JP2015091647A - Marking method, laser transfer film, ink composition, edible material as object to be transferred with mark applied and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a marking method that utilizes the transfer of a coloring component by irradiation with a laser beam and is applicable to marking of an edible material, to provide a laser transfer film that has a transfer layer for use in the marking method, to provide an ink composition for forming a transfer layer of the laser transfer film, to provide a method for producing a marked edible material as an object to be transferred by using the laser transfer film and to provide a marked edible material as an object to be transferred that is produced by the production method.SOLUTION: Marking is applied to an edible material as an object to be transferred by disposing a laser transfer film 1 having a substrate 11 and a transfer layer 12 in this order so as to direct the transfer layer 12 toward the side of an edible material as an object to be transferred, irradiating the laser transfer film 1 with a laser beam from the side of the substrate 11, and transferring at least a part of the transfer layer 12 to the edible material as an object to be transferred. The transfer layer 12 contains a polymer and a coloring component acceptable for blending with the edible material and is formed by using an ink composition containing the polymer, the coloring component and a solvent or a dispersion medium.

Description

  The present invention relates to a novel marking method using laser transfer, a laser transfer film provided with a transfer layer for use in the marking method, an ink composition for forming a transfer layer of the laser transfer film, and the laser transfer film The present invention relates to a method for producing a transfer target edible with a mark, and a transfer target edible with a mark manufactured by the manufacturing method.

Medicine (especially tablets and capsules) is marked (printed) for identification, and conventionally transfer printing using an ink composition and a rubber roller or the like has been performed. However, this method has a problem in that a desired product may be generated because desired marking cannot be performed due to ink splashing.
In addition, as a marking method using an ink composition, an ink-jet printing method has been developed. However, since a water-soluble dye is used, the light resistance of the marking image is insufficient, Therefore, there is a problem that the marking image may become unclear.

  On the other hand, as a method for solving such problems, a method for marking a composition for oral administration using laser light irradiation has been disclosed (see Patent Document 1). In this method, a discoloration-inducing oxide such as titanium oxide or iron oxide is previously contained in the composition for oral administration, and the surface of the composition for oral administration is scanned with laser light to aggregate the discoloration-inducing oxide. By inducing, discoloration is induced and marking is performed. However, this method requires a discoloration-inducing oxide separately and cannot be marked without using them, and the marking color is limited to gray or black.

  On the other hand, as a transfer method using laser light irradiation, a method using transfer of image components is disclosed (see Patent Document 2). In this method, using a donor sheet having a photothermal conversion layer and a transfer layer in this order on a substrate, the transfer layer is closely adhered to the surface of the object and superimposed, and laser light is irradiated from the substrate side of the donor sheet. Then, the component in the transfer layer at the corresponding site is melted by heat generation in the photothermal conversion layer, and this is transferred to the object.

  However, the method described in Patent Document 2 is limited to the manufacture of partition members such as separation ribs of color filters, black matrices of liquid crystal display devices, and partition walls of organic EL elements.

International Publication No. 2006/126561 JP 2001-130141 A

  The present invention has been made in view of the above circumstances, and includes a marking method applicable to edible marking using transfer of colored components by laser light irradiation, and a transfer layer for use in the marking method. A laser transfer film, an ink composition for forming a transfer layer of the laser transfer film, a method for producing an edible transfer target food using the laser transfer film, and the production method, It is an object of the present invention to provide a transfer target edible product that is marked.

In order to solve the above problems, in the first aspect of the present invention,
[1] A marking method for marking edible food to be transferred using a laser transfer film having a substrate and a transfer layer in this order, the transfer layer including a polymer and a coloring component that can be edible. The laser transfer film is arranged with the transfer layer facing the edible side to be transferred, and the laser transfer film is irradiated with laser light from the substrate side, and at least a part of the transfer layer is transferred to the transfer target Marking the transferable edible by transferring to edible, marking method,
[2] The marking method according to [1], wherein the polymer is at least one selected from the group consisting of a water-soluble polymer, a gastric soluble polymer, an enteric polymer, and a sustained-release polymer.
[3] The polymer is hydroxypropylcellulose, polyvinylpyrrolidone, copolypydone, hydroxypropylmethylcellulose, methylcellulose, polyvinyl alcohol / polyethylene glycol copolymer, polyvinyl alcohol, polyvinyl alcohol / acrylic acid / methyl methacrylate copolymer, aminoalkyl. One selected from the group consisting of methacrylate copolymer E, polyvinyl acetal diethylaminoacetate, methacrylic acid copolymer L, hydroxypropylmethylcellulose acetate succinate, carboxymethylethylcellulose, ethylcellulose, aminoalkyl methacrylate copolymer RS and ethyl acrylate / methyl methacrylate copolymer The marking method according to [1],
[4] The coloring component according to any one of [1] to [3], wherein the coloring component is insoluble or an insoluble coloring component whose amount of a polar solvent required to dissolve 1 g thereof is 100 mL or more. Marking method,
[5] The insoluble or insoluble coloring component is yellow iron sesquioxide, iron sesquioxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate. , Titanium oxide, red 40 aluminum lake, red 3 aluminum lake, blue 1 aluminum lake, blue 2 aluminum lake, yellow 5 aluminum lake, yellow 4 aluminum lake, riboflavin, β-carotene, carmine and carbon black The marking method according to [4], which is one or more selected from the group consisting of:
[6] The marking method according to any one of [1] to [3], wherein the coloring component is a readily soluble coloring component whose amount of polar solvent required to dissolve 1 g thereof is less than 100 mL. ,
[7] The readily soluble coloring component is red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red 40 No., Red 104, Red 105, Red 106, Green 3, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment and Blue No. 2 The marking method according to [6], which is one or more selected.
[8] The marking method according to any one of [4] to [7], wherein the polar solvent is one or more solvents selected from water, ethanol and acetone.
[9] The colored components are yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, yellow No. 4, blue No. 1, blue No. 2, titanium oxide, yellow iron sesquioxide, iron sesquioxide, red No. 2, red 3 No., Red No. 40, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Green No. 3, Red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Caramel dye, gardenia dye, anthocyanin dye, anato dye, paprika dye, safflower dye, safflower dye, flavonoid dye, cochineal dye, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, Aluminum stearate, barium sulfate, carbon [1] to [3], which is one or more selected from the group consisting of lac, carmine, β-carotene, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, riboflavin and riboflavin butyrate The marking method described,
[10] The colored component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, titanium oxide, red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Yellow No. 5 Aluminum Lake, Yellow No. 4 Aluminum Lake, Riboflavin, β-Carotene, Carmine and Carbon Black The marking method according to [9],
[11] The coloring component is red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, Selected from the group consisting of Red No. 104, Red No. 105, Red No. 106, Green No. 3, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment and Blue No. 2 The marking method according to [9],
[12] The marking method according to any one of [1] to [11], wherein the transfer layer further contains a plasticizer.
[13] The marking method according to [12], wherein the plasticizer is at least one selected from the group consisting of triserine, glycerin fatty acid ester, sucrose fatty acid ester, triethyl citrate, polyethylene glycol and higher alcohol.
[14] The base material is cellulose, ionomer, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene-vinyl alcohol copolymer. The marking method according to any one of [1] to [13], comprising one or more selected from the group consisting of ethylene-methacrylic acid copolymer and nylon,
[15] The marking method according to any one of [1] to [14], wherein the laser transfer film is disposed without being brought into contact with the edible food to be transferred.
[16] The marking method according to any one of [1] to [15], wherein the edible food to be transferred is a pharmaceutical, and the edible is a pharmaceutical.
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In the second aspect of the present invention,
[17] A laser transfer film comprising a base material and a transfer layer in this order, wherein the transfer layer contains a edible polymer and a coloring component,
[18] The laser transfer film according to [17], wherein the polymer is at least one selected from the group consisting of a water-soluble polymer, a gastric soluble polymer, an enteric polymer, and a sustained-release polymer. ,
[19] The polymer is hydroxypropylcellulose, polyvinylpyrrolidone, copolypydone, hydroxypropylmethylcellulose, methylcellulose, polyvinyl alcohol / polyethylene glycol copolymer, polyvinyl alcohol, polyvinyl alcohol / acrylic acid / methyl methacrylate copolymer, aminoalkyl. One selected from the group consisting of methacrylate copolymer E, polyvinyl acetal diethylaminoacetate, methacrylic acid copolymer L, hydroxypropylmethylcellulose acetate succinate, carboxymethylethylcellulose, ethylcellulose, aminoalkyl methacrylate copolymer RS and ethyl acrylate / methyl methacrylate copolymer The laser transfer film according to [17]. Lum,
[20] The coloring component according to any one of [17] to [19], wherein the coloring component is insoluble or an insoluble coloring component having an amount of a polar solvent required to dissolve 1 g thereof is 100 mL or more. Laser transfer film,
[21] The insoluble or insoluble soluble coloring component is yellow ferric oxide, ferric trioxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate , Titanium oxide, red 40 aluminum lake, red 3 aluminum lake, blue 1 aluminum lake, blue 2 aluminum lake, yellow 5 aluminum lake, yellow 4 aluminum lake, riboflavin, β-carotene, carmine and carbon black The laser transfer film according to [20], which is at least one selected from the group consisting of:
[22] The laser transfer according to any one of [17] to [19], wherein the coloring component is a readily soluble coloring component whose amount of polar solvent required to dissolve 1 g thereof is less than 100 mL. the film,
[23] The readily soluble coloring component is red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red 40 No., Red 104, Red 105, Red 106, Green 3, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment and Blue No. 2 The laser transfer film according to [22], which is one or more selected.
[24] The laser transfer film according to any one of [20] to [23], wherein the polar solvent is one or more solvents selected from water, ethanol and acetone.
[25] The coloring component is yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, yellow No. 4, blue No. 1, blue No. 2, titanium oxide, yellow iron sesquioxide, iron sesquioxide, red No. 2, red 3 No., Red No. 40, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Green No. 3, Red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Caramel dye, gardenia dye, anthocyanin dye, anato dye, paprika dye, safflower dye, safflower dye, flavonoid dye, cochineal dye, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, Aluminum stearate, barium sulfate, carbo [17] to [19], which is one or more selected from the group consisting of black, carmine, β-carotene, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, riboflavin and riboflavin butyrate The laser transfer film as described,
[26] The coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, titanium oxide, red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Yellow No. 5 Aluminum Lake, Yellow No. 4 Aluminum Lake, Riboflavin, β-Carotene, Carmine and Carbon Black One or more of the laser transfer films according to [25],
[27] The coloring component is red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, Selected from the group consisting of Red No. 104, Red No. 105, Red No. 106, Green No. 3, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment and Blue No. 2 1 or more types, The laser transfer film as described in [25],
[28] The laser transfer film according to any one of [17] to [27], wherein the transfer layer further contains a plasticizer.
[29] The laser transfer film according to [28], wherein the plasticizer is at least one selected from the group consisting of triserine, glycerin fatty acid ester, sucrose fatty acid ester, triethyl citrate, polyethylene glycol, and higher alcohol. ,
[30] The base material is cellulose, ionomer, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene-vinyl alcohol copolymer. The laser transfer film according to any one of [17] to [29], comprising at least one selected from the group consisting of ethylene-methacrylic acid copolymer and nylon,
[31] The laser transfer film according to any one of [17] to [30], wherein the edible material is a medicine.
I will provide a.

In the third aspect of the present invention,
[32] An ink composition for forming the transfer layer in a laser transfer film provided with a substrate and a transfer layer in this order, which contains a polymer and a coloring component that can be blended with edible foods, and a solvent or dispersion medium , Ink compositions,
[33] The ink composition according to [32], wherein the polymer is at least one selected from the group consisting of a water-soluble polymer, a gastric soluble polymer, an enteric polymer, and a sustained-release polymer. ,
[34] The polymer is hydroxypropylcellulose, polyvinylpyrrolidone, copolypydone, hydroxypropylmethylcellulose, methylcellulose, polyvinyl alcohol / polyethylene glycol copolymer, polyvinyl alcohol, polyvinyl alcohol / acrylic acid / methyl methacrylate copolymer, aminoalkyl. One selected from the group consisting of methacrylate copolymer E, polyvinyl acetal diethylaminoacetate, methacrylic acid copolymer L, hydroxypropylmethylcellulose acetate succinate, carboxymethylethylcellulose, ethylcellulose, aminoalkyl methacrylate copolymer RS and ethyl acrylate / methyl methacrylate copolymer The ink composition according to [32], wherein
[35] The coloring component according to any one of [32] to [34], wherein the coloring component is insoluble or an insoluble coloring component having an amount of a polar solvent required to dissolve 1 g thereof is 100 mL or more. Ink composition,
[36] The insoluble or insoluble soluble coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate , Titanium oxide, red 40 aluminum lake, red 3 aluminum lake, blue 1 aluminum lake, blue 2 aluminum lake, yellow 5 aluminum lake, yellow 4 aluminum lake, riboflavin, β-carotene, carmine and carbon black The ink composition according to [35], which is at least one selected from the group consisting of:
[37] The ink composition according to any one of [32] to [34], wherein the coloring component is a readily soluble coloring component whose amount of polar solvent required to dissolve 1 g thereof is less than 100 mL. object,
[38] The readily soluble coloring component is red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red 40 No., Red No. 104, Red No. 105, Red No. 106, Green No. 3, Gardenia Dye, Anthocyanin Dye, Anato Dye, Paprika Dye, Safflower Dye, Scarlet Dye, Flavonoid Dye, Cochineal Dye and Blue No. 2 [1] the ink composition according to [37], which is one or more selected.
[39] The ink composition according to any one of [35] to [38], wherein the polar solvent is one or more solvents selected from water, ethanol and acetone.
[40] The coloring component is yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, yellow No. 4, blue No. 1, blue No. 2, titanium oxide, yellow iron sesquioxide, iron sesquioxide, red No. 2, red 3 No., Red No. 40, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Green No. 3, Red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Caramel dye, gardenia dye, anthocyanin dye, anato dye, paprika dye, safflower dye, safflower dye, flavonoid dye, cochineal dye, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, Aluminum stearate, barium sulfate, carbo In any one of [32] to [34], which is at least one selected from the group consisting of black, carmine, β-carotene, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, riboflavin and riboflavin butyrate The ink composition according to the description,
[41] The coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, titanium oxide, red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Yellow No. 5 Aluminum Lake, Yellow No. 4 Aluminum Lake, Riboflavin, β-Carotene, Carmine and Carbon Black The ink composition according to [40], which is one or more of
[42] The coloring component is red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, Selected from the group consisting of Red No. 104, Red No. 105, Red No. 106, Green No. 3, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment and Blue No. 2 1 or more types of the ink composition as described in [40],
[43] The ink composition according to any one of [32] to [42], further comprising a plasticizer,
[44] The ink composition according to [43], wherein the plasticizer is at least one selected from the group consisting of triserine, glycerin fatty acid ester, sucrose fatty acid ester, triethyl citrate, polyethylene glycol, and higher alcohol. ,
[45] The ink composition according to any one of [32] to [44], wherein the edible material is a medicine.
I will provide a.

