JP2017065709A - Laminate for tube container, tube container, and method for manufacturing laminate for tube container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate for tube container capable of forming a tube container excellent in forgery-preventing property and designability.SOLUTION: A laminate for tube container has: an inner face side sealant layer; a base material formed on one surface of the inner face side sealant layer; an outer face side sealant layer formed on the surface in an opposite side to the inner face side sealant layer of the base material, and a stress luminescent layer which is arranged between the inner face side sealant layer and the outer face side sealant layer and contains stress luminescent particles and a binder resin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate for a tube container capable of forming a tube container excellent in anti-counterfeiting properties and design properties.

  The tube container can be used by filling and packaging the contents, and optionally extruding the amount required for use. For this reason, tube containers are widely used as containers for foods, cosmetics, pharmaceuticals, and the like.

Such a tube container is usually formed with a print layer for displaying images such as display items and patterns related to the contents.
Further, in order to differentiate between products, a tube container having improved design and the like by combining a hologram or the like with printing has been developed (see, for example, Patent Document 1).

Japanese Utility Model Publication No. 3-31941

However, due to recent technological advances, it is becoming possible to easily produce counterfeits of the hologram or the hologram itself. For this reason, there exists a problem that sufficient designability which enables differentiation between products cannot be obtained only by the combination of a hologram etc. and printing.
In addition, it is conceivable to provide an anti-counterfeit effect by using a hologram or the like, but it is difficult to obtain a sufficient anti-counterfeit effect due to the problem that it is difficult to judge authenticity in the dark, or for the same reason as the design property. There is a problem that it is becoming.

  This invention is made | formed in view of the said problem, and it aims at providing the laminated body for tube containers which can form the tube container excellent in the forgery prevention property and the designability.

  To achieve the above object, the present invention provides an inner surface side sealant layer, a substrate formed on one surface of the inner surface side sealant layer, and a surface of the substrate opposite to the inner surface side sealant layer. A tube container comprising: an outer surface side sealant layer formed on the inner surface side; and a stress light emitting layer disposed between the inner surface side sealant layer and the outer surface side sealant layer and containing stress light emitting particles and a binder resin. A laminate is provided.

According to the present invention, the tube container laminate (hereinafter sometimes simply referred to as a laminate) has a stress-stimulated luminescent layer, whereby a tube container capable of emitting light when stress is applied can be formed. .
For this reason, the said laminated body can form the tube container excellent in the forgery prevention property and the designability.

In the present invention, the stress-stimulated luminescent layer is preferably formed in a pattern. When the stress-stimulated luminescent layer is formed in a pattern, the stress-stimulated luminescent layer can emit light in a pattern when stress is applied to the tube container formed using the laminate of the present invention. it can.
For this reason, it is because the said laminated body can form the tube container excellent in the forgery prevention property and the designability because the said stress light emitting layer is formed in pattern shape.

  In this invention, it is preferable that the said laminated body for tube containers has a filling layer formed on the same plane as the said stress light emitting layer. This is because the presence of the stress-stimulated luminescent layer formed in a pattern can be made inconspicuous, and the laminate can form a tube container that is superior in anti-counterfeiting and design properties.

  The present invention provides an inner surface side sealant layer, a substrate formed on one surface of the inner surface side sealant layer, and an outer surface side sealant layer formed on the surface of the substrate opposite to the inner surface side sealant layer. And a cylindrical body part in which ends of the inner surface side sealant layer and the outer surface side sealant layer of the laminated body for a tube container are fused together, and one shoulder of the cylindrical body part is joined to the shoulder The tube container laminate is disposed between the inner surface side sealant layer and the outer surface side sealant layer, and contains stress-stimulated luminescent particles and a binder resin. A tube container having a light emitting layer is provided.

According to this invention, when the said laminated body has a stress light emission layer, it becomes a tube container which can light-emit when stress is added.
For this reason, the said tube container becomes the thing excellent in forgery prevention property and design property.

  The present invention includes a stress light emitting layer forming step of forming a stress light emitting layer containing stress light emitting particles and a binder resin on one surface of a base material; There is provided a method for producing a laminate for a tube container, comprising a sealant layer forming step of sandwiching between sealant layers.

  According to the present invention, by having the stress light emitting layer forming step and the sealant layer forming step, a laminate capable of forming a tube container capable of emitting light when stress is applied can be easily obtained.

  INDUSTRIAL APPLICATION This invention has the effect that the laminated body for tube containers which can form the tube container excellent in forgery prevention property and design property can be provided.

It is a schematic sectional drawing which shows an example of the laminated body for tube containers of this invention. It is a schematic sectional drawing which shows the other example of the laminated body for tube containers of this invention. It is a schematic sectional drawing which shows the other example of the laminated body for tube containers of this invention. It is a schematic sectional drawing which shows the other example of the laminated body for tube containers of this invention. It is a schematic plan view which shows the other example of the laminated body for tube containers of this invention. It is the sectional view on the AA line of FIG. It is a schematic plan view which shows the other example of the laminated body for tube containers of this invention. It is the BB sectional view taken on the line of FIG. It is a schematic sectional drawing which shows the other example of the laminated body for tube containers of this invention. It is a schematic sectional drawing which shows the other example of the laminated body for tube containers of this invention. It is a schematic sectional drawing which shows the other example of the laminated body for tube containers of this invention. It is a schematic sectional drawing which shows the other example of the laminated body for tube containers of this invention. It is a schematic sectional drawing which shows the other example of the laminated body for tube containers of this invention. It is the schematic which shows an example of the tube container of this invention. It is process drawing which shows an example of the manufacturing method of the laminated body for tube containers of this invention.

The present invention relates to a tube container laminate, a tube container, and a method for producing a tube container laminate.
Hereinafter, the manufacturing method of the laminated body for tube containers of this invention, a tube container, and the laminated body for tube containers is demonstrated in detail.

A. Laminate for tube container The laminate for a tube container of the present invention is opposite to the inner surface side sealant layer, the base material formed on one surface of the inner surface side sealant layer, and the inner surface side sealant layer of the base material. An outer surface side sealant layer formed on the side surface, and a stress light emitting layer disposed between the inner surface side sealant layer and the outer surface side sealant layer and containing stress light emitting particles and a binder resin. To do.

Such a laminate of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the laminate of the present invention. As shown in FIG. 1, the laminate 10 of the present invention includes an inner surface side sealant layer 3 a, a base material 1 formed on one surface of the inner surface side sealant layer 3 a, and the inner surface side sealant of the base material 1. An outer surface side sealant layer 3b formed on the surface opposite to the layer 3a, and a stress luminescent layer which is disposed between the inner surface side sealant layer 3a and the outer surface side sealant layer 3b and contains stress luminescent particles and a binder resin. 2.
In this example, the stress-stimulated luminescent layer 2 is disposed between the base material 1 and the inner surface side sealant layer 3a.

According to the present invention, since the laminate has a stress light emitting layer, a tube container capable of emitting light when stress is applied can be formed.
Therefore, the laminate can emit light due to stress applied when the contents are taken out, stress applied when the product is picked up, and the like, and can form a tube container capable of exhibiting design properties when the product is used. Become.
Moreover, the tube container which can perform authenticity determination can be obtained by enabling a tube container to light-emit when stress is added. In addition, as a method of authenticity determination, for example, a method performed in a bright place may be used. However, by using a low-luminance layer capable of confirming light emission only in a dark place as a stress light emitting layer, light is emitted only in the dark place. A method in which only an observer who knows that confirmation cannot be confirmed confirms light emission and determines authenticity can also be used.
Further, even in a dark place, anti-counterfeiting and design properties can be exhibited without preparing a separate light source or the like.
From such a thing, the said laminated body can form the tube container excellent in the forgery prevention property and the designability.

In addition, since the stress light emitting layer is disposed between the inner surface side sealant layer and the outer surface side sealant layer, the inner surface side sealant layer and the outer surface side sealant layer are fused to each other so that the tube container tube When the cylindrical body portion is formed, the stress light emitting layer may not be disposed between the fusion surfaces of both sealant layers. For this reason, when the laminated body is formed with a cylindrical body part, compared to a case where a stress-stimulated luminescent layer containing an inorganic material such as a stress-stimulated luminescent particle is disposed between the fusion surfaces of both sealant layers, The adhesive strength between both sealant layers is strong and uniform.
Moreover, the said laminated body becomes a thing with few peeling of a stress light emitting layer because it is the said arrangement | positioning location. Therefore, the laminate can form a tube container that can emit light stably when stress is applied.

The laminate of the present invention has an inner surface side sealant layer, a substrate, an outer surface side sealant layer, and a stress light emitting layer.
Hereinafter, each structure of the laminated body of this invention is demonstrated.

1. Stress-stimulated luminescent layer The stress-stimulated luminescent layer in the present invention contains stress-stimulated luminescent particles and a binder resin.

(1) Constituent material of stress-stimulated luminescent layer The stress-stimulated luminescent layer contains stress-stimulated luminescent particles and a binder resin.

(A) Stress-stimulated luminescent particles The stress-stimulated luminescent particles have a property that the particles themselves emit light by strain energy applied from the outside, and a property that changes the luminescence intensity in proportion to the strain energy. Anything is acceptable.

