JP6827277B2 - A printing ink composition for PTP packaging and a laminate using a printing ink composition for PTP packaging. - Google Patents

Description

The present invention relates to a printing ink for PTP (Press Through Pack) packaging used for packaging pharmaceutical products and the like, and a laminate using a printing ink for PTP packaging.

The PTP packaging used for packaging pharmaceutical products and the like is composed of a container for storing the pharmaceutical products and the like, and a lid material. The container for PTP packaging is made of a resin sheet and is provided with a storage portion for storing medicines and the like. The lid material has a printing layer and a heat-resistant coating layer formed on the upper surface of an aluminum foil as a base material and printed on the lower surface. A layer and a heat-sealing layer are formed, and the lid material is welded to the container by heat-sealing so as to cover the storage portion of the container in which a drug or the like is stored.

Since the printing layer provided on the lid material of PTP packaging uses thermosetting ink using amino resin, the printing layer is heat-cured and the lid material is heat-sealed to the container. , Formaldehyde is generated. The generation of formaldehyde not only inhibits the efficacy of some chemicals, but also adversely affects the human body as a carcinogen.

Patent Documents 1 and 2 aiming at solving the problem of formaldehyde in PTP packaging describe that a formaldehyde absorbent is used for the inner surface of the lid material of PTP packaging. In References 1 and 2, formaldehyde generated by the printing layer on the outer surface of the lid material absorbs formaldehyde in the heat-sealing layer on the inner surface of the lid material before reaching the drug or the like contained in the PTP packaging. is there.

Further, Patent Document 3 describes that the lid material is provided with a layer containing a nitrocellulose resin and an isocyanate-based curing agent in order to prevent the influence of formaldehyde on the contents in the container in the package. Patent Document 4 describes that a packaging ink composition containing a polyester urethane resin and a blocked isocyanate is used for PTP packaging.

In addition, Patent Document 5 describes a printing ink for PTP packaging that does not use a curing agent that may emit formaldehyde. Further, Patent Document 6 describes a vinyl polymer (A) having at least two 2-oxo-1,3 dioxolane-4-yl groups in one molecule, and at least two carboxyl groups in one molecule. / Or a heat-sealing lid material for PTP packaging that does not emit formaldehyde by using a compound having an acid anhydride group as a heat-resistant coating material for a lid material for PTP packaging and a main component of ink has been proposed.

Japanese Unexamined Patent Publication No. 2006-1591 JP-A-2015-67718 Japanese Patent No. 4371894 Japanese Unexamined Patent Publication No. 2015-199816 Japanese Unexamined Patent Publication No. 2014-28621 Japanese Unexamined Patent Publication No. 2005-138848

The formaldehyde absorbers described in Patent Documents 1 and 2 are contained in the heat seal layer on the inner surface of the lid material, and the formaldehyde generated on the outer surface of the lid material is determined by a base material such as an aluminum foil of the lid material. Since they are separated from each other, they cannot be fully effective unless they come into contact with formaldehyde that invades from the outside of the lid material. Furthermore, since formaldehyde generated on the outer surface of the lid material invades from the outer periphery of the lid material, the formaldehyde absorber may break through depending on the part of the lid material, and formaldehyde cannot be absorbed, resulting in PTP packaging. There is a possibility that the contained medicines will be affected by formaldehyde. Further, as in References 1 and 2, the formaldehyde absorber contained in the heat seal on the inner surface of the lid material comes into contact with the drug or the like contained in the PTP package, and therefore has a medicinal effect depending on the type of the drug or the like. It is fully conceivable that it will affect.

The isocyanate-based curing agent described in Patent Document 3 is generally used for two-component curing inks and the like, has excellent initial drying properties, and has a short complete curing time, so that it is suitable for post-processing of cured products. Are better. However, such a feature of the isocyanate-based curing agent means that it has no long-term storage stability as compared with the amino resin and the blocked isocyanate used in the present invention, and the isocyanate-based curing agent as described in Patent Document 3 When a curing agent is used, if the printing / coating process is not performed immediately after mixing the curing agent, the mixture will be thickened or gelled. The drawback of the isocyanate-based curing agent not having long-term storage stability can be dealt with by mixing the curing agent immediately before use, but the complexity of weighing when using the curing agent cannot be eliminated and curing is performed. Mismeasurement of the agent or forgetting to add it may cause a problem that the performance of the product becomes insufficient.

