JP4258673B2 - Laminate and ink film - Google Patents

Description

  The present invention relates to a laminate and an ink film. More specifically, the present invention relates to a printing ink composition that reflects infrared rays and a package printed with the ink composition.

  In PTP packaging, which is a form of drug packaging, transparent or translucent sheets such as vinyl chloride and polypropylene that have been molded to match the shape of the drug are printed with the brand and manufacturer name of the drug being packaged. Covered with an aluminum foil lid.

  As a means for detecting foreign matter in a package after packaging a medicine, a defect detection device using infrared rays is widely used.

  In this defect detection apparatus using infrared rays, even if the object to be inspected has a printed pattern, the defect detection accuracy can be improved by erasing or thinning the printed portion when viewed with an infrared image. Therefore, it is necessary to design the defect to be inspected so as to absorb infrared rays and to reflect the infrared rays in both the unprinted portion and the printed portion of the package.

  When printing in black, white, green or brown, a colorant having these colors absorbs infrared rays and cannot be used as it is. For this reason, in the prior art, printing that reflects infrared rays is created by blending colorants having other colors so as to be the same color as these colors. For example, when creating black, three primary colors are mixed. For example, when green is produced, the same color can be obtained by mixing blue and yellow.

However, there are colors that are difficult or impossible to reproduce by mixing with other hues, such as white. In such a color, it is not possible to form a print layer that reflects infrared rays. In this regard, Patent Document 1 describes a package that does not react with a defect detection device using infrared rays, but describes a method for forming a printed layer using a color that absorbs infrared rays such as white ink. It has not been.
JP 2004-239889 A

  The present invention has been made in view of the above problems, and it is a main object of the present invention to provide a printing ink that can form a printing layer that is particularly easy to reflect infrared rays.

  As a result of intensive studies, the present inventors have found that a printing ink containing spherical particles in particular can achieve the above object, and have completed the present invention.

That is, the present invention relates to the following laminate, package and ink film .
1. A printing ink composition comprising a colorant and spherical particles having a sphericity of 0.5 or more, comprising a colorant that absorbs infrared rays as the colorant, wherein the spherical particles have an average particle size of 4 to 30 μm Ri Oh spherical particles, said comprising the spherical particles separately from the colorant using a printing ink composition for forming an ink film to be used in defect detection method using an infrared, dry film thickness of the ink film A laminate obtained by printing on a substrate so that the thickness becomes 0.3 to 5 μm .
2. Item 2. The laminate according to Item 1, wherein the colorant that absorbs infrared rays is a white colorant.
3. Item 3. The laminate according to Item 2, wherein the white colorant includes at least one of titanium oxide and magnesium oxide.
4). Item 4. The laminate according to Item 2 or 3, wherein the colorant that absorbs infrared rays contains 1% by weight or more in the printing ink composition.
5. The spherical particles are metal, glass, acrylic, polyethylene, polystyrene, polypropylene, polyethylene terephthalate, polyurethane, cellulose, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic. Item 5. The laminate according to any one of Items 1 to 4, comprising at least one of ethyl acid copolymer, polyacrylonitrile, polyamide, silicon oxide, aluminum oxide, talc, slaked lime, barium sulfate, calcium carbonate, and calcium hydroxide. body.
6). Item 6. The laminate according to any one of Items 1 to 5, wherein the printing ink composition contains 0.1 to 50% by weight of spherical particles.
7). Further, cellulose, polyvinyl butyral, polyamide, polyolefin, polyurethane, acrylic, polyester, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer and ethylene-ethyl acrylate copolymer are used as vehicle components. The laminated body in any one of said claim | item 1-6 containing at least 1 sort (s) of coalescence.
8). Item 8. The laminate according to any one of Items 1 to 7, wherein the substrate is aluminum.
9. A package comprising the laminate according to any one of Items 1 to 8 as a packaging material.
10. A press-through pack (PTP) package using the laminate according to any one of Items 1 to 8 as a packaging material.
11. An ink film used in a defect detection method using infrared rays, wherein the ink film is a printing ink composition containing a colorant and spherical particles having a sphericity of 0.5 or more, and the colorant The ink film comprising a colorant that absorbs infrared rays, wherein the spherical particles are spherical particles having an average particle diameter of 4 to 30 μm, and formed using a printing ink composition containing the spherical particles separately from the colorant. An ink film having a dry film thickness of 0.3 to 5 μm .
12 . Item 12. The ink film according to Item 11 , wherein the colorant that absorbs infrared rays is a white colorant.
13 . Item 13. The ink film according to Item 12 , wherein the white colorant contains at least one of titanium oxide and magnesium oxide.
14 . Item 14. The ink film according to any one of Items 11 to 13 , wherein the colorant that absorbs infrared rays contains 1% by weight or more in the printing ink composition.
15 . The spherical particles are metal, glass, acrylic, polyethylene, polystyrene, polypropylene, polyethylene terephthalate, polyurethane, cellulose, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic. Item 15. The ink according to any one of Items 11 to 14 , comprising at least one of ethyl acid copolymer, polyacrylonitrile, polyamide, silicon oxide, aluminum oxide, talc, slaked lime, barium sulfate, calcium carbonate, and calcium hydroxide. Film.
16 . Item 16. The ink film according to any one of Items 11 to 15 , wherein the printing ink composition contains 0.1 to 50% by weight of spherical particles.