In the present invention, the wavelength of light emitted from the stress-stimulated luminescent particles (hereinafter sometimes referred to as a predetermined wavelength) is preferably within the range of visible light. This is because the observer can visually recognize the emitted light from the stress-stimulated light-emitting layer and can more effectively exhibit the effect of the present invention that is excellent in anti-counterfeiting effects.
Specifically, the visible light wavelength range may be in the range of 400 nm to 800 nm.
Moreover, the said predetermined wavelength shall have area | regions other than visible light, for example, a stress light emitting layer may be used for light emission of the fluorescent layer containing a fluorescent material.
The predetermined wavelength refers to the maximum peak wavelength of the emission spectrum of stress-stimulated luminescent particles within a wavelength range of 200 nm to 1000 nm.

The emission luminance of the stress luminescent particles, for example, from the viewpoint of the observer visible visually, is preferably 1.0mcd / cm ² or more, among others, are 10mcd / cm ² or more In particular, it is preferably 100 mcd / cm ² or more. This is because when the emission luminance is within the above range, it can be recognized as high luminance outdoors, and the reliability of authenticity determination using emission from the stress emission layer can be improved.

Examples of the stress-stimulated luminescent material constituting the stress-stimulated luminescent particles include a material (ceramics) in which an element serving as a luminescent center is added to an inorganic crystal skeleton whose structure is highly controlled. Here, a material that emits light at various wavelengths from ultraviolet to visible to infrared can be used by selecting an inorganic material and the type of the element that is the emission center.
The stress-stimulated luminescent material can be classified into a stress-stimulated luminescent material and a stress-stimulated phosphorescent material according to the decay time of luminescence due to given energy.
Examples of the fluorescent light-emitting material include strontium aluminate added with europium as a light emission center (SrAl ₂ O ₄ : Eu, green light emission), zinc sulfide added with manganese as a light emission center (ZnS: Mn, light emission in yellow green color) Etc.

The type of stress-stimulated luminescent material constituting the stress-stimulated luminescent particles is not limited to one using only one type, and two or more types may be used.
In the present invention, it is preferable that there are two or more kinds of the stress-stimulated luminescent materials. The stress-stimulated luminescent layer can have regions with different luminescent colors. For example, in the stress-stimulated luminescent layer 2 shown in FIG. 2, the region indicated by x is a first luminescent color region containing stress-stimulated luminescent particles made of the first stress luminescent material, and the region indicated by y is the first. It can be set as the area | region of the 2nd luminescent color containing the stress luminescent particle which consists of 2 stress luminescent materials. From such a thing, the laminated body of this invention can be made excellent in the forgery prevention effect etc.
Note that the reference numerals in FIG. 2 indicate the same members as those in FIG. 1, and a description thereof will be omitted here.
In the present invention, when two or more kinds of stress-stimulated luminescent materials are used, a mixture of stress-stimulated luminescent particles made of each stress-stimulated luminescent material, for example, the luminescent color from the first stress-stimulated luminescent particles and the second A stress-stimulated luminescent layer of one luminescent color in which luminescent colors from stress-stimulated luminescent particles are mixed may be used.

The shape of the stress-stimulated luminescent particles can be a conventionally known shape. Examples of the shape include a substantially spherical shape, a spheroid shape, a polyhedron shape, a scale shape, a disk shape, a fiber shape, and a needle shape.
In the present invention, it is preferable that the surface of the stress-stimulated luminescent particles has a fine uneven shape formed randomly. This is because the stress can easily be transmitted to the portion where the fine unevenness of the stress-stimulated luminescent particles is formed, and the stress-stimulated luminescent particles can efficiently emit light.
The concavo-convex shape may have a concavo-convex period and depth of nano size to several micrometers.

The average primary particle diameter of the stress-stimulated luminescent particles is not particularly limited as long as a stress-stimulated luminescent layer having a desired luminescence intensity can be obtained. For example, the average primary particle diameter is within a range of 0.1 μm to 50 μm. Especially, it is preferable that it exists in the range of 5.0 micrometers-20 micrometers. It is because it can be set as the stress light emitting layer excellent in emitted light intensity by being the said particle size.
The average primary particle size can be determined by a method of measuring using a laser diffraction scattering method. The laser diffraction / scattering method uses a diffraction / scattering phenomenon of light by uniformly dispersing particles in a dispersion medium and then irradiating the particles with laser light. The intensity pattern of the diffraction / scattered light is Depending on the size of the particle, different intensity patterns (intensity distributions) are observed depending on the angle of diffraction / scattered light, and the particle size distribution is obtained using the Franhofer diffraction theory or Mie scattering theory. . When the average primary particle size is determined using a laser diffraction / scattering method, it can be measured either dry or wet. When measuring by wet, water or ethanol can be measured as a dispersion.
Moreover, as a laser beam used for a laser diffraction scattering method, a semiconductor laser (wavelength 680 nm) etc. can be used.

The stress-stimulated luminescent particles are preferably coated with a water-resistant coating formed using a water-resistant material for improving water resistance. This is because it is possible to prevent the collapse of the crystal structure of the stress-stimulated luminescent material and the loss of luminescent property due to water. Moreover, it is because the water resistance, weather resistance, etc. of the said laminated body can be aimed at.
In addition, as a water resistance evaluation method, for example, a method of performing a water immersion test using warm water at a specified temperature using a laminate adjusted in a predetermined manner in JIS K 6404-3: 2015 can be used. . In the JIS standard, the water immersion test is carried out for 4 hours. In this test, the water immersion test is performed until the light emission intensity from the stress light emitting layer included in the laminate is reduced to half. It is possible to use a method of evaluating by continuing the test and setting the test time (time to immerse in water) as a time in which the luminescence intensity of the stress luminescent particles is halved.
The improvement in water resistance means that the half-life of the laminate using stress-stimulated luminescent particles with a water-resistant coating film and the half-life of laminates using stress-stimulated luminescent particles with no water-resistant coating formed. By comparison, it means that the half time is 2.0 times or more.
As the number of water-resistant coatings formed is increased and the thickness of the formed water-resistant coating is increased, the water resistance can be improved, but the work complexity and the effect of improving the water resistance are improved. In consideration of saturation, the target half-life is preferably 2.0 times or more and 10 times or less.

The water resistant material is not particularly limited as long as it can improve the water resistance of the stress-stimulated luminescent particles. For example, silane coupling agent, thermoplastic resin, thermosetting resin, metal alkoxide, metal oxidation And the like.
These water resistant materials may be used alone or in combination. When mixed and used, the water-resistant film may be composed of only one layer formed using a mixture of a plurality of water-resistant materials, and includes a plurality of layers having different water-resistant materials. Also good.

  The silane coupling agent is not particularly limited as long as it can improve the water resistance of the stress-stimulated luminescent particles, but those having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, 3- Those having an epoxy group such as glycidoxypropylmethyldimethoxysilane, those having a styryl group such as P-styryltrimethoxysilane, those having an acrylic group such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyl Those having a methacryl group such as trimethoxysilane, those having an isocyanate group such as 3-isocyanatopropyltriethoxysilane, trimethylsilyl chloride, hexamethyldisilazane, BSTFA (N, O-bis-trimethylsilyl-trifluoroa Setoa De), triethylsilyl chloride, chloromethyltrimethylsilane, trimethylsilylacetylene, mention may be made of hexamethyldisilane, N, a N'- bis trimethylsilyl urea.

The thermoplastic resin is not particularly limited as long as it can improve the water resistance of the stress-stimulated luminescent particles. For example, polymethyl methacrylate, polymethyl acrylate, polybenzyl methacrylate, polybutyl acrylate, polyisobutyl Acrylate ester resins such as acrylate, cellulose resins such as cellulose nitrate, methyl cellulose, ethyl cellulose, and cellulose acetate propionate, vinyl resins such as polyvinyl acetate and polyvinyl chloride vinyl acetate copolymer, acrylamide resins, and polystyrene resins Etc.
The thermosetting resin is not particularly limited as long as it can improve the water resistance of the stress-stimulated luminescent particles. For example, unsaturated polyester resin, acrylic urethane resin, epoxy-modified acrylic resin, melamine resin, Examples include epoxy-modified unsaturated polyester resins, alkyd resins, phenol resins, silicone resins, and fluorinated resins.

Examples of the metal element constituting the metal alkoxide include aluminum, zirconium, titanium, and silicon.
As the kind of the alkoxide, methoxide, ethoxide, propoxide, isopropoxide, oxyisopropoxide, butoxide and the like can be used.
Specific examples of the metal alkoxide include ethyl silicate and methyl silicate obtained by partially hydrolyzing and condensing tetraethoxysilane or tetramethoxysilane.
In the present invention, the metal alkoxide is preferably tetraethoxysilane, tetramethoxysilane, tetraethyl silicate, tetramethyl silicate, aluminum triisopropoxide, zirconium tetraisopropoxide, titanium tetraisopropoxide, or the like. This is because the stress-stimulated luminescent particles can be excellent in water resistance.

  Examples of the metal oxide include alumina and titanium dioxide.

  The thickness of the water-resistant film is not particularly limited as long as the desired water resistance can be obtained, but can be within a range of 0.1 μm to 10 μm, for example.

The method for forming the water-resistant coating is not particularly limited as long as it is a method capable of accurately forming a water-resistant coating covering the surface of the stress luminescent particles.
As the forming method, a method of mixing the water-resistant material and stress-stimulated luminescent particles can be used.
The above forming method may be mixed in an organic solvent as necessary.
As the formation method, when the water-resistant material is a metal oxide, a chemical vapor deposition method (CVD method or the like) can be used.