Patent Document 4 aims to provide an ink composition having heat resistance and adhesiveness, and does not particularly describe suppressing the generation of formaldehyde. The packaging ink composition containing the polyester urethane resin and the blocked isocyanate described in Patent Document 4 is used for the ink layer on the surface of the aluminum base material of the lid material of PTP packaging, and is provided with a heat-resistant coating on the ink layer. A binder resin containing a general epoxy resin and a melamine resin is used for the layer, and since it is not a resin containing blocked isocyanate, its effect on formaldehyde is unknown. The "printing condition (1): 180 ° C. for 30 seconds" described in paragraph [0061] of the specification of Patent Document 4 takes several times longer than usual, and is not suitable for actual printing conditions. However, "baking condition (2): 240 ° C for 10 seconds" is a baking condition for retort pouch foods, which is not suitable for baking conditions for pharmaceutical packaging, and has a problem that the temperature is too high and there is a lot of energy loss. It cannot be said that it is appropriate to use the ink composition described in Patent Document 4 for the assumed PTP packaging.

Therefore, an object of the present invention is to provide a printing ink composition for PTP packaging that suppresses the generation of formaldehyde or does not generate formaldehyde, and a laminate using the printing ink composition for PTP packaging.

The printing ink composition for PTP packaging of the present invention is a printing ink composition for PTP packaging used for the heat-resistant coating layer of the lid material of PTP packaging, and contains an epoxy resin, a polyvinyl butyral resin, and a formaldehyde absorber. It is characterized by.

The epoxy resin is a solid bisphenol A type epoxy resin having an epoxy equivalent of 2000 to 3500 g / eq.

As the formaldehyde absorber, any one of primary amines, secondary amines, amides, imines, amidines, imides, ureas, triazines, hydrazines, hydrazines, and guanidines can be used. Use.

The laminate of the present invention is a laminate used as a lid material for PTP packaging, and is an aluminum base material, a first printing layer provided on the upper surface of the aluminum base material, and the heat resistant material provided on the upper surface of the printing layer. It has a coating layer, has at least a heat seal layer on the lower surface of the aluminum base material, and the heat-resistant coating layer comprises a printing ink composition for PTP packaging containing an epoxy resin, a polyvinyl butyral resin, and a formaldehyde absorber. It is characterized by.

The first printing layer is composed of a solid coloring layer and a character printing layer.

A second printing layer is provided between the aluminum base material and the heat seal layer, and the second printing layer is composed of a solid coloring layer and a character printing layer.

Another form of the printing ink composition for PTP packaging of the present invention is a printing ink composition for PTP packaging, which comprises an ink composition for a heat-resistant coating layer of a lid material for PTP packaging and an ink composition for a printing layer of the lid material. The ink composition for a heat-resistant coating layer contains an epoxy resin and a blocked isocyanate curing agent, and the ink composition for a printing layer contains a vinyl chloride / vinyl acetate copolymer resin and a blocked isocyanate curing agent. It is characterized by.

The epoxy resin is a solid bisphenol A type epoxy resin having an epoxy equivalent of 2000 to 3500 g / eq.

The blocked isocyanate curing agent has any of active methylene, amine, oxime, and caprolactam as the blocking agent, and has a dissociation temperature of 90 to 120 ° C.

The vinyl chloride / vinyl acetate copolymer resin is copolymerized with vinyl alcohol or vinyl acrylate and functionalized with an OH group, and has a K value measured in accordance with JIS K7376-2 (ISO1628-2). Is 35 to 50.

Another form of the laminate of the present invention is a laminate used as a lid material for PTP packaging, which is an aluminum base material, the first print layer provided on the upper surface of the aluminum base material, and the first print layer. It has a heat-resistant coating layer provided on the upper surface, has at least a heat-sealing layer on the lower surface of the aluminum base material, and the heat-resistant coating layer comprises an ink composition for the heat-resistant coating layer containing an epoxy resin and a blocked isocyanate curing agent. The first printing layer is characterized by comprising an ink composition for the printing layer containing a vinyl chloride / vinyl acetate copolymer resin and a blocked isocyanate curing agent.

The first printing layer is composed of a solid coloring layer and a character printing layer, and the solid coloring layer and the character printing layer are made of an ink composition for a printing layer.

A second printing layer is provided between the aluminum base material and the heat seal layer, the second printing layer is made of the ink composition for the printing layer, and the second printing layer is a solid colored layer and a solid coloring layer. It is composed of a character printing layer, and the solid coloring layer and the character printing layer are composed of the printing layer ink composition.

The printing ink composition for PTP packaging of the present invention is a printing ink composition for PTP packaging used for the heat-resistant coating layer of the lid material of PTP packaging, and contains an epoxy resin, a polyvinyl butyral resin, and a formaldehyde absorber. By absorbing the formaldehyde generated during thermosetting with the formaldehyde absorber, the amount of formaldehyde generated can be suppressed.

The laminate of the present invention is a laminate used as a lid material for PTP packaging, and is an aluminum base material, a first printing layer provided on the upper surface of the aluminum base material, and the above-mentioned laminated body provided on the upper surface of the printing layer. It has a heat-resistant coating layer, has at least a heat-sealing layer on the lower surface of the aluminum substrate, and the heat-resistant coating layer comprises a printing ink composition for PTP packaging containing an epoxy resin, a polyvinyl butyral resin, and a formaldehyde absorber. As a result, the amount of formaldehyde generated can be suppressed more than before by absorbing the formaldehyde generated when the laminate is heat-sealed into the container of PTP packaging by the formaldehyde absorber.

