JP2005279944A - Slip for delivery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a slip for delivery, which can form an extremely clear laser-printed image, which prevents the disappearance of the laser-printed image, which is useful for the prevention of the forgery, tampering or the like of the laser-printed image, and which is excellent in water resistance, chemical resistance, etc., and extremely useful for door-to-door delivery. <P>SOLUTION: This slip for delivery is characterized as follows: a temporarily attached base material for the slip for delivery is temporarily attached onto releasing paper via a pressure-sensitive adhesive layer; in the base material for the slip for delivery, one surface of a paper base material is provided with a laser-light-irradiation color-development resin layer composed of a resin composition wherein a resin serves as a vehicle, which includes a color development agent developing a color by laser light irradiation, and wherein the content of the color development agent developing the color by the laser light irradiation is in the range of 0.01-50.0 wt% base on the resin; and the surface of the paper base material is temporarily attached to the surface of the pressure-sensitive adhesive layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a delivery slip, and more specifically, by irradiating a YAG laser, a very clear laser print image can be formed and the laser print image does not disappear. Further, the present invention relates to a delivery slip that is useful for preventing forgery or tampering, and is excellent in water resistance, chemical resistance, etc., and extremely useful for home delivery.

Conventionally, as a delivery slip affixed to the surface of an article for home delivery or the like, usually, a plurality of paper pieces are stacked up and down via carbon paper or the like, and one end thereof is temporarily bonded to form a booklet. A pressure-sensitive copying type recording is employed by recording with a hard writing instrument such as a ballpoint pen or a dot impact printer.
However, in the above-mentioned pressure-sensitive copying type delivery slip, printing by a thermal printer or laser printer that has been popular in recent years is a printing method that does not give a large impact or pressure. The problem is that it cannot be duplicated due to, or the like, or a problem that the thickness is increased because one end of the plurality of paper pieces are stacked on top of each other and temporarily bonded to form a booklet, and further, it consists of a plurality of paper pieces. For this reason, it is weak against moisture and cheap to cause wrinkles and dirt, so that automatic processing by a machine or the like is difficult, and for example, there is a problem that printing cannot be performed by a laser printer. In order to improve the above-mentioned problems, for example, a transparent first sheet, a second sheet for displaying information, which is temporarily attached to the surface of the first sheet so as to be peelable. A delivery slip is proposed that includes a first sheet, a pressure-sensitive adhesive layer formed on the back surface of the first sheet, and a third sheet that is detachably attached to the pressure-sensitive adhesive layer ( For example, see Patent Document 1.)
Also, for example, a slip adhesive sheet in which a main sheet part, a subsidiary sheet part, and a temporary fixing part are partitioned and formed on a single sheet sheet via a sewing line and temporarily attached to a release sheet with an adhesive. Proposing a non-adhesive film that seals the adhesive to the adhesive on the back side of the sub-form part, and the film has a color and a pattern that can be seen through from the front side of the copy slip part. (For example, see Patent Document 2).
JP-A-7-329452. JP 2002-297038 A.

However, with the delivery slips and slip-adhesive papers proposed above, printing with a thermal printer or laser printer is possible, but the printed image is a slip. For this reason, the printed image is still easy to disappear, and its forgery or tampering is very easy, and the printed image is inferior in water resistance, chemical resistance, etc. It has the problem that.
Therefore, the present invention can form a very clear laser-printed image and the laser-printed image does not disappear and is useful for preventing forgery or tampering. It is to provide a delivery slip that is excellent in chemical resistance and extremely useful for home delivery.

  As a result of various studies to solve the above problems, the present inventor configured a delivery slip by temporarily attaching a temporarily attached delivery slip base material to the release paper via an adhesive layer. In addition, as a delivery slip base material constituting the delivery slip, a resin is used as a vehicle on one side of the paper base material, and a coloring agent that develops color by laser beam irradiation, and A laser beam irradiation coloring resin layer is provided by a resin composition in which the content of the color former that develops color by laser beam irradiation is 0.01% to 50.0% by weight with respect to the resin, and A delivery slip in which the surface of the paper substrate is temporarily attached to the surface of the pressure-sensitive adhesive layer is manufactured, and thus the laser beam irradiation coloring resin layer constituting the delivery slip For example, when the YAG laser beam is irradiated on the surface of the laser beam, the laser beam irradiation coloring resin layer Absorbs the energy of the YAG laser beam and forms a very clear laser-printed image by black color formation by carbonization or white color formation by foaming, and the print state is clearly visible In addition, when a laser-printed image after printing is provided on the outer side thereof, for example, by providing a surface protective layer made of a resin layer or the like, the laser-printed image is protected by it and is not affected by external effects. The laser printed image does not disappear, become unclear, and can be prevented from being altered, counterfeited, falsified, etc. In addition, the laser has excellent water resistance and chemical resistance. The present invention has been completed by finding that it is possible to produce a delivery slip that has a printed image and is extremely useful for home delivery, for example.

  That is, the present invention temporarily attaches a temporarily attached delivery slip base material to the release paper via an adhesive layer, and the delivery slip base material is provided on one side of the paper base material. The resin is used as a vehicle, contains a color former that develops color by laser beam irradiation, and the content of the color former that develops color by laser beam irradiation is 0.01% to 50% relative to the resin. It has a constitution in which a laser beam irradiation coloring resin layer made of a resin composition consisting of 0% by weight is provided, and the surface of the paper base material is temporarily attached to the surface of the pressure-sensitive adhesive layer. This relates to a delivery slip characterized by the following.

  In the present invention, a YAG laser beam or the like is irradiated to the laser beam irradiation color developing resin layer constituting the delivery slip, and the above-described YAG laser beam is irradiated on the laser beam irradiation color developing resin layer. -Absorbs the energy of the light and forms a very clear laser-printed image by black colorization by carbonization or white color formation by firing at the part, and the print state can be clearly recognized and printed. The later laser-printed image is further erased without being affected by external effects, for example, when a surface protective layer made of a resin layer or the like is provided on the outside thereof. It is possible to prevent alteration, forgery, tampering, etc. without becoming unclear, and also has a laser-printed image with excellent water resistance, chemical resistance, etc. Can produce extremely useful delivery slips It is intended that it is.

