JPWO2015053326A1 - Stress light emitting sheet, stress light emitting laminate and use thereof - Google Patents

Abstract

The present invention relates to a single layer sheet capable of generating stress light or a laminate thereof. The stress-stimulated luminescent sheet of the present invention or the stress-stimulated luminescent layer in the stress-stimulated laminate of the present invention comprises a stress-stimulated luminescent material, polyurethane resin, polyester resin, polycarbonate resin, polyolefin resin, ethylene / vinyl acetate copolymer resin, styrene. Since it contains at least one binder polymer selected from the group consisting of butadiene copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, nylon resin, polyamide resin, polyvinyl alcohol, and fluorine resin, External force can be effectively transmitted to the stress luminescent material. Moreover, since the thread | sled of this invention light-emits itself with external force, it is possible to confirm the light emission of a thread | sled easily visually, for example by applying force by hand. Therefore, the anti-counterfeit paper provided with the thread of the present invention is easy to authenticate.

Description

This application claims priority based on Japanese Patent Application No. 2013-211124 for which it applied to Japan on October 8, 2013, and uses the content here.

  The present invention relates to a sheet and a laminate having a stress light emission function, a thread made of these, and an anti-counterfeit paper. In particular, the thread and anti-counterfeit paper of the present invention emit light by an external force, so that authenticity can be easily and accurately determined.

Bills, gift certificates, stock certificates, lottery tickets, admission tickets, and the like are subjected to various anti-counterfeiting measures in order to prevent unauthorized forgery or alteration. One of the measures for preventing forgery is to manufacture a sheet serving as a base for banknotes, gift certificates, and the like using an advanced manufacturing technique that cannot be easily counterfeited. As an example, there is an anti-counterfeit paper called “threaded paper” in which a thread obtained by cutting a base material such as a plastic film into a string having a width of about several mm is embedded in the paper (for example, Patent Document 1). As the thread, for example, various threads such as one having a hologram pattern, one recorded with magnetic information, one colored by light of a specific wavelength, one described with minute characters, etc. are used depending on the application. Has been.

However, even after establishing anti-counterfeiting technology, new ways of counterfeiting are being created one after another, and new anti-counterfeiting technology is always sought in order to counter emerging counterfeiting means. It has been. In addition, there is a need for a technique that enables forgery determination by a forgery prevention technique that can easily determine authenticity without using a special instrument. For example, in a store where a gift certificate or the like is purchased, there is a demand for a technique that allows the store clerk to easily determine the authenticity of the gift certificate that has been brought in on the spot.

On the other hand, materials that emit light by a mechanical external force are known. This is called stress light emission, and is a phenomenon in which light is repeatedly emitted mainly due to deformation in an elastic region or a plastic region, and light is emitted by a minute stress that does not cause destruction. As materials exhibiting stress luminescence, strontium aluminate (SrAl ₂ O ₄ : Eu) to which europium is added as an emission center, zinc sulfide (ZnS: Mn) to which manganese is added as an emission center are known.

JP 2003-306896 A

  An object of the present invention is to provide a new technique for preventing forgery. In particular, it is an object of the present invention to provide a composite material that enables simple authenticity determination without using a special instrument such as a black light or a magnetic detection device, a thread made of the composite material, and a forgery prevention sheet. .

The first aspect of the present invention is:
Fine particles of at least one stress luminescent material, and
Polyurethane resin, polyester resin, polycarbonate resin, polyolefin resin, ethylene / vinyl acetate copolymer resin, styrene / butadiene copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, nylon resin, polyamide resin, polyvinyl alcohol, fluorine A stress-stimulated luminescent sheet containing at least one binder polymer selected from the group consisting of a resin.

The binder polymer is preferably a polyurethane resin and / or a polyester resin.

The polyurethane resin is preferably a polyester-based polyurethane.

The second aspect of the present invention is:
A substrate, and
Fine particles of at least one stress luminescent material, and
Polyurethane resin, polyester resin, polycarbonate resin, polyolefin resin, ethylene / vinyl acetate copolymer resin, styrene / butadiene copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, nylon resin, polyamide resin, polyvinyl alcohol, fluorine It is a stress light emission laminated body provided with the stress light emission layer containing the at least 1 sort (s) of binder polymer selected from the group which consists of a resin.

The binder polymer is preferably a polyurethane resin and / or a polyester resin.

The polyurethane resin is preferably a polyester-based polyurethane.

The stress-stimulated laminate may further include at least one adhesive layer.

It is preferable that the outermost layer of the stress-stimulated laminate is the adhesive layer.

The substrate may contain the stress-stimulated luminescent material.

The substrate can be a film, a nonwoven fabric or paper.

3rd aspect of this invention is the thread | sled which consists of the said stress light-emitting sheet or the said stress light-emitting laminated body.

The thread may have a pearly luster.

The thread may have a micro character.

A fourth aspect of the present invention is anti-counterfeit paper having at least a part of the thread.

The anti-counterfeit paper may be a paper on which the thread is engraved.

The thread may be intermittently exposed on the surface.

In addition, the aspect of the present invention is for a clear light emission of a stress light emitting sheet or a stress light emitting layer containing fine particles of at least one kind of stress light emitting material.
Polyurethane resin, polyester resin, polycarbonate resin, polyolefin resin, ethylene / vinyl acetate copolymer resin, styrene / butadiene copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, nylon resin, polyamide resin, polyvinyl alcohol, fluorine Use of at least one binder polymer selected from the group consisting of a resin in the stress-stimulated luminescent sheet or stress-stimulated luminescent layer.