  According to the printing ink composition of the present invention, since specific spherical particles are included separately from the colorant, an excellent infrared reflection effect can be achieved. For this reason, even if it uses what absorbs infrared rays as a coloring agent (for example, white type coloring agents, such as titanium oxide and magnesium oxide), it becomes possible to form the printing layer which reflects infrared rays by the presence of spherical particles. .

  Thereby, when a package is comprised from the laminated body which has a printing layer by this invention ink membrane | film | coat or this invention ink composition, the package (especially PTP) used for the fault detection method (foreign matter detection method) which uses infrared rays. A package). Since such a package effectively reflects infrared rays, foreign matter can be detected with high detection accuracy.

  Hereinafter, the manner in which spherical particles (particles) reflect infrared rays in the printing layer of the printing ink composition of the present invention using a white colorant (such as titanium oxide) as the colorant will be described with reference to the drawings. The colorant itself is necessary to make the printed layer white and is included in the printed layer. If particles that transmit or reflect infrared rays are mixed in the print layer as shown in FIG. 1, the distance that incident infrared rays pass through the print layer containing the colorant can be shortened. That is, a printed layer in which incident infrared rays are difficult to be absorbed (that is, easily reflected) is formed.

  However, as shown in FIG. 2, the particle generally has an uneven surface, so that part of the incident infrared rays is irregularly reflected in the print layer. As a result, more infrared rays pass through the printing layer containing the colorant, and as a result, the infrared rays are absorbed by the colorant.

  In contrast, as shown in FIG. 3, when spherical particles are included, most of the incident infrared rays are reflected without reaching the substrate (light path A), or enter the printed layer containing the colorant. Even so, it is considered that the particles go out of the printed layer without repeating reflection between particles (light path B). In this case, when the size of the spherical particles is remarkably smaller than that of the printed layer, the effect of being spherical is reduced if the particles are aggregated or the particles are arranged vertically in the printed layer. For this reason, it is desirable that the size of the particles is about the size of one on the left and the right in the printing layer.

  In the present invention, even when a colorant that absorbs infrared rays is contained in the printing layer, the infrared reflectance can be increased without impairing color development by mixing predetermined spherical particles.

  As described above, the printing ink composition of the present invention reacts in a defect detection method using infrared rays while having the same color developability as compared with the white ink using a conventional titanium oxide, magnesium oxide or the like as a colorant. Infrared reflectance sufficient to not show.

