
In the packaging sheet according to one aspect of the present invention, the temporal color changing material may be designed such that at least one of color and color tone changes with time by reacting with moisture. In such a case, the third sheet is formed from a material having a moisture barrier property.

  The color-change materials with time as described above are widely known and easily available. For this reason, this packaging sheet can be formed easily.

(7)
In the packaging sheet according to one aspect of the present invention, the color-changing material with time may be designed so that at least one of color and color tone changes with time when exposed to light. In such a case, the third sheet is formed from a light shielding material. In addition, as a light shielding material, resin containing a ultraviolet absorber etc. is mentioned.

  The color-change materials with time as described above are widely known and easily available. For this reason, this packaging sheet can be formed easily.

(8)
In the packaging sheet according to one aspect of the present invention, the third sheet may be formed of a simple release layer and a blocking layer. In such a case, the simple release layer is in close contact with the surface opposite to the contact surface of the sheet having the time-dependent color change layer so as to be peelable. The blocking layer has a blocking property against a specific substance or light.

  For this reason, in this packaging sheet, the third sheet can be easily formed by using a method such as a co-extrusion method or an extrusion lamination method.

(9)
In the packaging sheet according to (8) above, the temporal color change material may be designed such that at least one of color and color tone changes with time due to oxidation. In such a case, the blocking layer is formed from a material having an oxygen barrier property.

  The color-change materials with time as described above are widely known and easily available. For this reason, this packaging sheet can be formed easily.

(10)
In the packaging sheet according to (8) above, the temporal color change material may be designed such that at least one of color and color tone changes over time by reacting with moisture. In such a case, the blocking layer is formed from a material having a moisture barrier property.

  The color-change materials with time as described above are widely known and easily available. For this reason, this packaging sheet can be formed easily.

(11)
In the packaging sheet according to the above (8), the temporal color changing material may be designed such that at least one of the color and the color tone changes with time when exposed to light. In such a case, the blocking layer is formed from a light shielding material. In addition, as a light shielding material, resin containing a ultraviolet absorber etc. is mentioned.

  The color-change materials with time as described above are widely known and easily available. For this reason, this packaging sheet can be formed easily.

(12)
In the packaging sheet according to one aspect of the present invention, a content protective layer may be formed on the inner surface of the recess. Here, the “content protective layer” means a layer provided to protect the packaging object from oxidation, moisture, and vibration.

  For this reason, in this packaging sheet, a packaging target object can be protected effectively.

(13)
A package according to another aspect of the present invention includes a packaging sheet, an extending portion, and an outer container. The packaging sheet is the above-described packaging sheet. The extending portion is extended from the third sheet. The outer container fixes the extending portion.

  For this reason, in this package, when it is going to take out a packaging sheet from an outer container, a 3rd sheet will be peeled naturally. Therefore, if such a package is used, it is possible to prevent the user from forgetting to peel off the third sheet, and the user can peel off the third sheet at an appropriate timing.

(14)
In the package according to another aspect of the present invention, the extending portion is preferably fixed to the opening portion of the outer container.

  In such a package, when the user tries to open the opening portion, the third sheet is naturally peeled off. Therefore, if such a package is used, it is possible to prevent the user from forgetting to peel off the third sheet, and the user can peel off the third sheet at an appropriate timing.

It is a top view of the press through pack sheet concerning a 1st embodiment of the present invention. It is AA sectional drawing of FIG. It is a perspective view of the storage box of the press through pack sheet concerning a 1st embodiment of the present invention. It is side surface perspective drawing of the storage box in the state where the press through pack sheet concerning a 1st embodiment of the present invention was stored in the storage box. It is a fragmentary sectional view of the press through pack sheet concerning modification (H) of a 1st embodiment. It is a top view of the press through pack sheet concerning modification (I) of a 1st embodiment. It is a perspective view of the storage box of the press through pack sheet concerning modification (I) of a 1st embodiment. It is a front perspective view of a storage box in the state where the press through pack sheet concerning modification (I) of a 1st embodiment was stored in a storage box. It is a side view which shows the example of the sheet | seat for food packaging which concerns on the modification (L) of 1st Embodiment. It is a top view of the press through pack sheet concerning a 2nd embodiment of the present invention. It is a top view of the press through pack sheet concerning the modification (A) of a 2nd embodiment.