  The stress luminescent sheet according to the first aspect of the present invention is a sheet composed of a single layer, and includes a binder polymer made of a specific resin, so that external force can be efficiently transmitted to the stress luminescent material, and vivid stress can be obtained. Light emission can be realized.

  The stress-stimulated laminate of the second aspect of the present invention is a sheet-like material composed of a plurality of layers, and the stress-stimulated luminescent layer contains a binder polymer composed of a specific resin, so that external force is efficiently transmitted to the stress-stimulated luminescent material. And vivid stress light emission can be realized.

Even if an adhesive layer is further formed on the surface, the binder polymer in the stress-stimulated luminescent material does not flow out of the stress-stimulated luminescent layer.

  The stress-stimulated luminescent sheet and the stress-stimulated laminate can provide a new technique for preventing forgery by vivid light emission. The stress-stimulated luminescent sheet and the stress-stimulated laminate can emit light with high brightness like lightning by applying an external force.

  The thread according to the third aspect of the present invention is made of the stress-stimulated luminescent sheet or the stress-stimulated laminate, and has a stress-stimulated luminescence function that emits light by an external force. Therefore, a special instrument such as a black light or a magnetic detection device is used. This makes it possible to make a simple authentication, and provides a high anti-counterfeit effect.

  The anti-counterfeit paper according to the fourth aspect of the present invention can perform simple authenticity determination without using a special instrument such as a black light or a magnetic detection device, and can exhibit a high anti-counterfeit effect.

Since the thread and anti-counterfeit paper of the present invention have the following effects, they can be preferably used as anti-counterfeit measures for banknotes, gift certificates, passports, stock certificates, identification cards, cards, admission tickets, stock certificates, checks, and the like.
(1) Light emission generated by applying an external force to the thread by scratching with a nail or bending with a finger can be visually confirmed, and easy authentication can be performed.
(2) When it has pearly luster, it has a color shift effect in which the hue continuously changes depending on the viewing angle under visible light, and it is possible to more easily determine the authenticity by visual observation.
(3) Forgery can be made even more difficult when micro characters are included.
(4) When combining the above (1) to (3), the effects of the above (1) to (3) can be exhibited at the same time, and no special instrument is required to confirm the effects. It is particularly easy to determine the authenticity.

The first aspect of the present invention is:
Fine particles of at least one stress luminescent material, and
Polyurethane resin, polyester resin, polycarbonate resin, polyolefin resin, ethylene / vinyl acetate copolymer resin, styrene / butadiene copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, nylon resin, polyamide resin, polyvinyl alcohol, fluorine A stress-stimulated luminescent sheet containing at least one binder polymer selected from the group consisting of a resin. The stress luminescent sheet of the present invention has a stress luminescent function.

The term “stress luminescent material” is a material that emits light by an externally applied force, and is synonymous with “stress luminescent material” or “stress luminescent material”. That is, the stress-stimulated luminescent material has a property that the material itself emits light upon receiving a force applied from the outside, and the luminescence intensity changes in proportion to the force.

The stress light emission function is preferably reversible light emission. This is because even if light is emitted once, it can be used repeatedly and is practical.

The stress-stimulated luminescent material exhibiting the stress-stimulated luminescence function has a basic structural formula such as europium-added strontium aluminate, as in the case of the inorganic luminescent material, but the difference from the inorganic luminescent material is that it gives a lattice defect to Sr. On the other hand, by adding an element serving as a luminescent center into an inorganic crystal skeleton whose structure is highly controlled, a stress luminescence phenomenon with high luminescence intensity is expressed. Examples of the stress luminescent material include strontium aluminate (SrAl ₂ O ₄ : Eu, luminescent in green) added with europium as an element of the luminescent center, and zinc sulfide (ZnS: Mn, yellow-green) added with manganese as the luminescent center. Luminescence), a composite semiconductor crystal having a coexistence structure of a wurtzite structure and a zinc-blende structure disclosed in JP-A-2004-43656, strontium and aluminum disclosed in JP-A-2004-059746 And a composite oxide of barium and the composite oxide of barium disclosed in JP-A No. 2006-124725. In particular, a so-called nanoparticle shape having a particle diameter of about 10 to 200 nm is preferable. In addition, it is preferable to use the strontium aluminate that emits light in a green region of 500 to 600 nm, which has a particularly high human visibility in the visible light region, since it is easy to confirm with the naked eye.

In the present invention, the stress-stimulated luminescent material can be used alone, but it is preferable to use two or more different stress-stimulated luminescent materials since the effect of preventing forgery is further enhanced.

The stress luminescent sheet of the present invention comprises at least one kind of stress luminescent material fine particles, as well as polyurethane resin, polyester resin, polycarbonate resin, polyolefin resin, ethylene / vinyl acetate copolymer resin, styrene / butadiene copolymer resin, At least one binder polymer selected from the group consisting of vinyl chloride resin, polyvinylidene chloride resin, nylon resin, polyamide resin, polyvinyl alcohol, fluorine resin, petroleum solvents such as methyl ethyl ketone, acetone, gasoline, etc. It can be manufactured by a method of dissolving and dispersing in an organic solvent such as applying the obtained paint on a substrate, then removing the organic solvent by drying, etc., and peeling the obtained sheet from the substrate .

The paint can be applied using a known coating technique. Examples of known coating techniques include, but are not limited to, rod coaters, bar coaters, air knife coaters, blade coaters, gravure coaters, die coaters, curtain coaters, and gate roll coaters.

  The compounding weight ratio of the stress luminescent material fine particles: binder polymer contained in the stress luminescent sheet of the present invention is not particularly limited, but is preferably 1: 100-3: 1, and 1: 50-3: 1. More preferably, 1:20 to 3: 1 is even more preferable, and 1: 2 to 3: 1 is even more preferable.