  Examples of the organic solvent include alcohol solvents such as ethyl alcohol, propyl alcohol, and butyl alcohol, ketone solvents such as acetone and methyl ethyl ketone, aromatic hydrocarbon solvents such as toluene, xylene, and benzene, methyl cellosolve, and ethyl cellosolve. , Glycol ether solvents such as propylcellsolve and butylcellsolve, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and other oxyethylene, oxypropylene addition polymers, ethylene glycol, propylene glycol , 1,2,6-hexanetriol and other alkylene glycols, glycerin, 2-pyrrolidone and the like can be preferably used. Solvents, can be preferably used ketone-based solvents.

  The water content of the organic solvent is not particularly limited as long as the water-resistant coating can be applied to the stress-luminescent particles, but it is preferably less than 0.5% by mass. This is because it is possible to suppress a decrease in light emission characteristics of the stress-stimulated luminescent particles due to moisture in the organic solvent.

The content of the stress-stimulated luminescent particles is not particularly limited as long as a stress-stimulated luminescent layer having a desired luminescence intensity can be obtained, and varies depending on the type of the stress-stimulated luminescent particles.
The said content can be made into the range of 1 mass%-50 mass% in a stress light emitting layer, for example.

The content of the stress-stimulated luminescent particles may be one type, that is, the content of the stress-stimulated luminescent particles may be uniform in the stress-stimulated luminescent layer. It is preferable that a light emitting layer has a site | part from which content of the said stress luminescent particle differs. This is because by making the stress light emitting layer have regions with different light emission intensities, the laminate can be made excellent in anti-counterfeiting effects and the like.
More specifically, the stress-stimulated luminescent layer 2 in FIG. 2 described above can have different contents of stress-stimulated luminescent particles in the region indicated by x and the region indicated by y.

As a method for forming the stress-stimulated luminescent particles, any method that can form stress-stimulated luminescent particles having a desired shape may be used. For example, the above-described forming method includes baking a stress-stimulated luminescent material composition containing components constituting the stress-stimulated luminescent material to form a sheet-like stress-stimulated luminescent material, and then pulverizing and classifying the luminescent particles. The method of obtaining can be used.
Examples of the method for pulverizing the sheet-like stress luminescent material include a method using a pulverizer such as a ball mill, a rod mill, an autogenous pulverizing mill, a SAG (semi-autogenous pulverizing) mill, a high-pressure pulverizing roll, and a vertical axis impactor (VSI) mill. it can.
In the present invention, the pulverization method is preferably a method using a longitudinal impactor (VSI) mill. This is because the shape of the stress-stimulated luminescent particles is likely to be complicated, and a rough uneven shape is easily formed on the surface of the stress-stimulated luminescent particles.
The vertical axis impactor (VSI) mill is a fine pulverizer that rotates impact teeth at high speed and pulverizes the raw material by impact force. For example, a rotary disk having a diameter of 100 mm to 1000 mm is rotated at 500 to 10,000 rotations / minute. What rotates at high speed can be used.
In addition, about the baking method of the said stress luminescent material composition, the method generally used for formation of a stress luminescent material can be used.

(B) Binder resin The binder resin is not particularly limited as long as it can stably disperse and fix the stress-stimulated luminescent particles and can transmit light emitted from the stress-stimulated luminescent particles. Examples thereof include a plastic resin, a thermosetting resin, and an ionizing radiation curable resin.

As the thermoplastic resin and the thermosetting resin, for example, the same resins as the thermoplastic resin and the thermosetting resin described in the section “(a) Stress luminescent particles” can be used.
The thermoplastic resin and the thermosetting resin are those copolymerized with a silicone resin, a fluorine-containing resin, or the like, or those having a siloxane bond or a fluorine atom introduced into the molecule of the thermoplastic resin or thermosetting resin. be able to.
The said thermoplastic resin and thermosetting resin can use 1 type, or 2 or more types, Furthermore, you may bridge | crosslink using various isocyanate resins.
The thermoplastic resin and the thermosetting resin contain various curing catalysts, for example, a metal soap such as cobalt naphthenate or zinc naphthenate, or benzoyl peroxide for initiating polymerization with heat or ultraviolet rays, Peroxides such as methyl ethyl ketone peroxide, benzophenone, acetophenone, anthraquinone, naphthoquinone, azobisisobutyronitrile, or diphenyl sulfide may be blended.

Examples of the ionizing radiation curable resin include epoxy acrylate, urethane acrylate, and acrylic-modified polyester.
The ionizing radiation curable resin may be used by blending a monofunctional monomer, a polyfunctional monomer, an oligomer, or the like for the purpose of introducing a crosslinked structure or adjusting the viscosity.

Only one type of binder resin may be used, or two or more types may be used in combination.
For example, the binder resin may include a first binder resin disposed so as to cover the stress luminescent particles and a second binder resin that disperses the stress luminescent particles covered with the first binder resin. .

The refractive index difference between the binder resin and the stress-stimulated luminescent particles is not particularly limited as long as the binder resin can transmit light emitted from the stress-stimulated luminescent particles, but is preferably 0.3 or less. Of these, 0.1 or less is preferable. When the refractive index difference is within the above range, the reflectance of the emitted light from the stress-stimulated luminescent particles at the interface between the binder resin and the stress-stimulated luminescent particles can be reduced. This is because the stress-stimulated luminescent layer can efficiently transmit light emitted from the stress-stimulated luminescent particles.
Moreover, when the said binder resin contains 1st binder resin and 2nd binder resin, it is preferable that the refractive index difference between the said 1st binder resin and 2nd binder resin is also small. This is because the reflectance of the emitted light from the stress luminescent particles at the interface between the first binder resin and the second binder resin can be reduced. Specifically, the refractive index difference between the first binder resin and the second binder resin can be the same as the refractive index difference between the binder resin and the stress luminescent particle refractive index.

  The volume modulus of the binder resin is preferably larger than the volume modulus of the stress luminescent particles. This is because, when a stress is applied to the laminate, the deformation applied to the stress luminescent layer can be effectively transmitted to the stress luminescent particles, and the stress luminescent layer can be made excellent in luminous efficiency.

(C) Other components The stress-stimulated luminescent layer has stress-stimulated luminescent particles and a binder resin, but may contain other materials as necessary.
Examples of the other materials include additives such as coloring materials such as pigments, curing accelerators, lubricants, light stabilizers, oxidation stabilizers, perfumes, and ultraviolet absorbers.
In addition, when the binder resin is a thermoplastic resin or a thermosetting resin, the other material may include a silicone resin, a fluorine-containing resin, silicone oil, silicone powder fine particles, and fluorine powder fine particles.
As the fluorinated resin, a tetrafluorinated resin as a fully fluorinated resin, a trifluorinated resin as a partially fluorinated resin, polyvinylidene fluoride, polyvinyl fluoride, a perfluoroalkoxy fluororesin as a fluorinated resin copolymer, and a tetrafluoride resin. An ethylene-hexafluoropropylene copolymer, an ethylene-tetrafluoroethylene copolymer, an ethylene-chlorotrifluoroethylene copolymer, or the like can be used.
In addition, content of said other material can be adjusted within the range which can permeate | transmit the light light-emitted from the stress light-emitting particle | grains in a stress light-emitting layer.

(2) Relief hologram The stress-stimulated luminescent layer in the present invention is not particularly limited as long as it has a function of emitting light when stress is applied, but may have other functions.
For example, the stress-stimulated luminescent layer may be one in which a relief hologram is recorded on the stress-stimulated luminescent layer and has a relief on the surface. It is possible to prevent light emission from the stress light emitting layer and forgery by the relief hologram recorded on the stress light emitting layer, and to reproduce the hologram image recorded on the stress light emitting layer by light emission from the stress light emitting layer. You can also
In addition, since the relief hologram is recorded on the surface of the stress light-emitting layer, the light emission of the stress light-emitting layer can directly reach the uneven relief, and the relief hologram can be reproduced with higher definition.
For this reason, it is because a laminated body becomes the thing excellent by forgery prevention property and design property.
3 and 4 are schematic cross-sectional views showing other examples of the laminate of the present invention. The laminate 10 has a stress-stimulated luminescent layer 2 on which a relief hologram is recorded and an uneven relief 12 is formed on the surface. The example which has is shown.
3 and 4 indicate the same members as those in FIG. 1, and the description thereof is omitted here.

The depth of the relief of the unevenness, that is, the distance between the bottom of the adjacent recess and the top of the projection is not particularly limited as long as a desired relief hologram image can be recorded. About 0.01 μm.
Further, the pitch of the concave and convex reliefs, that is, the period between the bottoms of adjacent concave portions or the top portions of adjacent convex portions is not particularly limited as long as a desired relief hologram image can be recorded. However, it can be, for example, around 1.0 μm.
Incidentally, the depth of the relief of the unevenness is specifically shown by g in FIG. 3, and the pitch of the relief of the unevenness is specifically shown by h in FIG. is there.

The recording surface of the relief hologram of the stress-stimulated luminescent layer, that is, the surface on which the uneven relief is formed is usually only on one surface of the stress-stimulated luminescent layer.
The recording location in the stress luminescent layer of the relief hologram may be, for example, the entire surface of the stress luminescent layer or a part of the stress luminescent layer.
In FIG. 3 and FIG. 4 which have already been described, an uneven relief 12 is formed on the surface opposite to the surface on which the substrate 1 of the stress-stimulated luminescent layer 2 is formed. In FIG. FIG. 4 shows an example in which the portion is the entire surface of the stress light emitting layer 2 and FIG. 4 shows the recording portion of the relief hologram as a partial region of the stress light emitting layer 2.