-First embodiment-
A press-through pack sheet (hereinafter referred to as “PTP sheet”) 100 according to the first embodiment of the present invention is mainly composed of a main body sheet 110 and a sealing sheet 140 as shown in FIGS. 1 and 2. Is done. Hereinafter, the main body sheet 110 and the sealing sheet 140 will be described in detail.

  <Details of PTP sheet components>

(1) Main Body Sheet The main body sheet 110 is mainly composed of a concave portion 111, a flat plate portion 112, and a slit portion 113, as shown in FIGS.

  The recessed part 111 is a recessed part formed in order to accommodate the packaging objects T, such as a pharmaceutical.

  As shown in FIGS. 1 and 2, five slit portions 113 are formed in the flat plate portion 112 at equal intervals along the width direction W (see FIG. 1) of the main body sheet 110, and an external force is applied. Break.

  The main body sheet 110 is mainly composed of a base sheet 130 and a cover sheet 120, as shown in FIG. Hereinafter, the base sheet 130 and the cover sheet 120 will be described in detail.

(1-1) Base Sheet The base sheet 130 is mainly composed of a base layer 130a and a time-dependent color change layer 130b, as shown in FIG.

  The base layer 130a is formed of a transparent resin such as a polyethylene resin, a polypropylene resin, a polystyrene resin, or a polyethylene terephthalate resin. The thickness of the base layer 130a is not particularly limited, but is 100 to 500 μm.

  The temporal color change layer 130b plays a role of notifying the user of the expiration date or the expiration date of the packaging target T, and is formed on the opposite side of the base layer 130a to the close side of the sealing sheet. The temporal color change layer 130b is formed of a gel-like variable color dye composition, and at least one of its color and tone as the variable color dye in the variable color dye composition reacts with oxygen in the atmosphere. Changes gradually. In the present embodiment, it is preferable that the temporal color change layer 130b changes from transparent (which may be colored) to opaque.

  The variable color dye composition is mainly composed of a redox dye, a reducing agent, a resin for forming a coating film, an alkaline substance, and water.

  Examples of the redox dye include thiazine dyes such as methylene blue, indico dyes such as potassium indicosulfonate, thioindigo dyes, and indophenol dyes. More specific examples include, for example, new methylene blue, neutral red, indigo carmine, acid red, safranin T, phenosafranine, capri blue, nile blue, diphenylamine, xylene cyanol, nitrodiphenylamine, ferroin, N-phenylanthranilic acid Etc.

  Examples of the reducing agent include ascorbic acid, erythorbic acid and salts thereof, ascorbate, D-arabinose, D-erythrose, D-galactose, D-xylose, D glucose, D-mannose, D-fructose, D- Examples thereof include reducing sugars such as lactose, metal salts such as nitrite, stannous salt, and ferrous salt.

  The resin for forming a coating film is not particularly limited, and examples thereof include cellulose and other transparent resins.

  An antioxidant may be added to the variable color dye composition for the purpose of adjusting the change over time of the redox dye. Antioxidants include tocophenol, aromatic amine, hydroquinone, aldehyde amine condensate, vitamins, quercetin, dibutyloxytoluene, butyloxyanisole, ethyl protocatechuate, gallic acid, isoamyl gallate, propyl gallate, etc. Is mentioned. The addition concentration of the antioxidant is preferably 500 ppm to 50000 ppm.

(1-2) Cover Sheet As shown in FIG. 2, the cover sheet 120 is mainly composed of an easily peelable layer 120a and an oxygen barrier layer 120b. In the present embodiment, the cover sheet 120 is provided with an extending portion 121 as shown in FIG.

  The easy release layer 120a is in close contact with the time-dependent color change layer 130b of the base sheet 130, but easily peels from the time-dependent color change layer 130b with a small external force.

  The oxygen barrier layer 120b is a layer for suppressing the permeation of oxygen to the temporal color change layer 130b of the base sheet 130. For example, a metal foil such as an aluminum foil, polyvinylidene chloride, polyvinyl alcohol, ethylene-acetic acid It is formed from a saponified vinyl copolymer (ethylene-polyvinyl alcohol copolymer) or the like.

(2) Sealing sheet The sealing sheet 140 is formed of, for example, a metal thin film and a resin such as a polyethylene resin, a polypropylene resin, a polystyrene resin, and a polyethylene terephthalate resin.

  The metal thin film is hard aluminum or the like.