Another form of the printing ink composition for PTP packaging of the present invention is a printing ink composition for PTP packaging, which comprises an ink composition for a heat-resistant coating layer of a lid material for PTP packaging and an ink composition for a printing layer of the lid material. The ink composition for the heat-resistant coating layer contains an epoxy resin and a blocked isocyanate curing agent, and the ink composition for a printing layer contains a vinyl chloride / vinyl acetate copolymer resin and a blocked isocyanate curing agent. , Realize an ink composition that does not generate formaldehyde during heat curing.

Another form of the laminate of the present invention is a laminate used as a lid material for PTP packaging, which is an aluminum base material, the first printing layer provided on the upper surface of the aluminum base material, and the first printing. An ink composition for the heat-resistant coating layer having a heat-resistant coating layer provided on the upper surface of the layer, having at least a heat-sealing layer on the lower surface of the aluminum base material, and the heat-resistant coating layer containing an epoxy resin and a blocked isocyanate curing agent. The first printing layer is composed of an ink composition for the printing layer containing a vinyl chloride / vinyl acetate copolymer resin and a blocked isocyanate curing agent, so that when the laminate is heat-sealed in a container of PTP packaging. It does not generate formaldehyde, and the problem caused by formaldehyde in the conventional PTP packaging can be surely solved.

It is sectional drawing of the laminated body of 1st Embodiment. It is sectional drawing of PTP packaging using the laminated body of 1st Embodiment. It is sectional drawing of the laminated body of 2nd Embodiment. It is sectional drawing of PTP packaging using the laminate of 2nd Embodiment.

The printing ink for PTP packaging of the present invention will be described below. The lid material for PTP packaging is a laminate in which a printing layer, a heat-resistant coating layer, a heat seal layer, etc. are provided on an aluminum base material, and the printing ink composition for PTP packaging according to the first embodiment of the present invention is PTP. An ink composition used for a heat-resistant coating layer that is the outermost layer of a packaging lid material.

The printing ink composition for PTP packaging of the first embodiment of the present invention contains at least an epoxy resin, a polyvinyl butyral resin, and a formaldehyde absorber. As the epoxy resin, it is preferable to use a solid bisphenol A type epoxy resin having an epoxy equivalent of 2000 to 3500 g / eq. The polyvinyl butyral resin may be any as long as it is compatible with the epoxy resin, and is not particularly limited.

The formaldehyde absorber may be any one of primary amines, secondary amines, amides, imines, amidines, imides, ureas, triazines, hydrazines, hydrazides, and guanidines. Is preferable, and hydrazides are most preferable. Specific examples of hydrazides include monohydrazide compounds such as lauric acid hydrazide, salicylate hydrazide, formhydrazide, acetohydrazide, propionate hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide and 3-hydroxy-2-naphthoic acid hydrazide. And dihydrazide oxalic acid, dihydrazide malonic acid, dihydrazide succinic acid, dihydrazide adipic acid, dihydrazide adipic acid, dihydrazide sebacic acid, dihydrazide dodecanoic acid, dihydrazide maleic acid, dihydrazide fumarate, diglycolic acid dihydrazide, diglycolic acid dihydrazide , Isophthalic acid dihydrazide, terephthalic acid dihydrazide, dimer acid dihydrazide and dihydrazide compounds such as dibasic acid dihydrazide such as 2,5-naphthoic acid dihydrazide can be used.

The printing ink composition for PTP packaging of the first embodiment also contains a curing catalyst and a solvent (methanol, propylene glycol monomethyl ether (PGM), toluene, etc.). An acid catalyst is preferably used as the curing catalyst, and aromatic sulfonic acid and a salt thereof can be used. The other solvents are not particularly limited, and can be appropriately blended as needed.

The ink composition for PTP packaging according to the first embodiment of the present invention absorbs formaldehyde generated during a thermosetting reaction when forming a heat-resistant coating layer by containing a formaldehyde absorber, and suppresses the generation of formaldehyde. Therefore, it is possible to reduce the adverse effects of formaldehyde on the human body.

Next, the invention of the laminate 1 using the printing ink composition for PTP packaging of the first embodiment will be described. The laminate 1 is used as a lid material for PTP packaging, and the printing ink composition for PTP packaging of the first embodiment is used for the heat-resistant coating layer 4 which is the outermost layer of the laminate 1.