  Hereinafter, the delivery slip according to the present invention will be described in more detail with reference to the drawings. First, an example of the delivery slip according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic plan view showing an example of the configuration of the plane of the delivery slip according to the present invention. FIG. 2 is a schematic cross-sectional view taken along line AA ′ in the schematic plan view shown in FIG. 1, and FIGS. 3 and 4 are schematic views showing the configuration of another example of the delivery slip according to the present invention. FIG. 5 is a schematic cross-sectional view of a delivery slip according to the present invention shown in FIG. 3, and a delivery slip formed by irradiating a YAG laser beam to form a laser print image. It is a schematic sectional drawing which shows an example of a layer structure.

  First, FIG. 1 shows a delivery slip A according to the present invention, and the delivery slip A according to the present invention comprises a sheet 1 of sheets, and further includes a perforation line 2 for cutting, etc. For example, a delivery slip 3, a receipt slip 4, a copy slip 5, and other required XX slips 6 etc. are arbitrarily provided and partitioned, and this is divided into a plurality of units as a unit, and according to the present invention. This forms a delivery slip A. Next, as shown in FIG. 2, the delivery slip A according to the present invention has a configuration in which a delivery slip base material 13 is temporarily attached to a release paper 11 via an adhesive layer 12 as shown in FIG. Thus, the delivery slip base material 13 includes, on one surface of the paper base material 14, a resin as a vehicle and a color former that develops color by laser beam irradiation, and the label. From the structure in which the laser beam irradiation coloring resin layer 15 is provided with a resin composition in which the content of the color former that develops color by irradiation with the laser beam is 0.01% to 50.0% by weight with respect to the resin. In addition, the paper substrate 14 has a layer structure in which the surface of the paper base material 14 is temporarily attached to the surface of the pressure-sensitive adhesive layer 12.

Next, as another example of the delivery slip according to the present invention, as shown in FIG. 3, the delivery slip base material 13 is temporarily attached to the release paper 11 via the adhesive layer 12. Thus, the delivery slip base material 13 includes, on one side of the paper base material 14, a resin as a vehicle and a color former that develops color by laser light irradiation. A laser beam irradiation coloring resin layer 15 of a resin composition in which the content of the color former that develops color upon irradiation with the laser beam is 0.01% to 50.0% by weight with respect to the resin; The laser beam irradiation coloring resin layer 15 has a structure in which a surface protective layer 16 made of a resin layer composed of a resin as a main component is laminated on one side, and An arrangement according to the present invention comprising a layer structure in which the surface is temporarily attached to the surface of the pressure-sensitive adhesive layer 12 described above. It can be exemplified use voucher A _1.

Furthermore, when another example is illustrated for the delivery slip according to the present invention, as shown in FIG. 4, a configuration in which a delivery slip base material 13 is temporarily attached on a release paper 11 via an adhesive layer 12. Thus, the delivery slip base material 13 includes, on one surface of the paper base material 14, a resin as a vehicle and a color former that develops color by laser beam irradiation, and the label. The laser beam irradiation coloring resin layer 15 is provided with a resin composition in which the content of the color former that develops color by irradiation with the laser beam is 0.01 wt% to 50.0 wt% with respect to the resin; The paper substrate 14 has the structure in which the surface protective layers 16 and 16a made of a resin layer made of a resin composition as a main component are laminated on both surfaces of the laser beam irradiation coloring resin layer 15. The present invention comprises a layer configuration in which the surface is temporarily attached to the surface of the pressure-sensitive adhesive layer 12. The shipping document A ₂ according can be exemplified.

Next, in the present invention, the delivery slip according to the present invention as described above is used, and the laser slip is applied to the delivery slip to form a laser print image. The laser beam irradiation method and the like will be described in the case where the delivery slip A _{1 according} to the present invention shown in FIG. 3 is used. As shown in FIG. 5, the delivery slip A _{1 according} to the present invention. When the laser beam 17 is irradiated on the surface of the surface protective layer 16 composed of a resin layer made of a resin composition mainly composed of a resin constituting the laser beam 17, the laser beam 17 is irradiated with the surface protective layer 16. The laser beam irradiation coloring resin layer 15 is absorbed, and the laser beam irradiation coloring resin layer 15 in that portion absorbs the energy of the laser beam 17 and the laser beam irradiation coloring resin layer 15 absorbs the energy. A laser beam irradiation colored tree that absorbs energy from the laser beam 17 In the portion of the oil layer 15, black color generation by carbonization or white color generation by firing is generated to form a laser print image 18 composed of, for example, letters, numbers, symbols, designs, etc. very clearly. Thus, the delivery slip recording body B according to the present invention using the delivery slip A _{1 according} to the present invention can be manufactured.
Thus, in the present invention, the above-described laser printing method is used to place the delivery slip, receipt slip, copy slip, and other required XX slips that constitute the delivery slip according to the present invention. The required matters are printed and the delivery slip recording body according to the present invention using the delivery slip according to the present invention is manufactured. After that, for example, the copy slip is handed over to the sender and the delivery slip is transferred to the package. The delivery slip according to the present invention is used by sticking to a patch and delivering it. After delivery, a receipt is obtained, and other XX forms are processed.