The type of relief hologram recorded on the stress-stimulated luminescent layer is only one type, that is, the relief hologram recorded on the stress-stimulated luminescent layer may show one image, but two or more types are included, That is, the relief hologram recorded in the stress-stimulated luminescent layer may show two or more images.
For example, different types of relief holograms can be recorded in the area indicated by x and the area indicated by y in FIG. 3 described above.

The method for recording a relief hologram on the stress-stimulated luminescent layer is not particularly limited as long as it is a method capable of forming an uneven relief capable of reproducing a desired hologram image, and a conventionally known method can be used.
In the recording method, for example, an original plate on which diffraction fringes or hologram interference fringes are recorded in a concavo-convex shape is used as a press mold, and the original plate is overlaid on a layer for forming a stress light emitting layer containing the stress light emitting particles and a binder resin. A method of forming a stress-stimulated luminescent layer having an uneven relief on the surface by transferring the concavo-convex relief of the original plate to the surface of the layer for forming the stress-stimulated luminescent layer by heating and pressure-bonding them by appropriate means such as a heating roll. Can be mentioned.
Further, when the laminate has a filling layer on which a relief hologram is recorded and is formed on the same plane as the stress-stimulated light emitting layer formed in a pattern, a relief hologram is simultaneously formed on the stress emitting layer and the filling layer. May be recorded. This is because the process can be simplified. Specifically, the recording method may be a method in which a master is stacked and thermocompression bonded to the stress-stimulated luminescent layer forming layer and the filling layer forming layer formed on the same plane.

(3) Others The stress-stimulated luminescent layer may be formed in a pattern, although it may not be formed in a pattern, that is, the stress-stimulated luminescent layer may be formed so as to cover the entire surface of the substrate. It is preferable. By forming the stress light emitting layer in a pattern, the stress light emitting layer can emit light in a pattern in plan view when stress is applied to the laminate. For this reason, it is because the laminated body will be excellent in anti-counterfeiting effect and the like by forming the stress light emitting layer in a pattern.

FIG. 5 is a schematic plan view showing another example of the laminate of the present invention, and FIG. 6 is a cross-sectional view taken along line AA of FIG.
FIG. 1 already described shows an example in which the stress light emitting layer 2 is formed on the entire surface of the substrate 1, and FIGS. 5 and 6 show examples in which the stress light emitting layer 2 is formed in a pattern. It is. 5 and 6 show an example in which no other layer is formed on the same plane as the stress light emitting layer 2 except the region where the stress light emitting layer 2 is formed in a pattern.
5 and 6 indicate the same members as those shown in FIG. 1, and a description thereof will be omitted here. FIG. 5 is a view of the laminated body 10 observed from the inner surface side sealant layer 3a side. Further, for the sake of easy explanation, description of the inner surface side sealant layer and the outer surface side sealant layer is omitted.

When the stress-stimulated luminescent layer is formed in a pattern, the shape of the stress-stimulated luminescent layer in plan view can be appropriately set according to the type and application of the laminate of the present invention.
For example, the planar view shape of the stress light emitting layer can be a dot shape, a line shape, or the like. Moreover, the planar view shape of the dot-like stress light-emitting layer can be an arbitrary shape such as a circular shape or a square shape.
Moreover, the planar view shape of the stress light emitting layer may represent a symbol, a character, or the like. The shape of the stress-stimulated luminescent layer in plan view may be, for example, a line-like stress luminescent layer that represents characters or the like, or a dot-like stress luminescent layer that represents characters or the like. Further, it may represent predetermined information using characters or the like.
FIG. 5 and FIG. 6 which have already been described show an example in the case where the stress emission layer 2 has a line shape in plan view.

  When the stress light emitting layer is formed in a pattern, the width of the stress light emitting layer is not particularly limited as long as it can emit light in a desired pattern shape, and the type and use of the laminate of the present invention It is set appropriately according to the above.

  The thickness of the stress-stimulated luminescent layer is not particularly limited as long as it can be a stress-stimulated luminescent layer having a desired luminescence intensity, but can usually be in the range of 0.1 μm to 6 μm, Especially, it is preferable that it exists in the range of 0.1 micrometer-4 micrometers.

The stress-stimulated luminescent layer only needs to be transparent to light having a predetermined wavelength emitted by the stress-stimulated luminescent particles.
The total light transmittance of the stress-stimulated luminescent layer is preferably 20% or more, more preferably 60% or more, and particularly preferably 90% or more. This is because it is easy to make the stress light emitting layer excellent in light emission intensity.
Here, the transmittance of the stress-stimulated luminescent layer can be measured according to JIS K7361-1 (a test method for the total light transmittance of a plastic-transparent material).

The number of the stress-stimulated luminescent layers formed may be one or more in one laminate, but it is two or more, that is, the stress-stimulated luminescent layer in which the laminate of the present invention is laminated in two or more layers. It may be a thing. This is because it is possible to easily form different stress luminescent layers such as the kind and content of the stress luminescent particles and the shape of the stress luminescent layer in plan view, and the laminate has an excellent anti-counterfeit effect.
Note that, as already described with reference to FIGS. 2, 5, and 6, a plurality of stress light emitting layers formed on the same plane are regarded as one stress light emitting layer.

The stress light emitting layer is disposed between the inner surface side sealant layer and the outer surface side sealant layer. Such a stress luminescent layer may be disposed in the thickness direction between the base material and the inner surface side sealant layer or between the base material and the outer surface side sealant layer.
In the present invention, it is particularly preferable that the arrangement location is between the base material and the inner surface side sealant layer. This is because, when the laminated body of the present invention is used to form the cylindrical body portion of the tube container, the arrangement location can suppress uneven fusion of the inner surface side sealant layer and the outer surface side sealant layer. Moreover, it is because the said arrangement | positioning location can suppress that a stress light emitting layer peels in the case of melt | fusion of the inner surface side sealant layer and the said outer surface side sealant layer.
The stress-stimulated luminescent layer may be formed so as to be in direct contact with the outer surface side sealant layer, or may be formed on the surface of the outer surface side sealant layer via another layer.
In addition, FIGS. 1-6 already demonstrated shows the example in which the said arrangement | positioning location is between the base material 1 and the inner surface side sealant layer 3a.

The method for forming the stress-stimulated luminescent layer is not particularly limited as long as the method can contain stress-stimulated luminescent particles and a binder resin.
As the above formation method, for example, a stress luminescent ink is formed by dispersing or dissolving a stress luminescent particle and a binder resin, which are constituent materials of the stress luminescent layer, in a solvent, and this stress luminescent ink is applied to the surface of the substrate. And the method of forming a stress light emitting layer by drying a solvent from the coating film of the stress light emitting ink can be mentioned.
Further, when the stress-stimulated luminescent layer is formed in a pattern, the forming method may be a method of applying a stress-stimulated luminescent ink in a pattern using a printing method or the like.
The printing method is not particularly limited as long as it is a printing method capable of forming a stress-stimulated light emitting layer having a desired pattern shape. For example, intaglio, letterpress, offset, screen, gravure, flexographic printing or inkjet printing, Examples of the printing method include spray printing and coating.

Examples of the solvent include cyclic hydrocarbons (cyclohexane, etc.), alcohols (methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, etc., and their aqueous solutions), ethers (tetrahydrofuran, methyl). Cellosolve, ethyl cellosolve, butyl cellosolve, t-butyl cellosolve, etc.), glycol derivatives such as ethylene glycol monobutyl ether, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, isophorone, diisobutyl ketone, etc. ), Aromatics (benzene, toluene, xylene, Solvesso No. 100, Solvesso No. 150, Cactus P-180, etc.), esters (ethyl acetate, butyl acetate) Isobutyl acetate, propylene glycol monomethyl ether acetate, cellosolve acetate, ethyl 3-ethoxypropionate and the like) and the like.
When a water-soluble resin is used as the binder resin, water and / or lower alcohols such as methanol, ethanol, propanol, and butyl alcohol, glycols, and cell solves can be used as the solvent.

  The method of forming the stress-stimulated luminescent ink is not particularly limited as long as it is a method capable of stably dispersing or dissolving the stress-stimulated luminescent particles and the binder resin in the solvent. For example, the binder resin is dispersed or dissolved in the solvent. An example is a method in which stress luminescent particles are added and stirred.

  The drying method is not particularly limited as long as the solvent can be sufficiently removed. Natural drying, contact heat drying at 40 ° C. to 80 ° C., hot air drying at 40 ° C. to 200 ° C., vacuum drying. Etc. can be used. In addition, as the drying method, ultraviolet ray irradiation, drying using a curing reaction by electron beam irradiation, or the like may be used alone or in combination.

2. Inner surface side sealant layer and outer surface side sealant layer The inner surface side sealant layer and outer surface side sealant layer in the present invention (hereinafter, both may be referred to simply as a sealant layer) sandwich the base material and the stress light emitting layer. It is formed as follows.
The inner surface side sealant layer and the outer surface side sealant layer are formed of a tube container in which the inner surface side sealant layer is disposed on the inner surface side and the outer surface side sealant layer is disposed on the outer surface side by fusing both sealant layers to each other. A cylindrical body part is formed.
Examples of a method for confirming that the sealant layer is on the inner surface side or the outer surface side include a method for confirming the orientation of an image displayed by a stress light emitting layer, a print layer, or the like included in the laminate.