The laminate 1 is composed of an aluminum base material 2, a first printing layer 3, a heat-resistant coating layer 4, a second printing layer 5, and a heat seal layer 6, and as shown in FIG. 1, the aluminum base material 2 The first printing layer 3 and the heat-resistant coating layer 4 are laminated in this order on the upper surface, and the second printing layer 5 and the heat seal layer 6 are laminated in this order on the lower surface of the aluminum base material 2.

The aluminum base material 2 is a general aluminum foil used as a lid material for PTP packaging, has a thickness of several tens of μm, and the material is not particularly limited. The first printing layer 3 provided on the upper surface of the aluminum base material 2 is composed of a solid white printing layer 7 and a character printing layer 8. The white solid printing layer 7 is formed by forming a white colored layer by solid coating, and a character printing layer 8 including characters, patterns, and the like is formed on the white solid printing layer 7.

For the white solid printing layer 7 and the character printing layer 8, an ink composition generally used for the printing layer of the lid material of PTP packaging can be used depending on the use, type, etc. of PTP packaging. As the ink composition, an ink composition containing an amino resin curing agent, a polyester-based urethane resin, a pigment, or the like is used. As the amino resin, a urea resin, a melamine resin, a guanamine resin, a copolymer resin thereof or the like can be used, but a butylated melamine resin or a butylated urea resin is preferable. The order in which the white solid printing layer 7 and the character printing layer 8 are laminated is not particularly limited, and one of them may be omitted.

The heat-resistant coating layer 4 is formed on the first printing layer 3 using the printing ink composition for PTP packaging of the first embodiment, and the printing ink composition for PTP packaging is at least an epoxy resin. , Polyvinyl butyral resin, and formaldehyde absorber.

The second printing layer 5 provided on the lower surface of the aluminum base material 2 is composed of a character printing layer 9 and a solid colored printing layer 10. The character printing layer 9 has characters, patterns, and the like printed on the lower surface of the aluminum base material 2, and the solid coloring printing layer 10 is formed by solid coating under the character printing layer 9. The second printing layer 5 is a layer appropriately provided according to the type and application of the PTP packaging. When the second printing layer 5 is not provided, the heat seal layer 6 is directly provided on the lower surface of the aluminum base material 2. Will be formed.

The heat-sealing layer 6 is used for sealing the laminate 1 in a container of PTP packaging by heat-sealing, and is formed by a heat-sealing adhesive. The heat-sealing adhesive is appropriately selected according to the material of the PTP packaging in which the laminate 1 is heat-sealed. For example, vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polypropylene-based, polyolefin-based, polyester-based, etc. Resin can be used.

The PTP packaging 11 using the laminate 1 as a lid material will be described. As shown in FIG. 2, the PTP package 11 is composed of a container 12 and a lid material 1, and the container 12 is provided with an accommodating portion 13 for accommodating the drug 15, for sealing the accommodating portion 13. In addition, the laminate 1 is heat-sealed on the flange 14 of the container 12.

Since the laminate 1 of the present invention absorbs formaldehyde generated when the container 12 is heat-sealed by the formaldehyde absorber contained in the heat-resistant coating layer 4, it is transferred to the pharmaceutical product 15 or the like contained in the PTP package 11. The effect of formaldehyde can be reduced.

The printing ink composition for PTP packaging of the present invention contains a formaldehyde absorber, so that formaldehyde generated during a thermosetting reaction when forming a heat-resistant coating layer and a laminate are heat-sealed as a lid material for PTP packaging. Formaldehyde generated at the time of printing can be absorbed, and the influence of formaldehyde on pharmaceuticals and the like in the PTP package can be significantly reduced.

Next, the printing ink composition for PTP packaging of the second embodiment of the present invention will be described. The printing ink composition for PTP packaging of the second embodiment is used for the ink composition for a heat-resistant coating layer used as the outermost layer of the lid material for PTP packaging and the printing layer for the lid material. Contains an ink composition for a printing layer.

The heat-resistant coating layer ink composition contains an epoxy resin and a blocked isocyanate curing agent, and the printing layer ink composition contains a vinyl chloride / vinyl acetate copolymer resin and a blocked isocyanate curing agent. The printing layer ink composition needs to be used for all printing layers provided on the lid material.

As the epoxy resin contained in the heat-resistant coating layer ink composition, it is preferable to use a solid bisphenol A type epoxy resin having an epoxy equivalent of 2000 to 3500 g / eq. The vinyl chloride / vinyl acetate copolymer resin contained in the ink composition for a printing layer is a copolymerized with vinyl alcohol or vinyl acrylate and functionalized with an OH group, and has a K value of 35 to 50. It is preferable to use one that is.

The blocked isocyanate curing agent contained in the heat-resistant coating layer ink composition and the printing layer ink composition has any of active methylene, amine, oxime, and caprolactam as the blocking agent and dissociates. It is preferable to use an ink having a temperature of 90 to 120 ° C. In particular, it is preferable to use an HDI-based isocyanate species blocked with an active methylene-based substance.