  Although the thickness of this sealing sheet 140 is not specifically limited, It is preferable that it is 10-50 micrometers.

  <Method for producing PTP sheet>

  The PTP sheet 100 according to the present embodiment can be manufactured using a known PTP sheet manufacturing method. Specifically, after the base layer 130a is formed by an extrusion method or the like, the color change over time is performed by applying a variable color pigment composition on the base layer 130a by a known method such as a roll coating method, a screen printing method, or a spray method. Layer 130b is formed. Next, the cover sheet raw material is poured on the color-changing layer 130b with time by a method such as a co-extrusion method or an extrusion laminating method to form a cover sheet. Next, the laminated sheet obtained in this manner is heated and pressed to form the recess 111 in the laminated sheet, and the main body sheet 110 is manufactured. Subsequently, after putting the packaging object T into the recess 111 of the main body sheet 110, the sealing sheet 140 is heat-sealed to the main body sheet 110, and the packaging object T is sealed in the recess 111. Finally, the slit portion 113 is formed.

  This series of operations can be carried out continuously.

<PTP sheet storage box>
The PTP sheet 100 according to the present embodiment is stored in a storage box 150 as shown in FIG. In the storage box 150, an opening portion OP is formed on the front surface portion 152.

  Then, as shown in FIG. 4, the PTP sheet 100 is housed in the storage box 150 with a part thereof being adhered to the drawer mount 160, and the extended portion 121 of the cover sheet 120 is the top of the storage box 150. Bonded to the surface portion 151.

  Therefore, when the user opens the storage box 150 using the opening part OP and then pulls out the drawer mount 160 and pulls out the PTP sheet 100 from the storage box 150, the cover sheet 120 is necessarily peeled off from the base sheet 130. become. That is, from the time when the PTP sheet 100 is pulled out from the storage box 150, the time-dependent color change layer 130b comes into contact with air, and a change in at least one of its color and tone is started.

  At this time, the PTP sheet 100 from which the cover sheet 120 is detached adheres to the drawer mount 160, but can be easily peeled off from the drawer mount 160 by applying a small force.

  <Modification>

(A)
In the PTP sheet 100 according to the previous embodiment, the oxygen barrier layer 120b is a metal foil such as an aluminum foil, polyvinylidene chloride, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer (ethylene-polyvinyl alcohol copolymer), etc. However, the oxygen barrier layer 120b may be, for example, an oxygen barrier transparent film as disclosed in JP-A-11-129384.

  Such an oxygen barrier transparent film can be obtained by forming a vapor-deposited thin film layer made of an inorganic oxide such as aluminum oxide, silicon oxide, magnesium oxide or a mixture thereof on a transparent resin film. In addition, a transparent primer layer may be formed on a transparent resin film as needed, and a gas barrier coating layer may be formed on a vapor deposition thin film layer.

(B)
Although not particularly mentioned in the previous embodiment, an oxygen absorption layer may be provided between the easily peelable layer 120 a and the oxygen barrier layer 120 b in the cover sheet 120.
In addition, this oxygen absorption layer is a thing by which an oxygen absorber is mix | blended with resin, for example.

  Examples of the oxygen absorbent include metal powder having reducibility, low metal oxide, and reducible metal compound. Examples of the metal powder having reducibility include reducible iron, reducible zinc, and reducible tin powder. Examples of the low metal oxide include ferrous oxide and iron trioxide. Examples of the reducing metal compound include iron carbide, silicon iron, iron carbonyl, ferrous hydroxide and the like. These oxygen absorbents can be used alone or in combination. These oxygen absorbers can be used as needed, alkali metal, alkaline earth metal hydroxide, carbonate, sulfite, thiosulfate, tertiary phosphate, organic acid salt, halide, activated carbon, active It can also be used in combination with auxiliaries such as alumina, activated clay, zeolite and diatomaceous earth. In addition to these, examples of the oxygen absorbent include polymer compounds having a polyhydric phenol in the skeleton, such as a polyhydric phenol-containing phenol / aldehyde resin. Furthermore, ascorbic acid, erythorbic acid, tocopherols and salts thereof, which are water-soluble substances, can be suitably used.

  The oxygen absorbing layer may be formed from an oxygen absorbing functional composition containing a component having a carbon-carbon unsaturated bond and a transition metal compound.