The above illustrations illustrate a few examples of the delivery slip, the laser printing method, etc. according to the present invention, and the present invention is not limited to this. . In the present invention, although not shown, the laser beam irradiation coloring resin layer constituting the delivery slip according to the present invention can be partially provided not only on the entire surface of the paper base but also on a portion to be recorded. Is.
Further, in the present invention, even if the surface of the laser beam irradiation coloring resin layer constituting the delivery slip according to the present invention is irradiated with a laser beam, a surface protective layer, and further a paper substrate It does not have any influence on etc.
In the present invention, although not shown, of course, the delivery slips according to the present invention shown in FIGS. 1, 2, and 4 are irradiated with laser beams in the same manner as described above, and laser printing is performed. The delivery slip recording body according to the present invention using the delivery slip according to the present invention formed with an image can be similarly manufactured.
Further, in the present invention, although not shown in the drawings, it is possible to design and manufacture a multi-layer delivery slip having various forms by arbitrarily laminating other base materials depending on the purpose of use and application. It can be done.

By the way, the delivery slip according to the present invention basically includes a resin as a main component of the vehicle, and further includes a color former that develops color by laser beam irradiation, and the laser beam irradiation. A laser beam irradiation colored resin layer made of a resin composition having a color developing agent content of 0.01 wt% to 50.0 wt%, for example, a YAG laser beam or the like. Absorbs the energy of the laser beam, and in that portion, a laser print image consisting of letters, numbers, symbols, designs, etc. It can be clearly formed.
Further, in the delivery slip according to the present invention, even if the YAG laser beam or the like is irradiated, the surface protective layer or the surface, the back surface or the like of the paper substrate is affected by the YAG laser beam. Without being subjected to this, it is possible to form a very clear and very clear laser-printed image and to clearly recognize the printed state.
Furthermore, in the delivery slip according to the present invention, a laser-printed image can be formed as described above, and a resin layer made of a resin composition containing a resin as a main component outside the laser-printed image. In the case where a surface protective layer made of, for example, is present, the surface protective layer located outside the surface protects the laser-printed image and eliminates its external influence, for example, modification , Prevent counterfeiting, tampering, etc.

Thus, in the delivery slip according to the present invention, for example, when the YAG laser beam or the like is irradiated, the laser beam irradiation coloring resin layer constituting the delivery slip according to the present invention Absorbs the energy of the YAG laser beam and forms a very clear laser-printed image by black color formation by carbonization or white color formation by firing, and the print state is clearly visible It can be done.
Further, in the delivery slip according to the present invention, for example, even if the YAG laser beam or the like is irradiated, the surface protective layer or the like constituting the delivery slip or the like according to the present invention is not limited to the YAG laser beam. In addition, the laser beam irradiation coloring resin layer constituting the delivery slip according to the present invention absorbs the energy of the YAG laser beam, and in that portion, An extremely clear laser print image can be formed by black color formation by carbonization or white color formation by firing, and the print state can be clearly seen, and the laser print image after printing is on the outside. Protected by the surface protective layer, etc. that is located, without being affected externally, and further, without disappearing, smearing, etc., and erasing, counterfeiting due to abrasion, abrasion with solvents, etc. Alteration, modification, Has the property that it is extremely difficult to perform other like, its safety, reliability and the like is very high.

In the present invention, the laser beam is YAG [yttrium (Y) / aluminum (A) / garnet (G)] laser beam (wavelength = 1.064 μm). It is preferable to perform printing.
In the above, when a carbon dioxide [CO ₂ ] laser (wavelength = 10.6 μm), which is usually used in laser printing, is used as the laser beam, carbon dioxide is used. [CO ₂ ] Laser printing is performed by irradiating a laser beam to cut and carbonize the surface, producing smoke during irradiation, inferior workability, etc. -It is not preferable because there are problems such as the occurrence of holes in the printed image portion.
Thus, in the present invention, the YAG laser beam described above has a property of transmitting through a transparent body, and using this property, the laser beam irradiation color resin layer is further surface protected. The amount of coloring agent added in the laser beam irradiation coloring resin layer to suppress the generation of smoke, etc. by being sandwiched between the layers, and the like. The film thickness of the color developing resin layer, etc. are controlled to adjust the color density, the effect on the surface protective layer, etc. The print image can be formed.

Next, in the present invention, materials, manufacturing methods, and the like constituting the delivery slip according to the present invention will be described. First, as the release paper constituting the delivery slip according to the present invention, for example, a paper substrate , Polypropylene film, polyethylene terephthalate film, polyvinyl chloride film, acetate film, polyamide film, etc., plastic film or foam film thereof, aluminum foil, fiber reinforced epoxy, polyamide, polyurethane and polyethylene film, etc. Can be used.
Thus, in the present invention, the base material constituting the release paper is, for example, silicone, alkyd, acrylate ester, stearamide in consideration of peelability from the adhesive layer described later. It is preferable that the surface is processed with a release agent such as others.

Next, in the present invention, the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer constituting the delivery slip according to the present invention is, for example, adhered to a surface that can be pressed with a pressure of about a finger pressure at room temperature and in a solvent-free state. Also, when peeling this from the adherend surface, an adhesive having viscoelastic properties that can be removed without leaving a trace, specifically, a so-called pressure-sensitive adhesive can be used. .
Specifically, for example, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and the like can be used.
Thus, these adhesives are coated on the above release paper by using a coating method such as a roll coat, a gravure roll coat, a kiss coat, etc. An adhesive layer can be formed.

Further, in the present invention, as the paper base material forming the delivery slip base material constituting the delivery slip or the like according to the present invention, for example, a conventionally known paper base material constituting conventional delivery slips is used. can do.
Specifically, since this is the basic material constituting the delivery slip according to the present invention, it is possible to use a material having bending resistance, rigidity, waist, strength, etc. Alternatively, various paper base materials such as unbleached paper base material, pure white roll paper, kraft paper, paperboard, processed paper, coated paper, and the like can be used.
In the present invention, the paper substrate, for example, those having a basis weight of 20g / m ² ~300g / m ² position, preferably, can be used as a basis weight of about 60~250g / m ² position.
In the present invention, a desired printed picture such as a character, a figure, a picture, a symbol, or the like can be arbitrarily formed on the paper base by a normal printing method.