In the fourth aspect of the present invention,
[46] A method for producing a transfer target edible with a mark, wherein a laser transfer film including a base material and a transfer layer in this order is disposed with the transfer layer facing the transfer target edible side, Irradiating the laser transfer film with laser light from the substrate side and transferring at least a part of the transfer layer to the transfer target edible, thereby marking the transfer target edible, A production method, wherein the layer comprises a polymer that can be edible and a coloring component;
[47] The production method according to [46], wherein the polymer is one or more selected from the group consisting of a water-soluble polymer, a gastric soluble polymer, an enteric polymer, and a sustained-release polymer.
[48] The polymer is hydroxypropylcellulose, polyvinylpyrrolidone, copolypydone, hydroxypropylmethylcellulose, methylcellulose, polyvinyl alcohol / polyethylene glycol copolymer, polyvinyl alcohol, polyvinyl alcohol / acrylic acid / methyl methacrylate copolymer, aminoalkyl. One selected from the group consisting of methacrylate copolymer E, polyvinyl acetal diethylaminoacetate, methacrylic acid copolymer L, hydroxypropylmethylcellulose acetate succinate, carboxymethylethylcellulose, ethylcellulose, aminoalkyl methacrylate copolymer RS, and ethyl acrylate / methyl methacrylate copolymer The production method according to [46],
[49] [46] to [48], wherein the coloring component is an insoluble or insoluble coloring component in which the amount of a polar solvent required to dissolve 1 g thereof is 100 mL or more. Manufacturing method,
[50] The insoluble or insoluble soluble coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate , Titanium oxide, red 40 aluminum lake, red 3 aluminum lake, blue 1 aluminum lake, blue 2 aluminum lake, yellow 5 aluminum lake, yellow 4 aluminum lake, riboflavin, β-carotene, carmine and carbon black The production method according to [49], which is one or more selected from the group consisting of:
[51] The production method according to any one of [46] to [48], wherein the coloring component is a readily soluble coloring component whose amount of polar solvent required to dissolve 1 g thereof is less than 100 mL. ,
[52] The readily soluble coloring component is red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red 40 No., Red 104, Red 105, Red 106, Green 3, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment and Blue No. 2 The production method according to [51], which is one or more selected.
[53] The production method according to any one of [49] to [52], wherein the polar solvent is one or more solvents selected from water, ethanol and acetone.
[54] The coloring component is yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, yellow No. 4, blue No. 1, blue No. 2, titanium oxide, yellow iron sesquioxide, iron sesquioxide, red No. 2, red 3 No., Red No. 40, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Green No. 3, Red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Caramel dye, gardenia dye, anthocyanin dye, anato dye, paprika dye, safflower dye, safflower dye, flavonoid dye, cochineal dye, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, Aluminum stearate, barium sulfate, carbo [46] to [48], which is one or more selected from the group consisting of black, carmine, β-carotene, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, riboflavin and riboflavin butyrate The manufacturing method described,
[55] The coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, titanium oxide, red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Yellow No. 5 Aluminum Lake, Yellow No. 4 Aluminum Lake, Riboflavin, β-Carotene, Carmine and Carbon Black The production method according to [54], which is one or more selected from the group consisting of:
[56] The coloring component is red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, Selected from the group consisting of Red No. 104, Red No. 105, Red No. 106, Green No. 3, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment and Blue No. 2 The production method according to [54], which is one or more of
[57] The production method according to any one of [46] to [56], wherein the transfer layer further contains a plasticizer.
[58] The production method according to [57], wherein the plasticizer is one or more selected from the group consisting of triserine, glycerin fatty acid ester, sucrose fatty acid ester, triethyl citrate, polyethylene glycol and higher alcohol.
[59] The base material is cellulose, ionomer, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene-vinyl alcohol copolymer. The production method according to any one of [46] to [58], comprising one or more selected from the group consisting of ethylene-methacrylic acid copolymer and nylon,
[60] The production method according to any one of [46] to [59], wherein the laser transfer film is disposed without contacting the edible food to be transferred,
[61] The production method according to any one of [46] to [60], wherein the edible food to be transferred is a pharmaceutical, and the edible is a pharmaceutical.
I will provide a.

In the fifth aspect of the present invention,
[62] [46] to [61] produced by the production method according to any one of [61], a transfer target edible with a mark,
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  According to the present invention, a marking method applicable to edible marking using transfer of a colored component by laser light irradiation, a laser transfer film provided with a transfer layer for use in the marking method, and the laser transfer film Ink composition for forming a transfer layer of the present invention, a method for producing a edible transfer target edible product using the laser transfer film, and a edible transfer target edible product produced by the production method Is provided.

It is a schematic sectional drawing which illustrates the laser transfer film concerning this invention. It is a schematic sectional drawing for demonstrating an example of the marking method which concerns on this invention. It is a schematic sectional drawing which illustrates other arrangement forms of a laser transfer film in the marking method concerning the present invention. It is a schematic sectional drawing which illustrates other arrangement forms of a laser transfer film in the marking method concerning the present invention. It is a schematic block diagram which illustrates typically the principal part of the marking apparatus suitable for using with the marking method which concerns on this invention. It is the imaging data of the tablet after the marking in Example 1. It is the imaging data of the tablet after marking in Example 2. It is the imaging data of the tablet after the marking in Example 3. It is the imaging data of the tablet after marking in Example 4. It is the imaging data of the tablet after marking in Example 5. It is the imaging data of the tablet after marking in Example 6. It is the imaging data of the tablet after marking in Example 7. It is the imaging data of the tablet after the marking in Example 8. It is the imaging data of the tablet after the marking in Example 9. It is the imaging data of the tablet after marking in Example 10. It is the imaging data of the tablet after the marking in Example 11. It is the imaging data of the tablet after the marking in Example 12. It is the imaging data of the tablet after marking in Example 13. It is the imaging data of the tablet after marking in Example 14. It is the imaging data of the tablet after marking in Example 15. It is the imaging data of the tablet after marking in Example 16. 19 is imaging data of a tablet after marking in Example 17. It is the imaging data of the tablet after marking in Example 18. It is the imaging data of the tablet after marking in Example 19. It is the imaging data of the tablet after marking in Example 20. FIG. It is the imaging data of the tablet after marking in Example 21. It is the imaging data of the tablet after marking in Example 22. It is an imaging data of the tablet after marking in Examples 23-30 and Comparative Example 1. It is an imaging data of the tablet after marking in Examples 31-38 and Comparative Example 1. It is the imaging data of the tablet after the marking in Examples 39-46 and Comparative Example 1. It is an imaging data of the tablet after marking in Examples 47-53 and comparative example 2. It is the imaging data of the tablet after the marking in Examples 54-61 and Comparative Example 2. It is an imaging data of the tablet after marking in Examples 62-69 and comparative example 2.

The present invention relates to a marking method for marking edible food to be transferred using a laser transfer film provided with a substrate and a transfer layer in this order.
In the present specification, “edible for transfer” means edible to be transferred, that is, marking of at least a part of the transfer layer, and any one can be selected according to the purpose. Pharmaceuticals or foods are preferred, and pharmaceuticals are particularly preferred.
In the present specification, “edible” means a solid substance that is orally ingested, and is not particularly limited as long as it has a certain shape and can be orally ingested, unlike liquid and powdered ones. In the present invention, any edible food can be selected according to the purpose, but a medicine or food is preferred, and a medicine is particularly preferred.
In the present specification, the “transfer layer” means a layer at least a part of which is transferred to edible food by laser irradiation, and can be formed using the ink composition according to the present invention. .

<Ink composition>
The ink composition according to the present invention is an ink composition for forming the transfer layer in a laser transfer film provided with a substrate and a transfer layer in this order, and a polymer and a coloring component (hereinafter, referred to as edible). Each of which is simply abbreviated as “polymer” or “coloring component”), and a solvent or dispersion medium. As the transfer layer, a layer for transferring to edible food to be transferred by laser light irradiation is suitable.

  As used herein, “can be formulated into edible” means that it does not cause significant harm when ingested by the body, such as pharmaceutically acceptable and hygiene in particular. Those that are acceptable are preferable, and those that are pharmaceutically acceptable are more preferable. Examples of pharmacologically acceptable ones include those listed in the pharmaceutical additive standards. As what can be accepted in terms of hygiene, those listed in the food additive standards can be exemplified. The pharmaceutical additive standard and the food additive standard may be any version.

(High molecular)
The polymer may be any one having solubility in a solvent and dispersibility in a dispersion medium, as long as it can be blended edible, solubility in a solvent and dispersibility in a dispersion medium. It may have both.
In the present specification, the “polymer” means a polymer having a molecular size larger than that of the oligomer, and the weight average molecular weight is 1000 to 1,000,000.
The glass transition temperature (Tg) of the polymer is −50 to 500 ° C.
The viscosity of the 2% polymer-containing liquid at 20 ° C. is 0.1 to 500,000 mPa · s.

  The said polymer may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

The polymer may be either a natural product-derived component or a chemically synthesized component, and can be arbitrarily selected according to the purpose. In the present specification, “derived from a natural product” means that it is a natural product or obtained by subjecting a natural product to a chemical treatment other than a synthetic reaction. (Weight average molecular weight 2,000) and the like.
The polymer is preferably one that can be blended with a medicine, and more preferably it is not blended with anything other than a medicine such as food, that is, one that is blended only with a medicine.

  Preferred examples of the polymer include water-soluble polymers, gastric polymers, enteric polymers, and sustained-release polymers.

The water-soluble polymer is a polymer that exhibits water-solubility regardless of pH, and preferred examples include cellulose derivatives, polyvinyl pyrrolidone, copolypydone (Collidon VA64), polyvinyl alcohol / polyethylene glycol copolymer, polyvinyl alcohol, and polyvinyl alcohol. Examples thereof include alcohol / acrylic acid / methyl methacrylate copolymers.
In the present specification, the “cellulose derivative” means one in which one or more hydrogen atoms in cellulose are substituted with a substituent other than a hydrogen atom.
Preferred examples of the cellulose derivative in the water-soluble polymer include hydroxyalkyl celluloses such as hydroxypropyl cellulose; hydroxyalkylalkyl celluloses such as hydroxypropylmethyl cellulose; alkyl celluloses such as methyl cellulose. Examples of hydroxypropylcellulose include HPC-H (hydroxypropylcellulose, Nippon Soda Co., Ltd., weight average molecular weight: 910,000) in addition to HPC-L, HPC-SL, and HPC-SSL used in Examples described later. Viscosity at 20 ° C./2% solution: 1,000 to 4,000 mPa · s), HPC-M (hydroxypropylcellulose, Nippon Soda Co., Ltd., weight average molecular weight: 620,000, at 20 ° C./2% solution The water-soluble polymer may be at least one selected from the group consisting of hydroxypropylcellulose, polyvinylpyrrolidone, copolypydone, hydroxypropylmethylcellulose, and methylcellulose. preferable.

The gastric polymer is a polymer that can be dissolved under acidic conditions, preferably at a pH of 3 or lower, and preferred examples include aminoalkyl (meth) acrylate copolymers and polyvinyl acetal diethylaminoacetate.
In this specification, “(meth) acrylate” is a concept including acrylate and methacrylate.
The gastric polymer is preferably at least one selected from the group consisting of aminoalkyl methacrylate copolymer E (Eudragit E100, Eudragit EPO) and polyvinyl acetal diethylaminoacetate (AEA).

The enteric polymer is a polymer that can be dissolved at a pH of 5 or more, preferably in the neutral range, and examples thereof include cellulose derivatives, (meth) acrylic acid copolymers, carboxyalkyl cellulose, shellac and the like.
In this specification, “(meth) acrylic acid” is a concept including acrylic acid and methacrylic acid.
Preferred examples of the cellulose derivative in the enteric polymer include hydroxyalkylalkylcellulose acetate succinates such as hydroxypropylmethylcellulose acetate succinate (Shin-Etsu AQOAT (registered trademark)).
Preferred examples of the carboxyalkyl cellulose include carboxymethyl ethyl cellulose (CMEC).
The enteric polymer is preferably at least one selected from the group consisting of methacrylic acid copolymer L, hydroxypropylmethylcellulose acetate succinate and carboxymethylethylcellulose.

The sustained-release polymer is a polymer that does not exhibit water solubility regardless of pH (water-insoluble), and preferred examples include cellulose derivatives, aminoalkyl (meth) acrylate copolymers, (meth) acrylate copolymers, and the like. it can.
Preferred examples of the cellulose derivative in the sustained-release polymer include alkyl celluloses such as ethyl cellulose.
Preferred examples of the (meth) acrylate copolymer include an ethyl acrylate / methyl methacrylate copolymer.
The sustained-release polymer is one selected from the group consisting of ethyl cellulose, aminoalkyl methacrylate copolymer RS (Eudragit RL100, Eudragit RLPO, Eudragit RL30D, Eudragit RS100) and ethyl acrylate / methyl methacrylate copolymer (Eudragit NE30D). The above is preferable.