  Examples of the component having a carbon-carbon unsaturated bond include, for example, rubbery polymers, copolymers of monomers that are copolymerizable with monomers of rubbery polymers, higher unsaturated fatty acids and derivatives thereof, and these A mixture is mentioned. Examples of the rubber-like polymer include butadiene, isoprene, 2-chloro-1,3-butadiene, 1chloro-1,3-butadiene, piperidine, 2,3-dimethyl-1,3-butadiene, 1- Examples thereof include rubbery polymers such as phenyl-1,3-butadiene. These rubbery polymers can be used alone or in combination. Examples of the copolymer include a styrene-butadiene copolymer, an acrylonitrile-styrene-butadiene copolymer (ABS resin), and a methyl methacrylate containing 2 to 70 parts by weight of a diene polymer with respect to the entire copolymer. -Styrene-butadiene copolymer (MBS resin), acrylonitrile-methyl methacrylate-styrene-butadiene copolymer (MABS resin), styrene-butadiene-styrene block copolymer (SBS resin), and the like. Examples of higher unsaturated fatty acids and derivatives thereof include linoleic acid, linoelaidic acid, and oleic acid.

  Examples of the transition metal compound include metal salts using Fe, Ni, Co, and Mn as metal species, and metal compounds that coordinate these metals.

  In view of the affinity between the component having a carbon-carbon unsaturated bond and the thermoplastic resin, salts of the metal and organic anions and organometallic coordination compounds are more preferable. Specific examples include metal salts composed of carboxylic acids such as acetic acid, butyric acid, heptanoic acid, octanoic acid, octylic acid and stearic acid, and metals having Fe, Ni, Co and Mn as metal species. Examples of the organometallic coordination compound include metal acetylacetonate using Fe, Ni, Co, and Mn as metal species.

(C)
Although not particularly mentioned in the previous embodiment, an oxygen permeation control layer may be provided on the time-dependent color change layer 130b in the base sheet 130. In such a case, the easy peeling layer 120a of the cover sheet 120 is in contact with the oxygen permeation control layer, not the time-dependent color change layer 130b.

  The oxygen permeation control layer basically has the same configuration as the oxygen barrier layer 120b of the cover sheet 120 according to the previous embodiment and the oxygen barrier layer of the cover sheet 120 according to the modification (A). However, the oxygen permeation control layer must be transparent so as not to hinder the user's confirmation of the color and tone change of the time-dependent color change layer 130b.

  Note that the oxygen permeation amount of the oxygen permeation control layer is inversely proportional to the layer thickness, and the oxygen permeability increases as the layer thickness decreases. Therefore, the control of the oxygen transmission amount can be realized by adjusting the layer thickness.

  In addition, when a vapor deposition thin film layer is included in the oxygen permeation control layer, the oxygen permeation amount can be controlled by adjusting the layer thickness of the vapor deposition thin film layer.

  Further, the oxygen permeation amount of the oxygen permeation control layer greatly depends on the material forming the oxygen permeation control layer. For this reason, when it is desired to change the time-dependent color change layer 130b early, an oxygen permeation control layer is formed from a material having a low oxygen barrier property, and when the time-dependent color change layer 130b is required to change color after a relatively long period of time. The oxygen permeation control layer may be formed from a material having a high oxygen barrier property.

(D)
In the previous embodiment, the time-dependent color change layer 130b that changes its color and tone by reacting with oxygen in the atmosphere has been adopted. However, the time and change of its color and tone by reacting with moisture in the air. A color change layer may be employed. In such a case, the oxygen barrier layer 120b of the cover sheet 120 is a moisture barrier layer.

  Such a time-dependent color changing layer is formed, for example, by adsorbing a discoloring dye having a lactone ring or a lactam ring to a porous metal oxide film. The porous metal oxide may be a porous metal oxide of at least one metal element selected from the group consisting of silicon, aluminum, titanium, zirconium, magnesium, indium, and tin.

  A color-changing dye having a lactone ring or a lactam ring exhibits a colorless or light color when the lactone ring or the lactam ring is closed, and is colored when the ring is opened. Examples of such discoloring dyes include fluorane dyes, triphenylmethane phthalide dyes, and lactam dyes.