  Next, in the present invention, the laser beam irradiation coloring resin layer forming the delivery slip base material constituting the delivery slip according to the present invention will be described. First, the laser beam irradiation coloring resin is described. As the resin forming the layer, for example, a mixture of one or more thermoplastic resins that can be melted by heat and extruded from an extrusion die such as an extruder, and further thermally fused to each other is used. Specifically, for example, low density polyethylene (LDPE), linear (linear) low density polyethylene (polymer polymerized using multisite catalyst, LLDPE), metallocene catalyst (single Site catalyst) ethylene-α-olefin copolymer polymerized using, medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene resin, ethylene-vinyl acetate Copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, An acid-modified polyolefin obtained by modifying a polyolefin resin such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid or itaconic acid. Heat of resin, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, polystyrene resin, polycarbonate resin, thermoplastic polyester resin, thermoplastic polyamide resin, etc. One type or two or more types of plastic resins can be used.

Next, in the present invention, as the color former that forms a color by laser beam irradiation for forming the laser beam irradiation color developing resin layer according to the present invention, a conventionally known one, for example, coloring of dyes / pigments, etc. Agents, clays, etc. can be used, specifically, yellow iron oxide, inorganic lead compounds, manganese violet, cobalt violet, mercury, cobalt, copper, bismuth, nickel and other metal compounds, pearlescent pigments , Silicon compounds, mica, kaolins, silica sand, diatomaceous earth, talc, titanium oxide coated mica, tin dioxide coated mica, antimony coated mica, tin + antimony coated mica, tin + antimony + titanium oxide coated mica 1 type or 2 types or more, such as a kind and others, can be used.
As for the amount used, it is desirable to add about 0.01 wt% to 50.0 wt%, preferably about 1.0 wt% to 10 wt% with respect to the thermoplastic resin. is there.

  Next, in the present invention, the laser beam irradiation coloring resin layer according to the present invention is formed. The resin is a main component of the vehicle, and further includes a color former that develops color by laser beam irradiation, and The resin composition in which the content of the color former that develops color by irradiation with the laser beam is from 0.01% by weight to 50.0% by weight will be described. In the present invention, for example, the above thermoplastic resin One or two or more kinds of main components of the vehicle are used, and one or more of the color formers that develop color by laser beam irradiation are contained in an amount of 0.01% to 50%. In addition, it is added within the range of 0% by weight, and if necessary, for example, when forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, Releasability, flame retardancy, anti-mold, electrical properties, strength, For the purpose of improving and modifying others etc., one or more kinds of various plastic compounding agents and additives are arbitrarily added, and if necessary, a solvent, a diluent, etc. are added sufficiently. By kneading, it is possible to prepare a resin composition containing a resin as a main component of the vehicle and a color former that develops color by laser beam irradiation.

  In the present invention, in the resin composition according to the present invention, examples of the plastic compounding agent and additive include a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, and a filler. , Reinforcing agents, antistatic agents, flame retardants, flameproofing agents, foaming agents, antifungal agents, pigments, dyes, dispersants, surfactants, antiblocking agents, etc., and further modification Resin for use can also be used, and the addition amount can be arbitrarily added from a very small amount to several tens of weight% according to the purpose.

Furthermore, in the above, as the compounding agent or additive, specifically, a lubricant having its own lubricity and little migration in the resin can be used. For example, liquid paraffin, white Vaseline, petroleum wax, microcrystalline wax, montan wax, polyethylene wax and the like, higher fatty acids having 8 to 22 carbon atoms, higher fatty acid aluminum, higher fatty acid calcium, higher fatty acid magnesium higher fatty acid zinc, higher fatty acid lithium Higher fatty acids or metal salts thereof, linear aliphatic monohydric alcohols having 8 to 18 carbon atoms, glycerin, sorbitol, propylene glycol, pentaerythritol, triethylene glycol, etc. Aliphatic alcohols, higher fatty acids having 4 to 22 carbon atoms and straight chain aliphatics having 8 to 18 carbon atoms Esters with polyhydric alcohols, butyl acetyl citrate, di-2-ethyl-hexyl adipate, azelaic acid-n-hexyl, ethanediol montanate, poly (1.3-butanediol adipate) ester, acetylricino -Esters of alcohol and fatty acid such as methyl oxalate, poly (1.3-butylene glycol, 1.4-butylene glycol, adipic acid octyl alcohol) ester, sugar wax, etc., hydrogenation Edible fats and oils, castor oil, spam acetyl wax, glycerides of acetylated monoglyceride sugar, ethylene bis-fatty acid amide represented by, for example, ethylene bisoleyl amide having 16 to 18 carbon atoms, higher fatty acid amide having 8 to 22 carbon atoms , Stearyl erucamide, erucic acid amide, oleyl palmitoamide, etc. 1 to 2 types of fatty acid amides, and others such as methylhydrodiene polysiloxane, dimethyl polysiloxane, methylphenyl polysiloxane, silicone oil jarodine such as polyoxyalkylene dimethylpolysiloxane, and glycerin ester of maleic acid modified rosin The above can be used.
In the present invention, among the lubricants as described above, erucic acid amide, ethylene bis oleyl amide, stearic acid amide, oleic acid amide, methylene bis stearic acid amide, etc., are themselves slippery, It is a very effective material.
As the addition amount of the above-mentioned lubricant, it is preferable to add at a ratio of about 0.08 wt% to 10.0 wt% with respect to 100 parts by weight of the thermoplastic resin.

In the present invention, other oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide, and zinc oxide; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; Carbonates such as magnesium and calcium carbonate, sulfates such as calcium sulfate and barium sulfate, silicates such as magnesium silicate, aluminum silicate, calcium silicate and aluminosilicate, and others such as kaolin, talc and diatomaceous earth Anti-blocking agent based on inorganic compounds, or high density polyethylene, ultra-high molecular weight polyethylene having a molecular weight of 300000 or more, polypropylene, polycarbonate, polyamide, polyester, melamine resin, diallyl phthalate resin, acrylic resin, etc. Organic consisting of fine powder It one free of compounds based antiblocking agents can be added two or more.
The addition amount is preferably about 0.01 to 3% by weight with respect to 100 parts by weight of the resin.