  The polymer is preferably at least one selected from the group consisting of a water-soluble polymer, a gastric polymer, an enteric polymer, and a sustained-release polymer. Hydroxypropyl cellulose, polyvinyl pyrrolidone, copolypydone, Hydroxypropyl methylcellulose, methylcellulose, polyvinyl alcohol / polyethylene glycol copolymer, polyvinyl alcohol, polyvinyl alcohol / acrylic acid / methyl methacrylate copolymer, aminoalkyl methacrylate copolymer E, polyvinyl acetal diethylaminoacetate, methacrylic acid copolymer L, hydroxypropyl methylcellulose Acetate succinate, carboxymethyl ethyl cellulose, ethyl cellulose, aminoalkyl methacrylate copolymer RS and ethyl acrylate - and more preferably from the group consisting of methyl methacrylate copolymer is at least one selected.

  In the ink composition, the content (blending amount) of the polymer with respect to the total amount of components other than the solvent and the dispersion medium is preferably 0.1 to 95% by mass, and more preferably 10 to 90% by mass. More preferably, it is 20-80 mass%, More preferably, it is 30-70 mass%, Most preferably, it is 35-65 mass%.

(Coloring ingredients)
The coloring component can be blended with edible food, and can be arbitrarily selected according to the purpose as long as it can color the edible food to be transferred. The colored component may be a colored component that itself exhibits a specific hue, such as a pigment, for example, by performing some treatment such as laser irradiation while itself is colorless and transparent, It may be a component that is not colorless and transparent (has a specific hue).

  The coloring components may be used alone or in combination of two or more, and when two or more are used in combination, their combination and ratio can be arbitrarily selected.

  As the coloring component, yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, yellow No. 4, blue No. 1, blue No. 2, titanium oxide, yellow iron sesquioxide, iron sesquioxide, red No. 2, red No. 3, Red No. 40, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Green No. 3, Red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Caramel Color Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment, Talc, Calcium carbonate, Magnesium carbonate, Magnesium oxide, Magnesium stearate, Calcium stearate, Zinc stearate Aluminum, barium sulfate, carbon Rack, carmine, beta-carotene, Yellow No. 5, sodium copper chlorophyllin, copper chlorophyll, riboflavin, riboflavin butyrate can be exemplified.

  The coloring components are yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, blue No. 2, titanium oxide, yellow ferric oxide, ferric oxide, red No. 2, red No. 3, talc, calcium carbonate, magnesium carbonate, oxidized One or more selected from the group consisting of magnesium, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate and barium sulfate are preferred.

The coloring component has a preferable combination with the polymer to be used depending on the degree of solubility in the solvent.
For example, the coloring component is insoluble or the amount of polar solvent required to dissolve 1 g of the polar solvent is 100 mL or more and the amount of polar solvent required to dissolve 1 g of the coloring component is 100 mL. It can be classified into less than easily soluble coloring components. Here, the temperature when the coloring component is dissolved in the polar solvent is 15 to 25 ° C. In addition, when dissolving the coloring component in a polar solvent, use a powdered coloring component, shake vigorously for 30 seconds every 5 minutes at the temperature, and check whether it dissolves in the polar solvent within 30 minutes. Is preferred. In the present specification, “the coloring component is insoluble” means that the coloring component is not dissolved in the solvent.
When the said insoluble or insoluble soluble coloring component is used, the marking given to edible becomes more difficult to discolor. Moreover, when the said easily soluble coloring component is used, the marking given to edible becomes clearer.

The polar solvent used for classification of the coloring component is a solvent having a large dipole moment. For example, if it is an organic solvent other than water, the mixture can be made homogeneous when mixed with water. A solvent is mentioned. More specifically, examples of the polar solvent include water; alcohols such as ethanol and 2-propanol; carboxylic acid esters such as ethyl acetate; ketones such as acetone; N, N-dimethylformamide, N, N-dimethylacetamide and the like. Amides; sulfoxides such as dimethyl sulfoxide can be exemplified.
The polar solvent is preferably one or more solvents selected from water, ethanol and acetone.

  The insoluble or insoluble soluble coloring components include yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, oxidation Examples include titanium, red No. 40 aluminum lake, red No. 3 aluminum lake, blue No. 1 aluminum lake, blue No. 2 aluminum lake, yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, riboflavin, β-carotene, carmine, and carbon black. it can.

  When using an insoluble or insoluble coloring component, such as when the ink composition is in a state where a part or all of the coloring component is dispersed without being dissolved, the weight average molecular weight of the polymer to be used together Is preferably 3,000 or more, more preferably 10,000 or more, and particularly preferably 30,000 or more. Similarly, when an ink composition in which a part or all of the coloring component is dispersed without being dissolved is used, the polymer used together has a weight average molecular weight of 55,000 or less. Is preferred. When such an ink composition is used, the weight applied to the edible product becomes clearer when the weight average molecular weight of the polymer is in such a range.

Among the colored components, a colored component having at least one kind as the polar solvent whose amount required to dissolve 1 g thereof is less than 100 mL is classified as the readily soluble colored component.
As the easily soluble coloring component, Red No. 2, Red No. 3, Red No. 102, Blue No. 1, Yellow No. 4, Yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, Examples include Red No. 104, Red No. 105, Red No. 106, Green No. 3, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment, and Blue No. 2.

  When using an ink composition in which all the coloring components are dissolved, such as when using the readily soluble coloring component, the weight average molecular weight of the polymer used in combination is preferably 3,000 or more. It is more preferably 10,000 or more, and particularly preferably 30,000 or more. Similarly, when using an ink composition in which all coloring components are dissolved, the weight average molecular weight of the polymer used in combination is preferably 100,000 or less, and 80,000 or less. More preferably. When such an ink composition is used, the weight applied to the edible product becomes clearer when the weight average molecular weight of the polymer is in such a range.

  In the present invention, for example, the insoluble or insoluble coloring component and the easily soluble coloring component may be used in combination, and the effects when these coloring components are used may be combined in a well-balanced manner.

  In the ink composition, the content of the coloring component with respect to the total amount of components other than the solvent and the dispersion medium is preferably 0.1 to 95% by mass, more preferably 1 to 85% by mass, It is especially preferable that it is 80 mass%.

(Solvent, dispersion medium)
The solvent is for dissolving components other than the solvent and the dispersion medium in the ink composition, and the dispersion medium is for dispersing components other than the solvent and the dispersion medium in the ink composition. Any of these can be arbitrarily selected according to the purpose.
Preferred examples of the solvent or dispersion medium include an organic medium (organic solvent, organic dispersion medium) and water, and the organic medium is preferably a polar solvent or a polar medium that can be uniformly mixed with water. More preferable examples include alcohols such as ethanol and 2-propanol; ketones such as acetone.

  As the solvent and the dispersion medium, one kind may be used alone, two or more kinds may be used in combination, and when two or more kinds are used in combination, their combination and ratio can be arbitrarily selected.

  The total content of the solvent and the dispersion medium is preferably 0.1 to 95% by mass of the total amount of the ink composition.

(Plasticizer)
The ink composition may further contain a plasticizer in addition to the polymer, the coloring component, the solvent, and the dispersion medium. For example, when one or more of the polymer, the coloring component, the solvent, and the dispersion medium have a function as a plasticizer, it is not necessary to use a separate plasticizer, but the contained component has a function as a plasticizer. When there is nothing, it is preferable to further contain a plasticizer.

  The plasticizer is not particularly limited as long as it can impart plasticity to the transfer layer, which will be described later, and can be blended edible.

  The said plasticizer may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

Examples of the plasticizer include triserine; glycerin fatty acid ester; sucrose fatty acid ester; alkyl citrate such as triethyl citrate; polyalkylene glycol such as polyethylene glycol; and higher alcohols.
The fatty acid in the glycerin fatty acid ester and the sucrose fatty acid ester is a monocarboxylic acid having 2 or more carbon atoms, and may be any of those having an unsaturated bond and those not having an unsaturated bond. Preferred are octanoic acid, decanoic acid, lauric Examples thereof include acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and the like, and those having 12 or more carbon atoms are preferable.

  The higher alcohol is an aliphatic alcohol having 6 or more carbon atoms, and may be any of those having an unsaturated bond and those having no unsaturated bond, but is preferably a monohydric alcohol, octyl alcohol, decyl alcohol, lauryl alcohol, Examples include myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol and the like, and those having 12 or more carbon atoms are preferred.

  The plasticizer is preferably at least one selected from the group consisting of triserine, glycerin fatty acid ester, sucrose fatty acid ester, triethyl citrate, polyethylene glycol and higher alcohol.

  In the ink composition, the content of the plasticizer relative to the total amount of components other than the solvent and the dispersion medium is preferably 0.1 to 95% by mass, more preferably 1 to 70% by mass, It is especially preferable that it is 50 mass%.

(Other ingredients)
The ink composition may contain, in addition to the polymer, coloring component, solvent, dispersion medium and plasticizer, other components not corresponding to these.
The other components are preferably those that can be blended with edible foods, and can be arbitrarily selected depending on the purpose, but those that can be blended with pharmaceuticals are preferred, such as antiseptics and antioxidants. And various additives such as fragrances.

  As the other components, one kind may be used alone, two or more kinds may be used in combination, and when two or more kinds are used in combination, their combination and ratio can be arbitrarily selected.

  In the ink composition, the content of the other components with respect to the total amount of components other than the solvent and the dispersion medium is preferably 90% by mass or less.

  In the ink composition, the components other than the solvent and the dispersion medium are all preferably edible components, more preferably pharmaceutically acceptable components, and comply with the standard for pharmaceutical additives. More preferred are the listed components.

  The properties of the ink composition are not particularly limited as long as the transfer layer can be formed on the substrate in a uniform thickness and blended state. For example, the viscosity of the ink composition is 1 to 800,000 mPa · s. It is preferable.

<Method for producing ink composition>
The ink composition can be obtained by blending each component such as the polymer, coloring component, solvent or dispersion medium, and, if necessary, a plasticizer and other components. After the blending of the respective components, the obtained product may be used as it is, or the ink composition obtained by performing a known refining operation as necessary may be used as the ink composition.

  The blending method is not particularly limited, and the order of addition of each component, the mixing method after the addition, and the like can be arbitrarily adjusted. For example, the mixing method may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer, a bead mill, etc .; a method of mixing by applying ultrasonic waves, and the like. Good.

  In the ink composition, all the components may be dissolved, or a part of the components may be dispersed without being dissolved (suspended state). It is preferable that they are dispersed.

  The blending conditions are not particularly limited as long as each blended component does not deteriorate. For example, the temperature during mixing of each component is preferably 0 to 100 ° C., and the blending time is 1 minute to 1 week. preferable.

<Laser transfer film>
The laser transfer film according to the present invention includes a base material and a transfer layer in this order, and the transfer layer includes a polymer and a coloring component that can be edible.

FIG. 1 is a schematic cross-sectional view illustrating a laser transfer film according to the present invention.
The laser transfer film 1 shown here is formed by laminating a transfer layer 12 on a substrate 11.

  It is preferable that the base material 11 is a film form or a sheet form, and it is preferable that the thickness is 0.1-10000 micrometers.

The substrate 11 may be composed of a single layer, or may be composed of two or more layers. When the base material 11 consists of multiple layers, these multiple layers may be the same as or different from each other. That is, all the layers may be the same, all the layers may be different, or only some of the layers may be different. And when several layers differ from each other, the combination of these several layers is not specifically limited. Here, the plurality of layers being different from each other means that at least one of the material and the thickness of each layer is different from each other.
In addition, when the base material 11 consists of multiple layers, it is good to make it the thickness of the total of each layer be the thickness of said preferable base material 11.

  The base material 11 should just have the translucency which can permeate | transmit the laser beam mentioned later, A natural product origin component and a synthetic resin can be illustrated as a preferable material.

Examples of the natural product-derived component include cellulose (cellophane).
Examples of the synthetic resin include ionomers, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polystyrene, polyacrylonitrile, ethylene vinyl acetate copolymer; Examples thereof include ethylene-vinyl alcohol copolymer; ethylene-methacrylic acid copolymer; nylon.

  The substrate 11 is made of cellulose, ionomer, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene- What consists of 1 or more types selected from the group which consists of a methacrylic acid copolymer and nylon is preferable.

  The material of the substrate 11 is preferably selected according to the type of solvent or dispersion medium in the ink composition to be used. For example, when the solvent or dispersion medium contains water or water, the substrate 11 is preferably made of a hydrophilic material such as cellulose or polyvinyl alcohol. Here, the “hydrophilic material” means a material having a hydrophilic group such as a hydroxyl group (—OH). By doing in this way, in the manufacturing method of the laser transfer film mentioned later, an ink composition can be made to adhere with high uniformity on the base material 11, and a laser transfer film of better quality is obtained.

  Since the transfer layer 12 is formed using the ink composition, the transfer layer 12 includes a coloring component that is a component of the composition, and the edible material to be transferred is at least part of the transfer layer by a method described later. Is transferred and marked.

  The transfer layer 12 may be formed on the entire surface of one main surface (surface) 11a of the substrate 11, or may be formed on a part of the surface, or may be formed on a part of the surface. In some cases, it may be patterned. When the transfer layer 12 is thus formed on a part of the surface, the shape of the transfer layer 12 when the laser transfer film 1 is viewed from the transfer layer 12 side can be arbitrarily set according to the purpose.

The thickness of the transfer layer 12 is preferably 0.1 to 100 mil (2.5 to 2540.0 μm), more preferably 0.1 to 50 mil (2.5 to 1270.0 μm), and 0 0.1 to 15 mil (2.5 to 381.0 μm) is more preferable, and 0.1 to 12 mil (2.5 to 304.8 μm) is particularly preferable.
In this specification, the unit “mil” is converted as 1 mil = 25.3999 μm.

  The transfer layer 12 may be composed of a single layer, or may be composed of two or more layers, as in the case of the base material 11, but even if it is composed of a single layer, a sufficient effect is usually obtained.