  The stress light emitting sheet of the present invention includes polyurethane resin, polyester resin, polycarbonate resin, polyolefin resin, ethylene / vinyl acetate copolymer resin, styrene / butadiene copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, nylon resin. Since it contains at least one binder polymer selected from the group consisting of polyamide resin, polyvinyl alcohol, and fluorine resin, external force can be efficiently transmitted to the stress-stimulated luminescent material, and vivid stress luminescence can be realized. be able to.

  As the binder polymer, a polyurethane resin and / or a polyester resin is preferable, a thermoplastic polyurethane resin is preferable, and a polyester polyurethane is particularly preferable.

Polyurethane resins, in particular thermoplastic polyurethane resins, can be obtained, for example, by reacting a polyisocyanate such as diisocyanate with a polyol such as diol and, if necessary, a chain extender.

  Examples of the diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate (HMDI) and 2,2,4-trimethylhexamethylene diisocyanate; 1,4-cyclohexane diisocyanate, dicycloalkylmethane-4,4′-diisocyanate, isophorone diisocyanate (IPDI). And alicyclic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), and araliphatic diisocyanates such as xylylene diisocyanate. As the diisocyanate, a compound in which an alkyl group (for example, a methyl group) is substituted on the main chain or ring may be used. Diisocyanate can be used individually or in combination of 2 or more types.

Examples of the diol, a polyester diol [aliphatic dicarboxylic acid component (such as C _4-12 aliphatic dicarboxylic acids such as adipic acid), an aliphatic diol component (ethylene glycol, propylene glycol, butanediol, such as neopentyl glycol C _{2- 12} aliphatic diol), _{C 4-12} polyester diols obtained from a lactone or the like) such as a lactone component (.epsilon.-caprolactone (aliphatic polyester diols), such as poly (ethylene adipate), poly (1,4-butylene Adipate), poly (1,6-hexylene adipate), poly-ε-caprolactone, etc.], polyether diol [aliphatic polyether diol such as polyethylene glycol, poly (oxytrimethylene) glycol, polypropylene glycol, polytetra Poly (oxy C _2-4 alkylene) glycols such as methylene ether glycol (PTMG), block copolymers of these poly (oxyalkylene) glycols (polyoxyethylene-polyoxypropylene block copolymers, etc.); aromatic poly Ether diols, for example, alkylene oxide adducts of aromatic diols such as bisphenol A-alkylene oxide adducts (C _2-4 alkylene oxide adducts such as ethylene oxide and propylene oxide)]; polyester ether diols (of diol components) Polyester diols using the above polyether diols as part); polycarbonate diols and the like can be used. These diols can be used alone or in combination of two or more. Of these diols, polyester diols and polyether diols (polytetramethylene ether glycol, etc.) (for example, polyester diols) are often used. Polyester diol is preferred.

Examples of chain extenders include glycols [short chain glycols such as C _2-10 alkane diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol; bishydroxyethoxybenzene (BHEB ) Etc.], and other diamines [aliphatic diamines such as C _2-10 alkylene diamines such as ethylene diamine, trimethylene diamine, tetramethylene diamine and hexamethylene diamine; alicyclic diamines such as isophorone diamine; Aromatic diamines such as range amines] can also be used. A chain extender can be used individually or in combination of 2 or more types.

Among thermoplastic polyurethane resins, in particular, diol [diol having polyester units or polyether units (polyester diol, polyether diol, etc.)], diisocyanate, and glycols as chain extenders (short chain glycols, etc.) And thermoplastic polyurethane elastomers obtained using This thermoplastic polyurethane elastomer has a hard segment (hard block) composed of a polyurethane of glycols and diisocyanate, a polyether diol [an aliphatic polyether diol such as poly (oxyethylene) glycol, etc.], a polyester diol (fat Soft segment (soft block) composed of a polyester diol, etc.). The polyurethane elastomer includes, for example, a polyester urethane elastomer, a polyester ether urethane elastomer, a polyether urethane elastomer, a polycarbonate urethane elastomer, etc., depending on the type of the soft segment. Of the polyurethane elastomers, polyester urethane elastomers, polyester ether urethane elastomers, polyether urethane elastomers and the like are preferable. In addition, the molecular weight (or weight average molecular weight) of the said polyether (polyoxyalkylene glycol) can be selected from the range of about 100-10,000, for example, Preferably it is 300-6,000 (for example, 300-5,000). ), More preferably about 500 to 4,000 (for example, 500 to 3,000).

Examples of the polyurethane resin include a one-pack type and a two-pack type, but a two-pack type is preferable. As the two-pack type, for example, “Samprene IB” (manufactured by Sanyo Chemical Industries), “Olestar Q” (manufactured by Mitsui Chemicals), “Chris Bon” (manufactured by DIC), “Nipporan” (Nippon Polyurethane Industry Co., Ltd.) etc. "Coronate HL" (Nippon Polyurethane Industry Co., Ltd.), "Sumijour N" (Suika Bayer Urethane Co., Ltd.) aliphatic polyfunctional isocyanate What was hardened | cured with can be used suitably.

Polyester resins include curable resins such as unsaturated polyester resins, thermoplastic resins such as PET (polyethylene terephthalate), PBT (polybutylene terephthalate), and PEN (polyethylene naphthalate), or (poly) urethane modified Mention may be made of modified polyester resins such as polyester resins.

  When a thermoplastic resin such as a thermoplastic polyester resin is used, its glass transition temperature is preferably 100 ° C. or lower, more preferably 50 ° C. or lower, still more preferably 20 ° C. or lower, even more preferably 0 ° C. or lower, − 10 degrees C or less is still more preferable, and -30 degrees C or less is still more preferable.