1. Printing ink composition The printing ink composition of the present invention comprises a colorant and spherical particles having a sphericity of 0.5 or more.

  The spherical particle in this invention is contained in this invention composition as components other than a coloring agent.

  The spherical particles have a sphericity of 0.5 or more, preferably 0.8 to 1.0. When the sphericity is less than 0.5, a desired infrared reflection effect cannot be obtained. The sphericity in the present invention is determined by observing spherical particles with an electron microscope (SEM), and selecting the shortest diameter (shortest diameter: observation field of view or a photograph thereof) of each of 20 particles selected arbitrarily. The shortest distance when a particle is sandwiched between two parallel segments) and the longest diameter (the longest diameter: the individual particles are sandwiched between two parallel segments in the observation field or on the photograph) Ratio of the longest distance) (shortest diameter / longest diameter) is calculated, and the average value of the ratios is shown. Known or commercially available spherical particles having such sphericity can be used. For example, suitable spherical particles can be obtained by a gas atomizing method in the case of metal powder, a spray drying method in the case of glass beads, and a saponification polymerization method or an emulsion polymerization method in the case of plastic beads.

  The average particle diameter of the spherical particles can be appropriately set according to the use, usage form, etc. of the ink composition of the present invention, but is usually 1 to 50 μm, particularly 4 to 30 μm, more preferably 4 to 20 μm. The average particle diameter of the spherical particles in the present invention is determined by observing the spherical particles with an electron microscope (SEM), and selecting the shortest diameter (shortest diameter: observation field of view or its photograph) of each of 20 particles selected arbitrarily. , The shortest distance when individual particles are sandwiched between two parallel line segments) and the longest diameter (longest diameter: on the observation field or in the photograph thereof, the individual particles are separated by two parallel line segments. The average ((shortest diameter + longest diameter) / 2) of the longest distance when sandwiched is calculated, and the total average value thereof is shown. In the present invention, it is desirable that the size of the spherical particles is a size arranged one by one on the plane in the printing layer, so that the particle size is close to the thickness of the printing layer, in particular 1 / th of the thickness of the printing layer. The particle size is preferably 2 or more and 8 or less times the thickness of the printing layer.

  The spherical particles are preferably a substance that hardly absorbs infrared rays because when the particles themselves absorb infrared rays, a printed layer that reflects the infrared rays cannot be formed. Examples of such materials include metals (including alloys and intermetallic compounds), glass, acrylic, polyethylene, polystyrene, polypropylene, polyethylene terephthalate, polyurethane, cellulose, polyvinyl chloride, polyvinyl alcohol, and ethylene-vinyl acetate copolymer. Polymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, polyacrylonitrile, polyamide, silicon oxide, aluminum oxide, talc, slaked lime, barium sulfate, calcium carbonate, and calcium hydroxide are used. It is preferable.

  The content of the spherical particles in the printing ink composition is not particularly limited, but is usually preferably 0.1 to 50% by weight, more preferably 1 to 20% by weight. By setting within the above range, it is possible to more reliably obtain a favorable ink hue, printability and the like together with a desired infrared reflection effect.

  A known pigment or dye can be used as the colorant. In particular, in the present invention, either a colorant that reflects infrared rays or a colorant that absorbs infrared rays can be employed as the colorant. That is, the ink composition of the present invention can obtain a predetermined infrared reflection effect even if it contains a colorant that absorbs infrared rays, but is particularly useful when all of the colorants are colorants that absorb infrared rays. It is.

  The colorant that absorbs infrared rays is not limited, but typical examples thereof include at least one of a black colorant, a white colorant, a green colorant, and a brown colorant. Examples of the black colorant include carbon black. Examples of white colorants include titanium oxide and magnesium oxide. Examples of the green colorant include cyanine green and phthalocyanine green. Examples of brown colorants include Bengala. Among these, a white colorant can be preferably employed in the ink composition of the present invention. In particular, the white colorant desirably contains at least one of titanium oxide and magnesium oxide. Furthermore, it is more preferable that all the colorants are at least one of titanium oxide and magnesium oxide.