Next, in the present invention, a method for forming a laser beam irradiation color developing resin layer according to the present invention using the resin composition as described above will be described. First, in the present invention, The resin is a main component of the vehicle, and further contains a color former that develops color when irradiated with a laser beam, and the content of the color former that develops color when irradiated with a laser beam is 0.01 to 50% by weight. After preparing a resin composition consisting of 0.0% by weight, the resin composition is used, and these are used, for example, by using a T-die extruder, an inflation molding machine, etc. The light irradiation color developing resin film is manufactured, and this is laminated on one or both surfaces of the paper substrate constituting the above-mentioned delivery slip substrate according to the present invention. It is possible to form such a laser beam irradiation colored resin layer. That.
Alternatively, in the present invention, as described above, the resin is a main component of the vehicle, and further includes a color former that develops color by laser light irradiation, and also contains a color former that develops color by laser light irradiation. After preparing a resin composition having an amount of 0.01% to 50.0% by weight, the resin composition is used, for example, using a T-die extruder, an extruder such as others. Then, the laser beam irradiation coloring resin film by the above resin composition is extrusion laminated on one surface of the paper base material constituting the above-mentioned delivery slip base material according to the present invention, or both surfaces thereof. Thus, the laser beam irradiation coloring resin layer according to the present invention can be formed.

  Alternatively, in the present invention, in the same manner as described above, first, in the above, the resin is the main component of the vehicle, and further contains a color former that develops color by laser beam irradiation, and the laser beam irradiation is performed. After preparing a resin composition having a color former content of 0.01 wt% to 50.0 wt%, the resin composition is used, and these are used for the above-mentioned delivery slip base according to the present invention. For example, a roll coat method, a gravure roll coat method, a spray coat method, a kiss coat method, an extrusion coat is applied to one side or both sides of a paper base material constituting the material. Then, it is applied or printed by the usual coating method or printing method, etc. to form a coating film or printing film by the above resin composition, and the laser beam irradiation coloring according to the present invention. A resin layer can be formed. The above examples illustrate one or two examples of the method of forming the laser beam irradiation color resin layer according to the present invention, and the present invention is not limited thereto.

In the present invention, the film thickness of the laser beam irradiation coloring resin layer according to the present invention is desirably about 1 μm to 50 μm, preferably about 5 μm to 30 μm.
In the above, when the thickness of the laser beam irradiation coloring resin layer according to the present invention is 1 μm or less, and less than 5 μm, color development or printing by a color former that develops color by laser beam irradiation is possible. Insufficient and unpreferable for reasons such as unclearness, and when the film thickness exceeds 50 μm, and more than 30 μm, coloring and printing with a color former that develops color by laser beam irradiation are sufficient, This is not preferable for reasons such as an increase in cost, a decrease in physical properties (strength) of the laser beam irradiation coloring resin layer, and a coloring of the color former itself that develops color by laser beam irradiation.

Next, in the present invention, the surface protective layer constituting the substrate for a delivery slip according to the present invention will be described. As the resin for forming the surface protective layer, the laser beam irradiation coloring according to the present invention described above is used. The resin forming the resin layer can be used in the same manner.
Specifically, it is possible to use a mixture of one or more thermoplastic resins that can be melted by heat and extruded from an extrusion die such as an extruder, and can be heat-sealed to each other. For example, low density polyethylene (LDPE), linear (linear) low density polyethylene (polymer polymerized using multisite catalyst, LLDPE), ethylene polymerized using metallocene catalyst (single site catalyst) α-olefin copolymer, medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer Polymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer Acid modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid or the like, or a polyolefin resin such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene. Modified polyolefin resin, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, polystyrene resin, polycarbonate resin, thermoplastic polyester resin, thermoplastic polyamide resin, etc. One or more of these thermoplastic resins can be used.

  Next, in the present invention, the resin composition mainly composed of the resin that forms the surface protective layer according to the present invention will be described. In the present invention, for example, one or more of the above-mentioned thermoplastic resins are used. As the main component of the vehicle, and further, if necessary, when forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, release properties, etc. For the purpose of improving and modifying the formability, flame retardancy, antifungal properties, electrical properties, strength, etc., one or more kinds of various plastic compounding agents and additives are arbitrarily added, Further, if necessary, a resin composition containing a resin as a main component of the vehicle can be prepared by adding a solvent, a diluent and the like and kneading the mixture sufficiently.

  In the present invention, in the fat composition as described above, as described above, examples of the plastic compounding agent and additive include a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, and a light stabilizer. , Fillers, reinforcing agents, antistatic agents, flame retardants, flame retardants, foaming agents, antifungal agents, pigments, dyes, dispersants, surfactants, antiblocking agents, etc., and more Further, a modifying resin or the like can be used, and the addition amount can be arbitrarily added from a very small amount to several tens of weight% depending on the purpose.