  The “elongation” of the binder polymer is preferably 60% or more, more preferably 100% or more, still more preferably 150% or more, still more preferably 200% or more, and still more preferably 400% or more and 900% or less.

  The tensile strength of the binder polymer is preferably 20 MPa or more, more preferably 30 MPa or more, still more preferably 40 MPa or more, and even more preferably 50 MPa or more.

The second aspect of the present invention is:
A substrate, and
Fine particles of at least one stress luminescent material, and
Polyurethane resin, polyester resin, polycarbonate resin, polyolefin resin, ethylene / vinyl acetate copolymer resin, styrene / butadiene copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, nylon resin, polyamide resin, polyvinyl alcohol, fluorine It is a stress light emission laminated body provided with the stress light emission layer containing the at least 1 sort (s) of binder polymer selected from the group which consists of a resin.

The material of the substrate is not particularly limited, and various inorganic or organic materials can be used alone or in combination. Examples of the inorganic material include transparent or translucent glass such as heat resistant glass, metal oxide such as indium tin oxide (ITO), metal, clay, ceramics, and carbon. Examples of organic materials include polyethylene resins, polypropylene resins, polycarbonate resins, (meth) acrylic resins, polyethylene terephthalate resins, saturated polyester resins, polyamide resins, ABS resins, polyvinyl chloride and other thermoplastic resins, and And thermosetting resins such as phenol resin, urethane resin, melamine resin, urea resin, and epoxy resin. In view of heat resistance, inorganic materials are preferable, and in terms of flexibility, organic materials are preferable.

At least a part of the substrate may be composed of fibers. As the fiber, fibers made of various inorganic or organic materials described above can be used. For example, glass fibers, carbon fibers, various resin fibers, and the like can be used.

The substrate can be in the form of, for example, a film, a nonwoven fabric, or paper. In particular, when used for threads and anti-counterfeit paper described later, it is preferable to use a film having high heat resistance as the base material. For example, a film made of cellophane, polypropylene, polyester, polyethylene terephthalate, nylon, polyvinyl alcohol, polyvinyl chloride, polycarbonate or the like can be used as the film, and a polyester film is preferable as a film having heat resistance, and a PET film. Is more preferable.

  The substrate may be subjected to various treatments as necessary. For example, corona discharge treatment, primer coating treatment, embossing treatment, installation of a transparent colored layer, and the like can be appropriately performed.

In addition, the said stress light-emitting material may be contained in the said base material. In this case, it is preferable to mix and knead the stress-stimulated luminescent material in the material constituting the base material and to form, for example, a film, a nonwoven fabric or a paper by a conventionally known method.

The method for providing the stress-stimulated luminescent layer on the substrate is not particularly limited. For example, you may laminate | stack the stress light emission sheet | seat of the 1st aspect of this invention on a base material. In addition, fine particles of at least one stress-stimulated luminescent material, polyurethane resin, polyester resin, polycarbonate resin, polyolefin resin, ethylene / vinyl acetate copolymer resin, styrene / butadiene copolymer resin, polyvinyl chloride resin, polychlorinated resin Dissolve at least one binder polymer selected from the group consisting of vinylidene resin, nylon resin, polyamide resin, polyvinyl alcohol, and fluorine resin in an organic solvent such as petroleum solvent such as methyl ethyl ketone, acetone, gasoline, etc. The obtained paint can be applied on a substrate, and then the organic solvent can be removed by drying or the like.

The paint can be applied using a known coating technique. Examples of known coating techniques include, but are not limited to, rod coaters, bar coaters, air knife coaters, blade coaters, gravure coaters, die coaters, curtain coaters, and gate roll coaters.

  The compounding weight ratio of the stress-stimulated luminescent material contained in the stress-stimulated luminescent layer is not particularly limited, but is preferably 1: 100-3: 1, more preferably 1: 50-3: 1. : 20 to 3: 1 is even more preferable, and 1: 2 to 3: 1 is even more preferable.

  The stress light emitting layer of the stress light emitting laminate of the present invention comprises polyurethane resin, polyester resin, polycarbonate resin, polyolefin resin, ethylene / vinyl acetate copolymer resin, styrene / butadiene copolymer resin, polyvinyl chloride resin, polyvinylidene chloride. Since it contains at least one binder polymer selected from the group consisting of resin, nylon resin, polyamide resin, polyvinyl alcohol, and fluorine resin, external force can be efficiently transmitted to the stress-stimulated luminescent material, and vivid Stress light emission can be realized.

  As the binder polymer, a polyurethane resin and / or a polyester resin is preferable, a thermoplastic polyurethane resin is preferable, and a polyester polyurethane is particularly preferable. Specifically, what was already described about the 1st form of the present invention can be used.

The stress-stimulated laminate of the second aspect of the present invention can further include at least one adhesive layer, and in particular, can include a heat-weldable layer as the adhesive layer. The outermost layer of the stress-stimulated laminate is preferably the adhesive layer, and more preferably a heat-weldable layer. The heat-weldable layer has a property of being melted by heating, and particularly when used for a thread and anti-counterfeit paper described later, the stress-stimulated laminate can be firmly fixed to the paper.

  Further, since the stress luminescent material is generally weak against water, the stress luminescent material in the stress luminescent layer can be protected from moisture in the outside by the adhesive layer. Therefore, when the adhesive layer is formed, vivid light emission can be maintained over a longer period.