  The content of the colorant (including the colorant that absorbs infrared rays) varies depending on the type of the colorant to be used, but is usually 1 to 50% by weight, particularly 10 to 20% by weight in the ink composition of the present invention. desirable. The content of the colorant that absorbs infrared rays is usually 1 to 50% by weight, particularly 10 to 20% by weight in the ink composition of the present invention. By setting the content of the colorant that absorbs infrared rays within the above range, in addition to the excellent infrared reflection effect, good color developability, printing performance, and the like can be obtained more reliably.

  In the printing ink composition of the present invention, components contained in a normal printing ink can be used. For example, in addition to a solvent and a vehicle, polyethylene wax for improving wear resistance, silicon dioxide for preventing blocking, and the like can be added as necessary.

  Examples of the solvent include aromatic hydrocarbons such as toluene, alicyclic hydrocarbons such as methylcyclohexane, esters such as ethyl acetate, ketones such as methyl ethyl ketone, alcohol solvents such as isopropyl alcohol and modified alcohol, and the like. A mixed solvent is used.

  Examples of the vehicle include cellulose, polyvinyl butyral, polyamide, polyolefin, polyurethane, acrylic, polyester, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer. It is preferable to select from at least one of the coalesced materials, but more preferably cellulose resin and polyvinyl butyral resin.

  The printing ink composition of the present invention may exhibit any color, but particularly preferably exhibits a white color (particularly white or pastel). That is, while the white printing layer according to the conventional technique absorbs infrared rays, the white printing ink composition of the present invention can form a printing layer that reflects infrared rays well. In particular, the excellent effect of infrared reflectance of 60% or more can be achieved.

  The printing / coating method using the printing ink composition of the present invention may be any method such as general gravure coating, silk screen, flexo and the like. For example, a gravure coat is preferably used.

  Although the dry film thickness of the printed ink film is not limited, it is generally preferably 0.3 to 5 μm, more preferably 0.8 to 2 μm. If the dry film is too thick, it can easily cause blocking problems.

2. Laminated body and package body The present invention relates to the above-described 1. And a laminate formed by printing on a printing medium using the printing ink composition. The printed material may be any of metal, paper, resin, and the like, but is particularly preferably a metal foil and more preferably an aluminum foil.

  The present invention also includes a package used as the packaging material. In particular, since the printing layer of the printing ink composition of the present invention reflects infrared rays well, it is preferably used as a package (particularly a PTP package) used for a defect detection method (foreign matter detection method) using infrared rays. it can. The configuration itself of the package (PTP package) may follow a known configuration.

3. Ink film The present invention is an ink film used in a defect detection method using infrared rays, wherein the ink film uses a printing ink composition containing a colorant and spherical particles having a sphericity of 0.5 or more. Ink film formed by

  As the printing ink composition, a printing ink composition containing a colorant and spherical particles having a sphericity of 0.5 or more is used. In this case, the ink composition is the same as the above-described 1. The ink composition may be prepared according to the ink composition.

  In general, the thickness (dry film thickness) of the ink film of the present invention is preferably from 0.3 to 5 μm, more preferably from 0.8 to 2 μm, for the same reason as in the printed layer.

  Further, as described in the item of the spherical particles, in the present invention, it is desirable that the size of the spherical particles is a size that is arranged one by one on a plane in the ink film, so that it is close to the thickness of the ink film. It is preferable that the particle diameter is, in particular, not less than 1/2 of the thickness of the ink film and not more than 8 times the thickness of the ink film.

  Since the ink film of the present invention reflects infrared rays satisfactorily in the same manner as described for the printing layer, it can be suitably used for a defect detection method using infrared rays. As a defect detection method using infrared rays, a known method or apparatus can be employed.