The laser transfer film according to the present invention is not limited to that shown in FIG. 1, and other configurations may be added or some configurations may be appropriately changed within a range not impairing the effects of the present invention.
For example, the laser transfer film may include a layer other than the transfer layer 12 between the base material 11 and the transfer layer 12 or on the transfer layer 12. Examples of other layers provided on the transfer layer 12 include a transfer promotion layer for promoting transfer of the transfer layer 12 (not shown). Similarly to the transfer layer 12, the other layers can be arbitrarily set in shape when the laser transfer film 1 is viewed from the transfer layer 12 side according to the purpose.

  In addition, the laser transfer film according to the present invention may be provided with, for example, a plurality of types of transfer layers formed on different substrates using different types of ink compositions. In this case, the plurality of types of transfer layers preferably have different hues. In this case, the number of types of the transfer layer may be appropriately selected according to the purpose, and is not particularly limited as long as it is two or more types.

  The laser transfer film according to the present invention essentially has a two-layer structure including the base material and the transfer layer. The laser transfer film according to the present invention has a very simple structure as described above, but can clearly and firmly mark the transfer target edible material described later, and has a high effect.

<Production method of laser transfer film>
The laser transfer film according to the present invention can be produced by a production method having a step of laminating a base material and a transfer layer (hereinafter sometimes abbreviated as “transfer layer forming step”).
For example, in the case of the laser transfer film 1 shown in FIG. 1, the transfer layer 12 can be formed by attaching the ink composition onto the substrate 11 and performing a drying process in the transfer layer forming step.

The ink composition can be deposited on the substrate 11 by a known method such as a printing method, a coating method, or a dipping method.
In the transfer layer forming step, the thickness of the transfer layer 12 can be adjusted by adjusting the amount of the ink composition deposited on the substrate 11 or the content of components other than the solvent and the dispersion medium in the ink composition. .

  The ink composition may be dried by a known method. For example, the ink composition may be dried under normal pressure, reduced pressure, or blowing conditions, or may be performed in the air or in an inert gas atmosphere.

<Marking method>
The marking method according to the present invention is a marking method for marking edible food to be transferred using a laser transfer film having a base material and a transfer layer in this order, and the transfer layer can be blended edible. And a coloring component, the laser transfer film is disposed with the transfer layer facing the edible food to be transferred, and the laser transfer film is irradiated with laser light from the substrate side, so that at least one of the transfer layers The transfer target edible is marked by transferring the portion to the transfer target edible. The above-described laser transfer film according to the present invention is used in such a marking method.

  In the marking method, when a laser transfer film having a transfer accelerating layer on the transfer layer as described above is used, in addition to the action of the polymer, the components in the transfer accelerating layer It is presumed that the coloring component is more firmly fixed to the transfer target edible food by the action.

  In the present invention, the mark is not particularly limited, and may be freely selected according to the design requirements of the user, but is preferably a mark having distinctiveness. The mark in this case is displayed on the target edible food in order to ensure the distinguishability from other edible foods (objects to be distinguished from the edible food to be transferred) depending on the description. . The mark attached by the marking method is characterized by a higher degree of design freedom than the mark attached by the conventional method. The design of the mark is not particularly limited, and can be configured by combining letters, numbers, figures, symbols, or the like alone or in combination of two or more. For example, product name, product abbreviation, company emblem or logo mark of the sales company, or various codes used in medicine, such as Japan standard product classification number, efficacy classification number, drug price listed drug code, unified product code, etc. It can be used as a mark.

  The edible food to be transferred may be a molded product, and the type thereof is not particularly limited. If it is a medicine, it may be a coloring agent (according to the present invention) together with a drug, a corrigent or other additives described later. Examples thereof include those formed by using a mixture containing a coloring component used independently of the coloring component used in the ink composition. The molded product is not particularly limited as long as it has a certain shape, unlike a powdered one. For example, if it is a pharmaceutical, a V-type mixer (Tokuju Kogyo Co., Ltd. Drugs obtained with Nipowdal Co., Ltd., Dalton Co., Ltd., tumbler mixers (Dalton Co., Ltd., Daiko Seiki Co., Ltd.) Solvent such as water by compressing the powdery or granular mixture containing it by compression molding with a tableting machine such as a single tableting machine, rotary tableting machine, dry tableting machine, etc., or using a molding machine It is obtained by filling the mold with the suspension or slurry dispersed in the mold and drying the solvent. Specific examples of the molded product include, but are not limited to, so-called naked tablets, intraoral quick disintegrating tablets, troches, chewables, pills and the like that can be easily understood by those skilled in the art. Examples of other specific forms of the molded product include, but are not limited to, foods such as so-called ramune confectionery, gum, rice cake, and fresh food in mouth that can be easily understood by those skilled in the art. The molded product may be provided with a coating layer having transparency so as to cover the identification mark so as not to impair the identification characteristic after marking with the identification mark.

The molded product may have a coating layer. Examples of the coating layer include a capsule coating layer, a film coating layer, and a sugar coating layer. As described above, the coating layer provided after marking is also included in the coating layer.
The molded article provided with the coating layer can be produced by applying a known method alone or in combination of two or more. For example, the capsule coating layer can be manufactured by a soft capsule manufacturing method such as a rotary die method or a dropping method, and the hard capsule is prepared in advance separately from the manufacturing of the composition for oral administration filled therein. You can also keep it. Moreover, although a film coat layer, a sugar-coating layer, etc. can be manufactured with a coating granulation method, a film coating method, a sugar-coating method, a compression coating method, etc., a manufacturing method is not limited to these.

  Examples of the molded product provided with the coating layer include a composition in which a core containing a drug and a taste-masking component is coated with a coating layer, and the surface of the coating layer can be marked according to the present invention. Examples of such a molded product include film-coated tablets, sugar-coated tablets, pills and the like. If it is a foodstuff, what has coating layers, such as chocolate and a mouth refresher, can be illustrated. The form of the core is not particularly limited, for example, a drug, a taste-masking component, and the like, and if necessary, after uniformly mixing other excipients and binders, a wet granulation method or a dry granulation method Examples thereof include granules obtained by granulation and the like, and non-parrels such as sugar nuclei and cellulose nuclei coated with a layer containing a drug in layers. Furthermore, those obtained by compression molding these granules into a tablet-like core can also be used. Also, a pill-like core obtained by stacking a plurality of layers, such as a pill, can be used.

  Examples of the molded product provided with the coating layer include capsules. The capsule coating layer can be filled with contents containing drugs, edible oils and fats, fragrances, etc., and the surface of the capsule coating layer can be marked by the present invention. The capsule may be either a soft capsule or a hard capsule. The content containing the drug or the like may be used as it is, but it may be mixed with other additives as necessary, and may be in the form of powder, granules, those formed, or liquid or slurry. As the capsule coating layer, gelatin capsules, agar capsules, hypromellose (HPMC) capsules, pullulan capsules, starch capsules and the like can be used, but are not limited thereto. When filling the contents with capsules, a commonly used rotary die capsule filling machine, seamless capsule filling machine, hard capsule filling machine (Qualicaps Co., Ltd.) or the like can be used.

FIG. 2 is a schematic cross-sectional view for explaining an example of the marking method according to the present invention, and corresponds to the case where the laser transfer film 1 shown in FIG. 1 is used.
In the marking method, first, as shown in FIG. 2A, the laser transfer film 1 is arranged with the transfer layer 12 facing the edible food 9 side to be transferred.

Here, in the main surface (surface) 12 a of the transfer layer 12, a region in the vicinity of the peripheral edge portion 12 c of the transfer layer 12 is not brought into contact with the surface 9 a of the transfer target edible 9, so that the surface 12 a of the transfer layer 12 is not touched. Only a part (the central portion of the surface 12a and the vicinity thereof) is brought into contact with the transfer target edible material 9 and the laser transfer film 1 is disposed. However, the arrangement form of the laser transfer film 1 is not limited to this. For example, as shown in FIG. 3, the entire surface 12 a of the transfer layer 12 is brought into contact with the surface 9 a of the edible food 9 to be transferred. 1 may be arranged, or as shown in FIG. 4, the transfer layer 12 and the transfer target edible 9 may be separated from each other, and the laser transfer film 1 may be arranged without contacting the transfer target edible 9. Good. The distance between the transfer layer 12 and the transfer target edible 9 when separated as described above (the distance between the surface 12a of the transfer layer 12 and the surface 9a of the transfer target edible 9) is 100 mm or less. Is preferred.
The area of the surface 12a of the transfer layer 12 is not particularly limited as long as the target marking is possible, and may be narrower or wider than the area of the surface 9a that is the marking target of the transfer target edible 9. Also good.

  Next, as shown in FIG. 2B, the laser transfer film 1 is irradiated with laser light L from the substrate 11 side. Then, the transfer layer 12 corresponding to the irradiated portion of the laser beam L is fixed and transferred to the surface 9a of the transfer target edible food 9. At least a part of the transfer layer 12 on the substrate 11 corresponding to the irradiation site of the laser beam L is transferred, and all the sites on the substrate 11 may be transferred depending on conditions.

As shown in FIG. 2C, the transferred transferable food 9 is marked with a hue corresponding to the coloring component in the transfer layer 12 in a pattern corresponding to the irradiation pattern of the laser light L. Here, the transfer layer transferred from the laser transfer film 1 is denoted by reference numeral 12 '.
In the present invention, even when the transfer layer 12 is brought into contact with the transfer target edible 9 and the laser transfer film 1 is arranged and marked, the transfer layer 12 remaining on the laser transfer film 1 and the transfer target are marked. Adherence with the edible substance 9 is suppressed, and a clearer pattern can be marked.

The laser light irradiation conditions are preferably adjusted as appropriate in consideration of the composition of the laser transfer film, particularly the transfer layer, and the edible material to be transferred.
The laser light is not particularly limited, and the laser medium (laser oscillation source) may be laser oscillated in any state of solid, liquid and gas, but is preferably a solid laser. Examples of the solid laser include YLF laser, YAG laser, YVO4 laser, and fiber laser. Among these, the fundamental, second, third, fourth, and fifth harmonic YVO4 laser oscillators are particularly preferable. Specifically, as the second harmonic oscillator, the Cosent's Prisma series (model name: 532-12-V), as the third harmonic oscillator, YVO4 laser DS20H-355 (manufactured by Photonics Industries International), AVIA 266-3000 (manufactured by Coherent) can be used as a harmonic oscillator.

  The wavelength of the laser light is preferably 200 to 1100 nm, more preferably 250 to 750 nm, and particularly preferably 300 to 600 nm.

  The average power of the laser light is preferably 0.1 to 50 W, more preferably 0.5 to 20 W, and particularly preferably 0.7 to 5 W. If the average power of the laser beam is too low, the transfer layer cannot be transferred well, and if the average power of the laser beam is too high, damage such as etching on the surface of the edible material to be transferred due to ablation, etc. There is a risk of peeling.

  The average frequency of the laser light is preferably 1 to 500 kHz, and more preferably 10 to 300 kHz. If the average frequency of the laser beam is too small, damage such as etching on the surface of the edible food to be transferred due to ablation, peeling of the transferred material, or the like may occur. In addition, the mark design is limited, and the processing amount of the marking device becomes insufficient. On the other hand, if the average frequency of the laser beam is too large, the transfer layer cannot be transferred satisfactorily.

  The pulse width at the time of laser light irradiation is preferably 1 to 50 ns, and more preferably 5 to 40 ns. If the pulse width is too large, the transfer layer cannot be transferred satisfactorily, and if the pulse width is too small, damage such as etching on the surface of the edible food to be transferred, peeling of the transferred material, etc. may occur due to ablation or the like. There is a fear.

  The energy amount (pulse energy) of one pulse at the time of laser light irradiation is preferably 0.01 to 10 mJ, and more preferably 0.05 to 1 mJ. If the amount of energy is too small, the transfer layer cannot be transferred satisfactorily. If the amount of energy is too large, damage such as etching on the surface of the edible food to be transferred, peeling of the transferred material, etc. may occur due to ablation. There is a fear.

  The peak power of the laser light is preferably 0.1 to 100 kW, and more preferably 1 to 50 kW. If the peak power of the laser beam is too small, the transfer layer cannot be transferred satisfactorily. If the peak power of the laser beam is too large, damage such as etching on the surface of the edible material to be transferred due to ablation, etc. There is a risk of peeling.

The laser scanning mechanism is not particularly limited, but is a galvanometer mirror type using a deflector that can change the rotation angle of the mirror according to an electric signal, and a resonance type deflector that is driven by a sine wave of a resonance frequency. A certain resonant scan type, a polygon mirror type using a plurality of mirrors, and the like can be exemplified, and a galvano mirror type is preferable.
The scanning speed is not particularly limited, but is preferably 20 to 20000 mm / sec, more preferably 100 to 10000 mm / sec, and particularly preferably 500 to 5000 mm / sec. If the scanning speed is too slow, damage such as etching on the surface of the edible food to be transferred due to ablation or the like, or peeling of the transferred material may occur. In addition, the mark design is limited, and the processing amount of the marking device becomes insufficient. On the other hand, if the scanning speed is too fast, the mark design is limited.

FIG. 5 is a schematic configuration diagram schematically illustrating a main part of a marking device suitable for use in the marking method according to the present invention.
The marking device 8 shown here includes a laser oscillator 81, a first reflection mirror 82, a second reflection mirror 83, and a lens 84 in a housing 80 and is schematically configured.
The first reflection mirror 82 is disposed so as to face the laser oscillator 81 so that the mirror surface (reflection surface) is at a predetermined angle with respect to the laser oscillator 81, and the second reflection mirror 83 is the mirror surface (reflection). The surface is disposed to face the first reflection mirror 82 such that the surface thereof is at a predetermined angle with respect to the first reflection mirror 82. Further, the lens 84 is disposed so as to face the second reflecting mirror 83 so that the light collecting surface is at a predetermined angle with respect to the second reflecting mirror 83. The laser transfer film 1 and the transfer target edible 9 are arranged such that the second reflection mirror 83, the lens 84, the laser transfer film 1 and the transfer target edible 9 are in series in this order. The first reflecting mirror 82 and the second reflecting mirror 83 may be capable of adjusting the direction of their mirror surfaces. The laser transfer film 1 and the transfer target edible 9 are respectively held at predetermined positions by holding means (laser transfer film holding means, transfer target edible holding means, not shown). One or more of the laser oscillator 81, the first reflecting mirror 82, the second reflecting mirror 83, the lens 84, the laser transfer film holding means and the transfer target edible holding means automatically adjust their arrangement position and arrangement angle. May be connected to control means (not shown). As such a thing, the thing of the galvanometer mirror type | mold using the deflector which can adjust the rotation angle of the 1st reflective mirror 82 and the 2nd reflective mirror 83 according to an electrical signal can be illustrated, for example.