  The material of the adhesive layer, particularly the heat-weldable layer, is not particularly limited as long as it has a property of melting by heat. As the material of the adhesive layer, for example, a heat-sensitive adhesive in which a thermoplastic resin is dispersed in an organic solvent can be used.

Thermoplastic resins include those used as base resins for conventional heat-sensitive adhesives such as vinyl acetate polymer, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyethylene, polyvinyl butyral, polyamide, and acrylic resin. Plastic resins can be widely used, but among these, an ethylene-vinyl acetate copolymer can be suitably used from the viewpoint of thermal adhesiveness and ease of dispersion in an organic solvent, and further contains vinyl acetate. An ethylene-vinyl acetate copolymer in an amount of 5 to 30% by weight is preferred.

The organic solvent is not particularly limited as long as it can disperse the thermoplastic resin, and organic solvents that are conventionally used as solvents for heat-sensitive adhesives such as toluene, ethyl acetate, methyl ethyl ketone, and acetone can be widely used. May be used. Among these, in particular, when the thermoplastic resin is an ethylene-vinyl acetate copolymer, a mixed solvent of toluene and ethyl acetate can be preferably used from the viewpoint of ease of dispersion. The mixing ratio of toluene and ethyl acetate is not particularly limited, but is preferably mixed at a weight ratio (toluene / ethyl acetate) of 60/40 to 80/20.

Examples of the method for dispersing the thermoplastic resin in the organic solvent include a mechanical pulverization method and a precipitation method from a solution. Examples of the method by mechanical pulverization include a method of pulverizing and dispersing in a solvent using a pulverizer having strong dispersion power. Examples of the method for precipitating from a solution include a method in which an organic solvent that does not dissolve the resin is added to a solution in which the thermoplastic resin to be dispersed is dissolved, and the resin is precipitated and dispersed. Among these, the method by mechanical pulverization can be suitably used because of easy control of the particle size of the dispersed thermoplastic resin.

The thermoplastic resin is preferably contained in a proportion of 3 to 20 parts by weight with respect to 100 parts by weight of the heat-sensitive adhesive, and is preferably dispersed so that the average particle diameter of the thermoplastic resin is about 10 to 50 μm.

The heat-sensitive adhesive preferably contains a solid plasticizer in order to improve heat sensitivity. Examples of the solid plasticizer include diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, dihydroabiethyl phthalate, dimethyl isophthalate, sucrose benzoate, ethylene glycol dibenzoate, trimethylolethane tribenzoate, and tribenzoyl glyceride tribenzoate. , Pentaerythritol tetrabenzoate, sucrose octaacetate, tricyclohexyl citrate, N-cyclohexyl-p-toluenesulfonamide and the like.

Moreover, in order to improve adhesive performance, you may contain a tackifier. Examples of the tackifier include terpene resin, aliphatic petroleum resin, aromatic petroleum resin, coumarone-indene resin, styrene resin, phenol resin, terpene-phenol resin, rosin derivative (rosin, polymerized rosin, hydrogenated rosin. And esters thereof with glycerin, pentaerythritol, etc., resin acid dimers, etc.).

  In the stress-stimulated laminate of the second aspect of the present invention, when an adhesive layer is further formed, the adhesive layer can be formed on the surface of the substrate and / or the surface of the stress-stimulated layer. Examples of the method for forming the adhesive layer include a method in which the heat-sensitive adhesive is applied to the surface of the substrate and / or the surface of the stress-stimulated luminescent layer and then appropriately dried.

The application method is not particularly limited, and it can be applied using various blade coaters, roll coaters, air knife coaters, bar coaters, gravure coaters, curtain coaters, etc., but is applied using a gravure coater for excellent productivity. It is preferable to do. The coating amount of the adhesive layer, the range of 1.0 to 5.0 g / ^{m 2} is preferred.

  In the stress-luminescent laminate of the second aspect of the present invention, the binder polymer contained in the stress-luminescent layer is preferably immiscible or low-affinity in the organic solvent in the adhesive layer. Thereby, even when an adhesive layer is formed on the surface of the stress light emitting layer, it is possible to avoid or reduce the outflow of the binder polymer from the stress light emitting layer.

A third aspect of the present invention is a thread made of the stress-stimulated luminescent sheet or the stress-stimulated laminate.

The thread of the present invention has a stress light emission function in at least a part thereof. Since the thread emits light by an external force, the authenticity can be determined visually. For example, if the thread is bent with a finger or a pressure is applied with a nail, it is possible to easily identify the authenticity determination by designing to emit light with the mechanical force.

The thread of the present invention preferably emits light even when it is bent by hand or rubbed with a finger, and the light emission intensity at that time is preferably at least visually visible.

The thread of the present invention may use two or more different stress luminescent materials. By providing two types of stress light emission functions with different light emission intensities and colors, more complicated light emission characteristics can be obtained, and the effect of preventing forgery can be enhanced. For example, by providing two or more types of stress light emission functions, an effect of being able to visually recognize light emission having different wavelengths can be obtained. Specifically, when stress is applied to a thread having a stress luminescence function, stress luminescent materials are arranged so that two or more types of luminescence exhibiting different wavelengths are generated. In addition, different colors of light can be confirmed.

The stress light emitting function may be provided on both sides of the thread or on one side. Moreover, you may be provided in the side surface.