The resin material that constitutes such a sealant layer may be any material that can be melted by heating and can be fused to each other.
Examples of the resin material include low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, and ethylene-ethyl acrylate. A polyolefin resin such as a copolymer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-propylene copolymer, a methylpentene polymer, polyethylene or polypropylene, with acrylic acid, methacrylic acid, maleic acid, Examples include acid-modified polyolefin resins modified with unsaturated carboxylic acids such as maleic anhydride, fumaric acid, itaconic acid, and the like, polyvinyl acetate resins, polyester resins, and polystyrene resins.
In the present invention, the resin material is preferably linear low density polyethylene. This is because linear low-density polyethylene has the advantage of improving impact resistance with less propagation of breakage due to its adhesiveness.
The said resin material can be used 1 type or in combination of 2 or more types.

  The inner surface side sealant layer and the outer surface side sealant layer may each have a thickness in the range of 100 μm to 210 μm.

The arrangement position in the thickness direction of the sealant layer is formed so as to sandwich both the base material and the stress light emitting layer, and the surface of the base material opposite to the stress light emitting layer and the base material of the stress light emitting layer. An inner surface side sealant layer and an outer surface side sealant layer may be formed on the surface opposite to each other.
Here, being formed on the surface is not limited to an embodiment formed so as to be in direct contact with the surface, but includes an embodiment formed via other layers. Therefore, the sealant layer may be disposed so as to be in direct contact with the base material or the stress-stimulated luminescent layer, or may be disposed via another layer.

The method for forming the sealant layer on the substrate or the surface of the stress-stimulated luminescent layer may be any method that can form a sealant layer having a desired thickness.
The above-mentioned forming method is, for example, a method in which a sealant layer obtained by forming the above-described constituent material into a film shape is disposed on the surface of a substrate or the like via an adhesive layer, and then pressure, heating, etc. are applied to the sealant layer. Examples include a method of forming a sealant layer by applying the above-described constituent material in a molten state to the surface of a material, etc., and cooling and solidifying the coating film.

3. Base material The base material in this invention is formed in one surface of an inner surface side sealant layer.
Moreover, the said base material supports a stress light emitting layer and a sealant layer.

As such a substrate, a film or sheet of a resin such as biaxially stretched polypropylene (PP), polyethylene terephthalate (PET), ethylene vinyl alcohol copolymer (EVOH), or the like can be used.
The thickness of the base material can be in the range of 10 μm to 50 μm.

4). Other Configurations The laminate of the present invention has a sealant layer, a base material, and a stress-stimulated luminescent layer, but may have other configurations as necessary.

(1) Filling layer The laminate of the present invention can include a filling layer formed on the same plane as the stress-stimulated luminescent layer when the stress-stimulated luminescent layer is formed in a pattern. This is because the presence of the stress-stimulated light-emitting layer formed in a pattern can be made inconspicuous, and the laminate is excellent due to the anti-counterfeiting effect and the like.
FIG. 7 is a schematic cross-sectional view showing another example of the laminate of the present invention, and FIG. 8 is a cross-sectional view taken along the line BB of FIG. 7 and 8 show an example in which the stress light emitting layer 2 is formed in a pattern, and the laminate 10 has a filling layer 4 formed on the same plane as the stress light emitting layer 2.
7 and FIG. 8 indicate the same members as those in FIG. 1, and a description thereof will be omitted here.

The filling layer is formed on the same plane as the stress light emitting layer.
Here, being formed on the same plane means being formed on the same plane as the plane on which the stress light emitting layer is formed, and the portion where the stress light emitting layer is not formed in plan view. It means that it is formed.
For example, in FIGS. 7 and 8 already described, the filling layer 4 is formed so that both the stress-stimulated luminescent layer 2 and the filling layer 4 are formed on the same surface of the substrate 1 so as to be in contact with the substrate 1. Together with the stress-stimulated luminescent layer 2, it can be formed on the same surface of the same member.
In addition, the filling layer is used to make the presence of the stress light emitting layer inconspicuous, and the formation of the filling layer makes the presence of the stress light emitting layer less noticeable than before the formation of the filling layer. .

The color of the filling layer is not particularly limited as long as the presence of the stress-stimulated luminescent layer can be made inconspicuous, and may be monochromatic or multicolored. From the viewpoint of having the same color and the same color, it is preferable to be a single color.
When the color of the filling layer is a single color, it is preferably the same color as that of the stress-stimulated luminescent layer, and in particular, the same color as that of the stress-stimulated luminescent layer. When the color is the color described above, it becomes possible to effectively obscure the presence of the stress light-emitting layer in which the color of the filling layer is formed in a pattern. This is because it becomes excellent.
The same color means that the color difference in the L ^* a ^* b ^* color system defined by JISZ8730 is 20 or less. The same color means that the color difference is within 0.5. The color of the stress-stimulated luminescent layer refers to the color when no light is emitted.
In addition, the color of the filling layer may represent a pattern by the filling layer, and may be such that the region where the stress light emitting layer is formed is recognized as a part of the pattern. This is because it is possible to make the laminate excellent in design and to make the presence of the stress-stimulated luminescent layer formed in a pattern inconspicuous.

The constituent material of the filling layer is not particularly limited as long as it can form a filling layer of a desired color, but may contain a resin material. Moreover, the said constituent material shall contain a white pigment and another component as needed.
In the present invention, it is preferable that the constituent material has a white pigment from the viewpoint that the color of the filling layer is the same color as that of the stress light emitting layer. Since the stress-stimulated luminescent particles contained in the stress-stimulated luminescent layer are generally white, having a white pigment makes it easy to make the color of the filling layer similar to the color of the stress-stimulated luminescent layer. This is because the presence of the light emitting layer can be effectively made inconspicuous.

The white pigment is not particularly limited as long as it has a property of not emitting light even when stress is applied, and examples thereof include titanium dioxide, zinc white, and antimony trioxide.
The particle size and content of the white pigment are not particularly limited as long as the color of the filling layer can be the same color as that of the stress light emitting layer. The particle diameter and content can be the same as the content of the particle diameter and content of the stress-luminescent particles described in the section “1.

As the resin material, a general resin material can be used. For example, a resin similar to the binder resin described in the section “1. Stress light emitting layer” can be used.
In the present invention, the resin material is preferably the same as the binder resin contained in the stress light-emitting layer, from the viewpoint that the color of the filling layer is similar to the color of the stress light-emitting layer. This is because it is easy to make the color of the filling layer similar to the color of the stress light emitting layer, and the presence of the stress light emitting layer can be effectively made inconspicuous.

Examples of the other components include additives generally used together with resin materials, and the same materials as the other materials described in the above section “1. Stress light emitting layer” may be used. it can.
In the present invention, from the viewpoint that the color of the filling layer is the same color as the stress luminescent layer, the other components are preferably the same as the other materials contained in the stress luminescent layer. However, the content ratio of the other components to the resin material is preferably the same as the content ratio of the other materials included in the stress light-emitting layer to the binder resin included in the stress light-emitting layer.
More specifically, for example, when the stress-stimulated luminescent layer contains a colorant, the filler layer preferably contains the same colorant as the colorant contained in the stress-stimulated luminescent layer. It is preferable that the content ratio with respect to the resin material is the same as the content ratio of the colorant in the stress light emitting layer with respect to the binder resin. This is because it is easy to make the filling layer have the same color as the stress light emitting layer, and the presence of the stress light emitting layer can be effectively made inconspicuous.

  The filling layer is not particularly limited as long as the stress light emitting layer can be made inconspicuous. The total light transmittance of the filling layer may be the same as that described in the section “1. Stress light emitting layer”, for example. In the present invention, from the viewpoint that the color of the filling layer is similar to the color of the stress light emitting layer, it is preferably the same as the stress light emitting layer.

  The thickness of the filling layer is not particularly limited as long as the stress light emitting layer can be made inconspicuous. The thickness can be the same as that described in the section “1. In the present invention, from the viewpoint that the color of the filling layer is the same color as the stress luminescent layer, the thickness is preferably the same as the thickness of the stress luminescent layer. This is because it is easy to make the color of the filling layer similar to the color of the stress light emitting layer, and the presence of the stress light emitting layer can be effectively made inconspicuous.

The formation place of the filling layer in plan view is not particularly limited as long as the stress light emitting layer is not formed, and includes, for example, all the places where the stress light emission layer is not formed. It may include a part of the portion where the stress light emitting layer is not formed.
7 and 8 already described are formed so that the stress light emitting layer 2 and the filling layer 4 are in direct contact with each other, and the stress light emitting layer 2 is formed at the formation position of the filling layer 4 in plan view. An example that includes all of the missing parts is shown.

The filling layer may be formed by any method that can stably form the filling layer on the same plane as the stress-stimulated luminescent layer. For example, a method similar to the method of forming the stress-stimulated luminescent layer may be used. it can.
As the forming method, for example, a method of preparing a filling layer by preparing a filling layer forming ink, forming a coating film of the filling layer forming ink using a printing method, and then drying the coating film, etc. Can be mentioned.
Further, the order of formation of the stress light emitting layer and the filling layer is not particularly limited, and any of them may be formed first or simultaneously.