The ink composition for the heat-resistant coating layer may contain a solvent (methanol, PGM, toluene, etc.) and the like, if necessary, in addition to the epoxy resin and the blocked isocyanate curing agent.

The ink composition for the printing layer contains a pigment, a polyester-based urethane resin, a solvent (methanol, PGM, toluene, etc.), etc., in addition to the vinyl chloride / vinyl acetate copolymer resin and the blocked isocyanate curing agent, if necessary. Can include.

The printing ink composition for PTP packaging according to the second embodiment of the present invention is a curing agent for an amino resin that generates formaldehyde as a curing agent contained in the heat-resistant coating layer ink composition and the printing layer ink composition. Instead, by using a blocked isocyanate curing agent that does not generate formaldehyde, it is possible to eliminate the generation of formaldehyde during the thermosetting reaction, and the influence of formaldehyde can be eliminated.

Next, the invention of the laminate 1'using the printing ink composition for PTP packaging of the second embodiment will be described. The laminate 1'is used as a lid material for PTP packaging, and the heat-resistant coating layer 4', the first printing layer 3', and the second printing layer 5'of the laminate 1'are used for the PTP packaging of the second embodiment. A printing ink composition is used. The same members as those in the first embodiment are described using the same reference numerals.

The laminate 1'is composed of an aluminum base material 2, a first printing layer 3', a heat-resistant coating layer 4', a second printing layer 5', and a heat-sealing layer 6, and as shown in FIG. 3, aluminum. The first printing layer 3'and the heat-resistant coating layer 4'are laminated on the upper surface of the base material 2 in this order, and the second printing layer 5'and the heat seal layer 6 are laminated on the lower surface of the aluminum base material 2 in this order. There is.

The aluminum base material 2 is a general aluminum foil used as a lid material for PTP packaging, has a thickness of several tens of μm, and the material is not particularly limited. The first printing layer 3'provided on the upper surface of the aluminum base material 2 is composed of a solid white printing layer 7'and a character printing layer 8'. The white solid printing layer 7'is a white colored layer formed by solid coating, and a character printing layer 8'including characters, patterns, etc. is formed on the white solid printing layer 7'. ..

For the white solid printing layer 7'and the character printing layer 8', the printing layer ink composition of the PTP packaging ink composition of the second embodiment is used. The ink composition for a printing layer contains a vinyl chloride / vinyl acetate copolymer resin and a blocked isocyanate curing agent.

The heat-resistant coating layer 4'is formed on the first printing layer 3'using the heat-resistant coating layer ink composition of the printing ink composition for PTP packaging of the second embodiment, and the heat-resistant coating layer 4'is formed on the first printing layer 3'. The ink composition for use contains at least an epoxy resin and a blocked isocyanate curing agent.

The second printing layer 5'provided on the lower surface of the aluminum base material 2 is composed of a character printing layer 9'and a solid colored printing layer 10'. The character printing layer 9'is a product in which characters, patterns, etc. are printed on the lower surface of the aluminum base material 2, and the solid colored printing layer 10'is formed by solid coating under the character printing layer 9'. ing. For the character printing layer 9'and the solid coloring printing layer 10', the printing layer ink composition of the PTP packaging ink composition of the second embodiment is used. The second printing layer 5'is a layer appropriately provided according to the type and application of the PTP packaging, and when the second printing layer 5'is not provided, the heat seal layer is directly applied to the lower surface of the aluminum base material 2. 6 will be formed.

The heat seal layer 6 is used for sealing the laminated body 1'in a container of PTP packaging by heat seal, and is formed by a heat seal adhesive. The heat-sealing adhesive is appropriately selected according to the material of the PTP packaging in which the laminate 1'is heat-sealed. For example, vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polypropylene-based, polyolefin-based, polyester-based, etc. Resin can be used.

The PTP packaging 11'using the laminate 1'as a lid material will be described. As shown in FIG. 4, the PTP package 11'is composed of a container 12 and a lid material 1, and the container 12 is provided with a storage unit 13 for storing the drug 15, in order to seal the storage unit 13. , The laminated body 1'is heat-sealed on the flange 14 of the container 12.

Since the laminate 1'of the present invention does not contain an amino resin that generates formaldehyde in the heat-resistant coating layer and the printing layer when the container 12 is heat-sealed, formaldehyde is not generated during the thermosetting reaction. , The problem caused by formaldehyde can be solved.

The printing ink composition for PTP packaging of the present invention uses a blocked isocyanate curing agent that does not generate formaldehyde as a curing agent during a thermosetting reaction when forming a laminate, and for PTP packaging of the laminate. Formaldehyde can be eliminated when heat-sealing as a lid material, the influence of formaldehyde on pharmaceuticals and the like in PTP packaging can be eliminated, and heat resistance equivalent to that of conventional products can be ensured. ..