  In addition, a marking apparatus is not limited to what is shown here, As long as edible to be transferred is appropriately marked, a part of the configuration may be appropriately added, changed, or omitted. For example, FIG. 1 shows the marking device 8 including the first reflection mirror 82 and the second reflection mirror 83, but the number of reflection mirrors may be other than two.

  By operating the marking device 8, the laser light L oscillated (irradiated) from the laser oscillator 81 is reflected by the first reflecting mirror 82 and the second reflecting mirror 83, and then enters the lens 84. The light is condensed and irradiated on a desired position of the laser transfer film 1. Thereby, the transferable edible material 9 is marked with a desired pattern.

  The laser beam irradiation may be a scanning method using the above galvanometer mirror or the like, or mask type marking that forms a pattern in a lump by forming an image of the laser beam that has passed through a mask having a pattern corresponding to a predetermined mark It may be a law.

  According to the marking method, for example, the laser light irradiation can be precisely controlled by a galvanometer mirror or the like, so that the degree of freedom of design of distinguishable marks is increased, and those designs are edible for transfer with an accuracy of ± 10 μm Can be marked. Therefore, a distinguishable mark can be applied to a transfer target edible having a high design property or a transfer target edible having a diameter of 2 to 3 mm, such as a mini tablet. In addition, since it is possible to input a signal of marking design information with a computer or the like, it is possible to easily change the design of the design.

The marked edible food to be transferred is, for example, discharged to a transfer drum or filled into a packaging container through inspection by a character inspection machine, a metal inspection machine, or the like. Therefore, the timing of marking according to the present invention is not particularly limited, and can be freely incorporated in the pharmaceutical or food production process. For example, since it can mark with respect to the transfer object edible food which is moving on the conveyance line before packing filling, it can apply also to what is called continuous production. In addition, marking may be performed after the transfer target edible food is automatically spread in a flat bread in which a certain amount of transfer target edible food is accommodated in the middle of the transport line, and then stationary. In addition, marking can be performed by batch processing using an automatic marking device having a laser oscillator. Specifically, the edible food to be transferred loaded in the hopper of the marking device is sequentially supplied from this hopper to the inspection unit, and then the front and back surfaces of the edible food to be transferred using a video inspection machine in the inspection unit. After confirming the presence or absence of dirt, chips, cracks, etc., marking can be performed by moving one or more edible foods to be transferred to a place where marking is performed.
In addition, the above process can be performed multiple times corresponding to marking in multiple colors, or a laser transfer film having a plurality of different transfer layers corresponding to marking in multiple colors can be transferred. Multiple markings may be performed per target edible food.

<Edible food to be transferred with mark and manufacturing method thereof>
According to the present invention, a manufacturing method of a transfer target edible with a mark, a laser transfer film provided with a base material and a transfer layer in this order, the transfer layer is arranged facing the transfer target edible side, Irradiating the laser transfer film with laser light from the substrate side and transferring at least a part of the transfer layer to the transfer target edible, thereby marking the transfer target edible, The layer includes a polymer that can be edible and a coloring component.
Such a manufacturing method can be performed by using the above-described laser transfer film according to the present invention and applying the marking method according to the present invention, and the marking applied to the transfer target edible is clear and strong. Have advantages.

  In the present invention, for example, when an ink composition in which a part or all of the coloring component is dispersed without being dissolved is used, the weight average molecular weight is preferably 3,000 to 55,000, more preferably 10 5,000 to 55,000, more preferably 30,000 to 55,000, and the content (blending amount) of the polymer with respect to the total amount of components other than the solvent and the dispersion medium is preferably 20 to 80. Using the ink composition of mass%, more preferably 30 to 70 mass%, the transfer layer is preferably coated with a thickness of 1 to 12 mil (2.5 to 304.8 μm), and the average power of the laser beam Is preferably marked as 1 to 4 W, whereby marking can be made in a significantly excellent state.

  In the present invention, for example, when an ink composition in which all coloring components are dissolved is used, the weight average molecular weight is preferably 3,000 to 100,000, more preferably 3,000 to 80,000, Preferably, the polymer of 3,000 to 55,000 is used, and the content (blending amount) of the polymer with respect to the total amount of components other than the solvent and the dispersion medium is preferably 20 to 80% by mass, more preferably 30 to 30%. Using the ink composition of 70% by mass, more preferably 35 to 65% by mass, the thickness of the transfer layer applied is preferably 1 to 12 mil (2.5 to 304.8 μm), more preferably 0.00. By marking with 5-7 mil (12.7-177.8 μm) and an average power of the laser beam of preferably 1 to 2 W, -You can king.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

Typical raw materials used in the following examples and comparative examples are shown below.
(High molecular)
Eudragit E100 (gastric soluble polymer, EVONIK, weight average molecular weight: 47,000, glass transition temperature: about 50 ° C.)
Eudragit EPO (gastric soluble polymer, EVONIK, weight average molecular weight: 47,000, glass transition temperature: about 50 ° C.)
AEA (gastric polymer, manufactured by Mitsubishi Chemical Foods, weight average molecular weight: 65,000, glass transition temperature: 80 to 90 ° C.)
Eudragit RL100 (sustained release polymer, EVONIK, weight average molecular weight: 32,000, glass transition temperature: about 55 ° C.)
Eudragit RLPO (sustained release polymer, manufactured by EVONIK, weight average molecular weight: 32,000, glass transition temperature: about 55 ° C.)
Eudragit RL30D (sustained release polymer, EVONIK, weight average molecular weight: 32,000, glass transition temperature: about −8 ° C.)
PVP (polyvinyl pyrrolidone, water-soluble polymer, manufactured by BASF, weight average molecular weight: 44,000-54,000, glass transition temperature: 149 ° C. with PVP K30)
HPC-L (hydroxypropylcellulose, water-soluble polymer, Nippon Soda Co., Ltd., weight average molecular weight: 140,000, viscosity at 20 ° C./2% solution: 6-10 mPa · s)
HPC-SL (hydroxypropylcellulose, water-soluble polymer, Nippon Soda Co., Ltd., weight average molecular weight: 100,000, viscosity at 20 ° C./2% solution: 3 to 5.9 mPa · s)
-HPC-SSL (hydroxypropylcellulose, water-soluble polymer, manufactured by Nippon Soda Co., Ltd., weight average molecular weight: 40,000, viscosity at 20 ° C./2% solution: 2-2.9 mPa · s)
-Kollidon VA64 (water-soluble polymer, manufactured by BASF, weight average molecular weight: 45,000 to 50,000)
AQOAT (enteric polymer, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: 18,000)
CMEC (enteric polymer, manufactured by Freund Corporation, weight average molecular weight: 49,000, glass transition temperature: 62 ° C.)
・ Ethylcellulose (sustained release polymer, manufactured by Nisshinsei Co., Ltd., weight average molecular weight: 77000)
-Purified shellac (enteric polymer, manufactured by Gifu Shellac Co., Ltd., weight average molecular weight: 2000)

[Example 1]
<Manufacture of ink composition>
Eudragit E100 (30 parts by mass, 16.7% by mass), yellow No. 5 aluminum lake (15 parts by mass, 8.3% by mass), triethyl citrate (5 parts by mass, 2.8% by mass), ethanol (130 parts by mass, 72.2% by mass) was added and mixed at 25 ° C. for 60 minutes to obtain a suspension as an ink composition. Each compounding component and its compounding ratio are shown in Table 1. In addition, the numerical value of “mass%” of each component described in the above procedure is a ratio of the blending amount of each component to the total amount of the blending component (that is, the content in the ink composition). On the other hand, the numerical value of “mass%” in Table 1 is the ratio of the amount of each component to the total amount of components other than the solvent and the dispersion medium. The same applies to the following embodiments.

<Manufacture of laser transfer film>
Using a base material having a thickness of 55 μm, in which cellophane, an adhesive layer and a low-density polyethylene film are laminated in this order, an applicator (Baker type applicator “SA-201” manufactured by Tester Sangyo Co., Ltd.) is used on the cellophane, The obtained suspension was applied to a thickness of 3 mil (76.2 μm) and dried at 25 ° C. for 12 hours to form a transfer layer, thereby obtaining a laser transfer film.

<Marking of tablets>
As shown in FIG. 2 (a), the obtained laser transfer film is placed on the tablet so that a part of the surface of the transfer layer is in contact with the surface of the tablet, and the substrate side of the laser transfer film (base material) The low-density polyethylene film side) was irradiated with laser light under the following conditions, whereby the transfer layer was transferred to the tablet surface to mark the tablet. As a laser beam irradiation apparatus, a product manufactured by Photonics Industries International was used. The imaging data of the tablet after marking is shown in FIG.

  In addition, as a tablet, the substantially disc shaped thing whose diameter is 7.0 mm was used. This tablet was added with lactose (59.5% by mass), crystalline cellulose (30.0% by mass), corn starch (10.0% by mass), magnesium stearate (0.5% by mass) according to a conventional method. It was obtained by mixing and molding by applying a pressure of 4410 N (450 kgf).

(Laser irradiation conditions)
Laser name: YVO4 laser Model: DS20H-355
Wavelength: 355nm
Peak power: 6kW
Average power at 20kHz: 3W
Pulse width at 20 kHz: 25 ns
Pulse energy at 20 kHz: 0.15 mJ
Beam mode: TEM _OO -M ² <1.1
Polarization Extinction Ratio (Polarization Ratio): 100: 1 Horizontal
Beam diameter: 0.9mm
Beam divergence angle (full angle): 1.3 mrad
Stability between pulses: 3% rms
Scanning speed: 2000mm / sec
Long-Term Instability: +/- 3%
Pointing Stability: <50 μrad
Pulse repetition rate: Single Shot to 100kHz

[Examples 2 to 5]
<Manufacture of ink composition and laser transfer film, marking of tablets>
As shown in Table 1, the ink composition and the laser transfer film were the same as in Example 1 except that other polymers (gastric polymer, sustained-release polymer) were used instead of Eudragit E100. And the tablets were marked. The blending amounts of ethanol in Examples 2 to 5 are the same as those in Example 1. Of the imaging data of the tablet after marking, FIG. 7 shows the data in Example 2, FIG. 8 shows the data in Example 3, FIG. 9 shows the data in Example 4, and FIG. 10 shows the data in Example 5. Show.

  In each of Examples 1 to 5, the tablets were marked, and the markings were excellent in both clarity and fastness (hereinafter sometimes collectively referred to as “marking characteristics”). Here, “fastness” means that the mark does not disappear (marking strength is high) when the marking surface is wiped with a waste cloth (Kim Towel (registered trademark)). The same applies to the following embodiments.

[Example 6]
<Manufacture of ink composition>
In a container, PVP (30 parts by mass, 16.7% by mass), yellow No. 5 aluminum lake (15 parts by mass, 8.3% by mass), triethyl citrate (5 parts by mass, 2.8% by mass), ethanol ( 130 parts by mass and 72.2% by mass) were added and mixed at 25 ° C. for 60 minutes to obtain a suspension as an ink composition. Each compounding component and its compounding ratio are shown in Table 1.

<Manufacture of laser transfer film>
Using the same substrate and applicator as used in Example 1, the resulting suspension was applied to a thickness of 1 mil (25.4 μm), 3 mil (76.2 μm) on the cellophane of the substrate, and 25 Two types of laser transfer films were obtained by drying at 0 ° C. and forming the transfer layers separately.

<Marking of tablets>
The tablets were marked in the same manner as in Example 1 except that the above two types of laser transfer films were used. The imaging data of the tablet after marking is shown in FIG.

[Examples 7 to 9]
<Manufacture of ink composition and laser transfer film, marking of tablets>
As shown in Table 1, an ink composition and a laser transfer film were produced in the same manner as in Example 6 except that another polymer (water-soluble polymer) was used instead of PVP, and the tablets were marked. did. However, the thickness of the transfer layer applied is only 1 mil (25.4 μm) in Examples 7 and 8, and 1 mil (25.4 μm), 3 mil (76.2 μm), and 7 mil (177.8 μm) in Example 9. ). The blending amounts of ethanol in Examples 7 to 9 are the same as in Example 6. Of the imaging data of the tablet after marking, FIG. 12 shows the data in Example 7, FIG. 13 shows the data in Example 8, and FIG. 14 shows the data in Example 9.

  Examples 6-9 were all excellent in marking characteristics.

[Example 10]
<Manufacture of ink composition>
AQOAT (30 parts by mass, 9.5% by mass), yellow No. 5 aluminum lake (15 parts by mass, 4.8% by mass), triethyl citrate (5 parts by mass, 1.6% by mass), ethanol ( 227 parts by mass, 72.0% by mass) and acetone (38 parts by mass, 12.1% by mass) were added and mixed at 25 ° C. for 60 minutes to obtain a suspension as an ink composition. Each compounding component and its compounding ratio are shown in Table 1.

<Manufacture of laser transfer film>
Using the same substrate and applicator as used in Example 1, the resulting suspension was applied to a thickness of 1 mil (25.4 μm), 3 mil (76.2 μm) on the cellophane of the substrate, and 25 Two types of laser transfer films were obtained by drying at 12 ° C. for 12 hours and forming the transfer layers separately.

<Marking of tablets>
The tablets were marked in the same manner as in Example 1 except that the above two types of laser transfer films were used. The imaging data of the tablet after marking is shown in FIG.

[Example 11]
<Manufacture of ink composition and laser transfer film, marking of tablets>
As shown in Table 1, CMEC was used in place of AQOAT, and the thickness at the time of applying the transfer layer was 3 mil (76.2 μm), 7 mil (177.8 μm), 10 mil (254.0 μm). In the same manner as in Example 10, an ink composition and a laser transfer film were produced, and tablets were marked. The blending amounts of ethanol and acetone are the same as in Example 10. The imaging data of the tablet after marking is shown in FIG.