  Examples of the fluorane dye include 2-N, N-dibenzylamino-6-diethylaminofluorane, 2- (2-chloroanilino) -6-diethylaminofluorane, 1,3-dimethyl-6-diethylaminofluorane, 6- Diethylamino-benzo [a] -fluorane, 2-anilino-3-methyl-6-N-ethyl-N-tetrahydrofurfurylaminofluorane, 2- (2-chloroanilino) -6-dibutylaminofluorane, 3- Cyclohexylmethylamino-6-methyl-7-anilinofluorane, 3-ethyl-isobutylamino-6-methyl-7-anilinofluorane, 3-dimethylamino-5,6-benzofluorane, 3-diethylamino- 7-methylaminofluorane, 3-diethylamino-7-phenylaminofluorane, 3-di Tilamino-7- (N-methyl-N-phenyl) aminofluorane, 3-diethylamino-6-methyl-7-phenylaminofluorane, 3-diethylamino-7-dibenzylaminofluorane, 2- (N- Phenyl-N-methylamino) -6- (Np-tolyl-N-ethylamino) fluorane, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3 -Yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-n-butyl-2-methyl) Indol-3-yl) phthalide, 2-anilino-3-methyl-6-dibutylaminofluorane, 3-dimethylamino-5,6-benzofluorane, 3-diethyl Mino-5-methyl-7-dibenzylaminofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-ethyl- (4′-methyl) phenylamino-7- Methylaminofluorane, 3-ethyl-isopentylamino-7,8-benzofluorane, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-ethyl-hexylamino-7 -Phenylaminofluorane, 3-dibutylamino-6-methyl-7-arininofluorane, 3-dibutylamino-6-methyl-7-xylidinofluorane, 3-dibutylamino-7-chloroalininofluorane , 3-ethylamino-6-methoxy-7-aminofluorane and the like.

  Examples of the triphenylmethanephthalide dye include crystal violet lactone and malachite green lactone. Examples of the lactam dye include 3,6-bis (diethylamino) fluorane-γ-anilinolactam, 3,6-bis ( Diethylamino) fluorane- (4′-nitro) -anilinolactam, 2- [3,6-bisdiethylamino-9- (o-chloroanilino) xanthyl] benzoic acid lactam, rhodamine lactam and the like.

  Examples of the metal of the porous metal oxide include silicon, aluminum, titanium, zirconium, magnesium, bismuth, antimony, indium, and tin. Among these, when at least one metal element selected from the group consisting of silicon, aluminum, titanium, zirconium, magnesium, indium, and tin is contained in the porous metal oxide, the adsorptivity of the discolorable dye, Discoloration is improved. Among these, aluminum and titanium are industrially important in terms of suitability of the oxide film, adsorption activity, pore distribution, etc., and these are widely used as appropriate in terms of price.

  Examples of methods for forming a porous metal oxide film include a method of applying a metal oxide hydrate coating solution to a substrate, and a method of placing a metal oxide powder on a substrate via an adhesive layer. There is.

  First, a method using a metal oxide hydrate will be described. Coating solution of metal oxide hydrate comprising at least one metal element selected from the group consisting of silicon, aluminum, titanium, zirconium, magnesium, indium and tin (dispersion of metal oxide hydrate, alcohol A solution or a sol is also obtained by hydrolyzing a metal alkoxide, metal acetylacetonate, or the like with an acid or an alkali, so that a high purity is obtained.

  Examples of the metal alkoxide include aluminum methylate, aluminum ethylate, aluminum isopropylate, mono sec-butoxyaluminum diisopropylate, aluminum sec-butyrate, tetramethyl silicate, tetraethyl silicate, tetra n-propyl silicate, tetraisopropyl silicate, Tetra n-butyl silicate, tetraethoxy titanium, tetraisopropoxy titanium, tetra n-butoxy titanium, tetraethoxy zirconium, tetraisopropoxy zirconium, tetra n-butoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, tetra n-butoxy zirconium , Diethoxymagnesium, triethoxyindium, triisopropyl Po carboxymethyl indium, tetraethoxy tin, triisopropoxide cis's, triisopropoxy bismuth, and triethoxy antimony, derivatives (including oligomers) can be mentioned.

  In general, examples of the metal acetylacetonate include an aluminum compound, a titanium compound, a zirconium compound, a magnesium compound, an indium compound, and a tin compound. These may be used alone or in combination.