Next, the effects of the printing ink composition for PTP packaging of the present invention will be described with reference to Examples 1 and 2 and Comparative Examples 1 and 2.

As Example 1, a sample using the printing ink composition for PTP packaging of the first embodiment is prepared. For the sample of Example 1, a hard aluminum foil having a thickness of 20 μm is prepared as an aluminum base material, a solid white colored layer and a black character layer are printed on the aluminum foil, and each is dried at 180 ° C. for 10 seconds. Then, a heat-resistant coating layer was applied and a laminate dried at 220 ° C. for 10 seconds was prepared as a sample.

The ink composition for the white solid colored layer is 6 parts by weight of the butylated urea resin "Beccamin P-138 (manufactured by DIC Corporation)", 21 parts by weight of the titanium dioxide pigment, and the vinyl chloride copolymer "Binnol E15 / 40A (Wacker)". Contains 12 parts by weight of "Chemical", 3 parts by weight of polyester urethane resin "Samplen IB-2000 (manufactured by Sanyo Kasei Kogyo Co., Ltd.)", 5 parts by weight of propylene glycol monomethyl ether (PGM) as a solvent, and toluene. 10 parts by weight and 40 parts by weight of methyl ethyl ketone (MEK) were contained.

The ink composition for the black character coloring layer consists of 3 parts by weight of the butylated urea resin "Beccamin P-138 (manufactured by DIC Corporation)", 7 parts by weight of carbon black pigment, and vinyl chloride copolymer "Binnol E15 / 40A (Wacker)". Contains 12 parts by weight of "Chemical", 3 parts by weight of polyester urethane resin "Samplen IB-2000 (manufactured by Sanyo Kasei Kogyo Co., Ltd.)", 8 parts by weight of PGM as a solvent, 30 parts by weight of toluene, MEK Was used in an amount containing 40 parts by weight.

The ink composition of the heat-resistant coating layer (printing ink composition for PTP packaging of the first embodiment) is a bisphenol A type solid epoxy containing 6 parts by weight of a butylated urea resin "Beccamin P-138 (manufactured by DIC Co., Ltd.)". 22 parts by weight of resin "JER1009 (manufactured by Mitsubishi Chemical Co., Ltd.)", 1 part by weight of polyvinyl butyral resin "Eslek BX-1 (manufactured by Sekisui Chemical Co., Ltd.)", and 0.1 parts of paratoluenesulfonic acid as a curing catalyst. By weight, silica "Fineseal E-50 (manufactured by Tokuyama Co., Ltd.)" is 4 parts by weight, methanol is 5 parts by weight, PGM is 8 parts by weight, toluene is 18 parts by weight, and MEK is the balance, for a total of 100 parts by weight. A part of the solution was prepared, and 10 parts by weight of the aldehyde absorber "Chemcatch P-9600 (manufactured by Otsuka Chemical Co., Ltd.)" was added thereto.

As Example 2, a sample using the printing ink composition for PTP packaging of the second embodiment is prepared. For the sample of Example 2, a hard aluminum foil having a thickness of 20 μm is prepared as an aluminum base material, a solid white colored layer and a black character layer are printed on the aluminum foil, and each is dried at 180 ° C. for 10 seconds. Then, a heat-resistant coating layer was applied and a laminate dried at 220 ° C. for 10 seconds was prepared as a sample.

The ink composition for a solid white colored layer (the ink composition for a printing layer of the printing ink composition for PTP packaging of the second embodiment) has a blocked isocyanate curing having an active methylene-based blocking agent having a dissociation temperature of 110 ° C. or lower. 6 parts by weight of agent (manufactured by Asahi Kasei Chemicals Co., Ltd.), 21 parts by weight of titanium dioxide pigment, 12 parts by weight of vinyl chloride copolymer "Binnol E15 / 40A (manufactured by Wacker Chemical Co., Ltd.)", polyester urethane resin "Samplen IB-" 2000 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) ”was contained in 3 parts by weight, and a solvent containing 5 parts by weight of PGM, 10 parts by weight of toluene, and 40 parts by weight of MEK was used.

The ink composition for the black character coloring layer (the ink composition for the printing layer of the printing ink composition for PTP packaging of the second embodiment) has a blocked isocyanate curing having an active methylene-based blocking agent having a dissociation temperature of 110 ° C. or lower. 3 parts by weight of agent (manufactured by Asahi Kasei Chemicals Co., Ltd.), 7 parts by weight of carbon black pigment, 12 parts by weight of vinyl chloride copolymer "Binnol E15 / 40A (manufactured by Wacker Chemical Co., Ltd.)", polyester urethane resin "Samplen IB-" 2000 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) ”was contained in 3 parts by weight, and a solvent containing 8 parts by weight of PGM, 30 parts by weight of toluene, and 40 parts by weight of MEK was used.