(2) Hologram layer The laminate of the present invention can include a hologram layer in which a hologram is recorded. It is possible to prevent forgery by the light emitted from the stress light emitting layer and the hologram recorded on the hologram layer. Further, the hologram image recorded on the hologram layer by the light emission from the stress light emitting layer can be reproduced. For this reason, it is because a laminated body becomes the thing excellent by forgery prevention property and design property.
FIG. 9 is a schematic cross-sectional view showing another example of the laminate of the present invention, in which the base material 1, the hologram layer 5, and the stress light emitting layer 2 are laminated in this order.

The hologram layer in the present invention is a hologram recorded.
Such a hologram layer can be appropriately selected according to the type and use of the laminate of the present invention. For example, a volume hologram layer in which a volume hologram is recorded or a relief hologram layer in which a relief hologram is recorded is used. Can be used.
Such volume hologram layer and relief hologram layer can be the same as those generally used as a hologram layer.

Specifically, a photopolymerizable material can be used as the material constituting the volume hologram layer. The photopolymerizable material is not particularly limited as long as the polymerization reaction can be advanced by irradiation with predetermined light and an interference fringe can be formed on the volume hologram layer. . As the photopolymerizable material, for example, at least one of a radically polymerizable compound or a cationically polymerizable compound is preferably used, and particularly from the viewpoint that a high-contrast hologram image can be recorded. It is preferable to use a compound and a cationically polymerizable compound in combination.
Further, the recording method of the volume hologram on the volume hologram layer is not particularly limited as long as a predetermined interference fringe can be recorded on the volume hologram layer forming layer containing the material and the like. As such a method, for example, reference light is incident from one surface side of the volume hologram layer forming layer, and object light is incident from the other surface side of the volume hologram layer forming layer to form the volume hologram layer formation. A method of forming a volume hologram layer by causing these lights to interfere with each other in the layer for use, or a side where the hologram master is disposed on the volume hologram layer formation layer, Includes a method of forming a volume hologram layer by causing light to enter from the opposite side and causing the incident light and reflected light reflected by the hologram master to interfere in the volume hologram layer forming layer. Can do.
The thickness of the volume hologram layer is not particularly limited as long as a desired hologram image can be recorded. Usually, it is preferably in the range of 1 μm to 50 μm, and more preferably in the range of 3 μm to 40 μm. It is preferable that it is in the range of 5 μm to 30 μm.

Examples of the material constituting the relief hologram layer include those containing a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, and the like.
Such thermoplastic resin, thermosetting resin, and ionizing radiation curable resin can be the same as those described in the above section “1. Stress light emitting layer”. Moreover, the said material can also use a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, etc. individually or in mixture, respectively.
Further, as a method for recording a relief hologram on the relief hologram layer, a conventionally known method can be used using the above materials. The recording method can be the same as that described in the section “1.
The depth and pitch of the relief of the unevenness are not particularly limited as long as a desired relief hologram can be recorded, and may be the same as the contents described in the above section “1. Stress light emitting layer”. it can.
The thickness of the relief hologram layer is not particularly limited as long as a desired hologram image can be recorded, but can usually be in a range of 0.1 μm to 6 μm, and in particular, 0.1 μm. It is preferable to be within a range of ˜4 μm.
The surface on which the relief is formed may be the stress light emitting layer side surface of the hologram layer, or the surface opposite to the surface on which the stress light emitting layer is formed.

The hologram layer can transmit visible light.
The total light transmittance of the hologram layer is preferably 20% or more, and more preferably 60% or more.
The transmittance measurement method can be the same as the method described in the section “1. Stress light emitting layer”.

  The hologram layer may include a colorant such as a pigment as necessary.

The location of the hologram layer in the thickness direction can be between the inner surface side sealant layer and the outer surface side sealant layer, but is preferably between the base material and the inner surface side sealant layer. This is because the arrangement location can facilitate the fusion of the inner surface side sealant layer and the outer surface side sealant layer when forming the cylindrical body portion of the tube container using the laminate of the present invention. is there. Moreover, it is because the said arrangement | positioning location can suppress that a hologram layer peels in the case of melt | fusion of the inner surface side sealant layer and the said outer surface side sealant layer.
The arrangement location may be between the stress-stimulated luminescent layer and the inner surface side sealant layer, or between the stress luminescent layer and the outer surface side sealant layer.
In addition, FIG. 9 which has already been described shows an example in which the arrangement location is between the base material 1 and the inner surface side sealant layer 3a and between the stress light emitting layer 2 and the inner surface side sealant layer 3a. .

The formation position of the hologram layer in plan view is not particularly limited as long as the hologram can be reproduced and the formation of the tube container is not hindered.
The above-mentioned formation location is preferably not formed in a pattern, that is, the hologram layer may cover the entire surface of the base material, or may cover a part of the base material.

(3) Vapor Deposition Layer The laminate of the present invention can include a stress emission layer on which a relief hologram is recorded or a vapor deposition layer formed so as to be in contact with the uneven relief forming surface of the hologram layer. This is because by having the vapor deposition layer, it is possible to easily provide a difference in refractive index with respect to the relief forming surface such as the stress-stimulated luminescent layer, and the hologram image can be reproduced more easily.
FIG. 10 is a schematic cross-sectional view showing another example of the laminate of the present invention, and shows an example in which the base material 1, the vapor deposition layer 6, the hologram layer 5 and the stress light emitting layer 2 are laminated in this order. Further, in FIG. 10, the hologram layer 5 is a relief hologram layer, and an uneven relief is formed on the surface of the hologram layer 5 opposite to the surface on which the stress light emitting layer 2 is formed, and vapor deposition is performed along the relief unevenness. Layer 6 is formed.

  The material constituting the vapor deposition layer is not particularly limited as long as it is a material that produces a refractive index difference between the stress light emitting layer and the hologram layer on which the relief hologram is formed. For example, Mg, Al, Ti , Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Rb, Pd, Ag, Cd, In, Sn, Sb, Te, Au, Pb, or Bi, etc., oxidation of these metals Or nitrides of these metals alone or in combination of these materials.

The thickness of the vapor deposition layer can be appropriately set from the viewpoints of desired reflectivity, color tone, design, application, etc., for example, preferably in the range of 50 to 1 μm, and more preferably in the range of 100 to 1000 μm. It is preferable.
In addition, the thickness is preferably 200 mm or less from the viewpoint of providing transparency to the vapor deposition layer, and may be more than 200 mm from the viewpoint of providing concealment to the vapor deposition layer. preferable.

  As a formation method of the said vapor deposition layer, the formation method of a general vapor deposition layer can be used, A vacuum vapor deposition method, sputtering method, an ion plating method etc. can be mentioned.

(4) Barrier layer The laminate of the present invention may have a barrier layer having a metal film or an inorganic oxide vapor deposition film.
In the laminate, the barrier layer has a metal film layer or an inorganic oxide vapor deposition film layer to prevent leakage of contents components such as various fragrances, and deterioration of contents due to oxygen gas and water vapor. This is because it is possible to prevent the deterioration of the contents due to prevention, sunlight, or the like. Moreover, when a barrier layer has a metal film, it is because a barrier layer can provide easily the design property by metal luster to the said laminated body.
FIG. 11 is a schematic cross-sectional view showing another example of the laminate of the present invention, in which the base material 1, the stress light emitting layer 2, and the barrier layer 7 are laminated in this order.

As the metal film, a metal foil having a metal material in a foil shape, a metal vapor deposition film in which a metal material is vapor-deposited in a film shape, or the like can be used.
Examples of the metal material constituting the metal film include aluminum.
As thickness of the said metal foil or a metal vapor deposition film, it can be in the range of 9 micrometers-15 micrometers.

Examples of the inorganic oxide material constituting the inorganic oxide vapor-deposited film include silicon oxide and aluminum oxide.
The thickness of the inorganic oxide vapor-deposited film can be, for example, in the range of 10 to 3000 mm, and particularly preferably in the range of 60 to v1000 mm.

When the barrier layer includes a metal vapor deposition film as the metal film and when the inorganic oxide vapor deposition film is included, the barrier layer usually has a supporting base material.
As a constituent material of the supporting base material, any material that can stably form the above metal vapor-deposited film may be used. Polyolefin resins such as polyethylene, polypropylene, polybutene, (meth) acrylic resins, polyvinyl chloride resins Polystyrene resin, polyvinylidene chloride resin, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin, Examples thereof include polyester resins and polyamide resins.
The thickness of the supporting substrate can be in the range of 12 μm to 20 μm.
In the present invention, the support substrate may be a separate body from the substrate, or is integral with the substrate, that is, the substrate is used as a support substrate. Also good. It is because the structure of a laminated body can be simplified because the said base material shall be used also as a support base material.

  The vapor deposition method may be any method that can form a metal vapor deposition film or an inorganic oxide vapor deposition film having a desired thickness. Physical vapor deposition such as vacuum vapor deposition, sputtering, ion plating, cluster-ion beam, etc. Or a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or the like. be able to.

The barrier layer may be transparent so as to transmit light emitted from the stress-stimulated luminescent layer, or may have light shielding properties.
When the barrier layer has transparency, the total light transmittance of the barrier layer can be the same as the total light transmittance of the stress light-emitting layer described in the section “1. Stress-light-emitting layer”.