  Water or alcohol-soluble resin (for example, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, starch, cellulose resin, acrylate resin, water-soluble polyamide, water-soluble epoxy resin), or as required Addition of additives such as curing agents, dispersants, antifoaming agents, leveling agents, etc. improves the coating strength and resistance during low temperature drying. Examples of the method for applying a coating liquid containing a metal oxide hydrate as a main component include a coater method, a printing method, a brush coating method, a dipping method, a spray method, and a spinner method. A coating solution containing the above metal oxide hydrate as a main component is applied to a substrate, dried, and then fired as necessary to produce a porous metal oxide film.

  Next, a method using a metal oxide powder will be described. Porous metal oxide powder containing at least one metal element selected from the group consisting of silicon, aluminum, titanium, zirconium, magnesium, indium and tin, vinyl acetate resin, vinyl chloride vinyl acetate copolymer resin , Sprayed on the base layer 130a coated with a thermoplastic resin such as a (meth) acrylic acid ester resin or an olefin resin or a thermosetting resin such as an epoxy resin or a urethane resin as an adhesive layer Or expand.

  The moisture barrier layer is formed of a resin having a moisture barrier property such as a fluororesin, polyvinylidene chloride, and cyclic polyolefin.

(E)
In the previous embodiment, the time-dependent color change layer 130b that changes its color and tone by reacting with oxygen in the atmosphere has been adopted, but the color and tone of the volatile matter contained therein are gradually evaporated. A time-dependent color change layer in which at least one of them may change may be employed. In such a case, the oxygen barrier layer 120b of the cover sheet 120 is a volatile barrier layer.

  Such a color-change layer with time includes, for example, a combination of a porous resin and a volatile liquid, a combination of a transparent gel body, a transparent porous resin and a volatile coloring liquid, or a reaction with a functional group-containing transparent gel body. This is realized by a combination with a mold coloring liquid.

  When the time-dependent color change layer is realized by a combination of a porous resin and a volatile liquid, the time-dependent color change layer is translucent in the initial state and becomes opaque as the volatile liquid evaporates.

  When the time-varying color change layer is realized by a combination of a transparent gel body or transparent porous resin and a volatile coloring liquid, the time-changing color changing layer is colored in the initial state and becomes transparent as the volatile coloring liquid evaporates. Become.

When the time-dependent color change layer is realized by a combination of a functional group-carrying transparent gel body and a binding colored liquid, the time-dependent color change layer is an ion of the functional group in the transparent gel body and the binding color liquid in the initial state. The color is obtained when bonding or hydrogen bonding is performed, and the color changes to the color of the functional group-containing transparent gel body as the bonding type colored liquid evaporates.
The volatile barrier layer is not particularly limited as long as it does not allow the selected volatile liquid to permeate or is difficult to permeate.

(F)
In the previous embodiment, the temporal color change layer 130b that changes its color and tone by reacting with oxygen in the atmosphere has been adopted. However, the temporal color change that changes its color and tone when exposed to light. A layer may be employed. In such a case, the oxygen barrier layer 120b of the cover sheet 120 is a light shielding layer.

Note that such a color-change layer with time is formed of a resin containing a compound that decomposes when exposed to light (for example, a biodegradable polymer).
As the light shielding layer, for example, a metal thin film, a vapor deposition thin film, a resin thin film containing an ultraviolet absorber, or the like is used.

(G)
In the previous embodiment, the time-dependent color changing layer 130b whose color and tone change by reacting with oxygen in the atmosphere has been adopted, but its color and tone change by reacting with carbon dioxide in the atmosphere. A time-varying color change layer may be employed. In such a case, the oxygen barrier layer 120b of the cover sheet 120 is a carbon dioxide barrier layer.

  Such a time-dependent color changing layer is, for example, a mixture of a variable dye that changes color due to a change in pH as disclosed in JP-B 64-2906 and an alkaline substance that reacts with carbon dioxide in the atmosphere. It is formed by impregnating a gel body with a solution.

  The carbon dioxide barrier layer is not particularly limited as long as it does not permeate carbon dioxide or is difficult to permeate.

(H)
In the previous embodiment, the cover sheet 120 having a two-layer structure is adopted, but a cover sheet 120A having a one-layer structure as shown in FIG. 5 may be adopted. In FIG. 5, reference numeral 100A indicates a PTP sheet according to this modification, reference numeral 110A indicates a main body sheet according to this modification, and other reference numerals are the same as those indicated by the same reference numerals shown in FIG. The thing is shown.

  In such a case, the cover sheet 120A is formed from, for example, a blended material obtained by adding “resin that forms the oxygen barrier layer 120b” to “resin that forms the easily peelable layer 120a”.