In the present invention, the “thread” means a long member having an elongated string or plate shape as a whole. The size of the thread is not particularly limited, but in the case of a string, the diameter or the longest side of the cross section is, for example, 1 μm or more, preferably 10 μm or more, more preferably 50 μm or more, and even more preferably 100 μm or more. And 10 cm or less, preferably 1 cm or less, more preferably 5 mm or less, and even more preferably 1 mm or less. Therefore, for example, 1 μm to 1 cm is preferable, 10 μm to 5 mm is more preferable, and 50 μm to 1 mm is even more preferable. The length is, for example, 1 cm or more, preferably 5 cm or more, more preferably 10 cm or more, and 5 m or less, preferably 3 m or less, more preferably 1 m or less. Note that the diameter or the longest side does not have to be constant in the longitudinal direction, and may partially vary along the longitudinal direction. Further, the cross section need not be circular or square, but can be any other shape such as an oval or a rectangle. The thickness is preferably in the range of 1 to 100 μm, more preferably 5 to 50 μm, and even more preferably 10 to 30 μm.

  On the other hand, when the thread is plate-like, the thickness is, for example, 1 μm or more, preferably 10 μm or more, more preferably 50 μm or more, even more preferably 100 μm or more, and 10 cm or less, preferably 1 cm or less, more preferably. Is 5 mm or less, and even more preferably 1 mm or less. Therefore, for example, 1 μm to 1 cm is preferable, 10 μm to 5 mm is more preferable, and 50 μm to 1 mm is even more preferable. The width is, for example, 1 mm or more, preferably 2 mm or more, more preferably 3 mm or more, and 50 cm or less, preferably 10 cm or less, more preferably 5 cm or less. The length is, for example, 1 cm or more, preferably 5 cm or more, more preferably 10 cm or more, and 5 m or less, preferably 3 m or less, more preferably 1 m or less. Note that the thickness may not be uniform in the longitudinal direction, and may vary partially in the longitudinal direction. The cross section is not necessarily square but may be any square shape such as a rectangle.

  The optical properties of the thread are not particularly limited, and may be transparent, translucent, or opaque. Also, the entire thread need not have the same optical properties. Thus, for example, some portions of the thread may be transparent while others are opaque.

  The thread of the present invention can be produced by appropriately slitting the stress-stimulated luminescent sheet or the stress-stimulated laminate. Slit processing includes a step of slitting to a predetermined width using a known apparatus such as a micro slitter.

  The thread of the present invention can have a pearly luster.

When the thread | sled of this invention consists of the said stress light emission laminated body, it is preferable that the said base material has a pearl luster. For example, when a transparent multilayer film having pearly luster is used as a base material, it is possible to combine both the color shift effect under reflected light and the effect of stress luminescence, and it is difficult to counterfeit the complicated change. The color shift effect means that when the viewing angle with the object is changed, the color is changed by gradually shifting the reflected light. This transparent multilayer film is obtained by laminating a plurality of polymers having two or more different refractive indexes, and is a film that exhibits pearly luster due to the light interference phenomenon. For example, a polymer obtained by repeatedly laminating 100 or more layers of a high refractive index and a low refractive index can be used. It is known that pearl luster cannot be reproduced by a copying method such as color copy or reading with a digital scanner and outputting with a printer because it has the feature that it looks shining in an iris color when viewed with specular reflection light. Therefore, by using the transparent multilayer film, not only a color shift effect but also such a copy prevention effect can be imparted. Furthermore, by providing a colored coating layer on a transparent multilayer film having pearly luster and viewing through the film, a new hue in which the original hue of the film is mixed can be generated. When the hue of the colored coating layer changes due to a temperature change, the color shift effect becomes very complicated, and as a result, a high forgery prevention effect can be obtained.

Moreover, the thread | sled of this invention may have a coating layer which has a pearl luster. Thereby, since a color shift effect can be obtained, the same anti-counterfeit effect as when the transparent multilayer film is used can be obtained. When the transparent multi-layer film having the above-mentioned pearly luster is used, the hue changes depending on the thickness of each layer and the total thickness. Since the method of providing the layer is sufficient by changing the pigment, there is also an advantage that a wide variety of variations can be increased at a lower cost than the production of the transparent multilayer film.

Examples of the pigment that can be used for the coating layer having pearly luster include natural pearl essence, mica powder, basic carbonate, titanium oxide-coated mica powder, metal oxide-coated mica powder, and Bengala-coated mica. The method for producing such a pearl pigment is not particularly limited, and conventionally known production methods (for example, Japanese Patent Publication Nos. 53-47375, 54-34010, 58-149959, etc.) Can be used.

The pearl pigment is mixed with an adhesive and applied to the surface of the layer constituting the thread. The adhesive is not particularly limited as long as it allows the pearl pigment to be fixed to the thread, and for example, an aqueous dispersion of binder particles combined with an ultrafine filler can be used. Colloidal silica, alumina sol, etc. can be used as ultrafine fillers, and acrylic polymer emulsion, silane group addition olefin polymer emulsion, polyvinyl alcohol, modified polyvinyl alcohol, ethylene-vinyl acetate copolymer emulsion, etc. as binders. Can be used.

A micro character may be given to the thread of the present invention.

When providing a micro character, there exists a structure which prints a micro character on a base material, for example, and then covers it with a temperature-responsive coating layer. Or the structure which provides a micro character after providing a temperature-reactive coating layer on a base material is mentioned. There is no particular limitation on the method for printing micro characters, but gravure printing and screen printing are suitable. As the ink used for the micro characters, known inks can be used.

Moreover, in this invention, the stress luminescent material can also be included in the ink used for the said micro character. A feature that makes micro characters readable by stress light emission can be given. Two or more types of micro characters may be provided.