  The method for forming the ink film can also be carried out in the same manner as the method for forming the printed layer. For example, an arbitrary system such as a general gravure coat, a silk screen, or a flexo may be used.

  EXAMPLES Hereinafter, an Example is shown and this invention is demonstrated more concretely. However, the scope of the present invention is not limited to the examples.

  In the present specification, the mixed solvent is a mixture of toluene / ethyl acetate / methyl ethyl ketone in a 1/1/1 ratio (weight ratio), and parts and% are based on mass unless otherwise specified. .

<Examples 1-5 and Comparative Examples 1-5>
A. Preparation of ink compositions For Examples 1 to 4, Comparative Example 1, Comparative Example 3 and Comparative Example 4, the following (1) to (4) were mixed in a sand mill, and then (5) and (6) were added. An ink composition was prepared.

(1) Pigment: 15 parts (2) Polyvinyl butyral resin: 5 parts (3) Nitrified cotton resin: 5 parts (4 ) Mixed solvent: 40 parts (5) Particle: Specified amount (* -1)
(6) Mixed solvent: Specified amount (* -2)
For Example 5 and Comparative Example 2, according to the following formulation, the following (1) to (4) were mixed in a sand mill, and then (5) and (6) were added to prepare an ink composition.

(1) Pigment: 10 parts (2) Polyvinyl butyral resin: 5 parts (3) Nitrified cotton resin: 5 parts (4 ) Mixed solvent: 50 parts (5) Particle: Specified amount (* -1)
(6) Mixed solvent: Specified amount (* -2)
Remarks of these examples and comparative examples are as follows.

  * -1: The amount described in Table 1 was added.

* -2: Adjustment was made by adding an amount such that the total ink blend amount was 100 parts.
The pigments and particles shown in Table 1 were used in the examples and comparative examples.

  The sphericity in Table 1 was measured as follows. After the particles to be added were observed with a scanning electron microscope and obtained as a photograph on a plane, the ratio of the shortest diameter to the longest diameter (shortest diameter / longest diameter) was measured for 20 particles arbitrarily selected, and the average The value was defined as sphericity.

B. Formation of printing layer Printing was carried out using each ink composition. Specifically, the ink diluted to 20 seconds with Zahn Cup # 3 was printed on a matte surface of an aluminum foil having a thickness of 20 μm as defined in JIS1N30 using a Helio 175 line solid plate. The infrared reflectance of the formed printed layer was measured. The results are shown in Table 1. The infrared reflectance was an average value of the reflectance when irradiated with infrared rays having wavelengths of 800 nm, 825 nm, 850 nm, and 900 nm, respectively. For the measurement, an ultraviolet-visible near-infrared spectrophotometer (“JASCO V570 type” manufactured by JASCO Corporation) was used. An outline of the measurement method using the photometer is shown in FIG. The specifications of the photometer were as follows: holder type: integrating sphere type, measurement size: length 8 mm × width 9 mm, integrating sphere inner diameter: 60 mm, integrating sphere inner wall coating agent: barium sulfate.

  As is clear from the results in Table 1, the titanium oxide (white color) system clears 60%, which is a practical measure of infrared reflectance, in any of Examples 1 to 4. In Comparative Example 1 (only titanium oxide), the practical infrared reflectance was not reached. Further, the phthalocyanine blue (blue color) system has conventionally shown a good infrared reflectance (Comparative Example 2), but the system to which spherical particles are added (Example 5) has a better reflectance than the Comparative Example. You can see that

  In Comparative Example 3, the effect of non-spherical aluminum paste (aluminum flakes) was confirmed, but the practical reflectance was not reached. In Comparative Example 4, the effect of increasing the thickness of the ink film while reducing the amount of spherical fine particles added was confirmed, but the practical reflectance was not reached. In Comparative Example 5, confirmation was made in a system without a pigment, but it was found that the practical reflectance was significantly exceeded. In Comparative Example 5, the pigment (titanium oxide) was removed from the ink composition of Comparative Example 4, and the thickness of the printing layer was 2 μm.