(I)
The PTP sheet 100 according to the previous embodiment is stored in the storage box 150 in a state where a part thereof is adhered to the drawer mount 160, and the extended portion 121 of the cover sheet 120 is formed on the top surface portion 151 of the storage box 150. Although bonded, the PTP sheet 100D shown in FIG. 6 may be stored in the storage box 150A shown in FIG. 7 as shown below.

  First, in the PTP sheet 100D, the extending portion 121A extends from one side end in the width direction W. In the storage box 150A, an opening portion OP is formed from the side surface portion 153A to the top surface portion 151A. Then, as shown in FIG. 8, the PTP sheet 100D is housed in the housing box 150A in a state where a part thereof is adhered to the bottom surface portion 154A, and the extended portion 121A of the cover sheet is an opening portion of the housing box 150A. Bonded near the tip of the OP.

  Therefore, when the user tries to open the opening part OP, the cover sheet is inevitably peeled off from the base sheet. That is, the time-varying color change layer 130b comes into contact with air from the time when the storage box 150A is opened, and at least one of its color and tone is started.

  At this time, the PTP sheet 100D from which the cover sheet is detached adheres to the bottom surface portion 154A of the storage box 150A, but can be easily peeled off from the bottom surface portion 154A by applying a small force.

(J)
In the previous embodiment, the temporal color change layer 130 b is provided over the entire surface of the base sheet 130, but the temporal color change layer may be provided only in the recess 111.

(K)
Although not particularly mentioned in the previous embodiment, a packaging object protection layer may be further provided on the inner surface of the recess 111.

(L)
In the previous embodiment, the present invention is applied to the PTP sheet 100. However, the present invention may be applied to a food packaging sheet 200 as shown in FIG.

  The food packaging sheet 200 is mainly composed of a main body sheet 210 and a sealing sheet 240, as shown in FIG. The main body sheet 210 is a substantially square sheet having a substantially cylindrical recess, and its layer structure is the same as that of the main body sheet 110 according to the previous embodiment. The sealing sheet 240 is a substantially square sheet, and the layer structure thereof is the same as that of the sealing sheet 140 according to the previous embodiment.

  In addition, the packaging target T in FIG. 9 is, for example, a sliced ham.

(M)
In the PTP sheet 100 according to the previous embodiment, the base sheet 130 has a two-layer structure, but the base sheet may have a single-layer structure. That is, the base sheet may be a color change sheet over time.

  In such a case, the base sheet is preferably formed from a resin containing a variable color pigment.

-Second Embodiment-
As shown in FIG. 10, the PTP sheet 100B according to the second embodiment of the present invention mainly includes a main body sheet 110B, a sealing sheet 140B, and a cover sheet 145B. Hereinafter, the main body sheet 110B, the sealing sheet 140B, and the cover sheet 145B will be described in detail.

  <Details of PTP sheet components>

(1) Main Body Sheet The main body sheet 110 </ b> B mainly includes a concave portion 111, a flat plate portion 112, and a slit portion 113 as shown in FIG. 10. In addition, the recessed part 111, the flat plate part 112, and the slit part 113 are as having demonstrated in 1st Embodiment.

  And this main body sheet | seat 110B is a one-layer structure as FIG. 10 shows, for example, is formed from transparent resins, such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyethylene terephthalate resin.

(2) Sealing Sheet As shown in FIG. 10, the sealing sheet 140 </ b> B mainly includes an adhesion layer 140 a, an oxygen barrier layer 140 b, and a time-dependent color change layer 140 c.

  The adhesion layer 140a is a layer having a function to adhere to the main body sheet 110B, and is formed of, for example, the same resin as the main body sheet 110B.

The oxygen barrier layer 140b is the same as the oxygen barrier layer 120b according to the first embodiment.
The temporal color change layer 140c is the same as the temporal color change layer 130b according to the first embodiment.

(3) Cover Sheet As shown in FIG. 10, the cover sheet 145B is mainly composed of an easily peelable layer 145a and an oxygen barrier layer 145b.

  The easily peelable layer 145a according to the present embodiment is the same as the easily peelable layer 120a of the cover sheet 120 according to the first embodiment.

  The oxygen barrier layer 145b according to the present embodiment is the same as the oxygen barrier layer 120b according to the first embodiment.