In Examples 10 to 11, in consideration of the solubility of the polymer (enteric polymer), a mixed solvent was used, and the blending amount thereof was increased from the solvent blending amounts of Examples 1 to 9.
Examples 10-11 were all excellent in marking characteristics.

[Example 12]
<Ink composition>
An ink composition was obtained in the same manner as in Example 1. Each compounding component and its compounding quantity are shown in Table 2.

<Manufacture of laser transfer film>
Using the same substrate and applicator as used in Example 1, the resulting suspension was applied onto a cellophane substrate and dried at 25 ° C. for 12 hours, with a thickness of 3 mil (76.76) at the time of application. 3 μm (17 μm), 7 mil (177.8 μm), and 10 mil (254.0 μm) transfer layers were separately formed to obtain three types of laser transfer films.

<Marking of tablets>
The tablets were marked in the same manner as in Example 1 except that the above three types of laser transfer films were used. The imaging data of the tablet after marking is shown in FIG.

[Example 13]
<Manufacture of ink composition>
Eudragit E100 (24 parts by mass, 13.4% by mass), PVP (6 parts by mass, 3.3% by mass), yellow No. 5 aluminum lake (15 parts by mass, 8.3% by mass), triethyl citrate in the container (5 parts by mass, 2.8% by mass) and ethanol (130 parts by mass, 72.2% by mass) were added and mixed at 25 ° C. for 60 minutes to obtain a suspension as an ink composition. Table 2 shows each blending component and the blending ratio.

<Manufacture of laser transfer film>
The obtained suspension was used, except that the transfer layer was coated with a thickness of 1 mil (25.4 μm), 3 mil (76.2 μm), 7 mil (177.8 μm), 10 mil (254.0 μm). In the same manner as in Example 12, four types of laser transfer films were obtained.

<Marking of tablets>
The tablets were marked in the same manner as in Example 12 except that the above four types of laser transfer films were used. The imaging data of the tablet after marking is shown in FIG.

[Examples 14 to 15]
<Manufacture of ink composition and laser transfer film, marking of tablets>
As shown in Table 2, an ink composition and a laser transfer film were produced in the same manner as in Example 13 except that another polymer was used instead of PVP, and tablets were marked. However, the thickness of the transfer layer applied was only 1 mil (25.4 μm) in Example 14, and 1 mil (25.4 μm) and 3 mil (76.2 μm) in Example 15. The compounding quantity of the ethanol of Examples 14-15 is the same as Examples 12-13. Of the imaging data of the tablets after marking, the data in Example 14 is shown in FIG. 19, and the data in Example 15 is shown in FIG.

[Example 16]
<Manufacture of ink composition and laser transfer film, marking of tablets>
As shown in Table 2, in the same manner as in Example 12, the ink composition and the laser were used except that AEA was used instead of Eudragit E100 and the transfer layer was coated with a thickness of only 1 mil (25.4 μm). A transfer film was produced and the tablets were marked. The blending amount of ethanol is the same as in Examples 12-15. The imaging data of the tablet after marking is shown in FIG.

  Examples 12-16 were all excellent in marking characteristics.

[Example 17]
<Manufacture of ink composition and laser transfer film, marking of tablets>
As shown in Table 2, PEG 6000 (manufactured by NOF Corporation, weight average molecular weight: 8,000) was used instead of triethyl citrate, and the thickness at the time of coating the transfer layer was 1 mil (25.4 μm), 3 mil (76 Except for the point of 2 .mu.m), an ink composition and a laser transfer film were produced in the same manner as in Example 12, and the tablets were marked. The blending amount of ethanol is the same as in Example 12. The imaging data of the tablet after marking is shown in FIG.
In Example 17, the marking characteristics were good.

[Example 18]
<Manufacture of ink composition>
Eudragit E100 (10 parts by mass, 6.2% by mass), yellow No. 5 aluminum lake (15 parts by mass, 9.4% by mass), triethyl citrate (5 parts by mass, 3.1% by mass), ethanol (130 parts by mass, 81.3% by mass) was added and mixed at 25 ° C. for 60 minutes to obtain a suspension as an ink composition. Table 2 shows each blending component and the blending ratio.

<Manufacture of laser transfer film, marking of tablets>
Using the suspension obtained above, the transfer layer was coated at a thickness of 1 mil (25.4 μm), 3 mil (76.2 μm), 7 mil (177.8 μm), 10 mil (254.0 μm). Except for the above, a laser transfer film was produced in the same manner as in Example 12, and the tablets were marked. The imaging data of the tablet after marking is shown in FIG.

  Example 18 was excellent in marking characteristics.

[Example 19]
<Manufacture of ink composition and laser transfer film, marking of tablets>
As shown in Table 2, Eudragit RL30D was used instead of Eudragit E100, water was used instead of ethanol, and the thickness of the transfer layer when applied was 1 mil (25.4 μm), 3 mil (76.2 μm), 7 mil. (177.8 μm) An ink composition and a laser transfer film were produced in the same manner as in Example 12 except that 10 mil (254.0 μm) was used, and tablets were marked. The blending amount of water is the same as the blending amount of ethanol in Example 12. The imaging data of the tablet after marking is shown in FIG.

[Example 20]
<Manufacture of ink composition and laser transfer film, marking of tablets>
As shown in Table 2, an ink composition and a laser transfer film were produced in the same manner as in Example 12 except that Eudragit NE30D was used instead of Eudragit E100, and water was used instead of ethanol. Marked. The blending amount of water is the same as the blending amount of ethanol in Example 12. The imaging data of the tablet after marking is shown in FIG.

  In Examples 19 to 20, all the tablets were marked.

[Example 21]
<Manufacture of ink composition and laser transfer film, marking of tablets>
As shown in Table 2, instead of yellow No. 5 aluminum lake, yellow iron sesquioxide was used, and the thickness when the transfer layer was applied was 1 mil (25.4 μm), 3 mil (76.2 μm), 7 mil (177.8 μm). The ink composition and the laser transfer film were produced and the tablets were marked in the same manner as in Example 12 except for the points described above. The blending amount of ethanol is the same as in Example 12. The imaging data of the tablet after marking is shown in FIG.

[Example 22]
<Manufacture of ink composition>
Eudragit E100 (15 parts by mass, 16.7% by mass), Blue No. 2 (7.5 parts by mass, 8.3% by mass), triethyl citrate (2.5 parts by mass, 2.8% by mass) in a container , Ethanol (65 parts by mass, 72.2% by mass) was added and mixed at 25 ° C. for 60 minutes to obtain a suspension as an ink composition. Table 2 shows each blending component and the blending ratio.

<Manufacture of laser transfer film, marking of tablets>
Using the suspension obtained above, the transfer layer was coated at a thickness of 1 mil (25.4 μm), 3 mil (76.2 μm), 7 mil (177.8 μm), 10 mil (254.0 μm). Except for the above, a laser transfer film was produced in the same manner as in Example 12, and the tablets were marked. The imaging data of the tablet after marking is shown in FIG.

  In Example 21, marking was performed in black as in the case of titanium oxide and the like, and the marking characteristics were high.

  Examples 1 to 22 use the ink composition in which the color component is not dissolved but dispersed. For example, in Examples 7, 8 and 16, the thickness of the transfer layer applied is 1 mil. Instead of 3 mil, the density of the mark was low. On the other hand, in Examples 6, 9, 18 and 19, as shown in FIGS. 11, 14, 23 and 24, the mark density was high and the thickness of the transfer layer applied was other than 1 mil. But the mark was clearer. Thus, when the weight average molecular weight of the polymer blended in the ink composition is 32,000 to 47,000, the clarity of the mark is generally higher. However, also in Examples 7, 8, and 16, the thickness at the time of coating the transfer layer can be adjusted by adjusting the marking conditions such as the amount of the polymer in the ink composition and the average power during laser light irradiation. Even in cases other than 1 mil, the clarity of the mark can be improved.

[Example 23]
<Manufacture of ink composition>
Eudragit E100 (5 parts by mass, 8.6% by mass), Red No. 3 (2 parts by mass, 3.5% by mass), triethyl citrate (1 part by mass, 1.7% by mass), ethanol (50 An ink composition was obtained by adding 60 parts by mass and mixing at 25 ° C. for 60 minutes (Example 23-3). Each compounding component and its compounding ratio are shown in Table 3.
In addition to this ink composition, an ink composition was obtained in the same manner as described above except that the blending ratio of each blending component was as shown in Table 3.
Thus, three types of ink compositions (Examples 23-1 to 23-3) were obtained.
In addition, the numerical value of “mass%” of each component described in the above procedure is a ratio of the blending amount of each component to the total amount of the blending component (that is, the content in the ink composition). On the other hand, the numerical value of “mass%” in Table 3 is the ratio of the amount of each component to the total amount of components other than the solvent and the dispersion medium. The same applies to the following embodiments.

<Manufacture of laser transfer film, marking of tablets>
Using the ink composition obtained above, among the laser light irradiation conditions, the average power is set to 1.4 W instead of 3 W, and the thickness at the time of applying the transfer layer is set to 1 mil (25.4 μm), and further marking A laser transfer film was produced and the tablet was marked in the same manner as in Example 1 except that the pattern was changed. The imaging data of the tablet after marking is shown in FIG.
The numerical value of “polymer blend ratio (mass%)” in FIG. 28 is the ratio of the polymer blend amount to the total amount of components other than the solvent and dispersion medium in the ink composition. The numerical value of “MW” means the weight average molecular weight of the polymer used. The same applies to the following drawings.

<Manufacture of ink composition and laser transfer film, marking of tablets>
[Example 24]
An ink composition and a laser transfer film were produced in the same manner as in Example 23, except that Kollidon VA64 was used instead of Eudragit E100, and each compounding component and its compounding ratio were as shown in Table 3, and the tablet Marked. Three types of ink compositions (Examples 24-1 to 24-3) were manufactured, and the thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 25]
Ink composition and laser transfer film were produced in the same manner as in Example 23, except that PVP was used in place of Eudragit E100 and each compounding component and its compounding ratio were as shown in Table 3. Marking the tablets did. Four types of ink compositions (Examples 25-1 to 25-4) were manufactured, and the thickness of the transfer layer when applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 26]
The ink composition was the same as in Example 23, except that HPC-SSL (3 parts by mass) was used instead of Eudragit E100 (5 parts by mass) and each compounding component and its compounding ratio were as shown in Table 3. Articles and laser transfer films were manufactured and tablets were marked. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 27]
A purified shellac was used instead of Eudragit E100, and the ink composition and the laser transfer film were produced in the same manner as in Example 23 except that each compounding component and its compounding ratio were as shown in Table 3. Marked. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 28]
An ink composition and a laser transfer film were produced in the same manner as in Example 23 except that AEA was used in place of Eudragit E100, and the respective blending components and blending ratios were as shown in Table 4, and the tablets were marked. did. Three types of ink compositions (Examples 28-1 to 28-3) were manufactured, and the thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 29]
Ink composition and laser transfer film were produced in the same manner as in Example 23 except that ethyl cellulose was used in place of Eudragit E100, and each compounding component and its blending ratio were as shown in Table 4, and the tablets were marked did. Four types of ink compositions (Examples 29-1 to 29-4) were manufactured, and the thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 30]
The ink composition was the same as in Example 23, except that HPC-L (3 parts by mass) was used instead of Eudragit E100 (5 parts by mass), and each compounding component and its compounding ratio were as shown in Table 4. Articles and laser transfer films were manufactured and tablets were marked. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Comparative Example 1]
An ink composition and a laser transfer film were produced in the same manner as in Example 23 except that Eudragit E100 was not used, and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

In Examples 23 to 30, all the tablets were marked, and the marking characteristics were excellent. Particularly in Examples 23 to 25 and 28 to 29, excellent marking characteristics were obtained at various polymer blend ratios. In Example 29, a white portion having a low density was observed at a portion other than the peripheral portion of the mark. However, in other examples, a clear mark was obtained as a whole. For example, in Example 26, a particularly clear mark was obtained. Obtained.
On the other hand, in Comparative Example 1 using an ink composition containing no polymer, the marking characteristics were inferior and the mark was unknown.

<Manufacture of ink composition and laser transfer film, marking of tablets>
[Example 31]
As shown in Table 5, the same ink composition as in Example 23-3 was obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 23 except that the average power was changed to 2 W instead of 1.4 W among the laser light irradiation conditions, and the tablet was manufactured. Marked. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG. 29 together with the imaging data of Comparative Example 1.

[Example 32]
An ink composition was obtained in the same manner as in Example 24 except that each blending component and the blending ratio thereof were as shown in Table 5. Four types of ink compositions (Examples 32-1 to 32-4) were obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 24 except that, of the laser light irradiation conditions, the average power was changed to 2 W instead of 1.4 W, and a tablet was produced. Marked. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 33]
As shown in Table 5, the same ink compositions as in Examples 25-3 and 25-4 were obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 25 except that, of the laser light irradiation conditions, the average power was changed to 1.4 W instead of 1.4 W, and a laser transfer film was produced. Marked. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 34]
An ink composition was obtained in the same manner as in Example 26 except that each blending component and the blending ratio thereof were as shown in Table 5. Two ink compositions (Examples 34-1 to 34-2) were obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 26 except that the average power was changed to 2 W instead of 1.4 W among the laser light irradiation conditions, and the tablets Marked. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 35]
An ink composition was obtained in the same manner as in Example 27 except that each blending component and the blending ratio thereof were as shown in Table 5. Two types of ink compositions (Examples 35-1 to 35-2) were obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 27 except that, of the laser light irradiation conditions, the average power was changed to 2 W instead of 1.4 W, and a tablet was produced. Marked. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 36]
An ink composition was obtained in the same manner as in Example 28 except that each blending component and the blending ratio thereof were as shown in Table 6. Two types of ink compositions (Examples 36-1 to 36-2) were obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 28 except that the average power was changed to 2 W instead of 1.4 W among the irradiation conditions of laser light, and a tablet was produced. Marked. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 37]
An ink composition was obtained in the same manner as in Example 29 except that each blending component and its blending ratio were as shown in Table 6. Three types of ink compositions (Examples 37-1 to 37-3) were obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 29 except that, of the laser light irradiation conditions, the average power was changed to 2 W instead of 1.4 W, and a tablet was produced. Marked. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 38]
As shown in Table 6, the same ink composition as in Example 30 was obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 30 except that, of the laser light irradiation conditions, the average power was changed to 2 W instead of 1.4 W, and a tablet was produced. Marked. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

  In Examples 31 to 38, the tablets were marked, and the marking characteristics were excellent. In Examples 31-38, the average power at the time of laser light irradiation is larger than in Examples 23-30, but the ink composition has a larger amount of polymer as a whole than in Examples 23-30. There was a tendency for good marks to be obtained. In Example 37, white portions were observed in some of the marks, and in Example 35, the density of the marks was low. However, in other Examples, clear marks were obtained as a whole, and Example 31 overall. In -38, a clearer mark was obtained than in Examples 23-30.