Furthermore, in the above, as a compounding agent and an additive, as described above, specifically, a lubricant having its own lubricity and less migration in the resin can be used, for example, , Liquid paraffin, white petrolatum, petroleum wax, microcrystalline wax, montan wax, polyethylene wax and the like, higher fatty acids having 8 to 22 carbon atoms, or higher fatty acid aluminum, higher fatty acid calcium, higher fatty acid magnesium higher fatty acid Zinc, higher fatty acids such as higher fatty acid lithium or metal salts thereof, linear aliphatic monohydric alcohol having 8 to 18 carbon atoms, glycerin, sorbitol, propylene glycol, pentaerythritol, triethylene Aliphatic alcohols such as glycol, higher fatty acids having 4 to 22 carbon atoms, and 8 to 1 carbon atoms Esters of linear aliphatic monohydric alcohols, butyl acetyl citrate, di-2-ethyl-hexyl adipate, azelaic acid-n-hexyl, ethanediol montanate, poly (1.3-butanedio- Alcohol, fatty acid, poly (1.3-butylene glycol, 1.4-butylene glycol, octyl alcohol adipate) ester, sugar wax, etc. Esters, hydrogenated edible fats and oils, castor oil, spam acetyl wax, glycerides of acetylated monoglyceride sugars, ethylene bis-fatty acid amides having 16 to 18 carbon atoms, for example, ethylene bis-oleylamide, 8 carbon atoms -22 higher fatty acid amide, stearyl erucamide, erucic acid amide, oleyl palmi 1 such as higher fatty acid amides such as amides, silicone oil jarodine such as methylhydrodiene polysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, polyoxyalkylene / dimethylpolysiloxane, and glycerin ester of maleic acid modified rosin Species or two or more can be used.
In the present invention, among the lubricants as described above, erucic acid amide, ethylene bis oleyl amide, stearic acid amide, oleic acid amide, methylene bis stearic acid amide, etc., are themselves slippery, It is a very effective material.
As the addition amount of the above-mentioned lubricant, it is preferable to add at a ratio of about 0.08 wt% to 10.0 wt% with respect to 100 parts by weight of the thermoplastic resin.

In the present invention, as described above, other oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide, and zinc oxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, etc. Hydroxides, carbonates such as magnesium carbonate and calcium carbonate, sulfates such as calcium sulfate and barium sulfate, silicates such as magnesium silicate, aluminum silicate, calcium silicate and aluminosilicate, other kaolin, talc, Anti-blocking agent of inorganic compounds such as diatomaceous earth, or high density polyethylene, ultra high molecular weight polyethylene with molecular weight of 300,000 or more, polypropylene, polycarbonate, polyamide, polyester, melamine resin, diallyl phthalate resin, acrylic Resin, other fine powder One free of organic compound-based antiblocking agent consists of, it can be added two or more.
The addition amount is preferably about 0.01 to 3% by weight with respect to 100 parts by weight of the resin.

  Next, in the present invention, a method for forming the surface protective layer according to the present invention using the resin composition as described above will be described. First, in the present invention, the resin is the main component of the vehicle. After preparing the resin composition to be used, the resin composition is used, and these are used, for example, using a T-die extruder, an inflation molding machine, etc., to produce a resin film by the above resin composition, This is laminated on one or both surfaces of the laser beam irradiation coloring resin layer constituting the delivery slip according to the present invention to form the surface protective layer according to the present invention. be able to.

  Alternatively, in the present invention, similarly to the above, first, after preparing a resin composition containing a resin as a main component of the vehicle as described above, the resin composition is used, -The surface of the resin layer irradiated with a light beam, or both surfaces thereof, for example, a roll coat method, a gravure roll coat method, a spray coat method, a kiss coat method, an extrusion coat Coating or printing by a normal coating method or printing method, such as coating, etc., to form a coating film or printing film by the above resin composition, and laser beam irradiation according to the present invention A coloring resin layer can be formed.

Further, in the present invention, a method for forming the surface protective layer according to the present invention using the resin composition as described above will be described. First, in the present invention, the resin is used as a main component of the vehicle. The resin composition and the laser beam irradiation coloring resin layer constituting the delivery slip according to the present invention are formed. The resin is a main component of the vehicle, and the color is developed by laser beam irradiation. A resin composition containing a color former and having a color former content of 0.01% to 50.0% by weight when irradiated with a laser beam. For example, a T-die co-extruder or other co-extrusion molding machine is used on one side of the paper base constituting the base for a delivery slip according to the present invention described above or on both sides of the resin composition. Etc., and the laser light according to the present invention From 2 layers without the illumination color resin layer and the surface protective layer can be formed at the same time three-layer co-extruded resin layer.
The above exemplification illustrates one or two examples of the method for forming the surface protective layer according to the present invention, and the present invention is not limited thereto.

In the present invention, the surface protective layer according to the present invention is preferably made of a transparent or transparent resin film in order to see through or protect the laser-printed image described above. In the present invention, the film thickness of the surface protective layer according to the present invention is desirably about 5 μm to 60 μm, preferably about 10 μm to 40 μm.
In the above, if the thickness of the surface protective layer according to the present invention is 5 μm, more preferably less than 10 μm, it is not preferable because the protective function is lost, and the film thickness exceeds 60 μm, and more than 40 μm. Further, the total thickness of the delivery slip according to the present invention is increased, which is not preferable because it causes an increase in cost.

In the present invention, in one or more layers such as a paper substrate, a laser beam irradiation coloring resin layer, or a surface protective layer constituting the substrate for a delivery slip according to the present invention, A desired printed pattern layer can be formed.
Thus, the printed pattern layer is mainly composed of one or more ordinary ink vehicles, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet ray, and the like. One or more additives such as an absorbent, a curing agent, a crosslinking agent, a lubricant, an antistatic agent, a filler, and the like are arbitrarily added, and a colorant such as a dye / pigment is added, and a solvent is added. The ink composition is prepared by sufficiently kneading with a diluent, and then the ink composition is used. For example, gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. The printing pattern layer according to the present invention can be formed by printing a desired printing pattern composed of characters, figures, symbols, patterns, etc. on the above-described coating thin film using a printing method such as .

Thus, in the present invention, when the delivery slip according to the present invention manufactured as described above is irradiated with a laser beam from one side as described above, the laser beam is -The laser beam irradiation coloring resin layer is reached, the laser beam irradiation coloring resin layer of the portion absorbs the energy of the laser beam, and the laser beam irradiation portion is carbonized. Black color development or white color development by foaming, for example, can be used to form a laser-printed image consisting of letters, numbers, symbols, designs, etc. very clearly. This makes it possible to manufacture a delivery slip with added value such as prevention of counterfeiting, alteration prevention, etc. of the product, whereby various functions of the delivery slip can be enhanced.
Next, the present invention will be described more specifically with reference to examples.