  <Modification>

(A)
In the previous embodiment, the cover sheet 145B having a two-layer structure is employed, but a cover sheet 145C having a one-layer structure as shown in FIG. 11 may be employed. In FIG. 11, reference numeral 100C indicates a PTP sheet according to this modification, reference numeral 110C indicates a main body sheet according to this modification, and other reference numerals are the same as those indicated by the same reference numerals shown in FIG. The thing is shown.

  In such a case, the cover sheet 145C is formed from, for example, a blended material obtained by adding “resin that forms the oxygen barrier layer 145b” to “resin that forms the easily peelable layer 145a”.

(B)
Although not particularly mentioned in the previous embodiment, the first embodiment and its modifications can be similarly applied to the PTP sheet 100B according to the second embodiment.

100, 100A, 100B, 100C, 100D Press-through pack sheet (packaging sheet)
110, 110A, 110B, 110C Main body sheet 111 Concave portion 112 Flat plate portion 113 Slit portion 120, 120A Cover sheet (third sheet)
120a Easy peeling layer 120b Oxygen barrier layer 121, 121A Extension part 130 Base sheet (first sheet)
130a Base layer 130b Temporal color changing layer 140, 140B Sealing sheet (second sheet)
140a Adhesion layer 140b Oxygen barrier layer 140c Temporal color change layer 145B, 145C Cover sheet 145a Easy release layer 145b Oxygen barrier layer 150, 150A Storage box 151, 151A Top surface portion 152 Front surface portion 153A Side surface portion 154A Front surface portion 160 Drawer mount 200 Food packaging Sheet (packaging sheet)
210 Main body sheet 240 Sealing sheet (second sheet)
OP Unsealed part T Packaging object W Body sheet width direction

  The packaging sheet according to the present invention has an indicator function and can be produced by using existing packaging sheet production equipment as it is, a press-through pack sheet for pharmaceutical packaging, and food packaging Useful as a packaging sheet or the like.

Claims (14)

A first sheet having a recess;
A second sheet closely contacting the first sheet so as to cover the opening of the recess,
With
At least one of the first sheet and the second sheet has a time-dependent color change layer formed of a time-dependent color change material in which at least one of color and color tone changes over time,
A packaging sheet in which a third sheet having a blocking property against a specific substance or light is detachably attached to a surface opposite to the adhesion surface of the sheet having the color change layer with time. In the sheet | seat which has the said time-dependent color change layer, the said time-dependent color change layer is formed over the whole surface. The temporal color change layer is provided at least in the recess,
The said 3rd sheet | seat is a packaging sheet of Claim 1 closely_contact | adhered to the surface on the opposite side to the inner bottom face of the said recessed part so that peeling is possible. The packaging sheet according to claim 3, wherein the color-changing material with time changes from transparent to opaque. The color-change material with time changes at least one of color and tone over time due to oxidation,
The packaging sheet according to any one of claims 1 to 4, wherein the third sheet is formed of a material having an oxygen barrier property. The color-change material with time changes at least one of color and tone over time by reacting with moisture,
The packaging sheet according to any one of claims 1 to 4, wherein the third sheet is formed of a material having a moisture barrier property. The color-change material with time changes at least one of color and tone over time by being exposed to light,
The packaging sheet according to claim 1, wherein the third sheet is formed from a light shielding material. The third sheet includes a simple release layer that is releasably in contact with a surface opposite to the contact surface of the sheet having the color-change layer with time, and a blocking layer having a blocking property to the specific substance or light. The packaging sheet according to claim 1, which is formed from The color-change material with time changes at least one of color and tone over time due to oxidation,
The packaging sheet according to claim 8, wherein the barrier layer is formed from a material having an oxygen barrier property. The color-change material with time changes at least one of color and tone over time by reacting with moisture,
The packaging sheet according to claim 8, wherein the barrier layer is formed from a material having a moisture barrier property. The color-change material with time changes at least one of color and tone over time by being exposed to light,
The packaging sheet according to claim 8, wherein the blocking layer is formed from a light blocking material. The packaging sheet according to any one of claims 1 to 11, wherein a content protective layer is formed on an inner surface of the recess. A packaging sheet according to any one of claims 1 to 12,
An extending portion extending from the third sheet;
A packaging body comprising an outer container for fixing the extending portion. The outer container has an opening part,
The package according to claim 13, wherein the extending portion is fixed to the opening portion.

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