<Manufacture of ink composition and laser transfer film, marking of tablets>
[Example 39]
An ink composition was obtained in the same manner as in Example 31, except that each blending component and its blending ratio were as shown in Table 7.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 31 except that the average power was 3 W instead of 2 W in the laser light irradiation conditions, and the tablets were marked. did. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG. 30 together with the imaging data of Comparative Example 1.

[Example 40]
As shown in Table 7, the same ink composition as in Example 32-4 was obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 32 except that the average power was changed to 3 W in the laser light irradiation conditions, and the tablets were marked. did. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 41]
An ink composition was obtained in the same manner as in Example 33 except that each blending component and its blending ratio were as shown in Table 7. Two types of ink compositions (Examples 41-1 to 41-2) were obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 33 except that the average power was changed to 3 W in the laser light irradiation conditions, and the tablets were marked. did. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 42]
An ink composition was obtained in the same manner as in Example 34 except that each blending component and the blending ratio thereof were as shown in Table 7. Three types of ink compositions (Examples 42-1 to 42-3) were obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 34 except that the average power was changed to 3 W instead of 2 W in the laser light irradiation conditions, and the tablets were marked. did. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 43]
An ink composition was obtained in the same manner as in Example 35 except that each blending component and the blending ratio thereof were as shown in Table 7. Two types of ink compositions (Examples 43-1 to 43-2) were obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 35 except that the average power was changed to 3 W in the laser light irradiation conditions, and the tablets were marked. did. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 44]
An ink composition was obtained in the same manner as in Example 36 except that each blending component and the blending ratio thereof were as shown in Table 7. Two types of ink compositions (Examples 44-1 to 44-2) were obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 36, except that the average power was changed to 3 W in the laser light irradiation conditions, and the tablets were marked. did. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 45]
As shown in Table 7, the same ink compositions as in Examples 37-2 and 37-3 were obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 37 except that the average power was changed to 3 W instead of 2 W in the laser light irradiation conditions, and the tablets were marked. did. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

[Example 46]
An ink composition was obtained in the same manner as in Example 38, except that each blending component and the blending ratio thereof were as shown in Table 7. Two types of ink compositions (Examples 46-1 to 46-2) were obtained.
Then, using the obtained ink composition, a laser transfer film was produced in the same manner as in Example 38 except that the average power was changed to 3 W in the laser light irradiation conditions, and the tablets were marked. did. The thickness when the transfer layer was applied was 1 mil (25.4 μm). The imaging data of the tablet after marking is shown in FIG.

  In Examples 39 to 46, the tablets were marked, and the marking characteristics were excellent. In Examples 39 to 46, the average power at the time of laser light irradiation was further increased compared to Examples 31 to 38, but the mark density was generally higher than in Examples 31 to 38. . However, in Examples 41, 42, and 44 to 46, white portions were seen in some of the marks. In Examples 39 to 42, clearer marks were obtained.

<Manufacture of ink composition and laser transfer film, marking of tablets>
[Example 47]
As shown in Table 8, the same ink compositions as in Examples 23-1 and 23-2 were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 23 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 48]
As shown in Table 8, the same ink compositions as in Examples 24-1, 24-2, and 24-3 were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 24 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 49]
As shown in Table 8, the same ink compositions as in Examples 25-1, 25-2 and 25-3 were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 25 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 50]
As shown in Table 8, the same ink composition as in Example 26 was obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 26 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 51]
An ink composition was obtained in the same manner as in Example 27 except that each blending component and the blending ratio thereof were as shown in Table 8. Three types of ink compositions (Examples 51-1 to 51-3) were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 27 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 52]
As shown in Table 9, the same ink compositions as in Examples 28-1 and 28-2 were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 28 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 53]
As shown in Table 9, the same ink compositions as in Examples 29-1, 29-2, 29-3, and 29-4 were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 29 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Comparative Example 2]
An ink composition and a laser transfer film were produced in the same manner as Example 47 except that Eudragit E100 was not used, and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

In Examples 47 to 53, the tablets were marked, and the marking characteristics were excellent. In Examples 47 to 53, the transfer layer was thicker than in Examples 23 to 30, but the mark density was generally higher than in Examples 23 to 30. . In particular, clear marks were obtained in Examples 47-49 and 53. Further, in Example 53 using the same ink composition as in Example 29, the marking characteristics were remarkably improved as compared with Example 29.
On the other hand, in Comparative Example 2 using an ink composition in which no polymer was blended, the marking characteristics were inferior, and the marks were unclear as well as having white portions.

<Manufacture of ink composition and laser transfer film, marking of tablets>
[Example 54]
As shown in Table 10, the same ink composition as in Example 23-1 was obtained.
Then, laser transfer was performed in the same manner as in Example 31 except that the obtained ink composition was used and the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG. 32 together with the imaging data of Comparative Example 2.

[Example 55]
As shown in Table 10, the same ink compositions as in Examples 32-2 and 32-3 were obtained.
Then, laser transfer was performed in the same manner as in Example 32 except that the obtained ink composition was used and the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 56]
An ink composition was obtained in the same manner as in Example 33 except that each blending component and its blending ratio were as shown in Table 10. Three types of ink compositions (Examples 56-1 to 56-3) were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 33 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 57]
As shown in Table 10, the same ink composition as in Example 34-1 was obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 34 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 58]
As shown in Table 10, the same ink composition as in Example 35-1 was obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 35 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 59]
An ink composition was obtained in the same manner as in Example 36, except that each blending component and the blending ratio thereof were as shown in Table 11. Two ink compositions (Examples 59-1 to 59-2) were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 36 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 60]
As shown in Table 11, the same ink compositions as in Examples 37-1 and 37-2 were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 37 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 61]
As shown in Table 11, the same ink composition as in Example 38 was obtained.
Then, laser transfer was performed in the same manner as in Example 38 except that the obtained ink composition was used and the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

  In Examples 54 to 61, the tablets were marked, and the marking characteristics were excellent. In Examples 54 to 61, the average power at the time of laser beam irradiation was made larger than in Examples 47 to 53, but in Examples 47 to 53, the marks were clearer as a whole. However, in Examples 55, 56 and 57, clear marks were obtained.

<Manufacture of ink composition and laser transfer film, marking of tablets>
[Example 62]
An ink composition was obtained in the same manner as in Example 39 except that each blending component and the blending ratio thereof were as shown in Table 12. Two types of ink compositions (Examples 62-1 to 62-2) were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 39 except that the thickness when the transfer layer was applied was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG. 33 together with the imaging data of Comparative Example 2.

[Example 63]
An ink composition was obtained in the same manner as in Example 40 except that each blending component and the blending ratio thereof were as shown in Table 12. Three types of ink compositions (Examples 63-1 to 63-3) were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 40 except that the thickness at the time of coating the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 64]
An ink composition was obtained in the same manner as in Example 41 except that each blending component and the blending ratio thereof were as shown in Table 12. Three types of ink compositions (Examples 64-1 to 64-3) were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 41 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 65]
As shown in Table 12, the same ink compositions as in Examples 42-1 and 42-2 were obtained.
Then, laser transfer was performed in the same manner as in Example 42 except that the obtained ink composition was used and the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 66]
As shown in Table 12, the same ink composition as in Example 43-2 was obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 43 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 67]
An ink composition was obtained in the same manner as in Example 44 except that each blending component and its blending ratio were as shown in Table 13. Four types of ink compositions (Examples 67-1 to 67-4) were obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 44 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 68]
An ink composition was obtained in the same manner as in Example 45 except that each compounding component and its compounding ratio were as shown in Table 13. Three types of ink compositions (Examples 68-1 to 68-3) were obtained.
Then, laser transfer was performed in the same manner as in Example 45 except that the obtained ink composition was used and the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

[Example 69]
As shown in Table 13, the same ink composition as in Example 46-1 was obtained.
Then, using the obtained ink composition, laser transfer was performed in the same manner as in Example 46 except that the thickness at the time of applying the transfer layer was changed to 3 mil (76.2 μm) instead of 1 mil (25.4 μm). Films were manufactured and tablets were marked. The imaging data of the tablet after marking is shown in FIG.

  In Examples 62 to 69, the tablets were marked, and the marking characteristics were excellent. In Examples 62 to 69, the average power at the time of laser light irradiation is further increased as compared with Examples 54 to 61, but white portions are generally seen in the marks as compared with Examples 54 to 61. The marks of 54 to 61 were clearer on the whole.

In each of Examples 23 to 69, the ink composition in which all the coloring components are dissolved is used.
Tablets with a large amount and a small amount of polymer in the ink composition than the tablets illustrated in Examples 23 to 69 have low mark density, white portions on the marks, faint marks, etc. Any of these occurred, and the clarity of the mark was inferior to the illustrated tablet. However, as shown in Examples 23 to 69, in addition to the blending amount and type of the polymer in the ink composition, the marking conditions such as the thickness at the time of applying the transfer layer and the average power at the time of laser light irradiation were determined. By adjusting, it is possible to improve the clarity of the mark even when the same ink composition is used.

  In Examples 23 to 69, the clarity of the mark was particularly high when the average power at the time of laser beam irradiation was 2 W or less, regardless of the thickness of the transfer layer applied. In addition, regardless of the type of polymer blended in the ink composition, the thickness of the transfer layer applied, the laser irradiation conditions, etc. When the blending ratio was 40.0 to 62.5% by mass, the clarity of the mark was generally higher. Further, the weight average molecular weight of the polymer blended in the ink composition is preferably 40,000 to 77,000, more preferably 40, regardless of the thickness at the time of coating the transfer layer, the laser light irradiation conditions, and the like. In the case of 000 to 50,000, the clarity of the mark was generally higher.

  The present invention can be used for marking various articles, and is particularly suitable for marking pharmaceuticals and foods.

  DESCRIPTION OF SYMBOLS 1 ... Laser transfer film, 11 ... Base material, 11a ... One main surface (surface) of a base material, 12 ... Transfer layer, 12 '... Transfer layer transferred, 12a ..Main surface (surface) of transfer layer, 12c: peripheral edge of transfer layer, 8 ... marking device, 80 ... housing, 81 ... laser oscillator, 82 ... first reflection Mirror, 83 ... second reflection mirror, 84 ... lens, 9 ... transfer target edible, 9a ... transfer target edible surface, L ... laser light

Claims (62)