  In the case of forming micro characters or micro images comprising a metal vapor deposition layer on a substrate, a paster processing method can be preferably used. The paster processing method itself is a well-known method. For example, characters and images are printed with ink having alkali resistance on the vapor deposition surface of a polyester film obtained by vacuum vapor deposition of metal aluminum, and then the film is immersed in an aqueous sodium hydroxide solution. A typical example is a method in which the exposed aluminum vapor deposition layer other than the printed portion is dissolved, and then the film is washed with water to remove aluminum hydroxide and then dried (Japanese Patent Laid-Open No. 63-21679). See). By doing so, the printed portion and the lower metal deposition portion synchronized with the printed portion remain on the film, and the film is exposed in other portions.

  Various functional layers such as a hologram pattern layer and a magnetic layer on which magnetic information is recorded can be formed on the base material in addition to pearly luster and micro letters. By these functional layers, the thread can exhibit a high anti-counterfeit function.

A fourth aspect of the present invention is anti-counterfeit paper having at least a part of the thread. For example. The thread may be present on a part of the surface of the anti-counterfeit paper.

The anti-counterfeit paper is preferably made of paper on which the thread is engraved. That is, it is preferable that the anti-counterfeit paper of the present invention is an anti-counterfeit paper in which the thread is inserted into the paper. As described above, when the thread is inserted into the paper, unlike the case where the thread is simply bonded to the surface of the paper, the thread is not easily dropped. In addition, there is an effect of preventing a malicious person from peeling off and diverting the thread. In the present invention, even if the thread is in the paper, it can be used without any problem if the light emission can be easily identified.

As a method of making the thread into the paper, the nozzle is inserted into the flow of the stock in the slice part of the long paper machine, and the thread is fed out while flowing water through the nozzle, and the paper is formed in the paper web formed on the paper web. A method of making a thread (Japanese Patent Laid-Open No. 51-130309), installing a thread insertion device into the stock flowing out of the flow box of a long paper machine, and making the thread and the stock non-contact with an air flow While making a thread (Japanese Patent Laid-Open No. 2-169790), using a multi-layer type circular paper machine, the thread is made by using a pipe having irregularities on the inner wall by making two or more layers. For example, a method of sending out between paper layers and forming a thread between paper layers (Japanese Patent Publication No. 5-40080) can be used.

In the anti-counterfeit paper of the present invention, the thread may be intermittently exposed on the surface. That is, when the thread is made into paper, the thread may be intermittently exposed on the paper surface. More specifically, a window opening portion having a thickness that is intermittently reduced is formed on the surface of the paper, and a thread is exposed in the window opening portion. The paper produced in this way is called “window-open thread paper”, and the portion where the thread is exposed has the advantage that it is easier to judge hue changes and to read micro characters.

As a method for producing the window-open thread paper, a method of manufacturing a paper suspension on a wire by burying a belt mechanism having a groove through which a thread is passed at the tip of a convex portion of a guide having a concave-convex portion (special feature). No. 5-85680) and a method of using a mesh processed into a concavo-convex shape for the upper screen of a circular paper machine and inserting the thread while making contact with the concavo-convex portion on the surface of the net to make the thread into the window opening portion. (US Pat. No. 4,462,866), or a compressed air nozzle is built in a rotating drum on the wire of a long paper machine, and the slurry on the thread previously inserted into the web is blown off intermittently with compressed air. And a method of exposing (JP-A-6-272200).

In the present invention, there is no particular limitation on the raw material of the paper to be threaded, but it is beaten by appropriately blending non-wood pulp such as wood pulp, hemp, cotton, straw, etc. What mixed the fiber, the inorganic fiber, etc. can be used. A filler is prepared by appropriately adding a filler, a paper strength enhancer, a sizing agent, a fixing agent, a yield improver, a drainage improver, an antifoaming agent, a dye, and a pigment.

[Example 1]
Polyurethane resin (trade name “Samprene IB” manufactured by Sanyo Chemical Industries, Ltd.) and isocyanate-based curing agent (product) using strontium aluminate (SrAl ₂ O ₄ : Eu) powder with europium added as the luminescent center. The name “Coronate” manufactured by Nippon Polyurethane Industry Co., Ltd.) was dispersed in toluene, and the resulting dispersion was coated on a base material of a transparent PET film (trade name “Lumirror” manufactured by Toray Industries, Inc.) having a thickness of 16 μm. The stress light emitting layer was formed by coating with a gravure coater in an amount of 12 g / m ² .

  An ethylene-vinyl acetate heat-sensitive adhesive was further applied to the front and back of the laminate thus obtained in a thickness of 5 μm to form a heat-sensitive adhesive layer. The laminated body thus obtained was slit to a width of 2.5 mm to obtain a thread.

When the heat sensitive adhesive was applied, the resin component did not flow out of the stress light emitting layer, and neither the crack of the stress light emitting layer nor the thread breakage occurred during the slit processing.

  When an external force was applied to the obtained thread with a nail, bright light emission was observed at the location where the external force was applied.

[Example 2]
Urethane-modified polyester resin (trade name “Byron UR” manufactured by Toyobo Co., Ltd.) and melamine-based curing agent (commercial product) using strontium aluminate (SrAl ₂ O ₄ : Eu) powder with europium added as the luminescent center. The name “Sumimar” manufactured by Sumitomo Chemical Co., Ltd.) was dispersed in toluene, and the resulting dispersion was gravure-coated on the base material of a transparent PET film (trade name “Lumirror” manufactured by Toray Industries, Inc.) with a thickness of 16 μm. The stress light emitting layer was formed by coating with a coater in an amount of 12 g / m ² .

  An ethylene-vinyl acetate heat-sensitive adhesive was further applied to the front and back of the laminate thus obtained in a thickness of 5 μm to form a heat-sensitive adhesive layer. The laminated body thus obtained was slit to a width of 2.5 mm to obtain a thread.