The arrangement position of the barrier layer in the thickness direction can be between the inner surface side sealant layer and the outer surface side sealant layer. For example, in the case where the barrier layer is permeable, the above arrangement location is on the inner surface side sealant layer side even if it is on the outer surface side sealant layer side from the stress light emitting layer, hologram layer and print layer described later. May be. Moreover, when the said barrier layer contains a metal film and it has light-shielding property, the said arrangement | positioning location is normally an inner surface side sealant layer side from a stress light emitting layer, a hologram layer, and a printing layer.
In the present invention, it is particularly preferable that the above-mentioned arrangement location is between the base material and the inner surface side sealant layer, in particular, the inner surface side sealant layer side from the stress light emitting layer, the hologram layer and the printing layer. Among the stress light emitting layer, the hologram layer, and the printing layer, it is preferably between the member on the innermost side sealant layer side and the inner surface side sealant layer. It is because the said laminated body becomes the thing excellent in the protection property of the content by being the said arrangement | positioning location.
In FIG. 11 already described, the barrier layer 7 is formed between the base material 1 and the inner surface side sealant layer 3a, and the barrier layer 7 is formed between the stress light emitting layer 2 and the inner surface side sealant layer 3a. An example is given.

(5) Print layer The laminated body of this invention has a print layer which displays images, such as a character and a pattern, normally.
In this invention, by having the said printing layer, the said laminated body becomes the thing excellent in the forgery prevention property and the designability.
12 and 13 are schematic cross-sectional views showing other examples of the laminate of the present invention, and show an example in which the laminate 10 has a printing layer 8.

As such a printing layer, what is generally used for the said laminated body can be used, for example, it can have a coloring material and a resin material.
Examples of the resin material include polycarbonates, polyesters, cellulose derivatives, norbornene resins, polyvinyl chlorides, polyvinyl acetates, acrylic resins, urethane resins, polypropylenes, polyethylenes, styrenes, and the like. These resins can be used.
As the coloring material, those generally used as a printing layer can be used, pigments such as inorganic pigments and organic pigments, acidic dyes, direct dyes, disperse dyes, oil-soluble dyes, metal-containing oil-soluble dyes, and sublimation properties. And dyes such as pigments.
In addition, as the coloring material, a fluorescent light emitting material such as an ultraviolet light emitting material and an infrared light emitting material that emits fluorescence by absorbing ultraviolet light or infrared light, particles that become a reflecting mirror such as a polarized cholesteric polymer liquid crystal pigment, glass beads, and the like are also used. Can do.

The image displayed by the print layer can be set as appropriate according to the use of the laminate of the present invention. For example, not only patterns, line drawings, characters, figures, symbols, but also the entire surface is colored. This embodiment is also included.
The printed layer may have transparency capable of transmitting light emitted from the stress-stimulated luminescent layer or may have light shielding properties.

The arrangement position in the thickness direction of the printed layer can be between the inner surface side sealant layer and the outer surface side sealant layer, and among them, it is preferably between the base material and the inner surface side sealant layer. This is because the arrangement location can facilitate the fusion of the inner surface side sealant layer and the outer surface side sealant layer when forming the cylindrical body portion of the tube container using the laminate of the present invention. is there. Moreover, it is because the said arrangement | positioning location can suppress that a printing layer peels in the case of melt | fusion of the inner surface side sealant layer and the said outer surface side sealant layer.
The arrangement location may be any of between the stress light emitting layer and the inner surface side sealant layer and between the stress light emitting layer and the outer surface side sealant layer. When the arrangement location is between the stress light emitting layer and the inner surface side sealant layer, the printed layer can be illuminated by light emitted from the stress light emitting layer. In addition, when the placement location is between the stress light emitting layer and the outer surface side sealant layer, by using the printing layer having a light-shielding property, the printing layer can be used without patterning the stress light emitting layer. The stress-stimulated luminescent layer can emit light in a pattern. Moreover, the printing layer can change the hue of the light emission from a stress light emitting layer by using what has permeability | transmittance as said printing layer.
In addition, FIG. 12 and FIG. 13 which have already been described show an example in which the above-mentioned arrangement location is between the base material 1 and the inner surface side sealant layer 3a.
Moreover, FIG. 12 already described shows an example in which the arrangement location is between the stress light emitting layer 2 and the outer surface side sealant layer 3b, and FIG. 13 shows the arrangement location of the stress light emission layer 2 and the inner surface side sealant layer. An example between 3b is shown.

  As a method for forming the printing layer, that is, as a printing method, a normal printing method such as a letterpress printing method, a flexographic printing method, and a silk printing method can be used. It is preferable in that the printed characters and patterns are beautiful.

(6) Adhesive layer The laminated body of this invention shall have an adhesive layer which adhere | attaches said each structure.
As an adhesive constituting such an adhesive layer, those generally used in the above laminate can be used, for example, a pressure-sensitive adhesive that exhibits an adhesive effect by applying pressure, and melts when heated. Alternatively, a heat-sensitive adhesive that softens and exhibits an adhesive effect can be used.
Moreover, as said adhesive agent, well-known adhesives, such as 2 liquid curable adhesives, such as 2 liquid curable urethane type adhesives, an ultraviolet curable adhesive, and a thermosetting adhesive, can be used.
Examples of the heat-sensitive adhesive include polyethylene, ethylene-α olefin copolymer, polypropylene, polybutene, polyisobutene, poisoisobutylene, polybutadiene, polyisoprene, ethylene-methacrylic acid copolymer, and ethylene-acrylic acid copolymer. Copolymers of ethylene and unsaturated carboxylic acids, or thermoplastic resins such as acid-modified polyolefin resins, ethylene-ethyl acrylate copolymers, ionomer resins, and ethylene-vinyl acetate copolymers modified with these Can be used.
Examples of the pressure sensitive adhesive include, for example, polyester urethane adhesives, polyether urethane adhesives, acrylic adhesives, polyester adhesives, polyamide adhesives, polyvinyl acetate adhesives, and epoxy adhesives. Adhesives, rubber adhesives, etc. can be used.

  About the thickness of the said contact bonding layer, it sets suitably according to the kind etc. of the adhesive agent to be used.

The method of disposing the adhesive layer between the members differs depending on the type of adhesive constituting the adhesive layer, but the film adhesive layer previously formed into a film using the adhesive is bonded. Examples thereof include a method of arranging between the members to be made, a method of applying a fluidized adhesive on the surface of one member to be bonded, and curing the adhesive.
When the adhesive is a heat-sensitive adhesive, examples of the method for arranging the adhesive layer include a method in which the adhesive is heated to be applied in a molten state and then cooled and solidified.

5. Manufacturing method The manufacturing method of the laminated body of the present invention may be any method as long as the above-described components can be stacked in a desired stacking order. For example, it is described in the section “C. Manufacturing method of tube container laminated body” described later. It can be the same as the contents of.

B. Tube container Next, the tube container of this invention is demonstrated.
The tube container of the present invention includes an inner surface side sealant layer, a base material formed on one surface of the inner surface side sealant layer, and an outer surface formed on the surface of the base material opposite to the inner surface side sealant layer. A cylindrical body part in which ends of the inner surface side sealant layer and the outer surface side sealant layer of the laminated body for a tube container having a side sealant layer are bonded to each other and one opening of the cylindrical body part The tube container laminate is disposed between the inner surface side sealant layer and the outer surface side sealant layer, and comprises the stress-luminescent particles and the binder resin. It has the stress light emitting layer to contain.

  Such a tube container of the present invention will be described with reference to the drawings. FIG. 14 is a schematic view showing an example of the tube container of the present invention. As illustrated in FIG. 14, the tube container 20 of the present invention includes an inner surface side sealant layer, a base material formed on one surface of the inner surface side sealant layer, and the inner surface side sealant layer of the base material. The inner surface side sealant layer of the laminate having the outer surface side sealant layer formed on the opposite surface and the ends of the outer surface side sealant layer are fused together, and the inner surface side sealant layer is disposed on the inner surface side. A cylindrical body portion 21 in which the outer surface side sealant layer is disposed on the outer surface side, and a head portion that is joined to one opening portion of the cylindrical body portion 21 and includes the shoulder portion 22 and the mouth and neck portion 23. The laminated body has a stress light emitting layer that is disposed between the inner surface side sealant layer and the outer surface side sealant layer and contains stress light emitting particles and a binder resin.

According to this invention, when the said laminated body has a stress light emission layer, it becomes a tube container which can light-emit when stress is added.
For this reason, the said tube container becomes the thing excellent in forgery prevention property and design property.

The tube container of the present invention has a cylindrical body and a head.
Hereinafter, each structure of the tube container of this invention is demonstrated.

1. Cylindrical body part The cylindrical body part in this invention is an inner surface side sealant layer, the base material formed in one surface of the said inner surface side sealant layer, and the said inner surface side sealant layer of the said base material on the opposite side. An end portion of the inner surface side sealant layer and the outer surface side sealant layer of the laminate for a tube container having an outer surface side sealant layer formed on the surface are fused.
In the cylindrical body portion, the inner surface side sealant layer is disposed on the inner surface side, and the outer surface side sealant layer is disposed on the outer surface side.
Moreover, the said laminated body for tube containers is arrange | positioned between the said inner surface side sealant layer and the said outer surface side sealant layer, and has a stress luminescent layer containing a stress luminescent particle and binder resin.

  In addition, since the laminated body which comprises the said cylindrical trunk | drum can be the same as the content as described in the term of the said "A. laminated body for tube containers", description here is abbreviate | omitted.

The cylindrical body part is a cylindrical member in which ends of the inner surface side sealant layer and the outer surface side sealant layer of the laminate are fused.
About the width | variety of the edge part of the said sealant layer, ie, the width | variety of a seal | sticker area | region, it sets suitably according to the size of the tube container of this invention, a use, etc.
The cylindrical body has two openings at both ends, the head is joined to one of the openings, and the other opening (hereinafter sometimes referred to as the opposite opening) is an opening. It remains in the state and is used as a filling port for the contents.