The heat-resistant coating layer ink composition (the heat-resistant coating layer ink composition of the printing ink composition for PTP packaging of the second embodiment) has a blocked isocyanate curing having an active methylene-based blocking agent having a dissociation temperature of 110 ° C. or lower. 5 parts by weight of agent (manufactured by Asahi Kasei Chemicals Co., Ltd.), 23 parts by weight of bisphenol A type solid epoxy resin "JER1009 (manufactured by Mitsubishi Chemical Co., Ltd.)", polyvinyl butyral resin "Eslek BX-1 (manufactured by Sekisui Chemical Co., Ltd.)" 1 part by weight, silica "Fineseal E-50 (manufactured by Tokuyama Co., Ltd.)" by 4 parts by weight, methanol as solvent by 5 parts by weight, PGM by 8 parts by weight, toluene by 18 parts by weight, and MEK by 40 parts by weight. Was used.

Comparative Example 1
A hard aluminum foil having a thickness of 20 μm is prepared as an aluminum base material, a solid white colored layer and a black character layer are printed on the aluminum foil, and each is dried at 180 ° C. for 10 seconds. Then, as a heat-resistant coating layer, a heat-resistant ink composition containing no formaldehyde absorber was applied, and a laminate dried at 220 ° C. for 10 seconds was prepared as a sample. The same ink composition as in Example 1 is used for the solid white coloring layer and the black character layer.

For the heat-resistant ink composition that does not contain the formaldehyde absorber of the heat-resistant coating layer, 6 parts by weight of the butylated urea resin "Beccamin P-138 (manufactured by DIC Co., Ltd.)" and the bisphenol A type solid epoxy resin "JER1009 (Mitsubishi Chemical Co., Ltd.)" ”, 22 parts by weight, polyvinyl butyral resin“ Eslek BX-1 (manufactured by Sekisui Chemical Co., Ltd.) ”by 1 part by weight, paratoluene sulfonic acid as a curing catalyst by 0.1 parts by weight, silica“ Fine Seal E -50 (manufactured by Tokuyama Co., Ltd.) ”was mixed in 4 parts by weight, methanol as a solvent in 5 parts by weight, PGM in 8 parts by weight, toluene in 18 parts by weight, and MEK as the balance, and a total of 100 parts by weight of the solution was used. ..

Comparative Example 2
A hard aluminum foil having a thickness of 20 μm is prepared as an aluminum base material, a solid white colored layer and a black character layer are printed on the aluminum foil, and each is dried at 180 ° C. for 10 seconds. Then, as a heat-resistant coating layer, a heat-resistant ink composition was applied, and a laminate dried at 220 ° C. for 10 seconds was prepared as a sample. As the white solid coloring layer, the black character layer, and the heat-resistant coating layer, the blocked isocyanate curing agent contained in the ink composition used in Example 2 is changed to one having a MEK oxime-based blocking agent.

The ink composition for a solid white colored layer contains 6 parts by weight of a blocked isocyanate curing agent (manufactured by Asahi Kasei Chemicals Co., Ltd.) having a MEK oxime-based blocking agent having a dissociation temperature of 130 ° C. or higher, 21 parts by weight of a titanium dioxide pigment, and chloride. Contains 12 parts by weight of vinyl copolymer "Binnol E15 / 40A (manufactured by Wacker Chemical Co., Ltd.)", 3 parts by weight of polyester urethane resin "Samplen IB-2000 (manufactured by Sanyo Kasei Kogyo Co., Ltd.)", and 5 parts of PGM as a solvent. The one containing 10 parts by weight of toluene and 40 parts by weight of MEK was used.

The ink composition for the black character coloring layer contains 3 parts by weight of a blocked isocyanate curing agent (manufactured by Asahi Kasei Chemicals Co., Ltd.) having a MEK oxime-based blocking agent having a dissociation temperature of 130 ° C. or higher, 7 parts by weight of a carbon black pigment, and chloride. Contains 12 parts by weight of vinyl copolymer "Binnol E15 / 40A (manufactured by Wacker Chemical Co., Ltd.)", 3 parts by weight of polyester urethane resin "Samplen IB-2000 (manufactured by Sanyo Kasei Kogyo Co., Ltd.)", and 8 parts of PGM as a solvent. The one containing 30 parts by weight of toluene, 40 parts by weight of MEK and 40 parts by weight of MEK was used.