When the heat sensitive adhesive was applied, the resin component did not flow out of the stress light emitting layer, and neither the crack of the stress light emitting layer nor the thread breakage occurred during the slit processing.

  When an external force was applied to the obtained thread with a nail, bright light emission was observed at the location where the external force was applied.

[Example 3]
A thread was obtained in the same manner as in Example 2 except that the urethane-modified polyester resin was replaced with a thermoplastic polyester resin (trade name “Byron” Toyobo Co., Ltd.).

  When an external force was applied to the obtained thread with a nail, bright light emission was observed at the location where the external force was applied.

[Example 4]
<Preparation of paper stock>
NBKP 20 parts by mass and LBKP 80 parts by mass were 350 ml C.I. S. F. This was beaten into 10 parts by weight of white clay, 0.3 parts by weight of paper strength enhancer (trade name “Polystron 191” manufactured by Arakawa Chemical Co., Ltd.), and sizing agent (trade name “Size Pine E” Arakawa Chemical Industries). A paper stock was prepared by adding 1.0 part by mass and an appropriate amount of a sulfuric acid band.

<Manufacture of paper mesh>
Many resin plates having a short side of 10 mm, a long side of 15 mm, and a thickness of 0.3 mm were prepared. Next, a resin plate was continuously pasted with an adhesive at an interval of 10 mm on a net (on a width of 1300 mm) on a circular net cylinder of a circular net paper machine so that the short side was located in the paper flow direction. Six rows were attached at equal intervals in the width direction of the upper net.

<Paper making>
The upper tank with the resin plate attached was attached to the first tank cylinder of the two-tank paper machine, and the upper net without any work was attached to the second tank circular net cylinder. The second paper layer formed in the second tank is superimposed on the first paper layer formed in the first tank, and the two layers are combined at a paper making speed of 30 m / min. Paper was manufactured. At this time, the thread (width 2.5 mm) created in Example 1 to Example 3 between the first layer (33 g / m ² in terms of dry weight) and the second layer (67 g / m ² ). ) Was inserted into a position corresponding to the center of the mold using the method described in JP-B-5-40080. Subsequently, the wet paper was dehydrated according to a conventional method, and then dried with a cylinder dryer to produce threaded paper 100 g / m ² made of two-layered laminated paper, thereby obtaining a forgery-preventing paper. No stress light emitting layer cracking or thread breakage due to heat, rubbing elongation, etc. at the paper making stage, and the stress light emitting function of the anti-counterfeit paper is not lost, and external force is applied to the thread part. As a result, the same light emission performance as the sled obtained in Examples 1 to 3 was confirmed.

[Comparative Example 1]
A thread was obtained in the same manner as in Example 1 except that an acrylic resin was used instead of the polyurethane resin. When an external force was applied to the obtained thread with a nail, light emission was observed at the location where the external force was applied, but it was inferior to the light emission of Example 1 in terms of vividness.

[Comparative Example 2]
A thread was obtained in the same manner as in Example 1 except that polystyrene was used instead of the polyurethane resin. When an external force was applied to the obtained thread with a nail, light emission was observed at the location where the external force was applied, but it was inferior to the light emission of Example 1 in terms of vividness.

[Comparative Example 3]
An anti-counterfeit paper was obtained in the same manner as in Example 4 except that the threads obtained in Comparative Examples 1 and 2 were used. When an external force was applied to the thread portion, light emission was confirmed, but it was inferior to the light emission of Example 4 in terms of vividness.

Claims (16)

Fine particles of at least one stress luminescent material, and
Polyurethane resin, polyester resin, polycarbonate resin, polyolefin resin, ethylene / vinyl acetate copolymer resin, styrene / butadiene copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, nylon resin, polyamide resin, polyvinyl alcohol, fluorine A stress-stimulated luminescent sheet comprising at least one binder polymer selected from the group consisting of a resin. The stress light-emitting sheet according to claim 1, wherein the binder polymer is a polyurethane resin and / or a polyester resin. The stress-stimulated luminescent sheet according to claim 2, wherein the polyurethane resin is a polyester-based polyurethane. A substrate, and
Fine particles of at least one stress luminescent material, and
Polyurethane resin, polyester resin, polycarbonate resin, polyolefin resin, ethylene / vinyl acetate copolymer resin, styrene / butadiene copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, nylon resin, polyamide resin, polyvinyl alcohol, fluorine A stress light emitting laminate comprising a stress light emitting layer containing at least one binder polymer selected from the group consisting of a resin. The stress-stimulated laminate according to claim 4, wherein the binder polymer is a polyurethane resin and / or a polyester resin. The stress-stimulated laminate according to claim 5, wherein the polyurethane resin is a polyester-based polyurethane. The stress-stimulated laminate according to any one of claims 4 to 6, further comprising at least one adhesive layer. The stress-stimulated laminate according to claim 7, wherein the outermost layer is the adhesive layer. The stress-stimulated laminate according to any one of claims 4 to 8, wherein the base material contains the stress-stimulated luminescent material. The stress-stimulated laminate according to any one of claims 4 to 9, wherein the substrate is a film, a nonwoven fabric, or paper. The thread | sled which consists of the stress light emission sheet | seat in any one of Claims 1 thru | or 3, or the stress light emission laminated body in any one of Claims 4 thru | or 10. 12. A thread according to claim 11 having a pearl luster. 13. A thread according to claim 11 or 12, comprising micro characters. An anti-counterfeit paper having at least a part of the thread according to claim 11. An anti-counterfeit paper made of paper on which the thread according to claim 11 is engraved. The anti-counterfeit paper according to claim 15, wherein the thread is intermittently exposed on the surface.