First, 95.0 parts by weight of polyethylene resin (manufactured by Sumitomo Mitsui Polyolefin Co., Ltd., trade name, Sumikasen 16P: density = 0.923 g / cm ³ , melt flow rate (MFR) = 3.7 g / 10 min), YAG A resin composition was prepared by sufficiently kneading 5.0 parts by weight of the coloring pigment (Merck Japan, trade name, Iriodin LS-825).
On the other hand, a thin paper having a basis weight of 45 g / m ² (manufactured by Tokushu Paper Co., Ltd., thickness 80 μm) was prepared.
Next, the resin composition prepared above was used on one side of the thin paper, which was heated to 330 ° C., and then extrusion-coated with an extruder to give a laser having a thickness of 20 μm. A light irradiation color developing resin layer was formed to produce a delivery slip base material according to the present invention.
Next, the delivery slip base material according to the present invention manufactured above is bonded to one surface of the release paper with the acrylic adhesive layer interposed therebetween with the surface of the thin paper opposed to the present invention. Such a delivery slip was manufactured.
Next, on the surface of the laser beam irradiation coloring resin layer of the delivery slip produced above, for example, a delivery slip, a receipt slip, a copy slip, and other required XX slips are arbitrarily divided into each of them. When the required items corresponding to the sections were laser-printed by irradiating the YAG laser, the clear dark-colored characters caused by the laser beam-irradiating colored resin layer emerged. After confirming that a character image can be printed, a delivery slip recording material according to the present invention was manufactured.
Using the delivery slip record produced above, it was possible to perform normal delivery processing by pasting it on the package.
In the above printing, no smoke was generated and no perforations were observed.
Moreover, even if the recording surface of the delivery slip recording body after printing was wet with water or rubbed, no disappearance of characters was recognized.

First, 95.0 parts by weight of polyethylene resin (manufactured by Sumitomo Mitsui Polyolefin Co., Ltd., trade name, Sumikasen 16P: density = 0.923 g / cm ³ , melt flow rate (MFR) = 3.7 g / 10 min), YAG A resin composition was prepared by sufficiently kneading 5.0 parts by weight of the coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name, PE-RMAZMD1239).
On the other hand, a thin paper having a basis weight of 45 g / m ² (manufactured by Tokushu Paper Co., Ltd., thickness 80 μm) was prepared.
Next, black ink is used on one surface of the above thin paper, and this is coated by the gravure roll method to form a black ink layer that can be visually recognized as black from the surface. On the ink layer, the resin composition prepared above is used, heated to 330 ° C., and then extrusion coated with an extruder to form a laser beam irradiation color developing resin layer having a thickness of 20 μm. To produce a delivery slip base material according to the present invention.
Next, the delivery slip base material according to the present invention manufactured above is bonded to one surface of the release paper with the acrylic adhesive layer interposed therebetween with the surface of the thin paper opposed to the present invention. Such a delivery slip was manufactured.
Next, on the surface of the laser beam irradiation coloring resin layer of the delivery slip produced above, for example, a delivery slip, a receipt slip, a copy slip, and other required XX slips are arbitrarily divided into each of them. When the required items corresponding to the compartments were laser-printed by irradiating the YAG laser, the clear white characters due to the above-mentioned laser light irradiation coloring resin layer came out, After confirming that a character image can be printed, a delivery slip recording material according to the present invention was manufactured.
Using the delivery slip record produced above, it was possible to perform normal delivery processing by pasting it on the package.
In the above printing, no smoke was generated and no perforations were observed.
Moreover, even if the recording surface of the delivery slip recording body after printing was wet with water or rubbed, no disappearance of characters was recognized.

First, 100.0 parts by weight of polyethylene resin (manufactured by Sumitomo Mitsui Polyolefin Co., Ltd., trade name, Sumikasen 16P: density = 0.923 g / cm ³ , melt flow rate (MFR) = 3.7 g / 10 min) is sufficiently kneaded. A first resin composition was prepared.
Next, 95.0 parts by weight of polyethylene resin (manufactured by Sumitomo Mitsui Polyolefin Co., Ltd., trade name, Sumikasen 16P: density = 0.923 g / cm ³ , melt flow rate (MFR) = 3.7 g / 10 min), YAG A second resin composition was prepared by sufficiently kneading 5.0 parts by weight of a laser coloring pigment (Merck Japan Co., Ltd., trade name, Iriodin LS-825). Furthermore, 100.0 parts by weight of polyethylene resin (manufactured by Sumitomo Mitsui Polyolefin Co., Ltd., trade name, Sumikasen 16P: density = 0.923 g / cm ³ , melt flow rate (MFR) = 3.7 g / 10 min) is sufficiently kneaded. A third resin composition was prepared.
On the other hand, a thin paper having a basis weight of 45 g / m ² (manufactured by Tokushu Paper Co., Ltd., thickness 80 μm) was prepared.
Next, the first, second, and third resin layer organisms are used on one side of the thin paper, and these are used in a three-layer / three-layer T-die co-extruder, According to a surface protective layer made of a first resin composition comprising 5 μm, a laser beam irradiation color developing resin layer comprising a second resin composition comprising a film thickness of 20 μm, and a third resin composition comprising a thickness of 5 μm A co-extruded laminated resin film consisting of three surface protective layers was extrusion coated to produce a delivery slip base material according to the present invention.
Next, the delivery slip base material according to the present invention manufactured above is bonded to one surface of the release paper with the acrylic adhesive layer interposed therebetween with the surface of the thin paper opposed to the present invention. Such a delivery slip was manufactured.
Next, on the surface of the laser beam irradiation coloring resin layer of the delivery slip produced above, for example, a delivery slip, a receipt slip, a copy slip, and other required XX slips are arbitrarily divided into each of them. When the required items corresponding to the sections were laser-printed by irradiating the YAG laser, the clear black characters caused by the laser beam irradiation coloring resin layer emerged. After confirming that a character image can be printed, a delivery slip recording material according to the present invention was manufactured.
Using the delivery slip record produced above, it was possible to perform normal delivery processing by pasting it on the package.
In the above printing, no smoke was generated and no perforations were observed.
Moreover, even if the recording surface of the delivery slip recording body after printing was wet with water or rubbed, no disappearance of characters was recognized.