  From the above results, the printing ink composition of the present invention has a higher infrared reflectance than the conventional white ink and the like, and has sufficient color developability. Moreover, the PTP packaging material using the ink of the present invention can be suitably used for a defect detection apparatus using infrared rays, and can provide white or pastel colors as a design.

It is the figure which showed typically a mode that the particle | grains which exist in a printing layer reflect infrared rays. It is the figure which showed typically a mode that the particle | grains which exist in a printing layer reflect infrared rays. It is the figure which showed typically a mode that the particle | grains which exist in a printing layer reflect infrared rays. It is the schematic of the method of measuring an infrared reflectance with a photometer.

Claims (16)

A printing ink composition comprising a colorant and spherical particles having a sphericity of 0.5 or more, comprising a colorant that absorbs infrared rays as the colorant, wherein the spherical particles have an average particle size of 4 to 30 μm Ri Oh spherical particles, said comprising the spherical particles separately from the colorant using a printing ink composition for forming an ink film to be used in defect detection method using an infrared, dry film thickness of the ink film A laminate obtained by printing on a substrate so that the thickness becomes 0.3 to 5 μm . The laminate according to claim 1, wherein the colorant that absorbs infrared rays is a white colorant. The laminate according to claim 2, wherein the white colorant contains at least one of titanium oxide and magnesium oxide. The laminate according to claim 2 or 3, wherein the colorant that absorbs infrared rays contains 1% by weight or more in the printing ink composition. The spherical particles are metal, glass, acrylic, polyethylene, polystyrene, polypropylene, polyethylene terephthalate, polyurethane, cellulose, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic. The laminate according to any one of claims 1 to 4, comprising at least one of ethyl acid copolymer, polyacrylonitrile, polyamide, silicon oxide, aluminum oxide, talc, slaked lime, barium sulfate, calcium carbonate, and calcium hydroxide. body. The laminate according to any one of claims 1 to 5, wherein the printing ink composition contains 0.1 to 50% by weight of spherical particles. Further, cellulose, polyvinyl butyral, polyamide, polyolefin, polyurethane, acrylic, polyester, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer and ethylene-ethyl acrylate copolymer are used as vehicle components. The laminated body in any one of Claims 1-6 containing at least 1 sort (s) of coalescence. The laminated body in any one of Claims 1-7 whose to-be-printed body is aluminum. Package comprising a stacked body according as a packaging material to one of claims 1 to 8. A press-through pack (PTP) package using the laminate according to any one of claims 1 to 8 as a packaging material. An ink film used in a defect detection method using infrared rays, wherein the ink film is a printing ink composition containing a colorant and spherical particles having a sphericity of 0.5 or more, and the colorant The ink film comprising a colorant that absorbs infrared rays, wherein the spherical particles are spherical particles having an average particle diameter of 4 to 30 μm, and formed using a printing ink composition containing the spherical particles separately from the colorant. An ink film having a dry film thickness of 0.3 to 5 μm . The ink film according to claim 11 , wherein the colorant that absorbs infrared rays is a white colorant. The ink film according to claim 12 , wherein the white colorant includes at least one of titanium oxide and magnesium oxide. The ink film according to any one of claims 11 to 13 , wherein the colorant that absorbs infrared rays contains 1% by weight or more in the printing ink composition. The spherical particles are metal, glass, acrylic, polyethylene, polystyrene, polypropylene, polyethylene terephthalate, polyurethane, cellulose, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic. The ink according to any one of claims 11 to 14 , comprising at least one of ethyl acid copolymer, polyacrylonitrile, polyamide, silicon oxide, aluminum oxide, talc, slaked lime, barium sulfate, calcium carbonate, and calcium hydroxide. Film. The ink film according to any one of claims 11 to 15 , wherein the printing ink composition contains 0.1 to 50% by weight of spherical particles.

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