The ink composition of the heat-resistant coating layer contains 5 parts by weight of a blocked isocyanate curing agent (manufactured by Asahi Kasei Chemicals Co., Ltd.) having a MEK oxime-based blocking agent having a dissociation temperature of 130 ° C. or higher, and a bisphenol A type solid epoxy resin "JER1009 (Mitsubishi). 23 parts by weight of "Chemical Co., Ltd.", 1 part by weight of polyvinyl butyral resin "Eslek BX-1 (manufactured by Sekisui Chemical Co., Ltd.)", and 4 parts by weight of silica "Fine Seal E-50 (manufactured by Tokuyama Co., Ltd.)" As the solvent, a solvent containing 5 parts by weight of methanol, 8 parts by weight of PGM, 18 parts by weight of toluene, and 40 parts by weight of MEK was used.

Samples of Examples 1 and 2 and Comparative Examples 1 and 2 were prepared, formaldehyde emission measurement and heat resistance test were performed, and the results are shown in Table 1.

Measurement of Formaldehyde Emission A 500 cm ² sample was prepared for each of Examples 1 and 2 and Comparative Examples 1 and 2, and each sample was placed in a 500 ml headspace bottle and heated at 100 ° C. for 2 hours to generate formaldehyde. Then, the temperature was returned to room temperature over 1 hour, and the formaldehyde concentration (ppm) in the headspace bottle was measured using a gas detector tube (No. 91 L detector tube manufactured by Gastec Co., Ltd.).

Heat resistance test In each of the samples of Examples 1 and 2 and Comparative Examples 1 and 2, the coating films on the printed surfaces were combined on each other and thermocompression bonded, and the temperature was 160 to 240 ° C. without blocking between the coating layers. We investigated in the range. As an evaluation, the highest temperature at which no blocking was observed is shown. The thermocompression bonding was performed under the conditions of a pressure of 0.3 MPa and 1 second at each temperature. The practical temperature is 200 ° C. or higher.

Referring to Table 1, the amount of formaldehyde emission in Example 1 was reduced by about 30% as compared with Comparative Example 1. Therefore, formaldehyde in the printing ink composition for PTP packaging according to the first embodiment of the present invention. The effectiveness of the absorbent is recognized. Further, regarding heat resistance, Example 1 and Comparative Example 1 are the same, and it can be seen that the printing ink composition for PTP packaging according to the first embodiment of the present invention has heat resistance equivalent to that of the conventional one.

Referring to Table 1, in Example 2 and Comparative Example 2 using the blocked isocyanate curing agent, the amount of formaldehyde emission is zero, and using the blocked isocyanate curing agent instead of the amino resin as the curing agent is a measure against formaldehyde. It turns out that it is extremely effective. Further, the heat resistance of Example 2 is almost the same as that of Example 1 and Comparative Example 1, and it can be seen that the performance required as an ink composition for PTP packaging is sufficiently satisfied. However, Comparative Example 2 using a blocked isocyanate curing agent of a different type from Example 1 has significantly lower heat resistance than the others, and is appropriately suitable for the performance required for the PTP packaging ink composition. It is necessary to select a blocked isocyanate curing agent.

As described above, the printing ink composition and laminate for PTP packaging of the present invention can solve the problem caused by formaldehyde while sufficiently ensuring the performance required for the conventional ink composition and laminate for PTP packaging. it can.

The printing ink composition for PTP packaging of the first embodiment of the present invention is an ink composition used for the heat-resistant coating layer, but the ink composition used for the printing layer is not limited, and the printing ink composition of the second embodiment is not limited. Unlike the ink composition for PTP packaging, it is not necessary to use a blocked isocyanate curing agent for the printing layer, and a conventional ink composition can be used.

1,1'Laminate 2 Aluminum base material 3,3'First printing layer 4,4' Heat-resistant coating layer 5 Second printing layer 6 Heat-sealing layer 7,7'White solid printing layer 8,8'Character printing layer 9 , 9'Character printing layer 10,10' Solid color printing layer 11,11' PTP packaging 12 Container 13 Storage unit 14 Flange 15 Pharmaceuticals

Claims (5)

A printing ink composition for PTP packaging used for a heat-resistant coating layer of a lid material for PTP packaging.
Butylated urea resins, bisphenol A type epoxy resin solid, polyvinyl butyral resins, silica, and, seen including formaldehyde absorbent hydrazines,
A printing ink composition for PTP packaging, wherein the epoxy equivalent of the bisphenol A type epoxy resin is 2000 to 3500 g / eq . A laminate having a heat-resistant coating layer made of the printing ink composition for PTP packaging according to claim 1 and used as a lid material for PTP packaging.
It has an aluminum base material, a first printing layer provided on the upper surface of the aluminum base material, and the heat-resistant coating layer provided on the upper surface of the printing layer.
A laminate characterized by having at least a heat seal layer on the lower surface of the aluminum base material. The laminate according to claim 2 , wherein the first printing layer is composed of a solid coloring layer and a character printing layer. The laminate according to claim 2 or 3 , wherein a second printing layer is provided between the aluminum base material and the heat seal layer. The laminate according to claim 4 , wherein the second printing layer is composed of a solid coloring layer and a character printing layer.