First, 100.0 parts by weight of polyethylene resin (manufactured by Sumitomo Mitsui Polyolefin Co., Ltd., trade name, Sumikasen 16P: density = 0.923 g / cm ³ , melt flow rate (MFR) = 3.7 g / 10 min) is sufficiently kneaded. A first resin composition was prepared.
Next, 95.0 parts by weight of polyethylene resin (manufactured by Sumitomo Mitsui Polyolefin Co., Ltd., trade name, Sumikasen 16P: density = 0.923 g / cm ³ , melt flow rate (MFR) = 3.7 g / 10 min), YAG A second resin composition was prepared by sufficiently kneading 5.0 parts by weight of a laser coloring pigment (Merck Japan Co., Ltd., trade name, Iriodin LS-825). On the other hand, a thin paper titanium paper (thickness 50 μm) having a basis weight of 45 g / m ² was prepared.
Next, the above-mentioned first and second resin layer organisms are used on one side of the above thin paper, and these are used in a two-type two-layer T-die co-extruder, and have a film thickness of 5 μm. A coextruded laminated resin film consisting of two layers, a surface protective layer made of a first resin composition and a laser light irradiation color developing resin layer made of a second resin composition having a thickness of 20 μm, -A substrate for a delivery slip according to the present invention was produced by extrusion coating with the surface of the light-irradiated coloring resin layer facing the surface of the thin paper.
Next, the delivery slip base material according to the present invention manufactured above is bonded to one surface of the release paper with the acrylic adhesive layer interposed therebetween with the surface of the thin paper opposed to the present invention. Such a delivery slip was manufactured.
Next, on the surface of the laser beam irradiation coloring resin layer of the delivery slip produced above, for example, a delivery slip, a receipt slip, a copy slip, and other required XX slips are arbitrarily divided into each of them. When the required items corresponding to the sections were laser-printed by irradiating the YAG laser, the clear black characters caused by the laser beam irradiation coloring resin layer emerged. After confirming that a character image can be printed, a delivery slip recording material according to the present invention was manufactured.
Using the delivery slip record produced above, it was possible to perform normal delivery processing by pasting it on the package.
In the above printing, no smoke was generated and no perforations were observed.
Moreover, even if the recording surface of the delivery slip recording body after printing was wet with water or rubbed, no disappearance of characters was recognized.

In each of the above examples, the film thickness of the material constituting each layer was measured with a μ-meter manufactured by Sony Corporation.
In each of the above embodiments, YAG laser printing was performed by laser irradiation at 16.5 A, 6 kHz from a YAG laser system (model name, DW5200) manufactured by Fuji Electric Co., Ltd. .

  Thus, in the present invention, when the delivery slip according to the present invention manufactured as described above is irradiated with a laser beam from one side as described above, the laser beam is -The laser beam irradiation coloring resin layer is reached, the laser beam irradiation coloring resin layer of the portion absorbs the energy of the laser beam, and the laser beam irradiation portion is carbonized. Black color development or white color development by foaming, for example, can be used to form a laser-printed image consisting of letters, numbers, symbols, designs, etc. very clearly. This makes it possible to manufacture delivery slips with added values such as prevention of product counterfeiting, prevention of alteration, etc., and various functions can be enhanced thereby.

It is a schematic plan view which shows an example of the structure about the delivery slip which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the delivery slip which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the delivery slip which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the delivery slip which concerns on this invention. An example of the layer structure of a delivery slip recording body using the delivery slip according to the present invention shown in FIG. 3 and irradiating a laser beam to form a laser print image is shown. It is a schematic sectional drawing.

Explanation of symbols

A, A ₁ , A ₂ Delivery slip 1 Sheet 1 sheet
2 Perforated line for cutting 3 Delivery slip 4 Receipt slip 5 Receipt slip 6 Other required XX slip 11 Release paper 12 Adhesive layer 13 Delivery slip base material 14 Paper base material 15 Laser beam irradiation color resin layer 16 16a Surface protective layer 17 Laser beam 18 Laser print image

Claims (7)

A temporary delivery slip base material is temporarily attached to the release paper via an adhesive layer, and the delivery slip base material is made of resin on one side of the paper base material with a resin as a vehicle. Resin comprising a color former that develops color by irradiation with laser light, and the content of the color former that develops color by irradiation with laser light is 0.01% to 50.0% by weight based on the resin The composition is provided with a laser beam irradiation color developing resin layer, and the surface of the paper base material is temporarily attached to the surface of the pressure-sensitive adhesive layer. Voucher. 2. The laser beam irradiation color developing resin layer according to claim 1, further comprising a surface protective layer made of a resin composition containing resin as a main component on one or both sides thereof. Delivery slip to be done. Paper substrate, shipping documents described in any one of the above claims 1-2, characterized in that a paper substrate made from a range of basis weight ^{20g / m 2 ~300g / m 2} . Resin is low density polyethylene (LDPE), linear (linear) low density polyethylene (polymer polymerized using multisite catalyst, LLDPE), ethylene polymerized using metallocene catalyst (single site catalyst) -Α-olefin copolymer, medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene resin, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene- Methacrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, polyvinyl chloride resin, polystyrene resin, polycarbonate resin, thermoplastic polyester resin, or The above-mentioned claim characterized by comprising a thermoplastic polyamide-based resin. Shipping documents as described in any one of to 3. The delivery slip according to any one of claims 1 to 4, wherein the color former that develops color by laser light irradiation comprises one or more of pigments or clays. . 6. The delivery according to any one of claims 1 to 5, wherein the content of the color former that develops color by laser beam irradiation is 1.0 to 10.0% by weight. Slip. The delivery slip according to any one of claims 1 to 6, wherein the laser beam irradiation coloring resin layer has a thickness of 1 µm to 50 µm.

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