A marking method for marking edible food to be transferred using a laser transfer film provided with a substrate and a transfer layer in this order,
The transfer layer includes a edible polymer and a coloring component;
The laser transfer film is disposed with the transfer layer facing the edible side to be transferred, and the laser transfer film is irradiated from the base material side to the laser transfer film, so that at least a part of the transfer layer is transferable. A marking method of marking the edible food to be transferred by transferring it to food.   The marking method according to claim 1, wherein the polymer is at least one selected from the group consisting of a water-soluble polymer, a gastric polymer, an enteric polymer, and a sustained-release polymer.   The polymer is hydroxypropylcellulose, polyvinylpyrrolidone, copolypydone, hydroxypropylmethylcellulose, methylcellulose, polyvinyl alcohol / polyethylene glycol copolymer, polyvinyl alcohol, polyvinyl alcohol / acrylic acid / methyl methacrylate copolymer, aminoalkyl methacrylate copolymer E. , Polyvinyl acetal diethylaminoacetate, methacrylic acid copolymer L, hydroxypropylmethylcellulose acetate succinate, carboxymethylethylcellulose, ethylcellulose, aminoalkyl methacrylate copolymer RS and ethyl acrylate / methyl methacrylate copolymer The marking method according to claim 1.   The marking method according to any one of claims 1 to 3, wherein the coloring component is insoluble or an insoluble coloring component having an amount of a polar solvent required to dissolve 1 g thereof is 100 mL or more.   The insoluble or insoluble soluble coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, titanium oxide Red 40 aluminum lake, red 3 aluminum lake, blue 1 aluminum lake, blue 2 aluminum lake, yellow 5 aluminum lake, yellow 4 aluminum lake, riboflavin, β-carotene, carmine and carbon black The marking method according to claim 4, wherein the marking method is at least one selected from the group consisting of:   The marking method according to any one of claims 1 to 3, wherein the coloring component is a readily soluble coloring component whose amount of polar solvent required to dissolve 1 g thereof is less than 100 mL.   The readily soluble coloring components are red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, red No. 104, Red No. 105, Red No. 106, Green No. 3, selected from the group consisting of gardenia pigment, anthocyanin pigment, annatto pigment, paprika pigment, safflower pigment, sockeye pigment, flavonoid pigment, cochineal pigment and blue No. 2 The marking method according to claim 6, wherein the marking method is one or more.   The marking method according to any one of claims 4 to 7, wherein the polar solvent is one or more solvents selected from water, ethanol, and acetone.   The said coloring component is yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, yellow No. 4, blue No. 1, blue No. 2, titanium oxide, yellow ferric oxide, ferric oxide, red No. 2, red No. 3, red No. 40, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Green No. 3, Red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Caramel Dye, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment, Talc, Calcium carbonate, Magnesium carbonate, Magnesium oxide, Magnesium stearate, Calcium stearate, Zinc stearate, Aluminum stearate , Barium sulfate, carbon black The marking according to any one of claims 1 to 3, which is at least one selected from the group consisting of carmine, β-carotene, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, riboflavin and riboflavin butyrate. Method.   The coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, titanium oxide, red No. 40 aluminum 1 selected from the group consisting of lake, red No. 3 aluminum lake, blue No. 1 aluminum lake, blue No. 2 aluminum lake, yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, riboflavin, β-carotene, carmine and carbon black The marking method according to claim 9, wherein the marking method is a seed or more.   The coloring components are red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, red No. 104. , Red 105, Red 106, Green 3, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment and Blue 2 The marking method according to claim 9, which is as described above.   The marking method according to claim 1, wherein the transfer layer further contains a plasticizer.   The marking method according to claim 12, wherein the plasticizer is at least one selected from the group consisting of triserine, glycerin fatty acid ester, sucrose fatty acid ester, triethyl citrate, polyethylene glycol, and higher alcohol.   The substrate is cellulose, ionomer, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene- The marking method as described in any one of Claims 1-13 which consists of 1 or more types selected from the group which consists of a methacrylic acid copolymer and nylon.   The marking method as described in any one of Claims 1-14 which arrange | positions the said laser transfer film, without making it contact with the said transfer object edible.   The marking method according to any one of claims 1 to 15, wherein the edible food to be transferred is a medicine, and the edible is a medicine.   A laser transfer film comprising a base material and a transfer layer in this order, wherein the transfer layer contains a polymer that can be edible and a coloring component.   The laser transfer film according to claim 17, wherein the polymer is at least one selected from the group consisting of a water-soluble polymer, a gastric polymer, an enteric polymer, and a sustained-release polymer.   The polymer is hydroxypropylcellulose, polyvinylpyrrolidone, copolypydone, hydroxypropylmethylcellulose, methylcellulose, polyvinyl alcohol / polyethylene glycol copolymer, polyvinyl alcohol, polyvinyl alcohol / acrylic acid / methyl methacrylate copolymer, aminoalkyl methacrylate copolymer E. , Polyvinyl acetal diethylaminoacetate, methacrylic acid copolymer L, hydroxypropylmethylcellulose acetate succinate, carboxymethylethylcellulose, ethylcellulose, aminoalkyl methacrylate copolymer RS and ethyl acrylate / methyl methacrylate copolymer The laser transfer film according to claim 17.   The laser transfer film according to any one of claims 17 to 19, wherein the coloring component is an insoluble or an insoluble coloring component in which the amount of a polar solvent required to dissolve 1 g thereof is 100 mL or more.   The insoluble or insoluble soluble coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, titanium oxide Red 40 aluminum lake, red 3 aluminum lake, blue 1 aluminum lake, blue 2 aluminum lake, yellow 5 aluminum lake, yellow 4 aluminum lake, riboflavin, β-carotene, carmine and carbon black The laser transfer film according to claim 20, which is one or more selected from the group consisting of:   The laser transfer film according to any one of claims 17 to 19, wherein the coloring component is a readily soluble coloring component whose amount of polar solvent required to dissolve 1 g thereof is less than 100 mL.   The readily soluble coloring components are red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, red No. 104, Red No. 105, Red No. 106, Green No. 3, selected from the group consisting of gardenia pigment, anthocyanin pigment, annatto pigment, paprika pigment, safflower pigment, sockeye pigment, flavonoid pigment, cochineal pigment and blue No. 2 The laser transfer film according to claim 22, wherein the laser transfer film is one or more.   The laser transfer film according to any one of claims 20 to 23, wherein the polar solvent is one or more solvents selected from water, ethanol, and acetone.   The said coloring component is yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, yellow No. 4, blue No. 1, blue No. 2, titanium oxide, yellow ferric oxide, ferric oxide, red No. 2, red No. 3, red No. 40, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Green No. 3, Red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Caramel Dye, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment, Talc, Calcium carbonate, Magnesium carbonate, Magnesium oxide, Magnesium stearate, Calcium stearate, Zinc stearate, Aluminum stearate , Barium sulfate, carbon black The laser according to any one of claims 17 to 19, which is at least one selected from the group consisting of: carmine, β-carotene, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, riboflavin and riboflavin butyrate. Transfer film.   The coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, titanium oxide, red No. 40 aluminum 1 selected from the group consisting of lake, red No. 3 aluminum lake, blue No. 1 aluminum lake, blue No. 2 aluminum lake, yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, riboflavin, β-carotene, carmine and carbon black The laser transfer film according to claim 25, wherein the laser transfer film is a seed or more.   The coloring components are red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, red No. 104. , Red 105, Red 106, Green 3, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment and Blue 2 The laser transfer film according to claim 25, which is as described above.   The laser transfer film according to any one of claims 17 to 27, wherein the transfer layer further contains a plasticizer.   29. The laser transfer film according to claim 28, wherein the plasticizer is at least one selected from the group consisting of triserine, glycerin fatty acid ester, sucrose fatty acid ester, triethyl citrate, polyethylene glycol and higher alcohol.   The substrate is cellulose, ionomer, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene- The laser transfer film according to any one of claims 17 to 29, comprising at least one selected from the group consisting of a methacrylic acid copolymer and nylon.   The laser transfer film according to any one of claims 17 to 30, wherein the edible material is a medicine.   An ink composition for forming the transfer layer in a laser transfer film provided with a base material and a transfer layer in this order, comprising an edible polymer and a coloring component, and a solvent or dispersion medium object.   The ink composition according to claim 32, wherein the polymer is at least one selected from the group consisting of a water-soluble polymer, a gastric polymer, an enteric polymer, and a sustained-release polymer.   The polymer is hydroxypropylcellulose, polyvinylpyrrolidone, copolypydone, hydroxypropylmethylcellulose, methylcellulose, polyvinyl alcohol / polyethylene glycol copolymer, polyvinyl alcohol, polyvinyl alcohol / acrylic acid / methyl methacrylate copolymer, aminoalkyl methacrylate copolymer E. , Polyvinyl acetal diethylaminoacetate, methacrylic acid copolymer L, hydroxypropylmethylcellulose acetate succinate, carboxymethylethylcellulose, ethylcellulose, aminoalkyl methacrylate copolymer RS and ethyl acrylate / methyl methacrylate copolymer The ink composition according to claim 32.   The ink composition according to any one of claims 32 to 34, wherein the coloring component is an insoluble or an insoluble coloring component having an amount of a polar solvent required to dissolve 1 g of the coloring component is 100 mL or more.   The insoluble or insoluble soluble coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, titanium oxide Red 40 aluminum lake, red 3 aluminum lake, blue 1 aluminum lake, blue 2 aluminum lake, yellow 5 aluminum lake, yellow 4 aluminum lake, riboflavin, β-carotene, carmine and carbon black 36. The ink composition according to claim 35, wherein the ink composition is one or more selected from the group consisting of:   35. The ink composition according to any one of claims 32 to 34, wherein the coloring component is a readily soluble coloring component whose amount of polar solvent required to dissolve 1 g thereof is less than 100 mL.   The readily soluble coloring components are red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, red No. 104, Red No. 105, Red No. 106, Green No. 3, selected from the group consisting of gardenia pigment, anthocyanin pigment, annatto pigment, paprika pigment, safflower pigment, sockeye pigment, flavonoid pigment, cochineal pigment and blue No. 2 The ink composition according to claim 37, wherein the ink composition is one or more.   The ink composition according to any one of claims 35 to 38, wherein the polar solvent is one or more solvents selected from water, ethanol, and acetone.   The said coloring component is yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, yellow No. 4, blue No. 1, blue No. 2, titanium oxide, yellow ferric oxide, ferric oxide, red No. 2, red No. 3, red No. 40, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Green No. 3, Red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Caramel Dye, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment, Talc, Calcium carbonate, Magnesium carbonate, Magnesium oxide, Magnesium stearate, Calcium stearate, Zinc stearate, Aluminum stearate , Barium sulfate, carbon black 35. The ink according to any one of claims 32 to 34, which is at least one selected from the group consisting of, carmine, β-carotene, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, riboflavin and riboflavin butyrate. Composition.   The coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, titanium oxide, red No. 40 aluminum 1 selected from the group consisting of lake, red No. 3 aluminum lake, blue No. 1 aluminum lake, blue No. 2 aluminum lake, yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, riboflavin, β-carotene, carmine and carbon black 41. The ink composition according to claim 40, wherein the ink composition is a seed or more.   The coloring components are red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, red No. 104. , Red 105, Red 106, Green 3, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment and Blue 2 The ink composition according to claim 40, which is as described above.   The ink composition according to any one of claims 32 to 42, further comprising a plasticizer.   44. The ink composition according to claim 43, wherein the plasticizer is at least one selected from the group consisting of triserine, glycerin fatty acid ester, sucrose fatty acid ester, triethyl citrate, polyethylene glycol, and higher alcohol.   45. The ink composition according to any one of claims 32 to 44, wherein the edible material is a medicine. A method for producing a transferable edible product with a mark,
A laser transfer film provided with a base material and a transfer layer in this order is arranged with the transfer layer facing the edible side to be transferred, and the laser transfer film is irradiated with laser light from the base material side, and the transfer Marking the transferable edible by transferring at least a portion of a layer to the transferable edible,
The manufacturing method in which the said transfer layer contains the polymer | macromolecule and coloring component which can be mix | blended edible.   The manufacturing method according to claim 46, wherein the polymer is at least one selected from the group consisting of a water-soluble polymer, a gastric polymer, an enteric polymer, and a sustained-release polymer.   The polymer is hydroxypropylcellulose, polyvinylpyrrolidone, copolypydone, hydroxypropylmethylcellulose, methylcellulose, polyvinyl alcohol / polyethylene glycol copolymer, polyvinyl alcohol, polyvinyl alcohol / acrylic acid / methyl methacrylate copolymer, aminoalkyl methacrylate copolymer E. , Polyvinyl acetal diethylaminoacetate, methacrylic acid copolymer L, hydroxypropylmethylcellulose acetate succinate, carboxymethylethylcellulose, ethylcellulose, aminoalkyl methacrylate copolymer RS and ethyl acrylate / methyl methacrylate copolymer The manufacturing method according to claim 46.   49. The production method according to any one of claims 46 to 48, wherein the coloring component is an insoluble or an insoluble coloring component whose amount of polar solvent required to dissolve 1 g thereof is 100 mL or more.   The insoluble or insoluble soluble coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, titanium oxide Red 40 aluminum lake, red 3 aluminum lake, blue 1 aluminum lake, blue 2 aluminum lake, yellow 5 aluminum lake, yellow 4 aluminum lake, riboflavin, β-carotene, carmine and carbon black The manufacturing method of Claim 49 which is 1 or more types selected from.   49. The method according to any one of claims 46 to 48, wherein the coloring component is a readily soluble coloring component whose amount of polar solvent required to dissolve 1 g thereof is less than 100 mL.   The readily soluble coloring components are red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, red No. 104, Red No. 105, Red No. 106, Green No. 3, selected from the group consisting of gardenia pigment, anthocyanin pigment, annatto pigment, paprika pigment, safflower pigment, sockeye pigment, flavonoid pigment, cochineal pigment and blue No. 2 The production method according to claim 51, wherein the production method is one or more.   53. The production method according to any one of claims 49 to 52, wherein the polar solvent is one or more solvents selected from water, ethanol, and acetone.   The said coloring component is yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, yellow No. 4, blue No. 1, blue No. 2, titanium oxide, yellow ferric oxide, ferric oxide, red No. 2, red No. 3, red No. 40, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Green No. 3, Red No. 40 Aluminum Lake, Red No. 3 Aluminum Lake, Blue No. 1 Aluminum Lake, Blue No. 2 Aluminum Lake, Caramel Dye, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment, Talc, Calcium carbonate, Magnesium carbonate, Magnesium oxide, Magnesium stearate, Calcium stearate, Zinc stearate, Aluminum stearate , Barium sulfate, carbon black 49. The production according to any one of claims 46 to 48, which is at least one selected from the group consisting of carmine, β-carotene, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, riboflavin and riboflavin butyrate. Method.   The coloring component is yellow ferric oxide, ferric oxide, barium sulfate, talc, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium stearate, calcium stearate, zinc stearate, aluminum stearate, titanium oxide, red No. 40 aluminum 1 selected from the group consisting of lake, red No. 3 aluminum lake, blue No. 1 aluminum lake, blue No. 2 aluminum lake, yellow No. 5 aluminum lake, yellow No. 4 aluminum lake, riboflavin, β-carotene, carmine and carbon black The manufacturing method according to claim 54, wherein the method is more than a seed.   The coloring components are red No. 2, red No. 3, red No. 102, blue No. 1, yellow No. 4, yellow No. 5, copper chlorophyllin sodium, copper chlorophyll, caramel dye, riboflavin butyrate, red No. 40, red No. 104. , Red 105, Red 106, Green 3, Gardenia pigment, Anthocyanin pigment, Anato pigment, Paprika pigment, Safflower pigment, Scarlet pigment, Flavonoid pigment, Cochineal pigment and Blue 2 The manufacturing method according to claim 54, which is the above.   The manufacturing method according to any one of claims 46 to 56, wherein the transfer layer further contains a plasticizer.   58. The production method according to claim 57, wherein the plasticizer is at least one selected from the group consisting of triserine, glycerin fatty acid ester, sucrose fatty acid ester, triethyl citrate, polyethylene glycol and higher alcohol.   The substrate is cellulose, ionomer, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene- 59. The production method according to any one of claims 46 to 58, comprising at least one selected from the group consisting of a methacrylic acid copolymer and nylon.   The manufacturing method according to any one of claims 46 to 59, wherein the laser transfer film is disposed without being in contact with the edible food to be transferred.   The production method according to any one of claims 46 to 60, wherein the edible food to be transferred is a medicine, and the edible is a medicine.   62. A transfer target edible product with a mark produced by the production method according to any one of claims 46 to 61.