  As a method for fusing the inner surface side sealant layer and the outer surface side sealant layer, the end portions of the inner surface side sealant layer and the outer surface side sealant layer, that is, the seal regions can be fused in a superimposed state. Any method may be used, and examples thereof include a heat sealing method and a high frequency sealing method.

2. Head The head in the present invention is joined to one opening of the cylindrical body.
The head includes a shoulder and a mouth and neck.

  As the constituent material of the shoulder and mouth and neck, those used for general tube containers such as resin materials can be used, and more specifically, thermoplastic resins such as high-density polyethylene are listed. Can do.

The joining of the head part to the cylindrical body part only needs to be able to seal one opening of the cylindrical body part. For example, the inner side sealant layer included in the cylindrical body part and the head The outer surface of the part can be fused.
The method of joining the cylindrical body part of the head can be the same as the manufacturing method of a general tube container, and both contact parts are heated in a state where the cylindrical body part and the head are in contact with each other. And a method of applying pressure.
Further, the joining method may be a method of joining a pre-molded head to the cylindrical body part, but a method of joining the head part to the cylindrical body part simultaneously with molding by a molding method such as injection molding. There may be.

3. Tube container The tube container of this invention has the said cylindrical trunk | drum and a head.
The tube container is usually filled with the contents from the opening on the opposite side into the cylindrical body with the mouth and neck included in the head sealed with a cap, and then the opening on the opposite side is heat sealed. It is sold as a tube container with contents by being sealed by, for example.

C. Next, the manufacturing method of the laminated body for tube containers of this invention is demonstrated.
The method for producing a laminated body for a tube container according to the present invention includes a stress light emitting layer forming step of forming a stress light emitting layer containing stress light emitting particles and a binder resin on one surface of a base material, the base material, and the stress light emission. And a sealant layer forming step of sandwiching the layer between the inner surface side sealant layer and the outer surface side sealant layer.

The manufacturing method of the laminated body of this invention is demonstrated with reference to drawings. FIG. 15 is a process diagram showing an example of a method for producing a laminate according to the present invention. As illustrated in FIG. 15, in the method for producing a laminate of the present invention, a substrate 1 is prepared, and a stress-luminescent ink 2a capable of forming a stress-luminescent layer is applied to one surface of the substrate 1 (FIG. 15). (A)) Next, the stress luminescent layer 2 is formed by removing the solvent from the coating film of the stress luminescent ink by drying (FIG. 15B), and then the substrate 1 and the stress luminescent layer 2 are formed. An adhesive layer (not shown) is formed so as to be sandwiched, that is, adhered to the surface of the base material 1 opposite to the stress light emitting layer 2 and the surface of the stress light emitting layer 2 opposite to the base material 1 Forming a layer (not shown), and then bonding the inner surface side sealant layer 3a and the outer surface side sealant layer 3b, which are preliminarily formed into a film shape, through the adhesive layer, thereby the base material 1 and the stress light emitting layer 2 is an inner surface side sealant layer 3a and an outer surface side sealant layer. A method for obtaining a laminated body 10 which is held by b (Fig. 15 (c)).
15A and 15B show the stress-stimulated luminescent layer forming step, and FIG. 15C shows the sealant layer forming step.

  According to the present invention, a laminate capable of forming a tube container capable of emitting light when stress is applied can be obtained by having the stress light emitting layer forming step and the sealant layer forming step.

The manufacturing method of the laminated body for tube containers of this invention has a stress light emitting layer formation process and a sealant layer formation process.
Hereinafter, each process of the manufacturing method of the laminated body for tube containers of this invention is demonstrated.

1. Stress Light Emitting Layer Forming Step The stress light emitting layer forming step in the present invention is a step of forming a stress light emitting layer containing stress light emitting particles and a binder resin on one surface of a substrate.
The method for forming the stress-stimulated luminescent layer on one surface of the base material in this step can be the same as that described in the above section “A. Laminate for tube container”, and is therefore described here. Is omitted.
Also, the stress-stimulated luminescent layer formed by this step can be the same as the content described in the section “A. Laminate for tube container”, and the description thereof is omitted here.

2. Sealant layer forming step The sealant layer forming step in the present invention is a step of sandwiching the base material and the stress-stimulated luminescent layer between the inner surface side sealant layer and the outer surface side sealant layer.

The method of sandwiching the substrate and the stress-stimulated luminescent layer in this step with the inner surface side sealant layer and the outer surface side sealant layer is opposite to the surface of the substrate opposite to the stress luminescent layer and the substrate of the stress luminescent layer. Examples thereof include a method of forming an inner surface side sealant layer and an outer surface side sealant layer respectively on the side surface.
The method for forming the sealant layer on the surface of the substrate or the like can be the same as the method for forming the sealant layer described in the above section “A. Laminate for tube containers”, The description in is omitted.

  Since the base material and the sealant layer used in this step can be the same as those described in the above section “A. Laminate for tube container”, description thereof is omitted here.

3. The manufacturing method of the laminated body for tube containers The manufacturing method of the laminated body of this invention has the said stress light emitting layer formation process and a sealant layer formation process, It has other processes as needed. Also good.
As said other process, the process of forming a hologram layer, a vapor deposition layer, a barrier layer, a filling layer, a printing layer, an adhesive layer etc. can be mentioned before the said sealant layer formation process, for example.
In addition, about the formation method of other structures, such as the said hologram layer, since the general formation method of each structure can be used, description here is abbreviate | omitted.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  The following examples illustrate the present invention in more detail.

[Example 1]
The laminate and the tube container of the present invention were produced by the following procedure.
(1) On one surface of a 12 μm thick polyethylene terephthalate film that will be the base material, a stress-stimulated ink is printed on a star pattern with a thickness of 10 μm by flexographic printing to form a patterned stress-stimulated layer. did.
(2) Next, a filling layer was formed by printing a pattern that would be negative when the pattern of the stress-stimulated luminescent layer was positive with KR-V02 half mat (NT) manufactured by Dainichi Seika. Stress-luminescent ink and KR-V02 half mat (NT) are similar colors.
(3) Next, an aluminum foil having a thickness of 15 μm was laminated on the surface opposite to the base of the stress-stimulated luminescent layer with a two-component curable urethane-based dry laminating adhesive to form a barrier layer.
(4) Next, a 130 μm-thick linear low-density polyethylene film was laminated on the aluminum foil via a two-component curable urethane-based dry laminating adhesive to form an inner surface side sealant layer.
(5) Next, a 130 μm-thick linear low-density polyethylene film is laminated on the surface of the substrate opposite to the side where the stress-stimulated luminescent layer is formed, with a two-component curable urethane-based dry laminating adhesive. And the outer surface side sealant layer was formed, and the laminated body of this invention was produced.
(6) Next, the outer surface side sealant layer and the inner surface side sealant layer are overlapped at the end of the laminated body so that the outer surface side sealant layer is on the outside, and the opposing surface is impulse-sealed to form a cylindrical body part did.
(7) Finally, high-density polyethylene was compression-molded into one opening of the cylindrical body, and the head including the shoulder and the mouth and neck was joined to produce the tube container of the present invention.

(Evaluation)
When the tube container manufactured in Example 1 was evaluated by visual observation, the entire surface of the cylindrical body portion was milky white in a state where no stress was applied to the tube container, and a star pattern was not observed.
When the tube container was bent and visually observed, light emission of a star pattern was observed on the curved portion of the tube container.

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Stress light emitting layer 3a ... Inner surface side sealant layer 3b ... Outer surface side sealant layer 4 ... Filling layer 5 ... Hologram layer 6 ... Deposition layer 7 ... Barrier layer 8 ... Print layer 10 ... Laminate for tube containers 12 ... Concave and convex relief 20 ... Tube container 21 ... Cylindrical body part 22 ... Shoulder part 23 ... Mouth and neck part

Claims (5)

An inner surface side sealant layer;
A substrate formed on one surface of the inner surface side sealant layer;
An outer surface side sealant layer formed on a surface opposite to the inner surface side sealant layer of the substrate;
A stress luminescent layer disposed between the inner surface side sealant layer and the outer surface side sealant layer, containing stress luminescent particles and a binder resin;
A laminate for a tube container, comprising:   The laminate for a tube container according to claim 1, wherein the stress light emitting layer is formed in a pattern.   The laminate for a tube container according to claim 2, wherein the laminate for a tube container has a filling layer formed on the same plane as the stress light emitting layer. An inner surface side sealant layer; a base material formed on one surface of the inner surface side sealant layer; and an outer surface side sealant layer formed on a surface of the base material opposite to the inner surface side sealant layer. A cylindrical body part in which ends of the inner surface side sealant layer and the outer surface side sealant layer of the laminate for a tube container are fused,
A head joined to one opening of the cylindrical body and including a shoulder and a mouth and neck;
Have
The tube container laminated body is disposed between the inner surface side sealant layer and the outer surface side sealant layer, and has a stress light emitting layer containing stress light emitting particles and a binder resin. A stress luminescent layer forming step of forming a stress luminescent layer containing stress luminescent particles and a binder resin on one surface of the substrate;
A sealant layer forming step of sandwiching the base material and the stress-stimulated luminescent layer with an inner surface side sealant layer and an outer surface side sealant layer;
The manufacturing method of the laminated body for tube containers characterized by having.